WO2018166407A1 - 提高或延长铅酸蓄电池或电池组使用寿命的方法 - Google Patents

提高或延长铅酸蓄电池或电池组使用寿命的方法 Download PDF

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Publication number
WO2018166407A1
WO2018166407A1 PCT/CN2018/078612 CN2018078612W WO2018166407A1 WO 2018166407 A1 WO2018166407 A1 WO 2018166407A1 CN 2018078612 W CN2018078612 W CN 2018078612W WO 2018166407 A1 WO2018166407 A1 WO 2018166407A1
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Prior art keywords
lead
charging
battery
electrode
acid battery
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PCT/CN2018/078612
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English (en)
French (fr)
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杨春晓
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杨春晓
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Publication of WO2018166407A1 publication Critical patent/WO2018166407A1/zh

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present invention relates to increasing or extending the useful life of a battery or battery pack, and more particularly to a method of increasing or extending the useful life of a lead-acid battery or battery pack.
  • Lead-acid batteries or battery packs have been widely used for many years due to their low manufacturing cost, high cost/price ratio, safety, stability, and recyclability, and they have a leading position in the secondary battery market.
  • lead-acid batteries or battery packs exhibit low specific energy and short service life.
  • the specific energy of lead-acid batteries or battery packs in application is about 20-40Wh/kg, and the cycle life is about 150-1500 times, the life of the float is about 5-20 years. There are many factors that affect the service life of lead-acid batteries or battery packs.
  • the technical problem to be solved by the present invention is to provide a method for improving or prolonging the service life of a lead-acid battery or a battery pack, in particular by solving or improving the softening or/and shedding of the positive active material of a lead-acid battery or a battery pack.
  • One or more problems of negative electrode specific surface area shrinkage, corrosion, passivation, early capacity loss, sulfation, and poor contact of active material and conductive current collector to increase or prolong the service life of lead-acid batteries or battery packs.
  • the service life includes, but is not limited to, one or more of a cycle life and a float life.
  • the lead-acid battery or battery pack that is, a lead-acid battery or a lead-acid battery pack.
  • the method for improving or prolonging the service life of a lead-acid battery or a battery pack includes: polarity inversion of a positive electrode and a negative electrode of a lead-acid battery or/and a lead-acid battery group; Charging or charging and discharging operation (hereinafter also referred to as polarity reversal and subsequent charging or charging and discharging operations), the total number of times the operation is performed or performed is one or more times (including one time, the same below).
  • the polarity inversion of the positive electrode and the negative electrode and subsequent charging or charging and discharging operations are performed, that is, the positive electrode and the negative electrode are reversed in polarity, and after the polarity is reversed, the polarity is reversed.
  • the electrodes are charged or charged and discharged.
  • the total cumulative number means that the lead-acid battery or battery pack occurs during the entire period of its existence or the lead-acid battery or battery pack is completed before the end of its service life and after the end of its service life.
  • Each of the positive and negative polarity inversions and subsequent charging or charging and discharging operations may be continuously performed discontinuously, or partially continuously and partially discontinuously performed.
  • the polarity of the positive or negative electrode of the lead-acid battery or the battery pack includes positive (positive polarity) or negative (negative polarity) of the electrode of the lead-acid battery or the battery, and the positive characteristics of the electrode generally include, at the electrode
  • the electrode reaction occurring on the electrode is a positive electrode reaction, and the electrode potential phase is relatively high.
  • the negative characteristic of the electrode generally includes that the electrode reaction occurring on the electrode is a negative electrode reaction and a relatively low electrode potential phase.
  • the polarity inversion means that the polarity of the original positive electrode changes from positive to negative or/and the polarity of the original negative electrode changes from negative to positive.
  • the charging or charging and discharging operation is performed on the electrode whose polarity is reversed, that is, the electrode which is the positive electrode before the polarity is reversed and the negative electrode after the polarity is reversed is charged or charged and discharged as the negative electrode, and the polarity is reversed.
  • the electrode which is the negative electrode before the rotation and the positive electrode after the polarity is reversed is charged or charged and discharged as the positive electrode.
  • the former causes the lead-acid battery negative electrode reaction to occur on the electrode, and the latter causes the lead-acid battery positive electrode reaction to occur on the electrode.
  • the original positive electrode here also referred to as electrode A
  • the original negative electrode also referred to herein as electrode B
  • the polarity of the positive electrode and the negative electrode is reversed and the positive and negative electrodes of the lead-acid battery or the battery pack during the charging or charging and discharging operation, and thus, the positive electrode and the negative electrode of the lead-acid battery or the battery pack are first.
  • the operation steps include, firstly, polarity reversal of the positive electrode and the negative electrode of the lead-acid battery or the battery pack, that is, the lead-acid battery or the battery pack.
  • the polarity of the original positive electrode (electrode A) is reversed to negative, and the polarity of the original negative electrode (electrode B) is reversed to positive by negative, and then after the polarity is reversed, the pass will be passed.
  • the polarity-reversed electrode is charged or charged and discharged
  • the original positive electrode (electrode A) is used as a negative electrode
  • the original negative electrode (electrode B) is used as a positive electrode to charge or charge and discharge the lead-acid battery or battery pack after the secondary polarity is reversed.
  • the charging or charging and discharging operation after the polarity inversion operation to the polarity inversion is completed that is, the polarity inversion and the subsequent charging or charging and discharging operations (at this time, the lead-acid battery or The first polarity inversion of the battery pack and subsequent charging or charging and discharging operations), the polarity inversion of the positive and negative electrodes and the subsequent charging or charging and discharging operations are performed, including
  • the positive electrode (electrode A) has an electrode potential that is converted from a relatively high phase to a relatively low phase, and the electrode reaction that occurs is reversed from the original lead acid battery positive electrode reaction to the lead acid battery negative electrode reaction, for the original negative electrode. (electrode B), the change is reversed.
  • the positive electrode is the original positive electrode (electrode A) of the lead-acid battery or the battery pack
  • the negative electrode charged or charged and discharged is the original negative electrode (electrode B) of the lead-acid battery or the battery pack, this time (second time)
  • the reverse polarity of the positive electrode and the negative electrode and the subsequent charging or charging and discharging operations include that, for the original positive electrode (electrode A), the electrode potential is converted from a relatively low phase to a relatively high phase.
  • the electrode reaction that occurred was reversed to the positive electrode of the lead-acid battery by the reaction of the negative electrode of the original lead-acid battery, and the change was reversed for the original negative electrode (electrode B).
  • the original positive electrode (electrode A) and the original negative electrode (electrode B) were subjected to a total of two (i.e., the first and second) polarity inversions and subsequent charging or charging and discharging operations.
  • 3 or more times of polarity inversion and subsequent charging or charging and discharging operations may be based on the above 2 (first, second) polarity inversion and subsequent charging or charging and discharging operations
  • the above-mentioned first or first, second polarity inversion and subsequent charging or charging and discharging operations are performed again or again, and can be performed according to the above 2 times (first time, second time)
  • the polarity inversion and subsequent charging or charging and discharging operations are analogously understood and implemented.
  • the polarity inversion is completed faster when actually occurring on the electrode, the time is shorter, and at the critical point of the polarity inversion,
  • the polarity of the electrode changes from the polarity of the critical end to the polarity of the other end of the critical, requiring less power, or, when passing this less charge, changing the polarity of the electrode from the critical polarity of the end.
  • the polarity reversal is completed. Therefore, due to the small amount of electricity involved, the influence of the polarity reversal on changing electrode composition and performance is generally small or negligible.
  • the polarity inversion mainly refers to a change in a polarity state
  • the polarity inversion and subsequent charge or charge and discharge operations cause the composition of the electrode Significant changes in performance, etc., are mainly related to the charging or charging and discharging operations after polarity reversal.
  • the polarity inversion and subsequent charging or charging and discharging operations include polarity reversal of the electrodes of the lead-acid battery or/and the lead-acid battery, and after the polarity is reversed, the polarity is passed.
  • the inverted electrode is subjected to an electrochemical reaction in which the electrode which is the positive electrode before the polarity is reversed is subjected to the reverse polarity reaction of the lead acid battery, and the electrode which is the positive electrode before the polarity is reversed is contained therein.
  • the lead oxide, the basic lead sulfate, and the lead sulfate are electrochemically reduced after the polarity is reversed, and the electrode which is the negative electrode before the polarity is reversed is subjected to the positive electrode reaction of the lead-acid battery after the polarity is reversed. , one or more of them.
  • the current in the polarity reversal and subsequent charging or charging and discharging operations includes a direct current, a pulse current, or a combined current of a pulse and a direct current.
  • the number of charging operations after any one polarity inversion is one or more (including one time, the same applies hereinafter).
  • Performing the polarity inversion of the positive and negative electrodes of the lead-acid battery or the battery pack and the subsequent charging or charging and discharging operations include: inverting the polarities of the positive and negative electrodes and subsequent charging or charging and discharging operations and The operation of the lead-acid battery or the battery pack is interspersed and alternately performed, and when the lead-acid battery or the battery pack is in operation, the original positive electrode and the original negative electrode are in one of the following three electrode working states.
  • the original positive electrode always operates as a positive electrode, and the original negative electrode always operates as a negative electrode; (2) the original positive electrode always operates as a negative electrode, and the original negative electrode always operates as a positive electrode; (3) the original positive electrode sometimes As a positive electrode, it may operate as a negative electrode. Accordingly, the original negative electrode may operate as a negative electrode or may operate as a positive electrode; the original positive electrode and the original negative electrode may have not been subjected to any of the positive electrodes. When the polarity of the negative electrode is reversed and the charging or charging/discharging operation thereafter, the positive electrode and the negative electrode of the lead-acid battery or the battery pack.
  • the polarity inversion of the positive and negative electrodes of the lead-acid battery or the battery pack and the subsequent charging or charging and discharging operations include: performing two consecutive or consecutive even times of positive and negative polarity inversion and subsequent charging. Or a charge/discharge operation, performing one or more consecutive positive or negative polarity inversions and subsequent charging or charging and discharging operations, one or more of them.
  • the polarity inversion of the positive electrode and the negative electrode and subsequent charging or charging and discharging operations include separately performing the positive and negative polarity inversion on only one of the battery cells in the battery pack. And subsequent charging or charging and discharging operations, or performing only the positive and negative polarity inversions and subsequent charging or charging and discharging operations on some (ie, two or more) single cells in the battery pack, This is referred to as a distinction operation.
  • the unit cell that is, a unit cell.
  • the polarity inversion of the positive and negative electrodes and subsequent charging or charging and discharging operations include operations of performing pulse charging or/and discharging; the pulse charging or/and discharging includes positive pulse, negative pulse, and positive and negative pulse mixing. One or more of pulse charging or / and discharging operations.
  • the polarity reversal of the positive and negative electrodes and subsequent charging or charging and discharging operations may be in any state of charge or operation of the lead-acid battery or the battery pack.
  • the discharge or/and charging operation (hereinafter referred to as discharge or/and charging operation before polarity inversion) is then started, started, and the polarity inversion and subsequent charging or charging and discharging operations are performed.
  • discharge or/and charging operation before polarity inversion is then started, started, and the polarity inversion and subsequent charging or charging and discharging operations are performed.
  • the latter case involves discharging the battery or battery pack until the voltage is reduced to 0V or 0V before and after polarity reversal, and then performing polarity reversal.
  • the polarity inversion of the lead-acid battery or the battery pack, the polarity inversion and subsequent charging or charging and discharging operations, the discharging or/and charging operation before the polarity inversion, and the distinguishing operation can be performed by programming.
  • the positive or negative electrode of the lead-acid battery or the battery pack may be subjected to polarity reversal, charging or charging/discharging operation after polarity inversion or discharge or/and charging operation before polarity inversion may be based on a certain physical quantity and quantity value. Start, stop, or not operate with the results of one or more of the chemical quantities and their change values and calculated values, measurement, signal acquisition, calculation, and the like.
  • the physical quantity value includes one of a voltage value, a current value, a current density value, a power value, a capacity value, a power value, a time value, a temperature value, a force value, a pressure value, a density value, a photometric value, and a frequency value, or a plurality of; the quantity value includes one or more of an accumulated value, an odd value, an even value, a proportional value, a battery or/and a charge and discharge cycle value of the battery; the chemical quantity includes a battery or / and the acidity value of the battery pack.
  • the physical quantity, quantity value, and chemical quantity value include physical quantity and quantity of the battery or/and the battery pack during charging, during discharging, during cyclic operation, during floating charging operation, in an open circuit or in a resting state. Value, chemical quantity, and other physical, quantitative, and chemical quantities associated with lead-acid batteries or/and lead-acid batteries.
  • the charging or charging and discharging operation is performed on the polarity-reversed electrode, wherein the charging or charging and discharging power is generally 0.5 times or more of the rated capacity of the electrode.
  • both positive and negative electrodes are positive and negative common electrodes (ie, electrodes common to positive and negative electrodes), and positive and negative common electrodes are used in the lead-acid battery or battery.
  • it can be used as a positive electrode or as a negative electrode, or some can be used as a positive electrode, some as a negative electrode, or used as a positive electrode at a certain time during operation or use of the lead-acid battery or battery pack.
  • the positive and negative electrode common electrodes When used as a negative electrode at a time, one or more of them; when forming a positive electrode and a negative electrode of a lead-acid battery or a battery pack, the positive and negative electrode common electrodes include, but are not limited to, the same active substance or the same active substance formula as each other.
  • the positive and negative electrode common electrodes, the positive and negative electrode common electrodes which are equivalent to each other, and the positive and negative electrode common electrodes of the same type; the equivalent of each other means that the electrodes are formed or charged and discharged.
  • the same positive and negative common electrodes are those that are being carried out Positive and negative electrode common electrodes which are identical to each other before being formed or charged and discharged, and which can form a positive electrode or a negative electrode after being formed or charged and discharged, which are identical to each other before being formed or charged and discharged, regardless of the manufacturing produced when the electrode is fabricated
  • the error, two or more electrodes are identical to each other in all electrode construction, manufacturing aspects (such as electrode structure, shape, size, formulation, material, manufacturing process, etc.) before being subjected to the formation or charge and discharge operation.
  • the polarity inversion of the positive and negative electrodes of the lead-acid battery or the battery pack and subsequent charging or charging and discharging operations may be implemented automatically or/and manually by a circuit having the lead acid
  • the positive and negative poles of the battery or/and lead-acid battery pack perform the functions of polarity reversal or polarity reversal and subsequent charging or charging and discharging operations, and the circuit can or actually be a lead-acid battery or/and a lead acid
  • the positive and negative poles of the battery pack are subjected to polarity inversion or polarity inversion, and the total accumulated number of charging or charging and discharging operations is ⁇ 1 times.
  • the method for implementing or implementing a charge or charge reverse operation of the positive and negative polarity reverse polarity or reverse polarity of a lead-acid battery or/and a lead-acid battery pack includes: The battery or battery pack is reverse charged.
  • the method for performing reverse polarity charging of a lead-acid battery or/and a lead-acid battery pack includes: polarity inversion and polarity of the output of the circuit connected to the lead-acid battery or battery electrode Reversing the charging or charging and discharging operation of the lead-acid battery or the battery pack to realize the polarity reversal or polarity reversal of the lead-acid battery or the battery pack and the subsequent charging or Charge and discharge operation.
  • the polarity reversal of the positive and negative poles of the lead-acid battery or the battery pack and the subsequent charging or charging and discharging operations are further characterized in that the starting or stopping is performed by automatic or/and manual or manual switching. Suspending the function of the circuit causes the circuit to start, stop or suspend the positive or negative polarity reversal or polarity reversal of the lead-acid battery or/and the lead-acid battery pack and subsequent charging or charging and discharging operations.
  • the method for improving or prolonging the service life of a lead-acid battery or/and a lead-acid battery pack of the present invention or the polarity reversal of the positive and negative electrodes of the lead-acid battery or/and the lead-acid battery pack and the subsequent charging or charging Lead-acid battery or / and lead-acid battery packs for discharge operation methods including flat grid, tubular, coiled, bipolar, horizontal lead, foam grid, column, stable Void body lead-acid battery or battery pack, also includes valve-regulated sealed lead-acid battery or battery pack, colloidal lead-acid battery or battery pack, lead carbon battery battery or battery pack, supercapacitor-lead acid battery (referred to as super battery) A battery or battery pack, and a hybrid lead-acid battery pack in which these types of lead-acid batteries are mixed and connected, as well as various other types of lead-acid batteries or battery packs.
  • the method for improving or prolonging the service life of a lead-acid battery or a battery pack can be applied to the repair, regeneration or production of a lead-acid battery or a battery pack, a lead-acid battery or a battery pack circuit or a charge and discharge device, a lead-acid battery or a battery pack.
  • the invention also provides a chemical conversion method for applying polarity reversal and subsequent charging or charging and discharging operations in a lead-acid battery or a battery pack manufacturing process, including a positive electrode of a lead-acid battery or/and a lead-acid battery group.
  • the negative electrode is subjected to polarity inversion and subsequent charging or charging and discharging operations, and the number of times the operation is performed or performed is one or more times.
  • polarity inversion in the formation method and subsequent charging or charging and discharging operations include: current, charging or working state of the lead-acid battery or battery pack before operation, before polarity reversal Of the physical quantity, the quantity value, the chemical quantity value, and the change value and the calculated value of the discharge or/and charging operation, the polarity reversal, the charge reversal after the polarity reversal, or the charge/discharge operation.
  • One or more measurement results, discharge or/and charging operation before polarity inversion, polarity inversion, polarity inversion, and subsequent charging or charging and discharging operations, distinguishing operations can be performed by programming, etc.,
  • the polarity inversion described earlier in the present invention and the subsequent charging or charging and discharging operations are the same.
  • the method for improving or prolonging the service life of a lead-acid battery or a battery pack provided by the present invention further comprising: inverting polarity of an electrode of the lead-acid battery or/and a lead-acid battery, and after the polarity is reversed
  • the electrode subjected to the polarity inversion is subjected to an electrochemical reaction in which the electrode which is the positive electrode before the polarity is reversed is subjected to the polarity reversal, and then the lead acid battery negative electrode reaction is performed, and the polarity is reversed before the polarity is reversed.
  • the lead oxide, the basic lead sulfate, and the lead sulfate contained in the electrode of the positive electrode are subjected to an electrochemical reduction reaction after the polarity is reversed, and the electrode which is a negative electrode before the polarity is reversed is subjected to the polarity inversion.
  • a lead-acid battery positive electrode reaction one or more of which is characterized in that the total cumulative number of times the method is implemented in the lead-acid battery or/and the lead-acid battery group is ⁇ 1, the method comprising the Performing polarity inversion and subsequent charging or charging and discharging operations on the positive and negative electrodes of the lead-acid battery or/and the lead-acid battery, and making the total cumulative number of operations ⁇ 1 times, the positive and negative electrodes are performed.
  • Polarity reversal and subsequent Electrically charging or discharging operation i.e., a positive electrode, a negative electrode polarity, and after the polarity inversion, will be charged through the electrode polarity or charge and discharge operation.
  • reaction products after the discharge of the positive electrode and the negative electrode are all PbSO 4 , and the product PbSO 4 is converted into the positive electrode active material PbO 2 and the negative electrode active material Pb after being charged; the original positive electrode of the lead-acid battery is used as the negative electrode, and the original negative electrode is used as the negative electrode.
  • the positive electrode charges the battery to cause the negative electrode reaction to occur on the original positive electrode.
  • the positive electrode reaction occurs on the original negative electrode, and the discharge product PbSO 4 of the original positive electrode can be converted into the negative electrode active material Pb.
  • the discharge of the original negative electrode The product PbSO 4 can be converted into the positive electrode active material PbO 2 , that is, the polarity of the positive and negative electrodes can be reversed, and since the electrode reaction in the electrode reaction formulas (1) and (2) is reversible, the original positive electrode of the lead-acid battery The polarity reversal with the original negative electrode is also reversible.
  • the original positive electrode of the lead-acid battery is used as the negative electrode
  • the original negative electrode is used as the positive electrode to charge the battery. It may even cause PbO 2 on the original positive electrode to directly convert to Pb, and Pb on the original negative electrode directly to PbO 2 . The conversion thus completes the reversible polarity reversal between the original positive electrode of the lead-acid battery and the original negative electrode.
  • a positive electrode and a negative electrode of a lead-acid battery are characterized in that, as the number of repetitions of charge and discharge increases, the bonding between the active material PbO 2 particles on the positive electrode gradually relaxes and detaches from each other, so that the positive electrode active material Expanding, loosening, softening, and falling off; as the number of repetitions of charge and discharge increases, the active material Pb particles on the negative electrode tend to be combined with each other, so that the specific surface area of the negative electrode shrinks and is knotted.
  • the specific surface area shrinkage of the active material caused by the combination of the active material Pb particles on the original negative electrode of the lead-acid battery can be reversed by the positive electrode reaction of the lead-acid battery.
  • the softening and shedding effect of the positive active material of the lead-acid battery, and the specific surface area shrinkage effect of the negative electrode can be reversible or reversed by the electrode reaction (1), (2), or the positive electrode and the negative electrode of the lead-acid battery are Polarity reversal and subsequent charging or charging and discharging operations can reverse or improve the lead-acid battery Softening or/and shedding of the polar active material and shrinkage of the specific surface area of the negative electrode.
  • the polarity reversal and subsequent charging or charging and discharging operations of the present invention are used to select an appropriate charging and discharging system (different charging and discharging systems are active for electrodes or electrodes by electrode reaction)
  • the physical and chemical structure and properties of the substance have different effects and changes, and the aging and energy efficiency are also different.
  • the active material particles are separated from each other and reacted with the negative electrode.
  • the resulting active material particles are combined with each other, reversed or canceled each other, which can greatly improve or even eliminate the softening or/and shedding of the positive active material of the lead-acid battery and the shrinkage of the specific surface area of the negative electrode, thereby significantly improving the service life of the lead-acid battery.
  • theoretically if it can solve the softening or/and shedding of the positive active material of the lead-acid battery or the battery pack, the specific surface area shrinkage of the negative electrode, and the failure mode in addition to the softening or/and shedding of the positive electrode active material and the shrinkage of the specific surface area of the negative electrode,
  • the service life of the battery or battery pack caused by other failure modes is known, and the service life of the lead-acid battery and the lead-acid battery pack may even be infinitely long or extremely long.
  • the polarity inversion of the present invention and subsequent charging or charging and discharging operations can also improve problems such as electrode/sink/catch corrosion, early capacity loss, electrode passivation, poor contact of active material and current collector, and the like.
  • repair, eliminate, reverse, suppress, prevent, enhance the battery's ability to resist overcharge damage, replace or reduce the need for overcharging of the battery to avoid or reduce battery water loss caused by overcharge, electrode potential during operation, and electrode Changes in environmental conditions will also eliminate, reverse or improve, repair the sulphation, enhance the battery's ability to resist under-charge and over-discharge damage, and thus help to significantly improve the service life of lead-acid batteries and battery packs.
  • the polarity reversal of the positive and negative electrodes of the present invention and the subsequent charging or charging and discharging operations are also beneficial to solve the problem that the electrode active material and the electrode current collector which are generated during the charging, discharging or use of the lead-acid battery are separated by the electrochemical reaction process, Poor contact.
  • Performing a distinguishing operation on the single cells in the lead-acid battery pack that is, separately performing the positive and negative polarity inversion of the present invention and the subsequent charging or charging and discharging operations for each of the single cells and some of the single cells in the battery pack. It is beneficial to increase or prolong the service life of the single battery in the battery pack, maintain and adjust the consistency of the mutual capacity between the single batteries in the battery pack, thereby improving the service life of the lead-acid battery pack at a lower cost.
  • a lead-acid battery or a lead-acid battery pack when the positive electrode and the negative electrode are electrodes common to the positive electrode and the negative electrode, the production and recovery thereof are characterized by higher efficiency and lower cost, and the polarity reversal of the present invention is performed. Subsequent charging or discharging operations can increase or prolong the service life, and the technical solutions of the electrodes common to the positive and negative electrodes can be implemented to make them practical.
  • Performing the polarity inversion of the present invention and subsequent charging or charging and discharging operations by the circuit is advantageous for improving or realizing the efficiency, accuracy, convenience, practicability, effectiveness, feasibility, and the like of the operation.
  • the polarity reversal of the positive and negative electrodes of the present invention and subsequent charging or charging and discharging operations also contribute to solving (including repairing, reversing, eliminating, suppressing, preventing) or improving the chemical or electrochemical reaction process in other lead-acid batteries.
  • applying the method of the present invention to a lead-acid battery or battery pack can significantly increase or prolong the service life of a lead-acid battery or battery pack.
  • the positive and negative polarity inversion of the present invention and the subsequent charging or charging and discharging operations are applied to the chemical conversion process, it is advantageous to alleviate or avoid the overcharge process in the conventional lead-acid battery formation process for the lead-acid battery or the battery pack.
  • the negative impact of the life cycle improve the utilization rate of the active material of the lead-acid battery, and thus the initial capacity of the battery or the battery pack, ensure the positive electrode with the positive and negative electrodes, and perform the polarity reverse in the cyclic charging and discharging operation multiple times.
  • the cycle charge and discharge performance of the lead-acid battery or battery pack after the subsequent charging or charging and discharging operations is symmetrical before and after each polarity inversion.
  • the polarity reversal of the positive and negative polarities of the present invention and subsequent charging or charging and discharging operations also contribute to improving the utilization rate of the active material in the lead-acid battery or the battery pack during the cycle operation, thereby the capacity of the battery or the battery pack during use.
  • Fig. 1 is a graph showing the working discharge capacity and the working discharge termination voltage data of a lead-acid battery in a cycle charge and discharge operation according to a sixth embodiment of the present invention.
  • FIG. 2 is a data diagram showing the working discharge capacity and the working discharge termination voltage of the lead-acid battery in the cycle charging and discharging operation of the seventh embodiment of the present invention.
  • Embodiment 3 is a thirteenth, twelfth positive and negative polarity reversal and subsequent charging of a lead-acid battery according to Embodiment 7 of the present invention during the 189-196th cycle charge and discharge operation process and during the process. Current and voltage data during charging and discharging operations.
  • Fig. 4 is a graph showing the working discharge capacity and the working discharge termination voltage of the lead-acid battery in the cycle charging and discharging operation of the eighth embodiment of the present invention.
  • Fig. 5 is a schematic view showing the positive and negative polarity reversal and the subsequent charging or charging and discharging operation of the embodiment 9 of the present invention interspersed during the cyclic charging and discharging operation of the tubular lead acid battery.
  • Fig. 6 is a graph showing the working discharge capacity and the working discharge termination voltage data of the cyclic charge and discharge operation of the lead-acid battery according to the embodiment 9 of the present invention.
  • Fig. 7 is a plan view showing the structure of an electrode current collector of a positive electrode and a negative electrode of an embodiment 11 of the present invention.
  • Fig. 8 is a graph showing the working discharge capacity and the working discharge termination voltage data of the cycle charge and discharge operation of the lead-acid battery according to the eleventh embodiment of the present invention.
  • Fig. 9 is a graph showing the working discharge capacity and the working discharge termination voltage of the lead-acid battery in the cycle charge and discharge operation of the embodiment 12 of the present invention.
  • Fig. 10 is a graph showing the working discharge capacity and the working discharge termination voltage of the lead-acid battery in the cycle charging and discharging operation of the thirteenth embodiment of the present invention.
  • Figure 11 is a graph showing the working discharge capacity and the working discharge termination voltage data of the lead-acid battery pack in the cycle charge and discharge operation of the embodiment 14 of the present invention.
  • FIG. 12 is a diagram showing a single positive and negative polarity reversal and subsequent charging or charging and discharging operations of the lead-acid battery pack according to Embodiment 14 of the present invention during the 23-28th cycle charging and discharging operation process and during the process. Current and voltage data plots.
  • W1 The total charge of the tubular lead-acid battery is 1-304 cycles of charge and discharge.
  • the tubular lead-acid battery has accumulated 305-652 cycles of charge and discharge.
  • the tubular lead-acid battery has accumulated 653-751 cycles of charge and discharge.
  • W4 The total volume of tubular lead-acid batteries is 752-774 cycles of charge and discharge.
  • the first phase of the tubular lead-acid battery has two consecutive positive and negative polarity inversions and subsequent charging or charging and discharging operations.
  • R2 The second phase of the tubular lead-acid battery has two consecutive positive and negative polarity inversions and subsequent charging or charging and discharging operations.
  • R3 The third phase of the tubular lead-acid battery has two consecutive positive and negative polarity inversions and subsequent charging or charging and discharging operations.
  • the lead-acid battery of the embodiment is a planar grid-type lead-acid battery, and the rated capacity is 2.32 Ah (2 h rate, 25 ° C), the rated voltage is 2 V, and the cycle charging and discharging work (referred to as cyclic work, the same below) system is: It is charged at a constant current of 0.2 times (rated capacity, the same below). When the voltage reaches 2.65V, it is charged at 2.65V constant voltage. The total time of two charging is 6 hours and 24 minutes, then 2h rate, 80%DOD ( After the discharge depth is discharged, the above charging and discharging processes are repeated, that is, the above charging and discharging cycles are performed, and the working environment temperature is 25 ⁇ 1 °C.
  • the remaining capacity of the lead-acid battery of the present embodiment (the amount of electricity that can be discharged by the battery according to the working discharge system, the same applies hereinafter) is 7.3% of its rated capacity (it is checked that the positive electrode active material softens and falls off, and the discharge capacity of the battery of the present embodiment is attenuated. )
  • the positive and negative polarity inversion of the present invention and the following charging or charging and discharging operations are started (for the sake of clarity, the positive and negative electrodes of the lead-acid battery of the present embodiment are sequentially named as electrode group A, electrode Group B, the same as below), includes the following steps:
  • the transfer electrode is connected: the positive electrode of the charge and discharge device is connected to the original negative electrode (electrode group B) of the lead-acid battery of the present embodiment, and the negative electrode of the charge and discharge device is connected to the present embodiment.
  • the original positive electrode (electrode group A) of the lead-acid battery is connected, and the next step is performed;
  • the lead-acid battery of this embodiment is completed by the current of 0.2 times (465.3 mA). When the battery voltage reaches 1.75V, the charging takes 547 minutes, the charging is stopped, and then the next step is performed. ;
  • the transfer electrode is connected: the positive electrode of the charge and discharge device is connected to the original positive electrode (electrode group A) of the lead-acid battery of the present embodiment, and the negative electrode of the charge and discharge device is connected to the present embodiment.
  • the original negative electrode (electrode group B) of the lead-acid battery is connected to prepare for the next step of charging or charging and discharging;
  • step 6) the battery is simultaneously put into operation and charged and discharged in the same working system.
  • Table 1 it can be seen that the lead-acid battery of the present embodiment has a significant recovery of the working discharge capacity after the above two consecutive polarity inversions and subsequent charging or charging and discharging operations, due to the lead acid of the present embodiment.
  • the discharge capacity attenuation of the battery is caused by the softening and falling off of the positive electrode active material. Therefore, the result indicates that the polarity inversion of the present embodiment and the subsequent charging or charging and discharging operation soften and fall off the positive electrode of the lead-acid battery of the present embodiment. The situation or extent is significantly reversed.
  • step 3 the amount of charge of the battery of the embodiment is relatively larger in step 3) of the embodiment (for example, a larger charging current, a longer charging time), it will be advantageous to make the original positive electrode (electrode of the battery of the embodiment).
  • the softening and shedding of the active substance of group A) is more reversed and restored.
  • the battery in which the polarity inversion and the subsequent charging or charging and discharging operation method of the present invention are implemented may also be a tubular lead-acid battery, a wound lead-acid battery, and a double.
  • Polar lead-acid battery horizontal lead-lead lead-acid battery, foam grid-type lead-acid battery, valve-regulated sealed lead-acid battery, colloidal lead-acid battery, lead carbon battery, supercapacitor-lead acid battery, column lead acid a battery, a lead-acid battery having a stable gap body; the polarity reversal of the present invention and subsequent charging or charging and discharging operations can also be started when the remaining capacity of the battery is 50%, 90%, 100% of the rated capacity; When the battery stops working, the voltage is not only 2.65V, but also any other possible voltage, such as 2.8V, 2V, 1.75V, 0.5V, 0V; when the battery is stopped, the battery can be in other stages of operation.
  • a constant current discharge phase or a constant current charging phase the basis for starting or stopping the polarity inversion of the present invention and subsequent charging or charging and discharging operations may also be other physical magnitudes or/and chemical magnitudes or/and quantities , including voltage value, current value, current density value, electricity value, power value, time value, temperature value, force value, pressure value, density value, photometric value, frequency value, cumulative value, odd value, even value, proportional value
  • voltage value current value, current density value, electricity value, power value, time value, temperature value, force value, pressure value, density value, photometric value, frequency value, cumulative value, odd value, even value, proportional value
  • the discharge current in step 1) is a current having an absolute value greater than 0, such as a current of 0.01, 0.1, 1, 3, 5, 10 times; the discharge can also be performed in stages and each stage The discharge current value is not necessarily the same; the discharge stop voltage can be 0V, or other voltages, such as 0.5, 0.2, -0.3, -1.7V, -2.33, -2.8V, etc.; can also be added to the charging phase, that is, After a certain period of discharge, the battery is charged for more than one stage, and then discharged after charging. The number of cycles of discharge, charge, discharge, and the like is not limited. After the charge and discharge cycle, the polarity is reversed. .
  • the charging or charging and discharging operation in step 1) is not necessarily based on voltage, but may be other physical quantities or/and chemical quantities or/and quantity values, including voltage values and currents.
  • the discharging step in step 1) can be omitted, that is, after the operation of the battery is stopped, step 2) is directly performed.
  • connection transformation in step 2) and step 5) may also be implemented by an automatic function of the device, device or circuit without manual operation.
  • the charging current in step 3) is a current having an absolute value greater than 0, such as a current of 0.01, 0.2, 1.1, 3.5, 5.3, 10 times; charging can also be performed in stages and each segment
  • the charging current value is not necessarily the same;
  • the charging stop voltage is not necessarily 1.75V, and may be other voltages, such as; 0.3, 0.5, 1.0, 2.0, 2.44, 2.65, 2.8V, etc.; Charging amount and time;
  • the discharge current in step 4) is a current having an absolute value greater than 0, such as a current of 0.01, 0.1, 1, 3, 5, 10.3 times; the discharge can also be performed in stages and each stage The discharge current value is not necessarily the same; the discharge phase can also be added to the charging phase, that is, after a certain period of discharge, the battery is charged for more than one stage, and then discharged after charging, such discharge, charging, discharging, and the like.
  • the number of cycles is not limited. After the charge and discharge cycle, the polarity is reversed.
  • step 4) may not be performed, but the step 5) may be directly entered after the end of charging in step 3).
  • the charging or charging/discharging operation in step 3 or step 4) is not necessarily based on voltage, but may be other physical quantities or/and chemical quantities or/and quantity values, including Voltage value, current value, current density value, electricity value, capacity value, power value, time value, temperature value, force value, pressure value, density value, photometric value, frequency value, cumulative value, odd value, even value, ratio
  • Voltage value current value, current density value, electricity value, capacity value, power value, time value, temperature value, force value, pressure value, density value, photometric value, frequency value, cumulative value, odd value, even value, ratio
  • the charging current in step 6) is a current having an absolute value greater than 0, such as a current of 0.01, 0.1, 1, 3, 5, 10 times; charging can also be performed in stages and in each segment
  • the charging current value is not necessarily the same;
  • the charging stop voltage is not necessarily 1.75V, and may be other voltages, such as; 0.3, 0.5, 1.0, 2.0, 2.4, 2.65, 2.78V, etc.;
  • the charging phase can also be added to the discharge phase. That is, after charging for a certain period of time, the battery is discharged for more than one stage, and then charged after discharging.
  • the number of cycles of charging, discharging, charging, discharging, and the like is not limited. After the charging and discharging cycle, the battery is again charged. Transfer to work or quasi-work.
  • step 6 after the operation of step 6) is completed, the operations of steps 1)-6) (i.e., steps 1) to 6) are continued one or more times, the following similarities) Then, the battery operation is performed one or more times, and the one or more steps 1) to 6) and the one or more times of the battery operation may be performed alternately and cyclically with each other, and the number of cycles is ⁇ 1. . In this way, the original positive electrode of the battery is always operated as the positive electrode, and the original negative electrode always operates as the negative electrode.
  • step 6 after the operation of step 6) is completed, the 1)-3) step operation or the 1)-6) step operation is performed once more than 1 time 1)- 3) Step operation, and then perform more than one battery operation, the 1)-1)-3) step operation or 1 or more 1)-6) step operation plus 1 time 1)-3) step operation and
  • the one or more battery operations may be performed alternately and cyclically with each other, and the number of cycles is ⁇ 1. In this way, the original positive electrode of the battery is always operated as a negative electrode, and the original negative electrode always operates as a positive electrode.
  • step 6 after the battery completes the operation of step 6), the battery is operated more than once, the 1)-6) step is performed once or more, and the 1)-3) step is performed once. Or 1)-6) step operation plus 1 time 1)-3) step operation is carried out in turn, cyclically, the order of rotation is not limited, the number of cycles is ⁇ 1, so that the original positive electrode of the battery is sometimes used as the positive electrode.
  • the operation may be performed as a negative electrode. Accordingly, the original negative electrode of the battery may operate as a negative electrode, and may operate as a positive electrode.
  • the battery operation is performed once or more, 1)-6) steps are performed once or more, 1)-3) steps are performed once, or 1)-6 is performed once or more Step operation plus 1) 1) -3)
  • the basis for switching between any two of the steps is the physical quantity or / and the quantity value or / and the chemical quantity value, including the voltage value, current value, current density Value, power value, power value, time value, temperature value, force value, pressure value, density value, photometric value, frequency value, cumulative value, odd value, even value, ratio value, battery or / and battery pack charging or One or more of the value of the discharge or charge cycle number, the battery or/and the acidity value of the battery.
  • one or more of the above physical quantity, quantity value, chemical quantity value, and their change value and calculated value include the battery during charging, during discharge, open circuit or static The physical quantity, quantity value, or chemical quantity value in the state.
  • steps 1) to 6) above in the operations of steps 1) to 6) above, other operations such as adjusting the temperature of the battery, adding acid to the battery, adding an additive, adding water, pressurizing, etc., may be performed simultaneously.
  • the charge and discharge current used in this embodiment is direct current.
  • the charge and discharge current used may also be a pulse current flow or a combined current of a pulse charge current and a direct current.
  • the rest time in the operations of steps 1) and 4), may be other time lengths, and the rest time may also be 0;
  • steps 1)-6) above may be performed by programming.
  • the above operation of the present example can improve and reverse the softening and falling off of the positive active material of the lead-acid battery, and can improve, repair, improve and restore the working discharge capacity of the lead-acid battery, thereby increasing or prolonging the service life of the lead-acid battery.
  • the method for improving or prolonging the service life of the lead-acid battery or the battery pack in the present embodiment is when the lead-acid battery or the battery pack of the present embodiment is softened or/and detached due to the positive active material, the specific surface area of the negative electrode is shrunk, the electrode is passivated, and the corrosion is early.
  • step (2) is performed: charging or charging and discharging the lead-acid battery or the battery pack of the embodiment after the polarity is reversed, so that the original positive electrode (electrode A of the lead-acid battery or the battery pack)
  • the reaction of the negative electrode of the lead-acid battery occurs, and the positive electrode of the lead-acid battery occurs on the original negative electrode (electrode B). If the capacity of the lead-acid battery or the battery pack is reduced or the degree of failure is large, the charging of the step may be relatively increased.
  • step (3) re-charging the lead-acid battery or the battery pack of the present embodiment again, so that the polarity of the original positive electrode (electrode A) of the lead-acid battery or the battery pack of the present embodiment is negative.
  • step (4) the lead-acid battery or battery of this embodiment after the polarity is reversed in step (3)
  • the group performs charging or charging and discharging, so that the lead-acid battery positive electrode reaction occurs on the original positive electrode (electrode A) of the lead-acid battery or the battery pack of the present embodiment, and the lead-acid battery negative electrode reaction occurs on the original negative electrode (electrode B), and finally In this embodiment, the lead-acid battery or the battery pack is fully charged.
  • the positive electrode of the lead-acid battery or the battery pack of the present example One or more failure modes or problems of softening or/and shedding of active material, shrinkage of specific surface area of the anode, electrode passivation, corrosion, early capacity loss, sulfation, poor contact of active material and current collector, improvement, mitigation, Repairing, reversing, or preventing, so that the working discharge capacity of the lead-acid battery or the battery pack of the embodiment is improved, restored, improved, or maintained, and then the lead-acid battery or battery pack of the embodiment is put into its normal circulation or floating charge. Go to normal use during work.
  • the lead-acid battery or the battery pack of the embodiment in which the polarity of the step (3) is reversed may be directly put into a charging cycle of a normal circulation or floating charging operation, and Next, run and work under its normal cycle or floating charge system.
  • the above-described two consecutive positive and negative polarity inversions and subsequent charging or charging and discharging operations of the present embodiment can be carried out with reference to or similar to the operation method or system in the first embodiment of the present invention.
  • the above-described two consecutive positive and negative polarity inversions and subsequent charging or charging and discharging operations of the present embodiment are repeatedly or interspersed during use or use of the lead-acid battery or battery pack of the present embodiment. After the end of life, the service life of the lead-acid battery or the battery pack of the embodiment is improved or prolonged.
  • the polarity of the positive and negative electrodes of the lead-acid battery or the battery pack of the present embodiment is reversed and then charged or charged and discharged, so that the original positive electrode (electrode A) of the lead-acid battery or the battery pack of the embodiment occurs.
  • the negative electrode of the lead-acid battery reacts, which causes the active material on the original positive electrode (electrode A) to be softened and detached, which is improved, reversed or removed.
  • the negative electrode of the lead-acid battery is reacted on the original positive electrode (electrode A).
  • the charging or charging and discharging operation of the original positive electrode (electrode A) on the original positive electrode (electrode A) or performing the reverse polarity reaction of the lead-acid battery negative electrode also makes the original a corrosion product, a corrosion film or a blunt formed or formed by a lead oxide, a basic lead sulfate, a lead sulfate or the like between the current collector and the active material, between the active material particles, inside the electrode or on the surface of the electrode (electrode A)
  • the film, the corrosion layer or the passivation layer is partially or completely reduced to metal lead, and the parts on the electrode form a good contact, bond or connection, and the density of the active material rises.
  • the positive electrode reacts, which causes the active material on the original negative electrode (electrode B) to expand to a certain extent, thereby alleviating, improving, reversing or preventing the original negative electrode (electrode B) that has occurred or is about to occur to some extent.
  • the problem of shrinkage of the specific surface area of the negative electrode, and the reaction of the positive electrode of the lead-acid battery occurring on the original negative electrode (electrode B), during the occurrence or progress thereof, also changes and affects the expansion agent in the original negative electrode (electrode B) or The adsorption capacity and adsorption state of the additive, the electrochemical process of changing the conversion of lead sulfate, the electrode potential, the overpotential, etc.
  • the original anode (electrode B) sulfation problem has already occurred or will occur in the obtained some relief, improvement, reversal or prevention.
  • the steps and operations of performing the polarity inversion and the subsequent charging or charging and discharging operations of the present invention on the lead-acid battery pack (the 2h rate rated capacity is 2Ah, the rated voltage is 4V, 25° C.)
  • the steps and operations performed on the battery in Embodiment 1 are basically the same, except that in the operation of this embodiment, the polarity inversion and subsequent charging or discharging operations are applied to the positive electrode of the lead-acid battery pack. And negative electrode.
  • the charge stop voltage after each polarity inversion is 3.0V or 4.5V.
  • the polarity inversion of the present invention and the subsequent charging or charging and discharging operations may be performed on a certain battery cell or some single cells in the battery pack, including the steps of charging and discharging.
  • the device is only turned on with one or some of the single cells and performs polarity inversion as described in Embodiment 1 of the present invention and subsequent charging or charging and discharging operations.
  • the battery pack has a circuit structure in which each of the single cells or some of the single cells and the charge and discharge circuits in the charge and discharge device are independently connected.
  • the polarity inversion and the subsequent charging or charging and discharging operations in Embodiment 1 of the present invention may also be performed after operating one or some of the battery cells in the battery pack. Then, the lead-acid battery pack is operated as a whole, or the order of operations is reversed.
  • the present embodiment relates to a process for converting the polarity inversion of the present invention and the subsequent charging or charging and discharging operation method for the production of a lead-acid battery or a battery pack, including, after the battery or the battery pack is acidified, The formed battery or the battery or battery pack which has undergone a certain formation process is subjected to the polarity inversion as described in Embodiment 1 or 3 of the present invention and the subsequent charging or charging and discharging operation steps.
  • the polarity inversion and subsequent charging or charging and discharging operation methods are used in a chemical conversion process in the production of a lead-acid battery or a battery pack, including, after the battery or the battery pack is acidated, Performing the polarity inversion of any of the positive and negative electrodes of the lead-acid battery or/and the lead-acid battery pack as described in Embodiment 1 or 3 of the present invention and the subsequent charging or charging and discharging operation steps, and making the pole
  • the sum of the number of charging operations and the number of discharging operations after the sexual reversal is 1 or 3 or 9 times, and then the original positive electrode of the battery or the battery pack is always used as the negative electrode, and the original negative electrode is always used as the positive electrode.
  • the polarity inversion performed and the subsequent charging or charging/discharging operation are the same as those of the polarity inversion described in the above embodiment of the present embodiment and the subsequent charging or discharging operation.
  • This embodiment relates to the use of the polarity inversion of the present invention and the subsequent charging or charging and discharging operation method for the repair or regeneration of a lead-acid battery or battery pack, including: according to the embodiment 1, 2 or 3 of the present invention
  • the polarity inversion described above and subsequent charging or charging and discharging operations are performed to repair or regenerate the lead-acid battery or battery pack.
  • the embodiment relates to a method for improving or prolonging the service life of a lead-acid battery, a battery charge and discharge device and a lead-acid battery, wherein the battery charge and discharge device of the embodiment is based on a current source circuit, a voltage source circuit and a forced charge or / and the forced discharge function, the polarity reversal of the positive and negative electrodes of the lead-acid battery of the present embodiment and subsequent charging or charging and discharging operations can be performed. All the operations of the lead-acid battery of the present embodiment in the following embodiments are realized by the function and operation of the battery charge and discharge device of the present embodiment, except that the manual operation is specifically described.
  • the battery charge and discharge device of this embodiment has a setting according to the setting.
  • the lead-acid battery of the embodiment is a flat grid type lead-acid battery, the rated capacity is 1.77 Ah (2h rate, 25 ° C), the rated voltage is 2V, and the structure of the positive plate is sandwiched between two negative plates, positive and negative.
  • the separator between the separators is an AGM separator.
  • the total capacity of the anode plate is relatively excess in the total capacity of the positive plate.
  • the thickness of the positive plate is 2.8 mm
  • the thickness of the negative plate is 1.9 mm
  • the grids of the positive and negative plates are rectangular.
  • the plate has the positive electrode paste prepared by the current common commercial positive lead paste formula (the content of sulfuric acid relative to the ball-milled lead powder is 4.5 wt.%, and the formula does not contain barium sulfate), and the battery is only used as a positive electrode when working, so it is called It is a positive electrode plate (for the sake of clarity in the following description, it is also named as electrode A in the present embodiment), and the negative electrode plate has a negative electrode paste prepared by the conventional common commercial negative electrode paste formulation, and the battery is only used as a negative electrode when working, so it is called It is a negative electrode plate (for the sake of subsequent statements, it is also named as electrodes B1 and B2 in this embodiment), and the lead powder used in the positive and negative lead pastes is the current common commercial ball-milled lead powder, and the cured and dried positive electrode plate.
  • the lead powder used in the positive and negative lead pastes is the current common commercial ball-milled lead powder, and the cured and dried positive electrode plate.
  • the method for improving or prolonging the service life of the lead-acid battery in the present embodiment is as follows: First, the lead-acid battery of the embodiment is subjected to cyclic charging and discharging work, and the circulating charge and discharge working system of the lead-acid battery of the embodiment is: when the battery is charged In the state, the battery is discharged with a constant current of 1031 mA. When the discharge time reaches 1 hour and 36 minutes (that is, the discharge capacity is 1649 mAh, which is 93% of the rated capacity), or the battery voltage is ⁇ 1.75 V, the discharge is stopped.
  • the battery is charged with a constant current of 412 mA, and after the measured battery voltage reaches 2.65 V, it is converted to continue charging the battery at a constant voltage of 2.65 V, and the total time of two (constant current, constant voltage) charging is 6 hours.
  • the battery charging process is finished, and then repeat the above-mentioned discharge process with a constant current of 1031 mA, thus repeatedly, cyclically discharged, charged, re-discharged, recharged, and the battery is charged and discharged, and the working temperature of the battery is 25 ⁇ 1 ° C; secondly, when the positive active material softens or/and falls off, sulfation, passivation, early capacity loss, corrosion, poor contact of the active material with the current collector, One or more of the specific surface area shrinkage factors of the negative electrode active material causes the lead acid storage battery of the embodiment to have a discharge capacity or discharge time less than a predetermined capacity value or a certain time value in the above operation (for example, In the examples, 900 mAh, 1 hour, 36 minutes, and 47 minutes, respectively, the battery is stopped, and the battery is subjected to at least one consecutive two times of positive and negative polarity reversal and subsequent charging or The charging and discharging operation causes the working-discharge capacity of the lead
  • Post-charge or charge-discharge operation to suppress, prevent, repair, improve, eliminate or reverse the softening or/and shedding of the positive active material of the lead-acid battery, and the negative electrode active material
  • the polarity reversal of the positive and negative plates and the subsequent charging or charging and discharging operations of the lead-acid battery of the present embodiment are set and executed by the battery charger and discharger of the embodiment and the setting program and the execution function thereof.
  • the battery voltage is lowered to around 0 V, and then the battery charge and discharge device of the embodiment is implemented by the human hand.
  • connection state of the lead-acid battery is connected from the positive and negative clamps of the charge and discharge device (positive output conductive clip, the same below) to the positive electrode plate (electrode A) of the lead-acid battery, the negative electrode clamp of the charge and discharge device (the negative output conductive clip, the same below) and lead Acid battery negative plate (electrode B1, B2) connection (this connection is called positive connection state, the same below), changed to, the charge and discharge device positive clip is connected with lead-acid battery negative plate (electrode B1, B2), charge and discharge device negative
  • the clip is connected to the positive electrode plate (electrode A) of the lead-acid battery (the connection is said to be reversed, the same applies hereinafter), or the reverse connection state is changed to the positive connection state, and then the battery after the electrode connection state is changed.
  • the battery is charged to a battery voltage of >0V, thereby realizing the polarity reversal of the electrode of the battery of the embodiment; the other is automatically operated by the battery charge and discharge device of the embodiment: when the lead-acid battery in the embodiment is in the positive connection state,
  • the constant current source in the battery charger and discharger of the embodiment performs forced discharge on the battery of the embodiment to change the voltage of the battery from a state of ⁇ 0V to a state of ⁇ 0V, or to charge the battery when the battery voltage is ⁇ 0V (or forcibly Charging) and changing the battery voltage from the state of ⁇ 0V to the state of ⁇ 0V, the polarity inversion operation of the lead-acid battery of the present embodiment is automatically realized.
  • the battery When the battery is in the positive state, the battery is continuously forced to discharge when the battery voltage is ⁇ 0V, so that the battery voltage tends to be more negative.
  • the main positive electrode of the battery (electrode A) is the reaction of the negative electrode of the lead-acid battery.
  • the charging process and the battery negative plate (electrodes B1, B2) mainly occur in the charging process in the positive electrode reaction of the lead-acid battery (refer to the electrode reaction formula (1), (2) of the present invention, the same applies hereinafter);
  • the battery When the battery is in the positive state, the battery is forcibly charged when the battery voltage is ⁇ 0V, so that the battery voltage tends to be corrected or 0V.
  • the main positive electrode of the battery (electrode A) is the reaction of the negative electrode of the lead-acid battery.
  • the discharge process and the battery negative plate (electrodes B1, B2) mainly occur in the discharge process in the positive electrode reaction of the lead-acid battery; when the battery in the embodiment is in the positive connection state, the battery is charged when the battery voltage is > 0 V, so that the battery The voltage tends to be corrected.
  • the main positive electrode of the battery (electrode A) is the charging process in the positive electrode reaction of the lead-acid battery, and the battery negative plate (electrodes B1, B2).
  • Mainly lead-acid battery is a negative electrode reaction in the charging process.
  • the polarity inversion operation of the positive and negative electrodes of the battery of the present embodiment and the charging or charging and discharging operation after the polarity inversion are realized by the forced discharge, forced charging function and operation of the battery charger and discharger of the present embodiment.
  • the charging and discharging operations of the lead-acid battery of the present embodiment are also performed by using the charging and discharging functions of the battery charger and discharger of the present embodiment to realize the cyclic charging and discharging operation of the battery of the embodiment (hereinafter, this embodiment) All operations and measurements of the lead-acid battery are performed by the battery charge and discharge device of the present embodiment, except for the manual operation.
  • the specific implementation process of the method for improving or prolonging the service life of the lead-acid battery in this embodiment is as follows:
  • the battery is charged and discharged according to the working system of the present embodiment.
  • the positive electrode of the lead-acid battery and the negative electrode plate occur on the positive electrode plate of the present embodiment.
  • the negative electrode reaction of the lead-acid battery as shown in Fig. 1, when the operation is charged and discharged to the 148th time, the working discharge capacity of the battery of this embodiment begins to show a phenomenon of successive decline.
  • connection state of the battery charge and discharge device of the embodiment to the lead-acid battery of the present embodiment is connected from the positive electrode clip of the charge and discharge device to the positive electrode plate (electrode A) of the lead-acid battery, the negative electrode clip of the charge and discharge device and the negative electrode plate of the lead-acid battery (electrodes B1, B2)
  • the positive connection state of the connection is changed to the reverse connection state in which the positive and negative clips of the charge and discharge device are connected to the negative electrode plates (electrodes B1 and B2) of the lead-acid battery, and the negative electrode clip of the charge and
  • a commonly known reverse pole connection is formed, and then the battery after the connected state is charged with a constant current of 1031 mA, so that the positive electrode plate (electrode A) of the lead-acid battery of this embodiment is charged with the negative electrode reaction of the lead-acid battery.
  • the charging process of the positive electrode of the lead-acid battery occurs on the negative electrode plate (electrodes B1 and B2) of the lead-acid battery of the present embodiment, and the battery voltage rises to 1.75 V after 3 hours and 15 minutes ( After the negative electrode plate or electrodes B1 and B2 are positive, the positive electrode plate or the electrode A is negative), the battery is continuously charged for 3 hours with a constant current of 1031 mA (the battery voltage rises from 1.75 V to 2.23 V in this process, and is still the negative electrode at this time).
  • the plate or the electrodes B1 and B2 are positive, the positive electrode plate or the electrode A is negative), and then the battery is discharged at a constant current of 1031 mA, so that the negative electrode of the lead-acid battery occurs on the positive electrode plate (electrode A) of the lead-acid battery of the embodiment.
  • the discharge process of the reaction the discharge process of the positive electrode of the lead-acid battery occurs on the negative electrode plate (electrodes B1 and B2) of the lead-acid battery of the present embodiment, and the discharge is stopped after 24 minutes to 0 V, and then the battery is again discharged.
  • the negative electrode plate (electrode B1, B2) of the lead-acid battery of the present embodiment a charging process of a negative electrode reaction of a lead-acid battery occurs, and the charging is performed for 31 minutes until the battery voltage is 1.75 V (at this time, the positive electrode plate or the electrode A is positive and negative).
  • the plate or electrodes B1 and B2 are negative), and then charged at a constant current of 412 mA for 16 hours and 35 minutes to a battery voltage of 2.65 V, and then charged to the battery at a constant voltage of 2.65 V for 3 hours (this constant current, constant voltage charging process positive electrode)
  • the plate or electrode A is positive or negative, or the electrodes B1 and B2 are negative.
  • the first and second positive and negative polarity inversions of the battery of the embodiment are completed. Charging or charging and discharging operations. Then, the battery is re-entered into the same charging and discharging cycle working state and system to perform the 180th working discharge and the subsequent cyclic charging and discharging work.
  • the results show that after the first and second positive and negative polarity inversions and subsequent charging or charging and discharging operations, the discharge capacity of the battery in the 180th working state rises to 1452.5 mAh, and its 181st time. The discharge capacity in the operating state has recovered to a normal discharge capacity of 1649 mAh (corresponding discharge time is 1 hour and 36 minutes).
  • the battery of the embodiment is continuously operated under the working system, and the conditions for triggering the polarity reversal of the positive and negative polarities and the subsequent charging or charging and discharging operations are changed by programming to: when the lead-acid battery of the embodiment operates When the discharge time is ⁇ 1 hour and 36 minutes, the battery operation is stopped and the third and fourth positive and negative polarity inversions and subsequent charging or charging and discharging operations are automatically started. As shown in Fig. 1, the working discharge capacity in the 18th-224th discharge-charge working cycle reaches the normal discharge time, 1 hour and 36 minutes (corresponding discharge capacity is 1649mAh), and the battery of this embodiment is charged and discharged during the cycle.
  • the positive electrode plate On the positive electrode plate (electrode A), the positive electrode reaction of the lead-acid battery occurs, and the negative electrode of the lead-acid battery occurs on the negative electrode plate (electrodes B1 and B2).
  • the discharge capacity of the battery is obtained. Start to fall, the discharge time is 1 hour and 35 minutes (when the battery discharge termination voltage has dropped to 1.75V), therefore, according to the set trigger condition and execution procedure, the battery charger and discharger of this embodiment will immediately implement this implementation.
  • the battery is automatically transferred from the working state to the positive plate, the negative polarity of the negative plate and the preparation and implementation stage of the charging or charging and discharging operation, that is, the 225th charge and discharge cycle is completed, and the battery voltage drops to 1.75V.
  • the battery is stopped, and the connection state between the battery and the charger and the discharger is in a positive state, that is, the positive electrode of the battery charger and discharger of the embodiment is the positive electrode plate of the lead-acid battery of the embodiment (electrode A) connected, the negative electrode of the battery charger and discharger of the embodiment is connected with the negative electrode plate (electrode B1, B2) of the lead-acid battery of the embodiment, and then the battery of the embodiment is automatically discharged at a constant current of 1031 mA and Forced discharge, and by the forced discharge function of the battery charger and discharger of the present embodiment, the continuous discharge and forced discharge operation caused the battery voltage of the present embodiment to be rapidly lowered from 1.75 V to 0 V over 23 minutes (this process makes the lead acid of the present embodiment
  • the process causes the lead-acid battery negative electrode reaction on the positive electrode plate or the electrode A of the lead-acid battery of the embodiment.
  • Charging process the negative electrode plate of the lead-acid battery of the present embodiment or the charging process of the positive electrode of the lead-acid battery on the electrodes B1 and B2)
  • the constant current forced discharge of 1031 mA was continued for 3 hours (at this time, the measured battery voltage dropped from -1.75 V to about -2.15 V, and this process still made the positive electrode plate (electrode A) of the lead-acid battery of this example).
  • the charging process of the negative electrode reaction of the lead-acid battery occurs, and the charging process of the positive electrode of the lead-acid battery occurs on the negative electrode plate (electrodes B1 and B2) of the lead-acid battery of the present embodiment), and then the charge and discharge device is then constant at 1031 mA.
  • the battery is forcibly charged by the current (the process is charged for 23 minutes, and the battery voltage is raised from about -2.15V to 0V (this process causes the lead-acid battery negative electrode to occur on the positive plate or the electrode A of the lead-acid battery of this embodiment).
  • the constant current charges the battery, and the battery voltage reaches 1.75V after 1 hour and 08 minutes (this process causes the positive electrode of the lead-acid battery or the positive electrode of the lead-acid battery on the positive electrode plate or the electrode A of the lead-acid battery of the embodiment)
  • the charging process of the reaction, the negative electrode plate of the lead-acid battery of the present embodiment or the charging process of the negative electrode of the lead-acid battery on the electrodes B1 and B2), and the battery is continuously charged for 8 hours and 41 minutes with a constant current of 412 mA, so that the measurement is made.
  • the battery voltage reaches 2.65V, then switch to charge the battery at a constant voltage of 2.65V, and keep this constant voltage charge for 3 hours (the positive plate or electrode A is positive and negative plate during constant current and constant voltage charging). Or the electrodes B1 and B2 are negative), after the constant voltage charging is completed, the third and fourth positive and negative polarity inversions of the battery of the embodiment and the subsequent charging or charging and discharging operations are completed, and then the present The battery of the embodiment is transferred back to its original, same cycle charging and discharging working state and system to perform the cycle charging and discharging operation of the 226th and subsequent times.
  • the battery of the embodiment is continuously operated under the working system.
  • the discharge time is 1 hour and 35 minutes, and the previous setting is triggered again.
  • the polarity of the positive and negative polarities and the start condition of the subsequent charging or charging and discharging operations so after the end of the 240th working discharge (the battery voltage is 1.75V at the end of the discharge), the charge and discharge device starts the present
  • the battery of the embodiment performs the polarity reversal of the positive electrode plate and the negative electrode plate of the fifth and sixth times, and the subsequent charging or charging and discharging operations, the operation method and the process, and the third and fourth positive and negative poles of the embodiment.
  • the sexual reversal and the following charging or charging and discharging operations are the same, and then the lead-acid battery of the embodiment is re-entered into the same cycle charging and discharging working state and system, and then the 241th and subsequent times of the battery of the embodiment are performed. Cycle charge and discharge work.
  • the discharge time of the battery of this embodiment was restored to 1 hour and 36 minutes in the 243th cycle operation (the first 241, 242 times of work cycle due to misoperation caused the discharge termination voltage is lower than 1.75V, resulting in over-discharge).
  • the battery of the embodiment is continuously operated under the working system, and during the 244th charging and discharging cycle, the polarity of the positive and negative polarities of the battery of the embodiment and the subsequent charging or charging and discharging operations are triggered.
  • the start condition is changed by programming to: when the discharge time of the battery of the embodiment is ⁇ 45 minutes, the battery operation is stopped and the seventh and eighth positive times of the lead-acid battery of the embodiment or the positive and negative plates thereof are automatically started.
  • the polarity of the negative electrode is reversed and the subsequent charging or charging and discharging operations.
  • FIG. 1 when the battery of the present embodiment is cycled to the 251th time, its discharge performance begins to decrease.
  • the working discharge time is 42 minutes (the corresponding working discharge capacity is 721 mAh), and the trigger setting is performed at this time.
  • the polarity of the positive and negative polarities is reversed and the start condition of the subsequent charging or charging and discharging operation. Therefore, after the end of the 268th discharge operation (the battery voltage is 1.75V at the end of the discharge), the battery operation is stopped, and the charge and discharge device is next.
  • the polarity inversion of the positive and negative plates of the seventh and eighth times of the battery of the embodiment is started, and the charging or charging and discharging operations are performed thereafter.
  • the operation method and process are the third and fourth positive of the embodiment.
  • the polarity polarity reversal and the subsequent charging or charging and discharging operations are basically the same, except that after the battery voltage reaches -1.75V, the constant current of 1031 mA is continuously maintained for 4 hours (instead of 3 hours, this is The process measures that the battery voltage is still decreasing from -1.75V to about -2.15V), after the polarity reversal of the seventh and eighth positive and negative plates and the subsequent charging or charging and discharging operations are completed.
  • the lead-acid battery of this embodiment is made heavy
  • the cycle charge and discharge operation of the 269th and subsequent times of the battery of the present embodiment is carried out in the same state as the cycle charge and discharge operation state and system.
  • the discharge time of the battery of this embodiment was restored to 1 hour and 12 minutes in the 269th cycle operation (discharge)
  • the capacity is 1252 mAh
  • the discharge time is restored to 1 hour and 36 minutes in the 270th cycle operation
  • the working discharge time is normal for 1 hour and 36 minutes in the following cycle to the 290th cycle charge and discharge operation.
  • the cycle charge and discharge working state and system are the same as the above 1-270th cycle work, and whenever When the working discharge time or the working discharge capacity of the lead-acid battery of the present embodiment is reduced to 1 hour 36 minutes or 1649 mAh or less, the lead-acid battery of the present embodiment is subjected to the first two polarity inversions similar to the above and thereafter.
  • Charging or charging and discharging operations that is, between 295th, 296th, 309th, 310th, 324th, 325th, 344th, 345th, 369th, 370th
  • the working discharge time or capacity of the lead-acid battery of the embodiment is the subsequent step in the operation.
  • One time or the second working discharge returns to 1 hour 36 minutes or 1649 mAh, which may be related to the degree of decline of the actual working discharge capacity of the battery before the start of each polarity inversion operation, and each polarity inversion and thereafter
  • the current, voltage, charge and discharge capacity, number of stages, etc. during charging or charging and discharging operations are related to the size and method.
  • the polarity inversion is repeated twice in the first period and the subsequent charging or charging and discharging operations are performed.
  • the demand for the amount of charge after the first polarity reversal in this period is also large, and the larger amount of charge after the second polarity reversal in this period is beneficial to ensure that the battery is fully charged, so if the second period of the period If the charge is relatively small after the polarity is reversed, the battery may be undercharged, which may cause the lead acid battery of the embodiment to pass the first two polarity inversions and the first time after the charging or charging and discharging operation.
  • the working discharge and charging process continue to supplement the battery charge.
  • the two consecutive polarity inversions and the subsequent charging or charging and discharging operations performed between the 405th and 406th times of the working discharge or between the 441th and 442th times are performed by the 405th time.
  • the 441th working discharge result shows that the working discharge capacity of the lead-acid battery of the present embodiment is less than the 179th, and the two consecutive polarity reversals between the 405th and the 406th times and
  • the subsequent charging or charging and discharging operation process is: after the 405th working discharge (the battery voltage is 1.75V at this time), while maintaining the battery charger and discharger in the positive state of the battery of the embodiment, the battery is continuously operated at a constant current of 1031 mA.
  • Discharge and forced discharge for 132min causing the battery voltage to drop from 1.75V to 0V, and then from 0V to -1.75V (wherein, from 1.75V to 0V, the main occurrence of lead on the positive plate or electrode A is lead)
  • the discharge process of the positive electrode of the acid battery, the negative electrode plate or the electrodes B1 and B2 mainly occur in the discharge process of the negative electrode of the lead-acid battery.
  • the positive plate or the electrode A mainly occurs.
  • Lead-acid storage The charging process of the negative electrode reaction, the negative electrode plate or the electrodes B1 and B2 mainly occur in the charging process of the positive electrode of the lead-acid battery), and the polarity of the negative electrode plate (electrodes B1, B2) is positive at -1.75V, and the positive electrode The polarity of the plate (electrode A) is negative, and then the battery is forced to discharge for 4 hours at a constant current of 1031 mA (the battery voltage continues to drop from -1.70 V to -2.087 V during this process, which is still the negative plate or electrode) B1, B2 is positive, the positive electrode plate or the electrode A is negative), and then the battery is forcibly charged at a constant current of 1031 mA, so that the negative electrode reaction of the lead-acid battery occurs on the positive electrode plate (electrode A) of the lead-acid battery of the embodiment.
  • the discharge process of the positive electrode of the lead-acid battery occurs on the negative plate (electrodes B1, B2) of the lead-acid battery of the present embodiment, and the forced charge is stopped after 35 minutes to 0V, and then the battery is 258.4.
  • the constant current of the mA is charged, so that the charging process of the positive electrode of the lead-acid battery on the positive electrode plate (electrode A) of the lead-acid battery of the present embodiment occurs on the negative electrode plate (electrode B1, B2) of the lead-acid battery of the present embodiment.
  • the charging process of the negative electrode of the acid battery is charged, and the charging is performed for 1 hour and 21 minutes until the battery voltage is 1.75V (at this time, the positive electrode plate or the electrode A is positive, the negative electrode plate or the electrodes B1 and B2 are negative), and then charged at a constant current of 412 mA. 14 hours, to the battery voltage 2.63V, and then charge the battery for 4 hours at a constant voltage of 2.65V (this constant current, constant voltage charging process positive plate or electrode A is positive, negative plate or electrode B1, B2 is negative) Then, the battery is re-entered into the same cycle charging and discharging working state and system to perform the 406th working discharge and the cycle of the number of times.
  • the two consecutive polarity reversals between the 441th and 442th times and the subsequent charging or charging and discharging operations are basically the same as those between the 405th and 406th times, except that between the 441th and the 442th
  • the forced discharge current after the first polarity inversion and the subsequent polarity inversion in the subsequent charge or charge and discharge operation is 1515 mA (that is, the forced discharge causes lead acid to occur on the positive electrode plate or the electrode A).
  • the charging process of the battery negative electrode reaction causes the charging process of the positive electrode of the lead-acid battery to occur on the negative electrode plate or the electrodes B1 and B2).
  • the lead-acid battery of this embodiment is being subjected to the first phase. Or before the polarity inversion of the first embodiment and the subsequent charging or charging and discharging operation, as shown in FIG.
  • the number of cycles or the service life of the effective operation is 145 cycles (continuous after 143 cycles)
  • the three-time discharge capacity is lower than 80% of the rated capacity, but the positive and negative polarity inversion and the subsequent charging or charging and discharging operation method, the lead-acid battery, the battery charge and discharge device, the lead of the embodiment
  • the number of effective working cycles has reached 408 times, an increase of 181%. It can be speculated that it will continue to follow the conditions of no collector corrosion, water loss, etc.
  • the above operation method can make the service life of the lead-acid battery of the embodiment continue to be extended.
  • the cost and benefit evaluation are performed by taking the first 8 polarity inversions and the subsequent charging or charging and discharging operations in this embodiment, the first 8 positive and negative polarity inversions of the battery are performed in this embodiment.
  • the total charge consumed by the subsequent charging or charging and discharging operation is about 47336 mAh, and the additional effective working times is 83 times, so the average additional charge per operation is 570 mAh, which is the lead of this embodiment.
  • the cost of adding 365 effective jobs is about 13.2% of the current commercial power lead-acid battery purchase cost, that is, if the charge and discharge device cost of the embodiment is not used, the method for improving or prolonging the service life of the lead-acid battery by applying the embodiment One year can reduce the cost of using the power battery to 13.2%.
  • the working discharge system is mild (the discharge depth and discharge current are less than 93% DOD, 1.16I 2 , and I 2 is 0.5 times current in this example), the average amount of charge consumed per work is increased. It is also lower, which increases the cost of each effective job. In addition, every one year of battery life increase, the environmental benefits are enormous.
  • the method of pulse charging is used to perform polarity inversion and subsequent charging or charging and discharging, which further improves the efficiency of the operation and reduces The cost of this operation increases the effectiveness of the operation.
  • the positive and negative polarity inversion of the present embodiment and the subsequent charge and discharge or charge and discharge operations cause the positive active material of the lead-acid battery of the present embodiment to be softened and peeled off to be improved, repaired, reversed, thereby
  • the working discharge capacity in the cycle operation of the lead-acid battery is improved or restored after the operation.
  • the positive and negative polarity inversion of the present embodiment and the subsequent charge, discharge or charge and discharge operations are also inevitable.
  • the problems of electrode passivation, early capacity loss, corrosion, poor contact of active material with current collector, and shrinkage of specific surface area of the anode during the cycle operation of the battery have the effects of improvement, repair, reversal, and prevention.
  • the positive and negative polarity inversion of the present embodiment is performed on the lead-acid battery of the embodiment periodically or irregularly (for example, in a manner of a predetermined number of cycles). And subsequent charge, discharge or charge and discharge operations, will effectively improve, repair, reverse, prevent softening or / and shedding of positive active materials, electrode passivation, corrosion, early capacity loss, sulfation, active substances and current collectors
  • the problem of poor contact and negative specific surface area shrinkage increases or prolongs the service life of the lead-acid battery of this embodiment.
  • the lead-acid battery of the embodiment has an identity identification system.
  • the battery charge and discharge device of the embodiment can identify the battery of the embodiment to determine the implementation. For example, the entire or recent working history of the battery, various related program settings, and the like, so that after the battery charger and discharger of the embodiment is connected to the battery of the embodiment, the polarity of the positive and negative poles of the battery of the embodiment is reversed. After charging or charging and discharging work.
  • the forced discharge time of the lead-acid battery of the embodiment to be forced to discharge to the battery voltage ⁇ 0V or -1.75V may also be 5 hours, 10 hours, 20 hours, so that the battery voltage can be reached. -2.3V, -2.65V, -2.78V, etc., to obtain a stronger positive electrode active material softening, shedding reversal effect.
  • the measured concentration of the electrolyte in the battery is higher than 55%, and the battery temperature is higher than 45 ° C, the positive and negative polarity reversal and subsequent charging or Charge and discharge operation, and after the concentration of the electrolyte is less than 50% (can be achieved by rehydration of the battery), and the temperature drops to less than 40 °C, the positive and negative polarity reversal and subsequent charging or charging and discharging operations are continued. .
  • the battery of the embodiment when the battery of the embodiment is operated or stopped, and the polarity of the positive and negative poles is reversed and the subsequent charging or discharging operation is performed or stopped, the battery of the embodiment is subjected to a liquid replacement operation.
  • the replenished liquid includes one or more of water, sulfuric acid solution and additive solution to repair battery water loss caused by long time, multiple times, large current charge, discharge, overcharge, oxidation, battery sealing problem, etc. Loss of acid, loss of additives and other losses, improve battery life.
  • the method for improving or prolonging the service life of the lead-acid battery of the present embodiment is applied to the lead-acid battery pack of the embodiment.
  • the rated voltage of the lead-acid battery pack of the embodiment is 12V, and the rated capacity is 12Ah, in the method implementation operation, the corresponding changes are made in the setting and execution of the values of voltage, current, capacity, etc. in operation, for example, after the lead-acid battery pack is forcibly discharged to the battery pack voltage ⁇ 0V, After the battery pack voltage continues to drop to -6V, -10.5V, -13V, -15V, the forced discharge is stopped, and the forced discharge current is 0.3 times, 0.5 times, 1 time, and 2 times.
  • the method, the circuit and the lead-acid battery for improving or prolonging the service life of the lead-acid battery in the embodiment wherein the circuit of the embodiment is based on the constant current source circuit, the constant voltage source circuit and the forced charging or/and the forced discharging function
  • the polarity reversal of the positive and negative electrodes of the lead-acid battery of the embodiment and the subsequent charging or charging and discharging operations can be realized, and the program execution function is also provided.
  • the lead-acid battery of the embodiment is a flat grid type lead-acid battery, and the rated capacity is 1.93 Ah (2h rate, 25 ° C), the rated voltage is 2V, and has a structure of sandwiching a positive plate between two negative plates, positive and negative.
  • the positive plates have a positive paste prepared by the positive electrode, and the battery is only used as a positive electrode when working, so it is called a positive plate (for the subsequent statement, In the present embodiment, it is also named as electrode A).
  • the negative electrode plate has a lead paste prepared by a conventional negative electrode formula, and the battery is used only as a negative electrode when working, and thus is called a negative electrode plate (for the subsequent statement, in this embodiment, It is also named as electrode B1, B2), the formulation of positive and negative lead paste is different, and the lead powder used in the positive electrode lead paste is 100% oxidation degree lead oxide powder, and the lead powder used in the negative plate lead paste is ball-milled lead. After the powder, the quality of the dry lead paste on the positive electrode plate after curing and drying was 31.1 g.
  • the density of the sulfuric acid solution in the lead-acid battery of the present embodiment is 1.27 g/cm 3 .
  • This embodiment eliminates or prevents the interference of the liquid-phase, open circuit, short circuit, mechanical damage, test failure and the like on the implementation process and the implementation result of the embodiment.
  • the method for improving or prolonging the service life of the lead-acid battery is as follows: First, the lead-acid battery of the embodiment is subjected to the cyclic charge and discharge operation.
  • the working system of the lead-acid battery of the embodiment is: when the battery of the embodiment is in a state of being charged
  • the discharge time reaches 1 hour and 36 minutes (that is, the discharge capacity is 1614 mAh, which is 83% of the rated capacity), or the battery voltage is ⁇ 1.75 V
  • the discharge is stopped, and then the discharge is stopped.
  • the battery is charged with a constant current of 404 mA, and when the battery voltage reaches 2.65 V, it is converted to continue charging the battery with a constant voltage of 2.65 V.
  • the total time of two (constant current, constant voltage) charging is 6 hours and 24 minutes.
  • the above-mentioned 1008 mA constant current discharging process is repeated, and the repeated, cyclic discharging, charging, re-discharging, and recharging are performed to make the battery charge and discharge work, and the battery working environment temperature is 25 ⁇ 1 °C.
  • the present embodiment is caused.
  • the discharge time or the discharge capacity of the lead-acid battery is less than or continuously less than a predetermined capacity value or a certain time value in the above operation, the operation of the battery of the embodiment is stopped, and at least one period of the battery of the embodiment is started.
  • the positive and negative polarity inversion and the subsequent charging or charging and discharging operations are performed twice, so that the working discharge capacity of the lead-acid battery of the embodiment is restored or improved after the operation is completed, and then the battery is reintroduced into the battery. Under the original work system, the cycle charge and discharge work continued. Then, in the cyclic operation of the lead-acid battery of the embodiment, the polarity of the positive and negative polarities of the same or similar to the above two consecutive times in the present embodiment are repeatedly, interspersed, and multi-period.
  • Charging or charging and discharging operations to inhibit, prevent, repair, improve, eliminate or reverse the softening or/and shedding of the positive active material of the lead-acid battery, the specific surface area shrinkage of the negative active material, electrode/sink/catch corrosion, passivation, One or more of early capacity loss, sulfation, and poor contact between the active material and the current collector to significantly increase or prolong the service life of the lead acid battery of the present embodiment.
  • the positive and negative polarity inversion and subsequent charging or charging and discharging operations of the lead-acid battery of the embodiment are set and executed by the circuit of the embodiment and the setting program and the execution function thereof, and the present embodiment is performed.
  • the charging and discharging operations of the battery of the embodiment are also performed by using the charging and discharging functions of the circuit of the embodiment to realize the circulating operation of the battery of the embodiment (hereinafter, all operations and measurements of the battery are specifically described below). It is manually and externally, and all of them are programmed and executed by the circuit of this embodiment.
  • the capacity of the electrolyte in the battery with respect to the positive electrode active material is excessive or sufficient.
  • the battery operation of the embodiment is stopped, and the first and second polarity reversal of the positive and negative poles of the battery of the embodiment are started. Subsequent charging or charging and discharging operations.
  • the battery of the present embodiment performs the cycle charge and discharge operation according to the set working system from the 18th charge and discharge cycle (the first 17 charge and discharge cycles are performed by overcharge, overdischarge, capacity detection, etc.). The operation is also calculated to the total number of times of the cycle charge and discharge operation.
  • the positive electrode of the lead-acid battery occurs on the positive electrode plate (electrode A) of the present embodiment, and the negative electrode of the lead-acid battery occurs on the negative electrode plate (electrodes B1, B2).
  • Electrode reaction, charge and discharge cycle 18-50 times, the battery of this example showed normal working ability, that is, the discharge capacity per work was 1614 mAh.
  • the working discharge capacity of the battery of the present embodiment began to show a decrease, that is, the working discharge capacities of the 51st-53th time were 1583, 1568, and 1554 mAh, respectively (the corresponding discharge time was 1 hour, respectively).
  • the battery of the present embodiment was reached.
  • the triggering conditions of the positive or negative polarity inversion and subsequent charging or charging and discharging operations discharge capacity three times ⁇ 1614 mAh) are performed, and then the first and second positive and negative polarity inversions of the battery of the embodiment are started.
  • connection state of the lead-acid battery is connected from the positive electrode clip of the circuit of the present embodiment to the positive electrode plate of the lead-acid battery (electrode A), and the positive electrode clip of the circuit of the present embodiment is connected with the negative electrode plate of the lead-acid battery (electrode B1, B2), and is changed.
  • the positive electrode clip of the circuit is connected with the negative electrode plate (electrode B1, B2) of the lead-acid battery, and the reverse connection state of the negative electrode clip of the circuit of the present embodiment and the positive electrode plate of the lead-acid battery (electrode A) is connected, and then, the constant is 1008 mA.
  • the current is charged in the battery of the embodiment after the connection state is changed, so that the charging process of the negative electrode of the lead-acid battery on the positive electrode plate (electrode A) of the battery of the embodiment occurs, and the negative electrode plate (electrode B1, B2) occurs.
  • the charging process of the positive electrode of the lead-acid battery reacts.
  • the battery voltage rises to 1.75V the battery is continuously charged with a constant current of 1008 mA for 3 hours (the battery voltage rises from 1.75V to 2.28V in this process), and then the constant current is 1008mA.
  • the battery is discharged, so that the discharge process of the lead-acid battery negative electrode reaction occurs on the positive electrode plate (electrode A) of the battery of the embodiment, and the lead-acid storage occurs on the negative electrode plate (electrodes B1, B2).
  • the discharge is stopped when the discharge reaches 0V, and then the polarity of the positive and negative polarities is reversed again for the battery (second time), that is, the circuit of the present embodiment and the lead acid of the embodiment are manually manually used.
  • connection state of the battery is changed from the positive electrode clip of the present embodiment to the negative electrode plate (electrode B1, B2) of the lead-acid battery, and the reverse connection state of the negative electrode clip of the circuit of the present embodiment and the positive electrode plate (electrode A) of the lead-acid battery is changed into
  • the positive electrode clip of the circuit is connected to the positive electrode plate (electrode A) of the lead-acid battery
  • the positive electrode clip of the circuit of the present embodiment is connected to the negative electrode plate of the lead-acid battery (electrode B1, B2), and then the battery is 251.5 mA.
  • the constant current is charged, so that the charging process of the lead-acid battery positive electrode reaction occurs on the positive electrode plate (electrode A) of the battery of the embodiment, and the charging process of the lead-acid battery negative electrode reaction occurs on the negative electrode plate (electrodes B1, B2).
  • the battery voltage is 1.75V, it is charged at a constant current of 404mA.
  • the battery voltage is 2.65V, the battery is charged at a constant voltage of 2.65V for 3 hours. At this point, the first battery of this embodiment is completed.
  • the second positive and negative polarity inversion and subsequent charging or charging and discharging operations are performed.
  • the battery of this embodiment is re-entered into the same discharge-charge cycle operation state or system as the previous 54th working discharge and the cycle charge and discharge operation.
  • the results show that after the first and second positive and negative polarity inversions and subsequent charging or charging and discharging operations, the discharge capacity of the battery of this embodiment in the 54th cycle operation rises to 1570 mAh (corresponding discharge time) For 1 hour and 33 minutes, the discharge capacity is less than 1614 mAh, which may be related to insufficient charging before working discharge, the same situation is the same below), and the discharge capacity in the 55th operation has returned to the normal discharge capacity under working condition, 1614 mAh ( The corresponding discharge time is 1 hour and 36 minutes).
  • the battery of the embodiment is continuously operated under the working system, and the starting condition for triggering the polarity of the positive and negative polarities of the battery and the subsequent charging or discharging operation is changed by programming to: when the discharging time of the battery of the embodiment When the battery is less than 1 hour and 36 minutes in four consecutive times, the battery operation is stopped, and the third and fourth positive and negative polarity inversions and subsequent charging or charging and discharging operations are started.
  • the discharge capacity of the battery of the present embodiment during the 55th-93th charge-discharge cycle operation is 1 hour and 36 minutes of the normal discharge time (corresponding discharge capacity is 1614 mAh), but it is operated in the charge-discharge cycle.
  • the discharge time of the battery began to show a decline, that is, the discharge time of the 94th-97th time was 1 hour 35 minutes, 1 hour 34 minutes, 1 hour 33 minutes, and 1 hour 33 minutes (corresponding discharge capacity). It is 1603, 1589, 1578, and 1567 mAh, respectively. Therefore, the charging and charging/discharging triggering conditions of the positive and negative polarity inversion of the battery of the embodiment are started. At this time, the battery of the embodiment is started to be the third and the third.
  • the operation method and process are basically the same as performing the first and second positive and negative polarity inversions and subsequent charging or charging and discharging operations, The difference is that the battery voltage is not discharged from the constant current of 1.75V to 0V before the third positive and negative polarity reversal, but the battery is stopped when the voltage drops to 1.75V.
  • the conversion or interchange is performed, that is, the connection state of the circuit of the embodiment and the lead-acid battery of the embodiment is changed from the positive connection state to the reverse connection state, and after the connection conversion or the interchange, the battery voltage is measured to be a negative value, and then, The constant current of 1008 mA charges the battery after the connection state is changed, and when the battery voltage rises from a negative value to 0 V to 1.75 V (the third positive and negative polarity inversion of the battery of this embodiment is completed in this process) After that, the battery is continuously charged at a constant current of 1008 mA for 3 hours. Then, the battery is discharged at a constant current of 1008 mA, and the discharge is stopped at 0 V.
  • the polarity of the positive and negative polarities of the battery is reversed again (fourth time).
  • the connection state of the circuit of the embodiment and the lead-acid battery from the reverse connection state to the positive connection state, and then charging the battery with a constant current of 251.5 mA until the battery voltage is 1.75 V
  • the 404mA constant current is charged, and when the battery voltage is 2.65V, the battery is charged at a constant voltage of 2.65V for 3 hours.
  • the third and fourth positive and negative polarity inversions of the battery of the embodiment are completed and then charged. Or charge and discharge Electrical operation.
  • the battery is re-entered into the same discharge-charge cycle operation state or system to perform the 98th working discharge and the cycle charge and discharge operation.
  • the results show that after the third and fourth positive and negative polarity inversions and subsequent charging or charging and discharging operations, the discharge capacity of the battery during the 98th cycle is 1489 mAh (corresponding discharge time 1 hour 28)
  • the fraction, which did not reach 1614 mAh, may be related to insufficient charging before discharge, and the discharge capacity in the 99th cycle has returned to the normal working discharge capacity, 1614 mAh (corresponding discharge time is 1 hour and 36 minutes).
  • the battery of the embodiment is continuously operated according to the working system, and the start condition for triggering the polarity of the positive and negative polarity of the battery and the subsequent charging or discharging operation is changed by programming (after the 99th working discharge):
  • the discharge time of the lead-acid battery of the embodiment is less than 1 hour and 36 minutes, the battery operation is stopped and the fifth and sixth positive and negative polarity inversions and subsequent charging or charging and discharging operations are automatically started on the battery.
  • the discharge time of the lead-acid battery of the present embodiment in the 99th-126th charge-discharge cycle operation is 1 hour and 36 minutes (the corresponding discharge capacity is 1614 mAh), and when it is cycled to the 127th.
  • the circuit of the embodiment immediately transfers the battery of the embodiment from the working state to the preparation and implementation stage of the positive or negative polarity inversion and subsequent charging or charging and discharging operations, that is, after the battery voltage drops to 1.75V.
  • the battery operation was stopped, and the battery of the present embodiment was continuously discharged with a constant current of 1008 mA, and by the forced discharge function of the circuit of the present embodiment, the continuous discharge operation lowered the battery voltage from 1.75 V to 0 V, and then from 0 V.
  • the charging process of the lead-acid battery negative electrode reaction occurs on the positive electrode plate or the electrode A of the battery of the embodiment, and the charging process of the lead-acid battery positive electrode reaction occurs on the negative electrode plate or the electrodes B1 and B2)
  • a constant current of 1008 mA for 3 hours (at this time, the measured battery voltage dropped from -1.75 V to about -2.12 V).
  • the circuit of this embodiment was followed by 1008 mA.
  • the constant current charges the battery (measured that the battery voltage rises from about -2.12V to 0V, and the charging takes 21 minutes).
  • the circuit of this embodiment automatically continues.
  • the constant current of 251.2 mA charges the battery until the battery voltage reaches 1.75V (this rises from -2.22V to 0V and then rises to 1.75V.
  • the sixth positive and negative polarities of the battery of this embodiment are completed.
  • the discharge process of the lead-acid battery negative electrode reaction occurs on the positive electrode plate or the electrode A of the battery of the embodiment, and the positive electrode of the lead-acid battery reacts on the negative electrode plate or the electrodes B1 and B2.
  • the charging process of the lead-acid battery positive electrode reaction occurs on the positive electrode plate or the electrode A of the battery of the present embodiment, and the negative electrode plate of the lead-acid battery occurs on the negative electrode plate or the electrodes B1 and B2.
  • the battery is continuously charged with a constant current of 404 mA until the battery voltage reaches 2.65 V, and then the battery is charged at a constant voltage of 2.65 V, and the constant voltage charging is maintained for 3 hours.
  • the battery of the embodiment is then returned to its previous discharge-charge cycle operation state or Under the system, the 128th working discharge and the cycle charge and discharge work are performed.
  • the discharge time of the battery of the present embodiment in the 128th cycle is 1 hour and 25 minutes (corresponding to The discharge capacity is 1428 mAh, this time does not reach 1614 mAh, which may be related to insufficient charging before working discharge), and the discharge capacity in the 129th working state has returned to the normal discharge time of 1 hour and 36 minutes (corresponding discharge capacity) It is 1614mAh).
  • the battery of the present implementation continues to operate according to the working system.
  • the discharge time of the battery in its 129-152th cycle operation is normal 1 hour and 36 minutes.
  • the discharge time is 1 hour and 35 minutes (the corresponding discharge capacity is 1612 mAh), and the start condition of the positive and negative polarity inversion of the battery and the subsequent charge or charge/discharge operation are set again.
  • the circuit of the present embodiment starts the seventh and eighth positive and negative polarity inversion and subsequent charging or charging of the battery of the embodiment.
  • the discharge operation, the operation method and the process are the same as the fifth and sixth positive and negative polarity inversions of the battery of the embodiment and the subsequent charging or charging and discharging operations, and then the battery of the embodiment is transferred back to the same During the discharge-charge cycle operation state or system, the 154th working discharge and the subsequent cycles of charge and discharge work are performed.
  • the results show that the seventh and eighth positive and negative polarity inversions and subsequent charging or charging and discharging After the operation,
  • the discharge time of the battery in this embodiment under the 154th and 155th cycles is 1 hour, 15 minutes, and 1 hour and 34 minutes respectively (the corresponding discharge capacity is 1260, 1579 mAh, which does not reach 1614 mAh, which may be related to the work discharge. Insufficient charging, and the two working discharges caused over-discharge due to misoperation, and the discharge capacity in the 156th working state has returned to the normal discharge time of 1 hour and 36 minutes (corresponding discharge capacity is 1614 mAh).
  • the battery of this embodiment is continuously operated according to the working system.
  • the discharge time of the battery in its 156-166th cycle is 1 hour and 36 minutes, when the battery is cycled to the 167th time.
  • the discharge time is 1 hour and 35 minutes (the corresponding discharge capacity is 1604 mAh), and the initial conditions of the positive and negative polarity reversal of the battery and the subsequent charging or charging and discharging operations are set again, and thus the 167th
  • the circuit of the embodiment begins to perform the ninth and tenth reverse polarity reversal and subsequent charging or charging and discharging of the battery of the embodiment.
  • the operation, operation method and process are still the same as the fifth and sixth positive and negative polarity inversions of the battery of the embodiment and the subsequent charging or charging and discharging operations, and then the battery of the embodiment is transferred back to the same
  • the 168th working discharge and the subsequent number of cycles of charge and discharge work are performed, and as a result, the ninth and tenth times of the positive and negative polarity inversion and subsequent charging or charging and discharging operations are performed.
  • this real The discharge time of the battery in the 168th and 169th cycles is 1 hour, 06 minutes, 1 hour and 16 minutes respectively (the corresponding discharge capacity is 1109, 1277 mAh, which does not reach 1614mAh. This may be insufficient before the discharge of the working discharge). Relevant), and the discharge capacity in the 170th working state is restored to the normal discharge time of 1 hour and 36 minutes (corresponding discharge capacity is 1614 mAh).
  • the battery of the embodiment is continuously operated according to the working system.
  • the start condition for triggering the polarity reversal of the battery positive and negative polarities and subsequent charging or charging and discharging operations is changed by programming to:
  • the working discharge time of the lead-acid battery of the embodiment is less than 46 minutes
  • the battery operation is stopped and the eleventh and twelfth positive and negative polarity inversions and subsequent charging or charging and discharging operations are started.
  • the discharge time is 1 hour and 36 minutes in the next 170-179 cycles, but the discharge capacity begins to decrease during the 180th cycle and is cycled at the 192th cycle.
  • the medium discharge time is 45 minutes (corresponding discharge capacity is 756 mAh), triggering the conditions for starting the battery positive and negative polarity inversion and subsequent charging or charging and discharging operations, so after the end of the 192th cycle discharge operation (discharge At the end of the battery voltage is 1.75V), the circuit of the embodiment begins to perform the eleventh and twelfth positive and negative polarity reversal and subsequent charging or charging and discharging operations on the battery of the embodiment, and the operation process is
  • the fifth and sixth positive and negative polarity inversions of the battery and the subsequent charging or charging and discharging operations are basically the same, except that after reaching -1.75V, the battery of the embodiment is continued to be 1031 mA.
  • the constant current was forced to discharge for 4 hours (instead of 3 hours, and the process measured that the battery voltage was still dropped from -1.75V to about -2.12V).
  • the discharge time of the battery of this embodiment was restored to 1 hour in the 193th cycle operation.
  • the fraction (corresponding capacity is 1560 mAh)
  • the discharge time is restored to 1 hour and 36 minutes in the 194th cycle operation
  • the discharge time is 1 hour in the next cycle of the 210th charge and discharge operation. Minute.
  • FIG. 3 shows the 189-196 cycle charge and discharge operation process of the lead-acid battery of the embodiment, and the eleventh and twelfth positive and negative polarity inversions and the subsequent charging or charging and discharging operations interposed during the process. Current and battery voltage changes during the process.
  • the working discharge time of the lead-acid battery of this embodiment is reduced to 1 hour and 36 minutes (the corresponding capacity is 1614 mAh).
  • the lead-acid battery of the embodiment is subjected to the first two-stage polarity reversal and the subsequent charging or charging and discharging operations, that is, the 220th (corresponding working discharge capacity) of the cyclic working discharge, respectively.
  • the working discharge capacity of the lead-acid battery of the present embodiment is quickly or immediately restored to 1614 mAh, so that the lead-acid battery of the embodiment retains the ability to continue normal operation.
  • the working discharge capacity of the lead-acid battery of the embodiment is restored to normal by only the charging operation, and one or more times are passed.
  • the working discharge capacity of the lead-acid battery of the embodiment is restored to normal.
  • the lead-acid battery of the embodiment is between 582 and 583 times of the cyclic discharge of the lead-acid battery of the embodiment.
  • the charging and discharging operation of the lead-acid battery of the present embodiment after the two positive and negative polarities are reversed is as follows: 430 mA constant current charging to 2.65 V is performed on the lead-acid battery after the current polarity reversal in this period. It took 13 hours and 54 minutes), and then charged at a constant voltage of 2.65V for 3 hours. Then, the lead-acid battery of the present embodiment was put into the cycle charging and discharging working system to perform the 583th working discharge. As a result, the battery of this example was at the 583th time. The working discharge time or capacity or capacity is restored to normal 1 hour 36 minutes or more than 1614 mAh.
  • the lead-acid battery of this embodiment has two consecutive polarity reversals in each period and subsequent charging or charging and discharging operations, and then the working discharge capacity recovery degree of the lead-acid battery of the embodiment is as follows.
  • the lead-acid battery can continuously maintain the normal number of cycles after each period of operation discharge capacity recovery (ie, two consecutive periods of polarity inversion in two phases and subsequent charging or charging and discharging operations).
  • the number of normal duty cycles to be recovered shall be the same as the degree of decrease in the actual working discharge capacity of the battery before the start of each polarity inversion operation, the polarity inversion of each period, and the subsequent charge or charge and discharge operations.
  • the service life of the lead-acid battery of the embodiment is defined as the battery life is terminated when the three consecutive working discharge capacities are less than 83% of the rated capacity (1602 mAh). Then, the lead-acid battery of this embodiment is subjected to the polarity reversal of any of the embodiments and the subsequent charging or charging and discharging operations, as shown in FIG. 2, and its service life is 53 cycles, that is, 51, 52 The working discharge capacity of 53 times is 1582.8, 1568.1, 1554 mAh, respectively, but the lead acid of this embodiment is obtained by the positive and negative polarity inversion of the present embodiment and the subsequent charging or charging and discharging operation method, lead-acid battery and circuit.
  • the number of cycles in which the battery discharge working discharge capacity reaches 83% or more of the rated capacity that is, the number of life cycles is extended to 608 times, an increase of 1047%, and it can be speculated that in the case of no collector corrosion, water loss, etc. According to the above operation method, the service life of the lead-acid battery of the embodiment can be continuously improved or extended.
  • the positive and negative polarity inversion of the present embodiment and the subsequent charge and discharge or charge and discharge operations cause the positive active material of the lead-acid battery of the present embodiment to be softened and peeled off to be improved, repaired, reversed, thereby In this embodiment, the working discharge capacity in the cyclic operation of the lead-acid battery is improved or restored after the operation.
  • the positive and negative polarity inversion of the present embodiment and the subsequent charge, discharge or charge and discharge operations are also inevitable.
  • the problems of electrode passivation, early capacity loss, corrosion, poor contact between active material and current collector, and shrinkage of specific surface area of the anode during the cycle operation of the battery of the present embodiment have the effects of improvement, repair, reversal, and prevention.
  • the positive and negative polarity inversion of the present embodiment is performed on the lead-acid battery of the embodiment periodically or irregularly (for example, in a manner of a predetermined number of cycles).
  • the circuit having the positive and negative polarity inversion and the subsequent charging or charging and discharging functions is integrated into the battery charging and repairing device to become a battery charging and repairing device. Part of the product.
  • the circuit having the positive and negative polarity inversion and subsequent charging or charging and discharging functions of the present embodiment is integrated into the configuration of the lead-acid battery and becomes a part of the lead-acid battery product.
  • the electrolyte density of the lead-acid battery of the present embodiment may be 1.29 g/cm 3 or 1.32 g/cm 3 .
  • the circuit having the positive and negative polarity inversion and the subsequent charging or charging and discharging functions of the present embodiment is neither integrated into the battery charge and discharge device nor integrated.
  • the method and circuit for improving or prolonging the service life of the lead-acid battery in the present embodiment are used in the lead-acid battery group of the present embodiment (rated voltage is 36V, rated capacity is 12 Ah), and this embodiment is implemented.
  • the method and circuit for improving or prolonging the service life of the lead-acid battery pack correspond to the battery pack in terms of setting, executing, and allowing the parameter values such as voltage, current, and capacity.
  • the method and circuit for improving or prolonging the service life of a lead-acid battery or a battery pack are used for a tubular lead-acid battery or a battery pack, a wound lead-acid battery or a battery pack, Bipolar lead-acid battery or battery pack, horizontal lead-lead lead-acid battery or battery pack, foam grid-type lead-acid battery or battery pack, valve-regulated sealed lead-acid battery or battery pack, colloidal lead-acid battery or battery pack , lead-carbon battery or battery pack, supercapacitor - lead-acid battery or battery pack, column lead-acid battery or battery pack.
  • the lead-acid battery of the embodiment is a flat-plate type lead-acid battery, which has a structure in which two negative plates are sandwiched by a positive plate, and the positive and negative electrodes are separated by an AGM separator, and the rectangular grid of the positive grid is 9 mm*.
  • the rectangular grid of 7.5mm and negative grid is 13mm*7mm
  • the material of the positive grid is lead calcium-tin aluminum alloy
  • the material of the negative grid is lead-calcium aluminum alloy
  • the thickness of positive plate is 2.8mm
  • the thickness of negative plate is 1.9.
  • the formulation of the positive lead paste is basically the same as that of the current common commercial positive lead paste, and the formula differs in that the lead powder used in the lead-acid battery of the embodiment is a high specific surface area lead oxide powder having an oxidation degree of 100%, and The amount of sulfuric acid used in the paste is zero, and the negative lead paste is the current common commercial negative lead paste.
  • the rated capacity of the lead-acid battery of this embodiment is 1.79 Ah (C 1.5 , 1.5 h rate, 25 ° C), the rated voltage is 2 V, the total capacity of the negative electrode is relatively excessive to the total capacity of the positive electrode, and the dry lead paste on the positive electrode plate after curing and drying
  • the mass is 32.36 g, and the density of the sulfuric acid solution in the lead-acid storage battery of this embodiment is 1.27 g/cm 3 , and is always in the following cycle of the battery cycle operation and polarity reversal and subsequent charging or charging and discharging operations of the present embodiment. Keep it adequate.
  • the positive electrode plate is only used as a positive electrode, and the two negative electrode plates are only used as a negative electrode when the battery is in operation.
  • the positive electrode plate of the lead-acid battery of the present embodiment is named.
  • the two negative plates of the lead-acid battery of this example were named as electrodes B1 and B2.
  • the method for improving or prolonging the service life of the lead-acid battery in the embodiment is that, in the cycle charging and discharging operation of the battery of the embodiment, whenever the working discharge frequency of the lead-acid battery of the embodiment reaches a preset number of times, or Its working discharge capacity, due to softening or/and shedding of positive active material, specific surface area shrinkage of negative active material, electrode/sink/catch corrosion, passivation, early capacity loss, sulphation, poor contact between active material and current collector.
  • a certain percentage value of its rated capacity for example, 85.5%, 80%
  • Two polarity inversions and subsequent charging or charging and discharging operations such as softening or/and shedding of the positive active material, specific surface area shrinkage of the negative active material, electrode/sink/catch corrosion, passivation, early capacity loss,
  • One or more of the problems of sulfation, poor contact between the active material and the current collector are inhibited, prevented, repaired, improved, eliminated or reversed, so that the embodiment After the operation of the acid storage battery, the working discharge capacity is restored or improved, and then the lead acid battery of the embodiment is re-introduced into the circulating charging and discharging work for use or work until the triggering or starting another period of lead acid in the embodiment
  • the positive and negative electrodes of the battery are subjected to two consecutive polarity inversions and subsequent charging or charging and discharging operations.
  • the polarity inversion of the positive electrode and the negative electrode and the subsequent charging or charging and discharging operations of any one of the two consecutive periods described in this embodiment include the following steps: (1) by reverse charging the lead-acid battery of the embodiment (current is 1194 mA)
  • the method makes the polarity of the original positive electrode (electrode A) of the lead-acid battery of the embodiment and the original negative electrode (electrode B1, B2) reverse or interchange, that is, the polarity of the original positive electrode (electrode A) is reversed.
  • Electrodes B1, B2 The polarity of the negative and original negative electrodes (electrodes B1, B2) is reversed to positive, which is the polarity reversal of two consecutive periods in this period and the first polarity reversal in the subsequent charging or charging and discharging operations.
  • the positive electrode (electrode B1, B2) and the negative electrode (electrode A) after the first polarity inversion are subjected to constant current charging at 1194 mA to 1.75 V or 2.0 V (at this time, the polarities of the electrodes B1 and B2) Positive, the polarity of the electrode A is negative), and then continue charging for 3 or 4 or 5 hours with a constant current charging mode of 1194 mA (in this process, the main electrode of B1 and B2 is the positive electrode of the lead-acid battery.
  • the main occurrence of the electrode A is the charging process of the negative electrode of the lead-acid battery); (2) the end of the previous step
  • the current is discharged at a constant current of 1194 mA to 0 V.
  • the main discharge occurs on the electrodes B1 and B2 is the discharge process of the positive electrode of the lead-acid battery, and the lead-acid battery mainly occurs on the electrode A.
  • the lead-acid battery of the present embodiment is subjected to reverse polarity charging (current of 298 mA) to the lead-acid battery of this embodiment.
  • the electrodes A, B1, and B2 are reversed in polarity again, that is, the electrodes B1 and B2 are inverted from the positive polarity to the negative polarity, and the electrode A is reversed from the negative polarity to the positive polarity. This is the polarity of the current period twice.
  • Inverting and the second polarity inversion in the subsequent charging or charging and discharging operation and then charging the lead-acid battery of the embodiment after the second polarity inversion to 1.75V with a constant current of 298 mA, Then, it is charged at a constant current of 477 mA to 2.65 V, and then subjected to constant voltage charging at a constant voltage of 2.65 V for 4 hours, and then discharged to 1.75 V at a current of 1194 mA, and then charged at a constant current of 477 mA to a constant current.
  • the system for circulating charge and discharge operation of the lead-acid battery of this embodiment is that, in the case of working discharge, the lead-acid battery of the present embodiment discharges to a constant current of 1194 mA (0.62 C 2 ) to 1.75 V, that is, a discharge of 100% DOD (discharge depth).
  • the lead-acid battery of the present embodiment is charged to 2.65V at a constant current of 477.6 mA, and then the lead-acid battery of the embodiment is subjected to constant voltage charging at a constant voltage of 2.65 V, and when the constant current of 477.6 mA, 2.65 V
  • the charging process of the lead-acid battery of the embodiment is terminated, and then the lead-acid battery of the embodiment is subjected to the above-mentioned working discharge process again, repeatedly and repeatedly. In the discharge and charging process, the cycle charging and discharging working process of the lead-acid battery of the embodiment is realized.
  • the electrode A is always positive, and the electrodes B1 and B2 are always negative, that is, the charging and discharging process of the positive electrode of the lead-acid battery occurs on the electrode A, and the lead acid occurs on the electrodes B1 and B2.
  • step (1) of the positive and negative polarity inversion and the subsequent charging or charging and discharging operation which are performed twice in this embodiment, the 1194 mA constant current is charged to 1.75 V or 2.0 V, and the constant is 1194 mA.
  • Stream charging , 8 are three hours before the first nine of 17 to 4 hours, 5 hours after 5.
  • the conditions for triggering or starting the positive polarity of the positive electrode, the negative polarity, and the subsequent charging or charging/discharging operation of the 22 consecutive stages, the charging state of the battery at the trigger or the start are not completely the same, for example, the 199th
  • the triggering or starting condition of the polarity reversal and the subsequent charging or charging and discharging operations performed twice in one period between 200 times is that the number of working cycles reaches the preset working discharge-charging cycle 199 times, and is in the After the end of 199 working discharges, the polarity of the positive and negative electrodes and the subsequent charging or charging and discharging operations are performed twice in succession; for example, the polarity inversion is performed twice in two consecutive periods between the 214th and the 215th times.
  • the triggering or starting condition of the subsequent charging or charging and discharging operation is that the working discharge capacity is lower than 85.5% of the rated capacity for the first time, and the positive and negative polarities are continuously performed twice after the end of the 215th working cycle constant voltage charging process.
  • Inversion and subsequent charging or charging and discharging operations for example, the polarity inversion performed in two consecutive phases between the 274th and the 275th cycles and the triggering or starting condition of the subsequent charging or charging and discharging operation is the working discharge
  • the amount is less than 80% of the rated capacity for four consecutive times; for example, the lead acid battery of this embodiment is started when the polarity inversion is performed twice in the first period between the 387th and the 388th times and the subsequent charging or charging and discharging operation is started.
  • the first time of the period in the step (1) of the polarity reversal and the subsequent charging or charging and discharging operation performed twice in the first period between the 406th and the 407th times
  • the positive electrode (electrode B1, B2) and the negative electrode (electrode A) after polarity inversion are subjected to a constant current charging of 1194 mA to a voltage of 2.0 V; and the positive electrode and the negative electrode are successively performed twice in a single period between the 436th and the 437th times.
  • the charging and discharging process is
  • the lead-acid battery of this embodiment after the second polarity inversion in this period is charged to 1.75V with a constant current of 298 mA, and then charged to 2.65 V with a constant current of 477 mA, and then a constant voltage of 2.65 V.
  • the working discharge capacity of the lead-acid battery in the cycle charge and discharge operation of the present embodiment is completed after the completion of the two consecutive positive and negative pole inversions of the present embodiment and subsequent charging or charging and discharging operations. They are all obviously upgraded or restored (after inspection, this is due to improvement, repair, and reversal of softening and shedding of the positive active material).
  • the service life of the lead-acid battery of this embodiment is defined as the working discharge capacity is less than 80% (1447 mAh) of its rated capacity three times in succession, it is regarded as the end of the service life of the lead-acid battery of this embodiment, and the lead acid of this embodiment is The service life of the battery is at most 272 working cycles.
  • the working discharge capacity of the lead-acid battery in the present embodiment is 1,434, 1353, and 1279 mAh at 270, 271, and 272 times, respectively, but the positive and negative poles are passed through this embodiment.
  • Sexual reversal and subsequent charging or charging and discharging operations so that the service life of the lead-acid battery of the present embodiment (the number of working discharge charging cycles of working discharge capacity above 80% of the rated capacity) is increased or extended to 495 times. It can be inferred that in the case of eliminating grid corrosion, electrode deformation, battery loss, battery short circuit, and open circuit factors, the lead-acid battery of this embodiment has a longer service life than 495 cycles.
  • the polarity inversion of the positive electrode and the negative electrode of the present embodiment and the subsequent charge and discharge or charge and discharge operations cause the positive active material of the lead-acid battery of the present embodiment to be softened and peeled off to be improved, repaired, reversed, thereby In this embodiment, the working discharge capacity in the cycle operation of the lead-acid battery is improved or restored after the operation.
  • the polarity of the positive electrode and the negative electrode of the embodiment and the subsequent charge, discharge or charge and discharge operations are also inevitable.
  • the problems of electrode passivation, early capacity loss, corrosion, poor contact of active material and current collector, and shrinkage of specific surface area of the anode during the cycle operation of the battery have the effects of improvement, repair, reversal, and prevention.
  • the polarity of the positive electrode and the negative electrode of the present embodiment are reversed periodically or irregularly (for example, in a manner of a predetermined number of cycles).
  • the pulse current, the pulse voltage may be used instead of the direct current, the constant voltage, and the polarity of the positive electrode, the negative polarity inversion, and the subsequent charging or charging and discharging operation steps of the present example may be performed.
  • the maximum value of the battery voltage during the post-charge or charge-discharge operation is less than 2.65V, such as 2.5V, 2.44V, 2.33V.
  • the lead-acid battery of the embodiment is a tubular lead-acid battery having a structure in which two planar grid-type negative electrodes sandwich a tubular positive electrode, and the positive electrode and the negative electrode are separated by an AGM separator, and the tubular positive electrode
  • the inner diameter of the outer sleeve is 6.3mm
  • the wall thickness is 0.25mm
  • the tube height is 75mm (including the length of the upper and lower plugs)
  • the diameter of the lead-calcium alloy conductive core in the tube is 2.5mm
  • the mass of the active material in the tube is 5.5g. It is composed of the current common commercial ball-grinding lead powder.
  • the outer frame size of the negative plate is 72mm*45m
  • the rectangular grid is 13mm*7mm
  • the thickness is 1.9mm.
  • the negative lead paste is the current common commercial negative lead paste.
  • the initial rated capacity of the lead-acid battery of this embodiment is 0.342 Ah (C 2 , 2 h rate, 25 ° C, active material utilization rate is 25.5%), the rated voltage is 2 V, and the total negative electrode capacity is excessively excess in the total positive electrode capacity.
  • the density of the sulfuric acid solution in the lead-acid battery of the example was 1.27 g/cm 3 , and was always sufficient during the battery cycle operation and the polarity inversion and the subsequent charging or charging and discharging operations of the present embodiment described below.
  • the tubular positive electrode is only used as a positive electrode when the lead-acid battery is in operation, and the two negative plates are used only as a negative electrode when the battery is in operation.
  • the lead-acid battery of the present embodiment will be used.
  • the tubular positive electrode was named tube electrode A, and the two negative plates of the lead-acid battery of this example were named plate electrodes B1 and B2.
  • This embodiment eliminates or prevents the interference of the implementation process and the implementation result of the present embodiment by factors such as loss of liquid, open circuit, short circuit, mechanical damage, and test failure.
  • the method for improving or prolonging the service life of the lead-acid battery in the embodiment is that, when the lead-acid battery of the embodiment is used or operated in the cycle charging and discharging work, after the cycle reaches a certain number of times or as needed (for example, the positive active material is softened or/ And one or more of falling-off, negative electrode active material specific surface area shrinkage, electrode/sink/catch corrosion, passivation, early capacity loss, sulfation, and active material and current collector contact failure factors lead the present embodiment
  • the working discharge capacity of the acid battery drops below a certain capacity value, it is desirable or necessary to increase the battery discharge capacity or increase or prolong the battery life.
  • the positive and negative electrodes of the lead-acid battery of this example is desirable or necessary to increase the battery discharge capacity or increase or prolong the battery life.
  • the positive and negative polarity inversion and the subsequent charging or charging and discharging operations of the present embodiment are repeatedly, interspersed, and multi-stage, by suppressing, preventing, repairing, improving, eliminating or reversing lead acid.
  • the polarity inversion and the subsequent charging or charging and discharging operations of any one of the two phases described in this embodiment include the following steps: (1) the method of performing reverse charging of the lead-acid battery of the embodiment to make the lead of the embodiment
  • the polarity of the original positive electrode (tubular electrode A) of the acid battery and the original negative electrode (plate electrode B1, B2) are reversed or interchanged, that is, the polarity of the original positive electrode (tube electrode A) is reversed to negative.
  • the polarity of the original negative electrode (plate electrodes B1, B2) is reversed to positive, which is the polarity inversion of two consecutive periods in this period and the first polarity inversion in the subsequent charging or charging and discharging operations.
  • the positive electrode (plate electrode B1, B2) and the negative electrode (tube electrode A) after the first polarity inversion are subjected to constant current charging for a certain period of time (the polarity of the plate electrodes B1, B2 is positive in this process).
  • the polarity of the tube electrode A is negative, and the charging process of the positive electrode of the lead-acid battery occurs mainly on the plate electrodes B1 and B2, and the charging process of the negative electrode of the lead-acid battery mainly occurs on the tube electrode A)
  • the lead-acid battery of the embodiment is constant at a constant current.
  • Flow discharge to 0V (in this process, the main discharge occurs on the plate electrodes B1 and B2 is the discharge process of the positive electrode of the lead-acid battery, and the discharge process of the negative electrode of the lead-acid battery mainly occurs on the tube electrode A);
  • the tube electrode A and the plate electrodes B1 and B2 of the lead-acid battery of the present embodiment are again polarized by the method of reversely charging the lead-acid battery of the present embodiment.
  • Inversion that is, the plate electrodes B1 and B2 are inverted from the positive polarity to the negative polarity, and the tubular electrode A is reversed from the negative polarity to the positive polarity, which is the polarity inversion of the two consecutive periods in this period and the subsequent charge or The second polarity inversion in the charge and discharge operation, and then charging the lead acid battery of the embodiment after the second polarity inversion to 2.65V and then 2.65V with one or more currents.
  • the constant voltage is charged for 4 hours at a constant voltage, and then discharged to 1.75V at a certain current, and then charged to 2.65V with a constant current at a constant current, and then charged at a constant voltage of 2.65V, and in the last two steps.
  • the constant current, 2.65V constant voltage charging When the time is a certain value, the charging of the lead-acid battery of the embodiment is stopped, and the step (3) is completed.
  • the tube type is On the electrode A, the charging and discharging processes of the positive electrode of the lead-acid battery occur, and the charging and discharging processes of the negative electrode of the lead-acid battery occur on the plate electrodes B1 and B2. At this point, the positive and negative polarities of the first and second consecutive phases are completed. Reverse and subsequent charging or charging and discharging operations.
  • the lead-acid battery has a plurality of working systems in the whole cycle of charging and discharging, and according to the sequence of work, there are sequential, charging and discharging working systems (1): in this embodiment, the lead-acid battery is formed. After completion, the lead-acid battery of the present embodiment is discharged at a constant current of 151.7 mA to 1.75 V, that is, a discharge of 100% DOD (discharge depth), and then, the lead-acid battery of the present embodiment is charged at a constant current of 60.8 mA for 7 hours 24 .
  • cycle charge and discharge work system (2) change the 60.8 mA, 7 hour 24 minute constant current charging process in the working system (1) to 60.8 mA, 8 24 hours constant current charging, the other working system content is unchanged, so that the lead-acid battery of this embodiment repeats and cycles the charging and discharging process of the working system;
  • the constant current charging of 60.8 mA in the ring and the constant voltage charging time of 2.65 V are equal to 9 hours 24, and the contents of other working systems are unchanged.
  • Cycle charging and discharging working system (4) Change the working system (3) to first perform constant current charging of 605.5 mA, and then, after the voltage reaches 2.65 V, convert to a constant voltage charging of 2.65 V for the battery of the embodiment, and The constant current charging of 605.5 mA in each cycle and the constant voltage charging time of 2.65 V are equal to 26 min, and then the constant current discharge of 1518.8 mA is performed to 1.75 V for the lead-acid battery of the present embodiment.
  • the lead-acid battery of this embodiment is made.
  • the lead-acid battery of the present embodiment is repeatedly and cyclically subjected to the charging and discharging process of the working system;
  • the circulating charging and discharging working system (6) the constant current charging and the constant voltage charging total time in the working system (5) Changed from 26min 35min, the contents of other working systems are unchanged, so that the lead-acid battery of this embodiment is repeated and cyclically charged and discharged during the working system;
  • the cut-off voltage is changed from 1.5V to 1.0V; the contents of other working systems are unchanged, so that the lead-acid battery of this embodiment is repeated and cyclically charged and discharged during the working system;
  • the lead-acid battery of the present embodiment is repeated and circulated to perform the charging and discharging process of the working system; the circulating charging and discharging working system (9): firstly performing constant current charging of 92.4 mA to 2.65 V, and then performing 2.65 V constant Pressurization to the total accumulated charging time is 9 hours and 24 minutes, then discharge to 1.75V with a constant current of 228mA, and then repeat the charging step of the system, the contents of other working systems are unchanged, so that the lead acid of this embodiment is made. The battery is repeated, the cycle charge and discharge process of the working system.
  • the specific operation process of the method for improving or prolonging the service life of the lead-acid battery of the embodiment is as shown in FIG. 5, in the process of circulating charge and discharge of the lead-acid battery of the embodiment, timely interspersed for one period of two consecutive periods. Secondary positive and negative polarity inversion and subsequent charging or charging and discharging operations.
  • the lead-acid battery of the present embodiment is first cycled according to the cyclic charging and discharging working system (1) of the present embodiment, and after the total accumulated 195 cycles of operation, the lead-acid battery of the embodiment is further in accordance with the present invention.
  • the cyclic charging and discharging working system of the embodiment (2) performs the cyclic working until the total accumulated 199 cycles of operation, and then the lead-acid storage battery of the embodiment is cycled according to the circulating charging and discharging working system of the embodiment (3). After the total accumulated 266 cycles of operation, the lead-acid battery of the present embodiment is cycled according to the cyclic charge and discharge working system (4) of the present embodiment, and after the total accumulated 304 cycles of operation, the lead-acid battery of the embodiment is started. Performing the first and second consecutive positive and negative polarity inversions and the subsequent charge and discharge operations: first, the first time of the operation of the lead-acid battery of the present embodiment by the method of reverse polarity charging at 1518 mA.
  • the polarities of the positive and negative poles are reversed, so that the polarity of the tube electrode A of the battery of the embodiment is reversed from negative to negative, and the polarity of the plate electrodes B1 and B2 is reversed from negative to positive, and then the current is 1518 mA.
  • the battery of this embodiment after the first polarity reversal in this period was subjected to constant current charging for 1 hour and 24 minutes (in this process, the polarity of the tube electrode A was negative, and the main electrode of the tube electrode A was the lead acid battery anode.
  • the polarity of the plate electrodes B1 and B2 is positive
  • the charging process of the positive electrode of the lead-acid battery is mainly occurred on the plate electrodes B1 and B2
  • the lead acid of the present embodiment is further applied at a current of 1518 mA.
  • the battery is discharged for 7s to 0V (in this process, the polarity of the tube electrode A is negative, and the main occurrence of the tube electrode A is the discharge process of the negative electrode of the lead-acid battery, and the polarity of the plate electrodes B1 and B2 is positive.
  • the discharge process of the positive electrode of the lead-acid battery is mainly occurred on the plate electrodes B1 and B2); then the second positive and negative polarities of the lead-acid battery of this embodiment are reversed by the method of constant current and reverse polarity charging of 300 mA.
  • the polarity of the tube electrode A of the battery of the present embodiment is reversed from negative to positive
  • the polarity of the plate electrodes B1, B2 is reversed from negative to negative
  • the lead of the present embodiment is continued at a current of 300 mA.
  • Acid battery is charged to 1.75 V, then charge with a constant current of 605.5mA for 26min to 2.43V, then discharge to a constant current of 1518mA to 1.75V, repeat 605.5mA constant current charging for 26min, 1518mA discharge twice, and then, make the lead-acid battery of this embodiment re-press
  • the circulating charging and discharging working electric system (4) of the present embodiment works until the total accumulated 411 cycles of operation, and then the lead-acid storage battery of the embodiment is cycled according to the circulating charging and discharging working system (5) of the embodiment.
  • the lead acid battery of the present embodiment is cycled according to the cyclic charge and discharge working system (6) of the present embodiment, until the total accumulated 475 cycles of operation, and then the lead acid of the embodiment is further
  • the battery is circulated according to the cyclic charging and discharging working system (7) of the embodiment, and after the total accumulated 652 cycles of operation, the lead-acid battery of the embodiment is subjected to the second consecutive two positive and negative polarity reversals and Subsequent charging or charging and discharging operation: firstly, the lead-acid battery of the embodiment is subjected to constant current discharge to 0 V at a current of 1518 mA, and then the lead acid of the embodiment is charged by the method of 1518 mA and reverse polarity charging.
  • the polarity of the battery is reversed, so that the polarity of the tube electrode A of the battery of the embodiment is reversed from negative to negative, and the polarity of the plate electrodes B1 and B2 is reversed from negative to positive, which is two consecutive periods.
  • the first polarity reversal of the positive and negative polarities and the first polarity reversal of the subsequent charging or charging and discharging operations, and then the constant polarity charging of the battery after the first polarity reversal of the operation is performed at a current of 1518 mA.
  • the lead-acid battery of the present embodiment is discharged to 0 V at a current of 1518 mA (the polarity of the tube electrode A is negative in this process,
  • the main occurrence of the tube electrode A is the discharge process of the negative electrode of the lead-acid battery.
  • the polarity of the plate electrodes B1 and B2 is positive, and the discharge process of the positive electrode of the lead-acid battery mainly occurs on the plate electrodes B1 and B2. ; then 300mA, reverse polarity charging
  • the second positive and negative polarities of the lead-acid battery of this embodiment are reversed, so that the polarity of the tubular electrode A of the battery of the embodiment is reversed from negative to positive, and the polarities of the plate electrodes B1 and B2 are from It is being reversed to negative, then charged to 1.75V with a constant current of 300mA, then discharged for 5 seconds at 1518mA, then charged for 2min with a constant current of 905mA, then discharged with a constant current of 1518mA for 29 seconds, then charged with 905mA constant current for 35min.
  • the lead-acid battery is circulated according to the cyclic charging and discharging working system (7) of the present embodiment. After the total of 714 cycles of the lead-acid battery in the embodiment, the lead-acid battery of the embodiment is recirculated according to the embodiment.
  • the discharge working system (8) performs the cyclic work until the total accumulated 732 cycles of operation, and then the lead-acid storage battery of the present embodiment is cycled according to the cyclic charging and discharging working system (9) of the present embodiment until the total cumulative 751 cycles After work
  • the third phase of the positive and negative polarity reversal and the subsequent charging or charging and discharging operations are performed twice, that is, when the lead-acid battery of the embodiment is in the charging state of the 752th cycle, the charging is stopped.
  • the polarity of the lead-acid battery of the present embodiment is reversed to the current of the battery of the embodiment with a current of 456 mA, so that the polarity of the tube electrode A of the battery of the embodiment is reversed from negative to negative.
  • the polarity of the electrodes B1, B2 is reversed from negative to positive, which is the first polarity reversal of the operation of the period, and then the battery of this embodiment after the first polarity inversion of the period with a current of 456 mA
  • Constant current charging is carried out for 4 hours and 15 minutes (in this process, the polarity of the tube electrode A is negative, and the main occurrence of the tube electrode A is the charging process of the negative electrode of the lead-acid battery, and the polarity of the plate electrodes B1 and B2 is Positive, the main electrode on the plate electrodes B1 and B2 is the charging process of the positive electrode reaction of the lead-acid battery), and then the second time of the operation of the battery of this embodiment is performed by the method of reverse polarity charging with a current of 456 mA.
  • Positive and negative polarities are reversed
  • the polarity of the electrode A is reversed from negative to positive
  • the polarity of the plate electrodes B1, B2 is reversed from negative to negative, and then continues to be charged to 2.65V with a constant current of 456mA, and then discharged to 1.75V with a constant current of 228mA
  • the discharge reaction occurring on the tubular electrode A is reversed from the discharge process of the negative electrode of the lead-acid battery.
  • the electrode reaction occurring on the plate electrodes B1 and B2 is reversed from the discharge process of the positive electrode of the lead-acid battery to the charging and discharging process of the negative electrode of the lead-acid battery), and then
  • the lead-acid battery of the present embodiment is subjected to a cyclic operation in accordance with the cycle charge and discharge working system (9) of the present embodiment.
  • the polarity of the tube electrode A is always positive during the cyclic operation, and the polarity of the plate electrodes B1 and B2 is always negative, that is, the positive electrode reaction of the lead-acid battery occurs on the tube electrode A.
  • the charging and discharging process the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on the plate electrodes B1 and B2.
  • the working discharge capacity of the lead-acid battery of the present embodiment is obviously improved. Or recovery (this is due to repair, improvement, elimination or reversal of the positive active material softening or / and shedding of lead-acid batteries, electrode / sink / current collector corrosion, passivation, early capacity loss, sulfation, activity One or more of the problems of poor contact between the substance and the current collector).
  • the rated capacity under the cyclic charging and discharging working system (4) of the present embodiment is defined as 106.6 mAh, and the battery life is terminated after three consecutive times less than 80% of the rated capacity, the battery life after the 278th cycle Has been terminated, or, if the rated capacity under the cycle charging and discharging working system (7) of the present embodiment is 288.8 mAh, and the battery life is terminated after three consecutive times less than 90% of the rated capacity, then the 582th The battery life has expired after the second cycle, or if the rated capacity under the cycle charge and discharge working system (9) of this embodiment is 562.2mAh, and the battery life is terminated after three consecutive times less than 88% of the rated capacity Then, the battery life has been terminated after the 750th cycle, but as shown in FIG.
  • the positive and negative polarities of the lead-acid battery of this embodiment are reversed and thereafter.
  • the electric or charging and discharging operation, the service life of the lead-acid battery of the embodiment is obviously improved or prolonged, and it can be presumed that the utility model is used without being interfered by problems such as corrosion, deformation, battery loss, short circuit, open circuit and the like.
  • the method of the embodiment can make the service life of the lead-acid battery of the embodiment more improved or prolonged.
  • the pulse current and the pulse voltage may be used instead of the direct current and the constant voltage to perform the polarity inversion in the two consecutive polarity inversions of the present example and the subsequent charging or charging and discharging operation steps. Subsequent charging or charging and discharging steps or processes are advantageous for improving the aging and energy efficiency of the polarity reversal of the lead-acid battery of the embodiment and the subsequent charging or charging and discharging operations.
  • the lead-acid battery pack of the embodiment is a flat-plate type lead-acid battery pack, the rated voltage of the battery pack is 4V, the designed rated capacity is 2.996Ah (C 3.5 , 3.5h rate, 25° C.), and the total anode capacity is relatively Excessive in the total positive electrode capacity, the lead-acid battery pack of the present embodiment is formed by two single-cell lead-acid batteries which are identical to each other, and each single cell is composed of three negative plates and two positive plates, and each two negative plates There is a positive plate between the positive and negative plates.
  • the outer frame of the positive and negative plates has the same size, the height ⁇ width is 38mm ⁇ 68mm, and the grids of the positive and negative plates are rectangular.
  • the grid is 11mm*5mm, the thickness of the positive plate is 2.1mm, and the thickness of the negative plate is 1.3.
  • the positive paste of the positive plate is the current common commercial positive lead paste (the formula includes ball-milled lead powder, sulfuric acid, positive electrode additive, but does not include Barium sulfate) and negative electrode paste are the current common commercial negative electrode pastes (the formulation includes ball-milled lead powder, sulfuric acid, and negative electrode additives).
  • the density of the sulfuric acid solution in the lead-acid battery of this embodiment is 1.27 g/cm 3 , and is as follows.
  • the battery pack of this embodiment is cyclically operated and After the polarity inversion and the negative electrode during the charging or discharging operation of the charge remains sufficient.
  • the positive electrode plate is only used as a positive electrode
  • the negative electrode plate is only used as a negative electrode.
  • the four positive plates of the lead-acid battery group of the present embodiment are used.
  • the plates are named as electrodes A1, A2, A3, and A4, respectively.
  • the six negative plates of the lead-acid battery pack of the present embodiment are named as electrodes B1, B2, B3, B4, B5, and B6, respectively.
  • the output end of the battery pack connected to the positive electrode plate of the lead-acid battery pack of the present embodiment is named as the output end K of the battery pack
  • the output end connected to the negative electrode plate of the lead-acid battery pack of the embodiment is named as the output end L of the battery pack.
  • the method for improving or prolonging the service life of the lead-acid battery pack in the embodiment is that when the lead-acid battery pack of the embodiment is used or operated in the cyclic charge and discharge operation (for example, the cycle charge and discharge work has been completed more than once) Due to the cyclic charge and discharge, overcharge, undercharge, high active material utilization rate, grid corrosion and passivation of the lead-acid battery pack of the present embodiment, the positive active material is softened or/and detached, sulfated, One or more of the reasons of passivation, early capacity loss, corrosion, poor contact of the active material with the current collector, shrinkage of the specific surface area of the negative electrode active material, etc., such that the working discharge capacity of the lead-acid battery pack of the present embodiment is decreased, as needed ( For example, in this embodiment, when the working discharge capacity of the lead-acid battery pack decreases and is lower than a certain capacity value, it is desirable or necessary to increase the working discharge capacity of the battery pack or increase or extend the service life of the battery pack, or at
  • the positive and negative polarities of the lead-acid battery pack of this example are automatically or/and manually performed for two consecutive positive and negative polarities.
  • Turning on and after charging or charging and discharging operations improving, repairing, eliminating, reversing, suppressing, preventing softening of the positive electrode active material, shrinkage of the specific surface area of the negative electrode, corrosion, electrode passivation, early capacity loss, sulfation, active substances and sets
  • the problem of poor fluid contact, etc. enables the lead-acid battery pack of the present embodiment to recover or improve the working discharge capacity after completing the polarity reversal of two consecutive phases and the subsequent charging or charging and discharging operations.
  • the lead-acid battery pack of the embodiment is put back into the cyclic charging and discharging work for use or work until it is triggered again or another period begins.
  • the positive and negative electrodes of the lead-acid battery pack of the present embodiment are subjected to two consecutive polarity inversions and subsequent charging or charging and discharging operations.
  • the polarity inversion and the subsequent charging or charging and discharging operations of any one of the two phases described in this embodiment include the steps of: (1) stopping the operation of the lead-acid battery pack of the embodiment, and then passing the lead-acid battery of the embodiment;
  • the method of performing reverse polarity charging causes the polarity of the original positive output terminal (battery output terminal K) of the lead-acid battery pack of the embodiment to be reversed or interchanged with the original negative output terminal (battery output terminal L).
  • the polarity of the original positive output terminal (battery output terminal K) is reversed to negative
  • the polarity of the original negative output terminal (battery output terminal L) is reversed to positive by negative
  • the constant current of the battery pack of the present embodiment after the first polarity inversion is performed ( For example, 0.7C 3.5 , 1.5 C 3.5 )
  • the voltage at the output of the battery pack is 3.5V (the polarity of the output terminal L of the battery pack is positive, and the polarity of the output terminal K of the battery pack is negative.
  • the electrode B1 The main occurrence of all or some of the electrodes in B2, B3, B4, B5, and B6 is lead-acid storage.
  • all or part of the electrodes A1, A2, A3, and A4 mainly occur in the charging process of the negative electrode of the lead-acid battery) and after reaching 3.5V, the charging is continued for a certain period of time (for example) 2 hours, 5 hours, during this process, the polarity of the output terminal L of the battery pack is positive, and the polarity of the output terminal K of the battery pack is negative);
  • the lead-acid battery pack of the embodiment has a certain Current (for example, 0.7C 3.5 , 1.5C 3.5 , 0.4C 3.5 , 0.1C 3.5 ) and reverse polarity charging method, so that the original positive output terminal (battery output terminal K) of the lead-acid battery pack of the present embodiment and the original negative electrode The polarity of the output (
  • the second positive and negative polarity inversion of the operation and the subsequent charging or charging and discharging operations The electrode reaction occurring on all or a part of the electrodes A1, A2, A3, and A4 is reversed from the discharge process of the negative electrode of the lead-acid battery to the charging process of the positive electrode of the lead-acid battery, and the electrodes B1, B2, B3, The electrode reaction occurring on all or part of the electrodes of B4, B5, B6 is reversed from the discharge process of the positive electrode of the lead-acid battery to the charging process of the negative electrode of the lead-acid battery, and then one or more currents or voltages ( For example, DC, constant voltage or pulse current, pulse voltage) charges the lead-acid battery pack of this embodiment after the second polarity inversion to 5.4V, and then performs constant voltage charging with a constant voltage of 5.2V.
  • the step (2) is completed, and then the battery pack of the embodiment is put back into the cycle charging and discharging work to be used or operated.
  • the polarity inversion and subsequent charging or charging and discharging operations of the lead-acid battery pack of the present embodiment also delay or repair the corrosion of the current collectors and the confluent fluid of the electrodes A1, A2, A3, and A4 to some extent.
  • the pulse current and the pulse voltage may be used instead of the direct current and the constant voltage to perform the polarity inversion in the two consecutive polarity inversions of the present example and the subsequent charging or charging and discharging operation steps. Subsequent charging or charging and discharging, thereby improving the aging and energy efficiency of the polarity reversal of the lead-acid battery pack of the present embodiment and subsequent charging or charging and discharging operations.
  • the specific operation of the method for improving or prolonging the service life of the lead-acid battery pack of the embodiment is that after the lead-acid battery pack of the embodiment is subjected to the cyclic charge and discharge operation more than once, the cycle of the lead-acid battery pack of the embodiment is
  • the working discharge capacity of the lead-acid battery pack of the present embodiment is softened, sulphated, oxidized, passivated, early capacity loss, active substances and sets due to charging, overcharging, undercharging, high active material utilization and the like.
  • the working discharge capacity of the lead-acid battery pack of the present embodiment causes the working discharge capacity of the lead-acid battery pack of the present embodiment to decrease, and the working discharge capacity of the lead-acid battery pack of the present embodiment drops to
  • the rated capacity C 2 , C 5 or C 20 is 60%, 75%, 80%, 90% or 95%, or the lead-acid battery pack of the embodiment is charged, the rate of increase of the charging voltage is increased by 10%.
  • the lead-acid battery pack of the present embodiment is automatically and/or manually operated for one period.
  • Sub-polarity inversion and subsequent charging or charging and discharging operations that is, operation step (1): reverse-charging the lead-acid battery pack of the present embodiment with a certain current source or/and a voltage source, and charging the anode
  • the voltage at which the current is one or more of C 2 , C 5 , 0.5 C 20 , 0.3 C 2 , 3 C 2 , or 5 C 5 or the reverse polarity is 0.5 U volts, U volts, 1.5 volts, 2 volts.
  • One or more of the electrodes A1, A2, ..., An of the lead-acid battery pack of the present embodiment are reversed from the original positive polarity to the negative polarity, and the electrodes B1, B2, ..., The polarity of Bn is reversed from the original negative polarity to positive polarity (this is the first polarity reversal of this period), and then, step (2) is operated: charging and discharging of the lead-acid battery pack of this embodiment is continued.
  • the charging or discharging current is one or more of C 2 , C 5 , 0.5 C 20 , 0.3 C 2 , 3 C 2 , or 5 C 5 or the charging or discharging voltage is 0.5 UV, U volt, 1.5 U volt, One or more of 2U volts, such that the electrodes A1, A2, ..., An of the lead-acid battery of the present embodiment are subjected to a charging or/and discharging reaction process of the negative electrode of the lead-acid battery, and the electrodes B1, B2 ..., or lead-acid battery charge / discharge reaction of the positive electrode and the electrode reaction occurs on Bn, when the lead-acid battery of the present embodiment, the charging or discharging battery group reaches 4C 2, 3C 5, 0.5C 20 , 0.3C 2, 3C 2 , or 5C 5 o'clock or when the voltage reaches 0.6UV, UV, 1.2UV, 2.1UV, then operate step (3): 3C 2 , 2.5C 5 , 0.5C 20 ,
  • the discharge process of the reaction of the negative electrode and the discharge process of the positive electrode of the lead-acid battery occur on the electrodes B1, B2, ..., Bn until the polarity of the electrodes A1, A2, ... An is reversed to the positive electrode by the negative polarity
  • the polarity of the electrodes B1, B2, ..., Bn is reversed from the positive polarity to the negative polarity (this is the second polarity reversal of the current period), and then the step (4) is operated: for the present embodiment lead-acid batteries continue charging or charging and discharging, charging or discharging current of C 2, 2C 5, 0.5C 20 , 0.1C 2, 3C 2, or one or more of 0.05C 5
  • the charging voltage is one or more of 0.7UV, 0.9UV, 1.1UV, and 1.7UV
  • the charging and discharging is DC or pulse charging and discharging, so that the electrodes A1 and A2 of the lead-acid battery of the embodiment are provided.
  • a certain value for example, 6C 2 , 3C 5 , 2C 20 , 8C 2 , 3C 2 , 0.5C 2 , or 2C 5 , or the battery voltage reaches a certain value.
  • the working discharge capacity or working capacity of the lead-acid battery pack of the present embodiment is restored or improved, and the positive and negative polarities of the current two consecutive times are ended.
  • the lead-acid battery pack of this embodiment is put into the circulating work to work or use.
  • the lead-acid battery of the embodiment is timely, periodically or irregularly (for example, in a manner of specifying the number of cycles) according to needs or settings.
  • the group performs one or more consecutive polarity inversions and subsequent charging or charging and discharging operations, so that the lead-acid battery pack of the present embodiment does not have a battery loss or short circuit.
  • the problem of poor contact with the current collector and shrinkage of the specific surface area of the negative electrode thereby repeatedly, repeatedly, repairing, restoring or improving the working discharge capacity or working capacity of the lead-acid battery pack of the present embodiment, thereby improving or prolonging the lead acid of the embodiment.
  • the embodiment relates to a method for improving or prolonging the service life of a lead-acid battery, a battery charge and discharge device, a lead-acid battery electrode current collector, a lead paste, a lead-acid battery electrode, and a lead-acid battery, wherein the charge and discharge device of the embodiment has lead
  • the positive and negative electrodes of the acid battery perform the functions of polarity reversal and subsequent charging or charging and discharging operations and the programmable execution function.
  • the battery charge and discharge device is switched on and off by the contact circuit of the relay circuit included therein.
  • the polarity reversal of the positive and negative poles of the output terminal is realized, so that when the output end of the battery charge and discharge device of the embodiment is connected to the lead acid battery electrode of the embodiment, the battery charge and discharge device of the embodiment can pass the polarity of the output end thereof.
  • the charging, charging or charging/discharging operation after the inversion and polarity inversion is performed on the lead-acid battery of the present embodiment, and the charging or charging/discharging operation is performed after the polarity is reversed and the polarity is reversed, and all of the following embodiments are used.
  • the operation of the battery is realized by the function and operation of the battery charger and discharger of this embodiment unless otherwise specified.
  • the lead-acid battery of the present embodiment has a rated voltage of 2V and a designed rated capacity of 745mAh (2h rate, 25°C).
  • the lead-acid battery of the embodiment includes two planar grid electrodes, and the two electrodes are positive and negative common electrodes. (ie, the electrode common to the positive electrode and the negative electrode), and the two electrodes are the same positive electrode and the negative electrode, that is, the manufacturing error caused when the electrode is manufactured is not considered, and the two lead-acid battery electrodes of this embodiment are formed before being formed.
  • the two electrodes are respectively formed into a positive electrode and The negative electrode, the two electrodes are named as electrode A and electrode B, respectively, and the average mass of the active material on each electrode is 12.17 g.
  • the two electrodes are separated by an AGM separator, and the two electrodes are lead acid in this embodiment.
  • the battery it is not always fixed as the positive electrode or the negative electrode.
  • the electrode A is used as the positive electrode and the electrode B is used as the negative electrode (denoted as A+/B-.
  • the electrode current collector of the lead-acid battery is made of pure lead (the lead content is 99.994%, the same below), as shown in Fig. 7, which is a planar grid type set.
  • the width of the current collector is 40 mm ⁇ 70 mm
  • the thickness of the frame 2 is 1.2 mm ⁇ 1.5 mm
  • the thickness of the grid sheet 3 in the current collector frame is 0.1 mm.
  • the grid sheet is evenly distributed.
  • the lead paste formulation of this embodiment includes lead oxide powder (100% oxidation degree) and BaSO 4 (0.8%, The mass percentage, relative to the lead oxide powder, the sulfuric acid, the water, the short fiber, the lead acid battery electrode of the embodiment, including the current collector of the embodiment and the lead paste of the embodiment, uniformly apply the lead paste of the embodiment to the present embodiment.
  • the lead liquid on the surface of the electrode plate is parallel to the surface of the frame of the current collector, and is placed in the air at room temperature (about 15 ° C) to dry slightly to obtain the electrode of the lead-acid battery of the embodiment, and the outer shape thereof is wide ⁇
  • the height x thickness is 40 mm x 70 mm x 1.2 mm.
  • the density of the sulfuric acid solution in the lead-acid battery of the present embodiment is 1.27 g/cm 3 .
  • the method for improving or prolonging the service life of the lead-acid battery in the embodiment is as follows: Firstly, the battery of the embodiment is subjected to cyclic charging and discharging work, and the working system is: when the battery is in the state of charging, the battery of the embodiment is performed with a constant current of 337 mA. Discharge, when the battery voltage ⁇ 1.75V, stop discharging, then charge the battery with a constant current of 201mA, and after measuring the battery voltage reaches 2.65V, convert to continue charging the battery at a constant voltage of 2.65V, twice ( Constant current, constant voltage) The total charging time is 7 hours and 24 minutes (except for special instructions).
  • the above discharge process is repeated with a constant current of 337 mA, so that the battery is cycled and discharged, and the battery working environment is repeated.
  • the temperature is 25 ⁇ 1 °C.
  • the battery is operated under the original working system, and the positive electrode of the battery before the polarity reversal is operated as a negative electrode after the polarity is reversed, and the battery negative electrode before the polarity is reversed.
  • the lead-acid battery of the embodiment is subjected to a single positive and negative polarity reversal and subsequent charging or charging and discharging operations, so that the electrode of the lead-acid battery of the embodiment is provided.
  • A sometimes works as a positive electrode and sometimes as a negative electrode
  • the corresponding electrode B sometimes operates as a negative electrode and sometimes as a positive electrode to improve, repair, eliminate, reverse, suppress or prevent softening or/and shedding of the positive active material of the battery of the present embodiment.
  • the cycle operation process of the battery of this embodiment is also implemented by the charging and discharging functions of the battery charger and discharger of the present embodiment (hereinafter all the operations and measurements of the battery are charged and discharged by the battery of the embodiment except that the manual operation is specifically described.
  • the appliance is programmed and implemented.
  • the battery charger and discharger of the embodiment automatically stops the operation of the battery, and prepares and officially performs the first single positive and negative polarity reversal and subsequent charging or charging and discharging operations.
  • the battery operation is stopped, and then the battery continues to discharge at a constant current of 337 mA for 1 hour, which causes the battery voltage to drop to 0.04 V, and then stops discharging.
  • the polarity of the positive and negative poles of the battery is reversed, that is, the polarity of the output end of the battery charger is reversed by the polarity of the battery (the polarity reversal at the output of the charger is touched by a relay circuit in the charger/discharger).
  • connection state between the charge and discharge device and the lead-acid battery of the embodiment is connected from the positive electrode output end of the charge and discharge device to the lead-acid battery electrode A, the negative electrode output end of the charge and discharge device and the lead-acid battery electrode.
  • B connection, change to, the negative output terminal of the charge and discharge device is connected with the lead acid battery electrode A, and the positive output end of the charge and discharge device is connected with the lead acid battery electrode B.
  • the connection state is changed, the measured The cell voltage is negative, and then the battery of this embodiment is charged with a constant current of 169 mA, so that the battery voltage rises from a negative value to 0 V and then rises to 1.75 V (the first polarity of the battery of this embodiment occurs in this process).
  • the discharge process of the lead-acid battery positive electrode reaction occurs on the electrode A, and the discharge process of the lead-acid battery negative electrode reaction occurs on the electrode B, and the battery voltage rises from 0V to 1.75V.
  • the charging process of the negative electrode of the lead-acid battery occurs on the electrode A, and the charging process of the positive electrode of the lead-acid battery occurs on the electrode B.
  • the electrode A is operated as a negative electrode
  • the electrode B is operated as a positive electrode
  • the battery is re-entered into the same discharge-charge cycle operation system to perform the 16th operation discharge and the subsequent number of cycles.
  • the results show that after the first single positive and negative polarity reversal and subsequent charging or charging and discharging operations, the battery has a discharge capacity of 938.2 mAh in the 16th cycle, which is significantly larger than the 15th time. of. During this polarity reversal and before the battery resumes operation, the charging capacity of the battery is 4477 mAh.
  • the battery of the embodiment is continuously operated under the working system, and after the 16th cycle operation, the trigger condition of the charging and charging/discharging operation of the battery positive and negative polarity reverse and the subsequent charging is resumed by programming.
  • the setting is: when the working discharge of the lead-acid battery of the embodiment reaches 12 consecutive times, the battery operation is stopped and the second single positive and negative polarity inversion and the subsequent charging or charging and discharging operations are started on the battery.
  • the electrode state of the battery of this embodiment is A-/B+, and at this time, the negative electrode reaction occurs on the electrode A, and the electrode B occurs.
  • the positive electrode reaction the discharge capacity gradually decreased from 938.2 mAh to 849 mAh during the 16-27th cycle.
  • the positive and negative electrodes of the battery were triggered.
  • Preparation and formal operation of the discharge operation that is, after the end of the 27th working discharge (the battery voltage is 1.75V), the battery operation is stopped, and the battery is continuously discharged at a constant current of 337 mA for 1 hour, which causes the battery voltage to drop.
  • connection state of the charge and discharge device and the lead-acid battery of the present embodiment is connected from the positive electrode output end of the charge and discharge device to the lead acid battery electrode B, the negative electrode output end of the charge and discharge device and the lead acid battery electrode. A connection is changed, the positive output end of the charge and discharge device is connected with the lead acid battery electrode A, and the negative output end of the charge and discharge device is connected with the lead acid battery electrode B.
  • the measured battery voltage is a negative value.
  • the battery of this embodiment is charged at a constant current of 269 mA, so that the battery voltage rises from a negative value to 0 V and then rises to 2.65 V (the second polarity reversal of the battery of this embodiment occurs in this process, wherein the battery voltage is from During the negative value rise to 0V, the discharge process of the lead-acid battery negative electrode reaction occurs on the electrode A, and the discharge process of the lead-acid battery positive electrode reaction occurs on the electrode B. The battery voltage rises from 0V to 2.65V during the process of the electrode A.
  • the charging process of the positive electrode reaction of the lead-acid battery occurs, and the charging process of the negative electrode reaction of the lead-acid battery occurs on the electrode B), and thus, the battery of the embodiment is completed.
  • the second single positive charge, and subsequent negative polarity or charge and discharge operation at this time the state of the battery electrodes from A- / B + is inverted to A + / B-.
  • the electrode A is operated as a positive electrode
  • the electrode B is operated as a negative electrode
  • the battery is re-entered into the same discharge-charge cycle operation system to perform the 28th operation discharge and the subsequent number of cycles.
  • the battery has a discharge capacity of 680 mAh in the 28th cycle operation state, even the 30th cycle operation.
  • the discharge capacity of 796mAh (this polarity reversal and the maximum discharge capacity after charging or charging and discharging operations) are lower than the 27th working discharge capacity, which should be insufficiently charged after the polarity is reversed.
  • the total charging capacity of the battery during this polarity reversal and before the battery is restored is 724mAh.
  • the battery of the embodiment is continuously operated under the working system, and after the 29th cycle operation, the trigger condition of the battery charging and charging and discharging operations of the battery positive and negative polarity inversion and the subsequent charging is changed by programming. It is set to: when the working discharge of the lead-acid battery of the embodiment reaches 13 consecutive times, the battery operation is stopped and the third single positive and negative polarity inversion and the subsequent charging or charging and discharging operations are started on the battery. .
  • the electrode state of the battery of the embodiment is A+/B-, at which time the positive electrode reaction occurs on the electrode A, the negative electrode reaction occurs on the electrode B, and the battery discharges during operation.
  • the discharge capacity is reduced to 611 mAh.
  • the start condition of the positive and negative polarity reversal of the battery and the subsequent charging or charging/discharging operation is triggered, and the battery is stopped.
  • the charge and discharge device starts to prepare and officially perform the third single positive and negative polarity inversion and subsequent charging or charging and discharging operations on the battery, that is, after the 40th working discharge is finished. (At this time, the battery voltage is 1.75V), the battery operation is stopped, and the battery continues to discharge at a constant current of 337 mA for 1 hour.
  • This process causes the battery voltage to drop to -0.05 V, and then stops discharging, and the battery is subjected to the first embodiment as in this embodiment.
  • the battery was subjected to the same operation of single positive and negative polarity inversion, and then the battery of the present embodiment in which the electrode connection state was changed was charged for 45 minutes with a constant current of 200 mA, and then continued with a constant current of 269 mA.
  • Charge the battery to 2.65V then discharge the battery to a constant current of 337mA to 1.75V, and then charge the battery with a constant current of 201mA until the battery voltage reaches 2.65V and the battery is constant at 2.65V.
  • Pressure charging the total time of the last two charges (constant current, constant voltage) is 7 hours and 24 minutes.
  • the third single positive and negative polarity inversion of the battery of the embodiment and the subsequent charging or Charge and discharge operation at this time the electrode state of the battery has been reversed from A+/B- to A-/B+. Then, the electrode A is operated as a negative electrode, and the electrode B is operated as a positive electrode, and the battery is re-entered into the same discharge-charge cycle operation system to perform the 41st operation discharge and the subsequent number of cycles.
  • the results show that after the third single positive and negative polarity reversal and subsequent charging or charging and discharging operations, the discharge capacity of the battery during the 41st cycle is 533 mAh, which is lower than the 40th cycle.
  • the discharge capacity is 611mAh, which is also related to the insufficient charge after the polarity reversal.
  • the total charge capacity of the battery during the period after the polarity reversal and the battery recovery work is 925mAh, especially the polarity reversal.
  • the first total charge after the turn is only 412mAh.
  • the battery of the embodiment is continuously operated under the working system, and after the 41st cycle operation, the trigger conditions of the charging and charging/discharging operations of the positive and negative polarity inversion and the subsequent charging or charging and discharging operations are changed by programming. Therefore, when the working discharge capacity of the lead-acid battery of the embodiment is lower than 360 mAh, the battery operation is stopped and the fourth single positive and negative polarity inversion and subsequent charging or charging and discharging operations are started.
  • the electrode state of the battery of this embodiment is A-/B+, at which time a negative electrode reaction occurs on the electrode A, and a positive electrode occurs on the electrode B.
  • the charger and discharger of the embodiment automatically stops the operation of the battery, and starts preparation and formal operation of the fourth single positive and negative polarity reversal and subsequent charging or charging and discharging operations of the battery, that is, After the end of the 51st working discharge (the battery voltage is 1.75V), the battery operation is stopped, and then the battery continues to discharge at a constant current of 337 mA for 1 hour. This process causes the battery voltage to drop to 0.03 V, and then stops discharging.
  • the operation method and the process are the same as the second single positive and negative polarity inversion of the battery in this embodiment, and the constant current of 169 mA after the electrode connection state is changed.
  • the battery is charged to 1.75V, and then the battery is continuously charged with a constant current of 269 mA for 4 minutes, and then the battery is charged to 2.65 V with a constant current of 337 mA, and then the battery is charged at a constant voltage of 2.65 V.
  • the electrode A is operated as a positive electrode
  • the electrode B is operated as a negative electrode
  • the battery is re-entered into the same discharge-charge cycle operation system to perform the 52nd working discharge and the subsequent number of cycles.
  • the results show that after the fourth single positive and negative polarity reversal and subsequent charging or charging and discharging operations, the discharge capacity of the battery in the 52nd cycle is raised to 920mAh, which should be opposite to the polarity. The charge after the turn is relatively sufficient.
  • the total charge capacity of the battery during the period after the polarity reversal and the battery recovery work is 5164 mAh, especially the first total charge after the polarity reversal reaches 3901 mAh.
  • the battery is continuously operated under the working system.
  • the electrode state of the battery in the 53th to 63rd charge and discharge cycles of the present embodiment is A+/B-, and the discharge capacity is reduced from 1071 mAh to 860 mAh.
  • the lead-acid battery of the embodiment When the lead-acid battery of the embodiment is in the 63rd working charge and discharge cycle, at this time, the polarity of the electrode A is positive, and the polarity of the electrode B is negative, and the cycle operation of the lead-acid battery of the embodiment is stopped, and then The current of 337 mA is discharged to the lead-acid battery of the embodiment for 1 hour, so that the voltage thereof is reduced from 1.75 V to 0.05 V, and then the positive output end of the charge and discharge device is automatically connected to the lead acid battery electrode B of the embodiment, and is charged and discharged. The negative output end of the electric appliance is connected with the lead acid battery electrode A of the embodiment.
  • the charge and discharge device measures the voltage of the lead-acid battery of the embodiment to -1.87 V, and then, for the lead-acid battery of the embodiment, the current is 337 mA.
  • the charging was performed for 14 hours and 42 minutes in the state of the connection, so that the voltages of the positive and negative electrodes of the lead-acid battery of the present embodiment (the measured values of the charging and discharging device, the same in the present embodiment) were raised from -1.87 V to 0 V and then increased.
  • the lead-acid battery of this embodiment has undergone the fifth single polarity reversal, that is, during the process from -1.87V to 0V, the main electrode of the lead-acid battery is the electrode A.
  • the main process of the lead and electrode B is the discharge process of the negative electrode of the lead-acid battery.
  • the main charging process on the electrode A is the charging process of the negative electrode of the lead-acid battery, on the electrode B.
  • the main occurrence is the charging process of the positive electrode reaction of the lead-acid battery.
  • the constant voltage is charged at 2.65 V for 5 hours, and then Then discharge at a constant current of 337 mA for 21 minutes to 1.75 V, and then charge the battery with a constant current of 201 mA until the battery voltage reaches 2.65 V, and the battery is subjected to constant voltage charging at 2.65 V, and the last two charges ( The total time of the constant current and the constant voltage is 9 hours and 24 minutes.
  • the electrode state has been inverted from A+/B- to A-/B+.
  • the electrode A is operated as a negative electrode
  • the electrode B is operated as a positive electrode
  • the battery is re-entered into the same discharge-charge cycle operation system to perform the 64th operation discharge and the subsequent number of cycles.
  • the results show that after the fifth single positive and negative polarity inversion and subsequent charging or charging and discharging operations, the discharge capacity of the battery of this embodiment at the 64th cycle is 914 mAh, and the 65th to 75th cycles
  • the discharge capacity of the work is higher than 1000mAh, which should be related to the relatively sufficient charge after the polarity is reversed. After the polarity is reversed and the battery is restored, the total charge capacity of the battery is 8159mAh.
  • the first total charge amount after polarity inversion is 6394 mAh
  • the total time of constant charge and constant voltage charge in the 65-75 cycle operation of the battery of this embodiment is changed to 9 hours and 24 minutes.
  • the charging and discharging process of the lead-acid battery negative electrode reaction occurs on the electrode A
  • the charging and discharging process of the lead-acid battery positive electrode reaction occurs on the electrode B, as shown in the figure. 8 is shown.
  • the lead-acid battery of the present embodiment can work after the single polarity reversal and after the charging or charging and discharging operation of the present embodiment.
  • the degree of recovery of the discharge capacity and the number of times the charge and discharge cycle of the lead-acid battery can continuously maintain the normal or higher discharge capacity after each working discharge capacity recovery (ie, after each single polarity inversion and thereafter)
  • the charging or charging and discharging operation between the normal operation of the lead-acid battery of the embodiment or the charging and discharging cycle of the higher discharge capacity) and the corresponding single polarity inversion and subsequent charging or charging and discharging operations The current, voltage, time, charge and discharge capacity, pulse or direct current, internal resistance of the battery, electrolyte density, degree of saturation of the electrolyte, and the manner of the method vary.
  • the first, fourth, and fifth single positive and negative polarity inversions of the present embodiment and subsequent charge, discharge, or charge and discharge operations of the present embodiment enable the positive active material of the lead-acid battery of the present embodiment.
  • Softening and shedding are improved, repaired, reversed, eliminated, suppressed, and prevented, so that the working discharge capacity in the cycle operation of the lead-acid battery of the present embodiment is improved or restored after the operation (discharge capacity of the 29th to 51st cycles) Low is caused by insufficient charging of the battery after the second and third polarity inversions.
  • the fourth and fifth single positive and negative polarity inversions and the subsequent charging of the fourth and fifth times in this embodiment Or the charge-discharge operation also restores the working discharge capacity of the battery of the embodiment from the 29th to 51st cycles, and the working discharge capacity due to insufficient charging is restored, which indicates that the present embodiment is suitable for a single time.
  • the polarity reversal of the positive and negative polarities and subsequent charging or charging and discharging operations have the effect of improving, repairing, reversing, restoring or preventing the problem of battery sulfation caused by insufficient continuous charging.
  • the polarity inversion of the positive and negative poles of the present embodiment and the subsequent charge and discharge or charge and discharge operations are also inevitable for the electrode passivation, early capacity loss, slight or occurring, which occurs during the cycle operation of the battery of the present embodiment.
  • Corrosion, poor contact between the active material and the current collector, and shrinkage of the specific surface area of the negative electrode have the effects of improving, repairing, reversing, suppressing, eliminating, and preventing.
  • the positive and negative polarity inversion of the present embodiment is performed on the lead-acid battery of the embodiment periodically or irregularly (for example, in a manner of a predetermined number of cycles).
  • the capacity is 745 mAh (according to the mass of the active material on the single electrode of the lead-acid battery of the foregoing embodiment), if the discharge capacity is determined to be less than 745 mAh for 3 consecutive times when the discharge depth is 100%, the battery life is terminated, according to the work in FIG.
  • the cumulative number of discharges of the lead-acid battery of the present embodiment before the first single positive and negative polarity reversal operation is 11 times, that is, at the end of the 14th working discharge.
  • the service life has been terminated.
  • the positive and negative polarity inversion of the present embodiment and the subsequent charging or charging and discharging operation method, the battery charge and discharge device, the lead-acid battery electrode current collector, and the lead-acid battery electrode, the working discharge capacity of the battery in this embodiment is ⁇ 745mAh.
  • the cumulative number of discharges is increased to 52 times, that is, the cycle life is increased by nearly 4 times, and it is believed that the positive and negative polarity of the lead-acid battery of this embodiment is reversed by using a suitable charging and discharging system or manner.
  • the subsequent charge or charge and discharge operation will cause the lead-acid battery of the present embodiment to soften due to active substances, shrinkage of the specific surface area of the electrode, corrosion, electrode passivation, early capacity loss, sulfation, poor contact of the active material and the current collector.
  • the lead-acid battery working capacity or the working discharge capacity decreased by one or more of the problems is improved, repaired, reversed, and prevented, so that the service life of the lead-acid battery of the embodiment is further and significantly improved. Or extended.
  • the active material utilization rate of the lead-acid battery electrode as the positive electrode in the present embodiment is significantly higher than that of the active electrode of the current commercial power electric lead-acid battery, mainly related to the thickness of the electrode of the embodiment and the lead oxide powder material used. Related to the current collector structure.
  • the two electrodes of the lead-acid storage in this embodiment are also positive and negative common electrodes which are equivalent to each other, because after the electrodes are formed, the two have the same function and performance, but in actual use, the polarity reversal and Changes and differences in factors such as post-charge or charge-discharge operating systems and cyclical work systems can lead to differences in performance and performance.
  • reducing the percentage of barium sulfate in the lead paste increasing the mechanical force of the lead paste on the fixed electrode, adding an additive to the lead paste to slow the softening and falling off of the active material, and other implementation methods or processes The same is true, so that after each single polarity inversion and subsequent charging or charging and discharging operations, the operating discharge capacity decay rate of the battery becomes slow.
  • the electrode current collector is also a square hole planar grid current collector, a wound grid current collector, a planar solid plate current collector, a core column current collector, and a foam grid assembly.
  • the fluid and the lead-type current collector are correspondingly prepared as a square-hole grid plate electrode, a wound electrode, a plate electrode or a bipolar battery electrode, a tubular or column electrode, a foam electrode, and a lead cloth electrode.
  • the current collector is a composite material current collector, the core material of the composite material current collector is copper, and the surface layer material has a pure lead thickness of 50 um; another composite in this embodiment
  • the core material of the type material current collector is aluminum, the transition layer material is Sn, and the surface layer material is 100 um thick lead alloy.
  • the polarity inversion operation of the output end of the battery charger and discharger of the embodiment is further controlled by the control circuit of the battery charger and discharge circuit of the embodiment to control the thyristor in the polarity inversion execution circuit. Turning on or off state to realize, or by managing, changing the operating state of the polarity inversion circuit composed of a transistor, an inductor, and a capacitor in the control execution circuit, or by controlling the forced discharge of the constant current source or the constant voltage source, Forced charging action transformation is implemented.
  • all or a portion of the charger and discharger circuit of the present embodiment is integrated with the battery as a product as a whole.
  • the method for improving or prolonging the service life of the lead-acid battery of the present embodiment is applied to the lead-acid battery pack of the embodiment.
  • the rated voltage of the lead-acid battery pack of the embodiment is 12V, and the rated capacity is 20Ah, in the method implementation operation, the change and the execution of the values of voltage, current, capacity, etc. in operation are mainly changed, for example, the lead-acid battery pack is reversely charged and causes polarity reversal.
  • the battery pack is charged to increase the battery pack voltage to 8V, 10.8V, 13.3V, and 15.5V, and the charging is stopped.
  • the charging current is 0.3 times, 0.5 times, 1 time, and 2 times.
  • the battery charge and discharge device of this embodiment is the same as that of the embodiment 11 of the present invention.
  • the lead-acid battery of the embodiment has a rated voltage of 2V and a designed rated capacity of 821mAh (2h rate, 25°C).
  • the lead-acid battery of the embodiment includes two planar grid electrodes, and the two electrodes are positive and negative common electrodes. (ie, the electrode common to the positive electrode and the negative electrode) is also the same common electrode for the positive and negative electrodes, that is, regardless of the manufacturing error caused when the electrode is fabricated, the two lead-acid battery electrodes of the present embodiment are all before each other before being formed.
  • the electrode composition and manufacturing aspects (such as electrode structure, shape, current collector, lead paste formulation and lead paste quality, manufacturing process, etc.) are exactly the same.
  • the two electrodes are respectively formed into a positive electrode and a negative electrode.
  • the two electrodes are defined as electrode A and electrode B, respectively.
  • the electrode A is used as the positive electrode and the electrode B is used as the negative electrode for the formation and operation of the battery.
  • the two electrodes are separated by an AGM separator, and the two of the embodiments are embodiment of the electrode current collector sheet of the present invention is the same as in Example 11, lead paste formulations include ball lead powder, BaSO 4 (0.8%, by mass percentage, with respect to the ball mill lead powder), sulfuric acid, water, short fibers
  • lead paste formulations include ball lead powder, BaSO 4 (0.8%, by mass percentage, with respect to the ball mill lead powder), sulfuric acid, water, short fibers
  • the average mass of the active material on each electrode sheet 13.41 g, a sulfuric acid solution of the present embodiment density lead-acid battery of Example 1.27g / cm 3, the present embodiment eliminates or prevents fluid loss, open circuit, short circuit, mechanical damage, test failure The factors that interfere with the implementation process and implementation results of this embodiment.
  • the method for improving or prolonging the service life of the lead-acid battery in the embodiment is as follows: Firstly, the battery of the embodiment is subjected to cyclic charging and discharging work, and the working system is: when the battery is in the state of charging, the battery is discharged with a constant current of 371 mA.
  • the discharge is stopped, then it is charged with a constant current of 222mA, and when the measured battery voltage reaches 2.65V, it is converted to continue charging the battery with a constant voltage of 2.65V, twice (constant current) , constant voltage)
  • the total charging time is 7 hours and 24 minutes (except for special instructions), and then repeat the above discharge process with a constant current of 371 mA, so that the battery is cycled and discharged, and the battery operating environment temperature is 25 ⁇ 1 ° C.
  • the number of working cycles of the lead-acid battery of the embodiment reaches a certain set value in the above cyclic operation (for example, the 15th, 31st, ..., respectively, set in the embodiment), the battery is stopped.
  • the work begins with a single positive and negative polarity reversal of the battery and subsequent charging or charging and discharging operations. After the operation is completed, the battery is operated under the original working system and the polarity is reversed. The positive electrode of the battery operates as a negative electrode after the polarity is reversed, and the negative electrode of the battery before the polarity reversal operates as a positive electrode after the polarity is reversed until the next positive or negative polarity reversal of the next positive or negative polarity is started. Subsequent charging or charging and discharging operation, in the cycle operation of the lead-acid battery of the embodiment, the single-time positive and negative polarity reversal and the subsequent charging or charging are performed on the lead-acid battery of the embodiment.
  • the electrode A of the lead-acid battery of the present embodiment sometimes operates as a positive electrode and sometimes as a negative electrode, and the corresponding electrode B sometimes operates as a negative electrode and sometimes as a positive electrode to improve and repair.
  • One or more of the problem of poor contact causes the working discharge charging capability of the battery of the embodiment to be improved, restored, improved or maintained after each operation, thereby achieving an increase or extension of the service life of the lead-acid battery of the embodiment.
  • the cycle operation process of the battery of the embodiment is also implemented by the charging and discharging functions of the battery charger and discharger of the embodiment (hereinafter all the operations and measurements of the battery are charged and discharged by the battery of the embodiment except that the manual is specifically described.
  • the appliance is programmed and implemented.
  • the electrode state of the battery of this embodiment is A+/B-, at which time the positive electrode reaction occurs on the electrode A, and the negative electrode reaction occurs on the electrode B, at the first During the -15 cycles, the discharge capacity of the battery of this example tends to decrease. After inspection, this is mainly caused by the softening and shedding of the positive active material (with high content of BaSO 4 and high active material utilization in the lead paste).
  • the battery charger and discharger of the embodiment automatically stops the operation of the battery, and prepares and officially performs the first single positive and negative polarity reversal and subsequent charging or charging and discharging operations on the battery. That is, after the end of the 15th working discharge (the battery voltage is 1.75V), the battery operation is stopped, and the battery continues to discharge at a constant current of 371 mA for 1 hour. This process reduces the battery voltage to 0.04 V, and then stops discharging.
  • the battery performs polarity reversal of its positive and negative poles, that is, the polarity of the output end of the charge and discharge device is reversed by the present embodiment (the polarity reversal at the output end of the charge and discharge device is through the contact of the relay circuit in the charger/discharger,
  • the state of connection between the charge and discharge device and the lead-acid battery is connected from the positive output end of the charge and discharge device to the lead-acid battery electrode A, and the negative output end of the charge and discharge device is connected to the lead-acid battery electrode B, and is changed into
  • the negative output end of the charge and discharge device is connected to the lead acid battery electrode A, and the positive and negative output end of the charge and discharge device is connected with the lead acid battery electrode B.
  • the battery of this embodiment after the connection state conversion is charged with a constant current of 186 mA, so that the battery voltage rises from a negative value to 0 V and then rises to 1.75 V (the first polarity reversal of the battery of this embodiment occurs in this process).
  • the discharge process of the lead-acid battery positive electrode reaction occurs on the electrode A
  • the discharge process of the lead-acid battery negative electrode reaction occurs on the electrode B
  • the battery voltage rises from 0V to 1.75V the battery voltage rises from 0V to 1.75V.
  • the charging process of the negative electrode reaction of the lead-acid battery on the electrode A and the charging process of the positive electrode reaction of the lead-acid battery on the electrode B occur.
  • the battery voltage reaches 1.75V
  • the battery is continuously charged to 2.65 with a constant current of 222 mA. V, then charge the battery for 4 hours and 16 minutes with a constant voltage of 2.65V, then discharge the battery to a constant current of 371mA to 1.75V, and then charge the battery with a constant current of 222mA until the battery voltage reaches 2.65V was changed to charge the battery at 2.65V for 5 hours.
  • the first single positive and negative polarity of the battery of this embodiment is completed.
  • the discharge capacity of the battery of this embodiment in the 16th cycle operation state is 888.3 mAh after the first single positive and negative polarity inversion and subsequent charging or charging and discharging operations.
  • the charging capacity of the battery during this polarity reversal and before the battery recovery cycle is 7031 mAh.
  • the battery of the embodiment is continuously operated under the working system.
  • the electrode state of the battery of the embodiment is A-/B+, and the electrode is A negative electrode reaction occurs on A, and a positive electrode reaction occurs on electrode B.
  • the discharge capacity is changed from 888.3 mAh to 905 mAh, wherein the discharge capacity is increased to the 27th duty cycle. 987.6mAh is because the battery was overcharged by manual intervention before the discharge (that is, the constant voltage charging time of 2.65V is 10 hours longer than the normal working system), and the working system of other cycles is unchanged.
  • the charge and discharge device of this embodiment The preparation and official operation of the second single positive and negative polarity inversion and subsequent charging or charging and discharging operations of the battery are automatically started, that is, after the end of the 31st working discharge (the battery voltage is 1.75V), the charger and discharger of this embodiment stops the battery operation, and continues to discharge the battery at a constant current of 371 mA for 1 hour. This process causes the battery voltage to drop to 0.02V, then stops discharging, and the polarity of the positive and negative electrodes is performed on the battery.
  • the polarity reversal at the output end of the charger and the discharger is realized by the opening and closing state of the relay circuit contacts in the charger/discharger
  • the connection state of the electric appliance and the lead-acid battery is connected from the positive output end of the charge and discharge device to the lead acid battery electrode B, and the negative output end of the charge and discharge device is connected with the lead acid battery electrode A, and is changed into a positive output terminal of the charge and discharge device.
  • the lead-acid battery electrode A is connected, and the negative electrode output end of the charge and discharge device is connected to the lead-acid battery electrode B.
  • the measured battery voltage is a negative value
  • the connected state is converted by the constant current of 186 mA.
  • the battery of the embodiment is charged for 15 minutes, and then the battery is charged at a constant current of 371 mA, so that the battery voltage rises from a negative value to 0 V and then rises to 2.65 V (the second polarity inversion of the battery of this embodiment occurs in this process,
  • the process in which the battery voltage rises from a negative value to 0V the discharge process of the lead-acid battery negative electrode reaction occurs on the electrode A, the discharge process of the lead-acid battery positive electrode reaction occurs on the electrode B, and the battery voltage rises from 0V to 2.65V.
  • the battery is discharged to 1.75V, and then the battery is charged with a constant current of 222mA for 7 hours and 25 minutes, and then the battery is charged with a constant voltage of 2.65V for 7 hours. 25 points, at this point, the second single positive and negative polarity inversion of the battery of the embodiment and the subsequent charging or charging and discharging operations are completed.
  • the electrode state of the battery has been changed from A-/B+ to A+. /B-.
  • the electrode A is operated as a positive electrode
  • the electrode B is operated as a negative electrode
  • the battery is re-entered into the same discharge-charge cycle operation system to perform the 32nd operation discharge and the subsequent number of cycles.
  • the results show that after the second single positive and negative polarity inversion and subsequent charging or charging and discharging operations, the battery has a discharge capacity of 1189 mAh in the 32nd cycle operation state, which should be opposite to the polarity. After the turn, the battery is fully charged.
  • the total charge capacity of the battery between the polarity reversal and the battery recovery cycle is 6659 mAh.
  • the battery is continuously operated under the working system. As shown in FIG.
  • the electrode state of the battery of this embodiment is A+/B-, and at this time, the positive electrode is generated on the electrode A.
  • the negative electrode reaction occurred on the electrode B.
  • the discharge capacity of the battery in the 32-45 cycle of the present example was reduced from 1189 mAh to 787 mAh.
  • the present embodiment is repeated, repeated, and interspersed, for example, the single positive and negative polarity reversal similar to the first or second time described above.
  • the charging or charging and discharging operation that is, between the 45th, 46th, 55th, 56th, 64th, and 65th times of the working cycle of the lead-acid battery of the embodiment in the cycle work process thereof , between the 73rd, 74th, the 82nd, the 83rd, the 94th, the 95th, the 104th, the 105th, or the third, fourth, bib .
  • FIG. 9 is a diagram showing the electrode of the lead-acid battery of the present embodiment during the cycle charging and discharging operation before or after the single positive and negative polarity inversion and the subsequent charging or charging and discharging operations of the present embodiment.
  • the charging method is changed to, after the end of the working discharge, the battery is charged with a constant current of 222 mA, and when the measured battery voltage reaches 2.65 V, , converted to a constant voltage of 2.65V to continue charging the battery, the total time of two (constant current, constant voltage) charging is 8 hours and 24 minutes.
  • the working discharge capacity of the lead-acid battery of the present embodiment is improved or restored year by year.
  • the positive and negative polarity inversion of the present embodiment and the subsequent charge and discharge or charge and discharge operations cause the positive active material of the lead-acid battery of the present embodiment to be softened and peeled off, improved, repaired, reversed, eliminated, Suppressing and preventing, so that the working discharge capacity in the cycle operation of the lead-acid battery of the embodiment is improved or restored after the operation, and on the other hand, the polarity of the positive and negative poles of the embodiment is reversed and then charged or discharged or charged.
  • the discharge operation also has the problems of electrode passivation, early capacity loss, corrosion, poor contact of active material and current collector, shrinkage of specific surface area of the anode, and sulfation which occur during the cycle operation of the battery of the present embodiment.
  • the cycle work is improved, repaired, reversed, thereby also making the lead-acid battery of the embodiment During the period of use, the corrosion problem is delayed, improved, repaired, reversed, and prevented.
  • the lead-acid battery in this embodiment In the normal cycle of the lead-acid battery in this embodiment, it is periodically or irregularly (for example, in the manner of specifying the number of cycles) and interspersed.
  • Performing the positive and negative polarity inversion and the subsequent charge, discharge or charge and discharge operations of the present embodiment for the lead-acid battery of the present embodiment will effectively improve, repair, reverse, eliminate, suppress, and prevent the softening of the positive active material or/or And the shedding, electrode passivation, corrosion, early capacity loss, sulfation, poor contact between the active material and the current collector, and the specific surface area shrinkage of the anode, thereby increasing or prolonging the service life of the lead-acid battery of the present embodiment.
  • the positive and negative polarity inversion of the present example and the subsequent charging or charging and discharging operations can also be performed using the rapid charge and discharge pulse current and the pulse voltage.
  • Some experimental data in this embodiment indicate the degree of recovery of the working discharge capacity of the lead-acid battery of the present embodiment after the single polarity inversion of the lead-acid battery of the present embodiment and the charging or charging and discharging operation thereafter.
  • the number of times that the lead-acid battery can continuously maintain the normal or high discharge capacity of the charge-discharge cycle after each working discharge capacity recovery ie, after each single polarity inversion and after the charge or charge and discharge operation
  • the number of charge and discharge cycles of the normal or high working discharge capacity of the lead-acid battery of the present embodiment) and the current, voltage, time, and time used in each single polarity inversion and subsequent charging or charging and discharging operations The charge/discharge capacity, pulse or direct current, internal resistance of the battery, electrolyte density, and degree of saturation of the electrolyte vary depending on the mode.
  • the specific capacity of the positive electrode active material of the battery is 61 mAh/g (2h rate, 25 ° C)
  • the rated capacity of the lead-acid battery electrode of this embodiment is 821 mAh (according to the foregoing Example of the average mass of the active material of a single electrode of a lead-acid battery)
  • the discharge capacity is defined three times below the rated capacity or 80% (657 mAh) of the rated capacity when the discharge depth is 100%, the judgment basis of the end of the battery life is determined. As shown in FIG.
  • the lead-acid storage battery of the present embodiment is charged or charged and discharged after the polarity of the positive and negative polarities is not reversed in this embodiment.
  • its service life will be roughly 25 and 36 times respectively.
  • the operating discharge capacity of the battery remains above the rated capacity after the 111th cycle operation.
  • the service life of the battery is obviously increased or prolonged, and it is presumed that the method for improving or prolonging the service life of the lead-acid battery in the present embodiment in the case of eliminating short-circuit, open circuit, water loss, pollution and the like which cause the battery to fail,
  • the service life of the lead-acid battery of this example was further improved or extended on the basis of 111 cycles.
  • the active material utilization rate of the lead-acid battery electrode as the positive electrode is significantly higher than that of the current commercial power lead-acid battery positive electrode, which is mainly related to the thickness of the electrode and the current collector structure of the present embodiment.
  • the two electrodes of the lead-acid storage in this embodiment are also positive and negative common electrodes which are equivalent to each other, because after the electrodes are formed, the two have the same function and performance, but in actual use, the polarity reversal and Changes and differences in factors such as post-charge or charge-discharge operating systems and cyclical work systems can lead to differences in performance and performance.
  • the lead-acid battery of the embodiment is a flat-plate lead-acid battery with a rated voltage of 2V and a rated capacity of 754mAh (C 2.5 , 2.5h rate, 25° C.), including two positive and negative electrode electrodes (ie, positive and negative electrodes).
  • the grid of the grid current collectors of the two electrodes is rectangular, and the two electrodes are also the same kind of positive and negative common electrodes, that is, the manufacturing error caused when manufacturing the electrodes is not considered, the two pieces of the implementation
  • the lead-acid battery electrodes are identical to each other in all electrode composition and manufacturing aspects (such as electrode structure, shape, current collector, lead paste formulation and lead paste quality, manufacturing process, etc.) before being formed, after being formed,
  • the two electrodes are respectively formed into a positive electrode and a negative electrode, and each of the planar grid-type positive and negative electrode common electrodes of the present embodiment has a thickness of 1.3 mm, and the width and height of the frame are 38 mm and 68 mm, in order to facilitate the subsequent description of the embodiment.
  • the two planar grid positive and negative common electrodes of the lead storage battery of the present embodiment are respectively named as electrode A and electrode B, and the formulation and quality of the lead paste of electrode A and electrode B are the same, that is, the electrodes A and B are Lead paste formula Ball-milled lead powder, barium sulfate (0.8wt% relative to ball-milled lead powder), and other commercially used negative electrode additives.
  • the quality of dry lead paste (after smearing, curing, drying) on electrodes A and B is 10.8g.
  • the electrode A is used as the positive electrode for circulating operation (that is, the charging and discharging process of the positive electrode of the lead-acid battery occurs on the electrode A during the cyclic charging and discharging process).
  • the electrode B is used as the negative electrode for the cyclic charging and discharging work (that is, the charging and discharging process of the negative electrode of the lead-acid battery occurs on the electrode B during the cyclic charging and discharging operation), and the intervals of the positive and negative electrodes or the electrodes A and B are separated.
  • the polarity state or polarity direction of the electrodes A and B during the cyclic charging and discharging operation can be expressed as A+/B- or A-/B+, wherein A+/B- represents the electrode A.
  • the polarity is positive and the polarity of the electrode B is negative.
  • A-/B+ indicates that the polarity of the electrode A is negative and the polarity of the electrode B is positive.
  • the density of the electrolyte sulfuric acid solution used in the lead-acid battery of the embodiment is 1.27 g/cm 3 , and the embodiment eliminates or prevents the factors such as loss of liquid, open circuit, short circuit, mechanical damage, test failure, etc., and the implementation process and implementation results of the embodiment. Interference.
  • the method for improving or prolonging the service life of the lead-acid battery of the embodiment is that the lead-acid battery of the embodiment can be charged and discharged to a certain number of times or the working discharge charging capacity is softened or/and detached due to the positive active material.
  • the negative electrode specific surface area shrinks, current collector or sink corrosion, passivation, early capacity loss, sulphation, poor contact between active material and current collector, etc., when it falls to a certain degree, it is automatic or And manually performing a single polarity inversion and subsequent charging or charging and discharging operations on the positive electrode and the negative electrode of the lead-acid battery of the present embodiment or performing a one-stage continuous two-stage polarity on the positive electrode and the negative electrode of the lead-acid battery of the present embodiment.
  • the lead-acid battery is circulated in the polarity state or the polarity direction of the electrode after the polarity is reversed.
  • the electrode A of the lead-acid battery of the embodiment is used as the positive electrode before the polarity is reversed, Cyclic work (ie, charge and discharge process of lead-acid battery positive electrode reaction on electrode A during cyclic charging and discharging work), after the polarity reversal, electrode A is cycled as a negative electrode (ie, in the cycle charge)
  • the charging and discharging process of the negative electrode of the lead-acid battery occurs on the electrode A), and the corresponding electrode B is cycled as the negative electrode before the polarity is reversed (ie, the electrode B is in the process of circulating charging and discharging)
  • the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs, and the cycle is performed as the positive electrode after the polarity reversal (that is, the lead-acid battery positive electrode occurs on the
  • the polarity state or the polarity direction in the cyclic working process after the reversal is also reversed; for the positive and negative electrodes of the lead-acid battery of the embodiment, the polarity inversion is repeated twice in succession and the subsequent charging or charging and discharging Operation, in the present lead-acid battery, during the period of two consecutive positive and negative polarity inversions and subsequent charging or charging and discharging operations, the polarity of the positive and negative polarities or the polarity direction and the current period are consecutive.
  • the polarity of the secondary positive electrode and the negative electrode is reversed and the same as before the charging or charging and discharging operation.
  • the polarity of the positive electrode and the negative electrode are reversed twice.
  • the first is to perform the cycle operation as the positive electrode (that is, the charge and discharge process of the positive electrode reaction of the lead-acid battery on the electrode A during the cyclic charge and discharge operation), and then the polarity of the positive and negative polarities is reversed twice in this period, the electrode A Still
  • the positive electrode is circulated, and the corresponding electrode B is circulated as a negative electrode before the polarity reversal for two consecutive periods in this period (ie, the charging and discharging process of the negative electrode reaction of the lead-acid battery on the electrode B during the cyclic charging and discharging operation)
  • the polarity reversals in this period it is still circulating as a negative electrode.
  • the circulating charge and discharge working system adopted in the lead-acid battery of the present embodiment is: discharging discharge to 1.75V at a current of 300 mA during the working discharge, and then performing constant current charging at a current of 140 mA for 4 hours and 57 minutes, and then with a current of 63 mA.
  • the constant current is charged for 5 hours and 44 minutes, and then charged at a constant current of 17 mA for 5 hours, and then the previous working discharge process is repeated, and the cycle and the cycle are repeated to make the lead-acid battery of the embodiment charge and discharge.
  • the lead-acid battery cycle operation of the embodiment and the implementation result of the method for improving or prolonging the service life of the lead-acid battery of the embodiment are as shown in FIG. 10, and the lead-acid battery of the embodiment works in the cycle work thereof.
  • the lead-acid battery of the embodiment works in the cycle work thereof.
  • the third and fourth single positive and negative polarity inversions and subsequent charging or charging and discharging operations are between the 51st and 52nd, the 55th and 56th, and the 57th of the number of duty cycles.
  • the lead-acid battery of the embodiment is in the state of charge after the 14th cycle is completed, at this time, The polarity of the electrode A is positive, the polarity of the electrode B is negative, the cycle operation of the lead-acid battery of the embodiment is stopped, and then the lead-acid battery of the embodiment is discharged for 10 min at a current of 300 mA, so that the voltage thereof is lowered from 1.75 V.
  • the positive and negative output terminals of the charging and discharging device are connected to the original positive electrode and the negative electrode of the lead-acid battery of the embodiment, that is, the positive output end of the charging and discharging device is connected with the lead acid battery electrode B of the embodiment.
  • the negative output end of the charge and discharge device is connected to the lead acid battery electrode A of the embodiment.
  • the charge and discharge device measures the voltage of the lead acid battery of the embodiment to be -2.07V, and then, for the lead acid battery of the embodiment.
  • the current is charged at a current of 150 mA in the state of the reverse pole connection, so that the voltages of the positive and negative electrodes of the lead-acid battery of the present embodiment (the measured values of the charge and discharge device, the same in the present embodiment) are from -2.07V. It rises to 0V and then rises to 1.76V.
  • the lead polarity battery of this embodiment has the first polarity reversal, that is, during the process of rising from -2.07V to 0V, lead acid is mainly generated on the electrode A.
  • the discharge process of the positive electrode of the battery reacts, and the discharge process of the negative electrode of the lead-acid battery occurs mainly on the electrode B.
  • the main electrode of the lead-acid battery reacts with the negative electrode of the lead-acid battery.
  • the charging process of the positive electrode of the lead-acid battery is mainly occurred on the electrode B.
  • the embodiment is further 300 mA.
  • the lead-acid battery is subjected to constant current charging for 3 hours and 36 minutes to 2.65V, then constant voltage charging at 2.65V for 4 hours, then discharging at a constant current of 300mA for 55 minutes to 1.75V, and then charging and discharging according to the cyclic working system.
  • the lead-acid battery of the present embodiment is re-introduced into the charging process of the cyclic operation to be charged, and then the 15th cycle or even thereafter until the 29th cycle operation.
  • the lead-acid battery of the present embodiment during the 15th to 29th cycle operation, the charging and discharging process of the lead-acid battery negative electrode reaction occurs on the electrode A, and the charging and discharging process of the lead-acid battery positive electrode reaction occurs on the electrode B, as shown in the figure. 10 is shown.
  • the lead-acid battery of the embodiment when the lead-acid battery of the embodiment is in the 29th cycle, at this time, the polarity of the electrode A Negative, the polarity of the electrode B is positive, the cycle charging and discharging operation of the lead-acid battery of the embodiment is stopped, and then the lead-acid battery of the embodiment is discharged for 33 minutes at a current of 300 mA, so that the voltage thereof is lowered from 1.75 V to 0 V.
  • the positive and negative output ends of the charging and discharging device are connected to the positive electrode and the negative electrode of the lead-acid battery of the embodiment in the 15th to 29th cycle charging and discharging operation, that is, the positive output end of the charging and discharging device and the present embodiment
  • the lead-acid battery electrode A is connected, and the negative output end of the charging and discharging device is connected with the lead-acid battery electrode B of the embodiment.
  • the charging and discharging device measures the voltage of the lead-acid battery of the embodiment to be -2.14V.
  • the lead-acid battery of the present embodiment is charged at a current of 150 mA in the state of the reverse pole connection for 6 hours and 13 minutes, so that the voltage between the positive electrode and the negative electrode of the lead-acid battery of the present embodiment is measured.
  • the following is the same as rising from -2.14V to 0V and then rising to 1.76V.
  • the lead-acid battery of this embodiment undergoes a second polarity reversal, that is, from -2.44V to 0V.
  • the main discharge occurred on the electrode A was the discharge process of the negative electrode of the lead-acid battery, and the discharge process of the positive electrode of the lead-acid battery was mainly occurred on the electrode B, and the electrode A was raised during the process of 0 V rising to 1.76 V.
  • the main occurrence is the charging process of the positive electrode reaction of the lead-acid battery.
  • the main charging process on the electrode B is the charging process of the negative electrode of the lead-acid battery, and the connection state of the output end of the charging and discharging device and the output end of the lead-acid battery of this embodiment is maintained.
  • the lead-acid battery of the present embodiment was subjected to constant current charging for 5 hours and 11 minutes to 2.65 V at 300 mA, then subjected to constant voltage charging at 2.65 V for 4 hours, and then discharged at a constant current of 300 mA for 49 minutes to 1.75. V, then the lead-acid battery of this embodiment is re-introduced into the charging process of the cyclic operation, and then, the 30th cycle or even the subsequent 45th cycle operation is performed.
  • the charge-discharge process of the lead-acid battery positive electrode reaction occurs on the electrode A
  • the charge-discharge process of the lead-acid battery negative electrode reaction occurs on the electrode B, as shown in the figure. 10 is shown.
  • the first single positive and negative polarity inversion and the subsequent charging or charging and discharging operations of the first embodiment of the present embodiment are basically the same, the difference is that the state of charge of the battery at the start of operation, the charging or charging and discharging system after the polarity is reversed, specifically: when the lead-acid battery of this embodiment is in the 45th cycle.
  • the polarity of the electrode A is positive
  • the polarity of the electrode B is negative
  • the cycle operation of the lead-acid battery of the embodiment is stopped
  • the lead-acid battery of the embodiment is performed at a current of 300 mA.
  • the voltage is reduced from 2.29V to 0V, and then the positive output end of the charging and discharging device is connected to the lead acid battery electrode B of the embodiment.
  • the negative output end of the charging and discharging device and the lead acid battery electrode of the embodiment The A phase is connected.
  • the charge and discharge device measures the voltage of the lead-acid battery of the embodiment to be -2.04V, and then, for the lead-acid battery of the embodiment, the battery is charged at the current of 900 mA for 2 hours.
  • the voltage between the positive electrode and the negative electrode of the lead-acid battery of the present embodiment (the measured value of the charge and discharge device, the same in the present embodiment) is raised from -2.04V to 0V and then rises to 2.52V, in the process, the lead of the embodiment
  • the discharge process of the negative electrode of the acid battery reacts, and during the process of 0V rising to 2.52V, the main charging process on the electrode A is the charging process of the negative electrode of the lead-acid battery.
  • the main electrode of the lead-acid battery is the positive electrode reaction of the lead-acid battery.
  • the lead-acid battery of the embodiment is charged with constant current for 20 minutes at 60 mA, and then the 674 mA pair is used.
  • the lead-acid battery of the embodiment was subjected to constant current charging for 1 hour, and then the lead-acid battery of the present embodiment was subjected to constant current charging for 20 minutes at 60 mA, and then the lead acid storage of the present embodiment was further charged at 505 mA.
  • the cell was charged for 1 hour, and then the lead-acid battery of the present embodiment was subjected to constant current charging for 20 minutes at 60 mA, and then the lead-acid battery of the present embodiment was charged with constant current for 1 hour at 379 mA, and then the lead-acid battery of the present embodiment was further treated at 60 mA.
  • the constant current charging was performed for 20 minutes, and then the lead-acid battery of the present embodiment was charged at a constant current of 284 mA for 1 hour, and then the lead-acid battery of the present embodiment was subjected to constant current charging for 20 minutes at 60 mA, and then the lead-acid battery of the present embodiment was further applied at 213 mA.
  • the cycle work system performs a charge and discharge operation, and then the lead acid battery of the embodiment is reintroduced into the charging process of the cycle operation, and then the cycle work is performed for the 46th time and thereafter until the 51st time.
  • the charge-discharge process of the lead-acid battery negative electrode reaction occurs on the electrode A
  • the charge-discharge process of the lead-acid battery positive electrode reaction occurs on the electrode B, as shown in the figure. 10 is shown.
  • the polarity of the positive electrode and the negative electrode are reversed and the charging or charging and discharging operations thereafter: when the lead-acid battery of the embodiment is in the state of charge after the completion of the 51st cycle, at this time
  • the polarity of the electrode A is negative
  • the polarity of the electrode B is positive
  • the cycle operation of the lead-acid battery of the embodiment is stopped, and then the lead-acid battery of the embodiment is forcibly discharged for 14 minutes with a current of 300 mA and 900 mA by the charge and discharge device.
  • the lead-acid battery of this embodiment keeps the connection state with the charging and discharging device unchanged from 1.75V to 0V and then to -1.75V (the value measured by the charging and discharging device, this In the embodiment, the same is the same, in the process, the lead-acid battery of the present embodiment has the first polarity reversal in the current two positive and negative polarity inversions and the subsequent charging or charging and discharging operations, that is, In the process of decreasing from -1.75V to 0V, the discharge process of the negative electrode of the lead-acid battery is mainly occurred on the electrode A, and the discharge process of the positive electrode of the lead-acid battery is mainly occurred on the electrode B, and is decreased at 0V.
  • the main charging process on the electrode A is the charging process of the positive electrode of the lead-acid battery.
  • the main process of the electrode B is the charging process of the negative electrode of the lead-acid battery, while maintaining the output of the charging and discharging device.
  • the lead-acid battery of the present embodiment is forcibly discharged for 1 hour at a current of 900 mA until the voltage of the lead-acid battery of the embodiment is -2.53 V, and then, at 900 mA.
  • the current is forcibly charged to the lead-acid battery of the embodiment for 1 hour and 13 minutes until the battery voltage rises from -2.53V to 0V and then rises to 2.65V.
  • the lead-acid battery of this embodiment has two consecutive positive and negative poles.
  • the second polarity reversal in the reversal and subsequent charging or charging and discharging operations that is, in the process of rising from -2.53V to 0V, the main discharge on the electrode A is the discharge of the positive electrode of the lead-acid battery.
  • the process and electrode B mainly occur in the discharge process of the negative electrode of the lead-acid battery. In the process of 0V rising to 2.65V, the lead-acid battery mainly occurs on the electrode A.
  • the charging process of the positive electrode of the lead-acid battery mainly occurs on the electrode B, and the state of the connection between the output end of the charging and discharging device and the output end of the lead-acid battery of the embodiment is kept unchanged, and then The battery was discharged at a constant current of 300 mA for 1 hour and 32 minutes to 1.75 V, and then the lead-acid battery of the present embodiment was put back into the charging process for charging, and then charged, and then the 52nd cycle was continued until the 55th cycle.
  • the charge-discharge process of the lead-acid battery negative electrode reaction occurs on the electrode A
  • the charge-discharge process of the lead-acid battery positive electrode reaction occurs on the electrode B, as shown in the figure. 10 is shown.
  • the polarity of the positive electrode and the negative electrode are reversed and the subsequent charging or charging and discharging operations are the same as the polarity of the positive electrode and the negative electrode in the first phase of the first embodiment.
  • the charge and discharge operations are basically the same or similar, except that the current, voltage, charge and discharge time, charge and discharge capacity, charge and discharge frequency, and number of times vary in operation.
  • the positive polarity of the positive electrode and the negative electrode and the subsequent charging or charging and discharging operations are as follows: the lead-acid battery of the embodiment which is in the charging state after the 57th working discharge is completed.
  • the constant current forced discharge state that is, the current of the lead-acid battery of the embodiment is lowered from 2.60V to 0V at a current of 300 mA for 2 hours and 22 minutes, and then the lead-acid battery of the embodiment is continuously forced at a current of 898 mA. Discharge, so that the voltage of the lead-acid battery of this embodiment drops from 0V to -2.58V in 1 hour and 15 minutes (this decreases from 2.60V to 0V, and then decreases from 0V to -2.58V.
  • the lead-acid battery of the present embodiment is subjected to forced charging of 898 mA, so that the lead-acid battery of the embodiment rises from -2.58 V to 0 V and then rises to 2.65 V after 1 hour and 18 minutes.
  • the second polarity reversal and then the lead-acid battery of the present embodiment is discharged to 1.85V at a current of 300 mA for 1 hour and 10 minutes, and then, for a lead-acid battery of the present embodiment, at a current of 450 mA for 1 hour. 08 minutes, constant current charging to 2 .65V, then the lead-acid battery of this embodiment is discharged at a current of 300 mA through a constant current of 4 s to 2.0 V.
  • the lead-acid battery of the present embodiment is charged at a current of 300 mA and charged at a constant current of 28 min to 2.65 V, and then to the present.
  • the lead-acid battery was charged at a constant voltage of 2.65 V for 1 hour (charge amount was 223 mAh), and then the lead-acid battery of the present embodiment was discharged at a constant current of 300 mA for 3 hours and 10 minutes to 1.75 V, thereby completing the first embodiment.
  • the positive polarity and the negative pole polarity inversion are repeated twice and the subsequent charging or charging and discharging operations (the whole process is 10 hours and 51 minutes), and then the lead acid battery of the embodiment is put into the charging process during the cycle working process. Then, the 58th cycle charge and discharge operation of the lead-acid battery of the present embodiment is performed.
  • the second single positive and negative polarity inversion and the subsequent charging or charging and discharging operations of the second embodiment of the present embodiment are changes in the current, voltage, charge and discharge time, charge and discharge capacity, charge and discharge frequency, and number of times involved in the operation.
  • the state of the electrode in the 56th-76th cycle of the lead-acid battery of this embodiment is as shown in FIG.
  • the working discharge capacity of the lead-acid battery of the present embodiment is improved or restored year by year.
  • the polarity inversion of the positive electrode and the negative electrode of the present embodiment and the subsequent charge and discharge or charge and discharge operations cause the positive electrode active material of the lead-acid battery of the present embodiment to be softened and peeled off to be improved, repaired, reversed, eliminated, suppressed, and prevented.
  • the working discharge capacity in the cycle operation of the lead-acid battery of the embodiment is improved or restored after the operation.
  • the polarity of the positive electrode and the negative electrode of the embodiment and the subsequent charge, discharge or charge and discharge operations are also
  • the problems of electrode passivation, early capacity loss, corrosion, poor contact of active material and current collector, shrinkage of specific surface area of the negative electrode, and sulfation of the battery during the cycle of the battery have been improved, repaired, reversed,
  • Corrosion problems during long-term use are delayed, improved, repaired, reversed, eliminated, suppressed, and prevented.
  • they are periodically or irregularly (for example, with a specified number of cycles).
  • the lead-acid battery of the embodiment is defined as having an operating discharge capacity of less than 65% of the rated capacity during the cycle operation, the number of effective cycle operations of the lead-acid battery of the embodiment shown in FIG. 10 is 75. Secondly, if the lead-acid battery of the present embodiment is defined as having an operating discharge capacity of less than 80% of the rated capacity during the cycle operation, the effective cycle of the lead-acid battery of the present embodiment as shown in FIG. It is 70 times.
  • the method for improving or prolonging the service life of the lead-acid battery in this embodiment will make the service life of the lead-acid battery of the present example A greater increase or extension is achieved based on the number of effective cycles available.
  • the lead-acid battery can continuously maintain the normal or high discharge capacity of the charge and discharge cycle after each working discharge capacity recovery (ie, the charge or charge and discharge operation after each or every period of polarity inversion)
  • the current and voltage of the normal operation of the lead-acid battery of the present embodiment or the charge and discharge cycle of the higher discharge capacity) and the corresponding current or voltage used in each phase or period of polarity reversal and subsequent charging or charging and discharging operations Time, charge and discharge capacity, pulse or DC, internal resistance of the battery, electrolyte density, electrolyte saturation level, and mode.
  • the trigger condition parameter for triggering and performing the polarity reversal of the positive and negative poles of the lead-acid battery of the present embodiment may be a number of cycles multiplied by a certain value of the total amount of charge, and when the battery is charged. The rate at which the voltage of a certain battery voltage rises, and the like.
  • the two electrodes of the lead-acid storage in this embodiment are also positive and negative common electrodes which are equivalent to each other, because after the electrodes are formed, the two have the same function and performance, but in actual use, the polarity is reversed and Subsequent changes and differences in factors such as charging or charging and discharging operating systems and cyclical operating systems may lead to differences in performance and performance.
  • the density of the electrolyte lead-acid battery of the present embodiment may be implemented 1.282g / cm 3 or 1.30g / cm 3.
  • the lead-acid battery pack of this embodiment is a full-tube lead-acid battery pack with a rated voltage of 4V and a rated capacity of 539mAh (C 3.5 , 3.5h rate, 25° C.) connected in series by two identical tubular-type lead-acid batteries.
  • Each of the electrodes of the full-tube lead-acid battery is a tubular electrode, and the tubular electrodes are positive and negative common electrodes (ie, electrodes common to the positive electrode and the negative electrode), and the tubular positive and negative
  • the extremely common electrode is the same in the electrode structure and active material formulation.
  • each of the full-tube lead-acid batteries includes three tubular positive and negative common electrodes.
  • the six tubular positive and negative electrodes of the lead battery pack of the present embodiment are generally used.
  • the electrodes are named as electrodes A1, A2, A3, A4, B1, and B2, respectively.
  • the six electrodes are arranged in each of the full-tube lead-acid batteries in the lead-acid battery pack of the present embodiment: the electrode B1 is sandwiched between electricity.
  • the mass of the active material in the A4 casing is 5.8g
  • the mass of the active material in the sleeve of the electrode B1 or B2 is 5.5g
  • the active substances in the electrodes A1, A2, A3, A4, B1, B2 are all ball-milled.
  • Powder, barium sulfate (0.8wt% relative to ball-milled lead powder) the two output terminals of the lead-acid battery of this embodiment are respectively named as battery terminals A, B, wherein the battery terminal A is connected to the electrode A1 or A2 or A3 or A4, the battery terminal B is connected to the electrode B1 or B2.
  • the electrodes A1, A2, A3, and A4 are cycled as the positive electrode ( That is, during the cyclic working process, the electrodes A1, A2, A3, and A4 are charged and discharged during the reaction of the positive electrode of the lead-acid battery), and the electrodes B1 and B2 are used as the negative electrode for the cyclic operation (that is, the electrodes B1 and B2 occur during the cyclic operation).
  • the charging and discharging process of the negative electrode of the lead-acid battery that is, the polarity of the terminal A of the battery pack is positive, and the polarity of the terminal B of the battery pack is negative, which is expressed as A+/B- (same reason, when the battery pack When the polarity of terminal A is negative and the polarity of battery terminal B is positive, It is expressed as A-/B+), and the separators of the positive and negative tube electrodes are separated by a separator.
  • the density of the sulfuric acid solution of the electrolyte used in the lead-acid battery group of the present embodiment is 1.27 g/cm 3 , and the present embodiment excludes or prevents the loss. Factors such as liquid, open circuit, short circuit, mechanical damage, test failure, etc. interfere with the implementation process and implementation results of this embodiment.
  • the method for improving or prolonging the service life of the lead-acid battery pack of the embodiment is that, when the lead-acid battery pack of the embodiment is circulated to a certain number of times or the working discharge charging capability is softened or/and detached from the positive active material, the ratio of the negative electrode is increased. Automatic or / and manual when one or more of surface area shrinkage, current collector or sink corrosion, passivation, early capacity loss, sulfation, poor contact of active material and current collector, etc. Performing a single polarity inversion and subsequent charging or charging and discharging operations on the positive and negative electrodes of the lead-acid battery pack of the present embodiment to improve, repair, reverse, prevent, suppress, and eliminate the softening and negative electrode ratio of the positive active material.
  • the lead-acid battery pack of the embodiment is re-introduced into the cyclic charging and discharging operation by the polarity state of the electrode after the polarity is reversed, until the next positive and negative polarity is started. Reverse and subsequent charging or charging and discharging operations.
  • the lead acid battery pack of the embodiment is re-introduced into the cyclic charging and discharging operation by the electrode polarity state after the polarity inversion.
  • Cycling operation for example, if the electrodes A1, A2, A3, and A4 of the lead-acid battery pack of the present embodiment are operated as a positive electrode before the polarity is reversed (that is, the electrodes A1, A2, and A3 during the cycle operation) On the A4, the charge and discharge process of the positive electrode reaction of the lead-acid battery occurs), after the polarity is reversed, the electrodes A1, A2, A3, and A4 are used as the negative electrode for the charge and discharge cycle (ie, the electrode A1 during the cycle operation).
  • the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs.
  • the corresponding electrodes B1 and B2 are cycled as the negative electrode before the polarity is reversed (that is, the electrode B1 during the cycle operation).
  • the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on B2), and the cycle is performed as the positive electrode after the polarity reversal (that is, the charging of the positive electrode of the lead-acid battery occurs on the electrodes B1 and B2 during the cyclic operation).
  • the electrodes A1, A2, A3, A4 or the electrodes B1, B2 during the cyclic operation before the polarity inversion are reversed
  • the electrodes A1, A2, A3, A4 Or the polar states or polar directions of the electrodes B1 and B2 during the cyclic operation after the polarity inversion are reversed.
  • Triggering or starting the triggering of any polarity reversal and subsequent charging or charging and discharging operations on the positive and negative poles of the lead-acid battery pack of the embodiment may be manual triggering or the arrival of the program according to a preset trigger condition.
  • the automatic triggering, the triggering condition may be one or more of a certain number of cyclic charging and discharging operations or cumulative times, a charging amount, a discharging amount, a charging and discharging rate, a current variation amount, a voltage variation amount, or the like, or a calculated value thereof.
  • Charging and discharging cycle lead-acid battery system of the present embodiment is employed: a discharge during operation, a current of 0.283C 3.5 were discharged to 3.5V, and then, at a current of 0.338 C 3.5 to 5.95V or constant current charging time is 9 After 24 hours, then constant voltage charging was carried out for 3 hours with a voltage of 5.3 V, and then the previous working discharge process was repeated, and the cycle of the lead-acid battery pack of this example was cyclically charged and discharged.
  • the lead-acid battery pack of the embodiment is in the process of circulating 6th, 7th, 17th, 18th, 25th, 26th, 33rd, 34th, 41st, 42nd, 56th, 57th times of the number of work cycles Performed or carried out in sequence for the first time, the second time, Vietnamese, the sixth single positive and negative polarity inversion, and the subsequent charging or charging and discharging operations, performed or
  • the method or process of performing positive and negative polarity inversion and subsequent charging or charging and discharging operations is as follows:
  • the positive and negative output terminals of the battery pack are connected in reverse polarity, that is, the positive output end of the charge and discharge device is connected to the negative output terminal (battery terminal B) of the lead-acid battery pack of the embodiment, and the negative output of the charge and discharge device
  • the terminal is connected to the positive output terminal (battery terminal A) of the lead-acid battery pack of the embodiment, and after the reverse pole is connected, the charge and discharge device measures the voltage of the lead-acid battery pack of the embodiment to be -5.53V, and then, the implementation
  • the lead-acid battery pack is charged at a current of 458 mA in the state of the reverse pole connection, so that the voltages of the positive and negative output terminals of the lead-acid battery pack of the present embodiment (the measured values of the charge and discharge device, the same in the present embodiment) From -5.53V When it reaches 0V and then rises to 5.8V, in this process, the first polarity reversal occurs in the lead-acid battery
  • the main occurrence of A4 is the charging process of the negative electrode reaction of lead-acid battery.
  • the main charging process on the electrodes B1 and B2 is the charging process of the positive electrode of the lead-acid battery.
  • the output of the charging and discharging device and the lead-acid battery of this embodiment are maintained.
  • the lead-acid battery pack of this embodiment is discharged at 152.7 mA for 14 minutes to 3.5 V, and then charged at a constant current of 229 mA for 8 hours to 5.72 V, and then, 152.7mA discharge for 2 minutes to 4.5V, and then charged at a constant current of 114mA for 3 hours to 5.5V, and then put the lead-acid battery pack of the embodiment into the seventh working discharge process of the cycle, for the seventh time. Even thereafter Work to cycle 17 times.
  • the polarity of the battery terminal A is negative
  • the polarity of the electrode pool terminal B is positive, as shown in FIG.
  • the positive and negative output terminals of the battery pack are connected in reverse polarity at that time, that is, the positive output end of the charging and discharging device is connected to the negative output terminal (battery group terminal A) of the lead-acid battery group of the embodiment, and the charging and discharging device The negative output terminal is connected to the positive output terminal (battery pack terminal B) of the lead-acid battery pack of the present embodiment.
  • the charge and discharge device measures the voltage of the lead-acid battery pack of the embodiment to be -4.54V.
  • the lead-acid battery pack of the present embodiment is charged at a current of 459 mA in the state of the reverse pole connection, so that the output voltage of the lead-acid battery pack of the present embodiment (the measured value of the charge and discharge device, the same in the present embodiment) From -4.54V to 0V It rises to 5.8V for 4 hours and 30 minutes.
  • the lead-acid battery pack of this embodiment has a second polarity reversal, that is, during the process of rising from -4.54V to 0V, electrodes A1, A2, and A3.
  • A4 is the discharge process of the negative electrode of lead-acid battery, the discharge process of the positive electrode of lead-acid battery on the electrodes B1 and B2, and the electrode A1 during the process of 0V rising to 5.8V.
  • A2, A3, and A4 mainly occur in the charging process of the positive electrode of the lead-acid battery.
  • the charging process of the negative electrode of the lead-acid battery occurs mainly on the electrodes B1 and B2.
  • the output of the charging and discharging device is maintained and the embodiment is
  • the lead-acid battery pack of this embodiment is discharged at 152.7 mA for 17 minutes to 3.5 V, and then charged at a constant current of 229 mA for 8 hours to 5.41 V, and then And then discharge at 152.7mA for 2 minutes to 4.23V, and then charge at a constant current of 114mA for 3 hours to 5.26V, and then put the lead-acid battery of the embodiment into the 18th working discharge process in the cycle work, get on 18 and thereafter until the first cycle for 25 times.
  • the polarity of the battery terminal A is positive, and the polarity of the electrode bank terminal B is negative, as shown in FIG. 11, that is, in the process
  • the charging and discharging process of the positive electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, A3, and A4, and the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on the electrodes B1 and B2, that is, the battery terminals A, B and the electrode
  • the polarity state or polarity direction of A1, A2, A3, A4, B1, B2 is returned to the state at which the lead-acid battery pack of the present embodiment is most initially cycled.
  • the single positive and negative polarity inversions similar to the first or second time of the present embodiment as described above are repeated, repeated, and interspersed as described above.
  • the charging or charging and discharging operation that is, the lead-acid battery pack of the embodiment is realized between the 25th and 26th, the 33rd and 34th, the 41st and the 42nd, and the 56th of the working cycle. 57th, ..., X, X+1 times or the third, fourth, fifth, sixth, ...., Y
  • the secondary positive and negative polarity inversions and subsequent charging or charging and discharging operations (X, Y are positive integers).
  • FIG. 11 is a diagram showing the battery pack terminal A in the cycle operation process of the lead-acid battery pack of the embodiment before or after the single charge and charge polarity reversal and subsequent charging or charging and discharging operations.
  • the polarity state or polarity direction of B, FIG. 12 shows the 23-28th cycle charge and discharge operation process of the lead-acid battery pack of the embodiment and the third single positive and negative poles interposed during the process.
  • the polarity reversal of the negative electrode and the subsequent charging or charging and discharging operations are basically the same, except that after the steps of "discharging at 152.7 mA for 2 minutes and then charging at 114 mA constant current for 3 hours" are completed after the operation. Then, the battery was discharged at a current of 153 mA for 2 hours and 58 minutes, and then the lead-acid battery pack of the present embodiment was put into the 26th cycle.
  • the working discharge capacity of the lead-acid battery pack of the present embodiment is improved or restored year by year.
  • the positive and negative polarity inversion of the present embodiment and the subsequent charge and discharge or charge and discharge operations of the present embodiment cause the positive active material of the lead-acid battery of the present embodiment to soften or/and fall off, electrode passivation, early capacity loss, and corrosion.
  • One or more of the problems of poor contact between the active material and the current collector and shrinkage of the specific surface area of the negative electrode are improved, repaired, reversed, suppressed, eliminated, and prevented.
  • the irregularity of the polarity of the positive and negative electrodes of the present embodiment and the subsequent charge and discharge or charge and discharge operations of the lead-acid battery pack of the present embodiment may be performed intermittently (for example, in a manner of specifying the number of cycles). Effectively improve, repair, reverse, eliminate, inhibit, prevent softening or/and shedding, passivation, corrosion, early capacity loss, sulfation, active substances and sets of positive active materials
  • the problem of poor contact between the body and the specific surface area of the negative electrode increases or prolongs the service life of the lead-acid battery pack of the present embodiment.
  • the electrodes A1, A2, A3, A4, B1, and B2 are alternately alternately charged or discharged as a positive electrode or a negative electrode
  • the cycle work makes the corrosion problem of the electrode generated as the positive electrode work improve, repair and reverse when the electrode is used as the negative electrode for the charge and discharge cycle, thereby also delaying the corrosion problem of the lead-acid battery pack of the present embodiment during long-term use.
  • the method for improving or prolonging the service life of the lead-acid battery pack in this embodiment will make the service life of the lead-acid battery pack of the present example more improved or prolonged based on the existing effective number of cycles.
  • the positive and negative polarity inversion of the present example and the subsequent charging or charging and discharging operations can also be performed using the rapid charge and discharge pulse current and the pulse voltage.
  • Some experimental data in this embodiment indicate the degree of recovery of the working discharge capacity of the lead-acid battery pack of the present embodiment after the single polarity inversion and the subsequent charging or charging and discharging operation of the lead-acid battery pack of this embodiment.
  • the number of times of charging and discharging cycles in which the lead-acid battery pack of the present embodiment can continuously maintain normal or high discharge capacity after each working discharge capacity is restored ie, charging or charging and discharging after each single polarity inversion
  • the number of charge and discharge cycles in which the lead-acid battery pack of the present embodiment operates normally or has a higher discharge capacity, and the current used in each single polarity inversion and subsequent charge or charge and discharge operations The voltage, time, charge and discharge capacity, pulse or DC, internal resistance of the battery or battery pack, electrolyte density, and the degree of electrolyte saturation vary.
  • the positive, negative or all electrodes of the full-tube lead-acid battery pack of the present embodiment are the same tubular positive and negative common electrodes, that is, manufacturing that is not considered when manufacturing the electrodes. Error, all the electrodes or all the tubular electrodes of the full-tube lead-acid battery pack of the present embodiment are formed and manufactured in all the electrodes before the formation (such as electrode structure, shape, conductive core, casing, and fluid pool). The formulation of the active material and the quality, the manufacturing process, and the like are completely the same. After being formed, the tubular electrodes of the full-tube lead-acid battery of the present embodiment are respectively formed into a positive electrode or a negative electrode.
  • the positive, negative or all electrodes of the full-tube lead-acid battery pack of the present embodiment are tubular positive and negative common electrodes equivalent to each other, that is, the electrodes are formed or charged. After discharge, each tubular electrode of the present embodiment has or exhibits the same function and performance without regard to error factors during operation or use of the lead-acid battery.
  • the lead-acid battery of the embodiment includes a flat-plate lead-acid battery, a tubular lead-acid battery, a wound lead-acid battery, a bipolar lead-acid battery, and a horizontal lead-lead lead acid.
  • the rated voltage U is 6V, 12V, 24V, 36V, 48V, 60V or 72V.
  • the rated capacity (C 2 , 2 hour rate, 25 ° C) of the lead-acid battery pack of this embodiment is 12Ah, 14Ah, 16Ah, 18Ah, 20Ah, 24Ah, 30Ah, 60Ah, 100Ah, 200Ah or 1000Ah
  • the lead-acid battery pack of the embodiment has the battery output terminals A, B, the battery output terminal A and the electrodes A1, A2, .. in the lead-acid battery group of this embodiment.
  • the phase is electrically connected.
  • the electrodes A1, A2, ..., An, B1, B2, ..., Bn in the lead-acid battery group are positive and negative common electrodes (i.e., electrodes common to the positive and negative electrodes). ) can be used or operated as a positive electrode of a lead-acid battery, or as a negative electrode of a lead-acid battery.
  • the polarity of the battery output terminal A is positive, and the polarity of the battery output terminal B is negative, that is, the lead-acid battery pack of the embodiment is
  • the electrodes A1, A2, ..., An occurred on the charge and discharge process of the positive electrode of the lead-acid battery, and the electrodes B1, B2, ..., Bn What happens is the charging and discharging process of the negative electrode reaction of the lead-acid battery.
  • the separators are separated by positive and negative electrodes.
  • the method for improving or prolonging the service life of the lead-acid battery pack of the embodiment is: when the lead-acid battery pack of the embodiment is in the use or work of the circulating work, the working cycle reaches a certain number of times or as needed (for example, due to The positive electrode active material softening, the negative electrode specific surface area shrinkage, corrosion, electrode passivation, early capacity loss, sulfation, poor contact between the active material and the current collector, etc., cause the working discharge capacity of the lead-acid battery pack of the present embodiment to decrease and be lower than a certain capacity.
  • the single-time positive or positive and/or manual operation of the lead-acid battery pack of the example is performed once between two working cycles.
  • reverse polarity reversal and subsequent charging or charging and discharging operations improve, eliminate, reverse, inhibit, prevent positive electrode active material softening, negative electrode specific surface area shrinkage, corrosion, electrode passivation, early capacity loss, sulfation, activity
  • the problem of poor contact between the substance and the current collector makes the working capacity of the lead-acid battery pack of the embodiment recover or After the completion of the positive and negative polarity inversion and subsequent charging or charging and discharging operations, the lead acid battery pack of the embodiment is re-introduced into the charging and discharging cycle by the polarity state after the polarity is reversed.
  • the positive and negative polarity inversion and subsequent charging or charging and discharging operations are intermittently, interspersed, alternately performed or occur, thereby improving or extending the embodiment.
  • the first single positive and negative polarity reversal and the subsequent charging or charging and discharging operations of the lead-acid battery pack of the embodiment include the following steps: when the lead-acid battery pack of the embodiment is in the initial cycle working process (this During this period, the polarity of the output terminal A of the lead-acid battery pack is positive, and the polarity of the output terminal B is negative, that is, the positive electrode of the lead-acid battery reacts on the electrodes A1, A2, ..., An.
  • the counter electrode comprises a charging mode, a single stage, multi stage, a constant current (e.g.
  • the present embodiment comprises a lead-acid battery group, single phase, multiple phase, constant current (e.g.
  • the lead acid battery pack of the embodiment is re-polarized after the polarity is reversed.
  • the polarity of the output terminal A of the lead-acid battery pack is negative, and the polarity of the output terminal B is positive, that is, the charge and discharge of the negative electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, ..., An.
  • the charging and discharging processes of the positive electrode reaction of the lead-acid battery occur on the electrodes B1, B2, ..., Bn.
  • the second single positive and negative polarity inversion and the subsequent charging or charging and discharging operations of the lead-acid battery pack of the embodiment include the following steps: when the lead-acid battery pack of the embodiment is in the first single positive and negative During the polarity reversal and the subsequent cyclic operation after the charging or charging and discharging operation (during this period, the polarity of the output terminal A of the lead-acid battery pack is negative, and the polarity of the output terminal B is positive, that is, the electrode
  • the charging and discharging process of the lead electrode battery negative electrode reaction occurs on A1, A2, ..., An, and the charge and discharge process of the lead acid battery positive electrode reaction occurs on the electrodes B1, B2, ..., Bn
  • the second reverse polarity charging is performed on the lead-acid battery pack of the embodiment, and the manner of the reverse polarity charging includes Single phase, multiple phases, constant current (eg 0.2
  • the lead acid battery pack of the embodiment is charged or Charge, discharge, charge or charge and discharge methods include single stage, multi-stage, constant current (eg 0.18C 2 , 0.7C 2 , 2C 2 , 5C 2 ), constant voltage (eg 0.6U, 1.3U, 2.2U, 3U) And one or more of a positive pulse and a negative pulse, and then the lead acid battery pack of the embodiment is reintroduced into the cycle work by the polarity state after the polarity is reversed, and the cycle is performed.
  • constant current eg 0.18C 2 , 0.7C 2 , 2C 2 , 5C 2
  • constant voltage eg 0.6U, 1.3U, 2.2U, 3U
  • the lead-acid battery pack of the embodiment has a pole of the output terminal A of the lead-acid battery pack of the present embodiment during the cyclic operation performed after the second single positive and negative polarity reversal and subsequent charging or charging and discharging operations.
  • the polarity is positive, and the polarity of the output terminal B is negative, that is, the charging and discharging process of the positive electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, ..., An, and the electrodes B1, B2, .... .., Bn on the lead-acid battery negative electrode reaction charge and discharge process.
  • the method of performing other secondary positive and negative polarity inversions and subsequent charging or charging and discharging operations is performed and the first embodiment of the present embodiment is implemented or The second single positive and negative polar polarity reversal and subsequent charging or charging and discharging methods are similar.
  • the positive or negative polarity inversion described above and the subsequent charging or charging and discharging operations are performed repeatedly, repeatedly, and interspersed in the present embodiment.
  • the one or more of the problems of softening or/and shedding of the positive electrode active material of the lead-acid battery pack of the present embodiment electrode passivation, early capacity loss, corrosion, sulfation, specific surface area shrinkage of the negative electrode, and poor contact between the active material and the current collector.
  • the improved, repaired, reversed, eliminated, suppressed, and prevented are improved, so that the working discharge capacity and service life of the lead-acid battery pack of the embodiment are improved or prolonged.
  • the method for improving or prolonging the service life of the lead-acid battery pack of the embodiment is to improve, repair, reverse, solve, and prevent during the cyclic working process of the lead-acid battery pack of the embodiment.
  • Battery pack operation due to one or more of problems such as softening or/and shedding of the positive active material, electrode passivation, early capacity loss, corrosion, sulfation, specific surface area shrinkage of the negative electrode, and poor contact between the active material and the current collector
  • the capacity of the lead-acid battery pack of the present embodiment is multi-period and interspersed in an odd-numbered or even-numbered positive and negative polarity reversal and subsequent charging or charging and discharging operations to complete the odd-numbered times or After the polarity of the positive and negative polarities of the even number of times and the subsequent charging or charging and discharging operations, the lead acid battery pack of the present embodiment is reintroduced into the charging and discharging cycle by the polarity state after the polarity is reversed
  • the odd or negative polarity reverses and the subsequent charging or charging and discharging operations.
  • the positive or negative polarity inversion of each odd or even number of times and the positive or negative polarity inversion and subsequent charging or charging and discharging operations of the subsequent charging or charging and discharging operations are the same as those described in the present embodiment.
  • the first or second single positive and negative polarity inversion and subsequent charging or charging and discharging operations are similar.
  • the positive electrode, the negative electrode, or all of the electrodes of the lead-acid battery pack of the present embodiment are all common positive and negative electrode common electrodes, that is, manufacturing errors caused when manufacturing the electrodes are not considered, this embodiment All the electrodes of the lead-acid battery pack are identical to each other in terms of all electrode composition and manufacturing (such as electrode structure, shape, current collector, fluid pool, active substance formulation and quality, other accessories, manufacturing process, etc.). After being formed, the electrodes of the lead-acid battery pack of the present embodiment are respectively formed into a positive electrode or a negative electrode.
  • the positive, negative or all electrodes of the lead-acid battery pack of the present embodiment are positive and negative common electrodes equivalent to each other, that is, after the electrodes are formed or charged and discharged, in lead.
  • the electrodes of the present embodiment have or exhibit the same function and performance regardless of the error factor.
  • the lead-acid battery group of the embodiment the battery pack charge and discharge device for improving or prolonging the service life of the lead-acid battery pack, and the polarity reversal of the positive and negative poles for increasing or prolonging the service life of the lead-acid battery pack and the subsequent charging or charging and discharging operations
  • the lead-acid battery pack of the embodiment comprises two equivalent lead-acid battery cells A and B (equivalent battery means that all parameters of the A and B batteries are the same except for manufacturing errors, Similarly, the rated voltage of the battery pack is 2V, and the rated capacity is equal to the rated capacity of the single cells in the lead-acid battery pack.
  • Each of the single cells in the battery pack of the embodiment has independent input and output of positive and negative circuits. end.
  • the battery pack charge and discharge device of the present embodiment has the functions of performing charge or charge/discharge operation of the positive and negative polarity inversion of any one of the single-acid batteries of the lead-acid battery of the present embodiment.
  • the method for distinguishing the polarity of the positive and negative poles of the present embodiment and the charging or charging and discharging operations thereafter is as follows: the lead-acid battery pack of the embodiment is subjected to a charging and discharging cycle under the rated voltage, and the operation is performed in the battery pack of the embodiment.
  • the single battery A bears, and the single battery B is in a non-cyclic working state.
  • the discharge capacity is decreased (the reason is that the positive active material softens, falls off, or the negative surface area shrinks or When sulfating, the same as below) to 90% of the rated capacity of the battery pack, the battery unit A is stopped by the trigger and execution program set in the battery pack charger and discharger of the embodiment, and is transferred to the non-circulating working state.
  • the single battery A in the state separately performs the positive and negative polarity inversion of the battery and the subsequent charging or charging and discharging operations to restore the working capacity of the battery cell A. After the completion of the operation, the battery unit A is in a non-cyclic working state and is to be switched.
  • the battery pack of the embodiment After the battery pack of the embodiment is operated for a period of time based on the single battery B, when the battery pack of the embodiment, that is, the battery cell B performing the work task, has a discharge capacity lower than 90% of the rated capacity of the battery pack of the embodiment, In the battery pack charger/discharger of the embodiment, the triggering and executing program is set, the battery unit B in the circulating working state is stopped, and the battery in the non-cyclic working state is passed through the battery.
  • the battery cell A having the qualified working ability after the polarity polarity inversion and the subsequent charging or charging and discharging operation is switched to the cyclic working state, so that the battery pack of the embodiment can be continuously cycled based on the cell A, and then,
  • the battery cells B that have been transferred from the original cyclic working state to the non-cyclic working state individually perform the charging and charging or discharging operations of the positive and negative polarity of the battery and the subsequent charging or charging and discharging operations, so that the working capacity of the single battery B is restored to the qualified operation. Capability, after the operation is completed, the battery B is in a non-cyclic working state, and is to be switched.
  • the positive and negative polarities are reversed and the subsequent charging or charging and discharging operations are performed on the single cells A and B in turn, so that the service life of the lead-acid battery pack of the embodiment is significantly improved or prolonged, compared with ordinary lead.
  • the service life of the acid battery pack is increased or extended by more than one time.
  • the lead-acid battery group of the embodiment includes three equivalent lead-acid battery cells A, B, and C.
  • the rated voltage of the battery pack is 4V, and the rated capacity is equal to the rated capacity of the single-cell in the lead-acid battery pack.
  • Each of the battery cells in the battery pack has its own independent input and output circuits of the positive and negative circuits.
  • the circuit of this embodiment has the functions of performing charge or charge/discharge operation of the positive and negative polarity inversion of any one of the lead-acid battery packs of the embodiment.
  • the method for distinguishing the polarity of the positive and negative poles and the charging or charging and discharging operations of the present embodiment is as follows: the lead-acid battery pack of the embodiment is subjected to a charge and discharge cycle under the rated voltage, and the battery pack is operated during operation.
  • the single cells A and B are in the charging and discharging cycle working state, and undertake the charging and discharging cycle work task of the battery pack, the single battery C is in the non-charge and discharge cycle working state, and the battery pack performs the charging and discharging cycle based on the single cells A and B, when the battery
  • the cycle discharge capacity of the group is decreased (including the positive electrode active material softening, detachment or negative electrode surface area shrinkage or sulphation, the same applies below) to 80% of the rated capacity of the battery pack, the trigger has been set in the circuit of this embodiment.
  • the voltage and voltage drop during operation are determined by the trigger and execution procedures that have been set in the circuit of this embodiment.
  • the faster battery cell A switches from the cyclic working state to the non-cyclic working state, and after the charging or charging and discharging operation of the original positive and negative polarity reversed and the subsequent non-cyclic working state
  • the battery cell B with the qualified working ability is switched to the cyclic working state, so that the battery pack can continue to work cyclically based on the single cells B and C, and the battery cells A that are transferred from the original working state to the non-cyclic working state are separately subjected to the battery positive,
  • the polarity of the negative electrode is reversed and the subsequent charging or charging and discharging operations are performed to restore the working ability of the battery cell A to the qualified working capability.
  • the battery cell A is in a non-cyclic working state and is to be switched.
  • the single cell C When the battery pack operates based on the single cells B, C, and its circulating working discharge capacity drops to 80% of the rated capacity of the battery pack, the single cell C with a faster voltage drop during operation in the battery pack and the non-cyclic working state are
  • the single battery A performs the same operation as above, so that the battery pack is cycled again based on the single cells A and B, and the single cell C resumes the qualified operation after the battery positive and negative polarity inversion and subsequent charging or charging and discharging operations.
  • the switching between the cycle state and the non-circulation state of each of the cells in the lead-acid battery group can also be triggered by specifying the number of cycles of the battery pack or the battery cells.
  • the positive and negative polarity inversions and subsequent charging or charging and discharging operations are performed on the single cells A, B, and C in turn (not necessarily in order or average number of times), so that the lead acid battery pack of the present embodiment
  • the service life is significantly improved or extended, and the service life of the ordinary lead-acid battery pack is increased or extended by more than one time.
  • the lead-acid battery group of the embodiment, the battery pack charge and discharge device for improving or prolonging the service life of the lead-acid battery pack, and the polarity reversal of the positive and negative poles for increasing or prolonging the service life of the lead-acid battery pack and the subsequent charging or charging and discharging operations The method for distinguishing operation, wherein the lead-acid battery pack of the embodiment comprises 7 equivalent lead-acid battery cells A, B, C, D, E, F, G, and the rated voltage of the battery pack is 12V, and the rated capacity is equal to The rated capacity of the single cells in the lead-acid battery pack, each of the cells in the battery pack has independent input and output terminals of the positive and negative circuits.
  • the battery pack charge and discharge device of the present embodiment has the functions of performing charge or charge/discharge operation of the positive and negative polarity inversion of any one of the single-acid batteries of the lead-acid battery of the present embodiment.
  • the method for distinguishing the polarity of the positive and negative poles and the charging or charging and discharging operations of the present embodiment is as follows: the lead-acid battery pack of the embodiment is subjected to a charge and discharge cycle under the rated voltage, and the battery pack is operated during operation.
  • the single cells A, B, C, D, E, F are in a cyclic working state, and bear the task of the battery pack.
  • the battery cells G are in a non-cyclic working state, and the battery pack is based on the single cells A, B, C, D, E, F.
  • the triggering and execution procedures have been set in the battery pack charger and discharger of the present embodiment, and the positive active material is used in the battery pack.
  • the single battery B which has the largest capacity attenuation caused by softening and falling off switches its cycle working state to the non-cyclic working state, and switches the single-cell G with the qualified working ability originally in the non-cyclic working state to the cyclic working state.
  • the battery cells B are individually switched from the original cycle working state to the non-cyclic working state.
  • the polarity of the positive and negative poles is reversed and the subsequent charging or charging and discharging operations are performed to restore the working ability of the battery cell B to the qualified working capability. After the operation is completed, the battery cells B are in a non-cyclic working state and are to be switched.
  • the battery pack When the battery pack operates based on the single cells A, C, D, E, F, G, and its working discharge capacity drops to 75% of the rated capacity of the battery pack, it has been set by the battery pack charge and discharge device of this embodiment.
  • the triggering and execution procedure is to switch the working cycle state to the non-cyclic working state for the single cell E with the largest capacity attenuation caused by the softening and falling off of the positive active material in the battery pack, and to be in the non-cyclic working state.
  • the single battery B with qualified working ability is switched to the cyclic working state, so that the battery pack can continue to cycle according to the single cells A, B, C, D, F, G, and shift from the original circulating working state to the non-cyclic working state.
  • the single battery E separately performs the positive and negative polarity reversal of the battery and the subsequent charging or charging and discharging operations, so that the working ability of the single battery E is restored to the qualified working ability, and the battery pack can be working or the operation is performed. In other states in the cycle work, after the operation is completed, the battery cell E is in a non-cyclic working state, and is to be switched.
  • the battery pack When the battery pack is cycled based on the cells A, B, C, D, F, and G, and its working discharge capacity drops to 65% of the rated capacity of the battery pack, it is caused by softening and falling off of the positive electrode active material in the battery pack.
  • the single cell with the largest capacity attenuation and the single cell in the non-cyclic working state perform the same operation as above, so that the battery pack is charged and discharged again based on six cells with qualified working capacity, and the capacity attenuation is maximized.
  • the battery cells are restored to the qualified working capacity after the battery's positive and negative polarity inversion and subsequent charging or charging and discharging operations, and are in a non-cyclic working state, to be switched.
  • the positive and negative polarity inversions and subsequent charging or charging and discharging of the single cells A, B, C, D, E, F or G are carried out alternately (not necessarily in order or average number of times).
  • the service life of the lead-acid battery pack of the present embodiment is significantly improved or prolonged, and the service life of the ordinary lead-acid battery pack is increased or extended by more than one time.
  • the lead-acid battery group of the embodiment includes 12 equivalent lead-acid battery cells A, B, C, D, E, F, G, H, I, J, k, L, and the battery pack is rated.
  • the voltage is 12V, and the rated capacity is equal to the rated capacity of the single battery in the lead-acid battery pack, 20Ah (2h rate, 25°C).
  • Each battery cell in the battery pack has independent input and output terminals of the positive and negative circuits.
  • the circuit of the present embodiment has the functions of performing charge or charge/discharge operation of the positive and negative polarity inversion of any one of the lead-acid battery packs of the present embodiment.
  • the positive and negative polarity inversion and the subsequent charging or charging and discharging operations are differentiated as follows: the lead-acid battery pack of the embodiment is subjected to a charging and discharging cycle at a rated voltage, and the battery pack is operated during the cycle.
  • the single cells A, B, C, D, E, F are in a cyclic working state, and the single cells G, H, I, J, k, L are in a non-cyclic working state, and the battery pack is based on the single cells A, B, C, D, E, F perform cyclic operation.
  • the triggering and execution procedures have been set in the circuit of the embodiment, and the softening of the positive active material in the battery pack is performed.
  • the single battery B that has fallen off and has a heavy capacity attenuation stops its operation and switches from the cyclic working state to the non-cyclic working state, and switches the single-cell G with the qualified working ability that was originally in the non-cyclic working state to the cyclic working state.
  • the battery positive and negative polarity reversal is performed separately for the battery cells B that are switched from the original cycle working state to the non-cyclic working state. and The charge or charge and discharge operation, so that the working capacity of the unit cell B is qualified to restore the ability of this operation is completed, so that the cell cycle in a non-operating state B, to be switched.
  • the trigger has been set in the circuit of this embodiment.
  • the execution program for the single cells C and D with large capacity attenuation to stop working and switch from the circulating working state to the non-cyclic working state, and the single cells H and I with the qualified working ability which were originally in the non-cyclic working state.
  • the cells C, D that are transferred from the original cycle working state to the non-cyclic working state are separately Performing charging or charging and discharging operations of the positive and negative polarity of the battery and subsequent charging, so that the working ability of the single cells C and D is restored to the qualified working ability.
  • the cells C and D are in a non-circulating manner. Working status, to be switched.
  • the cells A and E having a large capacity attenuation in the battery pack , F, G, and the cells B, C, D, and J in a non-cyclic working state perform the same operation as above, so that the battery pack can be cycled based on six single cells with qualified working ability, and the capacity attenuation is large.
  • the battery cells are restored to the qualified working capacity after the battery's positive and negative polarity inversion and subsequent charging or charging and discharging operations, and are in a non-cyclic working state, to be switched.
  • the switching between the circulating working state and the non-cyclic working state of each of the single cells in the lead-acid battery group can be realized by instantaneous switching.
  • one or more of the single cells A, B, C, D, E, F, G, H, I, J, K, L are taken simultaneously (not necessarily in order or average number of times)
  • the positive and negative polarities of the battery and the subsequent charging or charging and discharging operations make the service life of the lead-acid battery pack of the present embodiment significantly improved or prolonged, and the service life of the ordinary lead-acid battery pack is increased or extended by one time. the above.
  • the battery pack charge and discharge device, the lead-acid battery pack, and the positive or negative polarity reversal and the subsequent charging or charging and discharging operations of the lead-acid battery pack are improved or prolonged.
  • the method for distinguishing the operation, wherein the battery pack charge and discharge device of this embodiment is the same as that of the embodiment 16 of the present invention.
  • the lead-acid battery pack of the embodiment comprises 6 equivalent lead-acid battery cells A, B, C, D, E, F, and the rated voltage of the battery pack is 12V, and the rated capacity is equal to the single battery in the lead-acid battery group.
  • Rated capacity, 12Ah (2h rate, 25°C) each cell in the battery pack has its own independent input and output circuits for the positive and negative circuits.
  • the lead-acid battery pack of the embodiment is subjected to the charging and discharging cycle at the rated voltage, when the battery pack of the embodiment
  • the discharge capacity is decreased (including the positive electrode active material softening, detachment or negative electrode surface area shrinkage or sulfation, the same applies hereinafter) to 75% of the rated capacity of the battery pack, the trigger has been set in the battery pack charge and discharge device of this embodiment.
  • the method for improving or prolonging the service life of a lead-acid battery or a battery pack according to the embodiment includes the total cumulative number of lead-acid batteries or battery packs of the present embodiment being interspersed during the floating charging operation of the lead-acid battery or the battery pack.
  • Positive or negative polarity inversion and subsequent charging or charging and discharging operations described in the same or similar to all of the above embodiments of the present invention ie, Example 1 to Example 20
  • the method for forming a lead-acid battery or a battery pack according to the present embodiment includes using the same or similar polarity inversion as described in Embodiments 1 to 20 of the present invention and the subsequent charging or charging and discharging operation method.
  • the lead-acid battery or battery pack of the embodiment was formed.
  • the method for forming a lead-acid battery or a battery pack according to the embodiment further includes performing symmetric polarity inversion on the lead-acid battery or the battery pack and subsequent charging or charging and discharging operations, that is, the lead-acid battery in the embodiment.
  • all the electrodes (including the initial positive electrode and the negative electrode) of the lead-acid battery or the battery pack of the present embodiment are subjected to at least one formation of the positive electrode and one time as the formation of the negative electrode.
  • the method for forming a lead-acid battery or a battery pack improves the initial capacity of the lead-acid battery or the battery pack, and has a certain improvement effect on the softening of the active material caused by the chemical formation, and at the same time, ensures positive and negative effects.
  • the cycle charge and discharge performance of a lead-acid battery or battery pack of a very common electrode which is repeatedly applied during the cyclic charging and discharging operation, and which is subjected to polarity reversal and subsequent charging or charging and discharging operations, is reversed in each polarity. Relative before and after the transfer.
  • the chemical conversion method of the present embodiment is implemented in the formation of a tubular lead-acid battery, including: in a normal chemical conversion process (charge and discharge of the battery in a positive connection state, a positive connection state, that is, a charge and discharge device) Before the positive output terminal is connected to the positive electrode of the battery, that is, the tubular electrode A, and the negative output terminal of the charging and discharging device is connected to the negative electrode of the battery, that is, the plate electrode B), the reverse charging of the tubular lead-acid battery of the present embodiment is performed once.
  • a normal chemical conversion process charge and discharge of the battery in a positive connection state, a positive connection state, that is, a charge and discharge device
  • the reverse charging of the tubular lead-acid battery of the present embodiment is performed once.
  • the battery In the reverse connection state, the battery is charged and discharged, and the reverse connection state, that is, the positive output end of the charging and discharging device is connected to the negative electrode of the battery, that is, the plate electrode B, and the negative output end of the charging and discharging device is connected to the positive electrode of the battery, that is, the tubular electrode A)
  • the amount of charge charged by the reverse polarity is 5-10% of the normalization process, and then the tubular lead-acid battery of the embodiment is transferred to a normalization process to be formed.
  • the initial capacity of the tubular lead-acid battery in which the reverse polarity charging formation and the normalizing process are performed in this embodiment is relatively 10-20% higher.

Abstract

本发明公开了一种提高或延长铅酸蓄电池或电池组使用寿命的方法,包括,将铅酸蓄电池或电池组的正、负极进行极性反转及其后的充电或充放电操作,该操作进行或被进行的总累计次数为≥1次。本发明所公开的方法可显著提高或延长铅酸蓄电池或电池组的使用寿命。

Description

提高或延长铅酸蓄电池或电池组使用寿命的方法 技术领域
本发明涉及提高或延长蓄电池或蓄电池组的使用寿命,特别是涉及一种提高或延长铅酸蓄电池或电池组的使用寿命的方法。
背景技术
铅酸蓄电池或电池组由于制造成本低、性/价比高、安全、稳定、可回收,多年来应用广泛,并在二次电池市场销售份额中占有首席地位。然而在性能上,铅酸蓄电池或电池组表现出比能量低、使用寿命较短的不足,目前,应用中的铅酸蓄电池或电池组的比能量约为20-40Wh/kg,循环寿命约为150-1500次,浮充寿命约为5-20年。影响铅酸蓄电池或电池组使用寿命的因素很多,内部因素如活性物质组成、晶型、孔隙率、极板类型和尺寸、板栅材料和结构、隔板类型和性能、装配压力、电解液类型和配方、酸密度、杂质、电池一致性等,外部因素如放电深度、放电电流密度、充电电流密度、过充电、欠充电、温度、机械震动、受力变形情况等,归纳起来,主要的、常见的导致铅酸蓄电池或电池组使用寿命终止的电池或电池组失效模式有板栅腐蚀、正极活性物质软化脱落、硫酸盐化、失水、早期容量损失、电极钝化、负极表面积收缩、电池一致性差等。根据这些因素和失效模式,人们已经发展出了多种提高或延长铅酸蓄电池或电池组的使用寿命的方法、材料、设备、设施、配件等,并使得铅酸蓄电池或电池组的使用寿命获得了一定程度的提高或延长。然而,另一方面,社会的运行和发展仍需要铅酸蓄电池或电池组的使用寿命在现有的水平上有进一步地、甚至显著地提高或延长。
发明内容
本发明要解决的技术问题是提供一种提高或延长铅酸蓄电池或电池组的使用寿命的方法,所述方法尤其是通过解决或改善铅酸蓄电池或电池组的正极活性物质软化或/和脱落、负极比表面积收缩、腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与导电集流体接触不良其中的一种或多种问题,来提高或延长铅酸蓄电池或电池组的使用寿命。
所述使用寿命包括但不限于循环寿命、浮充寿命中的一种或多种。
所述铅酸蓄电池或电池组,即,铅酸蓄电池或铅酸蓄电池组。
为解决上述技术问题,本发明所提供的提高或延长铅酸蓄电池或电池组的使用寿命的方法包括:将铅酸蓄电池或/和铅酸蓄电池组的正极、负极进行极性反转及其后的充电或充放电操作(以下也简称为极性反转及其后的充电或充放电操作),该操作进行或被进行的总累计次数为1次以上(包括1次,以下同),所述将正极、负极进行极性反转及其后的充电或充放电操作,即,将正电极、负电极进行极性反转,并在该极性反转后,将经过该极性反转的电极进行充电或充放电操作。所述总累计次数是指,所述铅酸蓄电池或电池组在其存在的整个期间或所述铅酸蓄电池或电池组在其使用寿命终止前和使用寿命终止后的整个期间,所有发生在所述铅酸蓄电池或电池组身上的总共的、总累计 的所述正极、负极极性反转或极性反转及其后的充电或充放电操作的次数。各次所述正极、负极极性反转及其后的充电或充放电操作彼此之间可以连续进行、不连续进行,或者部分连续进行、部分不连续进行。
所述铅酸蓄电池或电池组正极或负极的极性包括,铅酸蓄电池或电池组的电极的正性(正极性质)或负性(负极性质),电极的正性特征一般包括,在该电极上发生的电极反应是正极电极反应、电极电位相较为高,电极的负性特征一般包括,在该电极上发生的电极反应是负极电极反应、电极电位相较为低。所述极性反转是指,原来正性电极的极性由正性变成负性或/和原来负性电极的极性由负性变成正性。
所述将经过极性反转的电极进行充电或充放电操作,即,将极性反转前为正极而极性反转后为负极的电极作为负极进行充电或充放电操作、将极性反转前为负极而极性反转后为正极的电极作为正极进行充电或充放电操作,前者使电极上发生铅酸蓄电池负极电极反应,后者使电极上发生铅酸蓄电池正极电极反应。
以将铅酸蓄电池或电池组的正极、负极进行第一次、第二次极性反转及其后的充电或充放电操作的过程为例,对所述正、负极极性反转及其后的充电或充放电操作作进一步地说明,为方便说明,以原来的正极(在此也标记为电极A)、原来的负极(在此也标记为电极B)来称呼,没有被进行过任何所述正极、负极极性反转及其后的充电或充放电操作时的所述铅酸蓄电池或电池组的正极、负极,如此,当将铅酸蓄电池或电池组的正极、负极进行第一次极性反转及其后的充电或充放电操作时,操作步骤包括,首先,将铅酸蓄电池或电池组的正电极、负电极进行极性反转,即,使铅酸蓄电池或电池组原来的的正极(电极A)的极性由正被反转成负,原来的负极(电极B)的极性由负被反转成正,然后在该次极性反转后,将经过该次极性反转的电极进行充电或充放电操作,即,将原来的正极(电极A)作为负极、将原来的负极(电极B)作为正极,对该次极性反转后的铅酸蓄电池或电池组进行充电或充放电操作,整个过程从该次极性反转操作到该次极性反转之后的充电或充放电操作完成,即为1次极性反转及其后的充电或充放电操作(此时,即完成了该铅酸蓄电池或电池组的第一次极性反转及其后的充电或充放电操作),该次所述正极、负极的极性反转及其后的充电或充放电操作所实现的包括,对于原来的正极(电极A),其电极电位由相较为高被转变成相较为低、其所发生的电极反应由原来的铅酸蓄电池正极电极反应被反转成铅酸蓄电池负极电极反应,对于原来的负极(电极B),变化相反。
可以知道,在上述1次极性反转及其后的充电或充放电操作基础上,再进行1次极性反转及其后的充电或充放电操作(此亦为该铅酸蓄电池或电池组的第二次极性反转及其后的充电或充放电操作),则在后一次(第二次)的极性反转后的充电或充放电操作过程中,被充电或充放电的正性电极则是铅酸蓄电池或电池组原来的正极(电极A),被充电或充放电的负性电极则是铅酸蓄电池或电池组原来的负极(电极B),该次(第二次)所述正极、负极的极性反转及其后的充电或充放电操作所实现的包括,对于原来的正极(电极A),其电极电位由相较为低被转变成相较为高、其所发生的电 极反应由原来的铅酸蓄电池负极电极反应被反转成铅酸蓄电池正极电极反应,对于原来的负极(电极B),变化相反。这样,对于原来的正极(电极A)、原来的负极(电极B)一共进行了2次(即第一次、第二次)极性反转及其后的充电或充放电操作。
3次或大于3次的极性反转及其后的充电或充放电操作,可在上述2次(第一次、第二次)极性反转及其后的充电或充放电操作的基础上再次或再多次进行类同第一次或第一次、第二次极性反转及其后的充电或充放电操作而实现,可根据上述2次(第一次、第二次)极性反转及其后的充电或充放电操作类推理解、实施。
所述极性反转及其后的充电或充放电操作中,所述极性反转在电极上实际发生时是较快完成的,时间较短,且,在极性反转的临界处,电极的极性从临界的这一端极性变化到临界的另一端极性,只需较少的电量,或者,当通过该较少的电量,使电极的极性从临界的这一端极性变化到临界的另一端极性,极性反转即为完成,因此,由于涉及的电量少,所述极性反转在改变电极构成、性能等方面的影响一般也比较小或可以忽略,严格来讲,所述极性反转在概念上和实际上都主要是指一种极性状态上的变化,而所述极性反转及其后的充电或充放电操作中,使电极的构成、性能等发生明显变化的,主要是与极性反转后的充电或充放电操作过程有重要关系。
所述极性反转及其后的充电或充放电操作,包括将铅酸蓄电池或/和铅酸蓄电池组的电极进行极性反转,并在该极性反转后,使经过该极性反转的电极进行如下电化学反应:使该极性反转前为正极的电极在该极性反转后进行铅酸蓄电池负极电极反应、使该极性反转前为正极的电极其所含有的铅氧化物、碱式硫酸铅、硫酸铅在该极性反转后进行电化学还原反应、使该极性反转前为负极的电极在该极性反转后进行铅酸蓄电池正极电极反应,其中的一种或多种。
所述极性反转及其后的充电或充放电操中的电流包括直流电流、脉冲电流、或脉冲与直流的复合电流。
所述极性反转及其后的充电或充放电操作中,任意一次极性反转后的充电操作次数为1次以上(包括1次,以下同)。
所述将铅酸蓄电池或电池组的正、负极进行极性反转及其后的充电或充放电操作包括,使所述正极、负极极性反转及其后的充电或充放电操作与所述铅酸蓄电池或电池组的工作,彼此穿插、交替地进行,并使所述铅酸蓄电池或电池组在工作时,其原来的正极、原来的负极处于以下三种电极工作状态中的一种:(1)原来的正极始终作为正极进行工作,原来的负极始终作为负极进行工作;(2)原来的正极始终作为负极进行工作,原来的负极始终作为正极进行工作;(3)原来的正极有时作为正极进行工作、有时作为负极进行工作,相应地,原来的负极有时作为负极进行工作、有时作为正极进行工作;所述其原来的正极、原来的负极为,在没有被进行过任何所述正极、负极极性反转及其后的充电或充放电操作时,所述铅酸蓄电池或电池组的正极、负极。
在上述第(1)、(2)、(3)中任一工作状态下,所述铅酸蓄电池或铅酸电池组在其任意两次的工作之间的所述正极、负极的极性反转及其后的充电或充放电操作次数为0次以上(包括0次,以下 同)。
所述将铅酸蓄电池或电池组的正、负极进行极性反转及其后的充电或充放电操作包括:进行连续两次或连续偶数次的正、负极极性反转及其后的充电或充放电操作、进行单次或连续奇数次的正、负极极性反转及其后的充电或充放电操作,其中的一种或多种。
针对铅酸蓄电池组,所述将正极、负极进行极性反转及其后的充电或充放电操作包括,仅对电池组中的某一个单电池单独地进行所述正、负极极性反转及其后的充电或充放电操作,或者仅对电池组中的某些(即两个或两个以上)单电池进行所述正、负极极性反转及其后的充电或充放电操作,此皆简称为区分操作。所述单电池,即,单体电池。
所述将正、负极进行极性反转及其后的充电或充放电操作包括进行脉冲充电或/和放电的操作;所述脉冲充电或/和放电包括正脉冲、负脉冲、正负脉冲混合脉冲充电或/和放电操作中的一种或多种。
出于工作目标和要求、工艺、安全、等的需要,所述将正极、负极进行极性反转及其后的充电或充放电操作可以在铅酸蓄电池或电池组的任何荷电或工作状态(包括工作前、工作中、工作后、静置)下直接启动、开始并进行,也可在所述极性反转及其后的充电或充放电操作之前先对铅酸蓄电池或电池组进行放电或/和充电操作(以下简称极性反转前的放电或/和充电操作),然后再启动、开始并进行所述极性反转及其后的充电或充放电操作。后一种情况包括,在极性反转前,对电池或电池组进行放电操作直到电压降低为0V或0V上下,然后再进行极性反转。
所述铅酸蓄电池或电池组的极性反转、极性反转及其后的充电或充放电操作、极性反转前的放电或/和充电操作、区分操作可通过编程执行。
所述铅酸蓄电池或电池组的正极、负极进行极性反转、极性反转后的充电或充放电操作或极性反转前的放电或/和充电操作可以根据某物理量值、数量值、化学量值以及它们的变化值、计算值中的一种或多种的设置、测量、信号采集、计算等结果而开始或停止或不动作。所述的物理量值包括电压值、电流值、电流密度值、电量值、容量值、功率值、时间值、温度值、力值、压强值、密度值、光度值、频率值中的一种或多种;所述的数量值包括累计数值、奇数值、偶数值、比例值、电池或/和电池组的充放循环次数值中的一种或多种;所述的化学量值包括电池或/和电池组的酸度值。所述的物理量值、数量值、化学量值包括电池或/和电池组在充电过程中、放电过程中、循环工作过程中、浮充工作过程中、开路或静置状态中的物理量值、数量值、化学量值以及其它与铅酸蓄电池或/和铅酸蓄电池组相关的物理量值、数量值、化学量值。
所述将经过极性反转的电极进行充电或充放电操作,其中,所述充电或充放电的电量一般为该电极额定容量的0.5倍以上。
所述将铅酸蓄电池或电池组的正、负极进行极性反转及其后的充电或充放电操作,其特征还在于,进行或被进行所述正、负极极性反转及其后的充电或充放电操作的铅酸蓄电池或电池组其正极和负极均为正负极通用电极(即,正极、负极通用的电极),所述正负极通用电极,在所述铅酸蓄电池或电池组中,既可作为正极使用、也可作为负极使用,或者某些作为正极使用、某些作为负极使 用,或者在所述铅酸蓄电池或电池组工作或使用过程中,某时作为正极使用、某时又作为负极使用,其中的一种或多种;构成铅酸蓄电池或电池组的正极和负极时,所述正负极通用电极包括但不限于,彼此具有相同活性物质或相同活性物质配方的正负极通用电极、彼此等价的正负极通用电极、彼此为同一种的正负极通用电极;所述彼此等价是指,电极在被化成或充放电后,彼此在铅酸蓄电池或电池组的工作或使用过程中,不考虑误差因素的情况下,具有或表现出相同的功能和性能;所述同一种的正负极通用电极是指那些在被进行化成或充放电之前彼此相同、在被进行化成或充放电之后可形成正极或负极的正负极通用电极,所述被进行化成或充放电之前彼此相同是指,不考虑制造电极时产生的制造误差,在被进行化成或充放电操作之前,两个或多个电极彼此在所有电极构成、制造方面(如电极结构、造形、尺寸、配方、材料、制做工艺等)完全相同。
所述将铅酸蓄电池或电池组的正、负极进行极性反转及其后的充电或充放电操作可以通过一种电路自动地或/和手动地实现,所述电路具有所述将铅酸蓄电池或/和铅酸蓄电池组的正极与负极进行极性反转或极性反转及其后的充电或充放电操作的功能,所述电路能够或实际上将铅酸蓄电池或/和铅酸蓄电池组的正极、负极进行极性反转或极性反转及其后的充电或充放电操作的总累计次数≥1次。
所述电路实现或实施对铅酸蓄电池或/和铅酸蓄电池组进行所述正极、负极极性反转或极性反转及其后的充电或充放电操作的方法包括:对所述铅酸蓄电池或电池组进行反极充电。
所述电路实现对铅酸蓄电池或/和铅酸蓄电池组进行反极充电的方法包括,通过连接于所述铅酸蓄电池或电池组电极上的所述电路输出端的极性反转及该极性反转后的对所述铅酸蓄电池或电池组进行的充电或充放电操作,来实现所述铅酸蓄电池或电池组的正、负极极性反转或极性反转及其后的充电或充放电操作。
所述将铅酸蓄电池或电池组的正、负极进行极性反转及其后的充电或充放电操作,其特征还在于,可以通过自动或/和手动或手动开关的方式,启动、停止或暂停所述电路的功能,使所述电路开始、停止或暂停对铅酸蓄电池或/和铅酸蓄电池组进行正、负极极性反转或极性反转及其后的充电或充放电操作。
本发明的提高或延长铅酸蓄电池或/和铅酸蓄电池组使用寿命的方法或所述将铅酸蓄电池或/和铅酸蓄电池组的正极、负极进行极性反转及其后的充电或充放电操作方法所应用于的铅酸蓄电池或/和铅酸蓄电池组,包括平面板栅式、管式、卷绕式、双极式、水平铅布式、泡沫板栅式、柱式、具有稳定空隙体电极式铅酸蓄电池或电池组,还包括阀控式密封铅酸蓄电池或蓄电池组、胶体铅酸蓄电池或蓄电池组、铅碳电池蓄电池或蓄电池组、超级电容器-铅酸蓄电池(简称超级电池)蓄电池或蓄电池组,以及这些类型的铅酸蓄电池混合连接而成的混合型的铅酸蓄电池组,以及其它各种类型的铅酸蓄电池或电池组。
本发明提高或延长铅酸蓄电池或电池组使用寿命的方法可应用于铅酸蓄电池或电池组、铅酸蓄电池或电池组的电路或充放电设备、铅酸蓄电池或电池组的修复、再生或生产制造时的化成工艺。
本发明还提供了一种将极性反转及其后的充电或充放电操作应用于铅酸蓄电池或电池组制造过程中的化成方法,包括将铅酸蓄电池或/和铅酸蓄电池组的正极、负极进行极性反转及其后的充电或充放电操作,该操作进行或被进行的次数为1次以上。
所述化成方法中的极性反转及其后的充电或充放电操作可具有的其它特征,包括:电流,操作进行前铅酸蓄电池或电池组的荷电或工作状态,极性反转前的放电或/和充电操作、极性反转、极性反转后的充电或充放电操作开始或停止所根据的某物理量值、数量值、化学量值以及它们的变化值、计算值中的一种或多种的测量结果,极性反转前的放电或/和充电操作、极性反转、极性反转及其后的充电或充放电操作、区分操作可通过编程执行等,与本发明前面阐述的极性反转及其后的充电或充放电操作的相同。
本发明所提供的提高或延长铅酸蓄电池或电池组使用寿命的方法,还包括使所述铅酸蓄电池或/和铅酸蓄电池组的电极发生极性反转,并在该极性反转后,使经过该极性反转的电极进行如下电化学反应:使该极性反转前为正极的电极在该极性反转后进行铅酸蓄电池负极电极反应、使该极性反转前为正极的电极其所含有的铅氧化物、碱式硫酸铅、硫酸铅在该极性反转后进行电化学还原反应、使该极性反转前为负极的电极在该极性反转后进行铅酸蓄电池正极电极反应,其中的一种或多种,其特征还在于,该方法实施于所述铅酸蓄电池或/和铅酸蓄电池组的总累计次数为≥1次,该方法包括所述将铅酸蓄电池或/和铅酸蓄电池组的正极、负极进行极性反转及其后的充电或充放电操作,且使该操作的总累计次数为≥1次,所述将正极、负极进行极性反转及其后的充电或充放电操作,即,将正电极、负电极进行极性反转,并在该极性反转后,将经过该极性反转的电极进行充电或充放电操作。
有益效果
Figure PCTCN2018078612-appb-000001
可见,正极、负极放电后的反应产物均为PbSO 4,产物PbSO 4经充电后又分别转化成正极活性物质PbO 2和负极活性物质Pb;将铅酸蓄电池原来的正极作为负极,原来的负极作为正极,对电池进行充电操作,使原来的正极上发生负极电极反应,原来的负极上发生正极电极反应,则原来正极的放电产物PbSO 4可以转化成负极活性物质Pb,同样,原来的负极的放电产物PbSO 4可以转化成正极活性物质PbO 2,即正、负极的极性可以反转,由于电极反应式(1)、(2)中的电极反应是可逆的,因此,铅酸蓄电池原来的正极与原来的负极之间的极性反转也是可逆的。另外,将铅酸蓄电池原来的正极作为负极,原来的负极作为正极,对电池进行充电操作,甚至可能会导致原来的正极上的PbO 2直接向Pb转化、原来的负极上的Pb直接向PbO 2转化,因而也完成铅酸蓄电池原来的正极与原来的 负极之间的可逆的极性反转。
又已知铅酸蓄电池在充放电时正极、负极的一个特点是,随着充放电反复次数的增加,正极电极上的活性物质PbO 2颗粒之间的结合逐渐松弛、彼此脱离,使得正极活性物质膨胀、疏松、软化、脱落;随着充放电反复次数的增加,负极电极上的活性物质Pb颗粒之间倾向于表现为彼此结合,使得负极比表面积收缩、板结。当使铅酸蓄电池原来的正极、原来的负极的极性发生反转,并通过该极性反转后的充电或充放电操作,使原来的正极上发生铅酸蓄电池负极电极反应的充电或充放电过程、使原来的负极上发生铅酸蓄电池正极电极反应的充电或充放电过程,则铅酸蓄电池原来的正极上活性物质PbO 2颗粒软化、脱落所导致的活性物质颗粒之间的脱离就可以通过所述铅酸蓄电池负极电极反应而获得逆转,同样,铅酸蓄电池原来的负极上活性物质Pb颗粒彼此结合所导致的活性物质比表面积收缩就可以通过所述铅酸蓄电池正极电极反应也获得逆转,即铅酸蓄电池正极活性物质的软化、脱落效应、负极的比表面积收缩效应,可以通过电极反应(1)、(2)实现可逆或彼此逆转,或者说,将铅酸蓄电池的正极、负极进行极性反转及其后的充电或充放电操作,可以逆转或改善铅酸蓄电池正极活性物质的软化或/和脱落、负极的比表面积收缩。
根据上述铅酸蓄电池的两个可逆性特点,通过本发明的极性反转及其后的充电或充放电操作、选择合适的充放电制度(不同的充放电制度通过电极反应对于电极或电极活性物质的物理及化学的结构、性质等产生的影响、改变作用有差异,时效、能效也有差异),借助或不借助添加剂等调节手段,使正极电极反应导致的活性物质颗粒彼此脱离与负极电极反应导致的活性物质颗粒彼此结合,发生逆转或相互抵消,可以大大改善甚至消除铅酸蓄电池的正极活性物质软化或/和脱落、负极比表面积收缩问题,从而显著提高铅酸蓄电池的使用寿命。理论上,如果能解决掉铅酸蓄电池或电池组的正极活性物质软化或/和脱落、负极比表面积收缩、以及除正极活性物质软化或/和脱落、负极比表面积收缩的失效模式以外且目前已知的其它失效模式造成的电池或电池组的使用寿命终止的问题,则铅酸蓄电池及铅酸蓄电池组的使用寿命甚至有可能趋向于无限长或极长。
另外,本发明的极性反转及其后的充电或充放电操作,也可以使电极/汇流体/集流体腐蚀、早期容量损失、电极钝化、活性物质与集流体接触不良等问题得到改善、修复、消除、逆转、抑制、防止,增强电池抵抗过充电损害的能力、取代或降低对电池过充电的需要而避免或减少因过充电而引起的电池失水,操作中电极电位、及电极环境条件的变化,也会对硫酸盐化具有消除、逆转或改善、修复作用,增强电池抵抗欠充电、过放电损害的能力,从而也有利于明显提高铅酸蓄电池及电池组的使用寿命。
本发明的正、负极极性反转及其后的充电或充放电操作也有利于通过电化学反应过程而解决铅酸蓄电池在充放电或使用过程中发生的电极活性物质与电极集流体脱离、接触不良的问题。
对铅酸蓄电池组中的单电池进行区分操作,即对电池组中的各单电池、某些单电池单独地进行本发明的正、负极极性反转及其后的充电或充放电操作,有利于提高或延长电池组中单电池的使用寿命,维护、调整电池组中单电池间彼此容量的一致性,从而以较低的成本提高铅酸蓄电池组的使 用寿命。
铅酸蓄电池或铅酸电池组,当其正极与负极为正极、负极通用的电极时,其生产和回收具有较高效率、较低成本的特点,而对其进行本发明的极性反转及其后的充电或和放电操作的可以提高或延长其使用寿命,使其正极、负极通用的电极的技术方案得以实施,使其具有实用性。
通过电路实施本发明的极性反转及其后的充电或充放电操作有利于提高或实现操作的效率、准确性、方便性、实用性、有效性、可行性等。
本发明的正、负极极性反转及其后的充电或充放电操作,也有助于解决(包括修复、逆转、消除、抑制、防止)或改善其它铅酸蓄电池中与化学或电化学反应过程相关的、影响铅酸蓄电池使用寿命的问题。
综上所述,将本发明的方法应用于铅酸蓄电池或电池组,能显著提高或延长铅酸蓄电池或电池组的使用寿命。
此外,本发明的正、负极极性反转及其后的充电或充放电操作应用于化成工艺时,有利于缓解或避免传统铅酸蓄电池化成工艺中的过充工艺对铅酸蓄电池或电池组的寿命的负面影响、提高铅酸蓄电池的活性物质利用率从而电池或电池组的初始容量、保证了具有正负极通用电极的、在循环充放电工作过程中多次、穿插地进行极性反转及其后的充电或充放电操作的铅酸蓄电池或电池组的循环充放电工作性能在各次极性反转前和后相对称。本发明的正、负极极性反转及其后的充电或充放电操作也有助于提高铅酸蓄电池或电池组在循环工作过程中的活性物质利用率从而电池或电池组使用过程中的容量。
附图说明
图1是本发明实施例6铅酸蓄电池循环充放电工作的工作放电容量及工作放电终止电压数据图。
图2是本发明实施例7铅酸蓄电池循环充放电工作的工作放电容量及工作放电终止电压数据图。
图3是本发明实施例7铅酸蓄电池在其第189-196次循环充放电工作过程期间及该过程期间穿插的第十一、第十二次正、负极性反转及其后的充电或充放电操作过程中的电流、电压数据图。
图4是本发明实施例8铅酸蓄电池循环充放电工作的工作放电容量及工作放电终止电压数据图。
图5是本发明实施例9正、负极性反转及其后的充电或充放电操作在管式铅酸蓄电池循环充放电工作过程中穿插进行的示意图。
图6是本发明实施例9铅酸蓄电池循环充放电工作的工作放电容量及工作放电终止电压数据图。
图7是本发明实施例11正负极通用电极的电极集流体结构平面示意图。
图8是本发明实施例11铅酸蓄电池循环充放电工作的工作放电容量及工作放电终止电压数据图。
图9是本发明实施例12铅酸蓄电池循环充放电工作的工作放电容量及工作放电终止电压数据图。
图10是本发明实施例13铅酸蓄电池循环充放电工作的工作放电容量及工作放电终止电压数据 图。
图11是本发明实施例14铅酸蓄电池组循环充放电工作的工作放电容量及工作放电终止电压数据图。
图12是本发明实施例14铅酸蓄电池组在其第23-28次循环充放电工作过程期间及该过程期间穿插的单次正、负极极性反转及其后的充电或充放电操作过程中的电流、电压数据图。
图中附图标记说明如下:
1:极耳
2:集流体边框
3:栅格薄板
4:圆孔
W1:管式铅酸蓄电池总累计第1-304次循环充放电工作。
W2:管式铅酸蓄电池总累计第305-652次循环充放电工作。
W3:管式铅酸蓄电池总累计第653-751次循环充放电工作。
W4:管式铅酸蓄电池总累计第752-774次循环充放电工作。
R1:管式铅酸蓄电池的第一期连续两次正、负极极性反转及其后的充电或充放电操作。
R2:管式铅酸蓄电池的第二期连续两次正、负极极性反转及其后的充电或充放电操作。
R3:管式铅酸蓄电池的第三期连续两次正、负极极性反转及其后的充电或充放电操作。
具体实施方式
以下结合具体实施例,对本发明的技术内容、特点和功效作进一步详细说明。
实施例1
本实施例的铅酸蓄电池为平面板栅式铅酸蓄电池,额定容量为2.32Ah(2h率,25℃),额定电压为2V,其循环充放电工作(简称循环工作,以下同)制度为:以0.2倍率(额定容量的,以下同)电流恒流充电,当电压达到2.65V后,以2.65V恒压充电,两次充电总时间为6小时24分,然后以2h率、80%DOD(放电深度)放电后,再重复进行上述的充、放电过程,即通过上述的充放电循环进行工作,工作环境温度为25±1℃。本实施例电池循环充放电工作和极性反转及其后的充电或充放电操作过程中,排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
当本实施例的铅酸蓄电池剩余容量(电池按工作放电制度可以放出的电量,以下同)为其额定容量的7.3%时(经检查为正极活性物质软化、脱落导致本实施例电池放电容量衰减),开始对其进行本发明的正、负极极性反转及其后的充电或充放电操作(为使陈述清楚,将本实施例铅酸蓄电池的正极、负极依次命名为电极群A、电极群B,以下同),包括以下步骤:
1)放电和第1次极性反转:停止电池的工作(此时电池处于工作中的恒压充电阶段),利用一充放电设备,以0.5倍率的电流(1164mA)对本实施例铅酸蓄电池进行强制放电,使电池电压从电 池停止工作时的2.65V下降一直降到0V,并最后下降到-0.073V,停止放电,然后静置30min(分钟,以下同),进行下一步;
2)第1次极性反转后变换电极连接:人工操作,使充放电设备的正极与本实施例铅酸蓄电池原来的负极(电极群B)连接、使充放电设备的负极与本实施例铅酸蓄电池原来的正极(电极群A)连接,进行一下步;
3)充电:以0.2倍率的电流(465.3mA)对完成第2)步的本实施例铅酸蓄电池进行充电,当电池电压达到1.75V时,充电耗时,547min,停止充电,然后进行下一步;
4)放电和第2次极性反转:在停止上一步的同时,以0.5倍率的电流对此时的电池开始进行强制放电,直至电池电压降至0V并最后达到-0.08V,放电耗时,9s,停止放电,并静置30min,然后进行一下步;
5)第2次极性反转后变换电极连接:人工操作,使充放电设备的正极与本实施例铅酸蓄电池原来的正极(电极群A)连接、使充放电设备的负极与本实施例铅酸蓄电池原来的负极(电极群B)连接,为一下步充电或充放电作准备;
6)充电:以0.2倍率的电流对完成第5)步后的本实施例铅酸蓄电池进行充电,在电压达至1.75V时,结束充电。
完成第6)步时,同时开始使电池进入工作状态并以之前相同的工作制度进行充放电工作。工作结果如表1所示,可见,本实施例的铅酸蓄电池通过上述连续两次极性反转及其后的充电或充放电操作后,工作放电容量有显著恢复,由于本实施例铅酸蓄电池的放电容量衰减是由正极活性物质软化、脱落所致,因此该结果表明,本实施例的极性反转及其后的充电或充放电操作使本实施例铅酸蓄电池的正极软化、脱落情况或程度被显著逆转。据此,若本实施例步骤3)中对本实施例电池的充电量相对更大(例如更大的充电电流、更长的充电时间),则将有利于使本实施例电池原来的正极(电极群A)的活性物质软化、脱落情况得到更大程度的逆转、恢复。
表1
  占额定容量的比例%
操作前,电池剩余容量 7.3
2次极性反转及其后的充电或充放电操作后,电池第一次工作放电容量 24.9
2次极性反转及其后的充电或充放电操作后,电池第二次工作放电容量 31.7
在本实施例的其它实施方式中,本发明的极性反转及其后的充电或充放电操作方法所实施于的电池,还可以是管式铅酸蓄电池、卷绕式铅酸蓄电池、双极式铅酸蓄电池、水平铅布式铅酸蓄电池、泡沫板栅式铅酸蓄电池、阀控式密封铅酸蓄电池、胶体铅酸蓄电池、铅炭电池、超级电容器-铅酸蓄电池、柱式铅酸蓄电池、具有稳定空隙体电极式铅酸蓄电池;本发明的极性反转及其后的充电或充放电操作还可在电池剩余容量为额定容量的50%、90%、100%时启动开始;电池停止工作时的电压 不仅仅是2.65V,还可以是其它任何可能的电压,如2.8V、2V、1.75V、0.5V、0V;停止电池工作时,电池还可以处于工作中的其它阶段,恒流放电阶段或恒流充电阶段;启动或停止本发明的极性反转及其后的充电或充放电操作的依据还可以是其它物理量值或/和化学量值或/和数量值,包括电压值、电流值、电流密度值、电量值、功率值、时间值、温度值、力值、压强值、密度值、光度值、频率值、累计数值、奇数值、偶数值、比例值、电池或/和电池组的充电或放电或充放循环次数值、电池或/和电池组的酸度值中的一种或多种。
在本实施例的其它实施方式中,步骤1)中的放电电流是绝对值大于0的电流,如0.01、0.1、1、3、5、10倍率的电流;放电还可以分阶段进行且每一段中放电电流值不一定相同;放电停止的电压可以是0V,还可以是其它电压,如0.5、0.2、-0.3、-1.7V、-2.33、-2.8V等;还可以加入充电阶段,即在放电一定时间后,对电池再进行1个阶段以上的充电,充电后再进行放电,这种放电、充电、放电、等等的循环次数不限,进行充放循环后,再进行极性反转。
在本实施例的其它实施方式中,步骤1)中充电或充放电操作结束的依据不一定是电压,还可以是其它物理量值或/和化学量值或/和数量值,包括电压值、电流值、电流密度值、电量值、功率值、时间值、温度值、力值、压强值、密度值、光度值、频率值、累计数值、奇数值、偶数值、比例值、电池或/和电池组的充电或放电或充放循环次数值、电池或/和电池组的酸度值中的一种或多种。
在本实施例的其它实施方式中,步骤1)中的放电步骤可以被省掉,即在停止电池的工作后,直接进行第2)步。
在本实施例的其它实施方式中,步骤2)、步骤5)中的连接变换还可以是不通过人工操作,而是通过设备、装置或电路的自动功能实现。
在本实施例的其它实施方式中,步骤3)中的充电电流是绝对值大于0的电流,如0.01、0.2、1.1、3.5、5.3、10倍率的电流;充电还可以分阶段进行且每一段中充电电流值不一定相同;充电停止的电压也不一定是1.75V,还可以是其它电压,如;0.3、0.5、1.0、2.0、2.44、2.65、2.8V等;充电停止的依据还可以是充电量、时间;
在本实施例的其它实施方式中,步骤4)中的放电电流是绝对值大于0的电流,如0.01、0.1、1、3、5、10.3倍率的电流;放电还可以分阶段进行且每一段中放电电流值不一定相同;放电阶段还可以加入充电阶段,即在放电一定时间后,再对电池进行一个阶段以上的充电,充电后再进行放电,这种放电、充电、放电、等等的循环次数不限,进行充放循环后,再进行极性反转。
在本实施例的其它实施方式中,还可以不进行步骤4)的放电操作,而是在步骤3)充电结束后直接进入到第5)步。
在本实施例的其它实施方式中,步骤3或步骤4)中的充电或充放电操作结束的依据不一定是电压,还可以是其它物理量值或/和化学量值或/和数量值,包括电压值、电流值、电流密度值、电量值、容量值、功率值、时间值、温度值、力值、压强值、密度值、光度值、频率值、累计数值、奇数值、偶数值、比例值、电池或/和电池组的充电或放电或充放循环次数值、电池或/和电池组的酸度值中的 一种或多种。
本实施例的其它实施方式中,步骤6)中的充电电流是绝对值大于0的电流,如0.01、0.1、1、3、5、10倍率的电流;充电还可以分阶段进行且每一段中充电电流值不一定相同;充电停止的电压也不一定是1.75V,还可以是其它电压,如;0.3、0.5,1.0,2.0,2.4、2.65,2.78V等;充电阶段还可以加入放电阶段,即在充电一定时间后,再对电池进行一个阶段以上的放电,放电后再进行充电,这种充电、放电、充电、放电、等等的循环次数不限,进行充放循环后,再将电池转入工作状态或准工作状态。
在本实施例的其它实施方式中,在完成第6)步的操作后,继续1次以上的1)-6)步操作(即第1)步到第6)步的操作,以下类同),然后再进行1次以上的电池工作,所述1次以上的1)-6)步操作与所述1次以上的电池工作之间彼此还可轮流地、循环地进行,循环的次数≥1。这样使电池原来的正极始终作为正极进行工作,原来的负极始终作为负极进行工作。
在本实施例的其它实施方式中,在完成第6)步的操作之后,继续进行1次1)-3)步操作或1次以上的1)-6)步操作加上1次1)-3)步操作,然后再进行1次以上的电池工作,所述1次1)-3)步操作或1次以上的1)-6)步操作加上1次1)-3)步操作与所述1次以上的电池工作之间彼此还可轮流地、循环地进行,循环的次数≥1。这样使电池原来的正极始终作为负极进行工作,原来的负极始终作为正极进行工作。
在本实施例的其它实施方式中,在电池完成第6)步的操作后,将1次以上的电池工作、1次以上的1)-6)步操作、1次1)-3)步操作或1次以上的1)-6)步操作加上1次1)-3)步操作轮流、循环地进行,轮流的顺序不限,循环的次数≥1,这样使电池原来的正极有时作为正极进行工作、有时作为负极进行工作,相应地,电池原来的负极有时作为负极进行工作,有时作为正极进行工作。
在本实施例的其它实施方式中,所述1次以上的电池工作、1次以上的1)-6)步操作、1次1)-3)步操作、或1次以上的1)-6)步操作加上1次1)-3)步操作中任意两者之间的切换启动依据,可为物理量值或/和数量值或/和化学量值,包括电压值、电流值、电流密度值、电量值、功率值、时间值、温度值、力值、压强值、密度值、光度值、频率值、累计数值、奇数值、偶数值、比例值、电池或/和电池组的充电或放电或充放循环次数值、电池或/和电池组的酸度值中的一种或多种。
在本实施例的其它实施方式中,上述的物理量值、数量值、化学量值以及它们的变化值、计算值中的一种或多种包括电池在充电过程中、放电过程中、开路或静置状态中的物理量值、数量值或化学量值。
在本实施例的其它实施方式中,在上述1)-6)步的操作中,可同时进行其它操作,如调节电池的温度、给电池加酸、加添加剂、加水、加压等。
本实施例所使用的充放电电流为直流电,在本实施例的其它实施方式中,所使用的充放电电流还可以为脉充电流或脉充电流与直流电流的复合电流。
在本实施例的其它实施方式中,在上述第1)、第4)步的操作中,静置时间可以为其它时间长 度,静置时间也可以为0;
在本实施例的其它实施方式中,上述1)-6)步的操作可通过编程执行。
本实例的上述操作,能改善、逆转铅酸蓄电池的正极活性物质软化、脱落,能改善、修复、提高、恢复铅酸蓄电池的工作放电容量,从而提高或延长铅酸蓄电池的使用寿命。
实施例2
本实施例提高或延长铅酸蓄电池或电池组使用寿命的方法为,当本实施例铅酸蓄电池或电池组因为正极活性物质软化或/和脱落、负极比表面积收缩、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良其中的一种或多种失效模式或问题,而导致电池或电池组的工作放电容量下降时,或者当需要预防或缓解上述七种失效模式或问题对铅酸蓄电池或电池组工作能力的损害时,或者当本实施例铅酸蓄电池或电池组工作达到一定循环次数或浮充时间时,对本实施例铅酸蓄电池或电池组的正极、负极进行如下极性反转及其后的充电或充放电操作,即,先进行步骤(1):对本实施例铅酸蓄电池或电池组进行反极充电,使得本实施例铅酸蓄电池或电池组原来的正极(在此定义为电极A)的极性由正被反转为负、原来的负极(在此定义为电极B)的极性由负被反转成正;然后进行步骤(2):对该极性反转后的本实施例铅酸蓄电池或电池组进行充电或充放电,使得该铅酸蓄电池或电池组原来的正极(电极A)上发生铅酸蓄电池负极电极反应、原来的负极(电极B)上发生铅酸蓄电池正极电极反应,对铅酸蓄电池或电池组容量下降或失效程度的大的,可相对加大本步骤充电或充放电的总电量;然后进行步骤(3):再次对本实施例铅酸蓄电池或电池组进行反极充电,使得本实施例铅酸蓄电池或电池组原来的正极(电极A)的极性由负被反转成正、原来的负极(电极B)的极性由正被反转成负;然后再进行步骤(4):对步骤(3)极性反转后的本实施例铅酸蓄电池或电池组进行充电或充放电,使得本实施例铅酸蓄电池或电池组原来的正极(电极A)上发生铅酸蓄电池正极电极反应、原来的负极(电极B)上发生铅酸蓄电池负极电极反应,最终使得本实施例铅酸蓄电池或电池组被充足电,这样,经本实施例上述连续两次进行的极性反转及其后的充电或充放电操作,本实例铅酸蓄电池或电池组的正极活性物质软化或/和脱落、负极比表面积收缩、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良其中的一种或多种失效模式或问题得到改善、缓解、修复、逆转、或防止,从而本实施例铅酸蓄电池或电池组的工作放电容量获得改善、恢复、提高或维护,然后将本实施例铅酸蓄电池或电池组投入到其正常的循环或浮充工作中去正常使用。本实施例上述步骤(4)中,也可将步骤(3)极性反转后的本实施例铅酸蓄电池或电池组直接投入到正常的循环或浮充工作的充电环节中去充电,并接下来在其正常的循环或浮充工作制度下进行运行、工作。本实施例上述连续两次进行的正、负极极性反转及其后的充电或充放电操作可参考或类同于本发明实施例1中的操作方法或制度进行。
将本实施例上述连续两次进行的正、负极极性反转及其后的充电或充放电操作,多次地、穿插地在本实施例铅酸蓄电池或电池组的工作或使用期间或使用寿命终止后进行,使得本实施例铅酸蓄 电池或电池组的使用寿命获得提高或延长。
本实施例通过对本实施例铅酸蓄电池或电池组正、负极进行极性反转及其后的充电或充放电操作,使得本实施例铅酸蓄电池或电池组原来的正极(电极A)上发生过铅酸蓄电池负极电极反应,这使得原来的正极(电极A)上的活性物质软化、脱落问题被改善、逆转或去除,此外,在该原来的正极(电极A)上铅酸蓄电池负极电极反应发生或进行的同时或同一过程中,本实施例使该原来的正极(电极A)上发生或进行铅酸蓄电池负极电极反应的所述极性反转后的充电或充放电操作,也使得原来的正极(电极A)上集流体与活性物质之间、活性物质颗粒之间、电极内部或表面的铅氧化物、碱式硫酸铅、硫酸铅等所形成或构成的腐蚀产物、腐蚀膜或钝化膜、腐蚀层或钝化层等,被部分或全部地还原成金属铅,并使电极上各部分形成良好的接触、结合或连接、活性物质密度回升或提高,使得原来的正极(电极A)上已发生或将要发生的腐蚀、钝化、早期容量损失、活性物质与集流体接触或结合不良的问题得到改善、逆转、去除或防止;本实施例通过对本实施例铅酸蓄电池或电池组正、负极进行极性反转及其后的充电或充放电操作,使得本实施例铅酸蓄电池或电池组原来的负极(电极B)上发生过铅酸蓄电池正极电极反应,这使得原来的负极(电极B)上的活性物质获得一定程度的膨胀,从而在一定程度上缓解、改善、逆转或预防了已发生或将要发生的原来的负极(电极B)上负极比表面积收缩问题,同时,该原来的负极(电极B)上发生的铅酸蓄电池正极电极反应,在其发生或进行过程中,也通过改变、影响原来的负极(电极B)中膨胀剂或添加剂的吸附能力和吸附状态、改变硫酸铅被转化的电化学过程、电极电位、过电位等与硫酸铅溶解、转化相关的因素,而使得原来的负极(电极B)上已发生或将要发生的硫酸盐化问题得到一定的缓解、改善、逆转或预防。
实施例3
本实施例的对铅酸蓄电池组(2h率额定容量为2Ah、额定电压为4V,25℃)进行本发明的极性反转及其后的充电或充放电操作的实施步骤和操作,与本发明实施例1中对电池实施的步骤和操作基本相同,所不同之处在于,在本实施例的操作中,将极性反转及其后的充电或放电操作应用于铅酸蓄电池组的正极和负极。
在本实施例的其它实施方式中,每次极性反转后的充电停止电压为3.0V或4.5V。
在本实施例的其它实施方式中,还可以对电池组中的某单电池或某些单电池进行本发明的极性反转及其后的充电或充放电的操作,包括步骤,将充放电设备仅与1个或某些单电池接通并进行如本发明实施例1中所述的极性反转及其后的充电或充放电操作。与此相对应的,所述电池组具有其各单电池或某些单电池与充放电设备中的充放电电路进行各自独立连接的电路结构。
在本实施例的其它实施方式中,如本发明实施例1中的极性反转及其后的充电或充放电操作,还可以在对电池组中的1个或某些单电池进行操作后,再对铅酸蓄电池组整体进行操作,或者操作的顺序反过来。
在本实施例的其它实施方式中,本实施例的上述操作通过编程执行。
实施例4
本实施例是涉及将本发明的极性反转及其后的充电或充放电操作方法用于铅酸蓄电池或电池组制造时的化成工艺,包括,在电池或电池组加酸后,将未经过化成的电池或已经过一定化成工艺的电池或电池组进行如本发明实施例1或3中的所述的极性反转及其后的充电或充放电操作步骤。
在本实施例的其它实施方式中,将极性反转及其后的充电或充放电操作方法用于铅酸蓄电池或电池组制造时的化成工艺,包括,在电池或电池组加酸后,将铅酸蓄电池或/和铅酸蓄电池组的正极与负极进行1次如本发明实施例1或3中所述的任一极性反转及其后的充电或充放电操作步骤,并使极性反转后的充电操作次数与放电操作次数之和为1次或3次或9次,然后将电池或电池组原来的正极始终作为负极进行工作使用,原来的负极始终作为正极进行工作使用。在本实施方式中,所进行的极性反转及其后的充电或充放电操作与本实施例上述实施方式中所述的极性反转及其后的充电或充放电操作的特征相同。
实施例5
本实施例是涉及将本发明的极性反转及其后的充电或充放电操作方法用于铅酸蓄电池或电池组的修复或再生,包括:按照本发明实施例1、2或3中所述的极性反转及其后的充电或充放电操作步骤进行,对铅酸蓄电池或电池组进行修复或再生。
实施例6
本实施例涉及提高或延长铅酸蓄电池使用寿命的方法、电池充放电器和铅酸蓄电池,其中本实施例的电池充放电器,基于其所包括的电流源电路、电压源电路及强制充电或/和强制放电功能,能对本实施例铅酸蓄电池的正、负极进行极性反转及其后的充电或充放电操作。以下本实施例的所有对本实施例铅酸蓄电池进行的操作除特别说明手动外,均为通过本实施例电池充放电器的功能及工作来实现的,本实施例电池充放电器具有按设定程序执行的功能。本实施例铅酸蓄电池为平面板栅式铅酸蓄电池,额定容量为1.77Ah(2h率,25℃),额定电压为2V,具有两片负极板之间夹一片正极板的结构,正、负极之间的隔板为AGM隔板,负极板总容量相对过剩于正极板总容量,正极板厚度为2.8mm,负极板厚度为1.9mm,正、负极板板栅栅格均为矩形,其正极板具有现行普通商用正极铅膏配方(其中硫酸相对于球磨铅粉的含量为4.5wt.%,且配方中不含有硫酸钡)制得的正极铅膏,电池工作时仅作为正极使用,因此称为正极板(为后续陈述清楚,在本实施例中也将其命名为电极A),负极板具有现行普通商用负极铅膏配方制得的负极铅膏,电池工作时仅作为负极使用,因此称为负极板(为后续陈述清楚,在本实施例中也将其命名为电极B1、B2),正、负极铅膏采用的铅粉均为现行普通商用球磨铅粉,固化、干燥后正极板上干铅膏的质量为29.69g,本实施例铅酸蓄电池 中的硫酸溶液密度为1.27g/cm 3,本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
本实施例提高或延长铅酸蓄电池使用寿命的方法为,首先,让本实施例铅酸蓄电池进行循环充放电工作,本实施例铅酸蓄电池的循环充放电工作制度为:当电池处于充电后的状态时,以1031mA的恒电流对电池进行放电工作,当放电时间达到1小时36分时(即放电容量为1649mAh、是额定容量的93%时)、或者电池电压≤1.75V时,停止放电,接着以412mA的恒电流对电池进行充电,并当测得电池电压达到2.65V后,转换成以2.65V恒压继续对电池充电,当两次(恒流、恒压)充电总时间达到6小时24分,电池充电过程结束,然后,再以1031mA的恒电流重复前述的放电过程,如此反复、循环地放电、充电、再放电、再充电,使电池循环充放工作,电池工作环境温度为25±1℃;其次,当正极活性物质软化或/和脱落、硫酸盐化、钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极活性物质比表面积收缩因素中的一种或多种导致本实施例铅酸蓄电池在上述工作中其放电容量或放电时间小于某一预先设定的容量值或者某一时间值时(例如,本实施例中设定的分别为900mAh、1小时36分、47分,如下),停止电池的工作,开始对电池进行至少一期连续两次的正、负极极性反转及其后的充电或充放电操作,使本实施例铅酸蓄电池在该操作完成后,工作放电容量得到恢复或提高,然后,将电池重新投入到其原来的工作制度下继续进行工作;然后如此,在本实施例铅酸蓄电池的循环充放电工作(简称循环工作,以下同)过程中,反复地、穿插地、多期地进行相同或类似于本实施例上述的连续两次的正、负极极性反转及其后的充电或充放电操作,从而抑制、防止、修复、改善、消除或逆转铅酸蓄电池的正极活性物质软化或/和脱落、负极活性物质比表面积收缩、电极/汇流体/集流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良问题中的一种或多种,来明显提高或延长本实施例铅酸电池的使用寿命。具体的,通过本实施例电池充放电器及其设定程序、执行功能,设定并执行对本实施例铅酸蓄电池进行正极板、负极板的极性反转及其后的充电或充放电操作,在进行本实施例铅酸蓄电池正极板、负极板极性反转操作时,一种是手动操作:将电池电压降至0V附近,然后凭借人手,将本实施例电池充放电器与本实施例铅酸蓄电池的连接状态从充放电器正极夹子(正极输出导电夹子,以下同)与铅酸蓄电池正极板(电极A)连接、充放电器负极夹子(负极输出导电夹子,以下同)与铅酸蓄电池负极板(电极B1、B2)连接(此种连接称正接状态,以下同),改换成,充放电器正极夹子与铅酸蓄电池负极板(电极B1、B2)连接、充放电器负极夹子与铅酸蓄电池正极板(电极A)连接(此种连接称反接状态,以下同),或者将反接状态改换成正接状态,然后对电极连接状态变换后的电池进行充电至电池电压>0V,从而实现本实施例电池其电极的极性反转;另一种是通过本实施例电池充放电器自动操作:在本实施例铅酸蓄电池处于正接状态时,通过本实施例电池充放电器中的恒流源对本实施例电池进行强制放电使得电池的电压从≥0V的状态转变成<0V的状态,或者在电池电压<0V时对电池进行充电(或称强制充电)并使电池电压从<0V的状态转变成≥0V的状态,即自动实现了对本实施例铅酸蓄电池的极性反转操作。当电池处于正接状态时,电池在电池电压<0V时被继续强制放电, 使得电池电压趋向于更负,则此时电池正极板(电极A)上主要发生的是铅酸蓄电池负极电极反应中的充电过程、电池负极板(电极B1、B2)上主要发生的是铅酸蓄电池正极电极反应中的充电过程(可参考本发明电极反应式(1)、(2),以下同);而本实施例电池处于正接状态时,电池在电池电压<0V时被强制充电,使得电池电压趋向于更正或0V,则此时电池正极板(电极A)上主要发生的是铅酸蓄电池负极电极反应中的放电过程、电池负极板(电极B1、B2)上主要发生的是铅酸蓄电池正极电极反应中的放电过程;当本实施例电池处于正接状态时,电池在电池电压>0V时被充电,使得电池电压趋向于更正,则此时电池正极板(电极A)上主要发生的是铅酸蓄电池正极电极反应中的充电过程、电池负极板(电极B1、B2)上主要发生的是铅酸蓄电池负极电极反应中的充电过程。这样,通过本实施例电池充放电器的强制放电、强制充电功能和操作实现了对本实施例电池正、负极的极性反转操作,以及极性反转后的充电或充放电操作。另外,也利用本实施例电池充放电器所具有的充电、放电功能来实施对本实施例铅酸蓄电池工作时的充电、放电操作,以实现本实施例电池的循环充放电工作(以下对本实施例铅酸蓄电池的所有操作及测量除了特别说明是手动外,均为通过本实施例电池充放电器进行设定程序、执行实现)。本实施例提高或延长铅酸蓄电池使用寿命的方法具体实施过程如下:
按上,最初设定当本实施例铅酸蓄电池的工作放电容量小于900mAh时,停止本实施例铅酸蓄电池工作并开始对该电池进行第一、第二次的正、负极极性反转及其后的充电或充放电操作。本实施例电池从化成结束后的第2次充放电工作循环开始按照本实施例工作制度进行充放循环工作,工作时本实施例电池正极板上发生铅酸蓄电池正极电极反应、负极板上发生铅酸蓄电池负极电极反应,如图1所示,工作充放循环到第148次的时候,本实施例电池的工作放电容量开始明显表现出逐次下降的现象,经检查,这是由于正极活性物质软化、脱落引起的(以下工作放电容量下降的原因与此同),当充放循环工作至第179次时,电池放电到1.75V时的工作放电容量降至899mAh(即剩余容量为额定容量的50.9%),即达到开始对本实施例电池进行正、负极极性反转及其后的充电或充放电操作的触发条件(放电容量<900mAh),此时,开始对本实施例电池进行第一、第二次正、负极极性反转及其后的充电或充放电操作的准备和正式操作,即,在第179次工作放电结束后(此时电池电压为1.75V),继续对电池以1031mA恒电流进行放电4min并至电池电压为0V时,停止放电,然后对该电池进行其正极板、负极板的极性反转,即,手动将本实施例电池充放电器与本实施例铅酸蓄电池的连接状态从充放电器正极夹子与铅酸蓄电池正极板(电极A)连接、充放电器负极夹子与铅酸蓄电池负极板(电极B1、B2)连接的正接状态,改换成,充放电器正极夹子与铅酸蓄电池负极板(电极B1、B2)连接、充放电器负极夹子与铅酸蓄电池正极板(电极A)连接的反接状态,形成俗称的反极连接,然后,以1031mA的恒电流对该变换了连接状态后的电池进行充电,使得本实施例铅酸蓄电池的正极板(电极A)上发生铅酸蓄电池负极电极反应的充电过程、本实施例铅酸蓄电池的负极板(电极B1、B2)上发生铅酸蓄电池正极电极反应的充电过程,当经3小时15min、电池电压上升至1.75V(此时负极板或电极B1、B2为正、正极板或电极A为负)后,继续以1031mA 的恒电流对电池充电3小时(此过程电池电压从1.75V上升至2.23V,此时仍是负极板或电极B1、B2为正、正极板或电极A为负),然后,以1031mA恒电流对电池进行放电,使得本实施例铅酸蓄电池的正极板(电极A)上发生铅酸蓄电池负极电极反应的放电过程、本实施例铅酸蓄电池的负极板(电极B1、B2)上发生铅酸蓄电池正极电极反应的放电过程,该放电经24min、至0V时停止放电,然后,再一次对该电池进行正、负极极性反转,即,手动将电池充放电器与本实施例铅酸蓄电池的连接状态从充放电器正极夹子与铅酸蓄电池负极板(电极B1、B2)连接、充放电器负极夹子与铅酸蓄电池正极板(电极A)连接的反接状态,改换成,充放电器正极夹子与铅酸蓄电池正极板(电极A)连接、充放电器负极夹子与铅酸蓄电池负极板(电极B1、B2)连接的正接状态,然后,对该电池以258.4mA的恒电流进行充电,使得本实施例铅酸蓄电池的正极板(电极A)上发生铅酸蓄电池正极电极反应的充电过程、本实施例铅酸蓄电池的负极板(电极B1、B2)上发生铅酸蓄电池负极电极反应的充电过程,该充电经31min、至电池电压1.75V时(此时正极板或电极A为正、负极板或电极B1、B2为负),再以412mA恒电流充电16小时35min、至电池电压2.65V,然后,再以2.65V恒电压对该电池充电3小时(此恒流、恒压充电过程正极板或电极A为正、负极板或电极B1、B2为负),该恒压充电完成后,至此,完成对本实施例电池的第一、第二次正、负极极性反转及其后的充电或充放电操作。然后,使该电池重新进入同前的充放电循环工作状态和制度下进行第180次工作放电及之后的循环充放工作。结果表明,经第一、第二次正、负极极性反转及其后的充电或充放电操作后,该电池在第180次工作状态下的放电容量上升达到1452.5mAh,而其第181次工作状态下的放电容量已恢复到正常放电容量1649mAh(对应的放电时间为1小时36分)。
接下来,使本实施例电池继续在工作制度下运行,并将触发正、负极极性反转及其后的充电或充放电操作的条件通过编程更改为:当本实施例铅酸蓄电池的工作放电时间<1小时36分时,停止电池工作并开始自动地对电池进行第三、第四次的正、负极极性反转及其后的充电或充放电操作。如图1所示,第181-224次放电-充电工作循环中工作放电容量均达到正常放电时间,1小时36分(对应的放电容量为1649mAh),该循环充放工作过程中本实施例电池正极板(电极A)上发生铅酸蓄电池正极电极反应、负极板(电极B1、B2)上发生铅酸蓄电池负极电极反应,当电池充放循环工作到第225次的时候,电池的放电工作能力开始下降,放电时间为1小时35分时(此时电池放电终止电压已降至1.75V),因此,根据设定的触发条件和执行程序,本实施例电池充放电器此时立即将本实施例电池由工作状态自动转入正极板、负极板的极性反转及其后的充电或充放电操作的准备和实施阶段,即第225次充放循环工作放电结束、电池电压降至1.75V后,电池被停止工作,使电池与充放电器的连接状态为正接状态,即:本实施例电池充放电器输出端正极与本实施例铅酸蓄电池正极板(电极A)相连接、本实施例电池充放电器输出端负极与本实施例铅酸蓄电池负极板(电极B1、B2)相连接,然后本实施例电池被自动地以1031mA的恒电流进行继续放电和强制放电,并且通过本实施例电池充放电器的强制放电功能,该继续放电和强制放电操作经23min使得本实施例电池电压较快地从1.75V下降到0V(此过程使得本实施例铅酸蓄电池的正极板或电极A上发生铅酸蓄电池 正极电极反应的放电过程、本实施例铅酸蓄电池的负极板或电极B1、B2上发生铅酸蓄电池负极电极反应的放电过程),然后再经36min使电池电压从0V下降到﹣1.75V(电池充放电器所测量和显示出的电池电压,以下同,此过程使得本实施例铅酸蓄电池的正极板或电极A上发生铅酸蓄电池负极电极反应的充电过程、本实施例铅酸蓄电池的负极板或电极B1、B2上发生铅酸蓄电池正极电极反应的充电过程),在到达﹣1.75V后,继续保持1031mA的恒电流强制放电3小时(这时测得电池电压从﹣1.75V下降到约﹣2.15V,此过程仍使得本实施例铅酸蓄电池的正极板(电极A)上发生铅酸蓄电池负极电极反应的充电过程、本实施例铅酸蓄电池的负极板(电极B1、B2)上发生铅酸蓄电池正极电极反应的充电过程),然后,充放电器接着以1031mA的恒电流对该电池进行强制充电(测得此过程充电耗时23分钟、电池电压从约﹣2.15V上升到0V(此过程使得本实施例铅酸蓄电池的正极板或电极A上发生铅酸蓄电池负极电极反应的放电过程、本实施例铅酸蓄电池的负极板或电极B1、B2上发生铅酸蓄电池正极电极反应的放电过程),当电池电压达到0V后,充放电器自动地继续以258.4mA的恒电流对电池充电,经1小时08分钟使电池电压达1.75V后(此过程使得本实施例铅酸蓄电池的正极板或电极A上发生铅酸蓄电池正极电极反应的充电过程、本实施例铅酸蓄电池的负极板或电极B1、B2上发生铅酸蓄电池负极电极反应的充电过程),再以412mA的恒电流对电池继续充电8小时41分钟,使得测得电池电压达2.65V,然后,切换成对该电池以2.65V恒压进行充电,并使此恒压充电保持3小时(此恒流、恒压充电过程中正极板或电极A为正、负极板或电极B1、B2为负),此恒压充电完成后,至此,完成对本实施例电池的第三、第四次正、负极极性反转及其后的充电或充放电操作,然后将本实施例电池转回到其原来的、同前的循环充放工作状态和制度下进行第226次及之后次数的循环充放电工作。结果表明,经第三、第四次正、负极极性反转及其后的充电或充放电操作后,本实施例电池在第228次的循环工作中放电时间恢复到1小时36分,并且在接下来一直到第239次循环工作中其工作放电时间都是正常的,为1小时36分。(第226、227次的工作循环由于误操作使得放电终止电压低于了1.75V,导致过放电)。
接下来,使本实施例电池继续在工作制度下运行,如图1所示,当本实施例电池在循环工作到第240次时,其放电时间为1小时35分时,再次触发之前设定的正、负极极性反转及其后的充电或充放电操作的开始条件,因而在第240次工作放电结束后(放电结束时电池电压为1.75V),充放电器接下来开始了将本实施例电池进行第五、第六次的正极板、负极板的极性反转及其后的充电或充放电操作,操作方法和过程与本实施例第三、第四次的正、负极极性反转及其后的充电或充放电操作相同,然后,使本实施例铅酸蓄电池重新进入同前的循环充放电工作状态和制度下接着进行本实施例电池的第241次及之后次数的循环充放电工作。结果,经第五、第六次的正、负极极性反转及其后的充电或充放电操作后,本实施例电池在第243次的循环工作中放电时间恢复到1小时36分(第241、242次的工作循环由于误操作使得放电终止电压低于了1.75V,导致过放电)。
接下来,使本实施例电池继续在工作制度下运行,并在进行第244次的充放循环过程中,将触发本实施例电池正、负极极性反转及其后的充电或充放电操作的开始条件通过编程更改为:当本实 施例电池的放电时间<45分钟时,停止电池工作并开始自动地对本实施例铅酸蓄电池或其正、负极板进行第七次、第八次的正、负极极性反转及其后的充电或充放电操作。如图1所示,当本实施例电池工作循环到第251次时其放电性能开始下降,第268次时,工作放电时间为42分(对应的工作放电容量为721mAh),此时触发设定的正、负极极性反转及其后的充电或充放电操作的开始条件,因而在第268次放电工作结束后(放电结束时电池电压为1.75V),停止电池工作,充放电器接下来开始对本实施例电池进行第七次、第八次的正极板、负极板的极性反转及其后的充电或充放电操作,操作方法和过程与本实施例第三、第四次的正、负极极性反转及其后的充电或充放电操作基本相同,所不同之处在于,在电池电压到达﹣1.75V后,继续保持1031mA的恒电流强制放电4小时(而不是3小时,此过程测得电池电压仍是从﹣1.75V下降到约﹣2.15V),该第七次、第八次的正极板、负极板的极性反转及其后的充电或充放电操作完成后,使本实施例铅酸蓄电池重新进入同前的循环充放电工作状态和制度下接着进行本实施例电池的第269次及之后次数的循环充放电工作。结果,经第七、第八次的正、负极极性反转及其后的充电或充放电操作后,本实施例电池在第269次的循环工作中放电时间恢复到1小时12分(放电容量为1252mAh),而在第270次的循环工作中放电时间恢复到1小时36分,并且在接下来一直到第290次的循环充放电工作中其工作放电时间都是正常的1小时36分。
如图1所示,本实施例铅酸蓄电池在接下来的第270-463次循环工作中,其循环充放电工作状态和制度都与上述第1-270次的循环工作的相同,且每当本实施例铅酸蓄电池的工作放电时间或工作放电容量降至1小时36分或1649mAh或以下时,即对本实施例铅酸蓄电池进行一期类似上述的连续两次的极性反转及其后的充电或充放电操作,即分别在其工作放电的第295、296次之间、第309、310次之间、第324、325次之间、第344、345次之间、第369、370次之间、第385、386次之间、第405、406次之间、第425、426次之间、第441、442次之间、第457、458次之间,分别地进行了连续的第九、十次、连续的第十一、十二次、......、连续的第二十七、二十八次的、共10期的极性反转及其后的充电或充放电操作,并使得本实施例铅酸蓄电池的工作放电时间或容量均在每期连续两次的极性反转及其后的充电或充放电操作的随后的第一次或第二次工作放电中恢复至1小时36分或1649mAh,从而使得本实施例铅酸蓄电池保有继续正常工作放电的能力。
如图1所示,本实施例中每期连续两次的极性反转及其后的充电或充放电操作后,本实施例铅酸蓄电池的工作放电时间或容量是在该操作随后的第1次或者是第2次工作放电中恢复至1小时36分或1649mAh,这可能与每期极性反转操作开始前电池的实际工作放电容量下降程度、进行每次极性反转及其后的充电或充放电操作过程中的电流、电压、充放电容量、阶段数等的大小、方法有关。例如,正极板上的活性物质颗粒软化、脱落的程度大、或电池实际工作放电容量下降程度较大的,在进行一期连续两次的极性反转及其后的充电或充放电操时,对该期第1次极性反转后的充电量需求相也大,而该期第2次极性反转后充电电量较大有利于保证电池充足电,因此,如果该期第2次极性反转后充电电量相对较小就有可能导致电池充电不足,就会使得本实施例铅酸蓄电池需要通过 连续两次极性反转及其后的充电或充放电操作后的第一次工作放电和充电过程来继续为其补足电池荷电量。例如,本实施例铅酸蓄电池其工作放电的第405、406次之间或第441、442次之间所进行的连续两次极性反转及其后的充电或充放电操作,由第405次或第441次工作放电结果可知,两者的本实施例铅酸蓄电池的工作放电容量下降程度均小于第179次的,第405、406次之间所进行的连续两次极性反转及其后的充电或充放电操作过程为:第405次工作放电后(此时电池电压为1.75V),在保持电池充放电器与本实施例电池的正接状态下,继续对电池以1031mA恒电流进行放电和强制放电132min,使得电池电压从1.75V降到0V时,然后又从0V下降到-1.75V(其中,从1.75V降到0V的过程中,正极板或电极A上主要发生的是铅酸蓄电池正极电极反应的放电过程、负极板或电极B1、B2上主要发生的是铅酸蓄电池负极电极反应的放电过程,从0V降到-1.75V的过程中,正极板或电极A上主要发生的是铅酸蓄电池负极电极反应的充电过程、负极板或电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的充电过程),达到-1.75V时负极板(电极B1、B2)的极性为正、正极板(电极A)的极性为负,然后,继续以1031mA的恒电流对该电池强制放电4小时(此过程电池电压从-1.75V继续下降至-2.087V,此时仍是负极板或电极B1、B2为正、正极板或电极A为负),然后,以1031mA恒电流对该电池进行强制充电,使得本实施例铅酸蓄电池的正极板(电极A)上发生铅酸蓄电池负极电极反应的放电过程、本实施例铅酸蓄电池的负极板(电极B1、B2)上发生铅酸蓄电池正极电极反应的放电过程,该强制充电经35min、至0V时停止,然后,再对该电池以258.4mA的恒电流进行充电,使得本实施例铅酸蓄电池的正极板(电极A)上发生铅酸蓄电池正极电极反应的充电过程、本实施例铅酸蓄电池的负极板(电极B1、B2)上发生铅酸蓄电池负极电极反应的充电过程,该充电经1小时21min、至电池电压1.75V时(此时正极板或电极A为正、负极板或电极B1、B2为负),再以412mA恒电流充电14小时、至电池电压2.63V,然后,再以2.65V恒电压对该电池充电4小时(此恒流、恒压充电过程正极板或电极A为正、负极板或电极B1、B2为负),然后,使该电池重新进入同前的循环充放电工作状态和制度下进行第406次的工作放电及之后次数的循环工作。第441、442次之间进行的连续两次极性反转及其后的充电或充放电操作与第405、406次之间的基本相同,所不同之处在于,第441、442次之间进行的连续两次极性反转及其后的充电或充放电操作中的第1次极性反转后的强制放电电流为1515mA(即,该强制放电使正极板或电极A上发生铅酸蓄电池负极电极反应的充电过程,使负极板或电极B1、B2上发生铅酸蓄电池正极电极反应的充电过程)。
本实施例中如果定义工作放电容量低于额定容量的80%者视为无效工作或不计入循环充放电工作次数(即电池使用寿命),则本实施例铅酸蓄电池在被进行第一期或第一次本实施例的极性反转及其后的充电或充放电操作之前,如图1所示,其有效工作的循环工作次数或使用寿命为145次循环(143次循环以后,连续三次工作放电容量均低于额定容量的80%),但是通过本实施例正、负极极性反转及其后的充电或充放电操作方法、铅酸蓄电池、电池充放电器,本实施例铅酸蓄电池的循环工作了463次之后,还可以继续正常工作,其有效工作循环次数达到408次,增加了181%,且据上 可以推测,在不产生集流体腐蚀、失水等情况下继续按照上述操作方法,可以使本实施例铅酸蓄电池的使用寿命获得继续延长。
另外,若以本实施例前8次极性反转及其后的充电或充放电操作为例进行成本与效益评估,本实施例中对电池进行的前8次正、负极极性反转及其后的充电或充放电操作所额外消耗的总充电量约为47336mAh,额外增加的有效工作次数为83次,因此平均增加每次工作次数所额外消耗的充电量为570mAh,为本实施例铅酸蓄电池额定容量的34.6%,结合现行商用动力铅酸蓄电池的情况进行计算,可得,增加每次有效工作的成本约是现行商用动力铅酸蓄电池购置成本的0.036%(电费以0.6元/度计算),增加365次有效工作的成本约是现行商用动力铅酸蓄电池购置成本的13.2%,即,如果不计本实施例充放电器成本,应用本实施例提高或延长铅酸蓄电池使用寿命的方法,一年可以使动力电池的使用成本降低至13.2%。如果在工作放电制度较轻缓的情况下(放电深度和放电电流小于本实例的93%DOD、1.16I 2,I 2为0.5倍率电流),则平均增加每次工作次数所额外消耗的充电量还要低,从而增加每次有效工作的成本也相应更低。此外,电池每增加一年的使用寿命,带来环保方面的效益是巨大的。另外,在本实施例的极性反转及其后的充电或充放电操作中采用脉冲充电的方法来进行极性反转及其后的充电或充放电,将进一步提高该操作的效率,降低该操作的成本,提高该操作的效益。
一方面如上所述,本实施例的正、负极极性反转及其后的充放电或充放电操作使得本实施例铅酸蓄电池的正极活性物质软化、脱落被改善、修复、逆转,从而使得本实施例铅酸蓄电池循环工作中的工作放电容量该操作之后获得提高或恢复,另一方面,本实施例的正、负极极性反转及其后的充放电或充放电操作,也必然对本实施例电池循环工作过程中发生、轻微发生或将要发生的电极钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极比表面积收缩的问题具有改善、修复、逆转、预防的作用。在本实施例铅酸蓄电池正常循环工作过程中,定期或不定期的(例如,以规定循环工作次数的方式)、穿插地对本实施例铅酸蓄电池进行本实施例的正、负极极性反转及其后的充放电或充放电操作,将会有效的改善、修复、逆转、预防正极活性物质软化或/和脱落、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩问题,从而提高或延长本实施例铅酸蓄电池的使用寿命。
在本实施例的其它实施方式中,本实施例的铅酸蓄电池具有身份标识系统,通过该电池身份标识系统,本实施例的电池充放电器可对本实施例电池进行身份识别,从而确定本实施例电池整个或近期的工作历史、各种相关的程序设定等,从而在将本实施例电池充放电器与本实施例电池连接后,对本实施例电池进行正、负极极性反转及其后的充电或充放电工作。
在本实施例的其它实施方式中,将本实施例铅酸蓄电池强制放电至电池电压<0V或﹣1.75V后的强制放电时间还可以是5小时、10小时、20小时,使电池电压可以达到﹣2.3V、﹣2.65V、﹣2.78V等,以获得更强的正极活性物质软化、脱落逆转效果。
在本实施例的其它实施方式中,还根据所测得的电池中电解液的浓度高于55%、并且电池温度 高于45℃时,暂停正、负极极性反转及其后的充电或充放电操作,并在电解液的浓度低于50%(可通过对电池补液实现)、温度下降到小于40℃后,续接启动正、负极极性反转及其后的充电或充放电操作。
在本实施例的其它实施方式中,当本实施例电池在工作、正、负极极性反转及其后的充电或充放电操作的进行或停止时,向本实施例电池进行补液操作,所补的液体包括水、硫酸溶液、添加剂溶液其中的一种或多种,以修复由于长时间、多次、大电流充、放电、过充电、氧化、电池密封问题等原因引起的电池失水、失酸、失添加剂等损耗,提高电池使用寿命。
在本实施例的其它实施方式中,将本实施例提高或延长铅酸蓄电池使用寿命的方法应用于本实施例铅酸蓄电池组,本实施例铅酸蓄电池组的额定电压为12V、额定容量为12Ah,在方法实施操作中,主要对操作中的电压、电流、容量等的数值的设定和执行上作了相应的变化,如,将铅酸蓄电池组强制放电至电池组电压<0V后,使电池组电压继续下降至﹣6V、﹣10.5V、﹣13V、﹣15V后停止强制放电,强制放电电流为0.3倍率、0.5倍率、1倍率、2倍率。
实施例7
本实施例提高或延长铅酸蓄电池使用寿命的方法、电路和铅酸蓄电池,其中,本实施例电路,基于其所包含的恒流源电路、恒压源电路及强制充电或/和强制放电功能,能实现对本实施例铅酸蓄电池的正、负极进行极性反转及其后的充电或充放电操作,也具有编程执行功能。本实施例铅酸蓄电池为平面板栅式铅酸蓄电池,额定容量为1.93Ah(2h率,25℃),额定电压为2V,具有两片负极板之间夹一片正极板的结构,正、负极板之间隔有隔板,负极板总容量相对过剩于正极板总容量,其正极板具有正极配方制得的铅膏,电池工作时仅作为正极使用,因而称为正极板(为后续陈述清楚,在本实施例中也将其命名为电极A),负极板具有常规负极配方制得的铅膏,电池工作时仅作为负极使用,因而称为负极板(为后续陈述清楚,在本实施例中也将其命名为电极B1、B2),正、负极铅膏的配方不同,且正极板铅膏采用的铅粉是100%氧化度的氧化铅粉,负极板铅膏采用的铅粉为球磨铅粉,固化、干燥后正极板上干铅膏的质量为31.1g。本实施例铅酸蓄电池中的硫酸溶液密度为1.27g/cm 3,本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
本实施例提高或延长铅酸蓄电池使用寿命的方法为,首先,让本实施例铅酸蓄电池进行循环充放电工作,本实施例铅酸蓄电池的工作制度为:当本实施例电池处于充电后状态时,使本实施例电池以1008mA的电流进行放电工作,当放电时间达到1小时36分(即放电容量为1614mAh、是额定容量的83%)、或者电池电压≤1.75V时,停止放电,接着以404mA的恒电流对电池进行充电,并当电池电压达到2.65V后,转换成以2.65V恒压继续对电池充电,当两次(恒流、恒压)充电总时间达到6小时24分,对电池充电过程结束然后,再重复前述的1008mA的恒电流放电过程,如此反复、循环的放电、充电、再放电、再充电,使电池循环充放工作,电池工作环境温度为25±1℃。其次, 当正极活性物质软化或/和脱落、硫酸盐化、钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极活性物质比表面积收缩因素中的一种或多种导致本实施例铅酸蓄电池在上述工作中其放电时间或放电容量小于或连续小于某一预先设定的容量值或者某一时间值时,停止本实施例电池的工作,开始对本实施例电池进行至少一期连续两次的正、负极极性反转及其后的充电或充放电操作,使本实施例铅酸蓄电池在该操作完成后,工作放电容量得到恢复或提高,然后,将电池重新投入到其原来的工作制度下继续进行循环充放电工作。然后如此,在本实施例铅酸蓄电池的循环工作过程中,反复地、穿插地、多期地进行相同或类似于本实施例上述的连续两次的正、负极极性反转及其后的充电或充放电操作,从而抑制、防止、修复、改善、消除或逆转铅酸蓄电池的正极活性物质软化或/和脱落、负极活性物质比表面积收缩、电极/汇流体/集流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良问题中的一种或多种,来明显提高或延长本实施例铅酸电池的使用寿命。具体的,通过本实施例电路及其设定程序、执行功能,设定并执行对本实施例铅酸蓄电池进行正、负极极性反转及其后的充电或充放电操作,在进行本实施例铅酸蓄电池正、负极极性反转操作时,如同本发明实施例6那样,一种是借助手动操作,另一种是通过本实施例电路的强制放电和强制充电功能、在本实施例电路与电池的连接状态处于正接状态下的自动操作(请参见本发明实施例6中的相应内容)。另外,也利用本实施例电路所具有的充电、放电功能来实施对本实施例电池工作时的充电、放电操作,以实现本实施例电池的循环工作(以下对电池的所有操作及测量除了特别说明是手动外,均为通过本实施例电路进行程序设定、执行实现)。本实施例铅酸蓄电池在进行或被进行循环工作和所有极性反转及其后的充电或充放电操作过程中,电池中的电解液相对于正极活性物质的容量是过剩或充足的。
按上,最初设定当本实施例铅酸蓄电池的放电容量连续三次小于1614mAh时,停止本实施例电池工作并开始对本实施例电池进行第一、第二次的正、负极极性反转及其后的充电或充放电操作。如图2所示,本实施例电池从第18次充放循环开始按照所设定的工作制度进行循环充放电工作(前面17次充放循环进行的是一些过充电、过放电、容量检测等操作,也计算到循环充放电工作的总次数中),工作时本实施例电池正极板(电极A)上发生铅酸蓄电池正极电极反应、负极板(电极B1、B2)上发生铅酸蓄电池负极电极反应,充放循环第18-50次,本实施例电池表现出正常的工作能力,即每次工作放电容量为均1614mAh。当充放循环工作到第51次时,本实施例电池的工作放电容量开始表现出下降,即第51-53次的工作放电容量分别为1583、1568和1554mAh(对应的放电时间分别为1小时34分、1小时33分和1小时31分),经检查,这是由于正极活性物质软化、脱落引起的(以下工作放电容量下降的原因与此同),此时,达到开始对本实施例电池进行正、负极极性反转及其后的充电或充放电操作的触发条件(放电容量连续三次<1614mAh),于是开始对本实施例电池进行第一、第二次正、负极极性反转及其后的充电或充放电操作的准备和正式操作,即,在第53次循环工作放电结束后(电池电压降至1.75V时),停止本实施例电池的工作,然后对本实施例电池以1008mA恒电流进行放电直至电池电压为0V,然后停止放电,然后对该电池进行其正、负极的极性 反转(第一次),即,手动将本实施例电路与本实施例铅酸蓄电池的连接状态从本实施例电路正极夹子与铅酸蓄电池正极板(电极A)连接、本实施例电路负极夹子与铅酸蓄电池负极板(电极B1、B2)连接的正接状态,改换成,本实施例电路正极夹子与铅酸蓄电池负极板(电极B1、B2)连接、本实施例电路负极夹子与铅酸蓄电池正极板(电极A)连接的反接状态,然后,以1008mA的恒电流对该变换了连接状态后的本实施例电池进行充电,使本实施例电池的正极板(电极A)上发生铅酸蓄电池负极电极反应的充电过程、负极板(电极B1、B2)上发生铅酸蓄电池正极电极反应的充电过程,当电池电压上升至1.75V后,继续以1008mA的恒电流对电池充电3小时(此过程电池电压从1.75V上升至2.28V),然后,以1008mA恒电流对电池进行放电,使本实施例电池的正极板(电极A)上发生铅酸蓄电池负极电极反应的放电过程、负极板(电极B1、B2)上发生铅酸蓄电池正极电极反应的放电过程,该放电至0V时停止放电,然后,再一次对该电池进行正、负极极性反转(第二次),即,手动将本实施例电路与本实施例铅酸蓄电池的连接状态从本实施例电路正极夹子与铅酸蓄电池负极板(电极B1、B2)连接、本实施例电路负极夹子与铅酸蓄电池正极板(电极A)连接的反接状态,改换成,本实施例电路正极夹子与铅酸蓄电池正极板(电极A)连接、本实施例电路负极夹子与铅酸蓄电池负极板(电极B1、B2)连接的正接状态,然后,对该电池以251.5mA的恒电流进行充电,使本实施例电池的正极板(电极A)上发生铅酸蓄电池正极电极反应的充电过程、负极板(电极B1、B2)上发生铅酸蓄电池负极电极反应的充电过程,至电池电压1.75V时,再以404mA恒电流充电,至电池电压2.65V时,再以2.65V恒电压对电池进行充电3小时,至此,完成对本实施例电池的第一、第二次正、负极极性反转及其后的充电或充放电操作。然后,使本实施例电池重新进入同前的放电-充电循环工作状态或制度下进行第54次工作放电及之后次数的循环充放电工作。结果表明,经第一、第二次正、负极极性反转及其后的充电或充放电操作后,本实施例电池在第54次循环工作中的放电容量上升至1570mAh(对应的放电时间为1小时33分,放电容量小于1614mAh这可能与工作放电前的充电不足有关,以下类似情况相同),而其第55次工作中的放电容量已恢复到工作状态下的正常放电容量,1614mAh(对应的放电时间为1小时36分)。
接下来使本实施例电池继续在工作制度下运行,并将触发电池正、负极极性反转及其后的充电或充放电操作的开始条件通过编程更改为:当本实施例电池的放电时间连续四次小于1小时36分时,停止电池工作,并开始对电池进行第三次、第四次的正、负极极性反转及其后的充电或充放电操作。如图2所示,本实施例电池在其第55-93次充放电循环工作中放电容量均为正常放电时间1小时36分(对应的放电容量为1614mAh),但在其充放循环工作到第94次的时候,电池的放电时间开始表现出下降,即第94-97次的放电时间分别为1小时35分、1小时34分、1小时33分和1小时33分(对应的放电容量分别为1603、1589、1578、1567mAh),因此达到开始对本实施例电池进行正、负极极性反转及其后的充电或充放电触发条件,此时,开始对本实施例电池进行第三、第四次正、负极极性反转及其后的充电或充放电操作,操作方法和过程与进行第一、第二次正、负极极性反转及其后的充电或充放电操作基本相同,所不同之处在于,进行第三次正、负极极性反转前 没有将电池的电压从1.75V恒流放电至0V,而是当电池在其电压降至1.75V后,停止电池的工作,并直接手动对该电池的电极连接进行变换或互换,即将本实施例电路与本实施例铅酸蓄电池的连接状态从正接状态改换成反接状态,连接变换或互换后此时测得电池电压为负值,然后,以1008mA的恒电流对变换了连接状态后的电池进行充电,当电池电压从负值上升到0V再到1.75V(此过程中完成了本实施例电池的第三次正、负极极性反转)后,继续以1008mA的恒电流对电池充电3小时,然后,以1008mA恒电流对电池进行放电,至0V时停止放电,然后,再一次(第四次)对该电池进行正、负极极性反转,即,手动将本实施例电路与铅酸蓄电池的连接状态从反接状态改换成正接状态,然后,对该电池以251.5mA的恒电流进行充电,至电池电压1.75V时,再以404mA恒电流充电,至电池电压2.65V时,再以2.65V恒电压对电池充电3小时,至此,完成对本实施例电池的第三、第四次正、负极极性反转及其后的充电或充放电操作。然后,使该电池重新进入同前的放电-充电循环工作状态或制度下进行第98次工作放电及之后次数的循环充放电工作。结果表明,经第三、第四次正、负极极性反转及其后的充电或充放电操作后,该电池在第98次循环工作中的放电容量为1489mAh(对应的放电时间1小时28分,没达到1614mAh这可能与工作放电前的充电不足有关),而其第99次循环工作中的放电容量已恢复到正常工作的放电容量,1614mAh(对应的放电时间为1小时36分)。
接下来使本实施例电池继续按工作制度运行,并将触发电池正、负极极性反转及其后的充电或充放电操作的开始条件通过编程更改(在第99次工作放电后)为:当本实施例铅酸蓄电池的放电时间小于1小时36分时,停止电池工作并开始自动地对电池进行第五、第六次的正、负极极性反转及其后的充电或充放电操作。如图2所示,本实施例铅酸蓄电池在其第99-126次充放电循环工作中的放电时间均为1小时36分(对应的放电容量均为1614mAh),当其循环工作到第127次的时候,电池的放电工作能力开始下降,放电时间为1小时35分(此时电池电压已降至1.75V,对应的放电容量为1607mAh),因此,根据设定的触发条件和程序,本实施例电路此时立即将本实施例电池由工作状态自动转入进行正、负极极性反转及其后的充电或充放电操作的准备和实施阶段,即在电池电压降至1.75V后,停止电池工作,并自动地以1008mA的恒电流对本实施例电池继续进行放电,并且通过该本实施例电路的强制放电功能,该继续放电操作使电池电压从1.75V下降到0V,然后再从0V下降到﹣1.75V(期间到达0V时静置10min,此从1.75V下降到0V再下降到-1.75V的过程中完成了本实施例电池的第五次正、负极极性反转,从1.75V下降到0V的过程中,本实施例电池的正极板或电极A上发生铅酸蓄电池正极电极反应的放电过程、负极板或电极B1、B2上发生铅酸蓄电池负极电极反应的放电过程,从0V下降到-1.75V的过程中,本实施例电池的正极板或电极A上发生铅酸蓄电池负极电极反应的充电过程、负极板或电极B1、B2上发生铅酸蓄电池正极电极反应的充电过程)在到达﹣1.75V后,继续保持以1008mA的恒电流强制放电3小时(此时测得电池电压从﹣1.75V下降到约﹣2.12V),强制放电3小时后,本实施例电路接着以1008mA的恒电流对该电池进行强制充电(测得电池电压从约﹣2.12V上升到0V,充电耗时21分钟),当电池电压达到0V 后,静置10min,然后,本实施例电路自动地继续以251.2mA的恒电流对电池充电,直至电池电压达1.75V(此从-2.12V上升到0V再上升到1.75V的过程中完成了本实施例电池的第六次正、负极极性反转,从-2.12V上升到0V的过程中,本实施例电池的正极板或电极A上发生铅酸蓄电池负极电极反应的放电过程、负极板或电极B1、B2上发生铅酸蓄电池正极电极反应的放电过程,从0V上升到1.75V的过程中,本实施例电池的正极板或电极A上发生铅酸蓄电池正极电极反应的充电过程、负极板或电极B1、B2上发生铅酸蓄电池负极电极反应的充电过程)后,再以404mA的恒电流对电池继续充电,直至测得电池电压达2.65V后,再对电池以2.65V恒压充电,并使此恒压充电保持3小时,至此,完成对本实施例铅酸蓄电池的第五、第六次正、负极极性反转及其后的充电或充放电操作,然后将本实施例电池转回到其同前的放电-充电循环工作状态或制度下进行第128次工作放电及之后次数的循环充放电工作。结果表明,经第五、第六次正、负极极性反转及其后的充电或充放电操作后,本实施例电池在第128次循环工作状态下的放电时间为1小时25分(对应的放电容量为1428mAh,此次未达到1614mAh这可能与工作放电前的充电不足有关),而其第129次工作状态下的放电容量已恢复到正常的放电时间1小时36分(对应的放电容量为1614mAh)。
接下来使本实施电池继续按工作制度运行,如图2所示,电池在其第129-152次循环工作中的放电时间均为正常的1小时36分,当本实施例电池在循环工作到第153次时,其放电时间为1小时35分(相应的放电容量为1612mAh),再次触发之前设定的电池正、负极极性反转及其后的充电或充放电操作的开始条件,因而在第153次放电工作结束后(放电结束时电池电压为1.75V),本实施例电路开始对本实施例电池进行第七、第八次的正、负极极性反转及其后的充电或充放电操作,操作方法和过程与本实施例电池第五、第六次的正、负极极性反转及其后的充电或充放电操作相同,然后将本实施例电池转回到其同前的放电-充电循环工作状态或制度下进行第154次工作放电及之后次数的循环充放电工作,结果表明,经第七、第八次的正、负极极性反转及其后的充电或充放电操作后,本实施例电池在第154、155次循环工作制度下的放电时间分别为1小时15分、1小时34分(对应的放电容量为1260、1579 mAh,均未达到1614mAh这可能与工作放电前的充电不足有关,且该两次工作放电由于误操作导致过放电),而其第156次工作状态下的放电容量已恢复到正常的放电时间1小时36分(对应的放电容量为1614mAh)。
接下来使本实施例电池继续按工作制度运行,如图2所示,电池在其第156-166次循环工作中的放电时间均为1小时36分,当电池在循环工作到第167次时,其放电时间为1小时35分时(相应的放电容量为1604mAh),再次触发之前设定的电池正、负极极性反转及其后的充电或充放电操作的开始条件,因而在第167次放电工作结束后(放电结束时电池电压为1.75V),本实施例电路接下来开始对本实施例电池进行第九、第十次的正、负极极性反转及其后的充电或充放电操作,操作方法和过程仍与本实施例电池第五、第六次的正、负极极性反转及其后的充电或充放电操作相同,然后将本实施例电池转回到其同前的放电-充电循环工作状态或制度下进行第168次工作放电及之后次数的循环充放电工作,结果,经第九、第十次的正、负极极性反转及其后的充电或充放电操作后,本 实施例电池在第168、169次循环工作状态下的放电时间分别为1小时06分、1小时16分(对应的放电容量为1109、1277 mAh,均未达到1614mAh这可能与工作放电前的充电不足有关),而其第170次工作状态下的放电容量则恢复到正常的放电时间1小时36分(对应的放电容量为1614mAh)。
接下来使本实施例电池继续按工作制度运行,在电池完成第170次循环工作后,将触发电池正、负极极性反转及其后的充电或充放电操作的开始条件通过编程更改为:当本实施例铅酸蓄电池的工作放电时间小于46分时,停止电池工作并开始对电池进行第十一、第十二次的正、负极极性反转及其后的充电或充放电操作。如图2所示,在接下来的第170-179次循环的工作中其放电时间都是1小时36分,但在第180次循环工作中放电容量开始下降,并在第192次的循环工作中放电时间为45分(对应的放电容量为756mAh),触发了开始电池正、负极极性反转及其后的充电或充放电操作的条件,因而在第192次循环放电工作结束后(放电结束时电池电压为1.75V),本实施例电路开始对本实施例电池进行第十一、第十二次的正、负极极性反转及其后的充电或充放电操作,该操作过程与本实施例电池第五、第六次的正、负极极性反转及其后的充电或充放电操作基本相同,所不同之处在于,在到达﹣1.75V后,继续对本实施例电池以1031mA的恒电流进行强制放电4小时(而不是3小时,此过程测得电池电压仍是从﹣1.75V下降到约﹣2.12V)。结果,经第十一、第十二次的电池正、负极极性反转及其后的充电或充放电操作后,本实施例电池在第193次的循环工作中放电时间恢复到1小时32分(对应的容量为1560mAh),而在第194次的循环工作中放电时间恢复到1小时36分,并且在接下来的直到第210次的循环充放工作中其放电时间都是1小时36分。图3示出了本实施例铅酸蓄电池第189-196次循环充放电工作过程及该过程期间穿插的第十一、十二次正、负极极性反转及其后的充电或充放电操作过程中的电流、电池电压变化情况。
如图2所示,本实施例铅酸蓄电池在接下来的第211-667次循环工作中,每当本实施例铅酸蓄电池的工作放电时间降至1小时36分(相应的容量为1614mAh)或以下时,即对本实施例铅酸蓄电池进行一期类似上述的连续两次的极性反转及其后的充电或充放电操作,即分别在循环工作放电的第220(相应的工作放电容量为1475mAh,以下同)、221次之间、第252(1292.8mAh)、253次之间、第296(1611mAh)、297次之间、第327(1610.4mAh)、328次之间、354(1590.5mAh)、355次之间、第382(1590mAh)、383次之间、第403(1602.3mAh)、404次之间、第423(1600mAh)、424次之间、第436(1610.9mAh)、437次之间、第447(1579.8mAh)、448次之间、第491(1605mAh)次、492次之间、第538(1612.6mAh)、539次之间、第582(1609.8mAh)、583次之间、第614(1611.8mAh)、615次之间、第641(1606.8mAh)、642次之间,分别地进行了连续的第十三与第十四次、连续的第十五与第十六次、......的正、负极极性反转及其后的充电或充放电操作,并使得本实施例铅酸蓄电池在每期连续两次的正、负极极性反转及其后的充电或充放电操作后,本实施例铅酸蓄电池的工作放电容量均很快地或随即地恢复至1614mAh,从而使得本实施例铅酸蓄电池保有继续正常工作的能力。
如图2所示,本实施例上述每期连续两次正、负极极性反转后,有仅通过充电操作就使得本实施例铅酸蓄电池工作放电容量恢复正常的,有通过一次或一次以上的充电-放电-充电操作后,使 得本实施例铅酸蓄电池工作放电容量恢复正常的,例如,在本实施例铅酸蓄电池循环工作放电的第582、583次之间的对本实施例铅酸蓄电池的连续两次正、负极极性反转后对本实施例铅酸蓄电池进行的充放电操作为:对本期两次极性反转后的本实施铅酸蓄电池进行404mA恒电流充电至2.65V(耗时13小时54分),然后再恒压2.65V充电3小时,然后将本实施例铅酸蓄电池投入到循环充放电工作制度下进行第583次工作放电,结果本实施例电池在第583次的工作放电时间或容量或能力即恢复至正常的1小时36分或1614mAh以上。
本实施例中的一些实验数据表明,本实施例铅酸蓄电池每期连续两次极性反转及其后的充电或充放电操作后随即本实施例铅酸蓄电池的工作放电容量恢复的程度以及本实施例铅酸蓄电池每期工作放电容量恢复后可连续保持正常循环工作的次数(即每两期连续两次极性反转及其后的充电或充放电操作之间本实施例铅酸蓄电池所被恢复的正常工作循环次数)应该与每期极性反转操作开始前电池的实际工作放电容量下降程度、每期连续两次极性反转及其后的充电或充放电操作中所采用的电流、电压、时间、充放电容量、脉冲或直流、频率、阶段数、电解液密度、电解液饱和程度、电池的内组、循环工作的总累计次数等的大小、方式方法有关。
本实施例中,若按照现行的电池使用寿命定义方法,将本实施例铅酸蓄电池的使用寿命定义为连续三次工作放电容量低于额定容量的83%时(1602mAh)视为电池使用寿命终止,则本实施例铅酸蓄电池在被进行任何本实施例的极性反转及其后的充电或充放电操作之前,如图2所示,其使用寿命为53次循环,即,第51、52、53次的工作放电容量分别为1582.8、1568.1、1554mAh,但是通过本实施例的正、负极极性反转及其后的充电或充放电操作方法、铅酸蓄电池及电路,本实施例铅酸蓄电池循环工作放电容量达到额定容量的83%或以上的循环次数即使用寿命循环次数被延长至608次,增加了1047%,且据上可以推测,在不产生集流体腐蚀、失水等情况下,按照上述操作方法,可以使本实施例铅酸蓄电池的使用寿命获得继续提高或延长。
一方面如上所述,本实施例的正、负极极性反转及其后的充放电或充放电操作使得本实施例铅酸蓄电池的正极活性物质软化、脱落被改善、修复、逆转,从而使得本实施例铅酸蓄电池循环工作中的工作放电容量在该操作之后获得提高或恢复,另一方面,本实施例的正、负极极性反转及其后的充放电或充放电操作,也必然对本实施例电池循环工作过程中发生、轻微发生或可能发生的电极钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极比表面积收缩的问题具有改善、修复、逆转、预防的作用。在本实施例铅酸蓄电池正常循环工作过程中,定期或不定期的(例如,以规定循环工作次数的方式)、穿插地对本实施例铅酸蓄电池进行本实施例的正、负极极性反转及其后的充放电或充放电操作,将会有效的改善、修复、逆转、预防正极活性物质软化或/和脱落、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩问题,从而提高或延长本实施例铅酸蓄电池的使用寿命。
在本实施例的其它实施方式中,本实施例具有正、负极极性反转及其后的充电或充放电功能的电路被整合到电池充电及修复仪的构成中,成为电池充电及修复仪产品的一部分。
在本实施例的其它实施方式中,本实施例具有正、负极极性反转及其后的充电或充放电功能的电路被整合到铅酸蓄电池的构成中,成为铅酸蓄电池产品的一部分。
在本实施例的其它实施方式中,本实施例铅酸蓄电池的电解液密度可以为1.29g/cm 3或1.32g/cm 3
在本实施例的其它实施方式中,本实施例具有正、负极极性反转及其后的充电或充放电功能的电路,既没有被整合到电池充放电器的构成中,也没有被整合到铅酸蓄电池的构成中,而是作为一个独立的产品。
在本实施例的其它实施方式中,将本实施例提高或延长铅酸蓄电池使用寿命的方法、电路用于本实施例铅酸蓄电池组(额定电压为36V、额定容量为12Ah),成为本实施例提高或延长铅酸蓄电池组使用寿命的方法、电路,应用时,本实施方式中的方法和电路在电压、电流、容量等参数值的设定和执行、允许范围方面作了相应于电池组参数的变化,如,将铅酸蓄电池组强制放电至电池组电压<0V后,使电池组电压继续下降至﹣7V、﹣10.7V、﹣12.6V、﹣15.3V后停止强制放电,强制放电电流为0.4倍率、0.6倍率、1倍率、2倍率。
在本实施例的其它实施方式中,将本实施例提高或延长铅酸蓄电池或电池组使用寿命的方法、电路用于管式铅酸蓄电池或蓄电池组、卷绕式铅酸蓄电池或蓄电池组、双极式铅酸蓄电池或蓄电池组、水平铅布式铅酸蓄电池或蓄电池组、泡沫板栅式铅酸蓄电池或蓄电池组、阀控式密封铅酸蓄电池或蓄电池组、胶体铅酸蓄电池或蓄电池组、铅碳蓄电池或蓄电池组、超级电容器-铅酸蓄电池或蓄电池组、柱式铅酸蓄电池或蓄电池组。
实施例8
本实施例铅酸蓄电池为一种平面板栅式铅酸蓄电池,具有两片负极板夹着一片正极板的结构,正极、负极之间隔有AGM隔板,正极板栅的矩形栅格为9mm*7.5mm、负极板栅的矩形栅格为13mm*7mm,正极板栅的材料为铅钙锡铝合金,负极板栅的材料为铅钙铝合金,正极板厚度为2.8mm,负极板厚度为1.9mm,正极铅膏的配方与现行普通商用正极铅膏的配方基本相同,配方不同之处在于,本实施例铅酸蓄电池采用的铅粉为氧化度为100%的高比表面积氧化铅粉,和膏时使用的硫酸量为零,负极铅膏为现行普通商用负极铅膏。本实施例铅酸蓄电池的额定容量为1.79Ah(C 1.5,1.5h率,25℃),额定电压为2V,负极总容量相对过剩于正极总容量,固化、干燥后正极板上干铅膏的质量为32.36g,本实施例铅酸蓄电池中的硫酸溶液密度为1.27g/cm 3,并在下述的本实施例电池循环工作和极性反转及其后的充电或充放电操作过程中始终保持充足。本实施例铅酸蓄电池工作时正极板仅作为正极使用,两片负极板在电池工作时仅作为负极使用,为便于后续极性反转操作的叙述,将本实施例铅酸蓄电池的正极板命名为电极A,将本实施例铅酸蓄电池的两片负极板命名为电极B1、B2。
本实施例提高或延长铅酸蓄电池使用寿命的方法为,在本实施例电池的循环充放电工作过程中,每当本实施例铅酸蓄电池的工作放电次数达到某预设的次数值时,或其工作放电容量,因正极活性 物质软化或/和脱落、负极活性物质比表面积收缩、电极/汇流体/集流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良问题中的一种或多种,而低于其额定容量的某一百分比值(例如85.5%、80%)时,即开始对本实例铅酸蓄电池的正极、负极自动或/和手动地进行一期连续两次的极性反转及其后的充电或充放电操作,使得正极活性物质软化或/和脱落、负极活性物质比表面积收缩、电极/汇流体/集流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良问题中的一种或多种得到抑制、防止、修复、改善、消除或逆转,使本实施例铅酸蓄电池在该操作完成后,工作放电容量得到恢复或提高,然后,将本实施例铅酸蓄电池重新投入到循环充放电工作中使用或工作,直到再次触发或开始又一期对本实施例铅酸蓄电池正极、负极进行连续两次的极性反转及其后的充电或充放电操作。本实施例所述任意一期连续两次的正极、负极极性反转及其后的充电或充放电操作包括步骤:(1)通过对本实施例铅酸蓄电池进行反极充电(电流为1194mA)的方法,使得本实施例铅酸蓄电池原来的正极(电极A)与原来的负极(电极B1、B2)的极性发生反转或互换,即原来的正极(电极A)的极性被反转成负、原来的负极(电极B1、B2)的极性被反转成正,此为该期连续两次的极性反转及其后的充电或充放电操作中的第一次极性反转,然后,对经该第一次极性反转后的正极(电极B1、B2)、负极(电极A)进行1194mA恒流充电至1.75V或2.0V(此时电极B1、B2的极性为正、电极A的极性为负),然后,以1194mA的电流恒流充电方式继续充电3或4或5小时(此过程中电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的充电过程,电极A上主要发生的是铅酸蓄电池负极电极反应的充电过程);(2)上步结束后,对本实施例铅酸蓄电池以1194mA的电流进行恒流放电至0V(此过程中电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的放电过程,电极A上主要发生的是铅酸蓄电池负极电极反应的放电过程);(3)当本实施例铅酸蓄电池的电压达到0V时,通过对本实施例铅酸蓄电池进行反极充电(298mA的电流)的方法,使得本实施例铅酸蓄电池的电极A、B1、B2再次发生极性反转,即将电极B1、B2从正极性反转成负极性,将电极A从负极性反转成正极性,此为该期连续两次的极性反转及其后的充电或充放电操作中的第二次极性反转,然后以298mA恒电流对经该第二次极性反转后的本实施例铅酸蓄电池进行充电至1.75V,然后再以477mA的电流恒流充电至2.65V,然后再以2.65V的恒电压进行恒压充电4小时,然后,再以1194mA的电流放电至1.75V,然后再以477mA的电流恒流充电至2.65V,然后再以2.65V恒压充电,并且在最后两步所述的477mA恒流、2.65V恒压充电的累计时间为6小时24分时停止对本实施例铅酸蓄电池充电,完成步骤(3),在所述步骤(3)中,所述第二次极性反转后,电极A上发生铅酸蓄电池正极电极反应的充、放电过程,电极B1、B2上发生铅酸蓄电池负极电极反应的充放电过程,至此完成本实施例一期连续两次的正极、负极极性反转及其后的充电或充放电操作。本实施例铅酸蓄电池其循环充放电工作的制度为,工作放电时,本实施例铅酸蓄电池以1194mA(0.62C 2)的恒电流放电至1.75V,即100%DOD(放电深度)的放电,然后对本实施例铅酸蓄电池以477.6mA的恒电流进行充电至2.65V,然后再以2.65V的恒电压对本实施例铅酸蓄电池进行恒压充电,并且当所述477.6mA恒流、2.65V恒压充电的总时间为6小时24分时,终止对本实施例铅酸蓄电池的充电过程, 然后,使本实施例铅酸蓄电池再一次进行上述的工作放电过程,反复、多次地进行如此地放电、充电过程,实现本实施例铅酸蓄电池的循环充放电工作过程。本实施例铅酸蓄电池在其循环工作中,电极A始终为正,电极B1、B2始终为负,即电极A上发生铅酸蓄电池正极电极反应的充放电过程,电极B1、B2上发生铅酸蓄电池负极电极反应的充放电过程。本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
如图4所示,本实施例铅酸蓄电池在其使用或循环工作过程中,分别在其工作放电的第199、200次之间、第214、215次之间、第223、224次之间、第232、233次之间、第241、242次之间、第254、255次之间、第263、264次之间、第274、275次之间、第280、281次之间、第283、284次之间、第293、294次之间、第312、313次之间、第328、329次之间、第358、359次之间、第387、388次之间、第406、407次之间、第417、418次之间、第426、427次之间、第436、437次之间、第451、452次之间、第466、467次之间、第486、487次之间,被进行了总累计为22期(共44次)的、本实施例所述的、每期为连续两次进行的正极、负极极性反转及其后的充电或充放电操作,其中,本实施例所述连续两次进行的正极、负极极性反转及其后的充电或充放电操作的步骤(1)中1194mA恒流充电至1.75V或2.0V后继续进行的1194mA恒流充电时间,前8期均为3小时、第9期至第17期为4小时、后5期为5小时。触发或开始所述22期连续两次进行的正极、负极极性反转及其后的充电或充放电操作的条件、触发或开始时电池所处的荷电状态不完全相同,例如,第199、200次之间一期连续两次进行的极性反转及其后的充电或充放电操作的触发或开始条件为工作循环次数达到预设的工作放电-充电循环次数199次,并在第199次工作放电结束后开始连续两次进行的正极、负极极性反转及其后的充电或充放电操作;例如,第214、215次之间一期连续两次进行的极性反转及其后的充电或充放电操作的触发或开始条件为工作放电容量首次低于额定容量的85.5%,并在第215次工作循环恒压充电过程结束后开始连续两次进行的正极、负极极性反转及其后的充电或充放电操作;例如,第274、275次之间一期连续两次进行的极性反转及其后的充电或充放电操作的触发或开始条件为工作放电容量连续四次低于额定容量的80%;例如,第387、388次之间一期连续两次进行的极性反转及其后的充电或充放电操作开始时,本实施例铅酸蓄电池正处于充电过程中;另外,第406、407次之间一期连续两次进行的极性反转及其后的充电或充放电操作的步骤(1)中所进行的对该期第一次极性反转后的正极(电极B1、B2)、负极(电极A)进行1194mA恒流充电所至的电压为2.0V;在第436、437次之间一期连续两次进行的正极、负极极性反转及其后的充电或充放电操作的步骤(3)中,本实施例铅酸蓄电池的电极A、B1、B2发生该期第二次极性反转后,其充放电过程为以298mA恒电流对经该期第二次极性反转后的本实施例铅酸蓄电池进行充电至1.75V,然后再以477mA的电流恒流充电至2.65V,然后再以2.65V的恒电压进行恒压充电4小时,然后,直接将本实施例铅酸蓄电池投入到工作循环中去使用或工作,这样省掉了其它期所述操作步骤(3)中的“再以1194mA的电流放电至1.75V,然后再以477mA的电流恒流充电至2.65V,然后再以2.65V恒压充电,并且在最后两步所述的477mA恒流、2.65V恒压充电的累计时间为6小时24分时停止 对本实施例铅酸蓄电池充电,完成步骤(3)”。
如图4所示,在完成每期本实施例的连续两次正极、负极极反转及其后的充电或充放电操作后,本实施例铅酸蓄电池在循环充放电工作中的工作放电容量都随即被明显地提升或恢复(经检查,这是由于改善、修复、逆转了正极活性物质软化、脱落)。如果将本实施例铅酸蓄电池的使用寿命定义为其工作放电容量连续三次低于其额定容量的80%(1447mAh)时视为本实施例铅酸蓄电池的使用寿命终止,则本实施例铅酸蓄电池的使用寿命至多为272次工作循环,(本实施例铅酸蓄电池在第270、271、272次的工作放电容量分别为1434、1353、1279mAh),但是本实施例通过所述正极、负极极性反转及其后的充电或充放电操作,使得本实施例铅酸蓄电池的使用寿命(工作放电容量在额定容量的80%以上的所有工作放电充电循环次数)被提高或延长到495次,且可推测,在排除板栅腐蚀、电极变形、电池失液、电池短路、断路因素的情况下,本实施例铅酸蓄电池会有比495次循环更长的使用寿命。
一方面如上所述,本实施例的正极、负极极性反转及其后的充放电或充放电操作使得本实施例铅酸蓄电池的正极活性物质软化、脱落被改善、修复、逆转,从而使得本实施例铅酸蓄电池循环工作中的工作放电容量该操作之后获得提高或恢复,另一方面,本实施例的正极、负极极性反转及其后的充放电或充放电操作,也必然对本实施例电池循环工作过程中发生、轻微发生或可能发生的电极钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极比表面积收缩的问题具有改善、修复、逆转、预防的作用。在本实施例铅酸蓄电池正常循环工作过程中,定期或不定期的(例如,以规定循环工作次数的方式)、穿插地对本实施例铅酸蓄电池进行本实施例的正极、负极极性反转及其后的充放电或充放电操作,将会有效的改善、修复、逆转、预防正极活性物质软化或/和脱落、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩问题,从而提高或延长本实施例铅酸蓄电池的使用寿命。
在本实施例的其它实施方式中,可以使用脉冲电流、脉冲电压代替直流电、恒电压进行本实例的连续两次的正极、负极极性反转及其后的充电或充放电操作步骤中的极性反转及其后的充电或充放电过程或步骤,从而提高本实施例铅酸蓄电池正极、负极极性反转及其后的充电或充放电操作的时效、能效。为了防止或减少析氧或析氢,也可限制极性反转及其后充电或充放电操作过程中电池电压达到的最大值小于2.65V,如2.5V、2.44V、2.33V。
实施例9
本实施例铅酸蓄电池为一种管式铅酸蓄电池,具有两片平面板栅式负电极夹着一根管式正电极的结构,正极、负极之间通过AGM隔板进行隔离,管式正电极的外套管内直径为6.3mm、管壁厚0.25mm、管高75mm(包括上、下塞头的长度)、管中铅-钙合金导电骨芯的直径为2.5mm、管内活性物质质量为5.5g,由现行普通商用球磨铅粉构成,负极板其外框尺寸为72mm*45m、矩形栅格为13mm*7mm,厚度为1.9mm,负极铅膏为现行普通商用负极铅膏。本实施例铅酸蓄电池最初预设的额定容量为0.342Ah (C 2,2h率,25℃,活性物质利用率为25.5%),额定电压为2V,负极总容量相对过剩于正极总容量,本实施例铅酸蓄电池中的硫酸溶液密度为1.27g/cm 3,并在下述的本实施例电池循环工作和极性反转及其后的充电或充放电操作过程中始终保持充足。本实施例铅酸蓄电池工作时管式正电极仅作为正极使用,两片负极板在电池工作时仅作为负极使用,为便于后续极性反转操作的叙述清楚,将本实施例铅酸蓄电池的管式正电极命名为管式电极A,将本实施例铅酸蓄电池的两片负极板命名为板式电极B1、B2。本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
本实施例提高或延长铅酸蓄电池使用寿命的方法为,当本实施例铅酸蓄电池在其循环充放电工作的使用或工作中,循环达到一定次数后或者根据需要(例如正极活性物质软化或/和脱落、负极活性物质比表面积收缩、电极/汇流体/集流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良因素中的一种或多种使本实施例铅酸蓄电池工作放电容量下降并低于某容量数值时或后,希望或需要提高电池工作放电容量或提高、延长电池使用寿命)在某两次循环工作之间,对本实例铅酸蓄电池的正、负极自动或/和手动地进行一期连续两次的极性反转及其后的充电或充放电操作,使本实施例铅酸蓄电池在该操作完成后,工作放电容量得到恢复或提高,然后,将本实施例铅酸蓄电池重新投入到循环充放电工作中继续使用或工作,直到再次触发或开始又一期对本实施例铅酸蓄电池正、负极进行连续两次的极性反转及其后的充电或充放电操作,如此,在本实施例铅酸蓄电池的循环充放电工作(简称循环工作,以下同)过程中,反复地、穿插地、多期地进行本实施例上述的正、负极极性反转及其后的充电或充放电操作,通过抑制、防止、修复、改善、消除或逆转铅酸蓄电池的正极活性物质软化或/和脱落、负极活性物质比表面积收缩、电极/汇流体/集流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良问题中的一种或多种,来明显提高或延长本实施例铅酸电池的使用寿命。本实施例所述任意一期连续两次的极性反转及其后的充电或充放电操作包括步骤:(1)通过对本实施例铅酸蓄电池进行反极充电的方法,使得本实施例铅酸蓄电池原来的正极(管式电极A)与原来的负极(板式电极B1、B2)的极性发生反转或互换,即原来的正极(管式电极A)的极性被反转成负、原来的负极(板式电极B1、B2)的极性被反转成正,此为该期连续两次的极性反转及其后的充电或充放电操作中的第一次极性反转,然后,对经该第一次极性反转后的正极(板式电极B1、B2)、负极(管式电极A)进行恒流充电一定时间(此过程中板式电极B1、B2的极性为正、管式电极A的极性为负,板式电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的充电过程,管式电极A上主要发生的是铅酸蓄电池负极电极反应的充电过程);(2)上步结束后,对本实施例铅酸蓄电池以一定的电流进行恒流放电至0V(此过程中板式电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的放电过程,管式电极A上主要发生的是铅酸蓄电池负极电极反应的放电过程);(3)当本实施例铅酸蓄电池的电压达到0V时,通过对本实施例铅酸蓄电池进行反极充电的方法,使得本实施例铅酸蓄电池的管式电极A、板式电极B1、B2再次发生极性反转,即将板式电极B1、B2从正极性反转成负极性,将管式电极A从负极性反转成正极性,此为该期连续两次的 极性反转及其后的充电或充放电操作中的第二次极性反转,然后以一种或多种电流对经该第二次极性反转后的本实施例铅酸蓄电池进行充电至2.65V,然后再以2.65V的恒电压进行恒压充电4小时,然后,再以一定的电流放电至1.75V,然后再以一定的电流恒流充电至2.65V,然后再以2.65V恒压充电,并且在最后两步所述的恒流、2.65V恒压充电的累计时间为某值时停止对本实施例铅酸蓄电池充电,完成步骤(3),在所述步骤(3)中,所述第二次极性反转完成后所进行的充放电过程中,管式电极A上发生铅酸蓄电池正极电极反应的充、放电过程,板式电极B1、B2上发生铅酸蓄电池负极电极反应的充、放电过程,至此,完成一期连续两次进行的正、负极极性反转及其后的充电或充放电操作。
本实施例铅酸蓄电池在其整个循环充放电工作过程中的工作制度有多种,按工作进行的先后顺序,依次的有,循环充放电工作制度(1):在本实施例铅酸蓄电池化成完成后,对本实施例铅酸蓄电池以151.7mA的恒电流放电至1.75V,即100%DOD(放电深度)的放电,然后,对本实施例铅酸蓄电池以60.8mA的恒电流进行充电7小时24分,如此重复、循环进行该工作制度的放电、充电过程;循环充放电工作制度(2):将工作制度(1)中的60.8mA、7小时24分恒电流充电过程改变成为60.8mA、8小时24恒流充电,其它工作制内容不变,使本实施例铅酸蓄电池重复、循环进行该工作制度的充、放电过程;循环充放电工作制度(3):将工作制度(2)中的60.8mA、8小时24分恒电流充电过程改变成为先进行60.8mA的恒流充电、然后当电压达到2.65 V后,转变成对本实施例电池进行2.65V的恒压充电,且使每个循环中60.8mA的恒流充电与2.65V的恒压充电总时间等于9小时24,其它工作制度内容不变,如此,使本实施例铅酸蓄电池重复、循环进行该工作制度的充、放电过程;循环充放电工作制度(4):将工作制度(3)改变成先进行605.5mA的恒流充电、然后当电压达到2.65 V后,转变成对本实施例电池进行2.65V的恒压充电,且使每个循环中605.5mA的恒流充电与2.65V的恒压充电总时间等于26min,然后对本实施例铅酸蓄电池进行1518.8mA的恒流放电至1.75V,如此,使本实施例铅酸蓄电池重复、循环进行该工作制度的作充、放电过程;循环充放电工作制度(5):将工作制度(4)中的恒流放电截止电压从1.75V改成1.5V,其它的工作制度内容不变,如此,使本实施例铅酸蓄电池重复、循环进行该工作制度的充、放电过程;循环充放电工作制度(6):将工作制度(5)中的恒流充电、恒压充电总时间从26min改成35min,其它的工作制度内容不变,使本实施例铅酸蓄电池重复、循环进行该工作制度的充、放电过程;循环充放电工作制度(7):将工作制度(6)中的恒流放电截止电压为从1.5V改成1.0V,;其它的工作制度内容不变,使本实施例铅酸蓄电池重复、循环进行该工作制度的充、放电过程;循环充放电工作制度(8):先进行92.4mA的恒流充电,到2.65V,然后进行2.65V恒压充电至总累计充电时间为9小时24min,然后,以152.8mA的恒电流放电至1.75V,然后再重复该制度的充电步骤,如此,使本实施例铅酸蓄电池重复、循环进行该工作制度的充、放电过程;循环充放电工作制度(9):先进行92.4mA的恒流充电,到2.65V,然后进行2.65V恒压充电至总累计充电时间为9小时24min,然后,以228mA的恒电流放电至1.75V,然后再重复该制度的充电步骤,其它的工作制度内容不变,如此,使本实 施例铅酸蓄电池重复、循环进行该工作制度的充、放电过程。
本实施例提高或延长本实施例铅酸蓄电池使用寿命的方法的具体操作过程为,如图5所示,在本实施例铅酸蓄电池的循环充放电工作过程中适时的穿插进行一期连续两次正、负极极性反转及其后的充电或充放电操作。如图6所示,先使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(1)进行循环工作,直至总累计195次循环工作后,再使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(2)进行循环工作,直至总累计199次循环工作后,再使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(3)地行循环工作,直至总累计266次循环工作后,再使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(4)进行循环工作,直至总累计304次循环工作后,对本实施例铅酸蓄电池开始进行第一期连续两次的正、负极极性反转及其后的充放电操作:即先以1518mA的电流、以反极充电的方法对本实施例铅酸蓄电池进行该期操作的第一次正、负极极性反转,使得本实施例电池的管式电极A的极性从正被反转成负、板式电极B1、B2的极性从负被反转成正,然后以1518mA的电流对该期第一次极性反转后的本实施例电池进行恒流充电1小时24分(此过程中管式电极A的极性为负,管式电极A上主要发生的是铅酸蓄电池负极电极反应的充电过程,板式电极B1、B2的极性为正,板式电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的充电过程),然后,再以1518mA的电流对本实施例铅酸蓄电池进行放电7s至0V(此过程中管式电极A的极性为负,管式电极A上主要发生的是铅酸蓄电池负极电极反应的放电过程,板式电极B1、B2的极性为正,板式电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的放电过程);然后以300mA恒流、反极充电的方法对本实施例铅酸蓄电池进行该期第二次正、负极极性反转,使得本实施例电池的管式电极A的极性从负被反转成正、板式电极B1、B2的极性从正被反转成负,然后,继续以300mA的电流使本实施例铅酸蓄电池充电至1.75V,然后再以605.5mA恒流充电26min至2.43V,然后再以1518mA恒流放电至1.75V,重复605.5mA恒流充电26min、1518mA放电二次,然后,使本实施例铅酸蓄电池重新按照本实施例的循环充放电工作电制度(4)进行工作,直至总累计411次循环工作后,再使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(5)进行循环工作,直至总累计440次循环工作后,再使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(6)进行循环工作,直至总累计475次循环工作后,再使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(7)进行循环工作,直至总累计652次循环工作后,对本实施例铅酸蓄电池开始进行第二期连续两次的正、负极极性反转及其后的充电或充放电操作:即先以1518mA的电流对本实施例铅酸蓄电池进行恒流放电至0V,然后以1518mA、反极充电的方法对本实施例铅酸蓄电池进行极性反转,使得本实施例电池的管式电极A的极性从正被反转为负、板式电极B1、B2的极性从负被反转为正,此为该期连续两次的正、负极极性反转及其后的充电或充放电操作的第一次极性反转,然后以1518mA的电流对该期操作第一次极性反转后的电池进行恒流充电2小时45分(此过程中管式电极A的极性为负,管式电极A上主要发生的是铅酸蓄电池负极电极反应的充电过程,板式电极B1、B2的极性为正,板式电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的充电过程),然后,再以1518mA 的电流对本实施例铅酸蓄电池进行放电至0V(此过程中管式电极A的极性为负,管式电极A上主要发生的是铅酸蓄电池负极电极反应的放电过程,板式电极B1、B2的极性为正,板式电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的放电过程);然后以300mA、反极充电的方法对本实施例铅酸蓄电池进行该期第二次正、负极极性反转,使得本实施例电池的管式电极A的极性从负被反转成正、板式电极B1、B2的极性从正被反转成负,然后300mA恒流充电至1.75V,然后再以1518mA放电5秒种,然后再以905mA恒流充电2min,然后再以1518mA恒流放电29秒,然后905mA恒流充35min再1518mA恒流放电至1.0V,再重复一次905mA恒流充35 min、1518mA恒流放电至1.0V,然后,以905mA充电2小时45min,然后再1518mA放电至1.0V,然后,使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(7)进行循环工作,直至本实施例铅酸蓄电池总累计714次循环工作后,再使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(8)进行循环工作,直至总累计732次循环工作后,再使本实施例铅酸蓄电池按照本实施例的循环充放电工作制度(9)进行循环工作,直至总累计751次循环工作后,进行第三期连续两次的正、负极极性反转及其后的充电或充放电操作,即当本实施例铅酸蓄电池正处于第752次循环工作的充电状态时,停止该充电,然后对本实施例电池以456mA的电流、以反极充电的方法对本实施例铅酸蓄电池进行极性反转,使得本实施例电池的管式电极A的极性从正被反转为负、板式电极B1、B2的极性从负被反转为正,此为该期操作的第一次极性反转,然后以456mA的电流对该期第一次极性反转后的本实施例电池进行恒流充电4小时15分(此过程中管式电极A的极性为负,管式电极A上主要发生的是铅酸蓄电池负极电极反应的充电过程,板式电极B1、B2的极性为正,板式电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的充电过程),然后,再以456mA的电流、以反极充电的方法使本实施例电池发生该期操作的第二次正、负极极性反转,即将管式电极A的极性从负被反转成正、板式电极B1、B2的极性从正被反转成负,然后继续以456mA恒流充电至2.65V,然后再以228mA恒流放电至1.75V(在该期操作的第二次正、负极极性反转及其后的充电或充放电操作过程中,管式电极A上发生的电极反应从铅酸蓄电池负极电极反应的放电过程被反转成铅酸蓄电池正极电极反应的充放电过程,板式电极B1、B2的上发生的电极反应从铅酸蓄电池正极电极反应的放电过程被反转成铅酸蓄电池负极电极反应的充放电过程),然后,使本实施例铅酸蓄电池按照本实施例循环充放电工作制度(9)进行循环工作。
本实施例铅酸蓄电池在其循环工作过程中,管式电极A的极性始终为正,板式电极B1、B2的极性始终为负,即管式电极A上发生铅酸蓄电池正极电极反应的充放电过程,板式电极B1、B2上发生铅酸蓄电池负极电极反应的充放电过程。
如图6所示,在完成每期本实施例的连续两次正、负极极反转及其后的充电或充放电操作后,本实施例铅酸蓄电池的工作放电容量都随即被明显地提升或恢复(经检查,这是由于修复、改善、消除或逆转铅酸蓄电池的正极活性物质软化或/和脱落、电极/汇流体/集流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良等问题中的一种或多种)。如果定义本实施例铅酸蓄电 池循环充放电工作制度(4)下的额定容量为106.6mAh,且连续三次低于该额定容量的80%时电池使用寿命终止,则,第278次循环后电池寿命已终止,或者,如果定义本实施例铅酸蓄电池循环充放电工作制度(7)下的额定容量为288.8mAh,且连续三次低于该额定容量的90%时电池使用寿命终止,则,第582次循环后电池寿命已终止,或者,如果定义本实施例铅酸蓄电池循环充放电工作制度(9)下的额定容量为562.2mAh,且连续三次低于该额定容量的88%时电池使用寿命终止,则,第750次循环后电池寿命已终止,但是如图5、图6所示,经本实施例的分别在本实施铅酸蓄电池循环充放电工作总累计循环次数的第304、305次之间、第652、653次之间、第751、752次之间所进行的第一、二、三期连续两次进行的本实施例铅酸蓄电池正、负极极性反转及其后的充电或充放电操作,本实施例铅酸蓄电池的使用寿命获得了明显的提高或延长,可以推测,在不受板栅腐蚀、变形、电池失液、短路、断路等问题干扰的情况下,使用本实施例的方法,可以使本实施例铅酸蓄电池的使用寿命获得更大的提高或延长。
在本实施例的其它实施方式中,可以使用脉冲电流、脉冲电压代替直流电、恒电压进行本实例的连续两次极性反转及其后的充电或充放电操作步骤中的极性反转及其后的充电或充放电步骤或过程,从而有利于提高本实施例铅酸蓄电池极性反转及其后的充电或充放电操作的时效、能效。
实施例10
本实施例铅酸蓄电池组为一种平面板栅式铅酸蓄电池组,该电池组的额定电压为4V,设计额定容量为2.996Ah(C 3.5,3.5h率,25℃),负极总容量相对过剩于正极总容量,本实施例铅酸蓄电池组由两个彼此相同的单格铅酸蓄电池串联而成,每个单格电池由三片负极板和两片正极板构成,每两片负极板之间夹有一片正极板,正、负极板之间隔有AGM隔板,正、负极板的外边框尺寸相同,高×宽为38mm×68mm,正、负极板所具有的板栅栅格为矩形栅格为11mm*5mm,正极板的厚度为2.1mm,负极板的厚度为1.3,正极板的铅膏为现行普通商用正极铅膏(其配方包括球磨铅粉、硫酸、正极添加剂,但不包括硫酸钡)、负极铅膏为现行普通商用负极铅膏(其配方包括球磨铅粉、硫酸、负极添加剂),本实施例铅酸蓄电池中的硫酸溶液密度为1.27g/cm 3,并在下述的本实施例电池组循环工作和正、负极极性反转及其后的充电或充放电操作过程中始终保持充足。本实施例铅酸蓄电池组循环工作时,正极板仅作为正极使用、负极板仅作为负极使用,为便于后续极性反转操作的叙述,将本实施例铅酸蓄电池组所具有的四片正极板分别命名为电极A1、A2、A3、A4,将本实施例铅酸蓄电池组所具有的六片负极板分别命名为电极B1、B2、B3、B4、B5、B6。将本实施例铅酸蓄电池组正极板所连接的电池组输出端命名为电池组输出端K、将本实施例铅酸蓄电池组负极板所连接的输出端命名为电池组输出端L。本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
本实施例提高或延长铅酸蓄电池组使用寿命的方法为,当本实施例铅酸蓄电池组在其循环充放电工作的使用或工作中(例如,已完成了1次以上的循环充放电工作),由于本实施例铅酸蓄电池组 的循环充放、过充电、欠充电、高活性物质利用率、板栅腐蚀及钝化等原因,导致因正极活性物质软化或/和脱落、硫酸盐化、钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极活性物质比表面积收缩等原因中的一种或多种而使得本实施例铅酸蓄电池组的工作放电容量下降,根据需要(例如本实施例铅酸蓄电池组工作放电容量下降并低于某容量数值时或后,希望或需要提高电池组工作放电容量或提高、延长电池组使用寿命)或按规定的循环次数在某两次循环工作之间,对本实例铅酸蓄电池组的正、负极自动或/和手动地进行一期连续两次的正、负极极性反转及其后的充电或充放电操作,改善、修复、消除、逆转、抑制、防止正极活性物质软化、负极比表面积收缩、腐蚀、电极钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良等问题,使本实施例铅酸蓄电池组在完成一期连续两次的极性反转及其后的充电或充放电操作后的工作放电容量得到恢复或提高,所述一期连续两次的正、负极极性反转及其后的充电或充放电操作完成后,将本实施例铅酸蓄电池组重新投入到循环充放电工作中使用或工作,直到再次触发或开始又一期对本实施例铅酸蓄电池组的正、负极进行连续两次的极性反转及其后的充电或充放电操作。本实施例所述任意一期连续两次的极性反转及其后的充电或充放电操作包括步骤:(1)停止本实施例铅酸蓄电池组的工作,然后通过对本实施例铅酸蓄电池组进行反极充电的方法,使得本实施例铅酸蓄电池组原来的正极输出端(电池组输出端K)与原来的负极输出端(电池组输出端L)的极性发生反转或互换,即原来的正极输出端(电池组输出端K)的极性由正被反转成负、原来的负极输出端(电池组输出端L)的极性由负被反转成正,此为该期连续两次的极性反转及其后的充电或充放电操作中的第一次极性反转,然后,对经第一次极性反转后的本实施例电池组进行恒流(例如0.7C 3.5、1.5 C 3.5)充电至电池组的输出端电压为3.5V(此时电池组输出端L的极性为正、电池组输出端K的极性为负,此过程中电极B1、B2、B3、B4、B5、B6中的全部电极或部分电极上主要发生的是铅酸蓄电池正极电极反应的充电过程,电极A1、A2、A3、A4中的全部或部分电极上主要发生的是铅酸蓄电池负极电极反应的充电过程)并且在达到3.5V后,继续充电一定时间(例如2小时、5小时,此过程中电池组输出端L的极性为正、电池组输出端K的极性为负);(2)上步结束后,对本实施例铅酸蓄电池组以一定的电流(例如0.7C 3.5、1.5C 3.5、0.4C 3.5、0.1C 3.5)、反极充电的方法,使得本实施例铅酸蓄电池组原来的正极输出端(电池组输出端K)与原来的负极输出端(电池组输出端L)的极性再次发生反转或互换,即原来的正极输出端(电池组输出端K)的极性由负被反转成正、原来的负极输出端(电池组输出端L)的极性由正被反转成负,此为该期连续两次的极性反转及其后的充电或充放电操作中的第二次极性反转,在该期操作的第二次正、负极极性反转及其后的充电或充放电操作过程中,电极A1、A2、A3、A4全部电极或部分电极上发生的电极反应从铅酸蓄电池负极电极反应的放电过程被反转成铅酸蓄电池正极电极反应的充电过程,电极B1、B2、B3、B4、B5、B6全部电极或部分电极上发生的电极反应从铅酸蓄电池正极电极反应的放电过程被反转成铅酸蓄电池负极电极反应的充电过程,然后以一种或多种电流或电压(例如直流、恒压或脉冲电流、脉冲电压)对经该第二次极性反转后的本实施例铅酸蓄电池组进行充电至5.4V,然后再以5.2V的恒电压进行恒压充电4小时,完成步骤 (2),然后,将本实施例电池组重新投入到循环充放电工作中去使用或工作。
另外,对本实施例铅酸蓄电池组进行极性反转及其后的充电或充放电操作,也在一定程度上延缓或修复了电极A1、A2、A3、A4的集流体、汇流体的腐蚀。
在本实施例的其它实施方式中,可以使用脉冲电流、脉冲电压代替直流电、恒电压进行本实例的连续两次极性反转及其后的充电或充放电操作步骤中的极性反转及其后的充电或充放电,从而提高本实施例铅酸蓄电池组极性反转及其后的充电或充放电操作的时效、能效。
在本实施例的其它实施方式中,本实施例阀控式密封铅酸蓄电池组(VRLAB)的额定电压为U伏,额定容量为C 2(2h率,25℃)、C 5(5h率,25℃)或C 20(20h率,25℃),其中U=6、12、24、36、48、60或72,C 2=6.5Ah、12Ah、14Ah、16Ah、20Ah、24Ah、30Ah或32Ah,或者,C 5=8.6Ah、15.9Ah、18.6Ah、21.2Ah、26.5Ah、31.9Ah、39.8Ah或42.5Ah或者,C 20=10.4Ah、19.2Ah、22.4Ah、25.6Ah、32Ah、38.4Ah、48Ah或51.2Ah。本实施例铅酸蓄电池组的正极为电极A1、A2、...、An(n=正整数),且连接于本实施例铅酸蓄电池组的输出端子A,本实施例铅酸蓄电池组的负极为电极B1、B2、...、Bn(n=正整数),且连接于本实施例铅酸蓄电池组的输出端子B。提高或延长本实施例铅酸电池组的使用寿命的方法的具体操作为,当本实施例铅酸蓄电池组进行过1次以上的循环充放电工作后,由于本实施例铅酸蓄电池组的循环充放、过充电、欠充电、高活性物质利用率等原因,导致本实施例铅酸蓄电池组的工作放电容量因活性物质软化脱落、硫酸盐化、钝化、早期容量损失、活性物质与集流体接触不良、负极活性物质比表面积收缩等原因中的一种或多种导致本实施例铅酸蓄电池组的工作放电容量下降,则每当本实施例铅酸蓄电池组的工作放电容量下降至其额定容量C 2、C 5或C 20的60%、75%、80%、90%或95%时,或者本实施例铅酸蓄电池组的循环充放工作过程中充电电压上升速率加快了10%、15%、20%、30%、或50%时,或者循环工作达到一定次数时,开始对本实施例铅酸蓄电池组自动或/和手动地进行一期连续两次的极性反转及其后的充电或充放电操作,即,操作第(1)步:以一定电流源或/和电压源对本实施例铅酸蓄电池组进行反极充电,反极充电的电流为C 2、C 5、0.5C 20、0.3C 2、3C 2、或5C 5中的一种或多种或反极充电的电压为0.5U伏、U伏、1.5U伏、2U伏中的一种或多种,使得本实施例铅酸蓄电池组的电极A1、A2、...、An的极性由原来的正极性被反转成负极性、电极B1、B2、...、Bn的极性由原来的负极性被反转成正极性(此为本期的第一次极性反转),然后,操作第(2)步:对本实施例铅酸蓄电池组继续进行充放电,充电或放电电流为C 2、C 5、0.5C 20、0.3C 2、3C 2、或5C 5中的一种或多种或充电或放电电压为0.5U伏、U伏、1.5U伏、2U伏中的一种或多种,使得本实施例铅酸蓄电池组的电极A1、A2、...、An上发生铅酸蓄电池负极电极反应的充电或/和放电反应过程、电极B1、B2、...、Bn上发生铅酸蓄电池正极电极反应的充电或/和放电反应过程,当对本实施例铅酸蓄电池组充电或放电的电量达到4C 2、3C 5、0.5C 20、0.3C 2、3C 2、或5C 5时或电压达到0.6U伏、U伏、1.2U伏、2.1U伏时,然后操作第(3)步:以3C 2、2.5C 5、0.5C 20、0.8C 2、6C 2、或2C 5电流中的一种或多种对本实施例铅酸蓄电池组进行反极充电,使得本实施铅酸蓄电池组的电极A1、A2、...、An上发生铅酸酸蓄电池负极电极反应的放电过程、电极B1、B2、...、Bn上发生铅 酸蓄电池正极电极反应的放电过程,直至电极A1、A2、...An的极性由负极性被反转成正极性、电极B1、B2、...、Bn的极性由正极性被反转成负极性(此为本期的第二次极性反转),然后操作第(4)步:对本实施例铅酸蓄电池组继续进行充电或充放电,充电或放电电流为C 2、2C 5、0.5C 20、0.1C 2、3C 2、或0.05C 5中的一种或多种或充电电压为0.7U伏、0.9U伏、1.1U伏、1.7U伏中的一种或多种,充放电为直流或脉冲充放电,使得本实施例铅酸蓄电池组的电极A1、A2、...、An上发生铅酸蓄电池正极电极反应的充电或/和放电过程、电极B1、B2、...、Bn上发生铅酸蓄电池负极电极反应的充电或/放电过程,此过程对本实施例铅酸蓄电池组充放电所充电或/和放电的电量达到一定值时,例如6C 2、3C 5、2C 20、8C 2、3C 2、0.5C 2、或2C 5,或电池组电压达到一定值时,例如0.7U伏、0.9U伏、1.05U伏或1.4U伏,本实施例铅酸蓄电池组工作放电容量或工作能力得到恢复或提高,结束本期连续两次的正、负极性反转及其后的充电或充放电操作,然后将本实施例铅酸蓄电池组投入到循环工作中去工作或使用。如此,类似的,按照本实施例的提高或延长铅酸蓄电池组的方法,根据需要或设定,适时、定期或不定期的(例如,以规定循环工作次数的方式)对本实施例铅酸蓄电池组在某两次循环工作之间,进行一期或多期连续两次的极性反转及其后的充电或充放电操作,使本实施例铅酸蓄电池组在不存在电池失液、短路、断路、板栅机械损坏等的情况下,有效地改善、修复、逆转、消除、抑制、预防正极活性物质软化或/和脱落、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩等问题,从而反复的、多次的使本实施例铅酸蓄电池组工作放电容量或工作能力得到修复、恢复或提高,从而提高或延长本实施例铅酸蓄电池组的使用寿命。
实施例11
本实施例涉及提高或延长铅酸蓄电池使用寿命的方法、电池充放电器、铅酸蓄电池电极集流体、铅膏、铅酸蓄电池电极和铅酸蓄电池,其中本实施例的充放电器具有将铅酸蓄电池的正、负极进行极性反转及其后的充电或充放电操作的功能和可编程执行功能,本实施例电池充放电器通过其所包括的继电器电路的触点开、闭状态变换来实现其输出端正、负极的极性反转,从而当本实施例电池充放电器输出端与本实施例铅酸蓄电池电极相连接后,本实施例电池充放电器可通过其输出端的极性反转及极性反转后的充电、充电或充放电操作而对本实施例铅酸蓄电池进行正、负极极性反转、极性反转后的充电或充放电操作,以下本实施例的所有对电池进行的操作除特别说明手动外,均为本实施例电池充放电器通过其功能及工作来实现的。本实施例铅酸蓄电池的额定电压为2V,设计额定容量为745mAh(2h率,25℃),本实施例铅酸蓄电池包括两片平面板栅式电极,该两片电极均为正负极通用电极(即正极、负极通用的电极),且该两片电极是同一种正负极通用电极,即,不考虑制造电极时产生的制造误差,该两片本实施例铅酸蓄电池电极在被化成之前,彼此在所有电极构成、制造方面(如电极结构、造形、集流体、铅膏配方和铅膏质量、制做工艺等)完全相同,在被化成之后,该两片电极则分别被形成正极和负极,将该两片电极分别命名为电极A、电极B,平均每片 电极上的活性物质质量为12.17g,该两片电极之间隔有AGM隔板,该两片电极在本实施例铅酸蓄电池工作时不是始终固定作为正极或负极,最开始时,将电极A作为正极、电极B作为负极(记为A+/B-,同理将电极A作为负极、电极B作为正极时记为A-/B+,以下同)进行电池的化成和工作,本实施例铅酸蓄电池电极集流体由纯铅(铅含量为99.994%,以下同)材料制得,如图7所示,为平面栅格式集流体,该集流体外形的宽×高为40mm×70mm,其边框2的厚×宽为1.2mm×1.5mm,集流体框内的栅格薄板3厚度为0.1mm,栅格薄板上匀均的开有直径为2.5mm的圆孔4,每两个圆孔4边缘之间的距离为2.5mm,本实施例铅膏配方中包括氧化铅粉(100%氧化度)、BaSO 4(0.8%,质量百分比,相对于氧化铅粉)、硫酸、水、短纤维,本实施例铅酸蓄电池电极,包括本实施例集流体和本实施例铅膏,将本实施例铅膏均匀涂布于本实施例集流体,使电极平板表面的铅膏平面平行于集流体的边框表面,并置于室温(约15℃)空气中晾至略干即获得本实施例铅酸蓄电池电极,其外形尺寸宽×高×厚为40mm×70mm×1.2mm。本实施例铅酸蓄电池中的硫酸溶液密度为1.27g/cm 3,本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
本实施例提高或延长铅酸蓄电池使用寿命的方法为:首先,让本实施例电池进行循环充放电工作,工作制度为:当电池处于充电后状态时,以337mA的恒电流对本实施例电池进行放电,当电池电压≤1.75V时,停止放电,接着以201mA的恒电流对电池进行充电,并当测得电池电压达到2.65V后,转换成以2.65V恒压继续对电池充电,两次(恒流、恒压)充电总时间为7小时24分(有特殊说明的除外),然后,再以337mA的恒电流重复前述的放电过程,如此反复放电、充电,使电池循环工作,电池工作环境温度为25±1℃。其次,当本实施例铅酸蓄电池在上述工作中其连续循环工作次数达到某一预先设定的数值或者其工作放电容量由于正极活性物质软化或/和脱落、负极比表面积收缩、集流体或汇流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良问题中的一种或多种而降到某一容量值时(例如,本实施例中设定的分别为循环工作连续15次、循环工作连续12次、循环工作连续13次、360mAh、870mAh、…,如下),停止电池的工作,开始对电池进行一次单次正、负极极性反转及其后的充电或充放电操作,该操作完成后,使电池在原来的工作制度下继续工作、并且使极性反转前的电池正极在极性反转后作为负极进行工作、极性反转前的电池负极在极性反转后作为正极进行工作,直到触发或开始下一次的单次正、负极极性反转及其后的充电或充放电操作,如此多次、穿插地在本实施例铅酸蓄电池循环工作过程中,对本实施例铅酸蓄电池进行单次正、负极极性反转及其后的充电或充放电操作,使本实施例铅酸蓄电池的电极A有时作为正极工作、有时作为负极工作,相应的电极B有时作为负极工作、有时作为正极工作,以改善、修复、消除、逆转、抑制或防止本实施电池的正极活性物质软化或/和脱落、负极比表面积收缩、电极/集流体/汇流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良问题中一种或多种,使本实施例电池的工作放电充电能力在每次该操作后得到改善、恢复、提高或维护,从而实现提高或延长本实施例铅酸蓄电池的使用寿命。本实施例电池的循环工作过程也由本实施例电池 充放电器所具有的充电、放电功能来实施(以下对电池的所有操作及测量除了特别说明是手动外,均为通过本实施例电池充放电器进行程序设定、执行实现)。
按上,通过编程最初设定当本实施例铅酸蓄电池工作放电次数连续累计达15次时,停止电池工作并开始对电池进行第一次单次正、负极极性反转及其后的充电或充放电操作。如图8所示,在第1-15次循环工作中,本实施例电池的电极状态为A+/B-,此时电极A上发生正极电极反应,电极B上发生负极电极反应,在第1-15次循环工作中,本实施例电池的放电容量逐渐降低,经检查,这主要是因为正极活性物质发生软化、脱落而引起的(与铅膏中高含量的BaSO 4及高活性物质利用率、电极未经标准固化工艺、深放电等有关,以下类同),在第15次放电后,放电容量为638mAh。此时根据程序设定,本实施例电池充放电器自动停止电池的工作,并对电池进行第一次单次正、负极极性反转及其后的充电或充放电操作的准备和正式操作,即,在第15次工作放电结束后(此时电池电压为1.75V),停止电池工作,然后对电池继续以337mA恒电流放电1小时,此过程使电池电压降至0.04V,然后停止放电,对该电池进行其正、负极的极性反转,即通过本实施例电池充放电器输出端的极性反转(充放电器输出端的极性反转是通过充放电器内的继电器电路触点开、闭状态变换实现的),将充放电器与本实施例铅酸蓄电池的连接状态从充放电器正极输出端与铅酸蓄电池电极A连接、充放电器负极输出端与铅酸蓄电池电极B连接,改换成,充放电器负极输出端与铅酸蓄电池电极A连接、充放电器正极输出端与铅酸蓄电池电极B连接,此连接状态变换后,测得的电池电压为负值,然后,以169mA的恒电流对本实施例电池进行充电,使电池电压从负值上升至0V然后再上升到1.75V(此过程中发生本实施例电池第一次极性反转,其中电池电压从负值上升至0V过程中,电极A上发生铅酸蓄电池正极电极反应的放电过程、电极B上发生铅酸蓄电池负极电极反应的放电过程,电池电压从0V上升至1.75V的过程中电极A上发生铅酸蓄电池负极电极反应的充电过程、电极B上发生铅酸蓄电池正极电极反应的充电过程)当电池电压达到1.75V后,继续以269mA的恒电流对电池充电至2.65V,然后再以337mA恒电流对电池进行放电,至1.75V,然后,再以201mA的恒电流对电池进行充电,直至电池电压达到2.65V改成以2.65V对电池进行恒压充电,最后两次的充电(恒流、恒压)的总时间为7小时24分,至此,完成对本实施例电池的第一次单次正、负极极性反转及其后的充电或充放电操作,此时电池的电极状态已从A+/B-被反转成A-/B+。然后,使电极A作为负极进行工作、电极B作为正极进行工作,使该电池重新进入同前的放电-充电循环工作制度下进行第16次工作放电及之后次数的循环工作。结果表明,经第一次单次正、负极极性反转及其后的充电或充放电操作后,该电池在第16次循环工作状态下的放电时容量为938.2mAh,明显大于第15次的。此次极性反转后与电池恢复工作前这段过程中,对电池的充电容量为4477mAh。
接下来使本实施例电池继续在工作制度下运行,并在第16次循环工作后,将下次开始电池正、负极极性反转及其后的充电或充放电操作的触发条件通过编程更改设定为:当本实施例铅酸蓄电池的工作放电连续次数达到12次时,停止电池工作并开始对电池进行第二次单次正、负极极性反转及其后的充电或充放电操作。如图8所示,本实施例电池在其第16-27次循环工作中,本实施例电池 的电极状态为A-/B+,此时电极A上发生的是负极电极反应,电极B上发生的是正极电极反应,第16-27次循环工作中,放电容量从938.2mAh逐渐下降至849mAh,当第27次电池放电结束时,根据程序设定,此时触发了对电池正、负极进行极性反转及其后的充电或充放电操作的开始条件,因此,本实施例充放电器自动地开始了对电池进行第二次单次正、负极极性反转及其后的充电或充放电操作的准备和正式操作,即,在第27次工作放电结束后(此时电池电压为1.75V),停止电池工作,对电池以337mA恒电流继续放电1小时,此过程使电池电压降至0.02V,然后停止放电,对该电池进行其正、负极的极性反转,即通过本实施例充放电器输出端的极性反转(充放电器输出端的极性反转是通过充放电器内的继电器电路触点开、闭状态变换实现的),将充放电器与本实施例铅酸蓄电池的连接状态从充放电器正极输出端与铅酸蓄电池电极B连接、充放电器负极输出端与铅酸蓄电池电极A连接,改换成,充放电器正极输出端与铅酸蓄电池电极A连接、充放电器负极输出端与铅酸蓄电池电极B连接,此连接状态变换后,测得的电池电压为负值,然后,以269mA的恒电流对本实施例电池进行充电,使电池电压从负值上升至0V然后再上升到2.65V(此过程中发生本实施例电池第二次极性反转,其中电池电压从负值上升至0V过程中,电极A上发生铅酸蓄电池负极电极反应的放电过程、电极B上发生铅酸蓄电池正极电极反应的放电过程,电池电压从0V上升至2.65V的过程中电极A上发生铅酸蓄电池正极电极反应的充电过程、电极B上发生铅酸蓄电池负极电极反应的充电过程),至此,完成对本实施例电池的第二次单次正、负极极性反转及其后的充电或充放电操作,此时电池的电极状态已从A-/B+被反转成A+/B-。然后,使电极A作为正极进行工作、电极B作为负极进行工作,使该电池重新进入同前的放电-充电循环工作制度下进行第28次工作放电及之后次数的循环工作。结果表明,经第二次单次正、负极极性反转及其后的充电或充放电操作后,该电池在第28次循环工作状态下的放电时容量为680mAh,甚至第30次循环工作放电容量796mAh(此次极性反转及其后的充电或充放电操作后的最大放电容量),均低于第27次的工作放电容量,这应该与极性反转后的对电池充电不足有关,此次极性反转后与电池恢复工作前这段过程中对电池的总充电容量为724mAh。
接下来使本实施例电池继续在工作制度下运行,并在第29次循环工作后,将下次开始电池正、负极极性反转及其后的充电或充放电操作的触发条件通过编程更改设定为:当本实施例铅酸蓄电池的工作放电连续次数达到13次时,停止电池工作并开始对电池进行第三次单次正、负极极性反转及其后的充电或充放电操作。如图8,在第28-40次循环工作中,本实施例电池的电极状态为A+/B-,此时电极A上发生正极电极反应,电极B上发生负极电极反应,当电池循环工作放电至第40次时放电容量降至611mAh,根据程序设定,此时触发了对电池正、负极进行正、负极极性反转及其后的充电或充放电操作的开始条件,于是,停止电池的工作,本实施例充放电器开始对电池进行第三次单次正、负极极性反转及其后的充电或充放电操作的准备和正式操作,即,在第40次工作放电结束后(此时电池电压为1.75V),停止电池工作,对电池以337mA恒电流继续放电1小时,此过程使电池电压降至﹣0.05V,然后停止放电,对该电池进行如同本实施例第一次对电池进行单次正、负 极极性反转的相同的操作,然后,以200mA的恒电流对变换了电极连接状态的本实施例电池进行充电45分钟,然后继续以269mA的恒电流对电池充电至2.65V,然后再以337mA恒电流对电池进行放电,至1.75V,然后,再以201mA的恒电流对电池进行充电,直至电池电压达到2.65V改成以2.65V对电池进行恒压充电,最后两次的充电(恒流、恒压)的总时间为7小时24分,至此,完成对本实施例电池的第三次单次正、负极极性反转及其后的充电或充放电操作,此时电池的电极状态已从A+/B-被反转成A-/B+。然后,使电极A作为负极进行工作、电极B作为正极进行工作,使该电池重新进入同前的放电-充电循环工作制度下进行第41次工作放电及之后次数的循环工作。结果表明,经第三次单次正、负极极性反转及其后的充电或充放电操作后,该电池在第41次循环工作中的放电容量为533mAh,低于第40次循环工作中的放电容量611mAh,这也与此次极性反转后的充电不足有关,此次极性反转后与电池恢复工作前这段过程中对电池的总充电容量为925mAh,尤其是极性反转后的第一次总充电量仅412mAh。
接下来使本实施例电池继续在工作制度下运行,并在第41次循环工作后将下次开始正、负极极性反转及其后的充电或充放电操作的触发条件通过编程更改设定为:当本实施例铅酸蓄电池的工作放电容量低于360mAh时,停止电池工作并开始对电池进行第四次单次正、负极极性反转及其后的充电或充放电操作。如图8所示,本实施例电池在其第41-51次循环工作中,本实施例电池的电极状态为A-/B+,此时电极A上发生负极电极反应,电极B上发生正极电极反应,当电池循环工作到第51次时,其工作放电容量降到354mAh,根据程序设定,此时触发了对电池正、负极进行极性反转及其后的充电或充放电操作的开始条件,于是,本实施例充放电器自动停止电池的工作,开始对电池进行第四次单次正、负极极性反转及其后的充电或充放电操作的准备和正式操作,即,在第51次工作放电结束后(此时电池电压为1.75V),停止电池工作,然后对电池以337mA恒电流继续放电1小时,此过程使电池电压降至0.03V,然后停止放电,对该电池进行其正、负极的极性反转操作,操作方法及过程与本实施例对电池进行第二次单次正、负极极性反转的相同,在电极连接状态变换后,以169mA的恒电流对本实施例电池进行充电至1.75V,然后继续以269mA的恒电流对电池充电4分钟,然后再以337mA恒电流对电池进行充电至2.65V,然后再以2.65V的恒电压对电池进行充电4小时,然后以337mAh的恒电流对电池进行放电至1.75V,然后,再以201mA的恒电流对电池进行充电,直至电池电压达到2.65V改成以2.65V对电池进行恒压充电,最后两次的充电(恒流、恒压)的总时间为7小时24分,至此,完成对本实施例电池的第四次单次正、负极极性反转及其后的充电或充放电操作,此时电池的电极状态已从A-/B+被反转成A+/B-。然后,使电极A作为正极进行工作、电极B作为负极进行工作,使该电池重新进入同前的放电-充电循环工作制度下进行第52次工作放电及之后次数的循环工作。结果表明,经第四次单次正、负极极性反转及其后的充电或充放电操作后,该电池在第52次循环工作状态下的放电容量回升至920mAh,这应该与极性反转后的充电相对充足有关,此次极性反转后与电池恢复工作前这段过程中对电池的总充电容量为5164mAh,尤其是极性反转后的第一次总充电量达3901mAh。
接下来使电池继续在工作制度下运行,如图8所示,本实施例电池在第53-第63次充放循环工作中的电极状态为A+/B-,放电容量从1071mAh降到860mAh。当本实施例铅酸蓄电池处于完成第63次工作充放循环后,此时,电极A的极性为正,电极B的极性为负,停止本实施例铅酸蓄电池的循环工作,然后以337mA的电流对本实施例铅酸蓄电池进行放电1小时,使得其电压从1.75V降至0.05V,然后自动地,将充放电器的正输出端与本实施例铅酸蓄电池电极B连接,充放电器的负输出端与本实施例铅酸蓄电池电极A相连接,连接后,充放电器测得本实施例铅酸蓄电池的电压为-1.87V,然后,对本实施例铅酸蓄电池以337mA的电流在该连接的状态下进行充电14小时42分钟,使得本实施例铅酸蓄电池的正、负极的电压(充放电设备测得值,本实施例中以下同)从-1.87V上升到0V再上升到2.65V,此过程中本实施例铅酸蓄电池发生了第五次单次极性反转,即,从-1.87V上升到0V的过程中,电极A上主要发生的是铅酸蓄电池正极电极反应的放电过程、电极B上主要发生的是铅酸蓄电池负极电极反应的放电过程,而在0V上升到2.65V的过程中,电极A上主要发生的是铅酸蓄电池负极电极反应的充电过程,电极B上主要发生的是铅酸蓄电池正极电极反应的充电过程,在保持充放电器输出端与本实施例铅酸蓄电池输出端的连接状态不变的情况下,再以2.65V进行恒压充电5小时,然后再以337mA恒流放电21分钟至1.75V,然后然后,再以201mA的恒电流对电池进行充电,直至电池电压达到2.65V改成以2.65V对电池进行恒压充电,最后两次的充电(恒流、恒压)的总时间为9小时24分至此,至此,完成对本实施例电池的第五次单次正、负极极性反转及其后的充电或充放电操作,此时电池的电极状态已从A+/B-被反转成A-/B+。然后,使电极A作为负极进行工作、电极B作为正极进行工作,使该电池重新进入同前的放电-充电循环工作制度下进行第64次工作放电及之后次数的循环工作。结果表明,经第五次单次正、负极极性反转及其后的充电或充放电操作后,本实施例电池在第64次循环工作的放电容量为914mAh,且第65-75次循环工作的放电容量都高于1000mAh,这应该与该次极性反转后的充电量相对充足有关,此次极性反转后与电池恢复工作前这段过程中对电池的总充电容量8159mAh,尤其是极性反转后的第一次总充电量达6394mAh,且本实施例电池在第65-75次循环工作中的恒充、恒压充电总时间被变更为9小时24分钟。
本实施例铅酸蓄电池在第64-75次的循环工作过程中,电极A上发生铅酸蓄电池负极电极反应的充放电过程,电极B上发生铅酸蓄电池正极电极反应的充放电过程,如图8所示。
根据本实施例中的实验数据以及本行业现有技术常识可知,本实施例铅酸蓄电池每次单次极性反转后及其后的充电或充放电操作后本实施例铅酸蓄电池的工作放电容量恢复的程度以及本实施例铅酸蓄电池每次工作放电容量恢复后可连续保持正常或较高放电容量的充放循环工作的次数(即每次单次极性反转后及其后的充电或充放电操作之间本实施例铅酸蓄电池所正常工作或较高放电容量的充放循环次数)与相应地每次单次极性反转及其后的充电或充放电操作中所采用的电流、电压、时间、充放电容量、脉冲或直流、电池的内阻、电解液密度、电解液饱和程度的大小、方式的不同而不同。
如上所述,一方面,本实施例的第一、第四和第五次单次正、负极极性反转及其后的充放电或充放电操作使得本实施例铅酸蓄电池的正极活性物质软化、脱落被改善、修复、逆转、消除、抑制、防止,从而使得本实施例铅酸蓄电池循环工作中的工作放电容量该操作之后获得提高或恢复(第29-第51次循环工作的放电容量低是因为第二、第三次极性反转后对电池的充电不足造成的),另一方面,本实施例第四和第五次单次正、负极极性反转及其后的充电或充放电操作,也使本实施例电池的工作放电能力从第29-51次循环工作的、因充电不足而导致的工作放电能力下降情况中得以恢复,此表明,本实施例适当的单次正、负极极性反转及其后的充电或充放电操作对由于连续充电不足而导致的电池硫酸盐化问题具有改善、修复、逆转、恢复或防止的作用。此外,本实施例的正、负极极性反转及其后的充放电或充放电操作,也必然对本实施例电池循环工作过程中发生、轻微发生或将要发生的电极钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极比表面积收缩的问题具有改善、修复、逆转、抑止、消除、预防的作用。在本实施例铅酸蓄电池正常循环工作过程中,定期或不定期的(例如,以规定循环工作次数的方式)、穿插地对本实施例铅酸蓄电池进行本实施例的正、负极极性反转及其后的充放电或充放电操作,将会有效的改善、修复、逆转、消除、抑制、预防正极活性物质软化或/和脱落、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩问题,从而提高或延长本实施例铅酸蓄电池的使用寿命。
现行商业应用的动力电铅酸蓄电池在额定工作条件下电池正极活性物质的比容量为55-61mAh/g(2h率,25℃),按61 mAh/g计算本实施例铅酸蓄电池电极的额定容量为745mAh(根据前述本实施例铅酸蓄电池的单只电极上活性物质质量),如果定义100%放电深度时放电容量连续3次低于745mAh为电池使用寿命终止,则根据图8中的工作放电容量数据,本实施例铅酸蓄电池在其第一次单次正、负极极性反转操作前工作放电容量≥745mAh的放电累计次数为11次,即在其第14次工作放电结束时电池使用寿命已终止。但是通过本实施例的正、负极极性反转及其后的充电或充放电操作方法、电池充放电器、铅酸蓄电池电极集流体、铅酸蓄电池电极,本实施例电池工作放电容量≥745mAh的放电累计次数被增加至52次,即循环使用寿命增加了近4倍,且可以相信,采用合适的充放电制度或方式对本实施例铅酸蓄电池进行类似本实施例的正、负极极性反转及其后的充电或充放电操作,会使本实施例铅酸蓄电池因活性物质软化、电极比表面积收缩、腐蚀、电极钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良等问题其中的一种或多种所造成的铅酸蓄电池工作能力或工作放电容量下降得到改善、修复、逆转、预防,从而使得本实施例铅酸蓄电池的使用寿命获得的进一步的、显著的提高或延长。
本实施例铅酸蓄电池电极作为正极工作时的活性物质利用率明显高于现行商用动力电铅酸蓄电池正电极的活性物质利用率,主要是与本实施例电极的厚度、使用的氧化铅粉材料及集流体构造有关。
本实施例铅酸蓄电的的两片电极也是彼此等价的正负极通用电极,因为在电极被化成后,两者具有相同的功能和性能,但实际使用中,极性反转及其后的充电或充放电操作制度、循环工作制度 等因素的变化和差异,会导致两者在功能和性能的表现上出现差异。
在本实施例的其它实施方式中,降低铅膏中硫酸钡的百分含量、增加固定电极上铅膏的机械力、在铅膏中增加减缓活性物质软化、脱落的添加剂,其它实施方法或过程不变,这样使得每次单次极性反转及其后的充电或充放电操作后,电池的工作放电容量衰减速度变缓。
在本实施例的其它实施方式中,电极集流体还为方孔式平面栅格式集流体、卷绕式栅格集流体、平面实心板式集流体、芯柱式集流体、泡沫板栅式集流体、铅布式集流体,相应制得的电极为方孔式栅格平板电极、卷绕式电极、平板电极或双极式电池电极、管式或柱式电极、泡沫电极、铅布电极。
在本实施例的其它实施方式中,集流体为复合型材料集流体,该复合型材料集流体的芯体材料为铜、表面层材料为纯铅厚度为50um;本实施例中另一种复合型材料集流体的芯体材料为铝,过渡层材料为Sn,表面层材料为100um厚的铅合金。
在本实施例的其它实施方式中,本实施例电池充放电器输出端的极性反转操作,还通过本实施例电池充放电器电路的控制电路管理控制极性反转执行电路中的晶闸管的通、断状态变换来实现、或通过管理控制执行电路中由晶体管、电感、电容构成的极性反转电路的工作状态变换来实现、或通过管理控制恒流源或恒压源的强制放电、强制充电动作变换来实现。
在本实施例的其它实施方式中,本实施例充放电器电路的全部或一部分与电池整合在一起,在整体上作为一个产品。
在本实施例的其它实施方式中,将本实施例提高或延长铅酸蓄电池使用寿命的方法应用于本实施例铅酸蓄电池组,本实施例铅酸蓄电池组的额定电压为12V、额定容量为20Ah,在方法实施操作中,主要对操作中的电压、电流、容量等的数值的设定和执行上作了相应的变化,如,将铅酸蓄电池组进行反极充电并导致极性反转发生后,对电池组充电使电池组电压上升至8V、10.8V、13.3V、15.5V后停止停止充电,充电电流为0.3倍率、0.5倍率、1倍率、2倍率。
实施例12
本实施例电池充放电器与本发明实施例11中的相同。
本实施例铅酸蓄电池的额定电压为2V,设计额定容量为821mAh(2h率,25℃),本实施例铅酸蓄电池包括两片平面板栅式电极,该两片电极均为正负极通用电极(即正极、负极通用的电极),同时也是同一种正负极通用电极,即,不考虑制造电极时产生的制造误差,该两片本实施例铅酸蓄电池电极在被化成之前,彼此在所有电极构成、制造方面(如电极结构、造形、集流体、铅膏配方和铅膏质量、制做工艺等)完全相同,在被化成之后,该两片电极则分别被形成正极和负极,将该两片电极分别定义为电极A、电极B,最开始时,将电极A作为正极、电极B作为负极进行电池的化成和工作,该两片电极之间隔有AGM隔板,本实施例的该两片电极的集流体与本发明实施例11中的相同,铅膏配方中包括球磨铅粉、BaSO 4(0.8%,质量百分比,相对于球磨铅粉)、硫酸、水、短 纤维,平均每片电极上的活性物质质量为13.41g,本实施例铅酸蓄电池中的硫酸溶液密度为1.27g/cm 3,本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
本实施例提高或延长铅酸蓄电池使用寿命的方法为:首先,让本实施例电池进行循环充放电工作,工作制度为:当电池处于充电后状态时,以371mA的恒电流对电池进行放电,当电池电压≤1.75V时,停止放电,接着以222mA的恒电流对其进行充电,并当测得电池电压达到2.65V后,转换成以2.65V恒压继续对电池充电,两次(恒流、恒压)充电总时间为7小时24分(有特殊说明的除外),然后,再以371mA的恒电流重复前述的放电过程,如此反复放电、充电,使电池循环工作,电池工作环境温度为25±1℃。其次,当本实施例铅酸蓄电池在上述循环工作中工作循环次数达到某一设定的数值时(例如,本实施例中设定的分别为第15次、第31次、…),停止电池的工作,开始对电池进行一次单次正、负极极性反转及其后的充电或充放电操作,该操作完成后,使电池在原来的工作制度下继续工作、并且使极性反转前的电池正极在极性反转后作为负极进行工作、极性反转前的电池负极在极性反转后作为正极进行工作,直到触发或开始下次的单次正、负极极性反转及其后的充电或充放电操作,如此多次、穿插地在本实施例铅酸蓄电池循环工作过程中,对本实施例铅酸蓄电池进行单次正、负极极性反转及其后的充电或充放电操作,使本实施例铅酸蓄电池的电极A有时作为正极工作、有时作为负极工作,相应的电极B有时作为负极工作、有时作为正极工作,以改善、修复、消除、逆转、抑制或防止本实施电池的正极活性物质软化或/和脱落、负极比表面积收缩、电极/集流体/汇流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良问题中一种或多种,使本实施例电池的工作放电充电能力在每次该操作后得到改善、恢复、提高或维护,从而实现提高或延长本实施例铅酸蓄电池的使用寿命。本实施例电池的循环工作过程也由本实施例电池充放电器所具有的充电、放电功能来实施(以下对电池的所有操作及测量除了特别说明是手动外,均为通过本实施例电池充放电器进行程序设定、执行实现)。
按上,最初设定当本实施例铅酸蓄电池工作放电次数达到并完成第15次、第31次时,停止电池工作并开始对电池进行一次单次正、负极极性反转及其后的充电或充放电操作。如图9所示,在第1-15次循环工作中,本实施例电池的电极状态为A+/B-,此时电极A上发生正极电极反应,电极B上发生负极电极反应,在第1-15次循环工作中,本实施例电池的放电容量总体趋向降低,经检查,这主要是因为正极活性物质软化、脱落作用而引起的(与铅膏中高含量的BaSO 4、高活性物质利用率、深度放电有关,以下类同),在第15次放电后,放电容量为942mAh。此时根据程序设定,本实施例电池充放电器自动停止电池的工作,对电池进行第一次单次正、负极极性反转及其后的充电或充放电操作的准备和正式操作,即,在第15次工作放电结束后(此时电池电压为1.75V),停止电池工作,对电池继续以371mA恒电流放电1小时,此过程使电池电压降至0.04V,然后停止放电,对该电池进行其正、负极的极性反转,即通过本实施例充放电器输出端的极性反转(充放电器输出端的极性反转是通过充放电器内的继电器电路触点开、闭状态变换实现的),将充放电器与铅酸蓄电 池的连接状态从充放电器正极输出端与铅酸蓄电池电极A连接、充放电器负极输出端与铅酸蓄电池电极B连接,改换成,充放电器负极输出端与铅酸蓄电池电极A连接、充放电器正极输出端与铅酸蓄电池电极B连接,此连接状态变换后,测得的电池电压为负值,然后,以186mA的恒电流对连接状态变换后的本实施例电池进行充电,使电池电压从负值上升至0V然后再上升到1.75V(此过程中发生本实施例电池第一次极性反转,其中电池电压从负值上升至0V过程中,电极A上发生铅酸蓄电池正极电极反应的放电过程、电极B上发生铅酸蓄电池负极电极反应的放电过程,电池电压从0V上升至1.75V的过程中电极A上发生铅酸蓄电池负极电极反应的充电过程、电极B上发生铅酸蓄电池正极电极反应的充电过程),当电池电压达到1.75V后,继续以222mA的恒电流对电池充电至2.65V,然后再以2.65V的恒电压对电池进行充电4小时16分,然后以371mA恒电流对电池进行放电,至1.75V,然后,再以222mA的恒电流对电池进行充电,直至电池电压达到2.65V改成以2.65V对电池进行恒压充电5小时,充电结束后,至此,完成对本实施例电池的第一次单次正、负极极性反转及其后的充电或充放电操作,此时电池的电极状态已从A+/B-被改换成A-/B+。然后,使电极A作为负极进行工作、电极B作为正极进行工作,使该电池重新进入同前的放电-充电循环工作制度下进行第16次工作放电及之后次数的循环工作。结果表明,经第一次单次正、负极极性反转及其后的充电或充放电操作后,本实施例电池在第16次循环工作状态下的放电容量为888.3mAh。此次极性反转后与电池恢复循环工作前这段过程中对电池的充电容量为7031mAh。
接下来使本实施例电池继续在工作制度下运行,如图9所示,在本实施例电池第16-31次循环工作中,本实施例电池的电极状态为A-/B+,此时电极A上发生负极电极反应,电极B上发生正极电极反应,在本实施例电池第16-31次循环工作中,放电容量从888.3mAh变化至905mAh,其中,第27次工作循环中放电容量增加至987.6mAh是因为在此次放电前通过人工干预对电池进行了一次过充电(即2.65V恒压充电时间比正常工作制度下多了10小时),其它循环次数的工作制度不变。当第31次循环工作放电结束时,根据程序设定,此时触发了对电池正、负极进行极性反转及其后的充电或充放电操作的开始条件,因此,本实施例充放电器自动地开始了对电池进行第二次单次正、负极极性反转及其后的充电或充放电操作的准备和正式操作,即,在第31次工作放电结束后(此时电池电压为1.75V),本实施例充放电器停止电池工作,对电池以371mA恒电流继续放电1小时,此过程使电池电压降至0.02V,然后停止放电,对该电池进行其正、负极的极性反转,即通过本实施例充放电器输出端的极性反转(充放电器输出端的极性反转是通过充放电器内的继电器电路触点开、闭状态变换实现的),将充放电器与铅酸蓄电池的连接状态从充放电器正极输出端与铅酸蓄电池电极B连接、充放电器负极输出端与铅酸蓄电池电极A连接,改换成,充放电器正极输出端与铅酸蓄电池电极A连接、充放电器负极输出端与铅酸蓄电池电极B连接,此连接状态变换后,测得的电池电压为负值,然后,以186mA的恒电流对连接状态变换后的本实施例电池充电15分钟,再以371mA的恒电流对电池进行充电,使电池电压从负值上升至0V然后再上升至2.65V(此过程中发生本实施例电池第二次极性反转,其中电池电压从负值上升至0V过程中,电极A上发生铅酸蓄电池负极电 极反应的放电过程、电极B上发生铅酸蓄电池正极电极反应的放电过程,电池电压从0V上升至2.65V的过程中电极A上发生铅酸蓄电池正极电极反应的充电过程、电极B上发生铅酸蓄电池负极电极反应的充电过程),然后再以2.65V恒电压对电池充电4小时,然后再以371mA的恒电流对电池进行放电至1.75V,然后,再以222mA的恒电流对电池进行充电7小时25分,然后再以2.65V恒电压对电池充电7小时25分,至此,完成对本实施例电池的第二次单次正、负极极性反转及其后的充电或充放电操作,此时电池的电极状态已从A-/B+被改换成A+/B-。然后,使电极A作为正极进行工作、电极B作为负极进行工作,使该电池重新进入同前的放电-充电循环工作制度下进行第32次工作放电及之后次数的循环工作。结果表明,经第二次单次正、负极极性反转及其后的充电或充放电操作后,该电池在第32次循环工作状态下的放电时容量为1189mAh,这应该与极性反转后的对电池的充分充电有关,此次极性反转后与电池恢复循环工作之间对电池的总充电容量为6659mAh。接下来使电池继续在工作制度下运行,如图9所示,在第32-45次循环工作中,本实施例电池的电极状态为A+/B-,此时电极A上发生的是正极电极反应,电极B上发生的是负极电极反应,本实施例电池在第32-45次循环工作中的放电容量从1189mAh降到787mAh。
在本实施例铅酸蓄电池的循环充放工作过程中,反复、多次、穿插地进行本实施例如上所述类似于第一次或第二次的单次正、负极极性反转及其后的充电或充放电操作,即实现了本实施例铅酸蓄电池在其循环工作过程中工作循环次数的第45、46次之间、第55、56次之间、第64、65次之间、第73、74次之间、第82、83次之间、第94、95次之间、第104、105次之间进行或被进行的第三次、第四次、......、第九次的单次正、负极极性反转及其后的充电或充放电操作。图9中标示出了本实施例铅酸蓄电池在经过本实施例各次单次正、负极极性反转及其后的充电或充放电操作之前或之后,在循环充放工作过程中,电极A、B的极性状态或极性方向情况。本实施例铅酸蓄电池在第46次及之后次数的循环工作制度中,充电方法变更成,工作放电结束后,接着以222mA的恒电流对其进行充电,并当测得电池电压达到2.65V后,转换成以2.65V恒压继续对电池充电,两次(恒流、恒压)充电总时间为8小时24分。
如图9所示,本实施例铅酸蓄电池的工作放电容量都同比地得到提升或恢复。一方面如上所述,本实施例的正、负极极性反转及其后的充放电或充放电操作使得本实施例铅酸蓄电池的正极活性物质软化、脱落被改善、修复、逆转、消除、抑制、防止,从而使得本实施例铅酸蓄电池循环工作中的工作放电容量该操作之后获得提高或恢复,另一方面,本实施例的正、负极极性反转及其后的充放电或充放电操作,也必然对本实施例电池循环工作过程中发生、轻微发生或将要发生的电极钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极比表面积收缩、硫酸盐化的问题具有改善、修复、逆转、抑止、消除、预防的作用,例如,由于电极A、B反复交替地作为正极或负极进行充放循环工作,使得作为正极工作时产生的电极腐蚀问题在电极作为负极进行充放循环工作时得到改善、修复、逆转,从而也使得本实施例铅酸蓄电池在长期使用过程中的腐蚀问题得到延缓、改善、修复、逆转、防止,在本实施例铅酸蓄电池正常循环工作过程中,定期或不定期的(例如,以规定 循环工作次数的方式)、穿插地对本实施例铅酸蓄电池进行本实施例的正、负极极性反转及其后的充放电或充放电操作,将会有效的改善、修复、逆转、消除、抑制、预防正极活性物质软化或/和脱落、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩问题,从而提高或延长本实施例铅酸蓄电池的使用寿命。
本实施例中,也可以使用快速充放电脉冲电流、脉冲电压进行本实例的正极、负极极性反转及其后的充电或充放电操作。
本实施例中的一些实验数据表明,本实施例铅酸蓄电池每次单次极性反转后及其后的充电或充放电操作后本实施例铅酸蓄电池的工作放电容量恢复的程度以及本实施例铅酸蓄电池每次工作放电容量恢复后可连续保持正常或较高放电容量的充放循环工作的次数(即每次单次极性反转后及其后的充电或充放电操作之间本实施例铅酸蓄电池所正常或较高工作放电容量的充放循环次数)与相应地每次单次极性反转及其后的充电或充放电操作中所采用的电流、电压、时间、充放电容量、脉冲或直流、电池的内阻、电解液密度、电解液饱和程度的大小、方式的不同而不同。
按现行商品化动力电铅酸蓄电池在额定工作条件下电池正极活性物质的比容量61 mAh/g(2h率,25℃)计算,本实施例铅酸蓄电池电极的额定容量为821mAh(根据前述本实施例铅酸蓄电池的单只电极的活性物质质量平均值),如果定义100%放电深度时放电容量连续三次低于额定容量或额定容量的80%(657mAh)时作为电池使用寿命终止的判断依据,则如图9所示,根据第1-15次的放电容量衰减趋势线可以认为,本实施例铅酸蓄电池在不经本实施例正、负极极性反转及其后的充电或充放电操作时,其使用寿命基本上将分别为25次和36次。然而事实上,本实施例电池经本实施例的正、负极极性反转及其后的充电或充放电操作后,电池的工作放电容量在第111次循环工作之后仍保持在额定容量之上,电池的使用寿命被明显提高或延长,且可推测,在排除使电池失效的短路、断路、失水、污染等因素的情况下,本实施例提高或延长铅酸蓄电池使用寿命的方法,将使本实例铅酸蓄电池的使用寿命在111次循环的基础上获得更大的提高或延长。本实施例铅酸蓄电池电极作为正极工作时的活性物质利用率明显高于现行商用动力铅酸蓄电池正电极的活性物质利用率,主要是与本实施例电极的厚度、集流体构造有关。
本实施例铅酸蓄电的的两片电极也是彼此等价的正负极通用电极,因为在电极被化成后,两者具有相同的功能和性能,但实际使用中,极性反转及其后的充电或充放电操作制度、循环工作制度等因素的变化和差异,会导致两者在功能和性能的表现上出现差异。
实施例13
本实施例铅酸蓄电池为平面板栅式铅酸蓄电池,额定电压为2V,额定容量为754mAh(C 2.5,2.5h率,25℃),包括两片正负极通电极(即正极、负极通用的电极),该两片电极的板栅集流体的栅格为矩形,且该两片电极也是同一种正负极通用电极,即,不考虑制造电极时产生的制造误差,该两片本实施例铅酸蓄电池电极在被化成之前,彼此在所有电极构成、制造方面(如电极结构、造 形、集流体、铅膏配方和铅膏质量、制做工艺等)完全相同,在被化成之后,该两片电极则分别被形成正极和负极,每片本实施例平面板栅式正负极通用电极的厚度为1.3mm,,边框的宽和高度为38mm和68mm,为了便于本实施例的后续说明,将本实施例铅蓄电池的两个平面板栅式正负极通用电极分别命名为电极A和电极B,电极A与电极B的铅膏的配方、质量均相同,即,电极A、B的铅膏配方均由球磨铅粉、硫酸钡(相对于球磨铅粉为0.8wt%)、其它商业常用负极添加剂构成,电极A、B上的干铅膏(经过涂片、固化、干燥后的)质量均为10.8g,本实施例铅酸蓄电池在其最初始的循环充放电工作过程中,电极A作为正极进行循环工作(即循环充放工作过程中电极A上发生的是铅酸蓄电池正极电极反应的充放电过程)、电极B作为负极进行循环充放工作(即循环充放工作过程中电极B上发生的是铅酸蓄电池负极电极反应的充放电过程),正、负电极或电极A、B之间隔有隔板,本实施例铅酸蓄电池在循环充放工作过程中其电极A、B的极性状态或极性方向可表示为A+/B-或A-/B+,其中A+/B-表示电极A的极性为正、电极B的极性为负,同理,A-/B+表示电极A的极性为负、电极B的极性为正。本实施例铅酸蓄电池使用的电解液硫酸溶液的密度为1.27g/cm 3,本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
本实施例提高或延长本实施例铅酸蓄电池的使用寿命的方法为,每当本实施例铅酸蓄电池循环充放工作到某一定次数时或工作放电充电能力由于正极活性物质软化或/和脱落、负极比表面积收缩、集流体或汇流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良等问题中的一种或多种而下降到一定程度时,即自动或/和手动地对本实施例铅酸蓄电池的正极、负极进行一次单次极性反转及其后的充电或充放电操作或者对本实施例铅酸蓄电池的正极、负极进行一期连续两次的极性反转及其后的充电或充放电操作,从而改善、消除、抑制、修复、预防或逆转前述的一种或多种问题,使本实施例铅酸蓄电池的工作放电充电能力得到改善、恢复或提高,然后,再将本实施例铅酸蓄电池重新投入到循环充放工作中去进行循环工作。对于对本实施例铅酸蓄电池的正极、负极进行一次单次极性反转及其后的充电或充放电操作,在该次极性反转及其后的充电或充放电操作后,使得本实施例铅酸蓄电池以该次极性反转后的电极的极性状态或极性方向进行循环工作,例如,若本实施例铅酸蓄电池的电极A在该次极性反转前是作为正极进行循环工作(即在循环充放工作过程中电极A上发生铅酸蓄电池正极电极反应的充放电过程),则在该次极性反转后,电极A是作为负极进行循环工作(即在循环充放工作过程中电极A上发生铅酸蓄电池负极电极反应的充放电过程),相应的电极B若在该次极性反转前是作为负极进行循环工作(即循环充放工作过程中电极B上发生铅酸蓄电池负极电极反应的充放电过程),则在该次极性反转后是作为正极进行循环工作(即循环充放工作过程中电极B上发生铅酸蓄电池正极电极反应的充放电过程),同理,若电极A或电极B在该次极性反转前的循环工作过程中的极性状态或极性方向反之,则,电极A或电极B在该次极性反转后的循环工作过程中的极性状态或极性方向亦反之;对于对本实施例铅酸蓄电池的正极、负极进行一期连续两次的极性反转及其后的充电或充放电操作,本实施铅酸蓄电池在该期连续两次 正极、负极极性反转及其后的充电或充放电操作后进行循环工作时的正极、负极极性状态或极性方向与该期连续两次正极、负极极性反转及其后的充电或充放电操作前进行循环工作时的相同,例如,若本实施例铅酸蓄电池的电极A在该期连续两次正极、负极极性反转前是作为正极进行循环工作(即在循环充放工作过程中电极A上发生铅酸蓄电池正极电极反应的充放电过程),则在该期连续两次正极、负极极性反转后,电极A还是作为正极进行循环工作,相应的电极B若在该期连续两次极性反转前是作为负极进行循环工作(即循环充放工作过程中电极B上发生铅酸蓄电池负极电极反应的充放电过程),则在该期连续两次极性反转后仍是作为负极进行循环工作。
本实施例铅酸蓄电池采用的循环充放电工作制度为:工作放电时,以300mA的电流进行放电至1.75V,然后,以140mA的电流进行恒流充电4小时57分钟,然后再以63mA的电流恒流充电5小时44分钟,然后再以17mA的电流恒流充电5小时,然后再重复之前的工作放电过程,如此反复、循环,使本实施例铅酸蓄电池循环充放工作。
本实施例铅酸蓄电池循环工作和本实施例提高或延长本实施例铅酸蓄电池使用寿命方法的实施结果,如图10所示,本实施例铅酸蓄电池在其循环工作过程中,在其工作循环次数的第14、15次之间、第29、30次之间、第45、46次之间、第60、61次之间进行或被进行了依次为第一次、第二次、第三次、第四次的单次正极、负极极性反转及其后的充电或充放电操作,在其工作循环次数的第51、52次之间、第55、56次之间、第57、58次之间进行或被进行了依次为第一期、第二期、第三期的连续两次正极、负极极性反转及其后的充电或充放电操作,所进行或被进行的正极、负极极性反转及其后的充电或充放电操作的具体方法或过程如下:
对于本实施例第一次单次正极、负极极性反转及其后的充电或充放电操作:当本实施例铅酸蓄电池处于完成第14次循环工作后的充电状态下时,此时,电极A的极性为正,电极B的极性为负,停止本实施例铅酸蓄电池的循环工作,然后以300mA的电流对本实施例铅酸蓄电池进行放电10min,使得其电压从1.75V降至0V,然后将充放电设备的正、负输出端与本实施例铅酸蓄电池原来的正极、负极进行反极连接,即,充放电设备的正输出端与本实施例铅酸蓄电池电极B连接,充放电设备的负输出端与本实施例铅酸蓄电池电极A相连接,反极连接后,充放电设备测得本实施例铅酸蓄电池的电压为-2.07V,然后,对本实施例铅酸蓄电池以150mA的电流在该反极连接的状态下进行充电,使得本实施例铅酸蓄电池的正、负极的电压(充放电设备测得值,本实施例中以下同)从-2.07V上升到0V再上升到1.76V,此过程中本实施例铅酸蓄电池发生了第一次极性反转,即,从-2.07V上升到0V的过程中,电极A上主要发生的是铅酸蓄电池正极电极反应的放电过程、电极B上主要发生的是铅酸蓄电池负极电极反应的放电过程,而在0V上升到1.76V的过程中,电极A上主要发生的是铅酸蓄电池负极电极反应的充电过程,电极B上主要发生的是铅酸蓄电池正极电极反应的充电过程,在保持充放电设备输出端与本实施例铅酸蓄电池输出端的连接状态不变的情况下,再以300mA对本实施例铅酸蓄电池进行恒流充电3小时36分钟至2.65V,然后,以2.65V进行恒压充电4小时,然后再以300mA恒流放电55分钟至1.75V,然后再按循环工作制度进行一次充放操作,然后将本实施 例铅酸蓄电池重新投入到循环工作的充电过程中去充电,然后进行第15次乃至其后直到第29次的循环工作。本实施例铅酸蓄电池在第15-29次的循环工作过程中,电极A上发生铅酸蓄电池负极电极反应的充放电过程,电极B上发生铅酸蓄电池正极电极反应的充放电过程,如图10所示。
对于本实施例第二次单次正极、负极极性反转及其后的充电或充放电操作:当本实施例铅酸蓄电池处于完成第29次循环工作后,此时,电极A的极性为负,电极B的极性为正,停止本实施例铅酸蓄电池的循环充放工作,然后以300mA的电流对本实施例铅酸蓄电池进行放电33分钟,使得其电压从1.75V降至0V,然后将充放电设备的正、负输出端与本实施例铅酸蓄电池在第15-29次循环充放工作中的正极、负极进行反极连接,即,充放电设备的正输出端与本实施例铅酸蓄电池电极A连接,充放电设备的负输出端与本实施例铅酸蓄电池电极B相连接,反极连接后,充放电设备测得本实施例铅酸蓄电池的电压为-2.14V,然后,对本实施例铅酸蓄电池以150mA的电流在该反极连接的状态下进行充电6小时13分钟,使得本实施例铅酸蓄电池的正极、负极之间的电压(充放电设备测得值,本实施例中以下同)从-2.14V上升到0V再上升到1.76V,此过程中本实施例铅酸蓄电池发生了第二次极性反转,即,从-2.14V上升到0V的过程中,电极A上主要发生的是铅酸蓄电池负极电极反应的放电过程、电极B上主要发生的是铅酸蓄电池正极电极反应的放电过程,而在0V上升到1.76V的过程中,电极A上主要发生的是铅酸蓄电池正极电极反应的充电过程,电极B上主要发生的是铅酸蓄电池负极电极反应的充电过程,在保持充放电设备输出端与本实施例铅酸蓄电池输出端的连接状态不变的情况下,再以300mA对本实施例铅酸蓄电池进行恒流充电5小时11分钟至2.65V,然后,以2.65V进行恒压充电4小时,然后再以300mA恒流放电49分钟至1.75V,然后将本实施例铅酸蓄电池重新投入到循环工作的充电过程中去,然后,进行第30次乃至其后直到第45次的循环工作。本实施例铅酸蓄电池在第30-45次的循环工作过程中,电极A上发生铅酸蓄电池正极电极反应的充放电过程,电极B上发生铅酸蓄电池负极电极反应的充放电过程,如图10所示。
对于本实施例第三次单次正极、负极极性反转及其后的充电或充放电操作与本实施例第一次单次正极、负极极性反转及其后的充电或充放电操作过程基本相同,所不同之处在于开始操作时电池所处的荷电状态、极性反转后的充电或充放电制度不同,具体的为:当本实施例铅酸蓄电池处于完成第45次循环工作后的充电状态中时,此时,电极A的极性为正,电极B的极性为负,停止本实施例铅酸蓄电池的循环工作,然后以300mA的电流对本实施例铅酸蓄电池进行放电2小时35min,使得其电压从2.29V降至0V,然后将充放电设备的正输出端与本实施例铅酸蓄电池电极B连接,充放电设备的负输出端与本实施例铅酸蓄电池电极A相连接,此时,充放电设备测得本实施例铅酸蓄电池的电压为-2.04V,然后,对本实施例铅酸蓄电池以900mA的电流在该连接状态下进行充电2小时,使得本实施例铅酸蓄电池的正极、负极之间的电压(充放电设备测得值,本实施例中以下同)从-2.04V上升到0V再上升到2.52V,此过程中本实施例铅酸蓄电池发生了第三次极性反转,即,从-2.04V上升到0V的过程中,电极A上主要发生的是铅酸蓄电池正极电极反应的放电过程、电极B上主要发生的是铅酸蓄电池负极电极反应的放电过程,而在0V上升到2.52V的过程中,电极A上主要发生的 是铅酸蓄电池负极电极反应的充电过程,电极B上主要发生的是铅酸蓄电池正极电极反应的充电过程,在保持充放电设备输出端与本实施例铅酸蓄电池输出端的连接状态不变的情况下,再以60mA对本实施例铅酸蓄电池进行恒流充电20分钟,然后,再以674mA对本实施例铅酸蓄电池进行恒流充电1小时,然后再以60mA对本实施例铅酸蓄电池进行恒流充电20分钟,然后再以505mA对本实施例铅酸蓄电池恒流充电1小时,然后再以60mA对本实施例铅酸蓄电池进行恒流充电20分钟,然后再以379mA对本实施例铅酸蓄电池恒流充电1小时,然后再以60mA对本实施例铅酸蓄电池进行恒流充电20分钟,然后再以284mA对本实施例铅酸蓄电池恒流充电1小时,然后再以60mA对本实施例铅酸蓄电池进行恒流充电20分钟,然后再以213mA对本实施例铅酸蓄电池恒流充电1小时,然后以2.65V进行恒压充电1小时,然后再以60mA对本实施例铅酸蓄电池进行恒流充电20分钟,然后再以300mA恒流放电45分钟至1.75V,然后再按循环工作制度进行一次充放电操作,然后将本实施例铅酸蓄电池重新投入到循环工作的充电过程中去,然后,进行第46次乃至其后直到第51次的循环工作。本实施例铅酸蓄电池在第46-51次的循环工作过程中,电极A上发生铅酸蓄电池负极电极反应的充放电过程,电极B上发生铅酸蓄电池正极电极反应的充放电过程,如图10所示。
对于本实施例第一期连续两次正极、负极极性反转及其后的充电或充放电操作:当本实施例铅酸蓄电池处于完成第51次循环工作后的充电状态下时,此时,电极A的极性为负,电极B的极性为正,停止本实施例铅酸蓄电池的循环工作,然后以充放电设备以300mA和900mA的电流对本实施例铅酸蓄电池进行强制放电14分钟和20分钟,使得本实施例铅酸蓄电池在保持与充放电设备的连接状态不变的情况下电池电压从1.75V降至0V然后再降至-1.75V(充放电设备测得的值,本实施例,以下同),此过程中本实施例铅酸蓄电池发生了本期连续两次正极、负极极性反转及其后的充电或充放电操作中的第一次极性反转,即,从-1.75V下降到0V的过程中,电极A上主要发生的是铅酸蓄电池负极电极反应的放电过程、电极B上主要发生的是铅酸蓄电池正极电极反应的放电过程,而在0V下降到-1.75V的过程中,电极A上主要发生的是铅酸蓄电池正极电极反应的充电过程,电极B上主要发生的是铅酸蓄电池负极电极反应的充电过程,在保持充放电设备输出端与本实施例铅酸蓄电池输出端的连接状态不变的情况下,再以900mA的电流对本实施例铅酸蓄电池进行强制放电1小时至本实施例铅酸蓄电池的电压为-2.53V,然后,以900mA的电流对本实施例铅酸蓄电池进行强制充电1小时13分钟至电池电压从-2.53V上升至0V再上升至2.65V,此过程中本实施例铅酸蓄电池发生了本期连续两次正极、负极极性反转及其后的充电或充放电操作中的第二次极性反转,即,从-2.53V上升到0V的过程中,电极A上主要发生的是铅酸蓄电池正极电极反应的放电过程、电极B上主要发生的是铅酸蓄电池负极电极反应的放电过程,而在0V上升到2.65V的过程中,电极A上主要发生的是铅酸蓄电池负极电极反应的充电过程,电极B上主要发生的是铅酸蓄电池正极电极反应的充电过程,在保持充放电设备输出端与本实施例铅酸蓄电池输出端的连接状态不变的情况下,然后再以300mA恒流放电1小时32分钟至1.75V,然后将本实施例铅酸蓄电池重新投入到循环工作的充电过程中去充电,然后进行第52次乃至其后直到第55次的循环工作。本实施例铅酸蓄电池在第 52-55次的循环工作过程中,电极A上发生铅酸蓄电池负极电极反应的充放电过程,电极B上发生铅酸蓄电池正极电极反应的充放电过程,如图10所示。
对于本实施例第二、三期连续两次正极、负极极性反转及其后的充电或充放电操作与本实施例第一期连续两次正极、负极极性反转及其后的充电或充放电操作基本相同或类似,所不同之处在于,操作中相关的电流、电压、充放电时间、充放电容量、充放电频率、次数上有所变化。例如,本实施例第三期连续两次正极、负极极性反转及其后的充电或充放电操作为:将完成了第57次工作放电后正处于充电状态中的本实施例铅酸蓄电池直接切换到恒流强制放电状态,即以300mA的电流、经2小时22分钟使本实施例铅酸蓄电池的电压从2.60V下降到0V,然后以898mA的电流继续对本实施例铅酸蓄电池进行强制放电,使得本实施例铅酸蓄电池的电压经1小时15分钟、从0V下降到-2.58V(此从2.60V下降到0V,再从0V下降至-2.58V为本期第1次极性反转),然后,再对本实施例铅酸蓄电池进行898mA电流的强制充电,使本实施例铅酸蓄电池经1小时18分钟、电压从-2.58V上升至0V然后又上升至2.65V(此为本期第2次极性反转),然后,再对本实施例铅酸蓄电池以300mA电流、经1小时10分钟放电至1.85V,然后,再对本实施例铅酸蓄电池以450mA的电流、经1小时08分钟、恒流充电至2.65V,然后对本实施例铅酸蓄电池以300mA的电流、经4s恒流放电至2.0V,然后,再对本实施例铅酸蓄电池以300mA的电流、经28min恒流充电至2.65V,然后再对本实施例铅酸蓄电池以2.65V恒压充电1小时(充电量为223mAh),然后,再对本实施例铅酸蓄电池以300mA、经2小时10分钟恒流放电至1.75V,至此完成本实施例第三期连续两次正极、负极极极性反转及其后的充电或充放电操作(整个过程为10小时51分钟),然后,将本实施例铅酸蓄电池投入到循环工作过程中的充电过程中,然后进行本实施例铅酸蓄电池第58次循环充放电工作。
对于本实施例第四次单次正极、负极极性反转及其后的充电或充放电操作与本实施例第二次单次正极、负极极性反转及其后的充电或充放电操作基本相同或类似,所不同之处在于,操作中相关的电流、电压、充放电时间、充放电容量、充放电频率、次数上有所变化。
本实施例铅酸蓄电池其第56-76次循环工作中的电极状态如图10所示。
如图10所示,完成每次或每期极性反转及其后的充电或充放电操作后,本实施例铅酸蓄电池的工作放电容量都同比地获得提升或恢复。本实施例的正极、负极极性反转及其后的充放电或充放电操作使得本实施例铅酸蓄电池的正极活性物质软化、脱落被改善、修复、逆转、消除、抑制、防止,从而使得本实施例铅酸蓄电池循环工作中的工作放电容量该操作之后获得提高或恢复,另一方面,本实施例的正极、负极极性反转及其后的充放电或充放电操作,也会对本实施例电池循环工作过程中发生、轻微发生或将要发生的电极钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极比表面积收缩、硫酸盐化的问题具有改善、修复、逆转、抑止、消除、预防的作用,例如,由于电极A、B反复交替地作为正极或负极进行充放循环工作,使得作为正极工作时产生的电极腐蚀问题在电极作为负极进行充放循环工作时得到改善、修复、逆转、消除、抑制、防止,从而也使得本实施例铅酸蓄电池在长期使用过程中的腐蚀问题得到延缓、改善、修复、逆转、消除、抑制、防止, 在本实施例铅酸蓄电池正常循环工作过程中,定期或不定期的(例如,以规定循环工作次数的方式)、穿插地对本实施例铅酸蓄电池进行本实施例的正极、负极极性反转及其后的充放电或充放电操作,将会有效的改善、修复、逆转、消除、抑制、预防正极活性物质软化或/和脱落、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩问题,从而提高或延长本实施例铅酸蓄电池的使用寿命。
如果定义本实施例铅酸蓄电池在循环工作中当其工作放电容量为额定容量的65%以下为无效工作,则,如图10中所示的本实施例铅酸蓄电池的有效循环工作次数为75次,如果定义本实施例铅酸蓄电池在循环工作中当其工作放电容量为额定容量的80%以下为无效工作,则,如图10中所示的本实施例铅酸蓄电池的有效循环工作次数为70次。可以推测,在排除使电池失效的短路、断路、失液、污染、机械损坏等因素的情况下,本实施例提高或延长铅酸蓄电池使用寿命的方法,将使本实例铅酸蓄电池的使用寿命在现有的有效循环次数基础上获得更大的提高或延长。
本实施例中的一些实验数据表明,本实施例铅酸蓄电池每次或每期极性反转后及其后的充电或充放电操作后本实施例铅酸蓄电池的工作放电容量恢复的程度以及本实施例铅酸蓄电池每次工作放电容量恢复后可连续保持正常或较高放电容量的充放循环工作的次数(即每次或每期极性反转后及其后的充电或充放电操作之间本实施例铅酸蓄电池所正常工作或较高放电容量的充放循环次数)与相应地每次或每期极性反转及其后的充电或充放电操作中所采用的电流、电压、时间、充放电容量、脉冲或直流、电池的内阻、电解液密度、电解液饱和程度的大小、方式的不同而不同。
本实施例触发并进行本实施例铅酸蓄电池正极、负极极性反转的触发条件参数除了是一定的循环数外,还可以是循环数乘以充电总量的某个值、给电池充电时某电池电压区间之电压上升的速率值等。
本实施例铅酸蓄电的的两片电极也是彼此等价的正负极通用电极,因为在电极被化成后,两者具有相同的功能和性能,但在实际使用中,极性反转及其后的充电或充放电操作制度、循环工作制度等因素的变化和差异,会导致两者在功能和性能的表现上出现差异。
在本实施例的其它实施方式中,本实施例铅酸蓄电池的电解液密度可以为1.282g/cm 3或1.30g/cm 3
实施例14
本实施例铅酸蓄电池组为全管式铅酸蓄电池组,额定电压为4V,额定容量为539mAh(C 3.5,3.5h率,25℃)由两只彼此相同的的全管式铅酸蓄电池串联而成,每只全管式铅酸蓄电池的所有电极均为管式电极,且该些管式电极均为正负极通用电极(即正极、负极通用的电极),且该些管式正负极通用电极在电极结构和活性物质配方上相同,每个管式正负极通用电极的套管内直径为6.3mm,,套管高度为75mm(包括管塞),套管内铅-钙合金导电骨芯直径为2.5mm,每只全管式铅酸蓄电池包括3个管式正负极通用电极,为了便于本实施例的后续说明,将本实施例铅蓄电池组的6个管式 正负极通用电极分别命名为电极A1、A2、A3、A4、B1、B2,这6个电极在本实施例铅酸蓄电池组中的每只全管式铅酸蓄电池中排布方式为:电极B1夹在电A1、A2之间或电极B2夹在电极A3、A4之间,电极A1或A2或A3或A4套管中活性物质的质量为均为5.8g,电极B1或B2套管中的活性物质质量均为5.5g,电极A1、A2、A3、A4、B1、B2中的活性物质均由球磨铅粉、硫酸钡(相对于球磨铅粉为0.8wt%)构成,将本实施例铅酸蓄电池组的两个输出端子分别命名为电池组端子A、B,其中电池组端子A连接于电极A1或A2或A3或A4,电池组端子B连接于电极B1或B2,本实施例铅酸蓄电池组在其最初始的循环充放电工作过程中,电极A1、A2、A3、A4作为正极进行循环工作(即循环工作过程中电极A1、A2、A3、A4上发生的是铅酸蓄电池正极电极反应的充放电过程)、电极B1、B2作为负极进行循环工作(即循环工作过程中电极B1、B2上发生的是铅酸蓄电池负极电极反应的充放电过程),即此时电池组端子A的极性为正、电池组端子B的极性为负,表示为A+/B-(同理,当电池组端子A的极性为负、电池组端子B的极性为正时,表示为A-/B+),正、负管式电极之间隔有隔板,本实施例铅酸蓄电池组使用的电解液硫酸溶液的密度为1.27g/cm 3,本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。
提高或延长本实施例铅酸蓄电池组的使用寿命的方法为,每当本实施例铅酸蓄电池组循环工作到某一定次数时或工作放电充电能力由于正极活性物质软化或/和脱落、负极比表面积收缩、集流体或汇流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良等问题中的一种或多种而下降到一定程度时,即自动或/和手动地对本实施例铅酸蓄电池组的正、负极进行一次单次极性反转及其后的充电或充放电操作,以改善、修复、逆转、防止、抑制、消除由于正极活性物质软化、负极比表面积收缩、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良其中的一种或多种原因造成的工作放电容量或工作能力下降、使用寿命终止的问题,使本实施例铅酸蓄电池组的工作放电容量或工作能力恢复或提高,然后在该次极性反转及其后的充电或充放电操作后,使本实施例铅酸蓄电池组以该次极性反转后的电极极性状态重新投入循环充放电工作中去进行循环工作,直到开始下次正、负极极性反转及其后的充电或充放电操作。所述在该次极性反转及其后的充电或充放电操作后,使本实施例铅酸蓄电池组以该次极性反转后的电极极性状态重新投入循环充放电工作中去进行循环工作,例如,若本实施例铅酸蓄电池组的电极A1、A2、A3、A4在该次极性反转前是作为正极进行循环工作(即在循环工作过程中电极A1、A2、A3、A4上发生铅酸蓄电池正极电极反应的充放电过程),则在该次极性反转后,电极A1、A2、A3、A4是作为负极进行充放循环工作(即在循环工作过程中电极A1、A2、A3、A4上发生铅酸蓄电池负极电极反应的充放电过程),相应的电极B1、B2若在该次极性反转前是作为负极进行循环工作(即循环工作过程中电极B1、B2上发生铅酸蓄电池负极电极反应的充放电过程),则在该次极性反转后是作为正极进行循环工作(即循环工作过程中电极B1、B2上发生铅酸蓄电池正极电极反应的充放电过程),同理,若电极A1、A2、A3、A4或电极B1、B2在该次极性反转前的循环工作过程中的极性状态或极性方向反之,则, 电极A1、A2、A3、A4或电极B1、B2在该次极性反转后的循环工作过程中的极性状态或极性方向亦反之。触发或开始对本实施例铅酸蓄电池组的正、负极进行任意一次极性反转及其后的充电或充放电操作的触发方式,可以是手动触发或程序根据预设定的触发条件的到达情况而自动触发,触发条件可以是一定的循环充放电工作次数或累计次数、充电量、放电量、充放电速率、电流变化量、电压变化量等中的一种或多种或它们的计算值。
本实施铅酸蓄电池组采用的循环充放电工作制度为:工作放电时,以0.283C 3.5的电流进行放电至3.5V,然后,以0.338 C 3.5的电流进行恒流充电至5.95V或时间为9小时24分,然后再以5.3V的电压进行恒压充电3小时,然后再重复之前的工作放电过程,如此反复、循环,使本实施例铅酸蓄电池组循环充放工作。
本实施铅酸蓄电池组循环工作和本实施例提高或延长本实施例铅酸蓄电池组使用寿命的方法的实施结果,如图11所示,本实施例铅酸蓄电池组在循环工作过程中,在其工作循环次数的第6、7次之间、第17、18次之间、第25、26次之间、第33、34次之间、第41、42次之间、第56、57次之间进行或被进行了依次为第一次、第二次、.....、第六次的单次正、负极极性反转及其后的充电或充放电操作,所进行或被进行的正、负极极性反转及其后的充电或充放电操作的方法或过程如下:
对于第一次单次正、负极极性反转及其后的充电或充放电操作:当本实施例铅酸蓄电池组处于完成第6次循环工作后的充电状态下时,此时,电极A1、A2、A3、A4的极性为正,电极B1、B2的极性为负,停止本实施例铅酸蓄电池组的循环工作,将充放电设备的正、负输出端与本实施例铅酸蓄电池组此时的正、负极输出端子进行反极连接,即,充放电设备的正输出端与本实施例铅酸蓄电池组的负极输出端子(电池组端子B)连接,充放电设备的负输出端与本实施例铅酸蓄电池组的正极输出端子(电池组端子A)相连接,反极连接后,充放电设备测得本实施例铅酸蓄电池组的电压为-5.53V,然后,对本实施例铅酸蓄电池组以458mA的电流在该反极连接的状态下进行充电,使得本实施例铅酸蓄电池组的正、负极输出端的电压(充放电设备测得值,本实施例中以下同)从-5.53V上升到0V再上升到5.8V,此过程中本实施例铅酸蓄电池组发生了第一次极性反转,即,从-5.53V上升到0V的过程中,电极A1、A2、A3、A4上主要发生的是铅酸蓄电池正极电极反应的放电过程、电极B1、B2上主要发生的是铅酸蓄电池负极电极反应的放电过程,而在0V上升到5.8V的过程中,电极A1、A2、A3、A4上主要发生的是铅酸蓄电池负极电极反应的充电过程,电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的充电过程,在保持充放电设备输出端与本实施例铅酸蓄电池组输出端子的连接状态不变的情况下,再以152.7mA对本实施例铅酸蓄电池组进行放电14分钟至3.5V,然后再以229mA的电流恒流充电8小时至5.72V,然后,再以152.7mA放电2分钟至4.5V,然后,再以114mA恒流充电3小时至5.5V,然后将本实施例铅酸蓄电池组投入到循环工作的第7次工作放电过程中去,进行第7次乃至其后直到第17次的循环工作。本实施例铅酸蓄电池组在第7-17次的循环工作中,电池组端子A的极性为负、电极池组端子B的极性为正,如图11所示,即,此过程中,电极A1、A2、A3、A4上发生铅酸蓄电池负极电极反应的充放电过程,电极B1、B2上发生铅酸蓄电 池正极电极反应的充放电过程。
对于第二次单次正、负极极性反转及其后的充电或充放电操作:当本实施例铅酸蓄电池组处于完成第17次循环工作后的充电状态下时,此时,电极A1、A2、A3、A4的极性为负,电极B1、B2的极性为正,停止本实施例铅酸蓄电池组的循环工作,将充放电设备的正、负输出端与本实施例铅酸蓄电池组此时的正、负极输出端子进行反极连接,即,充放电设备的正输出端与本实施例铅酸蓄电池组此时的负输出端子(电池组端子A)连接,充放电设备的负输出端与本实施例铅酸蓄电池组此时的正输出端子(电池组端子B)相连接,反极连接后,充放电设备测得本实施例铅酸蓄电池组的电压为-4.54V,然后,对本实施例铅酸蓄电池组以459mA的电流在该反极连接的状态下进行充电,使得本实施例铅酸蓄电池组的输出电压(充放电设备测得值,本实施例中以下同)从-4.54V上升到0V再上升到5.8V,历时4小时30分钟,此过程中本实施例铅酸蓄电池组发生了第二次极性反转,即,从-4.54V上升到0V的过程中,电极A1、A2、A3、A4上主要发生的是铅酸蓄电池负极电极反应的放电过程、电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的放电过程,而在0V上升到5.8V的过程中,电极A1、A2、A3、A4上主要发生的是铅酸蓄电池正极电极反应的充电过程,电极B1、B2上主要发生的是铅酸蓄电池负极电极反应的充电过程,在保持充放电设备输出端与本实施例铅酸蓄电池组输出端子的连接状态不变的情况下,再以152.7mA对本实施例铅酸蓄电池组进行放电17分钟至3.5V,然后再以229mA的电流恒流充电8小时至5.41V,然后,再以152.7mA放电2分钟至4.23V,然后,再以114mA恒流充电3小时至5.26V,然后将本实施例铅酸蓄电池组投入到循环工作中的第18次工作放电过程中去,进行第18次以及其后直到第25次的循环工作。本实施例铅酸蓄电池组在第18-25次的循环工作中,电池组端子A的极性为正、电极池组端子B的极性为负,如图11所示,即,此过程中,电极A1、A2、A3、A4上发生铅酸蓄电池正极电极反应的充放电过程,电极B1、B2上发生铅酸蓄电池负极电极反应的充放电过程,也即,电池组端子A、B以及电极A1、A2、A3、A4、B1、B2的极性状态或极性方向返回到了本实施例铅酸蓄电池组最初始进行循环工作时的状态。
在本实施例铅酸蓄电池组的循环工作过程中,反复、多次、穿插地进行如上所述类似于本实施例第一次或第二次的单次正、负极极性反转及其后的充电或充放电操作,即实现了本实施例铅酸蓄电池组在其工作循环次数的第25、26次之间、第33、34次之间、第41、42次之间、第56、57次之间、......、第X、X+1次之间进行或被进行的第三次、第四次、第五次、第六次、.....、第Y次的单次正、负极极性反转及其后的充电或充放电操作(X、Y为正整数)。图11中标示出了本实施例铅酸蓄电池组在经过各次单次正、负极极性反转及其后的充电或充放电操作之前或之后,在循环工作过程中,电池组端子A、B的极性状态或极性方向情况,图12中示出了本实施例铅酸蓄电池组第23-28次循环充放电工作过程及该过程期间穿插进行的第三次单次正、负极极性反转及其后的充电或充放电操作过程中的电流、电压变化情况,第三次单次正、负极极性反转及其后的充电或充放电操作过程与第一次单次正、负极极性反转及其后的充电或充放电操作过程基本相同,所不同之处在于,在操作后期的“以152.7mA放电2分钟、再以114mA恒流充电3小时”的步骤完成后,再以153mA 的电流放电2小时58分钟,然后才将本实施例铅酸蓄电池组投入到第26次循环工作中去。
如图11所示,完成每次单次极性反转及其后的充电或充放电操作用后,本实施例铅酸蓄电池组的工作放电容量都同比地得到提升或恢复,经检查,这是由于本实施例的正、负极极性反转及其后的充放电或充放电操作使得本实施例铅酸蓄电池组的正极活性物质软化或/和脱落、电极钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极比表面积收缩的问题中的一种或多种得到改善、修复、逆转、抑止、消除、预防,在本实施例铅酸蓄电池组正常循环工作过程中,定期或不定期的(例如,以规定循环工作次数的方式)、穿插地对本实施例铅酸蓄电池组进行本实施例的正、负极极性反转及其后的充放电或充放电操作,将会有效的改善、修复、逆转、消除、抑制、预防正极活性物质软化或/和脱落、钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩问题,从而提高或延长本实施例铅酸蓄电池组的使用寿命,例如,由于电极A1、A2、A3、A4、B1、B2反复交替的作为正极或负极进行充放循环工作,使得作为正极工作时产生的电极腐蚀问题在电极作为负极进行充放循环工作时得到改善、修复、逆转,从而也使得本实施例铅酸蓄电池组在长期使用过程中的腐蚀问题得到延缓、改善、修复、逆转、防止,从而也有利于大大提高或延长本实施例铅酸蓄电池组的使用寿命,可以推测,在排除使电池失效的短路、断路、失水、污染等因素的情况下,本实施例提高或延长铅酸蓄电池组使用寿命的方法,将使本实例铅酸蓄电池组的使用寿命在现有的有效循环次数基础上获得更大的提高或延长。
本实施例中,也可以使用快速充放电脉冲电流、脉冲电压进行本实例的正极、负极极性反转及其后的充电或充放电操作。
本实施例中的一些实验数据表明,本实施例铅酸蓄电池组每次单次极性反转后及其后的充电或充放电操作后本实施例铅酸蓄电池组的工作放电容量恢复的程度以及本实施例铅酸蓄电池组每次工作放电容量恢复后可连续保持正常或较高放电容量的充放循环工作的次数(即每次单次极性反转后及其后的充电或充放电操作之间本实施例铅酸蓄电池组所正常工作或较高放电容量的充放循环次数)与相应地每次单次极性反转及其后的充电或充放电操作中所采用的电流、电压、时间、充放电容量、脉冲或直流、电池或电池组的内阻、电解液密度、电解液饱和程度的大小、方式的不同而不同。
在本实施例的其它实施方式中,本实施例全管式铅酸蓄电池组的正、负极或说所有电极均为同一种管式正负极通用电极,即,不考虑制造电极时产生的制造误差,本实施例全管式铅酸蓄电池组的所有电极或说所有管式电极在被化成之前,彼此在所有电极构成、制造方面(如电极结构、造形、导电骨芯、套管、汇流体、活性物质配方和质量、制做工艺等)完全相同,在被化成之后,本实施例全管式铅酸蓄电池组的各管式电极则分别被形成正极或负极。
在本实施例的其它实施方式中,本实施例全管式铅酸蓄电池组的正、负极或说所有电极均为彼此等价的管式正负极通用电极,即,在电极被化成或充放电之后,在铅酸蓄电池组的工作或使用过程中,不考虑误差因素的情况下,本实施例的各管式电极具有或表现出相同的功能和性能。
实施例15
本实施例铅酸蓄电池组,其所包括的铅酸蓄电池为平面板栅式铅酸蓄电池、管式铅酸蓄电池、卷绕式铅酸蓄电池、双极式铅酸蓄电池、水平铅布式铅酸蓄电池、泡沫板栅式铅酸蓄电池、阀控式密封铅酸蓄电池、胶体铅酸蓄电池、铅碳电池、超级电容器-铅酸蓄电池,其中的一种或多种,本实施例铅酸蓄电池组的额定电压U为6V、12V、24V、36V、48V、60V或72V,本实施例铅酸蓄电池组的额定容量(C 2,2小时率,25℃)为12Ah、14Ah、16Ah、18Ah、20Ah、24Ah、30Ah、60Ah、100Ah、200Ah或1000Ah,本实施例铅酸蓄电池组具有电池组输出端子A、B,电池组输出端子A与本实施例铅酸蓄电池组中的电极A1、A2、......、An(n=正整数)相导电连接,电池组输出端子B与本实施例铅酸蓄电池组中的电极B1、B2、......、Bn(n=正整数)相导电连接。本实施例铅酸蓄电池组中的电极A1、A2、......、An、B1、B2、......、Bn均为正负极通用电极(即正极、负极通用的电极),既可作为铅酸蓄电池的正极使用或工作,也可作为铅酸蓄电池的负极使用或工作。本实施例铅酸蓄电池组在最初的循环充放电工作过程中,其电池组输出端子A的极性为正、电池组输出端子B的极性为负,即,本实施例铅酸蓄电池组在最初的循环工作过程中,其电极A1、A2、......、An上发生的是铅酸蓄电池正极电极反应的充放电过程,电极B1、B2、......、Bn上发生的是铅酸蓄电池负极电极反应的充放电过程。正、负电极之间隔有隔板。
本实施例提高或延长本实施例铅酸蓄电池组使用寿命的方法为,当本实施例铅酸蓄电池组在其循环工作的使用或工作中,工作循环达到一定次数时或根据需要(例如,由于正极活性物质软化、负极比表面积收缩、腐蚀、电极钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良等原因导致本实施例铅酸蓄电池组工作放电容量下降并低于某容量数值时或后,希望或需要提高电池组工作放电容量或提高、延长电池组使用寿命时)在某两次工作循环之间,自动或/和手动地对本实例铅酸蓄电池组进行一次单次正、负极极性反转及其后的充电或充放电操作,改善、消除、逆转、抑制、防止正极活性物质软化、负极比表面积收缩、腐蚀、电极钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良等问题,使得本实施例铅酸蓄电池组的工作能力恢复或提高,完成该次正、负极极性反转及其后的充电或充放电操作后,将本实施例铅酸蓄电池组以该次极性反转后的极性状态、重新投入到充放循环工作中使用或工作,直到再次触发或开始又一次对本实施例铅酸蓄电池组进行正、负极极性反转及其后的充电或充放电操作,如此,使得本实施例铅酸蓄电池组的循环工作与本实施例的对本实施例铅酸蓄电池组进行正、负极极性反转及其后的充电或充放电操作彼此间歇的、穿插的、交替的进行或发生,从而提高或延长本实施例铅酸蓄电池组的使用寿命。
对本实施例铅酸蓄电池组进行第一次单次正、负极极性反转及其后的充电或充放电操作包括步骤:当本实施例铅酸蓄电池组在最初始的循环工作过程中(此期间本实施例铅酸蓄电池组输出端子A的极性为正、输出端子B的极性为负,即,电极A1、A2、......、An上发生铅酸蓄电池正极电极反应的充放电过程,电极B1、B2、......、Bn上发生铅酸蓄电池负极电极反应的充放电过程),工 作循环达到某一定次数时,例如,5次、9次、20次或60次,对本实施例铅酸蓄电池组进行反极充电,所述反极充电的方式包括,单一阶段、多阶段、恒流(例如0.1C 2、0.5C 2、1.2C 2、6C 2)、恒压(例如U、1.3U、2U、5U)、正脉冲、负脉冲其中的一种或多种,并最终使得本实施例铅酸蓄电池组的输出端子A、B的极性,从而电极A1、A2、......、An、B1、B2、......Bn的极性,发生反转,且,该次极性反转后,对本实施例铅酸蓄电池组进行充电或充放电,充电或充放电的方式包括,单一阶段、多阶段、恒流(例如0.15C 2、0.4C 2、0.8C 2、7C 2)、恒压(例如0.8U、1.5U、2U、4U)、正脉冲、负脉冲其中的一种或多种,然后,使本实施例铅酸蓄电池组以该次极性反转后的极性状态,重新投入到循环工作中去进行循环工作,本实施例铅酸蓄电池组在完成第一次单次正、负极极性反转及其后的充电或充放电操作后所进行的循环工作过程中,本实施例铅酸蓄电池组输出端子A的极性为负、输出端子B的极性为正,即,电极A1、A2、......、An上发生铅酸蓄电池负极电极反应的充放电过程,电极B1、B2、......、Bn上发生铅酸蓄电池正极电极反应的充放电过程。
对本实施例铅酸蓄电池组进行第二次单次正、负极极性反转及其后的充电或充放电操作包括步骤:当本实施例铅酸蓄电池组在上述第一次单次正、负极极性反转及其后的充电或充放电操作后的循环工作过程中(此期间本实施例铅酸蓄电池组输出端子A的极性为负、输出端子B的极性为正,即,电极A1、A2、......、An上发生铅酸蓄电池负极电极反应的充放电过程,电极B1、B2、......、Bn上发生铅酸蓄电池正极电极反应的充放电过程),工作循环完成某一定次数时,例如,9次、13次、20次或40次,对本实施例铅酸蓄电池组进行第二次反极充电,所述该次反极充电的方式包括,单一阶段、多阶段、恒流(例如0.2C 2、0.5C 2、1.5C 2、3C 2)、恒压(例如U、1.1U、2U、4U)、正脉冲、负脉冲其中的一种或多种,并最终使得本实施例铅酸蓄电池组的输出端子A、B的极性,从而电极A1、A2、......、An、B1、B2、......Bn的极性,发生反转,且,该次极性反转后,对本实施例铅酸蓄电池组进行充电或充放电,充电或充放电的方式包括,单一阶段、多阶段、恒流(例如0.18C 2、0.7C 2、2C 2、5C 2)、恒压(例如0.6U、1.3U、2.2U、3U)、正脉冲、负脉冲其中的一种或多种,然后,使本实施例铅酸蓄电池组以该次极性反转后的极性状态,重新投入到循环工作中去进行循环工作,本实施例铅酸蓄电池组在完成第二次单次正、负极极性反转及其后的充电或充放电操作后所进行的循环工作过程中,本实施例铅酸蓄电池组输出端子A的极性为正、输出端子B的极性为负,即,电极A1、A2、......、An上发生铅酸蓄电池正极电极反应的充放电过程,电极B1、B2、......、Bn上发生铅酸蓄电池负极电极反应的充放电过程。
在本实施例铅酸蓄电池组的循环充放工作过程中,实施其它次的单次正、负极极性反转及其后的充电或充放电操作的方法与实施上述本实施例第一次或第二次单次正、负极极性反转及其后的充电或充放电的方法相类同。如此,在本实施例铅酸蓄电池组的循环充放工作过程中反复、多次、穿插地进行本实施例如上所述的正、负极极性反转及其后的充电或充放电操作,使得本实施例铅酸蓄电池组的正极活性物质软化或/和脱落、电极钝化、早期容量损失、腐蚀、硫酸盐化、负极比表面积收缩、活性物质与集流体接触不良等问题中一种或多种得到改善、修复、逆转、消除、抑制、防止, 从而使得本实施例铅酸蓄电池组的工作放电容量、使用寿命获得提高或延长。
在本实施例的其它实施方式中,提高或延长本实施例铅酸蓄电池组使用寿命的方法为,在本实施例铅酸蓄电池组的循环工作过程中,为了改善、修复、逆转、解决、防止因正极活性物质软化或/和脱落、电极钝化、早期容量损失、腐蚀、硫酸盐化、负极比表面积收缩、活性物质与集流体接触不良等问题中一种或多种而导致的电池组工作能力下降或使用寿命终止,对本实施例铅酸蓄电池组多期地、穿插地进行奇次数或偶次数的正、负极极性反转及其后的充电或充放电操作,完成每期奇次数或偶次数的正、负极极性反转及其后的充电或充放电操作后,将本实施例铅酸蓄电池组以该期极性反转后的极性状态、重新投入到充放循环工作中使用或工作,获得本实施例铅酸蓄电池组的工作能力恢复或提高,直到再次触发或开始又一期对本实施例铅酸蓄电池组进行奇次数或偶次数的正、负极极性反转及其后的充电或充放电操作。每期奇次数或偶次数的正、负极极性反转及其后的充电或充放电操作中的任一次正、负极极性反转及其后的充电或充放电操作与本实施例前述的第一次或第二次单次正、负极极性反转及其后的充电或充放电操作相类同。
在本实施例的其它实施方式中,本实施例铅酸蓄电池组的正极、负极或说所有电极均为同一种正负极通用电极,即,不考虑制造电极时产生的制造误差,本实施例铅酸蓄电池组的所有电极在被化成之前,彼此在所有电极构成、制造方面(如电极结构、造形、集流体、汇流体、活性物质配方和质量、其它配件、制做工艺等)完全相同,在被化成之后,本实施例铅酸蓄电池组的各电极则分别被形成正极或负极。
在本实施例的其它实施方式中,本实施例铅酸蓄电池组的正、负极或说所有电极均为彼此等价的正负极通用电极,即,在电极被化成或充放电后,在铅酸蓄电池组的工作或使用过程中,不考虑误差因素的情况下,本实施例的各电极具有或表现出相同的功能和性能。
实施例16
本实施例铅酸蓄电池组、提高或延长铅酸蓄电池组使用寿命的电池组充放电器和提高或延长铅酸蓄电池组使用寿命的正、负极极性反转及其后的充电或充放电操作的区分操作方法,其中,本实施例铅酸蓄电池组包括两只等价的铅酸蓄电池单电池A、B(等价电池是指,除了制造误差外,A、B电池的所有参数相同,以下类同),该电池组的额定电压为2V,额定容量等于铅酸蓄电池组中单电池的额定容量,本实施例电池组中的每只单电池均具有各自独立的正、负极电路输入、输出端。
本实施例电池组充放电器具有对本实施例铅酸蓄电池组中任意一个单体电池单独进行其正、负极极性反转及其后的充电或充放电操作功能。
本实施例正、负极极性反转及其后的充电或充放电操作的区分操作方法为:使本实施例铅酸蓄电池组在额定电压下进行充放循环工作,工作由本实施例电池组中的单电池A承担,单电池B处于非循环工作状态,当本实施例电池组,也即执行工作任务的单电池A,其放电容量下降(原因包括正极活性物质软化、脱落或负极表面积收缩或硫酸盐化,以下同)至电池组额定容量的90%时,通 过本实施例电池组充放电器中已设定好的触发和执行程序,将单电池A停止工作,转入非循环工作状态,并将电池组中的处于非循环工作状态的具有合格工作能力的单电池B切换到循环工作状态,并使电池组基于单电池B可以继续工作,对于由原循环工作状态转入非循环工作状态的单电池A单独地进行其电池正、负极极性反转及其后的充电或充放电操作,以使该单电池A的工作能力恢复到合格工作能力,该操作完成后,使单电池A处于非循环工作状态、待切换。
本实施例电池组基于单电池B工作一段时间后,当本实施例电池组,也即执行工作任务的单电池B,其放电容量低于本实施例电池组的额定容量的90%时,通过本实施例电池组充放电器中已设定好的触发和执行程序,将该处于循环工作状态的单电池B停止工作,并将电池组中的处于非循环工作状态的、经其电池正、负极极性反转及其后的充电或充放电操作后已具有合格工作能力的单电池A切换到循环工作状态,以使本实施例电池组重新基于单电池A可以继续循环工作,然后,对由原循环工作状态转入非循环工作状态的单电池B单独地进行其电池正、负极极性反转及其后的充电或充放电操作,以使该单电池B的工作能力恢复到合格工作能力,该操作完成后,使单电池B处于非循环工作状态、待切换。
按照上述方法,轮流地对单电池A、B进行正、负极极性反转及其后的充电或充放电操作,使本实施例铅酸蓄电池组的使用寿命获得显著提高或延长,比普通铅酸蓄电池组的使用寿命提高或延长达1倍以上。
实施例17
本实施例铅酸蓄电池组、提高或延长铅酸蓄电池组使用寿命的电路和提高或延长铅酸蓄电池组使用寿命的正、负极极性反转及其后的充电或充放电操作的区分操作方法,其中,本实施例铅酸蓄电池组包括3只等价的铅酸蓄电池单电池A、B、C,该电池组的额定电压为4V,额定容量等于铅酸蓄电池组中单电池的额定容量,该电池组中的每只单体电池均具有各自独立的正、负极电路输入输出端。
本实施例电路具有对本实施例铅酸蓄电池组中任意一个单电池单独进行其正、负极极性反转及其后的充电或充放电操作功能。
本实施例正、负极极性反转及其后的充电或充放电操作的区分操作方法为:使本实施例铅酸蓄电池组在额定电压下进行充放循环工作,工作时该电池组中的单电池A、B处于充放循环工作状态,承担所在电池组的充放循环工作任务,单电池C处于非充放循环工作状态,电池组基于单电池A、B进行充放循环工作,当电池组的循环工作放电容量下降(原因包括正极活性物质软化、脱落或负极表面积收缩或硫酸盐化,以下同)至电池组额定容量的80%时,通过本实施例电路中已设定好的触发和执行程序,对于工作时电压下降较快的单电池B将其切换到非循环工作状态,而将原处于非循环工作状态的具有合格工作能力的单电池C切换到循环工作状态,以使电池组基于单电池A、C可以继续循环工作,对于由原循环工作状态转入非循环工作状态的单电池B单独地进行其电池正、 负极极性反转及其后的充电或充放电操作,以使该单电池B的工作能力恢复到合格工作能力,该操作完成后,使单电池B处于非循环工作状态、待切换。
当电池组基于单电池A、C进行工作,且其循环工作放电容量下降至电池组额定容量的80%时,通过本实施例电路中已设定好的触发和执行程序,对于工作时电压下降较快的单电池A将其由循环工作状态切换到非循环工作状态,而将原处于非循环工作状态的、经其电池正、负极极性反转及其后的充电或充放电操作后已具有合格工作能力的单电池B切换到循环工作状态,以使电池组基于单电池B、C可以继续循环工作,对于由原工作状态转入非循环工作状态的单电池A单独地进行电池正、负极极性反转及其后的充电或充放电操作,以使该单电池A的工作能力恢复到合格工作能力,该操作完成后,使单电池A处于非循环工作状态、待切换。
当电池组基于单电池B、C进行工作,且其循环工作放电容量下降至电池组额定容量的80%时,对于电池组中工作时电压下降较快的单电池C及处于非循环工作状态的单电池A进行类同上述操作,使得电池组再次基于单电池A、B而循环工作,而单电池C经电池正、负极极性反转及其后的充电或充放电操作后,恢复合格工作能力,处于非循环工作状态、待切换。
本实施例铅酸蓄电池组中各单电池在循环工作状态和非循环工作状态之间的切换也可以通过规定电池组或单电池的循环工作次数进行触发。
按照上述方法,轮流地(不一定按顺序或平均次数)对单电池A、B、C进行正、负极极性反转及其后的充电或充放电操作,使本实施例铅酸蓄电池组的使用寿命获得显著提高或延长,比普通铅酸蓄电池组的使用寿命提高或延长达1倍以上。
实施例18
本实施例铅酸蓄电池组、提高或延长铅酸蓄电池组使用寿命的电池组充放电器和提高或延长铅酸蓄电池组使用寿命的正、负极极性反转及其后的充电或充放电操作的区分操作方法,其中,本实施例铅酸蓄电池组包括7只等价铅酸蓄电池单电池A、B、C、D、E、F、G,该电池组的额定电压为12V,额定容量等于铅酸蓄电池组中单电池的额定容量,该电池组中的每只单体电池均具有各自独立的正、负极电路输入输出端。
本实施例电池组充放电器具有对本实施例铅酸蓄电池组中任意一个单体电池单独进行其正、负极极性反转及其后的充电或充放电操作功能。
本实施例正、负极极性反转及其后的充电或充放电操作的区分操作方法为:使本实施例铅酸蓄电池组在额定电压下进行充放循环工作,工作时该电池组中的单电池A、B、C、D、E、F处于循环工作状态,承担电池组的工作任务,单电池G处于非循环工作状态,电池组基于单电池A、B、C、D、E、F进行循环工作,当电池组的工作放电容量下降至电池组额定容量的80%时,通过本实施例电池组充放电器中已设定好的触发和执行程序,对于电池组中因正极活性物质软化、脱落所造成的容量衰减程度最大的单电池B将其由循环工作状态切换到非循环工作状态,而将原处于非循环工作 状态的具有合格工作能力的单电池G切换到循环工作状态,以使电池组基于单电池A、C、D、E、F、G可以继续循环工作,对于由原循环工作状态转入非循环工作状态的单电池B单独地进行其电池正、负极极性反转及其后的充电或充放电操作,以使该单电池B的工作能力恢复到合格工作能力,该操作完成后,使单电池B处于非循环工作状态、待切换。
当电池组基于单电池A、C、D、E、F、G进行工作,且其工作放电容量下降至电池组额定容量的75%时,通过本实施例电池组充放电器中已设定好的触发和执行程序,对于电池组中因正极活性物质软化、脱落所造成的容量衰减程度最大的单电池E将其由工作循环状态切换到非循环工作状态,而将原处于非循环工作状态的具有合格工作能力的单电池B切换到循环工作状态,以使电池组基于单电池A、B、C、D、F、G可以继续循环工作,对于由原循环工作状态转入非循环工作状态的单电池E单独地进行其电池正、负极极性反转及其后的充电或充放电操作,以使该单电池E的工作能力恢复到合格工作能力,该操作进行时电池组可以正在工作或处在循环工作中的其它状态,该操作完成后,使单电池E处于非循环工作状态、待切换。
当电池组基于单电池A、B、C、D、F、G进行循环工作,且其工作放电容量下降至电池组额定容量的65%时,对于电池组中因正极活性物质软化、脱落所造成的容量衰减程度最大的单电池及处于非循环工作状态的单电池进行类同上述操作,使得电池组再次基于六只具有合格工作能力的单电池而进行充放循环工作,而使容量衰减程度最大的单电池则经电池正、负极极性反转及其后的充电或充放电操作后,恢复合格工作能力,处于非循环工作状态、待切换。
按照上述方法,轮流地、单独地(不一定按顺序或平均次数)对单电池A、B、C、D、E、F或G进行正、负极极性反转及其后的充电或充放电操作,本实施例铅酸蓄电池组的使用寿命获得显著提高或延长,比普通铅酸蓄电池组的使用寿命提高或延长达1倍以上。
实施例19
本实施例铅酸蓄电池组、提高或延长铅酸蓄电池组使用寿命的电路和提高或延长铅酸蓄电池组使用寿命的正、负极极性反转及其后的充电或充放电操作的区分操作方法,其中,本实施例铅酸蓄电池组包括12只等价的铅酸蓄电池单电池A、B、C、D、E、F、G、H、I、J、k、L,该电池组的额定电压为12V,额定容量等于铅酸蓄电池组中单电池的额定容量,20Ah(2h率,25℃),该电池组中的每只单电池均具有各自独立的正、负极电路输入输出端。
本实施例电路具有对本实施例铅酸蓄电池组中任意一个单体电池单独进行其正、负极极性反转及其后的充电或充放电操作功能。
本实施例正、负极极性反转及其后的充电或充放电操作的区分操作为:使本实施例铅酸蓄电池组在额定电压下进行充放循环工作,循环工作时该电池组中的单电池A、B、C、D、E、F处于循环工作状态,单电池G、H、I、J、k、L处于非循环工作状态,电池组基于单电池A、B、C、D、E、F进行循环工作,当电池组的工作放电容量下降至电池组额定容量的80%时,通过本实施例电路中 已设定好的触发和执行程序,对于电池组中因正极活性物质软化、脱落而容量衰减较重的单电池B将其停止工作并由循环工作状态切换到非循环工作状态,而将原处于非循环工作状态的具有合格工作能力的单电池G切换到循环工作状态,以使电池组基于单电池A、C、D、E、F、G可以继续循环工作,对于由原循环工作状态转入非循环工作状态的单电池B单独地进行电池正、负极极性反转及其后的充电或充放电操作,以使该单电池B的工作能力恢复到合格工作能力,该操作完成后,使单电池B处于非循环工作状态、待切换。
当电池组基于单电池A、C、D、E、F、G进行充放循环工作,且其放电容量下降至电池组额定容量的50%时,通过本实施例电路中已设定好的触发和执行程序,对于容量衰减较大的单电池C、D将其停止工作并由循环工作状态切换到非循环工作状态,而将原处于非循环工作状态的具有合格工作能力的单电池H、I切换到循环工作状态,以使电池组基于单电池A、E、F、G、H、I可以继续工作,然后,对由原循环工作状态转入非循环工作状态的单电池C、D单独地进行电池正、负极极性反转及其后的充电或充放电操作,以使该单电池C、D的工作能力恢复到合格工作能力,该操作完成后,使单电池C、D处于非循环工作状态、待切换。
当电池组基于单电池A、E、F、G、H、I进行循环工作,且其放电容量下降至电池组额定容量的70%时,对于电池组中容量衰减较大的单电池A、E、F、G及处于非循环工作状态的单电池B、C、D、J进行类同上述操作,使得电池组再次基于六只具有合格工作能力的单电池而可以循环工作,而容量衰减较大的的单电池则经电池正、负极极性反转及其后的充电或充放电操作后,恢复合格工作能力,处于非循环工作状态、待切换。
本实施例进行铅酸蓄电池组中各单电池在循环工作状态与非循环工作状态之间的切换,可通过瞬时切换实现。
按照上述方法,轮流地对单电池A、B、C、D、E、F、G、H、I、J、K、L中的一个或多个同时地(不一定按顺序或平均次数)进行电池正、负极极性反转及其后的充电或充放电操作,使本实施例铅酸蓄电池组的使用寿命获得显著提高或延长,比普通铅酸蓄电池组的使用寿命提高或延长达1倍以上。
实施例20
本实施例提高或延长铅酸蓄电池组使用寿命的电池组充放电器、铅酸蓄电池组和提高或延长铅酸蓄电池组使用寿命的正、负极极性反转及其后的充电或充放电操作的区分操作方法,其中,本实施例电池组充放电器与本发明实施例16中的类同。本实施例铅酸蓄电池组包括6只等价的铅酸蓄电池单电池A、B、C、D、E、F,该电池组的额定电压为12V,额定容量等于铅酸蓄电池组中单电池的额定容量,12Ah(2h率,25℃),该电池组中的每只单电池均具有各自独立的正、负极电路输入输出端。
对该电池组进行正、负极极性反转及其后的充电或充放电操作的区分操作为:使本实施例铅酸蓄 电池组在额定电压下进行充放循环工作,当本实施例电池组放电容量下降(原因包括正极活性物质软化、脱落或负极表面积收缩或硫酸盐化,以下同)至电池组额定容量的75%时,通过本实施例电池组充放电器中已设定好的触发和执行程序,将电池组停止工作,对电池组中放电容量衰减较重的一个或多个行进行其电池正、负极极性反转及其后的充电或充放电操作,操作方法类同于本发明其它实施例中的相关操作,使该一个或多个单电池的工作能力恢复到合格工作能力,该操作完成后,使电池组恢复到工作状态。每当本实施例电池组的放电容量下降到额定容量的75%时,重复上述操作,使本实施例铅酸蓄电池组的使用寿命获得了显著提高或延长,比普通铅酸蓄电池组的使用寿命提高或延长了达1倍以上。
实施例21
本实施例提高或延长铅酸蓄电池或电池组的使用寿命的方法,包括在铅酸蓄电池或电池组的浮充工作过程中,穿插地对本实施例铅酸蓄电池或电池组进行总累计次数为1次或1次以上地、相同或类同于本发明以上所有实施例(即实施例1—实施例20)中所述的正、负极极性反转及其后的充电或充放电操作,以改善、修复、逆转、消除、抑制、防止铅酸蓄电池或电池组的正极活性物质软化或/和脱落、电极钝化、早期容量损失、腐蚀、硫酸盐化、负极比表面积收缩、活性物质与集流体接触不良等中一种或多种,使本实施例铅酸蓄电池或电池组的工作能力得到恢复或提高或预防下降,然后重新将本实施例铅酸蓄电池或电池组投入到浮充工作中去,直到再次触发或开始又一次对本实施例铅酸蓄电池或铅酸蓄电组进行正、负极极性反转及其后的充电或充放电操作。
实施例22
本实施例对铅酸蓄电池或电池组的化成方法,包括采用相同或相类同于本发明实施例1-实施例20中所述的极性反转及其后的充电或充放电操作方法对本实施例铅酸蓄电池或电池组进行化成。本实施例对铅酸蓄电池或电池组的化成方法,还包括,对铅酸蓄电池或电池组进行对称的极性反转及其后的充电或充放电操作,即,在本实施例铅酸蓄电池或电池组投入到循环充放工作之前,使得本实施例铅酸蓄电池或电池组的所有电极(包括最初的正极、负极)均至少经历过一次作为正极的化成和一次作为负极的化成。本实施例对铅酸蓄电池或电池组的化成方法,使得铅酸蓄电池或电池组的初始容量获得提高,对于化成所造成的活性物质软化问题有一定的改善作用,同时,也保证了具有正负极通用电极的、在循环充放工作过程中多次、穿插地进行极性反转及其后的充电或充放电操作的铅酸蓄电池或电池组的循环充放工作性能在各次极性反转前和后相对称。
在本实施例的其它实施方式中,将本实施例的化成方法实施于管式铅酸蓄电池的化成,包括,在正常的化成工艺(正接状态下对电池充放电,正接状态,即充放电设备的正输出端与电池的正极即管式电极A相连、充放电设备的负输出端与电池的负极即板式电极B相连)进行前,先对本实施例管式铅酸蓄电池进行1次反极充电(反接状态下对电池充放电,反接状态,即充放电设备的正输出 端与电池的负极即板式电极B相连、充放电设备的负输出端与电池的正极即管式电极A相连)化成,反极充电化成所充入的电量为正常化成工艺化成充电量的5—10%,然后,将本实施例管式铅酸蓄电池转入正常化成工艺进行化成。结果,在电池初始容量方面,与仅进行了正常化成工艺的相同的其它管式铅酸蓄电池相比,本实施例进行了反极充电化成、正常化成工艺的管式铅酸蓄电池的初始容量相对高出10-20%。

Claims (19)

  1. 一种提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述方法包括将铅酸蓄电池或/和铅酸蓄电池组的正极、负极进行极性反转及其后的充电或充放电操作,该操作进行或被进行的总累计次数为≥2次,所述将正极、负极进行极性反转及其后的充电或充放电操作,即,将正电极、负电极进行极性反转,并在该极性反转后,将经过该极性反转的电极进行充电或充放电操作。
  2. 根据权利要求1所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述将铅酸蓄电池或/和铅酸蓄电池组的正、负极进行极性反转及其后的充电或充放电操作,包括将铅酸蓄电池或/和铅酸蓄电池组的电极进行极性反转,并在该极性反转后,使经过该极性反转的电极进行如下电化学反应:使该极性反转前为正极的电极在该极性反转后进行铅酸蓄电池负极电极反应、使该极性反转前为正极的电极其所含有的铅氧化物、碱式硫酸铅、硫酸铅在该极性反转后进行电化学还原反应、使该极性反转前为负极的电极在该极性反转后进行铅酸蓄电池正极电极反应,其中的一种或多种。
  3. 根据权利要求1所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述将正、负极进行极性反转及其后的充电或充放电操作,包括使所述正、负极极性反转及其后的充电或充放电操作与所述铅酸蓄电池或电池组的工作,彼此穿插、交替地进行,并使所述铅酸蓄电池或电池组在工作时,其原来的正极、原来的负极处于以下三种电极工作状态中的一种:(1)原来的正极始终作为正极进行工作,原来的负极始终作为负极进行工作;(2)原来的正极始终作为负极进行工作,原来的负极始终作为正极进行工作;(3)原来的正极有时作为正极进行工作、有时作为负极进行工作,相应地,原来的负极有时作为负极进行工作、有时作为正极进行工作;所述其原来的正极、原来的负极为,在没有被进行过任何所述正极、负极极性反转及其后的充电或充放电操作时,所述铅酸蓄电池或电池组的正极、负极。
  4. 根据权利要求1所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述将正、负极进行极性反转及其后的充电或充放电操作包括:进行连续两次或连续偶数次的正、负极极性反转及其后的充电或充放电操作、进行单次或连续奇数次的正、负极极性反转及其后的充电或充放电操作,其中的一种或多种。
  5. 根据权利要求1所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,针对铅酸蓄电池组,所述正、负极极性反转及其后的充电或充放电操作包括区分操作,即仅对铅酸蓄电池组中的某一个单电池单独地进行所述正、负极极性反转及其后的充电或充放电操作,或者仅对铅酸蓄电池组中的某些单电池进行所述正、负极极性反转及其后的充电或充放电操作。
  6. 根据权利要求1所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述将正、负极进行极性反转及其后的充电或充放电操作包括进行脉冲充电或/和放电的操作。
  7. 根据权利要求6所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述脉冲充电或/和放电包括正脉冲、负脉冲、正负脉冲混合脉冲充电或/和放电操作中的一种或多种。
  8. 根据权利要求1所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,在进行 所述正、负极极性反转及其后的充电或充放电操作之前,还可以对铅酸蓄电池或电池组进行正、负极极性反转前的放电或/和充电操作。
  9. 根据权利要求1、8所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述正、负极极性反转、极性反转后的充电或充放电操作或极性反转前的放电或/和充电操作可以根据某物理量值、数量值、化学量值以及它们的变化值、计算值中的一种或多种的设置、测量、信号采集、计算结果而开始或停止。
  10. 根据权利要求9所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述的物理量值包括电压值、电流值、电流密度值、电量值、容量值、功率值、时间值、温度值、力值、压强值、密度值、光度值、频率值中的一种或多种;所述的数量值包括累计数值、奇数值、偶数值、比例值、电池或/和电池组的充放循环次数值中的一种或多种;所述的化学量值包括电池或/和电池组的酸度值。
  11. 根据权利要求9所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述的物理量值、数量值、化学量值以及它们的变化值、计算值中的一种或多种包括电池或/和电池组在充电过程中、放电过程中、循环工作过程中、浮充工作过程中、开路或静置状态中的物理量值、数量值或化学量值。
  12. 根据权利要求1所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,进行或被进行所述正、负极极性反转及其后的充电或充放电操作的铅酸蓄电池或电池组其正极和负极均为正负极通用电极,所述正负极通用电极,在所述铅酸蓄电池或电池组中,既可作为正极使用、也可作为负极使用,或者某些作为正极使用、某些作为负极使用,或者在所述铅酸蓄电池或电池组工作或使用过程中,某时作为正极使用、某时又作为负极使用,其中的一种或多种;构成铅酸蓄电池或电池组的正极和负极时,所述正负极通用电极包括但不限于,彼此具有相同活性物质或相同活性物质配方的正负极通用电极、彼此等价的正负极通用电极、彼此为同一种的正负极通用电极。
  13. 根据权利要求1-8、10-12中任一项所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述将正、负极进行极性反转及其后的充电或充放电操作通过一种电路实现,所述电路具有所述将铅酸蓄电池或/和铅酸蓄电池组的正极、负极进行极性反转或极性反转及其后的充电或充放电操作的功能,所述电路能够或实际上实现或实施该功能的总累计次数为≥1次。
  14. 根据权利要求13所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述电路实现或实施所述正、负极极性反转或极性反转及其后的充电或充放电操作的方法包括:对所述铅酸蓄电池或电池组进行反极充电;或者其特征在于,所述电路将铅酸蓄电池或/和铅酸蓄电池组的正、负极进行极性反转或极性反转及其后的充电或充放电操作包括自动或/和手动进行。
  15. 根据权利要求1-8、10-12、14中任一项所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,将所述提高或延长铅酸蓄电池或电池组使用寿命的方法应用于铅酸蓄电池或电池组、铅酸蓄电池或电池组的电路或充放电设备、铅酸蓄电池或电池组的修复、再生或生产制造时 的化成工艺。
  16. 一种提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述方法应用于铅酸蓄电池或电池组制造过程中的化成工艺,其特征还在于,所述方法包括将铅酸蓄电池或/和铅酸蓄电池组的正极、负极进行极性反转及其后的充电或充放电操作,该操作进行或被进行的次数为≥1次,所述将正极、负极进行极性反转及其后的充电或充放电操作,即,将正电极、负电极进行极性反转,并在该极性反转后,将经过该极性反转的电极进行充电或充放电操作。
  17. 一种提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,包括使所述铅酸蓄电池或/和铅酸蓄电池组的电极发生极性反转,并在该极性反转后,使经过该极性反转的电极进行如下电化学反应:使该极性反转前为正极的电极在该极性反转后进行铅酸蓄电池负极电极反应、使该极性反转前为正极的电极其所含有的铅氧化物、碱式硫酸铅、硫酸铅在该极性反转后进行电化学还原反应、使该极性反转前为负极的电极在该极性反转后进行铅酸蓄电池正极电极反应,其中的一种或多种;其特征还在于,所述方法实施于所述铅酸蓄电池或/和铅酸蓄电池组的总累计次数为≥2次。
  18. 根据权利要求17所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述方法包括将铅酸蓄电池或/和铅酸蓄电池组的正极、负极进行极性反转及其后的充电或充放电操作,该操作包括权利要求1所述的方法或操作,所述将正极、负极进行极性反转及其后的充电或充放电操作,即,将正电极、负电极进行极性反转,并在该极性反转后,将经过该极性反转的电极进行充电或充放电操作。
  19. 根据权利要求1、16或17所述提高或延长铅酸蓄电池或电池组使用寿命的方法,其特征在于,所述将经过极性反转的电极进行充电或充放电操作、电化学反应,其中,所述充电或充放电、电化学反应的电量为该电极额定容量的0.5倍以上。
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