WO2019086021A1 - Method for solving problems of expanding, softening, and falling-off of positive electrode active substance of storage battery - Google Patents

Method for solving problems of expanding, softening, and falling-off of positive electrode active substance of storage battery Download PDF

Info

Publication number
WO2019086021A1
WO2019086021A1 PCT/CN2018/113859 CN2018113859W WO2019086021A1 WO 2019086021 A1 WO2019086021 A1 WO 2019086021A1 CN 2018113859 W CN2018113859 W CN 2018113859W WO 2019086021 A1 WO2019086021 A1 WO 2019086021A1
Authority
WO
WIPO (PCT)
Prior art keywords
battery
electrode
positive
charging
negative
Prior art date
Application number
PCT/CN2018/113859
Other languages
French (fr)
Chinese (zh)
Inventor
杨春晓
Original Assignee
杨春晓
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 杨春晓 filed Critical 杨春晓
Publication of WO2019086021A1 publication Critical patent/WO2019086021A1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4242—Regeneration of electrolyte or reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/627—Expanders for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a method for solving the problem of battery failure, in particular to a method for solving the problems of expansion, softening and falling off of a positive electrode active material of a battery, and a method for solving other failure problems of the battery separately or simultaneously.
  • Storage batteries including but not limited to lead-acid batteries, iron-nickel batteries, cadmium-nickel batteries, hydrogen-nickel batteries, ferrate batteries, lithium ion batteries, etc.
  • the problem to be solved by the present invention is to provide a method for solving the problems of expansion, softening and falling off of a positive electrode active material of a battery to increase or extend the service life of the battery or the battery pack, or to provide a solution for solving or improving the positive electrode of the battery or the battery pack.
  • One or more problems to increase or extend the life of the battery or battery pack One or more problems to increase or extend the life of the battery or battery pack.
  • the salinization includes, but is not limited to, sulfation.
  • the service life includes, but is not limited to, one or more of a cycle life and a float life.
  • the battery or battery pack ie a battery or a battery pack.
  • the solution to the above problems includes, but is not limited to, solving, repairing, reversing, eliminating, improving, mitigating, suppressing, preventing, and avoiding the above problems.
  • the present invention provides a method for solving the problems of expansion, softening, and shedding of a positive electrode active material of a battery, comprising: causing a positive electrode or a positive electrode active material of the battery or battery group to be a battery negative electrode
  • the electrode reaction is reduced to a metal or a valence by an electrochemical reduction reaction, or the positive or/and negative electrode of the battery or/and battery pack is subjected to polarity inversion and subsequent charging or charging and discharging operations.
  • the total cumulative number of operations is ⁇ 1 times; the positive polarity and the negative electrode are reversed in polarity and then charged or charged and discharged, that is, the polarity of the positive electrode and the negative electrode are reversed, and the polarity is reversed.
  • the electrode subjected to the polarity inversion is subjected to a charging or charging and discharging operation.
  • the total cumulative number refers to all occurrences of the battery or battery during the entire period of its existence or the battery or battery pack 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 battery or battery pack includes positive (positive polarity) or negative (negative polarity) of the electrode of the battery or battery, and positive characteristics of the electrode generally include electrodes occurring on the electrode
  • the reaction is a positive electrode reaction, and the electrode potential phase is relatively high.
  • the negative characteristics of the electrode generally include 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 battery negative electrode reaction to occur on the electrode, and the latter causes the battery positive electrode reaction to occur on the electrode.
  • the polarities of the positive and negative polarities are reversed and thereafter.
  • the charging or charging and discharging operation is further described.
  • the original positive electrode here also referred to as electrode A
  • the original negative electrode also referred to herein as electrode B
  • electrode A the original positive electrode
  • electrode B the original negative electrode
  • the operation steps include first, inverting the polarity of the positive electrode and the negative electrode of the battery or the battery pack, that is, the pole of the original positive electrode (electrode A) of the battery or the battery pack.
  • the polarity is reversed to negative, the polarity of the original negative electrode (electrode B) is reversed to positive by negative, and then after the polarity is reversed, the electrode that has undergone the polarity reversal is charged or charged.
  • Discharge operation ie, the original positive electrode (electrode A) as the negative electrode, the original negative electrode (electrode B) is used as the positive electrode, and the battery or battery pack after the secondary polarity is reversed is charged or charged and discharged, and the whole process is reversed from the polarity to the secondary pole.
  • the charging or charging and discharging operation after the sexual reversal is completed that is, the polarity reversal and the subsequent charging or charging and discharging operations (at this time, the first polarity reversal of the battery or the battery pack is completed and Subsequent charging or charging/discharging operation), the polarity inversion of the positive electrode and the negative electrode and the subsequent charging or charging and discharging operations are performed, including the electrode potential of the original positive electrode (electrode A) The higher the electrode is converted to a lower phase, and the electrode reaction that occurs is reversed from the original battery positive electrode reaction to the battery negative electrode reaction, and the change is reversed for the original negative electrode (electrode B).
  • the second polarity inversion and subsequent charging or charging and discharging operations are positively charged or charged and discharged during the charging or charging and discharging operation after the next (second time) polarity inversion.
  • the electrode is the original positive electrode (electrode A) of the battery or battery pack, and the negative electrode that is charged or charged and discharged is the original negative electrode (electrode B) of the battery or the battery pack.
  • the second (second time) the positive and negative electrodes The polarity reversal and subsequent charging or charging and discharging operations are realized.
  • the electrode potential is converted from a relatively low phase to a relatively high phase, and the electrode reaction occurs.
  • the battery negative electrode reaction is reversed to the battery positive electrode reaction, and the change is 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 and subsequent charging or charging and discharging operations include polarity inversion of the battery or/and the battery pack, and after the polarity is reversed, the electrode that has undergone the polarity inversion is reversed.
  • the electrode which is the positive electrode before the polarity is reversed is subjected to the battery negative electrode reaction after the polarity is reversed or is reduced to a metal or a valence by an electrochemical reduction reaction, and the polarity is reversed.
  • the electrode which is the negative electrode is subjected to the positive electrode reaction of the battery after the polarity is reversed, one or more of which are.
  • 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 poles of the 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 with the battery Or the operation of the battery pack is interspersed and alternately performed, and when the 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: (1) the original The 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 operates as a positive electrode, sometimes As a negative electrode, 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 be reversed in polarity without any of the positive and negative electrodes.
  • the positive or negative electrode of the battery or battery pack during subsequent charging or charging and discharging operations.
  • the polarity of the positive and negative electrodes of the battery or battery pack between any two of its operations and thereafter The number of charging or charging and discharging operations is 0 or more (including 0 times, the same below).
  • the polarity inversion of the positive electrode and the negative electrode and the subsequent charging or charging and discharging operations include separately performing the positive and negative polarity inversion and subsequent charging on only one of the battery cells in the battery pack or Charging and discharging operation, or performing only the positive and negative polarity reversal and subsequent charging or charging and discharging operations on some (ie, two or more) single cells in the battery pack, or only for the battery cells A part of the electrodes in the battery perform the positive and negative polarity inversion and subsequent charging or charging and discharging operations. This is referred to as a distinction operation.
  • the unit cell that is, a unit cell.
  • 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.
  • the active material of the positive electrode or/and the negative electrode of the secondary battery is one or more of a simple substance or a compound having two or more kinds of stable oxidation valence states.
  • the elements having two or more stable oxidation valence states include, but are not limited to, lead, iron, copper, nickel, manganese, silver, phosphorus, sulfur, chlorine, vanadium, chromium, cobalt, arsenic, selenium, bromine, One or more of tin, antimony, bismuth, iodine, tungsten, and antimony.
  • the battery or battery pack includes, but is not limited to, a lead-acid battery, an iron-nickel battery, an iron-ferrate battery, a copper-ferrate battery, a battery of a cadmium-nickel battery, or a battery pack, one of which or A variety.
  • the ferrate includes, but is not limited to, K 2 FeO 4 , Na 2 FeO 4 , BaFeO 4 .
  • the method for solving the problem of expansion, softening and falling off of the positive electrode active material of the battery is also used to solve other problems of the battery separately, or to solve the problems of expansion, softening and falling off of the positive electrode active material of the battery, and also to solve other problems of the battery.
  • Such other problems include, but are not limited to, corrosion of the battery (including but not limited to electrodes, sinks, current collector corrosion), passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, active materials and conductive sets.
  • the positive and negative electrodes of the battery or the battery pack that are charged and discharged are positive and negative common electrodes (ie, electrodes common to the positive electrode and the negative electrode), and the positive and negative electrode are used in the battery or the battery pack. 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 battery or battery pack, and sometimes used as a negative electrode.
  • the positive electrode, the negative electrode, the positive and negative electrode common electrodes include, but are not limited to, a positive electrode or/and a negative electrode including a swelling agent, an electrode active material or an active material thereof
  • the positive and negative electrode common electrode of the expansion agent or the positive electrode or the negative electrode, the positive electrode and the negative electrode common electrode having the same active substance or the same active substance formula
  • the equivalent positive and negative electrode common electrodes, one or more of the same or the same positive and negative electrode common electrodes, each of which is equivalent to each other, means that the electrodes have the same function after being formed into one another.
  • the same or the same positive and negative common electrode means that the positive electrode and the negative electrode of the battery are in the electrode structure, size, and formula All the electrodes are completely identical in terms of materials, manufacturing processes, etc. (ie, all electrodes are identical in composition), or the same or the same positive and negative common electrodes mean that those are being converted or charged.
  • the positive and negative electrode common electrodes which are identical to each other before discharge and which are formed into 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
  • the electrode or the positive electrode and the negative electrode are in various aspects, such as but not limited to a current collector, an active substance formulation, and an active substance quality (such as, but not limited to, a paste formulation and a quality of a paste).
  • a current collector an active substance formulation
  • an active substance quality such as, but not limited to, a paste formulation and a quality of a paste.
  • the manufacturing error ie, the removal or elimination, removal of the existence or influence of manufacturing errors
  • two or more electrodes are identical to each other in all electrode construction, manufacturing aspects (eg, electrode structure, shape, size, formulation, materials, manufacturing process, etc.).
  • the expansion agent serves to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material.
  • the expansion agent includes, but is not limited to, barium sulfate, calcium sulfate, silica, silicate, humic acid, lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide.
  • the bulking agent is present in the active substance or active substance formulation in an amount of from 0.01% to 50% by mass.
  • the active material includes, but is not limited to, metal lead, lead paste, lead powder, lead compound, lead powder mixture, lead compound mixture, NiOOH, Ni(OH) 2 , iron powder, iron oxide, Fe, Fe (OH) 2 , FeOOH, ferrate, copper, copper compound, one or more of them, or a mixture of one or more of them and one or more of a swelling agent, other additives ;
  • the lead paste comprises: a dry lead paste and a wet lead paste
  • the lead powder includes, but is not limited to, lead oxide powder having a certain degree of oxidation
  • the lead compounds include, but are not limited to, lead monoxide, lead trioxide, lead trioxide, lead dioxide, lead hydroxide, lead sulfate, basic lead sulfate, lead carbonate, basic lead carbonate, and other lead oxidation. , other lead hydroxides, other lead salts, one or more of them;
  • the lead powder mixture is: a substance mixed with the lead powder and other substances, such as an additive;
  • the lead compound mixture is a substance in which the lead compound is mixed with other substances such as an additive.
  • the active material formulation includes, but is not limited to, the positive electrode, the negative electrode, and the formulation of the active material before the electrode is formed.
  • the polarity inversion of the positive and negative poles of the battery or battery pack and subsequent charging or charging and discharging operations may be implemented automatically or/and manually by a circuit having the battery or/and
  • the positive and negative poles of the 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 reverse the polarity of the positive and negative electrodes of the battery or/and the battery pack.
  • the total cumulative number of revolutions or polarity inversions and subsequent charging or charging and discharging operations is ⁇ 1 times.
  • the method for implementing or implementing the charging or charging/discharging operation of the positive electrode, the negative polarity, or the polarity reversal of the battery or/and the battery pack includes: reversing the battery or the battery pack One or more of charging, forced discharging, and reverse charging.
  • the reverse connection that is, in the reverse connection state (the positive and negative clips of the charge and discharge device or the positive output terminal are connected to the battery negative plate or the negative electrode, the negative electrode clip of the charge and discharge device or the negative output terminal is connected with the positive electrode plate or the positive electrode of the battery), Charge it.
  • the reverse charging is performed, including but not limited to, causing polarity inversion of the positive and negative terminals of the battery.
  • the charge and discharge device that is, a charge or/and a discharger.
  • the method for implementing reverse charging of a battery or/and a battery pack by the circuit includes, but is not limited to, polarity inversion through an output of the circuit connected to the battery or battery electrode and after the polarity is reversed
  • the charging or charging and discharging operations of the battery or the battery pack are performed to achieve positive or negative polarity inversion or polarity inversion of the battery or battery pack and subsequent charging or charging and discharging operations.
  • the circuit includes, but is not limited to, a power supply, a management circuit of a battery or a battery pack, and a charge and discharge device, including but not limited to: a charger, a charger, a repairer, a tester, a charge and discharge device, a battery, or Battery management system.
  • the battery or/and the battery pack to which the method for solving the problem of expansion, softening and falling off of the positive electrode active material of the battery is applied, including but not limited to: planar grid type, tubular type, wound type, bipolar type, horizontal lead Cloth, foam grid, column, stabilized void body electrode, sintered, pouch battery or battery pack, or include but not limited to valve-regulated sealed battery or battery pack, gel battery or battery pack, lead carbon Battery battery or battery pack, supercapacitor-battery (abbreviated as super battery) battery or battery pack, or hybrid battery pack including but not limited to these types of batteries, and various other types of batteries or battery packs .
  • the full tubular battery has a tubular positive electrode and a tubular negative electrode.
  • the method for improving or prolonging the service life of a battery or a battery pack of the present invention can be applied to a process of repairing, regenerating or manufacturing a battery or a battery pack, a battery or a battery pack, or a charge/discharge device, a battery or a battery pack.
  • the shape, structure, and configuration of the battery include, but are not limited to, the shape, structure, and configuration of a conventional, general-purpose battery disclosed in the prior art, the shape of the disclosed, ordinary, general battery.
  • the structure, configuration but not limited to: the battery includes a positive electrode (positive electrode), a negative electrode (negative electrode), an electrolyte, a diaphragm (or a plate), a current sink (or row), an output terminal, a battery well (or a shell);
  • a separator is interposed between the positive electrode and the negative electrode, and electrodes of the same polarity (or electrodes of the electrode group) are electrically connected to the fluid (or row) to form an electrical connection with each other, and connect the positive electrode.
  • the fluid (or row) is electrically connected to the positive output terminal of the battery, and the fluid (or row) connected to the negative electrode is electrically connected to the negative output terminal of the battery.
  • the conductive connecting strip and the output terminal of each battery are used.
  • the positive electrode may be electrically connected to the battery positive output terminal, and the negative electrode may be negative with the battery
  • the output terminal is electrically connected;
  • the positive electrode, the negative electrode, the diaphragm (or plate), the electrolyte are in the battery tank (or the shell), and the electrolyte is in contact with the positive electrode, the negative electrode, the separator (or the plate);
  • the electrode includes the electrode set a fluid, an active material, at least a part or one end of which is in conductive contact or bonding with the active material, or at least a part or one end of the current collector itself is disposed inside or on the surface of the active material, and the other end of the current collector Conductively connected to at least one of a fluid or a cell-connector (or strip) or a battery output terminal.
  • the invention can solve, prevent, inhibit, repair, reverse the expansion of the positive active material of the battery or the battery pack by performing positive or negative polarity reversal and subsequent charging or charging and discharging operations on the battery or the battery pack.
  • the problem is that the battery life is terminated, thereby increasing or extending the service life of the battery or battery pack.
  • the electrode reaction of a lead-acid battery is:
  • 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, and the original negative electrode is used as the positive electrode to charge the battery, and even PbO 2 on the original positive electrode is directly converted to Pb, and Pb on the original negative electrode is directly converted to PbO 2 . Therefore, the reversible polarity reversal between the original positive electrode of the lead-acid battery and the original negative electrode is also completed.
  • the positive electrode increases the number of repetitions of charge and discharge, and the binding between the active material PbO 2 particles on the electrode gradually relaxes and detaches from each other, so that the positive electrode active material expands, loosens, softens, and falls off; As the number of repetitions of charge and discharge increases, the active material Pb particles on the electrode tend to appear to be bonded to each other, so that the specific surface area of the negative electrode shrinks and is knotted.
  • the detachment between the original positive electrode active material PbO 2 particles of the lead-acid battery can be reversed by the reaction of the negative electrode.
  • lead The combination between the original negative electrode active material Pb particles of the acid storage battery can also be reversed by the positive electrode reaction, that is, the expansion, softening, shedding effect of the positive electrode active material of the lead-acid battery, and the specific surface area shrinkage effect of the negative electrode, which can pass through the above electrodes.
  • reaction (1) (2) is reversed, or the expansion, softening, shedding of the positive electrode active material of the lead-acid battery, and the specific surface area shrinkage effect of the negative electrode are carried out by the polarity inversion and the subsequent charging or charging and discharging operations of the present invention. It is also reversible.
  • an appropriate charging and discharging system is selected (different charging and discharging systems are generated by electrode reaction for the physical and chemical structure and properties of the electrode or the electrode active material).
  • the influence and the change effect are also different.
  • an adjustment means such as an additive
  • the active material particles are separated from each other by the reaction of the positive electrode, and the active material particles are combined with each other to cause reversal or mutual offset, which can greatly improve or even
  • the problem of swelling, softening, falling off, and specific surface area shrinkage of the positive electrode active material of the lead-acid battery is eliminated, thereby significantly increasing or prolonging the service life of the lead-acid battery.
  • the positive electrode active material of the lead-acid battery or the lead-acid battery pack is swelled, softened, detached, the specific surface area of the negative electrode is shrunk, and the failure mode of the positive electrode active material is expanded, softened, detached, and the specific surface area of the negative electrode is shrunk,
  • the service life of batteries or battery packs caused by other failure modes currently known, the service life of lead-acid batteries and battery packs may even tend to be infinite or extremely long.
  • the electrochemical reaction process experienced by the battery or the lead-acid battery during use is not limited to the ordinary working cycle charging and discharging operation.
  • the electrochemical reaction process which causes the positive electrode, negative electrode, electrolyte, current collector, fluid pool, liquid/solid interface, solid/solid interface of the battery or lead-acid battery to be beneficial to disable the battery or lead-acid battery.
  • the problem is solved, and the performance of the battery or the lead-acid battery is improved, so that the corrosion of the battery or the lead-acid battery (including but not limited to the electrode, the fluid, the current collector corrosion), the passivation, the sulfation, the negative ratio Surface area shrinkage, poor contact or/and shedding of active material with current collector, loss of early capacity, one or more of them, can be solved, repaired, reversed, eliminated, improved, alleviated, suppressed, prevented, and avoided.
  • the corrosion of the battery or the lead-acid battery including but not limited to the electrode, the fluid, the current collector corrosion
  • the passivation including but not limited to the electrode, the fluid, the current collector corrosion
  • the passivation including but not limited to the passivation, the sulfation, the negative ratio Surface area shrinkage, poor contact or/and shedding of active material with current collector, loss of early capacity, one or more of them.
  • the positive electrode active material is NiOOH/Ni(OH) 2
  • the negative electrode active material is Fe/Fe(OH) 2 /FeOOH, due to the positive electrode NiOOH and Ni(OH) 2 active material.
  • the difference in density is likely to cause the electrode to expand and deform, soften and fall off after the cycle, and the negative electrode is prone to passivation.
  • the ferrate in the iron-ferrate battery is prone to self-decomposition, and the problem can be solved, repaired, reversed, eliminated, improved, alleviated, suppressed, prevented, and avoided by the method provided by the present invention.
  • 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 inversion and subsequent charging of the present invention are performed thereon. Or the technical solution of the discharge operation can increase or prolong its service life, and make the electrode common to the positive electrode and the negative electrode practical, and make it practical.
  • Performing a distinguishing operation on the battery or the 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 on the battery cells or the battery cells, the partial cells, and the partial electrodes in the battery. It is beneficial to maintain and adjust the consistency of the capacity of the single cells in the battery pack, and to improve or extend the service life of the battery or battery pack.
  • the method of the present invention is applied to a battery or a battery pack, which can solve the expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, and negative electrode of the positive electrode active material of the battery.
  • the positive and negative polarity inversion of the present invention and subsequent charging or charging and discharging operations can also increase the active material utilization rate of the battery and thus the battery capacity, including the initial capacity of the battery and the capacity 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 the cycle charge and discharge operation according to the first 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 charge and discharge operation of the third embodiment of the present invention.
  • the embodiment relates to a method for solving the problem of expansion, softening, falling off of a positive electrode active material of a lead-acid battery or/and 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, Based on the current source circuit, the voltage source circuit, and the forced charging or/and forced discharging function included in the present embodiment, the polarity of the positive and negative electrodes of the lead-acid battery of the present embodiment can be reversed and charged or charged and discharged.
  • the battery charge and discharge device of this embodiment has a setting according to the setting.
  • the lead-acid battery of the embodiment has a rated capacity of 1.77 Ah (2 h rate, 25 ° C) and a rated voltage of 2 V, and the positive electrode has a current common commercial positive lead paste formula (in which the content of sulfuric acid relative to the ball-milled lead powder is 4.5 wt.%).
  • the positive lead paste prepared without the barium sulfate in the formula the battery is only used as a positive electrode during operation, so it is called a positive electrode plate (for the sake of subsequent explanation, it is also named as electrode A in the present embodiment), the negative electrode
  • the board has a negative electrode paste prepared by the conventional common commercial negative lead paste formula, and the battery is only used as a negative electrode when it is in operation, so it is called a negative electrode plate (for the subsequent statement, it is also named as electrodes B1 and B2 in this embodiment).
  • the lead powder used in the positive and negative lead pastes is the current common commercial ball-milled lead powder.
  • the quality of the dry lead paste on the positive electrode plate after curing and drying is 29.69 g.
  • the density of the sulfuric acid solution in the lead-acid storage battery of this embodiment is 1.27 g/ Cm 3 , 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, test failure and the like.
  • 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, sulphates, passivates, 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 inhibit, prevent, repair, improve, eliminate or reverse the softening or/and shedding of the positive active material of the lead-acid battery, and the activity of the negative electrode
  • One or more of mass surface area shrinkage, electrode/sink/catch corrosion, passivation, early capacity loss, sulphation, poor contact of active material and current collector to significantly increase or prolong lead in this example The life of the acid battery.
  • 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 the 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.
  • Lead acid battery of this embodiment Before entering a new cycle of charging and discharging the same time and after the first 269 cycles of charging and discharging of the present embodiment, followed by a battery and the operating state of the 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 lead-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 the constant current is 412 mA.
  • 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 reaches 408 times, an increase of 181%. It can continue to follow the above operation method without causing current collector corrosion and water loss.
  • the service life of the lead-acid battery of this embodiment is continuously 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
  • 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 expansion or / and softening / / and shedding of the active material, electrode passivation, corrosion, early capacity loss, sulfation, activity
  • the problem that the substance is in poor contact with the current collector and the specific surface area of the negative electrode shrinks, thereby improving or prolonging the service life of the lead-acid battery of the embodiment.
  • 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 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 lead-acid battery of the embodiment includes but is not limited to a planar grid-type lead-acid battery, a tubular lead-acid battery, a full-tube lead-acid battery, a wound lead-acid battery, and a double Polar lead-acid battery, or horizontal lead cloth, foam grid type, column type, lead-acid battery with stable gap body, or valve-regulated sealed lead-acid battery, colloidal lead-acid battery, lead carbon battery, super Capacitor - a lead-acid battery (super battery) battery, one or more of which.
  • the lead-acid battery of the embodiment may be replaced with other types of batteries of the same capacity, including but not limited to: iron-nickel batteries, iron-ferrate batteries, A cadmium-nickel battery, one or more of which, the above method of the present embodiment can be applied to the other type of battery, and the maximum value of the absolute value of the voltage allowed during charging can be adjusted to suit different types.
  • the rated working voltage of the battery may be replaced with other types of batteries of the same capacity, including but not limited to: iron-nickel batteries, iron-ferrate batteries, A cadmium-nickel battery, one or more of which, the above method of the present embodiment can be applied to the other type of battery, and the maximum value of the absolute value of the voltage allowed during charging can be adjusted to suit different types.
  • the rated working voltage of the battery may be replaced with other types of batteries of the same capacity, including but not limited to: iron-nickel batteries, iron-ferrate batteries, A cadmium-nickel battery, one or more of which, the above method of the present
  • the lead-acid battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the lead-acid battery of the embodiment are both positive and negative common electrodes, and the positive electrode of the lead-acid battery of the embodiment,
  • a negative electrode, a positive electrode and a negative electrode including but not limited to a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an anode or/and a negative electrode including an expansion agent in an electrode active material or an active material formulation, Positive and negative electrode common electrodes having the same active substance or the same active substance formulation, positive and negative electrode common electrodes equivalent to each other, positive and negative common electrodes of the same or the same, one or more of them.
  • the expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
  • the method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
  • the specific operation of the method for solving the problem that the battery positive active material expands, softens, falls off, or/and increases or prolongs the service life of the battery or the battery pack of the embodiment is that when the battery or the battery pack of the embodiment is subjected to one or more cycles of charging After the discharge operation, due to the cyclic charge and discharge, overcharge, undercharge, high active material utilization rate of the battery or the battery pack of the present embodiment, the working discharge capacity of the battery or the battery pack of the present embodiment is expanded by the positive active material or/ And softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, reduction of specific surface area of the negative electrode, poor contact of the active material with the conductive current collector, memory effect, decomposition of the active substance itself, or the like
  • the operating discharge capacity of the battery or the battery pack of the present embodiment is decreased, the operating discharge capacity of the battery or the battery pack of this embodiment is reduced to 60%, 75% of its rated capacity C 2 , C 5 or C 20 ,
  • the battery or the battery pack of the embodiment is reversely charged by a certain current source or/and a voltage source, and the current of the reverse polarity charging is C 2 , One or more of C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or a reverse pole charging voltage of one or more of 0.5U, U, 1.5U, 2U, such that
  • the polarity of the electrodes A1, A2, ..., An of the battery or the battery pack of the embodiment is reversed from the original positive polarity to the negative polarity, and the polarities of the electrodes B1, B2, ..., Bn are from the original negative polarity.
  • the charging or discharging current is C 2 , One or more of C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or one or more of charging or discharging voltages of 0.5 U, U, 1.5 U, 2 U Therefore, the charging or/and discharging reaction process of the battery negative electrode reaction occurs on the electrodes A1, A2, ..., An of the battery or the battery of the present embodiment, and the battery positive electrode occurs on the electrodes B1, B2, ..., Bn.
  • the charging or/and discharging reaction process of the reaction when the amount of charge or discharge of the battery or battery pack of the embodiment reaches 4C 2 , 3C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or the voltage reaches 0.6U , U, 1.2U, 2.1U, then operate step (3): one or more of 3C 2 , 2.5C 5 , 0.5C 20 , 0.8C 2 , 6C 2 , or 2C 5 current
  • the battery or the battery pack is subjected to reverse polarity charging, so that the discharge process of the battery negative electrode reaction occurs on the electrodes A1, A2, ..., An of the battery or the battery pack of the present embodiment, and the electrodes B1, B2, ..., Bn occur.
  • the pool group continues to be charged or charged and discharged, and the charging or discharging current is one or more of C 2 , 2C 5 , 0.5C 20 , 0.1C 2 , 3C 2 , or 0.05C 5 or the charging voltage is 0.7U, 0.9.
  • U, 1.1U, and 1.7U, charge and discharge are DC or pulse charge and discharge, so that the battery positive electrode reaction occurs on the electrodes A1, A2, ..., An of the battery or the battery pack of the embodiment.
  • the charging or/and discharging process, the charging or discharging process of the negative electrode of the battery occurs on the electrodes B1, B2, ..., Bn, and the process of charging or discharging the battery or the battery pack of the embodiment is charged or/and discharged.
  • the working discharge capacity or working capacity of the battery or the battery pack of the embodiment is restored or improved, and the positive and negative polarity reversal and subsequent charging or charging and discharging operations of the current two consecutive times are ended, and then the battery of the embodiment or The battery pack is put into a cycle to work or use.
  • the battery or the 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 battery or battery pack of the present embodiment does not have a battery loss or short circuit. Effectively improve, repair, reverse, eliminate, inhibit, prevent expansion and/or softening or/and shedding, corrosion, passivation, early capacity loss, salinization, etc. of the active material in the case of circuit breakage or grid mechanical damage, etc.
  • Crystallization reduction of specific surface area of the negative electrode, poor contact of the active material with the conductive current collector, memory effect, decomposition of the active material itself, one or more problems, thereby repeatedly or repeatedly causing the battery or the battery pack of the present embodiment to work.
  • the discharge capacity or working capacity is repaired, restored or improved to increase or lengthen the service life of the battery or battery pack of the present embodiment.
  • the battery of this embodiment includes, but is not limited to, a lead-acid battery, an iron-nickel battery, an iron-ferrate battery, a cadmium-nickel battery, one or more of which.
  • the lead-acid battery of the embodiment includes but is not limited to a flat-plate lead-acid battery, a tubular lead-acid battery, a full-tube lead-acid battery, a wound lead-acid battery, a bipolar lead-acid battery, and a horizontal lead-lead lead.
  • Acid battery foam grid lead-acid battery, column lead-acid battery, lead-acid battery with stable gap body, valve-regulated sealed lead-acid battery, colloidal lead-acid battery, lead carbon battery, supercapacitor-lead acid
  • a battery (super battery) type lead-acid battery one or more of which.
  • the battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the battery in this embodiment are both positive and negative common electrodes, and the positive electrode, the negative electrode, the positive and negative electrodes of the battery of the embodiment are generally used.
  • Electrode including but not limited to, a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an active electrode or a negative electrode including an expansion agent in an electrode active material or an active material formulation, and/or a positive electrode or/and a negative electrode, having the same active substance or
  • the expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
  • the mass percentage of the expansion agent in the active substance or active substance formulation is 0.01% or more, 0.02% or more, 0.03% or more, 0.05% or more, 0.08% or more, 0.1%.
  • the mass percentage of the expansion agent in the active substance or active substance formulation is less than or equal to 5%, 10%, 20%, 30%, 40%, 50%, wherein One or more.
  • the method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
  • the embodiment relates to a method for solving the problem of expansion, softening and falling off of a positive electrode active material of a lead-acid battery or/and a method for improving or prolonging the service life of a lead-acid battery, a battery charge and discharge device, a lead paste or an active material, a lead-acid battery electrode and a lead-acid battery.
  • the charge and discharge device of the present embodiment has a function of performing polarity reversal of the positive and negative poles of the lead-acid battery and subsequent charging or charging and discharging operations, and a programmable execution function, when the battery charge and discharge device output of the embodiment
  • the battery charger and discharger of the embodiment can perform the lead-acid battery of the embodiment by the polarity reversal at the output end and the charging, charging or charging/discharging operation after the polarity reversal.
  • the charge and discharge operations of the positive and negative polarities are reversed, and the polarity is reversed. All the operations on the battery in the following embodiments are the functions of the battery charge and discharge device of the present embodiment, unless otherwise specified. Work to achieve.
  • the lead-acid battery of the present embodiment has a rated voltage of 2V and a designed rated capacity of 821 mAh (2h rate, 25 ° C).
  • the lead-acid battery of the embodiment includes two electrodes, and both electrodes are positive and negative common electrodes (ie, positive electrodes).
  • the common electrode of the negative electrode is also the same or the same positive and negative common electrode, that is, regardless of the manufacturing error (ie, removing, eliminating, eliminating the existence or influence of manufacturing error) generated when the electrode is fabricated, the two pieces
  • the lead-acid battery electrodes of the present embodiment 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 into
  • the two electrodes are respectively formed into a positive electrode and a negative electrode, and the two electrodes are respectively defined as an electrode A and an electrode B.
  • the electrode A is used as a positive electrode and the electrode B is used as a negative electrode to perform formation and operation of the battery.
  • a separator spacing the electrodes, the two electrodes, an active material or a lead paste formulations of the present embodiment comprises a ball lead powder, BaSO 4 (0.8%, by mass percentage, with respect to the lead powder ball milling), 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, breaking, Short-circuit, mechanical damage, test failure and other factors interfere with the implementation process and implementation results of this embodiment.
  • the method for solving the problems of expansion, softening, and falling off of the positive electrode active material of the lead-acid battery or/and the service life of the lead-acid battery is as follows: First, the battery of the embodiment is subjected to the cycle charging and discharging work, and the working system is: when the battery When in the state of charging, the battery is discharged with a constant current of 371 mA. When the battery voltage is ⁇ 1.75 V, the discharge is stopped, then it is charged with a constant current of 222 mA, and after the measured battery voltage reaches 2.65 V, the conversion is performed. The battery is continuously charged at a constant voltage of 2.65V.
  • the total time of two (constant current, constant voltage) charging is 7 hours and 24 minutes (except for special instructions), and then the above discharge process is repeated with a constant current of 371 mA.
  • the battery is cycled, and the operating temperature of the battery 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.
  • 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
  • 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
  • the corresponding electrode B sometimes operates as a negative electrode and sometimes as a positive electrode to solve and improve.
  • 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.
  • 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 the polarity reversal of the positive and negative electrodes, that is, the polarity of the output end of the charger and the discharger is reversed, and the connection state of the charge and discharge device and the lead-acid battery is from the positive and negative terminals of the charge and discharge device and the lead-acid battery.
  • the 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, and is changed, the negative electrode output end of the charge and discharge device is connected with the lead acid battery electrode A, and the positive electrode 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 the embodiment in which the connection state is changed is charged with a constant current of 186 mA, so that the battery voltage rises from a negative value.
  • 0V then rises again to 1.75V (in this process, the first polarity reversal of the battery of this embodiment occurs, in which the battery voltage rises from a negative value to 0V, the discharge process of the positive electrode reaction of the lead-acid battery occurs on the electrode A, The discharge process of the negative electrode reaction of the lead-acid battery occurs on the electrode B.
  • the charging process of the lead-acid battery negative electrode reaction occurs on the electrode A, and the lead-acid battery positive electrode reaction occurs on the electrode B.
  • Charging process when the battery voltage reaches 1.75V, continue to charge the battery to 2.65V with a constant current of 222mA, then charge the battery for 4 hours and 16 minutes with a constant voltage of 2.65V, and then conduct the battery with a constant current of 371mA. Discharge, to 1.75V, and then charge the battery with a constant current of 222mA until the battery voltage reaches 2.65V and then charge the battery for 2.5 hours at 2.65V. After the charging is completed, the battery of this embodiment is completed.
  • the first single positive and negative polar polarity reversal and subsequent charging or charging and discharging operations at this time the electrode state of the battery has been changed 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 16th operation discharge and the subsequent number of cycles.
  • the results show that 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 at this time 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 was discharged to 1.75V, and then the battery was charged at a constant current of 222mA for 7 hours and 25 minutes, and then the battery was charged for 7 hours at a constant voltage of 2.65V. 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 was operated as a positive electrode, and the electrode B was operated as a negative electrode, and the battery was 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. Next, 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. 2 is a diagram showing the electrode of the lead-acid battery of the embodiment in the cycle of 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 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 expanded, softened, and detached to be improved, repaired, reversed, Eliminating, 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; on the other hand, the polarity of the positive and negative poles of the embodiment is reversed and the subsequent charge and discharge Or the charge-discharge operation, also inevitably occurs during the cycle of the battery of the embodiment, slight or occurring electrode 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, sulfation The problem has the effect of improving, repairing, reversing, suppressing, eliminating, and preventing.
  • the electrodes A and B repeatedly alternately function as a positive electrode or a negative electrode for charging and discharging, the problem of electrode corrosion generated when working as a positive electrode is used as a negative electrode at the electrode. Improved, repaired, and reversed during the charging and discharging cycle, thereby also making the lead acid storage of the present embodiment The corrosion problem of the pool during long-term use is delayed, improved, repaired, reversed, and prevented.
  • the positive electrode active material softening will be effectively improved, repaired, reversed, eliminated, suppressed, and prevented. Or / and shedding, electrode passivation, corrosion, early capacity loss, sulfation, poor contact of the active material with the current collector, and shrinkage of the specific surface area of the negative electrode, 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 and discharge cycle after the discharge capacity of each working battery is restored 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 higher 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 battery positive active material 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 implementation
  • the average mass of the active material of a single electrode of a lead-acid battery) if 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 is based on the end of the battery life. As shown in FIG.
  • the lead-acid storage battery of the present embodiment does not undergo the charging or charging/discharging operation of the positive and negative polarity inversion and the subsequent embodiment.
  • the service life will be basically 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 improved or prolonged.
  • the method for improving or prolonging the service life of the lead-acid battery in the present embodiment makes The service life of the example lead-acid battery is greatly 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 includes, but is not limited to, a flat-plate lead-acid battery, a tubular lead-acid battery, a full-tube lead-acid battery, a wound lead-acid battery, a bipolar lead-acid battery, and a horizontal lead cloth.
  • a lead-acid battery (super battery) type lead-acid battery one or more of which, the above method can also be applied to other types of lead-acid batteries.
  • the lead-acid battery of the embodiment may be replaced with other types of batteries of the same capacity, including but not limited to: iron-nickel batteries, iron-ferrate batteries, A cadmium-nickel battery, one or more of which, the above method of the present embodiment can be applied to the other type of battery, and the maximum value of the absolute value of the voltage allowed during charging can be adjusted to suit different types.
  • the rated working voltage of the battery may be replaced with other types of batteries of the same capacity, including but not limited to: iron-nickel batteries, iron-ferrate batteries, A cadmium-nickel battery, one or more of which, the above method of the present embodiment can be applied to the other type of battery, and the maximum value of the absolute value of the voltage allowed during charging can be adjusted to suit different types.
  • the rated working voltage of the battery may be replaced with other types of batteries of the same capacity, including but not limited to: iron-nickel batteries, iron-ferrate batteries, A cadmium-nickel battery, one or more of which, the above method of the present
  • the battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the battery in this embodiment are both positive and negative common electrodes, and the positive electrode, the negative electrode, the positive and negative electrodes of the battery of the embodiment are generally used.
  • Electrode including but not limited to, a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an active electrode or a negative electrode including an expansion agent in an electrode active material or an active material formulation, and/or a positive electrode or/and a negative electrode, having the same active substance or
  • the expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
  • the mass percentage of the above-mentioned expansion agent or barium sulfate in the active substance or active substance formulation of the present embodiment is greater than or equal to 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.10%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, one or more of them.
  • the mass percentage of the above-mentioned expansion agent or barium sulfate in the active substance or active substance formulation of the present embodiment is less than or equal to 5%, 10%, 20%, 30%, 40%, 50. %, one or more of them.
  • 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 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.
  • 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 the 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 method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
  • the battery or battery pack of the embodiment includes, but is not limited to, a flat grid battery, a tubular battery, a full tubular battery, a wound battery, a bipolar battery, a horizontal lead cloth battery, a foam grid battery, and a valve.
  • the rated voltage U of the battery or battery pack of this embodiment is 1.2V, 1.5V, 2V, 4V, 6V, 12V 24V, 36V, 48V, 60V or 72V, 120V, 240V, 360V, 480V, 600V or other voltage value
  • the rated capacity of the battery or battery pack of this embodiment (C 2 , 2 hour rate, 25 ° C) is 12Ah, 14Ah 16Ah, 18Ah, 20Ah, 24Ah, 30Ah, 60Ah, 100Ah, 200Ah or 1000Ah
  • the battery or battery pack of the embodiment has output terminals A, B, output terminal A and electrodes A1 and A2 in the battery or battery pack of the embodiment.
  • the electrodes A1, A2, ..., An, B1, B2, ..., Bn in the battery or the battery pack of this embodiment are positive and negative common electrodes (i.e., electrodes common to the positive and negative electrodes). ), it can be used or operated as the positive electrode of the battery, or it can be used or operated as the negative electrode of the battery.
  • the polarity of the output terminal A is positive, and the polarity of the output terminal B is negative, that is, the battery or the battery pack of the embodiment is in the initial cycle operation.
  • the charging and discharging processes of the positive electrode of the battery occur on the electrodes A1, A2, ..., An.
  • the negative electrode of the battery occurs on the electrodes B1, B2, ..., Bn.
  • the separators are separated by positive and negative electrodes.
  • the method for solving the problem of expansion, softening, falling off of the positive electrode active material of the battery or/and improving or prolonging the service life of the battery or the battery pack of the embodiment is that when the battery or the battery pack of the embodiment is used or operated in the cycle work When the working cycle reaches a certain number of times or as needed (for example, due to expansion or/and softening or/and shedding of the positive active material, corrosion, passivation, early capacity loss, salinization, crystallization, specific surface area shrinkage, active substances and Poor contact of the conductive current collector, memory effect, decomposition of the active material itself, one or more problems of which cause the battery or battery pack of the present embodiment to reduce the working discharge capacity and lower than a certain capacity value, or hope to increase the battery or When the battery pack has a working discharge capacity or increases the battery life or battery life, a single positive and negative polarity reversal of the battery or battery pack of this example is performed automatically or/and manually between two working cycles.
  • the charging or charging and discharging operation such that the circulating operation of the battery or the battery pack of the present embodiment and the positive or negative polarity reversal of the battery or the battery pack of the present embodiment and the subsequent charging or charging and discharging operations are performed on each other. Intermittent, interspersed, alternating, or occurring to increase or extend the useful life of the battery or battery pack of the present embodiment.
  • Performing the first single positive and negative polarity inversion and the subsequent charging or charging and discharging operations on the battery or the battery pack of the embodiment includes the steps of: when the battery or the battery pack of the embodiment is in the initial cycle working process (this During this period, the polarity of the battery or battery pack output terminal A is positive, and the polarity of the output terminal B is negative, that is, the charge and discharge of the battery positive electrode reaction occurs on the electrodes A1, A2, ..., An.
  • the charging and discharging process of the battery negative electrode reaction occurs on the electrodes B1, B2, ..., Bn), when the working cycle reaches a certain number of times, for example, 5 times, 9 times, 20 times or 60 times, example battery or battery pack reverse polarity charge
  • the counter electrode comprises a charging mode, a single stage, multi stage, a constant current (e.g. 0.1C 2, 0.5C 2, 1.2C 2 , 6C 2), a constant voltage (e.g. One or more of U, 1.3U, 2U, 5U), positive pulse, negative pulse, and finally the polarity of the output terminals A, B of the battery or battery pack of the present embodiment, and thus the electrodes A1, A2.
  • the battery or battery charge or discharge, or charging and discharging comprises charge, single phase, multiple phase, constant current (e.g. 0.15C 2, 0.4C 2, 0.8C 2 , 7C 2), One or more of a constant voltage (for example, 0.8U, 1.5U, 2U, 4U), a positive pulse, and a negative pulse, and then, the polarity state of the battery or the battery pack of this embodiment is reversed by the polarity Re-introducing into the cyclic work to perform the cyclic work.
  • constant current e.g. 0.15C 2, 0.4C 2, 0.8C 2 , 7C 2
  • a constant voltage for example, 0.8U, 1.5U, 2U, 4U
  • the polarity of the battery or battery pack output terminal A is negative, and the polarity of the output terminal B is positive, that is, the charging and discharging of the battery negative electrode reaction occurs on the electrodes A1, A2, ..., An.
  • the charging and discharging processes of the battery positive electrode reaction occur on the electrodes B1, B2, ..., Bn.
  • Performing the second single positive and negative polarity inversion and the subsequent charging or charging and discharging operations on the battery or the battery pack of the embodiment includes the steps of: when the battery or the battery pack of the embodiment is in the first single positive and negative During polarity reversal and subsequent cycle operation after charging or charging and discharging operation (during this period, the polarity of the battery or battery pack output terminal A of this embodiment is negative, and the polarity of the output terminal B is positive, that is, the electrode On the A1, A2, ..., An, the charging and discharging process of the battery negative electrode reaction occurs, and the charging and discharging processes of the battery positive electrode reaction occur on the electrodes B1, B2, ..., Bn), the working cycle
  • the second reverse polarity charging is performed on the battery or the battery pack of the embodiment, and the manner of the reverse polarity charging includes a single stage and multiple One or more of a phase, a constant current (
  • the battery or the battery pack output terminal A of this embodiment The polarity of the output terminal is positive, and the polarity of the output terminal B is negative, that is, the charging and discharging process of the battery positive electrode reaction occurs on the electrodes A1, A2, ..., An, and the electrodes B1, B2, .... .., Bn The charging and discharging process of the negative electrode reaction of the battery occurs.
  • 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 interspersedly, so that
  • the positive electrode active material positive electrode active material of the battery or the battery pack of the present embodiment is expanded or/and softened or/and peeled off, corroded, passivated, early capacity loss, salinization, crystallization, specific surface area shrinkage of the negative electrode, active material and conductive current collector Contact failure, memory effect, decomposition of active substance itself, one or more problems, which are improved, repaired, reversed, eliminated, suppressed, prevented, solved, so that the working discharge capacity and use of the battery or battery pack of the present embodiment Life expectancy is increased or extended.
  • the battery of this embodiment includes, but is not limited to, a lead-acid battery, an iron-nickel battery, an iron-ferrate battery, a cadmium-nickel battery, one or more of which.
  • the lead-acid battery of the embodiment includes but is not limited to: a planar grid type lead-acid battery, a tubular lead-acid battery, a full-tube lead-acid battery, a wound lead-acid battery, a bipolar lead-acid battery, and a horizontal lead cloth.
  • the battery or the battery pack of the embodiment in the cyclic operation of the battery or the battery pack of the embodiment, in order to improve, repair, reverse, solve, and prevent expansion or/and softening or/and shedding, corrosion due to the active material of the positive electrode, Battery or battery operation caused by one or more of passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact of active material with conductive current collector, memory effect, and decomposition of active material itself The capacity or the end of the service life is terminated.
  • the positive or negative polarity reversal and the subsequent charging or charging and discharging operations are performed in an odd or even number of times, and the odd number of times or each period is completed.
  • the battery or the battery pack of the present embodiment is re-introduced into the charging and discharging cycle by the polarity state after the polarity is reversed in the current period.
  • 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 battery or the battery pack of the present embodiment are the same or the same positive and negative common electrode, that is, before the electrode is formed, all the electrodes are Or the positive electrode and the negative electrode are identical to each other in various aspects, such as but not limited to a current collector, an active substance formulation, and an active material quality (such as, but not limited to, a paste formulation and a paste quality), a manufacturing process, and the like (ie, , in all respects the same), or, regardless of manufacturing errors (ie, removing, eliminating, eliminating the presence or influence of manufacturing errors) generated when the electrodes are fabricated, all of the electrodes of the battery or battery of the present embodiment are In all electrode composition, manufacturing aspects (such as electrode structure, shape, current collector, fluid pool, active material formulation and quality, other accessories, manufacturing process, etc.) are identical, after being formed, the battery or battery pack of this embodiment Each electrode is formed into a positive electrode or a negative electrode, respectively.
  • the positive, negative or all electrodes of the battery or the battery pack of the present embodiment are positive and negative common electrodes equivalent to each other, that is, after the electrodes are formed, they have the same function and Performance, or, after the electrode is formed or charged and discharged, in the case of operation or use of the battery or battery pack, regardless of error factors (such as but not limited to manufacturing errors, measurement errors) (ie, remove, eliminate, remove) The presence or influence of the error), the electrodes of this embodiment have or exhibit the same function and performance.
  • the polarity inversion of the present example and the polarity inversion in the subsequent charging or charging and discharging operation steps may be performed using a pulse current, a pulse voltage instead of a direct current, a constant voltage, and the like.
  • the charging or charging and discharging step or process is advantageous for improving the aging and energy efficiency of the battery polarity inversion and the subsequent charging or charging and discharging operations of the embodiment.
  • the battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the battery in this embodiment are both positive and negative common electrodes, and the positive electrode, the negative electrode, the positive and negative electrodes of the battery of the embodiment are generally used.
  • Electrode including but not limited to, a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an active electrode or a negative electrode including an expansion agent in an electrode active material or an active material formulation, and/or a positive electrode or/and a negative electrode, having the same active substance or
  • the expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
  • the mass percentage of the above-mentioned expansion agent or barium sulfate in the active substance or active substance formulation of the present embodiment is greater than or equal to 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.10. %, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, one or more of them.
  • the mass percentage of the above-mentioned expansion agent or barium sulfate in the active substance or active substance formulation of the present embodiment is less than or equal to 5%, 10%, 20%, 30%, 40%, 50. %, one or more of them.
  • the positive and negative electrodes are positive and negative common electrodes, and (1) the battery in this embodiment is a lead-acid battery, and the positive electrode or/and the negative electrode, the positive and negative electrodes.
  • the general electrode or its active substance or active substance formulation includes a swelling agent barium sulfate, and the mass percentage of the barium sulfate in the positive electrode or/and the negative electrode, the positive and negative electrode common electrode or the active substance or active substance thereof is 0.01 %, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 10%, one or more of them; or (2)
  • the battery of the embodiment is a lead-acid battery, the positive electrode or/and
  • the negative electrode, the positive and negative electrode common electrode or the active material or active material formulation thereof include a swelling agent barium sulfate, silicon dioxide and calcium sulfate, and the barium sulfate is used in the positive electrode or/and the negative electrode, the positive electrode and the negative electrode or the active material thereof.
  • the mass percentage of the active substance formulation is 0.01%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 10%, one or more of the silica, calcium sulfate In the positive or / and negative, positive and negative pass
  • the mass percentage of the electrode or the active substance or active substance thereof is 0.03%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 10%, one or more of them; or (3)
  • the storage battery of the embodiment is an iron-nickel storage battery, and the positive electrode or/and the negative electrode, the positive and negative electrode common electrode or the active material or active material formulation thereof include a swelling agent lithium hydroxide in the positive electrode.
  • the battery of the embodiment has positive and negative electrodes which are positive and negative common electrodes, and have the same active substance or the same active substance formula as each other:
  • the battery of the embodiment is a lead-acid battery.
  • the active material or active substance formula of the positive electrode and the negative electrode are: lead powder or lead oxide powder 100Kg, short fiber 0.06Kg, acetylene black 0.28Kg, barium sulfate 0.8Kg, sulfuric acid solution (sulfuric acid content is 45%) 8.7Kg, water 8.25Kg; or
  • the battery of this embodiment is a lead-acid battery, and the active material or active substance of the positive electrode and the negative electrode are: lead powder or lead oxide powder 100Kg, lignin 0.16Kg, humic Acid 0.2Kg, barium sulfate 0.4Kg, silica 0.06Kg, sulfuric acid solution (45% by mass of sulfuric acid) 8.7Kg, water 8.25Kg; or (3) Battery of this embodiment is
  • the positive electrode, the negative electrode, and the positive and negative electrode common electrodes of the battery of the present embodiment not only have the same active substance or the same active substance formulation as described above, but are identical to each other before being chemicalized or charged and discharged. That is, before the electrode is formed, all of the electrodes or the positive electrode, the negative electrode, the positive and negative electrode common electrodes are in various aspects, such as but not limited to a current collector, an active substance formulation, and an active substance mass (such as but not limited to a lead paste). The formulation and the quality of the lead paste), the manufacturing process, etc.
  • the positive electrode, the negative electrode, the positive and negative electrode common electrodes have a current collector or a paste process, a smear or powder filling process, a curing or sintering process, and all other electrodes formed before or after being subjected to a chemical formation or charge and discharge operation. And manufacturing is exactly the same.
  • the positive and negative electrodes are positive and negative common electrodes equivalent to each other, and the electrodes are formed into a working charging and discharging condition (for example, Not limited to: first 0.14C constant current charging for 5 hours, then constant voltage charging for 4 hours, then 0.05C constant current charging for 2 hours, then 0.5C rate discharge, ambient temperature is 25 ° C, C is the rated capacity of the battery), this implementation
  • a working charging and discharging condition for example, Not limited to: first 0.14C constant current charging for 5 hours, then constant voltage charging for 4 hours, then 0.05C constant current charging for 2 hours, then 0.5C rate discharge, ambient temperature is 25 ° C, C is the rated capacity of the battery
  • the polarity of the positive electrode and the negative electrode of the battery is reversed for the second time, and the positive electrode after the first polarity inversion is inverted to the negative electrode, and the first polarity is reversed.
  • the turned-off negative electrode is inverted into a positive electrode, and then the negative electrode formed by inverting the second polarity and the positive electrode formed after the second polarity is inverted are subjected to the same charging and discharging conditions ( For example, but not limited to: first 0.14C constant current charging for 5 hours, then constant voltage charging for 4 hours, then 0 .05C constant current charging for 2 hours, then 0.5C rate discharge, ambient temperature is 25 ° C, C is the rated capacity of the battery) for cyclic charging and discharging, obtaining the battery, positive electrode, negative electrode, positive and negative electrode common electrode of the present embodiment
  • the average value of the 21st reverse discharge capacities exhibited during the first to the 21st cycle charging and discharging after the second polarity inversion is 10.5 Ah, and
  • the positive, negative, positive and negative common electrodes have the same charge or/and discharge performance under the same polarity, or
  • the positive electrode, the negative electrode, the positive and negative electrode common electrodes have the same charging or/and discharging performance under the same polarity, and the difference in the average value of the discharge capacity of 0.5 Ah belongs to a normal error between each other.
  • the forward charging or/and discharging refers to charging and discharging performed or performed before the positive polarity, the negative electrode, and the positive and negative electrode common electrodes are subjected to a certain polarity inversion;
  • the reverse charging or/and discharging It refers to charging and discharging that are performed or performed after the positive polarity, the negative electrode, and the positive and negative electrode common electrodes are subjected to the polarity reversal.
  • the method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
  • the present embodiment solves the problem that the positive electrode active material expands, softens, falls off, or/and increases or prolongs the service life of the battery or the battery pack, including interspersed with the battery of the embodiment or during the floating operation of the battery or the battery pack.
  • the polarity of the positive and negative polarities described in the above or all of the above embodiments of the present invention are the same or similar to the total cumulative number of times of the battery pack.
  • the method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
  • the battery of this embodiment is an iron-nickel battery or an iron-ferrate battery, and has a rated capacity of 10 Ah (C 5, 5 h, 25 ° C).
  • a rated capacity 10 Ah (C 5, 5 h, 25 ° C).
  • the battery of this embodiment is expanded or/and softened or/and Shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact of active material with conductive current collector, memory effect, decomposition of active material itself, one or more problems leading to work
  • the positive and negative polarity inversion and subsequent charging or charging and discharging operations of the battery of the embodiment are performed by the charging and discharging device to solve the expansion or/and the positive active material of the battery of the embodiment.
  • the problem is to increase or lengthen the service life of the battery of this embodiment.
  • the steps of performing the positive and negative polarity inversion and the subsequent charging or charging and discharging operations on the battery of the embodiment include: (1) the polarity reversal of the battery of the embodiment is performed by the method of reverse polarity charging, that is, the positive electrode ( A nickel electrode or a ferrate electrode is defined as an electrode A) connected to the negative output end of the charge and discharge device of the present embodiment, and a negative electrode (iron electrode, defined as electrode B) and a positive output terminal of the charge and discharge device of the embodiment.
  • the polarity of the final electrode B is made negative with respect to the polarity of the electrode A, and the electrode A
  • the polarity is positive with respect to the polarity of the electrode B, and the positive or negative polarity inversion and subsequent charging or charging and discharging operations solve and improve the expansion or/and softening or/and shedding and corrosion of the positive active material.
  • the working discharge capacity is increased or restored to a normal rated capacity value, thereby increasing or prolonging the service life of the battery of this embodiment.
  • the polarity of the electrode A is negative, and the polarity of the electrode B is positive.
  • this method also solves and improves the expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, active substance and The contact current of the conductive current collector, the memory effect, and the decomposition of the active material itself, one or more problems, the working discharge capacity of the battery of the embodiment is improved or restored to a normal rated capacity value, thereby making the battery of the embodiment The service life is increased or extended.
  • the battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the battery in this embodiment are both positive and negative common electrodes, and the positive electrode, the negative electrode, the positive and negative electrodes of the battery of the embodiment are generally used.
  • Electrode including but not limited to, a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an active electrode or a negative electrode including an expansion agent in an electrode active material or an active material formulation, and/or a positive electrode or/and a negative electrode, having the same active substance or
  • the expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
  • the mass percentage of the above-mentioned expansion agent in the active substance or active substance formulation of the present embodiment is greater than or equal to 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.10%, 0.2. %, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, one or more of them.
  • the mass percentage of the above-mentioned expansion agent in the active substance or active substance formulation of the present embodiment is less than or equal to 5%, 10%, 20%, 30%, 40%, 50%, wherein One or more.
  • the method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the method of the embodiment increases or extends the service life of the battery to 1.3 times or more. -10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
  • the present embodiment is the same as or includes the embodiments 1-21 and 23 described in the Chinese Patent Application No. 201710975570.6, and the examples 1-21 and 23 described in the Chinese Patent Application No. 201710975568.2. And Examples 1-10 described in Examples 1-3 of the Chinese Patent Application No. 201810452604.8, Examples 1-9 described in Chinese Patent Application No. 201811297354.1, and Chinese Patent Application No. 201811296518.9.
  • the method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Disclosed is a method for solving the problems of expanding, softening, and falling-off of a positive electrode active substance of a storage battery, the method comprising: subjecting the positive electrode or the positive electrode active substance of a storage battery or/and a storage battery pack to a storage battery negative electrode reaction, or reducing same to a metal or 0 valence by means of an electrochemical reduction reaction, or subjecting the positive electrode or a negative electrode of the storage battery or/and the storage battery pack to polarity reversal and subsequent charging or charging and discharging operations. The method is also used for solving other problems of the storage battery, which include, but are not limited to, one or more of the corrosion, passivation, salinization, crystallization, and specific surface area shrinkage of the electrode active substance, the poor contact of the active substance with a current collector or/and the active substance falling off of the current collector, and the premature capacity loss, memory effect, and decomposition of the active substance itself. The method can solve problems such as the expansion, softening, and falling-off of the positive electrode active substance of the storage battery, and significantly improve or extend the service life of the battery or the battery pack.

Description

解决蓄电池正极活性物质膨胀、软化、脱落问题的方法Method for solving problems of expansion, softening and falling off of positive electrode active material of battery 技术领域Technical field
本发明涉及一种解决蓄电池失效问题的方法，特别涉及一种解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，以及单独或同时解决蓄电池其它失效问题的方法。The invention relates to a method for solving the problem of battery failure, in particular to a method for solving the problems of expansion, softening and falling off of a positive electrode active material of a battery, and a method for solving other failure problems of the battery separately or simultaneously.
背景技术Background technique
蓄电池，包括但不限于铅酸蓄电池、铁-镍蓄电池、镉-镍蓄电池、氢-镍蓄电池、高铁酸盐蓄电池、锂离子蓄电池等，能循环充放工作，从而大大降低社会的生产、生活、环保成本，且蓄电池的使用寿命越长，则其产生的经济效益和社会效益就越大。导致蓄电池使用寿命终止的原因很多，重要的原因如正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、负极比表面积收缩、活性物质失活、盐化、结晶化、活性物质与集流体接触不良、记忆效应、活性物质自身分解等问题。Storage batteries, including but not limited to lead-acid batteries, iron-nickel batteries, cadmium-nickel batteries, hydrogen-nickel batteries, ferrate batteries, lithium ion batteries, etc., can be recharged and discharged, thus greatly reducing the production and life of society. The environmental protection cost, and the longer the service life of the battery, the greater the economic and social benefits it generates. There are many reasons for the end of battery life. Important reasons are positive electrode active material expansion or / and softening and / or shedding, corrosion, passivation, early capacity loss, negative electrode specific surface area shrinkage, active material deactivation, salinization, crystallization The problem of poor contact between the active substance and the current collector, memory effect, and decomposition of the active substance itself.
发明内容Summary of the invention
本发明所要解决的问题是提供一种解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，以提高或延长蓄电池或电池组的使用寿命，或者，提供一种解决或改善蓄电池或电池组的正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题，来提高或延长蓄电池或电池组的使用寿命。The problem to be solved by the present invention is to provide a method for solving the problems of expansion, softening and falling off of a positive electrode active material of a battery to increase or extend the service life of the battery or the battery pack, or to provide a solution for solving or improving the positive electrode of the battery or the battery pack. Active material swelling or/and softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact of active material with conductive current collector, memory effect, decomposition of active substance itself, One or more problems to increase or extend the life of the battery or battery pack.
所述盐化，包括但不限于，硫酸盐化。The salinization includes, but is not limited to, sulfation.
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。The service life includes, but is not limited to, one or more of a cycle life and a float life.
所述蓄电池或电池组，即，蓄电池或蓄电池组。The battery or battery pack, ie a battery or a battery pack.
所述解决上述问题，包括但不限于：对上述问题的解决、修复、逆转、消除、改善、缓解、抑制、防止、避免。The solution to the above problems includes, but is not limited to, solving, repairing, reversing, eliminating, improving, mitigating, suppressing, preventing, and avoiding the above problems.
为解决本发明上述技术问题之一，本发明提供了一种解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，包括：使所述蓄电池或/和蓄电池组的正极或正极活性物质进行蓄电池负极电极反应或通过电化学还原反应而被还原成金属或0化合价，或者，将所述蓄电池或/和蓄电池组的正极或/和负极进行极性反转及其后的充电或充放电操作，该操作的总累计次数≥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。In order to solve the above problems of the present invention, the present invention provides a method for solving the problems of expansion, softening, and shedding of a positive electrode active material of a battery, comprising: causing a positive electrode or a positive electrode active material of the battery or battery group to be a battery negative electrode The electrode reaction is reduced to a metal or a valence by an electrochemical reduction reaction, or the positive or/and negative electrode of the battery or/and battery pack is subjected to polarity inversion and subsequent charging or charging and discharging operations. The total cumulative number of operations is ≥1 times; the positive polarity and the negative electrode are reversed in polarity and then charged or charged and discharged, that is, the polarity of the positive electrode and the negative electrode are reversed, and the polarity is reversed. After the rotation, the electrode subjected to the polarity inversion is subjected to a charging or charging and discharging operation.
所述总累计次数是指，所述蓄电池或电池组在其存在的整个期间或所述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。The total cumulative number refers to all occurrences of the battery or battery during the entire period of its existence or the battery or battery pack before the end of its service life and after the end of its service life. The total, total cumulative total of the positive and negative polarity inversions or polarity inversions on the group and the number of subsequent charging or charging and discharging operations. 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.
所述蓄电池或电池组正极或负极的极性包括，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。The polarity of the positive or negative electrode of the battery or battery pack includes positive (positive polarity) or negative (negative polarity) of the electrode of the battery or battery, and positive characteristics of the electrode generally include electrodes occurring on the electrode The reaction is a positive electrode reaction, and the electrode potential phase is relatively high. The negative characteristics of the electrode generally include 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.
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，前者使电极上发生蓄电池负极电极反应，后者使电极上发生蓄电池正极电极反应。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 battery negative electrode reaction to occur on the electrode, and the latter causes the battery positive electrode reaction to occur on the electrode.
以将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蓄电池或电池组的正极、负极，如此，当将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，将蓄电池或电池组的正电极、负电极进行极性反转，即，使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蓄电池正极电极反应被反转成蓄电池负极电极反应，对于原来的负极(电极B)，变化相反。Taking the process of performing the first and second polarity inversions and the subsequent charging or charging and discharging operations on the positive electrode and the negative electrode of the battery or the battery pack as an example, the polarities of the positive and negative polarities are reversed and thereafter. The charging or charging and discharging operation is further described. For convenience of explanation, the original positive electrode (here also referred to as electrode A) and the original negative electrode (also referred to herein as electrode B) are referred to, and have not been subjected to any of the above. The polarity of the positive electrode and the negative electrode are reversed, and the positive electrode and the negative electrode of the battery or the battery pack during the charging or charging/discharging operation, and thus, the positive polarity and the negative electrode of the battery or the battery pack are reversed for the first time. In the subsequent charging or charging and discharging operation, the operation steps include first, inverting the polarity of the positive electrode and the negative electrode of the battery or the battery pack, that is, the pole of the original positive electrode (electrode A) of the battery or the battery pack. The polarity is reversed to negative, the polarity of the original negative electrode (electrode B) is reversed to positive by negative, and then after the polarity is reversed, the electrode that has undergone the polarity reversal is charged or charged. Discharge operation, ie, the original positive electrode (electrode A) as the negative electrode, the original negative electrode (electrode B) is used as the positive electrode, and the battery or battery pack after the secondary polarity is reversed is charged or charged and discharged, and the whole process is reversed from the polarity to the secondary pole. The charging or charging and discharging operation after the sexual reversal is completed, that is, the polarity reversal and the subsequent charging or charging and discharging operations (at this time, the first polarity reversal of the battery or the battery pack is completed and Subsequent charging or charging/discharging operation), the polarity inversion of the positive electrode and the negative electrode and the subsequent charging or charging and discharging operations are performed, including the electrode potential of the original positive electrode (electrode A) The higher the electrode is converted to a lower phase, and the electrode reaction that occurs is reversed from the original battery positive electrode reaction to the battery negative electrode reaction, and the change is reversed for the original negative electrode (electrode B).
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蓄电池负极电极反应被反转成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。It can be known that, based on the above-mentioned primary polarity inversion and subsequent charging or charging and discharging operations, one polarity inversion and subsequent charging or charging and discharging operations are performed (this is also the battery or battery pack). The second polarity inversion and subsequent charging or charging and discharging operations) are positively charged or charged and discharged during the charging or charging and discharging operation after the next (second time) polarity inversion. The electrode is the original positive electrode (electrode A) of the battery or battery pack, and the negative electrode that is charged or charged and discharged is the original negative electrode (electrode B) of the battery or the battery pack. The second (second time) the positive and negative electrodes The polarity reversal and subsequent charging or charging and discharging operations are realized. For the original positive electrode (electrode A), the electrode potential is converted from a relatively low phase to a relatively high phase, and the electrode reaction occurs. The battery negative electrode reaction is reversed to the battery positive electrode reaction, and the change is reversed for the original negative electrode (electrode B). Thus, 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。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.
所述极性反转及其后的充电或充放电操作，包括将蓄电池或/和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蓄电池负极电极反应或通过电化学还原反应而被还原成金属或0化合价、使该极性反转前为负极的电极在该极性反转后进行蓄电池正极电极反应，其中的一种或多种。The polarity inversion and subsequent charging or charging and discharging operations include polarity inversion of the battery or/and the battery pack, and after the polarity is reversed, the electrode that has undergone the polarity inversion is reversed. Performing an electrochemical reaction in which the electrode which is the positive electrode before the polarity is reversed is subjected to the battery negative electrode reaction after the polarity is reversed or is reduced to a metal or a valence by an electrochemical reduction reaction, and the polarity is reversed. The electrode which is the negative electrode is subjected to the positive electrode reaction of the battery after the polarity is reversed, one or more of which are.
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。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.
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)。In the polarity inversion and subsequent charging or charging and discharging operations, the number of charging operations after any one polarity inversion is one or more (including one time, the same applies hereinafter).
所述将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蓄电池或电池组的工作，彼此穿插、交替地进行，并使所述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，所述蓄电池或电池组的正极、负极。Performing the polarity inversion of the positive and negative poles of the 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 with the battery Or the operation of the battery pack is interspersed and alternately performed, and when the 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: (1) the original The 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 operates as a positive electrode, sometimes As a negative electrode, 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 be reversed in polarity without any of the positive and negative electrodes. The positive or negative electrode of the battery or battery pack during subsequent charging or charging and discharging operations.
在上述第(1)、(2)、(3)中任一工作状态下，所述蓄电池或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)。In any of the above operating states (1), (2), (3), the polarity of the positive and negative electrodes of the battery or battery pack between any two of its operations and thereafter The number of charging or charging and discharging operations is 0 or more (including 0 times, the same below).
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，或者仅对蓄电池单体电池中的部分电极进行所述正、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。The polarity inversion of the positive electrode and the negative electrode and the subsequent charging or charging and discharging operations include separately performing the positive and negative polarity inversion and subsequent charging on only one of the battery cells in the battery pack or Charging and discharging operation, or performing only the positive and negative polarity reversal and subsequent charging or charging and discharging operations on some (ie, two or more) single cells in the battery pack, or only for the battery cells A part of the electrodes in the battery perform the positive and negative polarity inversion and subsequent charging or charging and discharging operations. This is referred to as a distinction operation. The unit cell, that is, a unit cell.
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。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.
所述蓄电池其正极或/和负极的活性物质为具有二种或二种以上稳定氧化价态的元素的单质、化合物中的一种或多种。The active material of the positive electrode or/and the negative electrode of the secondary battery is one or more of a simple substance or a compound having two or more kinds of stable oxidation valence states.
所述具有二种或二种以上稳定氧化价态的元素包括但不限于：铅、铁、铜、镍、锰、银、磷、硫、氯、钒、铬、钴、砷、硒、溴、锡、锑、碲、碘、钨、铋其中的一种或多种。The elements having two or more stable oxidation valence states include, but are not limited to, lead, iron, copper, nickel, manganese, silver, phosphorus, sulfur, chlorine, vanadium, chromium, cobalt, arsenic, selenium, bromine, One or more of tin, antimony, bismuth, iodine, tungsten, and antimony.
所述蓄电池或蓄电池组，包括但不限于：铅酸蓄电池、铁-镍蓄电池、铁-高铁酸盐电池、铜- 高铁酸盐电池、镉-镍蓄电池的电池或电池组，其中的一种或多种。The battery or battery pack includes, but is not limited to, a lead-acid battery, an iron-nickel battery, an iron-ferrate battery, a copper-ferrate battery, a battery of a cadmium-nickel battery, or a battery pack, one of which or A variety.
所述高铁酸盐包括但不限于：K 2FeO 4、Na 2FeO 4、BaFeO 4。 The ferrate includes, but is not limited to, K 2 FeO 4 , Na 2 FeO 4 , BaFeO 4 .
所述解决蓄电池正极活性物质膨胀、软化、脱落问题方法，也用于单独地解决蓄电池的其他问题，或在解决蓄电池正极活性物质膨胀、软化、脱落问题的同时也用于解决蓄电池的其他问题，所述其他问题包括但不限于：蓄电池的腐蚀(包括但不限于电极、汇流体、集流体腐蚀)、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题。The method for solving the problem of expansion, softening and falling off of the positive electrode active material of the battery is also used to solve other problems of the battery separately, or to solve the problems of expansion, softening and falling off of the positive electrode active material of the battery, and also to solve other problems of the battery. Such other problems include, but are not limited to, corrosion of the battery (including but not limited to electrodes, sinks, current collector corrosion), passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, active materials and conductive sets. One or more of the problems of poor fluid contact, memory effects, and decomposition of the active substance itself.
所述将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；构成蓄电池或电池组的正极和负极时，所述正极、负极、正负极通用电极包括但不限于：包括膨胀剂的正极或/和负极、其电极活性物质或活性物质配方中包括膨胀剂的正负极通用电极或/和正极或/和负极、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、彼此为同一种的或相同的正负极通用电极，其中的一种或多种；所述彼此等价是指，电极被化成后，彼此具有相同的功能和性能，或者，电极在被化成或充放电后，彼此在蓄电池或电池组的工作或使用过程中，不考虑误差因素(例如但不限于：制造误差、测量误差)的情况下(即刨除、排除、去掉误差的存在或影响)，具有或表现出相同的功能和性能；所述同一种的或相同的正负极通用电极是指，所述蓄电池的正极与负极在电极结构、尺寸、配方、材料、制做工艺等所有电极构成方面完全相同(即，所有的电极构成方面都相同)，或者，所述同一种的或相同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，电极被化成之前，所述电极或所述正极、负极，在各方面，例如但不限于集流体、活性物质配方和活性物质质量(例如但不限于铅膏配方和铅膏质量)、制做工艺等方面，完全相同(即，在各方面都相同)，或者，不考虑制造电极时产生的制造误差(即刨除、排除、去掉制造误差的存在或影响)，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。Performing a polarity inversion of the positive and negative electrodes of the battery or the battery pack and subsequent charging or charging and discharging operations, and further characterized in that the positive and negative polarity inversion and subsequent charging or The positive and negative electrodes of the battery or the battery pack that are charged and discharged are positive and negative common electrodes (ie, electrodes common to the positive electrode and the negative electrode), and the positive and negative electrode are used in the battery or the battery pack. 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 battery or battery pack, and sometimes used as a negative electrode. One or more; when constituting the positive electrode and the negative electrode of the battery or the battery pack, the positive electrode, the negative electrode, the positive and negative electrode common electrodes include, but are not limited to, a positive electrode or/and a negative electrode including a swelling agent, an electrode active material or an active material thereof The positive and negative electrode common electrode of the expansion agent or the positive electrode or the negative electrode, the positive electrode and the negative electrode common electrode having the same active substance or the same active substance formula, The equivalent positive and negative electrode common electrodes, one or more of the same or the same positive and negative electrode common electrodes, each of which is equivalent to each other, means that the electrodes have the same function after being formed into one another. And performance, or, after the electrodes are formed or charged and discharged, in the operation or use of the battery or battery pack, regardless of error factors (such as, but not limited to, manufacturing errors, measurement errors) (ie, removal, Excluding or removing the existence or influence of the error), having or exhibiting the same function and performance; the same or the same positive and negative common electrode means that the positive electrode and the negative electrode of the battery are in the electrode structure, size, and formula All the electrodes are completely identical in terms of materials, manufacturing processes, etc. (ie, all electrodes are identical in composition), or the same or the same positive and negative common electrodes mean that those are being converted or charged. The positive and negative electrode common electrodes which are identical to each other before discharge and which are formed into 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 Means that before the electrode is formed, the electrode or the positive electrode and the negative electrode are in various aspects, such as but not limited to a current collector, an active substance formulation, and an active substance quality (such as, but not limited to, a paste formulation and a quality of a paste). In terms of the process, etc., they are identical (that is, the same in all respects), or, regardless of the manufacturing error (ie, the removal or elimination, removal of the existence or influence of manufacturing errors) generated when the electrodes are fabricated, are being processed or charged and discharged. Prior to operation, two or more electrodes are identical to each other in all electrode construction, manufacturing aspects (eg, electrode structure, shape, size, formulation, materials, manufacturing process, etc.).
所述膨胀剂用来防止、抑制、改善电极比表面积收缩或电极活性物质比表面积收缩。The expansion agent serves to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material.
所述膨胀剂包括但不限于：硫酸钡、硫酸钙、二氧化硅、硅酸盐、腐殖酸、木素磺酸盐、铝的氧化物或氢氧化物、钛的氧化物或氢氧化物、锂的氧化物或氢氧化物，其中的一种或多种。The expansion agent includes, but is not limited to, barium sulfate, calcium sulfate, silica, silicate, humic acid, lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide. An oxide or hydroxide of lithium, one or more of which.
所述膨胀剂在活性物质或活性物质配方中的质量百分含量为0.01％-50％。The bulking agent is present in the active substance or active substance formulation in an amount of from 0.01% to 50% by mass.
所述活性物质，包括但不限于：金属铅、铅膏、铅粉、铅化合物、铅粉混和物、铅化合物混和 物、NiOOH、Ni(OH) 2，铁粉、铁氧化物、Fe、Fe(OH) 2、FeOOH、高铁酸盐、铜、铜化合物，其中的一种或多种，或它们其中的一种或多种与膨胀剂、其它添加剂其中的一种或多种形成的混和物； The active material includes, but is not limited to, metal lead, lead paste, lead powder, lead compound, lead powder mixture, lead compound mixture, NiOOH, Ni(OH) 2 , iron powder, iron oxide, Fe, Fe (OH) 2 , FeOOH, ferrate, copper, copper compound, one or more of them, or a mixture of one or more of them and one or more of a swelling agent, other additives ;
所述铅膏包括：干铅膏、湿铅膏；The lead paste comprises: a dry lead paste and a wet lead paste;
所述铅粉包括但不限于：具有一定氧化度的氧化铅粉；The lead powder includes, but is not limited to, lead oxide powder having a certain degree of oxidation;
所述铅化合物包括但不限于：一氧化铅、三氧化二铅、四氧化三铅、二氧化铅、氢氧化铅、硫酸铅、碱式硫酸铅、碳酸铅、碱式碳酸铅、其它铅氧化物、其它铅氢氧化物、其它铅盐，其中的一种或多种；The lead compounds include, but are not limited to, lead monoxide, lead trioxide, lead trioxide, lead dioxide, lead hydroxide, lead sulfate, basic lead sulfate, lead carbonate, basic lead carbonate, and other lead oxidation. , other lead hydroxides, other lead salts, one or more of them;
所述铅粉混和物为：所述铅粉与其它物质，如添加剂，混和后的物质；The lead powder mixture is: a substance mixed with the lead powder and other substances, such as an additive;
所述铅化合物混和物为：所述铅化合物与其它物质，如添加剂，混和后的物质。The lead compound mixture is a substance in which the lead compound is mixed with other substances such as an additive.
所述活性物质配方包括但不限于：所述正极、负极的，在电极化成之前的，活性物质的配方。The active material formulation includes, but is not limited to, the positive electrode, the negative electrode, and the formulation of the active material before the electrode is formed.
所述将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蓄电池或/和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蓄电池或/和蓄电池组的正极、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。The polarity inversion of the positive and negative poles of the battery or battery pack and subsequent charging or charging and discharging operations may be implemented automatically or/and manually by a circuit having the battery or/and The positive and negative poles of the 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 reverse the polarity of the positive and negative electrodes of the battery or/and the battery pack. The total cumulative number of revolutions or polarity inversions and subsequent charging or charging and discharging operations is ≥1 times.
所述电路实现或实施对蓄电池或/和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：对所述蓄电池或电池组进行反极充电、强制放电、反接后充电，其中的一种或多种。The method for implementing or implementing the charging or charging/discharging operation of the positive electrode, the negative polarity, or the polarity reversal of the battery or/and the battery pack includes: reversing the battery or the battery pack One or more of charging, forced discharging, and reverse charging.
所述反接后充电，即反接状态下(充放电器正极夹子或正极输出端与蓄电池负极板或负极连接、充放电器负极夹子或负极输出端与蓄电池正极板或正极连接)，对蓄电池进行充电。After the reverse connection, that is, in the reverse connection state (the positive and negative clips of the charge and discharge device or the positive output terminal are connected to the battery negative plate or the negative electrode, the negative electrode clip of the charge and discharge device or the negative output terminal is connected with the positive electrode plate or the positive electrode of the battery), Charge it.
所述反接后充电，包括但不限于，使蓄电池的正、负极发生极性反转。The reverse charging is performed, including but not limited to, causing polarity inversion of the positive and negative terminals of the battery.
所述充放电器，即充电或/和放电器。The charge and discharge device, that is, a charge or/and a discharger.
所述电路实现对蓄电池或/和蓄电池组进行反极充电的方法包括但不限于，通过连接于所述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蓄电池或电池组进行的充电或充放电操作，来实现所述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。The method for implementing reverse charging of a battery or/and a battery pack by the circuit includes, but is not limited to, polarity inversion through an output of the circuit connected to the battery or battery electrode and after the polarity is reversed The charging or charging and discharging operations of the battery or the battery pack are performed to achieve positive or negative polarity inversion or polarity inversion of the battery or battery pack and subsequent charging or charging and discharging operations.
所述电路包括但不限于：电源、蓄电池或电池组的管理电路、充放电设备，所述充放电设备包括但不限于：充电器、充电机、修复仪、测试仪、充放电器、电池或电池组管理系统。The circuit includes, but is not limited to, a power supply, a management circuit of a battery or a battery pack, and a charge and discharge device, including but not limited to: a charger, a charger, a repairer, a tester, a charge and discharge device, a battery, or Battery management system.
本发明的解决蓄电池正极活性物质膨胀、软化、脱落问题的方法所应用于的蓄电池或/和蓄电池组，包括但不限于：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、烧结式、袋式蓄电池或电池组，或包括但不限于阀控式密封蓄电池或蓄电池组、胶体蓄电池或蓄电池组、铅碳电池蓄电池或蓄电池组、超级电容器-蓄电池(简称超级电池)蓄电池或蓄电池组，或包括但不限于这些类型的蓄电池混合连接而成的混合型的蓄电池组，以及其它各种类型的蓄电池或电池组。所述全管式蓄电池具有管式正电极、管式负电极。The battery or/and the battery pack to which the method for solving the problem of expansion, softening and falling off of the positive electrode active material of the battery is applied, including but not limited to: planar grid type, tubular type, wound type, bipolar type, horizontal lead Cloth, foam grid, column, stabilized void body electrode, sintered, pouch battery or battery pack, or include but not limited to valve-regulated sealed battery or battery pack, gel battery or battery pack, lead carbon Battery battery or battery pack, supercapacitor-battery (abbreviated as super battery) battery or battery pack, or hybrid battery pack including but not limited to these types of batteries, and various other types of batteries or battery packs . The full tubular battery has a tubular positive electrode and a tubular negative electrode.
本发明提高或延长蓄电池或电池组使用寿命的方法可应用于蓄电池或电池组、蓄电池或电池组的电路或充放电设备、蓄电池或电池组的修复、再生或生产制造时的化成工艺。The method for improving or prolonging the service life of a battery or a battery pack of the present invention can be applied to a process of repairing, regenerating or manufacturing a battery or a battery pack, a battery or a battery pack, or a charge/discharge device, a battery or a battery pack.
除特别说明外，所述蓄电池的形状、结构、构造包括但不限于现有技术中公开的、普通的、一般的蓄电池的形状、结构、构造，该公开的、普通的、一般的蓄电池的形状、结构、构造包括但不限于：蓄电池包括正极(正电极)、负极(负电极)、电解液、隔膜(或板)、电流汇流体(或排)、输出端子、电池槽(或壳)；所述正极、负极间插有(或隔有)隔板，同一种极性的电极(或电极群其电极)都导电连接于汇流体(或排)从而彼此形成导电连接，连接正电极的汇流体(或排)与蓄电池正极输出端子进行导电连接，连接负电极的汇流体(或排)与蓄电池负极输出端子进行导电连接，当形成蓄电池组时，用导电连接条与各蓄电池的输出端子进行导电连接并形成各蓄电池间的串联、并联；作为可选，所述正电极可与蓄电池正极输出端子进行导电连接，所述负电极可与蓄电池负极输出端子进行导电连接；所述正极、负极、隔膜(或板)、电解液处于电池槽(或壳)中，电解液与正极、负极、隔膜(或板)相接触；所述电极包括电极集流体、活性物质，所述集流体本身至少有一部分或一端与活性物质导电性接触或结合，或者，所述集流体本身至少有一部分或一端设置在活性物质内部或表面，所述集流体另一端与汇流体或单体电池间连接体(或条)或蓄电池输出端子中的至少一种导电性连接。Unless otherwise stated, the shape, structure, and configuration of the battery include, but are not limited to, the shape, structure, and configuration of a conventional, general-purpose battery disclosed in the prior art, the shape of the disclosed, ordinary, general battery. The structure, configuration, but not limited to: the battery includes a positive electrode (positive electrode), a negative electrode (negative electrode), an electrolyte, a diaphragm (or a plate), a current sink (or row), an output terminal, a battery well (or a shell); A separator is interposed between the positive electrode and the negative electrode, and electrodes of the same polarity (or electrodes of the electrode group) are electrically connected to the fluid (or row) to form an electrical connection with each other, and connect the positive electrode. The fluid (or row) is electrically connected to the positive output terminal of the battery, and the fluid (or row) connected to the negative electrode is electrically connected to the negative output terminal of the battery. When the battery pack is formed, the conductive connecting strip and the output terminal of each battery are used. Conductively connecting and forming a series connection and a parallel connection between the batteries; alternatively, the positive electrode may be electrically connected to the battery positive output terminal, and the negative electrode may be negative with the battery The output terminal is electrically connected; the positive electrode, the negative electrode, the diaphragm (or plate), the electrolyte are in the battery tank (or the shell), and the electrolyte is in contact with the positive electrode, the negative electrode, the separator (or the plate); the electrode includes the electrode set a fluid, an active material, at least a part or one end of which is in conductive contact or bonding with the active material, or at least a part or one end of the current collector itself is disposed inside or on the surface of the active material, and the other end of the current collector Conductively connected to at least one of a fluid or a cell-connector (or strip) or a battery output terminal.
有益效果Beneficial effect
本发明通过对所述蓄电池或蓄电池组进行正、负极极性反转及其后的充电或充放电操作，可解决、防止、抑制、修复、逆转蓄电池或蓄电池组的正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解等，其中的一种或多种问题，所导致的蓄电池使用寿命终止，从而提高或延长蓄电池或蓄电池组的使用寿命。The invention can solve, prevent, inhibit, repair, reverse the expansion of the positive active material of the battery or the battery pack by performing positive or negative polarity reversal and subsequent charging or charging and discharging operations on the battery or the battery pack. Softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact of active material with conductive current collector, memory effect, decomposition of active substance, etc., one or more The problem is that the battery life is terminated, thereby increasing or extending the service life of the battery or battery pack.
例如，对于铅酸蓄电池，铅酸蓄电池的电极反应为：For example, for lead-acid batteries, the electrode reaction of a lead-acid battery is:
正极：
Figure PCTCN2018113859-appb-000001
positive electrode:
Figure PCTCN2018113859-appb-000001
负极：
Figure PCTCN2018113859-appb-000002
negative electrode:
Figure PCTCN2018113859-appb-000002
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。 It can be seen that the 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. Similarly, 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. In addition, the original positive electrode of the lead-acid battery is used as the negative electrode, and the original negative electrode is used as the positive electrode to charge the battery, and even PbO 2 on the original positive electrode is directly converted to Pb, and Pb on the original negative electrode is directly converted to PbO 2 . Therefore, the reversible polarity reversal between the original positive electrode of the lead-acid battery and the original negative electrode is also completed.
又常规铅酸蓄电池在充放电时，正极随着充放电反复次数的增加电极上的活性物质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；负极随着充放电反复次数的增加电极上的活性物质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。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，则铅酸蓄电池原来正极活性物质PbO 2颗粒之间的脱离就可以通过负极电极反应而获得逆转，同样，铅酸蓄电池原来的负极活性物质Pb颗粒之间的结合就可以通过正极电极反应也获得逆转，即铅酸蓄电池正极活性物质的膨胀、软化、脱落效应、负极的比表面积收缩效应，彼此可以通过上述电极反应(1)(2)进行逆转，或者说，通过本发明的极性反转及其后的充电或充放电操作，铅酸蓄电池正极活性物质的膨胀、软化、脱落、负极的比表面积收缩效应也是可逆的。 In addition, when the conventional lead-acid battery is charged and discharged, the positive electrode increases the number of repetitions of charge and discharge, and the binding between the active material PbO 2 particles on the electrode gradually relaxes and detaches from each other, so that the positive electrode active material expands, loosens, softens, and falls off; As the number of repetitions of charge and discharge increases, the active material Pb particles on the electrode tend to appear to be bonded to each other, so that the specific surface area of the negative electrode shrinks and is knotted. When the original positive electrode of the lead-acid battery is used as the negative electrode and the original negative electrode is used as the positive electrode to charge the battery, the detachment between the original positive electrode active material PbO 2 particles of the lead-acid battery can be reversed by the reaction of the negative electrode. Similarly, lead The combination between the original negative electrode active material Pb particles of the acid storage battery can also be reversed by the positive electrode reaction, that is, the expansion, softening, shedding effect of the positive electrode active material of the lead-acid battery, and the specific surface area shrinkage effect of the negative electrode, which can pass through the above electrodes. The reaction (1) (2) is reversed, or the expansion, softening, shedding of the positive electrode active material of the lead-acid battery, and the specific surface area shrinkage effect of the negative electrode are carried out by the polarity inversion and the subsequent charging or charging and discharging operations of the present invention. It is also reversible.
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、改变作用也不同)，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膨胀、软化、脱落、负极比表面积收缩问题，从而显著提高或延长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铅酸蓄电池组的正极活性物质膨胀、软化、脱落、负极比表面积收缩、以及除正极活性物质膨胀、软化、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，则铅酸蓄电池及电池组的使用寿命甚至有可能趋向于无限长或极长。By the polarity inversion of the present invention and subsequent charging or charging and discharging operations, an appropriate charging and discharging system is selected (different charging and discharging systems are generated by electrode reaction for the physical and chemical structure and properties of the electrode or the electrode active material). The influence and the change effect are also different. With or without the use of an adjustment means such as an additive, the active material particles are separated from each other by the reaction of the positive electrode, and the active material particles are combined with each other to cause reversal or mutual offset, which can greatly improve or even The problem of swelling, softening, falling off, and specific surface area shrinkage of the positive electrode active material of the lead-acid battery is eliminated, thereby significantly increasing or prolonging the service life of the lead-acid battery. Theoretically, if the positive electrode active material of the lead-acid battery or the lead-acid battery pack is swelled, softened, detached, the specific surface area of the negative electrode is shrunk, and the failure mode of the positive electrode active material is expanded, softened, detached, and the specific surface area of the negative electrode is shrunk, The service life of batteries or battery packs caused by other failure modes currently known, the service life of lead-acid batteries and battery packs may even tend to be infinite or extremely long.
另外，本发明的方法或极性反转及其后的充电或充放电操作，使蓄电池或铅酸蓄电池在使用过程中所经历的电化学反应过程不仅仅局限于普通工作循环充放电操作中的电化学反应过程，这使得蓄电池或铅酸蓄电池的正电极、负电极、电解液、集流体、汇流体、液/固界面、固/固界面等方面发生了有利于使蓄电池或铅酸蓄电池失效问题获得解决、使蓄电池或铅酸蓄电池性能提高的变化，从而也可以使蓄电池或铅酸蓄电池的腐蚀(包括但不限于电极、汇流体、集流体腐蚀)、钝化、硫酸盐化、负极比表面积收缩、活性物质与集流体接触不良或/和脱落、早期容量损失、其中的一种或多种，得到解决、修复、逆转、消除、改善、缓解、抑制、防止、避免。In addition, the method of the present invention or the polarity inversion and subsequent charging or charging and discharging operations, the electrochemical reaction process experienced by the battery or the lead-acid battery during use is not limited to the ordinary working cycle charging and discharging operation. The electrochemical reaction process, which causes the positive electrode, negative electrode, electrolyte, current collector, fluid pool, liquid/solid interface, solid/solid interface of the battery or lead-acid battery to be beneficial to disable the battery or lead-acid battery. The problem is solved, and the performance of the battery or the lead-acid battery is improved, so that the corrosion of the battery or the lead-acid battery (including but not limited to the electrode, the fluid, the current collector corrosion), the passivation, the sulfation, the negative ratio Surface area shrinkage, poor contact or/and shedding of active material with current collector, loss of early capacity, one or more of them, can be solved, repaired, reversed, eliminated, improved, alleviated, suppressed, prevented, and avoided.
又例如，对于铁-镍蓄电池，通常正极活性物质为NiOOH/Ni(OH) 2，其负极活性物质为Fe/Fe(OH) 2/FeOOH，由于正极的NiOOH与Ni(OH) 2活性物质间的密度差异易导致电极经循环后膨胀变形、软化、脱落、负极铁电极容易发生钝化，这些问题，均可通过本发明提供的方法，对所述蓄电池或蓄电池组进行正、负极极性反转及其后的充电或充放电操作，实现解决、修复、逆转、消除、改善、缓解、抑制、防止、避免。 For another example, for an iron-nickel battery, generally, the positive electrode active material is NiOOH/Ni(OH) 2 , and the negative electrode active material is Fe/Fe(OH) 2 /FeOOH, due to the positive electrode NiOOH and Ni(OH) 2 active material. The difference in density is likely to cause the electrode to expand and deform, soften and fall off after the cycle, and the negative electrode is prone to passivation. These problems can be reversed by positive or negative polarity of the battery or battery pack by the method provided by the present invention. Turn around and charge or charge and discharge operations to solve, repair, reverse, eliminate, improve, mitigate, suppress, prevent, and avoid.
又例如，对于铁-高铁酸盐电池中的高铁酸盐易发生自身分解，该问题可通过本发明提供的方法 实现解决、修复、逆转、消除、改善、缓解、抑制、防止、避免。For another example, the ferrate in the iron-ferrate battery is prone to self-decomposition, and the problem can be solved, repaired, reversed, eliminated, improved, alleviated, suppressed, prevented, and avoided by the method provided by the present invention.
蓄电池或电池组，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。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 inversion and subsequent charging of the present invention are performed thereon. Or the technical solution of the discharge operation can increase or prolong its service life, and make the electrode common to the positive electrode and the negative electrode practical, and make it practical.
对蓄电池或电池组进行区分操作，即对电池组或电池中的各单电池、部分单电池、部分电极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，有利于维护、调整电池组中单电池间彼此容量的一致性，提高或延长蓄电池或电池组的使用寿命。Performing a distinguishing operation on the battery or the 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 on the battery cells or the battery cells, the partial cells, and the partial electrodes in the battery. It is beneficial to maintain and adjust the consistency of the capacity of the single cells in the battery pack, and to improve or extend the service life of the battery or battery pack.
综上所述，将本发明的方法应用于蓄电池或蓄电池组，能解决蓄电池的正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题，显著提高或延长蓄电池或电池组的使用寿命。In summary, the method of the present invention is applied to a battery or a battery pack, which can solve the expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, and negative electrode of the positive electrode active material of the battery. The specific surface area shrinkage, poor contact of the active material with the conductive current collector, memory effect, decomposition of the active material itself, one or more problems, significantly increase or prolong the service life of the battery or battery pack.
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还可提高蓄电池的活性物质利用率从而电池容量，包括电池初始容量和使用过程中的容量。In addition, the positive and negative polarity inversion of the present invention and subsequent charging or charging and discharging operations can also increase the active material utilization rate of the battery and thus the battery capacity, including the initial capacity of the battery and the capacity during use.
附图说明DRAWINGS
图1是本发明实施例1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。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the working discharge capacity and the working discharge termination voltage data of a lead-acid battery in the cycle charge and discharge operation according to the first embodiment of the present invention.
图2是本发明实施例3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。2 is a data diagram 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 third embodiment of the present invention.
具体实施方式Detailed ways
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。The technical content, features and effects of the present invention will be further described in detail below in conjunction with specific embodiments.
实施例1Example 1
本实施例涉及解决铅酸蓄电池正极活性物质膨胀、软化、脱落问题或/和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，额定容量为1.77Ah(2h率,25℃)，额定电压为2V，其正极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。 The embodiment relates to a method for solving the problem of expansion, softening, falling off of a positive electrode active material of a lead-acid battery or/and 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, Based on the current source circuit, the voltage source circuit, and the forced charging or/and forced discharging function included in the present embodiment, the polarity of the positive and negative electrodes of the lead-acid battery of the present embodiment can be reversed and charged or charged and discharged. 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 function that the program performs. The lead-acid battery of the embodiment has a rated capacity of 1.77 Ah (2 h rate, 25 ° C) and a rated voltage of 2 V, and the positive electrode has a current common commercial positive lead paste formula (in which the content of sulfuric acid relative to the ball-milled lead powder is 4.5 wt.%). And the positive lead paste prepared without the barium sulfate in the formula, the battery is only used as a positive electrode during operation, so it is called a positive electrode plate (for the sake of subsequent explanation, it is also named as electrode A in the present embodiment), the negative electrode The board has a negative electrode paste prepared by the conventional common commercial negative lead paste formula, and the battery is only used as a negative electrode when it is in operation, so it is called a negative electrode plate (for the subsequent statement, it is also named as electrodes B1 and B2 in this embodiment). The lead powder used in the positive and negative lead pastes is the current common commercial ball-milled lead powder. The quality of the dry lead paste on the positive electrode plate after curing and drying is 29.69 g. The density of the sulfuric acid solution in the lead-acid storage battery of this embodiment is 1.27 g/ Cm 3 , 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, test failure and the like.
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：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. Then, 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. 24 points, 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, sulphates, passivates, 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-acid battery of the embodiment to be restored or improved after the operation is completed, and then the battery is re-introduced into its original working system to continue the work; then, in the present embodiment, the lead During the cyclic charge and discharge operation of the acid battery (referred to as the cycle operation, the same applies hereinafter), the polarity reversal of the positive and negative polarities of the same or similar to the above two times in the present embodiment is repeated repeatedly, interspersedly, and in multiple stages. Post-charge or charge-discharge operation to inhibit, prevent, repair, improve, eliminate or reverse the softening or/and shedding of the positive active material of the lead-acid battery, and the activity of the negative electrode One or more of mass surface area shrinkage, electrode/sink/catch corrosion, passivation, early capacity loss, sulphation, poor contact of active material and current collector to significantly increase or prolong lead in this example The life of the acid battery. Specifically, 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. When performing the polarity reversal operation of the positive electrode plate and the negative electrode plate of the lead-acid battery of the present embodiment, one is manual operation: 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. The 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. 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. At this time, 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); 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. At this time, 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. At this time, 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. Thus, 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. In addition, 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:
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)。Pressing, initially setting when the working discharge capacity of the lead-acid battery of the embodiment is less than 900 mAh, stopping the operation of the lead-acid battery of the embodiment and starting the first and second polarity reversal of the positive and negative poles of the battery. Subsequent charging or charging and discharging operations. In the second embodiment of the present embodiment, 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. After inspection, this is due to the positive active material. Softening and falling off (the reason for the decrease in discharge capacity below) is the same. When the charging and discharging cycle is operated until the 179th time, the working discharge capacity when the battery is discharged to 1.75V is reduced to 899mAh (that is, the remaining capacity is rated capacity). 50.9%), that is, the trigger condition (discharge capacity <900 mAh) for starting the charging and charging/discharging operation of the positive and negative polarity inversion of the battery of the embodiment is started, and at this time, the battery of the embodiment is started first. Preparation and formal operation of the second positive and negative polarity inversion and subsequent charging or charging and discharging operations, that is, after the end of the 179th working discharge (this The battery voltage is 1.75V), continue to discharge the battery at a constant current of 1031mA for 4min and when the battery voltage is 0V, stop the discharge, and then reverse the polarity of the positive and negative plates of the battery, that is, manually The 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 discharge device and the positive electrode plate (electrode A) of the lead-acid battery are connected. 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. In the process, 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 the 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. In 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. Perform positive and negative polarity reversal, that is, manually connect the battery charge and discharge device to the lead-acid battery of the present embodiment from the positive and negative clips of the charge and discharge device and the negative electrode plate (electrode B1, B2) of the lead-acid battery, and the charge and discharge device The reverse connection state of the negative electrode clip and the positive electrode plate (electrode A) of the lead-acid battery is changed, the positive electrode clip of the charge and discharge device is connected with 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 ( The positive connection state of the electrodes B1 and B2) is connected, and then the battery is charged at a constant current of 258.4 mA, so that the charging process of the positive electrode of the lead-acid battery occurs on the positive electrode plate (electrode A) of the lead-acid battery of the embodiment. In 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. After the constant voltage charging is completed, 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).
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)。Next, 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. 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). When the battery is charged and discharged to the 225th cycle, 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. After that, 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 discharge process of the positive electrode of the lead-acid battery on the positive electrode plate or the electrode A of the battery, the discharge process of the negative electrode of the lead-acid battery or the negative electrode of the lead-acid battery on the electrodes B1 and B2 of the present embodiment), and then 36 minutes The battery voltage is lowered from 0V to -1.75V (the battery voltage measured and displayed by the battery charger and discharger. In the same manner, 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) After -1.75V, 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 discharge process of the electrode reaction, the negative electrode plate of the lead-acid battery or the discharge process of the positive electrode of the lead-acid battery on the electrodes B1 and B2 of the present embodiment), when the battery voltage reaches 0V, the charge and discharge device automatically continues to 258.4 mA. 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 results show that after the third and fourth positive and negative polarity inversions and subsequent charging or charging and discharging operations, the discharge time of the battery of this embodiment is restored to 1 hour and 36 minutes in the 228th cycle operation, and In the next 239th cycle, the working discharge time was normal, 1 hour and 36 minutes. (The 226th and 227th duty cycles caused the discharge termination voltage to be lower than 1.75V due to an erroneous operation, resulting in overdischarge).
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)。Next, the battery of the embodiment is continuously operated under the working system. As shown in FIG. 1 , when the battery of the embodiment is in the cycle to the 240th time, 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. As a result, after the fifth and sixth positive and negative polarity inversions and subsequent charging or charging and discharging operations, 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).
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。Next, 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. As shown in FIG. 1, when the battery of the present embodiment is cycled to the 251th time, its discharge performance begins to decrease. At the 268th time, 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. Lead acid battery of this embodiment Before entering a new cycle of charging and discharging the same time and after the first 269 cycles of charging and discharging of the present embodiment, followed by a battery and the operating state of the system. As a result, after the seventh and eighth positive and negative polarity inversions and subsequent charging or charging and discharging operations, 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), and the discharge time is restored to 1 hour and 36 minutes in the 270th cycle operation, and the working discharge time is normal for 1 hour and 36 minutes in the following cycle to the 290th cycle charge and discharge operation. .
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。As shown in FIG. 1, in the next 270-463th cycle of the lead-acid battery of the embodiment, 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 Between successive times, between 385th and 386th, between 405th and 406th, between 425th and 426th, between 441th and 442th, and between 457th and 458th, successively Ninth, tenth, consecutive eleventh, twelfth, ..., consecutive twenty-seventh, twenty-eighth, a total of ten periods of polarity reversal and subsequent charging or Charge and discharge operation, and the working discharge time or capacity of the lead-acid battery of the embodiment is reversed twice in each period and then The subsequent first or second working discharge of the charging or charging and discharging operation is restored to 1 hour 36 minutes or 1649 mAh, so that the lead acid battery of the present embodiment retains the ability to continue normal working discharge.
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)。As shown in FIG. 1 , after the polarity inversion twice in each period and the subsequent charging or charging and discharging operations in this embodiment, 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. For example, when the active material particles on the positive electrode plate are softened, the degree of falling off is large, or the actual operating discharge capacity of the battery is decreased to a large extent, 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. For example, in the lead-acid battery of the present embodiment, 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. Or 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. During the process from 0V to -1.75V, 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. During the discharge process, 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 lead-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 the constant current is 412 mA. Charging for 14 hours, to the battery voltage of 2.63V, and then charging 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).
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％，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，可使本实施例铅酸蓄电池的使用寿命获得继续延长。In this embodiment, if it is defined that the working discharge capacity is less than 80% of the rated capacity, it is regarded as invalid work or not counted in the cycle charge and discharge operation (ie, battery life), then 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. 1, 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 After the acid battery has been operated for 463 times, it can continue to work normally. The number of effective working cycles reaches 408 times, an increase of 181%. It can continue to follow the above operation method without causing current collector corrosion and water loss. The service life of the lead-acid battery of this embodiment is continuously extended.
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、预防正极活性物质膨胀或/和软化或/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。On the one hand, as described above, 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 cycle operation of the lead-acid battery is improved or restored after the operation. On the other hand, 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. In the normal cycle operation process of the lead-acid battery of the embodiment, 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 expansion or / and softening / / and shedding of the active material, electrode passivation, corrosion, early capacity loss, sulfation, activity The problem that the substance is in poor contact with the current collector and the specific surface area of the negative electrode shrinks, thereby improving or prolonging the service life of the lead-acid battery of the embodiment.
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。In other embodiments of the present embodiment, 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.
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。In other embodiments of the present embodiment, 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.
在本实施例的其它实施方式中，本实施例上述铅酸蓄电池包括但不限于平面板栅式铅酸蓄电池、管式铅酸蓄电池、全管式铅酸蓄电池、卷绕式铅酸蓄电池、双极式铅酸蓄电池，或水平铅布式、泡沫板栅式、柱式、具有稳定空隙体电极式铅酸蓄电池，或阀控式密封铅酸蓄电池、胶体铅酸蓄电池、铅碳电池蓄电池、超级电容器-铅酸蓄电池(超级电池)蓄电池，其中的一种或多种。In other embodiments of the present embodiment, the lead-acid battery of the embodiment includes but is not limited to a planar grid-type lead-acid battery, a tubular lead-acid battery, a full-tube lead-acid battery, a wound lead-acid battery, and a double Polar lead-acid battery, or horizontal lead cloth, foam grid type, column type, lead-acid battery with stable gap body, or valve-regulated sealed lead-acid battery, colloidal lead-acid battery, lead carbon battery, super Capacitor - a lead-acid battery (super battery) battery, one or more of which.
在本实施例的其它实施方式中，本实施例上述铅酸蓄电池可被替换成相同容量的其它类型蓄电池，所述其它类型蓄电池包括但不限于：铁－镍蓄电池、铁－高铁酸盐蓄电池、镉－镍蓄电池，其中的一种或多种，本实施例上述方法，可应用于该其它类型蓄电池，可将充电时所允许达到的电压的绝对值的最大值调低，以适应不同类型的蓄电池额定工作电压。In other embodiments of the present embodiment, the lead-acid battery of the embodiment may be replaced with other types of batteries of the same capacity, including but not limited to: iron-nickel batteries, iron-ferrate batteries, A cadmium-nickel battery, one or more of which, the above method of the present embodiment can be applied to the other type of battery, and the maximum value of the absolute value of the voltage allowed during charging can be adjusted to suit different types. The rated working voltage of the battery.
在本实施例的其它实施方式中，本实施例铅酸蓄电池包括正极、负极，或者，本实施例铅酸蓄电池正、负电极均为正负极通用电极，本实施例铅酸蓄电池的正极、负极、正负极通用电极，包括但不限于，包括膨胀剂的正极或/和负极、其电极活性物质或活性物质配方中包括膨胀剂的正负极通用电极或/和正极或/和负极、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、彼此为同一种的或相同的正负极通用电极，其中的一种或多种。所述膨胀剂用来防止、抑制、改善电极比表面积收缩或电极活性物质比表面积收缩，所述膨胀剂包括但不限于：硫酸钡、硫酸钙、二氧化硅、硅酸盐、腐殖酸、木素磺酸盐、铝氧化物或氢氧化物、钛氧化物或氢氧化物，锂氧化物或氢氧化物，其中的一种或多种。In other embodiments of the present embodiment, the lead-acid battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the lead-acid battery of the embodiment are both positive and negative common electrodes, and the positive electrode of the lead-acid battery of the embodiment, A negative electrode, a positive electrode and a negative electrode, including but not limited to a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an anode or/and a negative electrode including an expansion agent in an electrode active material or an active material formulation, Positive and negative electrode common electrodes having the same active substance or the same active substance formulation, positive and negative electrode common electrodes equivalent to each other, positive and negative common electrodes of the same or the same, one or more of them. The expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
本实施例方法使蓄电池或电池组的使用寿命获得显著提高或延长，当放电深度(DOD)包括但不限于1-100％时，本实施例方法使蓄电池或电池组的使用寿命提高或延长至1.3倍以上－10倍以上，或/和，循环寿命提高或延长了50次以上－500次以上、500次以上－3000次以上，其中的一种或多种。The method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack. When the depth of discharge (DOD) includes but is not limited to 1-100%, the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
实施例2Example 2
本实施例蓄电池或电池组的额定电压为U,额定容量为C 2(2h率,25℃)、C 5(5h率,25℃)或C 20(20h率,25℃)，其中U＝1.2V、1.5V、2V、4V、6V、12V、24V、36V、48V、60V或72V、240V、360V、480V、600V、或其它电压值，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。本实施例蓄电池或电池组的正极为电极A1、A2、...、An(n＝正整数)，且连接于本实施例蓄电池或电池组的输出端子A，本实施例蓄电池或电池组的负极为电极B1、B2、...、Bn(n＝正整数)，且连接于本实施例蓄电池或电池组的输出端子B。解决蓄电池正极活性物质膨胀、软化、脱落问题或/和提高或延长本实施例蓄电池或电池组的使用寿命的方法的具体操作为，当本实施例蓄电池或电池组进行过1次以上的循环充放电工作后，由于本实施例蓄电池或电池组的循环充放、过充电、欠充电、高活性物质利用率等原因，导致本实施例蓄电池或电池组的工作放电容量因正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解等原因中的一种或多种导致本实施例蓄电池或电池组的工作放电容量下降，则每当本实施例蓄电池或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，或者本实施例蓄电池或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，开始对本实施例蓄电池或电池组自动或/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蓄电池或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、U、1.5U、2U中的一种或多种，使得本实施例蓄电池或电池组的电极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：对本实施例蓄电池或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、U、1.5U、2U中的一种或多种，使得本实施例蓄电池或电池组的电极A1、A2、...、An上发生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，当对本实施例蓄电池或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、U、1.2U、2.1U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蓄电池或电池组进行反极充电， 使得本实施蓄电池或电池组的电极A1、A2、...、An上发生蓄电池负极电极反应的放电过程、电极B1、B2、...、Bn上发生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：对本实施例蓄电池或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、0.9U、1.1U、1.7U中的一种或多种，充放电为直流或脉冲充放电，使得本实施例蓄电池或电池组的电极A1、A2、...、An上发生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，此过程对本实施例蓄电池或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,或蓄电池或电池组电压达到一定值时，例如0.7U、0.9U、1.05U或1.4U，本实施例蓄电池或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，然后将本实施例蓄电池或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蓄电池或电池组的方法，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)对本实施例蓄电池或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，使本实施例蓄电池或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、预防正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题，从而反复的、多次的使本实施例蓄电池或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蓄电池或电池组的使用寿命。 The rated voltage of the battery or battery pack of this embodiment is U, and the rated capacity is C 2 (2h rate, 25°C), C 5 (5h rate, 25°C) or C 20 (20h rate, 25°C), where U=1.2 V, 1.5V, 2V, 4V, 6V, 12V, 24V, 36V, 48V, 60V or 72V, 240V, 360V, 480V, 600V, or other voltage values, C 2 = 6.5Ah, 12Ah, 14Ah, 16Ah, 20Ah, 24 Ah, 30 Ah or 32 Ah, or, C 5 = 8.6 Ah, 15.9 Ah, 18.6 Ah, 21.2 Ah, 26.5 Ah, 31.9 Ah, 39.8 Ah or 42.5 Ah or C 20 = 10.4 Ah, 19.2 Ah, 22.4 Ah, 25.6 Ah , 32Ah, 38.4Ah, 48Ah or 51.2Ah. The positive electrode of the battery or the battery pack of the embodiment is the electrodes A1, A2, ..., An (n = positive integer), and is connected to the output terminal A of the battery or the battery pack of the embodiment, the battery or the battery pack of the embodiment. The negative electrode is an electrode B1, B2, ..., Bn (n = positive integer), and is connected to the output terminal B of the battery or battery pack of the present embodiment. The specific operation of the method for solving the problem that the battery positive active material expands, softens, falls off, or/and increases or prolongs the service life of the battery or the battery pack of the embodiment is that when the battery or the battery pack of the embodiment is subjected to one or more cycles of charging After the discharge operation, due to the cyclic charge and discharge, overcharge, undercharge, high active material utilization rate of the battery or the battery pack of the present embodiment, the working discharge capacity of the battery or the battery pack of the present embodiment is expanded by the positive active material or/ And softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, reduction of specific surface area of the negative electrode, poor contact of the active material with the conductive current collector, memory effect, decomposition of the active substance itself, or the like When the operating discharge capacity of the battery or the battery pack of the present embodiment is decreased, the operating discharge capacity of the battery or the battery pack of this embodiment is reduced to 60%, 75% of its rated capacity C 2 , C 5 or C 20 , 80%, 90% or 95%, or the charging voltage rise rate increases during the cyclic charging and discharging operation of the battery or battery pack of this embodiment When 10%, 15%, 20%, 30%, or 50%, or when the cycle work reaches a certain number of times, the battery or battery pack of this embodiment is automatically or/and manually subjected to a polarity reverse polarity twice in a single period. And then the charging or charging and discharging operation, that is, the operation of step (1): the battery or the battery pack of the embodiment is reversely charged by a certain current source or/and a voltage source, and the current of the reverse polarity charging is C 2 , One or more of C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or a reverse pole charging voltage of one or more of 0.5U, U, 1.5U, 2U, such that The polarity of the electrodes A1, A2, ..., An of the battery or the battery pack of the embodiment is reversed from the original positive polarity to the negative polarity, and the polarities of the electrodes B1, B2, ..., Bn are from the original negative polarity. Is reversed to positive polarity (this is the first polarity reversal of the current period), and then, operation (2): continue charging and discharging the battery or battery pack of the embodiment, the charging or discharging current is C 2 , One or more of C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or one or more of charging or discharging voltages of 0.5 U, U, 1.5 U, 2 U Therefore, the charging or/and discharging reaction process of the battery negative electrode reaction occurs on the electrodes A1, A2, ..., An of the battery or the battery of the present embodiment, and the battery positive electrode occurs on the electrodes B1, B2, ..., Bn. The charging or/and discharging reaction process of the reaction, when the amount of charge or discharge of the battery or battery pack of the embodiment reaches 4C 2 , 3C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or the voltage reaches 0.6U , U, 1.2U, 2.1U, then operate step (3): one or more of 3C 2 , 2.5C 5 , 0.5C 20 , 0.8C 2 , 6C 2 , or 2C 5 current The battery or the battery pack is subjected to reverse polarity charging, so that the discharge process of the battery negative electrode reaction occurs on the electrodes A1, A2, ..., An of the battery or the battery pack of the present embodiment, and the electrodes B1, B2, ..., Bn occur. The discharge process of the battery positive electrode reaction until the polarity of the electrodes A1, A2, ... An is reversed to positive polarity by the negative polarity, and the polarity of the electrodes B1, B2, ..., Bn is reversed by the positive polarity Negative polarity (this is the second polarity reversal of this period), and then operate step (4): for the battery or electricity of this embodiment The pool group continues to be charged or charged and discharged, and the charging or discharging current is one or more of C 2 , 2C 5 , 0.5C 20 , 0.1C 2 , 3C 2 , or 0.05C 5 or the charging voltage is 0.7U, 0.9. One or more of U, 1.1U, and 1.7U, charge and discharge are DC or pulse charge and discharge, so that the battery positive electrode reaction occurs on the electrodes A1, A2, ..., An of the battery or the battery pack of the embodiment. The charging or/and discharging process, the charging or discharging process of the negative electrode of the battery occurs on the electrodes B1, B2, ..., Bn, and the process of charging or discharging the battery or the battery pack of the embodiment is charged or/and discharged. For a certain value, such as 6C 2 , 3C 5 , 2C 20 , 8C 2 , 3C 2 , 0.5C 2 , or 2C 5 , or when the battery or battery voltage reaches a certain value, such as 0.7U, 0.9U, 1.05U or 1.4 U, the working discharge capacity or working capacity of the battery or the battery pack of the embodiment is restored or improved, and the positive and negative polarity reversal and subsequent charging or charging and discharging operations of the current two consecutive times are ended, and then the battery of the embodiment or The battery pack is put into a cycle to work or use. Thus, similarly, according to the method for improving or extending the battery or the battery pack according to the embodiment, the battery or the 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. During a two-cycle operation, the group performs one or more consecutive polarity inversions and subsequent charging or charging and discharging operations, so that the battery or battery pack of the present embodiment does not have a battery loss or short circuit. Effectively improve, repair, reverse, eliminate, inhibit, prevent expansion and/or softening or/and shedding, corrosion, passivation, early capacity loss, salinization, etc. of the active material in the case of circuit breakage or grid mechanical damage, etc. Crystallization, reduction of specific surface area of the negative electrode, poor contact of the active material with the conductive current collector, memory effect, decomposition of the active material itself, one or more problems, thereby repeatedly or repeatedly causing the battery or the battery pack of the present embodiment to work. The discharge capacity or working capacity is repaired, restored or improved to increase or lengthen the service life of the battery or battery pack of the present embodiment.
本实施例蓄电池包括但不限于，铅酸蓄电池、铁－镍蓄电池、铁－高铁酸盐蓄电池、镉－镍蓄电池，其中的一种或多种。The battery of this embodiment includes, but is not limited to, a lead-acid battery, an iron-nickel battery, an iron-ferrate battery, a cadmium-nickel battery, one or more of which.
本实施例铅酸蓄电池包括但不限于平面板栅式铅酸蓄电池、管式铅酸蓄电池、全管式铅酸蓄电池、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、柱式铅酸蓄电池、具有稳定空隙体电极式铅酸蓄电池、阀控式密封铅酸蓄电池、胶体铅酸蓄电池、铅碳电池蓄电池、超级电容器-铅酸蓄电池(超级电池)式铅酸蓄电池，其中的一种或多种。The lead-acid battery of the embodiment includes but is not limited to a flat-plate lead-acid battery, a tubular lead-acid battery, a full-tube lead-acid battery, a wound lead-acid battery, a bipolar lead-acid battery, and a horizontal lead-lead lead. Acid battery, foam grid lead-acid battery, column lead-acid battery, lead-acid battery with stable gap body, valve-regulated sealed lead-acid battery, colloidal lead-acid battery, lead carbon battery, supercapacitor-lead acid A battery (super battery) type lead-acid battery, one or more of which.
在本实施例的其它实施方式中，本实施例蓄电池包括正极、负极，或者，本实施例蓄电池正、负电极均为正负极通用电极，本实施例蓄电池的正极、负极、正负极通用电极，包括但不限于，包括膨胀剂的正极或/和负极、其电极活性物质或活性物质配方中包括膨胀剂的正负极通用电极或/和正极或/和负极、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、彼此为同一种的或相同的正负极通用电极，其中的一种或多种。所述膨胀剂用来防止、抑制、改善电极比表面积收缩或电极活性物质比表面积收缩，所述膨胀剂包括但不限于：硫酸钡、硫酸钙、二氧化硅、硅酸盐、腐殖酸、木素磺酸盐、铝氧化物或氢氧化物、钛氧化物或氢氧化物、锂氧化物或氢氧化物，其中的一种或多种。In other embodiments of the present embodiment, the battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the battery in this embodiment are both positive and negative common electrodes, and the positive electrode, the negative electrode, the positive and negative electrodes of the battery of the embodiment are generally used. Electrode, including but not limited to, a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an active electrode or a negative electrode including an expansion agent in an electrode active material or an active material formulation, and/or a positive electrode or/and a negative electrode, having the same active substance or The positive and negative electrode common electrodes of the same active material formulation, the positive and negative electrode common electrodes of the same active substance, and the positive and negative common electrodes of the same or the same, one or more of them. The expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
在本实施例的其它实施方式中，所述膨胀剂在活性物质或活性物质配方中的质量百分含量为0.01％以上、0.02％以上、0.03％以上、0.05％以上、0.08％以上、0.1％以上、0.2％以上、0.3％以上、0.4％以上、0.5％以上、0.6％以上、0.8％以上、1％以上、2％以上，其中的一种或多种。In other embodiments of the present embodiment, the mass percentage of the expansion agent in the active substance or active substance formulation is 0.01% or more, 0.02% or more, 0.03% or more, 0.05% or more, 0.08% or more, 0.1%. The above, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.6% or more, 0.8% or more, 1% or more, 2% or more, one or more of them.
在本实施例的其它实施方式中，所述膨胀剂在活性物质或活性物质配方中的质量百分含量小于或等于5％、10％、20％、30％、40％、50％，其中的一种或多种。In other embodiments of the present embodiment, the mass percentage of the expansion agent in the active substance or active substance formulation is less than or equal to 5%, 10%, 20%, 30%, 40%, 50%, wherein One or more.
本实施例方法使蓄电池或电池组的使用寿命获得显著提高或延长，当放电深度(DOD)包括但不限于1-100％时，本实施例方法使蓄电池或电池组的使用寿命提高或延长至1.3倍以上－10倍以上，或/和，循环寿命提高或延长了50次以上－500次以上、500次以上－3000次以上，其中的一种或多种。The method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack. When the depth of discharge (DOD) includes but is not limited to 1-100%, the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
实施例3Example 3
本实施例涉及解决铅酸蓄电池正极活性物质膨胀、软化、脱落问题或/和提高或延长铅酸蓄电池使用寿命的方法、电池充放电器、铅膏或活性物质、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，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。The embodiment relates to a method for solving the problem of expansion, softening and falling off of a positive electrode active material of a lead-acid battery or/and a method for improving or prolonging the service life of a lead-acid battery, a battery charge and discharge device, a lead paste or an active material, a lead-acid battery electrode and a lead-acid battery. The charge and discharge device of the present embodiment has a function of performing polarity reversal of the positive and negative poles of the lead-acid battery and subsequent charging or charging and discharging operations, and a programmable execution function, when the battery charge and discharge device output of the embodiment After being connected to the lead-acid battery electrode of the embodiment, the battery charger and discharger of the embodiment can perform the lead-acid battery of the embodiment by the polarity reversal at the output end and the charging, charging or charging/discharging operation after the polarity reversal. The charge and discharge operations of the positive and negative polarities are reversed, and the polarity is reversed. All the operations on the battery in the following embodiments are the functions of the battery charge and discharge device of the present embodiment, unless otherwise specified. Work to achieve.
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个电极，该两个电极均为正负极通用电极(即正极、负极通用的电极)，同时也是同一种的或相同的正负极通用电极，即，不考虑制造电极时产生的制造误差(即刨除、排除、去掉制造误差的存在或影响)，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，该两个电极则分别被形成正极和负极，将该两个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，该两个电极之间隔有隔板，本实施例的该两片电极，铅膏或活性物质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。 The lead-acid battery of the present embodiment has a rated voltage of 2V and a designed rated capacity of 821 mAh (2h rate, 25 ° C). The lead-acid battery of the embodiment includes two electrodes, and both electrodes are positive and negative common electrodes (ie, positive electrodes). The common electrode of the negative electrode) is also the same or the same positive and negative common electrode, that is, regardless of the manufacturing error (ie, removing, eliminating, eliminating the existence or influence of manufacturing error) generated when the electrode is fabricated, the two pieces The lead-acid battery electrodes of the present embodiment 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 into The two electrodes are respectively formed into a positive electrode and a negative electrode, and the two electrodes are respectively defined as an electrode A and an electrode B. At the beginning, the electrode A is used as a positive electrode and the electrode B is used as a negative electrode to perform formation and operation of the battery. a separator spacing the electrodes, the two electrodes, an active material or a lead paste formulations of the present embodiment comprises a ball lead powder, BaSO 4 (0.8%, by mass percentage, with respect to the lead powder ball milling), 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, breaking, Short-circuit, mechanical damage, test failure and other factors interfere with the implementation process and implementation results of this embodiment.
本实施例解决铅酸蓄电池正极活性物质膨胀、软化、脱落问题或/和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，以解决、改善、修复、消除、逆转、抑制或防止本实施例铅酸蓄电池的正极活性物质膨化或/和软化或/和脱落、负极比表面积收缩、腐蚀(包括但不限于电极、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、活性物质自身分解问题中一种或多种，使本实施例铅酸蓄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，从而实现解决铅酸蓄电池正极活性物质膨胀、软化、脱落问题或/和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)。The method for solving the problems of expansion, softening, and falling off of the positive electrode active material of the lead-acid battery or/and the service life of the lead-acid battery is as follows: First, the battery of the embodiment is subjected to the cycle charging and discharging work, and the working system is: when the battery When in the state of charging, the battery is discharged with a constant current of 371 mA. When the battery voltage is ≤ 1.75 V, the discharge is stopped, then it is charged with a constant current of 222 mA, and after the measured battery voltage reaches 2.65 V, the conversion is performed. The battery is continuously charged at a constant voltage of 2.65V. The total time of two (constant current, constant voltage) charging is 7 hours and 24 minutes (except for special instructions), and then the above discharge process is repeated with a constant current of 371 mA. Repeatedly discharging and charging in this way, the battery is cycled, and the operating temperature of the battery is 25±1 °C. Next, when 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. In the discharge operation, 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 solve and improve. Repairing, eliminating, reversing, suppressing or preventing the expansion of the positive active material of the lead-acid battery of the present embodiment and/or softening or/and shedding, shrinkage of the specific surface area of the negative electrode, corrosion (including but not limited to electrodes, sinks, current collector corrosion), One or more of passivation, early capacity loss, sulfation, poor contact of active material with current collector, and decomposition of active material itself, so that the working discharge charging capacity of the lead-acid battery of the present embodiment is obtained after each operation Improve, restore, improve or maintain, thereby solving the problem of expansion, softening, shedding of the positive active material of the lead-acid battery or/and improving or prolonging 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.
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2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，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。 Pressing, initially setting when the number of working discharges of the lead-acid battery in this embodiment reaches and completes the 15th and 31st, stops the battery operation and starts a single positive and negative polarity reversal of the battery and thereafter. Charging or charging and discharging operations. As shown in FIG. 2, in the 1st-15th cycle operation, 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. 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). , related to deep discharge, the following similar), after the 15th discharge, the discharge capacity is 942mAh. At this time, according to the program setting, 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 the polarity reversal of the positive and negative electrodes, that is, the polarity of the output end of the charger and the discharger is reversed, and the connection state of the charge and discharge device and the lead-acid battery is from the positive and negative terminals of the charge and discharge device and the lead-acid battery. The 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, and is changed, the negative electrode output end of the charge and discharge device is connected with the lead acid battery electrode A, and the positive electrode output end of the charge and discharge device is connected with the lead acid battery electrode B. After the connection state is changed, the measured battery voltage is a negative value, and then the battery of the embodiment in which the connection state is changed is charged with a constant current of 186 mA, so that the battery voltage rises from a negative value. 0V then rises again to 1.75V (in this process, the first polarity reversal of the battery of this embodiment occurs, in which the battery voltage rises from a negative value to 0V, the discharge process of the positive electrode reaction of the lead-acid battery occurs on the electrode A, The discharge process of the negative electrode reaction of the lead-acid battery occurs on the electrode B. During the process of the battery voltage rising from 0V to 1.75V, the charging process of the lead-acid battery negative electrode reaction occurs on the electrode A, and the lead-acid battery positive electrode reaction occurs on the electrode B. Charging process), when the battery voltage reaches 1.75V, continue to charge the battery to 2.65V with a constant current of 222mA, then charge the battery for 4 hours and 16 minutes with a constant voltage of 2.65V, and then conduct the battery with a constant current of 371mA. Discharge, to 1.75V, and then charge the battery with a constant current of 222mA until the battery voltage reaches 2.65V and then charge the battery for 2.5 hours at 2.65V. After the charging is completed, the battery of this embodiment is completed. The first single positive and negative polar polarity reversal and subsequent charging or charging and discharging operations, at this time the electrode state of the battery has been changed 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 16th operation discharge and the subsequent number of cycles. The results show that 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.
接下来使本实施例电池继续在工作制度下运行，如图2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2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。Next, the battery of the embodiment is continuously operated under the working system. As shown in FIG. 2, in the 16th to 31st cycle of the battery of the embodiment, the electrode state of the battery of the embodiment is A-/B+, and the electrode at this time A negative electrode reaction occurs on A, and a positive electrode reaction occurs on electrode B. In the 16th to 31st cycle of the battery of the present embodiment, 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. When the 31st cycle operation discharge ends, according to the program setting, the start condition of the polarity inversion of the battery positive and negative electrodes and the subsequent charging or charging and discharging operation is triggered at this time. Therefore, 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. Inversion, that is, the polarity reversal at the output end of the charger and the discharger according to the present embodiment (the polarity reversal at the output end of the charger/discharger is realized by the opening and closing state of the relay circuit contacts in the charger/discharger), and the charging and discharging are performed. 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. After the connection state is changed, the measured battery voltage is a negative value, and then 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 charging process of the positive electrode reaction of the lead-acid battery on the middle electrode A, the charging process of the negative electrode reaction of the lead-acid battery on the electrode B), and then charging the battery for 4 hours at a constant voltage of 2.65 V, and then a constant current of 371 mA The battery was discharged to 1.75V, and then the battery was charged at a constant current of 222mA for 7 hours and 25 minutes, and then the battery was charged for 7 hours at a constant voltage of 2.65V. 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. At this time, the electrode state of the battery has been changed from A-/B+ to A+. /B-. Then, the electrode A was operated as a positive electrode, and the electrode B was operated as a negative electrode, and the battery was 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. Next, the battery is continuously operated under the working system. As shown in FIG. 2, in the 32-45th cycle operation, 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. In the reaction, 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.
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2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。During the cyclic charging and discharging operation of the lead-acid battery of the embodiment, 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. After 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, ..... . The ninth single positive and negative polar polarity reversal and subsequent charging or charging and discharging operations. FIG. 2 is a diagram showing the electrode of the lead-acid battery of the embodiment in the cycle of 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 embodiment. The polarity state or polarity direction of A and B. In the cycle working system of the lead-acid battery of the present embodiment in the 46th and subsequent times, 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.
如图2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膨胀、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。As shown in FIG. 2, the working discharge capacity of the lead-acid battery of the present embodiment is improved or restored year by year. On the one hand, as described above, 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 expanded, softened, and detached to be improved, repaired, reversed, Eliminating, 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; on the other hand, the polarity of the positive and negative poles of the embodiment is reversed and the subsequent charge and discharge Or the charge-discharge operation, also inevitably occurs during the cycle of the battery of the embodiment, slight or occurring electrode 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, sulfation The problem has the effect of improving, repairing, reversing, suppressing, eliminating, and preventing. For example, since the electrodes A and B repeatedly alternately function as a positive electrode or a negative electrode for charging and discharging, the problem of electrode corrosion generated when working as a positive electrode is used as a negative electrode at the electrode. Improved, repaired, and reversed during the charging and discharging cycle, thereby also making the lead acid storage of the present embodiment The corrosion problem of the pool during long-term use is delayed, improved, repaired, reversed, and prevented. In the normal circulation process of the lead-acid battery in this embodiment, it is periodically or irregularly (for example, in a manner of specifying the number of cycles of operation), By performing the charge and discharge or charge and discharge operations of the positive and negative polarities of the present embodiment on the lead-acid battery of the present embodiment, the positive electrode active material softening will be effectively improved, repaired, reversed, eliminated, suppressed, and prevented. Or / and shedding, electrode passivation, corrosion, early capacity loss, sulfation, poor contact of the active material with the current collector, and shrinkage of the specific surface area of the negative electrode, thereby increasing or prolonging the service life of the lead-acid battery of the present embodiment.
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。In 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.
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。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 and discharge cycle after the discharge capacity of each working battery is restored (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 higher 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.
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61mAh/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2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，进一步地，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，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。According to the current commercial power electric lead-acid battery under the rated working conditions, the specific capacity of the battery positive active material 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 implementation The average mass of the active material of a single electrode of a lead-acid battery), if 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 is based on the end of the battery life. As shown in FIG. 2, according to the discharge capacity attenuation trend line of the 1st to 15th times, it can be considered that the lead-acid storage battery of the present embodiment does not undergo the charging or charging/discharging operation of the positive and negative polarity inversion and the subsequent embodiment. At the time, the service life will be basically 25 and 36 times respectively. However, in fact, after the positive and negative polarity inversion of the battery of this embodiment and the subsequent charging or charging and discharging operations, 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 improved or prolonged. Further, in the case of eliminating short-circuit, open circuit, water loss, pollution and the like which cause the battery to fail, the method for improving or prolonging the service life of the lead-acid battery in the present embodiment makes The service life of the example lead-acid battery is greatly improved or extended on the basis of 111 cycles. In the present embodiment, 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.
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。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.
本实施例上述铅酸蓄电池，包括但不限于平面板栅式铅酸蓄电池、管式铅酸蓄电池、全管式铅酸蓄电池、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、柱式铅酸蓄电池、具有稳定空隙体电极式铅酸蓄电池、阀控式密封铅酸蓄电池、胶体铅酸蓄电池、铅碳电池蓄电池、超级电容器-铅酸蓄电池(超级电池)式铅酸蓄电池，其中的一种或多种，本实施例上述方法亦可应用于其它类型铅酸蓄电池。The lead-acid battery of the embodiment includes, but is not limited to, a flat-plate lead-acid battery, a tubular lead-acid battery, a full-tube lead-acid battery, a wound lead-acid battery, a bipolar lead-acid battery, and a horizontal lead cloth. Lead-acid battery, foam grid lead-acid battery, column lead-acid battery, lead-acid battery with stable gap body, valve-regulated sealed lead-acid battery, colloidal lead-acid battery, lead carbon battery, super capacitor - A lead-acid battery (super battery) type lead-acid battery, one or more of which, the above method can also be applied to other types of lead-acid batteries.
在本实施例的其它实施方式中，本实施例上述铅酸蓄电池可被替换成相同容量的其它类型蓄电池，所述其它类型蓄电池包括但不限于：铁－镍蓄电池、铁－高铁酸盐蓄电池、镉－镍蓄电池，其中的一种或多种，本实施例上述方法，可应用于该其它类型蓄电池，可将充电时所允许达到的电压的绝对值的最大值调低，以适应不同类型的蓄电池额定工作电压。In other embodiments of the present embodiment, the lead-acid battery of the embodiment may be replaced with other types of batteries of the same capacity, including but not limited to: iron-nickel batteries, iron-ferrate batteries, A cadmium-nickel battery, one or more of which, the above method of the present embodiment can be applied to the other type of battery, and the maximum value of the absolute value of the voltage allowed during charging can be adjusted to suit different types. The rated working voltage of the battery.
在本实施例的其它实施方式中，本实施例蓄电池包括正极、负极，或者，本实施例蓄电池正、负电极均为正负极通用电极，本实施例蓄电池的正极、负极、正负极通用电极，包括但不限于，包括膨胀剂的正极或/和负极、其电极活性物质或活性物质配方中包括膨胀剂的正负极通用电极或/和 正极或/和负极、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、彼此为同一种的或相同的正负极通用电极，其中的一种或多种。所述膨胀剂用来防止、抑制、改善电极比表面积收缩或电极活性物质比表面积收缩，所述膨胀剂包括但不限于：硫酸钡、硫酸钙、二氧化硅、硅酸盐、腐殖酸、木素磺酸盐、铝氧化物或氢氧化物、钛氧化物或氢氧化物、锂氧化物或氢氧化物，其中的一种或多种。In other embodiments of the present embodiment, the battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the battery in this embodiment are both positive and negative common electrodes, and the positive electrode, the negative electrode, the positive and negative electrodes of the battery of the embodiment are generally used. Electrode, including but not limited to, a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an active electrode or a negative electrode including an expansion agent in an electrode active material or an active material formulation, and/or a positive electrode or/and a negative electrode, having the same active substance or The positive and negative electrode common electrodes of the same active material formulation, the positive and negative electrode common electrodes of the same active substance, and the positive and negative common electrodes of the same or the same, one or more of them. The expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
在本实施例的其它实施方式中，本实施例上述膨胀剂或硫酸钡在活性物质或活性物质配方中的质量百分比含量为大于或等于0.01％、0.02％、0.03％、0.05％、0.08％、0.10％、0.2％、0.3％、0.4％、0.5％、0.6％、0.8％、1％、2％、3％、4％，其中的一种或多种。In other embodiments of the present embodiment, the mass percentage of the above-mentioned expansion agent or barium sulfate in the active substance or active substance formulation of the present embodiment is greater than or equal to 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.10%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, one or more of them.
在本实施例的其它实施方式中，本实施例上述膨胀剂或硫酸钡在活性物质或活性物质配方中的质量百分比含量小于或等于5％、10％、20％、30％、40％、50％，其中的一种或多种。In other embodiments of the present embodiment, the mass percentage of the above-mentioned expansion agent or barium sulfate in the active substance or active substance formulation of the present embodiment is less than or equal to 5%, 10%, 20%, 30%, 40%, 50. %, one or more of them.
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。In other embodiments of the present embodiment, 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.
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。In other embodiments of the present embodiment, 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.
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。In other embodiments of the present embodiment, 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 the operation are mainly changed, for example, the lead-acid battery pack is reversely charged and causes polarity reversal. After the occurrence of the battery pack, 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.
本实施例方法使蓄电池或电池组的使用寿命获得显著提高或延长，当放电深度(DOD)包括但不限于1-100％时，本实施例方法使蓄电池或电池组的使用寿命提高或延长至1.3倍以上－10倍以上，或/和，循环寿命提高或延长了50次以上－500次以上、500次以上－3000次以上，其中的一种或多种。The method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack. When the depth of discharge (DOD) includes but is not limited to 1-100%, the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
实施例4Example 4
本实施例蓄电池或电池组，包括但不限于平面板栅式蓄电池、管式蓄电池、全管式蓄电池、卷绕式蓄电池、双极式蓄电池、水平铅布式蓄电池、泡沫板栅式蓄电池、阀控式密封蓄电池、胶体蓄电池、铅碳电池、超级电容器－蓄电池，其中的一种或多种，本实施例蓄电池或电池组的额定电压U为1.2V、1.5V、2V、4V、6V、12V、24V、36V、48V、60V或72V、120V、240V、360V、480V、600V或其它电压值,本实施例蓄电池或电池组的额定容量(C 2，2小时率，25℃)为12Ah、14Ah、16Ah、 18Ah、20Ah、24Ah、30Ah、60Ah、100Ah、200Ah或1000Ah，本实施例蓄电池或电池组具有输出端子A、B，输出端子A与本实施例蓄电池或电池组中的电极A1、A2、......、An(n＝正整数)相导电连接，输出端子B与本实施例蓄电池或电池组中的电极B1、B2、......、Bn(n＝正整数)相导电连接。本实施例蓄电池或电池组中的电极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)，既可作为蓄电池的正极使用或工作，也可作为蓄电池的负极使用或工作。本实施例蓄电池或电池组在最初的循环充放电工作过程中，其输出端子A的极性为正、输出端子B的极性为负，即，本实施例蓄电池或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。 The battery or battery pack of the embodiment includes, but is not limited to, a flat grid battery, a tubular battery, a full tubular battery, a wound battery, a bipolar battery, a horizontal lead cloth battery, a foam grid battery, and a valve. Controlled sealed battery, gel battery, lead carbon battery, super capacitor-battery, one or more of them, the rated voltage U of the battery or battery pack of this embodiment is 1.2V, 1.5V, 2V, 4V, 6V, 12V 24V, 36V, 48V, 60V or 72V, 120V, 240V, 360V, 480V, 600V or other voltage value, the rated capacity of the battery or battery pack of this embodiment (C 2 , 2 hour rate, 25 ° C) is 12Ah, 14Ah 16Ah, 18Ah, 20Ah, 24Ah, 30Ah, 60Ah, 100Ah, 200Ah or 1000Ah, the battery or battery pack of the embodiment has output terminals A, B, output terminal A and electrodes A1 and A2 in the battery or battery pack of the embodiment. , ..., An (n = positive integer) phase conductive connection, output terminal B and electrodes B1, B2, ..., Bn in the battery or battery pack of the present embodiment (n = positive integer The phase is electrically connected. The electrodes A1, A2, ..., An, B1, B2, ..., Bn in the battery or the battery pack of this embodiment are positive and negative common electrodes (i.e., electrodes common to the positive and negative electrodes). ), it can be used or operated as the positive electrode of the battery, or it can be used or operated as the negative electrode of the battery. In the initial cycle charging and discharging operation of the battery or the battery pack of the embodiment, the polarity of the output terminal A is positive, and the polarity of the output terminal B is negative, that is, the battery or the battery pack of the embodiment is in the initial cycle operation. During the process, the charging and discharging processes of the positive electrode of the battery occur on the electrodes A1, A2, ..., An. The negative electrode of the battery occurs on the electrodes B1, B2, ..., Bn. The charging and discharging process of the reaction. The separators are separated by positive and negative electrodes.
本实施例解决蓄电池正极活性物质膨胀、软化、脱落问题或/和提高或延长本实施例蓄电池或电池组使用寿命的方法为，当本实施例蓄电池或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，由于正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题导致本实施例蓄电池或电池组工作放电容量下降并低于某容量数值时或后，希望或需要提高蓄电池或电池组工作放电容量或提高、延长蓄电池或电池组使用寿命时)在某两次工作循环之间，自动或/和手动地对本实例蓄电池或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、防止正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题，使得本实施例蓄电池或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，将本实施例蓄电池或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蓄电池或电池组进行正、负极极性反转及其后的充电或充放电操作，如此，使得本实施例蓄电池或电池组的循环工作与本实施例的对本实施例蓄电池或电池组进行正、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蓄电池或电池组的使用寿命。The method for solving the problem of expansion, softening, falling off of the positive electrode active material of the battery or/and improving or prolonging the service life of the battery or the battery pack of the embodiment is that when the battery or the battery pack of the embodiment is used or operated in the cycle work When the working cycle reaches a certain number of times or as needed (for example, due to expansion or/and softening or/and shedding of the positive active material, corrosion, passivation, early capacity loss, salinization, crystallization, specific surface area shrinkage, active substances and Poor contact of the conductive current collector, memory effect, decomposition of the active material itself, one or more problems of which cause the battery or battery pack of the present embodiment to reduce the working discharge capacity and lower than a certain capacity value, or hope to increase the battery or When the battery pack has a working discharge capacity or increases the battery life or battery life, a single positive and negative polarity reversal of the battery or battery pack of this example is performed automatically or/and manually between two working cycles. Subsequent charging or charging and discharging operations to improve, eliminate, reverse, suppress, and prevent positive active materials Expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact of active material with conductive current collector, memory effect, decomposition of active substance itself, one of The battery or the battery pack of the present embodiment is restored or improved by the operation of the battery or the battery pack of the present embodiment. After the polarity reversal of the positive and negative poles and subsequent charging or charging and discharging operations are completed, the battery or battery pack of the embodiment is used. The polarity state after the polarity is reversed, re-introduced into the charging and discharging cycle operation, or used until the triggering or starting again, the polarity of the positive and negative polarities of the battery or the battery pack of the embodiment is reversed and thereafter The charging or charging and discharging operation, such that the circulating operation of the battery or the battery pack of the present embodiment and the positive or negative polarity reversal of the battery or the battery pack of the present embodiment and the subsequent charging or charging and discharging operations are performed on each other. Intermittent, interspersed, alternating, or occurring to increase or extend the useful life of the battery or battery pack of the present embodiment.
对本实施例蓄电池或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：当本实施例蓄电池或电池组在最初始的循环工作过程中(此期间本实施例蓄电池或电池组输出端子A的极性为正、输出端子B的极性为负，即，电极A1、A2、......、An上发生蓄电池正极电极反应的充放电过程，电极B1、B2、......、Bn上发生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，对本实施例蓄电池或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蓄电池或电池组的输出端子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，对本实施例蓄电池或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，使本实施例蓄电池或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，本实施例蓄电池或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，本实施例蓄电池或电池组输出端子A的极性为负、输出端子B的极性为正，即，电极A1、A2、......、An上发生蓄电池负极电极反应的充放电过程，电极B1、B2、......、Bn上发生蓄电池正极电极反应的充放电过程。 Performing the first single positive and negative polarity inversion and the subsequent charging or charging and discharging operations on the battery or the battery pack of the embodiment includes the steps of: when the battery or the battery pack of the embodiment is in the initial cycle working process (this During this period, the polarity of the battery or battery pack output terminal A is positive, and the polarity of the output terminal B is negative, that is, the charge and discharge of the battery positive electrode reaction occurs on the electrodes A1, A2, ..., An. Process, the charging and discharging process of the battery negative electrode reaction occurs on the electrodes B1, B2, ..., Bn), when the working cycle reaches a certain number of times, for example, 5 times, 9 times, 20 times or 60 times, example battery or battery pack reverse polarity charge, the counter electrode comprises a charging mode, a single stage, multi stage, a constant current (e.g. 0.1C 2, 0.5C 2, 1.2C 2 , 6C 2), a constant voltage (e.g. One or more of U, 1.3U, 2U, 5U), positive pulse, negative pulse, and finally the polarity of the output terminals A, B of the battery or battery pack of the present embodiment, and thus the electrodes A1, A2. The polarity of ....., An, B1, B2, ... Bn is reversed, and the polarity is reversed After transfection manner, embodiments of the present embodiment the battery or battery charge or discharge, or charging and discharging comprises charge, single phase, multiple phase, constant current (e.g. 0.15C 2, 0.4C 2, 0.8C 2 , 7C 2), One or more of a constant voltage (for example, 0.8U, 1.5U, 2U, 4U), a positive pulse, and a negative pulse, and then, the polarity state of the battery or the battery pack of this embodiment is reversed by the polarity Re-introducing into the cyclic work to perform the cyclic work. In the cycle work performed by the battery or the battery pack in this embodiment after completing the first single positive and negative polarity reversal and subsequent charging or charging and discharging operations In this embodiment, the polarity of the battery or battery pack output terminal A is negative, and the polarity of the output terminal B is positive, that is, the charging and discharging of the battery negative electrode reaction occurs on the electrodes A1, A2, ..., An. In the process, the charging and discharging processes of the battery positive electrode reaction occur on the electrodes B1, B2, ..., Bn.
对本实施例蓄电池或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：当本实施例蓄电池或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(此期间本实施例蓄电池或电池组输出端子A的极性为负、输出端子B的极性为正，即，电极A1、A2、......、An上发生蓄电池负极电极反应的充放电过程，电极B1、B2、......、Bn上发生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，对本实施例蓄电池或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蓄电池或电池组的输出端子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，对本实施例蓄电池或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，使本实施例蓄电池或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，本实施例蓄电池或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，本实施例蓄电池或电池组输出端子A的极性为正、输出端子B的极性为负，即，电极A1、A2、......、An上发生蓄电池正极电极反应的充放电过程，电极B1、B2、......、Bn上发生蓄电池负极电极反应的充放电过程。 Performing the second single positive and negative polarity inversion and the subsequent charging or charging and discharging operations on the battery or the battery pack of the embodiment includes the steps of: when the battery or the battery pack of the embodiment is in the first single positive and negative During polarity reversal and subsequent cycle operation after charging or charging and discharging operation (during this period, the polarity of the battery or battery pack output terminal A of this embodiment is negative, and the polarity of the output terminal B is positive, that is, the electrode On the A1, A2, ..., An, the charging and discharging process of the battery negative electrode reaction occurs, and the charging and discharging processes of the battery positive electrode reaction occur on the electrodes B1, B2, ..., Bn), the working cycle When a certain number of times is completed, for example, 9 times, 13 times, 20 times or 40 times, the second reverse polarity charging is performed on the battery or the battery pack of the embodiment, and the manner of the reverse polarity charging includes a single stage and multiple One or more of a phase, a constant current (eg, 0.2 C 2 , 0.5 C 2 , 1.5 C 2 , 3 C 2 ), a constant voltage (eg, U, 1.1 U, 2 U, 4 U), a positive pulse, a negative pulse, and Finally, the polarity of the output terminals A, B of the battery or the battery pack of the present embodiment, and thus the electrodes The polarity of A1, A2, ..., An, B1, B2, ..., Bn is reversed, and after the polarity is reversed, the battery or battery pack of this embodiment is subjected to Charging or charging and discharging, charging or charging and discharging methods include single-stage, multi-stage, constant current (for example, 0.18C 2 , 0.7C 2 , 2C 2 , 5C 2 ), constant voltage (for example, 0.6U, 1.3U, 2.2U). , 3U), positive pulse, negative pulse one or more, and then, in this embodiment, the battery or the battery pack is re-introduced into the cycle work by the polarity state after the polarity is reversed. In the cycle operation of the battery or the battery pack of the present embodiment after completing the second single positive and negative polarity inversion and subsequent charging or charging and discharging operations, the battery or battery pack output terminal A of this embodiment The polarity of the output terminal is positive, and the polarity of the output terminal B is negative, that is, the charging and discharging process of the battery positive electrode reaction occurs on the electrodes A1, A2, ..., An, and the electrodes B1, B2, .... .., Bn The charging and discharging process of the negative electrode reaction of the battery occurs.
在本实施例蓄电池或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，在本实施例蓄电池或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，使得本实施例蓄电池或电池组的正极活性物质正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题，得到改善、修复、逆转、消除、抑制、防止、解决，从而使得本实施例蓄电池或电池组的工作放电容量、使用寿命获得提高或延长。During the cyclic charging and discharging operation of the battery or the battery pack of the present embodiment, 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. In this way, during the cyclic charging and discharging operation of the battery or the battery pack of the present embodiment, the positive or negative polarity inversion described above and the subsequent charging or charging and discharging operations are performed repeatedly, repeatedly, and interspersedly, so that The positive electrode active material positive electrode active material of the battery or the battery pack of the present embodiment is expanded or/and softened or/and peeled off, corroded, passivated, early capacity loss, salinization, crystallization, specific surface area shrinkage of the negative electrode, active material and conductive current collector Contact failure, memory effect, decomposition of active substance itself, one or more problems, which are improved, repaired, reversed, eliminated, suppressed, prevented, solved, so that the working discharge capacity and use of the battery or battery pack of the present embodiment Life expectancy is increased or extended.
本实施例蓄电池包括但不限于：铅酸蓄电池、铁－镍蓄电池、铁－高铁酸盐蓄电池、镉－镍蓄电池，其中的一种或多种。The battery of this embodiment includes, but is not limited to, a lead-acid battery, an iron-nickel battery, an iron-ferrate battery, a cadmium-nickel battery, one or more of which.
本实施例铅酸蓄电池包括但不限于：平面板栅式铅酸蓄电池、管式铅酸蓄电池、全管式铅酸蓄电池、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、柱式铅酸蓄电池、具有稳定空隙体电极式铅酸蓄电池、阀控式密封铅酸蓄电池、胶体铅酸蓄电池、铅碳电池蓄电池、超级电容器-铅酸蓄电池(超级电池)式铅酸蓄电池，其中的一种或多种。The lead-acid battery of the embodiment includes but is not limited to: a planar grid type lead-acid battery, a tubular lead-acid battery, a full-tube lead-acid battery, a wound lead-acid battery, a bipolar lead-acid battery, and a horizontal lead cloth. Lead-acid battery, foam grid-type lead-acid battery, column lead-acid battery, lead-acid battery with stable gap body, valve-regulated sealed lead-acid battery, colloidal lead-acid battery, lead carbon battery, supercapacitor-lead Acid battery (super battery) type lead-acid batteries, one or more of them.
在本实施例的其它实施方式中，在本实施例蓄电池或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膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解等问题中一种或多种而导致的蓄电池或电池组工作能力下降或使用寿命终止，对本实施例蓄电池或电池组多期地、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，将本实施例蓄电池或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，获得本实施例蓄电池或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蓄电池或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。In other embodiments of the present embodiment, in the cyclic operation of the battery or the battery pack of the embodiment, in order to improve, repair, reverse, solve, and prevent expansion or/and softening or/and shedding, corrosion due to the active material of the positive electrode, Battery or battery operation caused by one or more of passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact of active material with conductive current collector, memory effect, and decomposition of active material itself The capacity or the end of the service life is terminated. For the battery or the battery pack of the embodiment, the positive or negative polarity reversal and the subsequent charging or charging and discharging operations are performed in an odd or even number of times, and the odd number of times or each period is completed. 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 battery or the battery pack of the present embodiment is re-introduced into the charging and discharging cycle by the polarity state after the polarity is reversed in the current period. Use or work to obtain the recovery or improvement of the working capacity of the battery or the battery pack of the embodiment until the battery is activated or restarted again for the present embodiment. A battery pack or an odd number even number of positive and negative electrode after the polarity inversion and charge or discharge operation. 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.
在本实施例的其它实施方式中，本实施例蓄电池或电池组的正极、负极或说所有电极均为同一种的或相同的正负极通用电极，即，电极被化成之前，所述所有电极或所述正极、负极，彼此在各方面，例如但不限于集流体、活性物质配方和活性物质质量(例如但不限于铅膏配方和铅膏质量)、制做工艺等方面，完全相同(即，在各方面都相同)，或者，不考虑制造电极时产生的制造误差(即刨除、排除、去掉制造误差的存在或影响)，本实施例蓄电池或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，本实施例蓄电池或电池组的各电极则分别被形成正极或负极。In other embodiments of the present embodiment, the positive electrode, the negative electrode or all of the electrodes of the battery or the battery pack of the present embodiment are the same or the same positive and negative common electrode, that is, before the electrode is formed, all the electrodes are Or the positive electrode and the negative electrode are identical to each other in various aspects, such as but not limited to a current collector, an active substance formulation, and an active material quality (such as, but not limited to, a paste formulation and a paste quality), a manufacturing process, and the like (ie, , in all respects the same), or, regardless of manufacturing errors (ie, removing, eliminating, eliminating the presence or influence of manufacturing errors) generated when the electrodes are fabricated, all of the electrodes of the battery or battery of the present embodiment are In all electrode composition, manufacturing aspects (such as electrode structure, shape, current collector, fluid pool, active material formulation and quality, other accessories, manufacturing process, etc.) are identical, after being formed, the battery or battery pack of this embodiment Each electrode is formed into a positive electrode or a negative electrode, respectively.
在本实施例的其它实施方式中，本实施例蓄电池或电池组的正、负极或说所有电极均为彼此等价的正负极通用电极，即，电极被化成后，彼此具有相同的功能和性能，或者，在电极被化成或充放电后，在蓄电池或电池组的工作或使用过程中，不考虑误差因素(例如但不限于制造误差、测量误差)的情况下(即刨除、排除、去掉误差的存在或影响)，本实施例的各电极具有或表现出相同的功能和性能。In other embodiments of the present embodiment, the positive, negative or all electrodes of the battery or the battery pack of the present embodiment are positive and negative common electrodes equivalent to each other, that is, after the electrodes are formed, they have the same function and Performance, or, after the electrode is formed or charged and discharged, in the case of operation or use of the battery or battery pack, regardless of error factors (such as but not limited to manufacturing errors, measurement errors) (ie, remove, eliminate, remove) The presence or influence of the error), the electrodes of this embodiment have or exhibit the same function and performance.
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蓄电池极性反转及其后的充电或充放电操作的时效、能效。In other embodiments of the present embodiment, the polarity inversion of the present example and the polarity inversion in the subsequent charging or charging and discharging operation steps may be performed using a pulse current, a pulse voltage instead of a direct current, a constant voltage, and the like. The charging or charging and discharging step or process is advantageous for improving the aging and energy efficiency of the battery polarity inversion and the subsequent charging or charging and discharging operations of the embodiment.
在本实施例的其它实施方式中，本实施例蓄电池包括正极、负极，或者，本实施例蓄电池正、负电极均为正负极通用电极，本实施例蓄电池的正极、负极、正负极通用电极，包括但不限于，包 括膨胀剂的正极或/和负极、其电极活性物质或活性物质配方中包括膨胀剂的正负极通用电极或/和正极或/和负极、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、彼此为同一种的或相同的正负极通用电极，其中的一种或多种。所述膨胀剂用来防止、抑制、改善电极比表面积收缩或电极活性物质比表面积收缩，所述膨胀剂包括但不限于：硫酸钡、硫酸钙、二氧化硅、硅酸盐、腐殖酸、木素磺酸盐、铝氧化物或氢氧化物、钛氧化物或氢氧化物、锂氧化物或氢氧化物，其中的一种或多种。In other embodiments of the present embodiment, the battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the battery in this embodiment are both positive and negative common electrodes, and the positive electrode, the negative electrode, the positive and negative electrodes of the battery of the embodiment are generally used. Electrode, including but not limited to, a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an active electrode or a negative electrode including an expansion agent in an electrode active material or an active material formulation, and/or a positive electrode or/and a negative electrode, having the same active substance or The positive and negative electrode common electrodes of the same active material formulation, the positive and negative electrode common electrodes of the same active substance, and the positive and negative common electrodes of the same or the same, one or more of them. The expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
在本实施例的其它实施方式中，本实施例上述膨胀剂或硫酸钡在活性物质或活性物质配方中的质量百分比含量大于或等于0.01％、0.02％、0.03％、0.05％、0.08％、0.10％、0.2％、0.3％、0.4％、0.5％、0.6％、0.8％、1％、2％、3％、4％，其中的一种或多种。In other embodiments of the present embodiment, the mass percentage of the above-mentioned expansion agent or barium sulfate in the active substance or active substance formulation of the present embodiment is greater than or equal to 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.10. %, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, one or more of them.
在本实施例的其它实施方式中，本实施例上述膨胀剂或硫酸钡在活性物质或活性物质配方中的质量百分比含量小于或等于5％、10％、20％、30％、40％、50％，其中的一种或多种。In other embodiments of the present embodiment, the mass percentage of the above-mentioned expansion agent or barium sulfate in the active substance or active substance formulation of the present embodiment is less than or equal to 5%, 10%, 20%, 30%, 40%, 50. %, one or more of them.
在本实施例的其它实施方式中，本实施例蓄电池，其正、负极均为正负极通用电极，(1)本实施例蓄电池为铅酸蓄电池，所述正极或/和负极、正负极通用电极或其活性物质或活性物质配方中包括膨胀剂硫酸钡，该硫酸钡在所述正极或/和负极、正负极通用电极或其活性物质或活性物质配方中的质量百分含量为0.01％、0.05％、0.1％、0.4％、0.8％、1.0％、2.0％、10％，其中的一种或多种；或者(2)本实施例蓄电池为铅酸蓄电池，所述正极或/和负极、正负极通用电极或其活性物质或活性物质配方中包括膨胀剂硫酸钡、二氧化硅、硫酸钙，该硫酸钡在所述正极或/和负极、正负极通用电极或其活性物质或活性物质配方中的质量百分含量为0.01％、0.05％、0.1％、0.4％、0.8％、1.0％、2.0％、10％，其中的一种或多种、该二氧化硅、硫酸钙在所述正极或/和负极、正负极通用电极或其活性物质或活性物质配方中的质量百分含量为0.03％、0.05％、0.1％、0.4％、0.8％、1.0％、2.0％、10％，其中的一种或多种；或者(3)本实施例蓄电池为铁－镍蓄电池，所述正极或/和负极、正负极通用电极或其活性物质或活性物质配方中包括膨胀剂氢氧化锂，该氢氧化锂在所述正极或/和负极、正负极通用电极或其活性物质或活性物质配方中的质量百分含量为0.01％、0.05％、0.1％、0.4％、0.8％、1.0％、2.0％、10％，其中的一种或多种。In other embodiments of the present embodiment, in the battery of the embodiment, the positive and negative electrodes are positive and negative common electrodes, and (1) the battery in this embodiment is a lead-acid battery, and the positive electrode or/and the negative electrode, the positive and negative electrodes. The general electrode or its active substance or active substance formulation includes a swelling agent barium sulfate, and the mass percentage of the barium sulfate in the positive electrode or/and the negative electrode, the positive and negative electrode common electrode or the active substance or active substance thereof is 0.01 %, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 10%, one or more of them; or (2) The battery of the embodiment is a lead-acid battery, the positive electrode or/and The negative electrode, the positive and negative electrode common electrode or the active material or active material formulation thereof include a swelling agent barium sulfate, silicon dioxide and calcium sulfate, and the barium sulfate is used in the positive electrode or/and the negative electrode, the positive electrode and the negative electrode or the active material thereof. Or the mass percentage of the active substance formulation is 0.01%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 10%, one or more of the silica, calcium sulfate In the positive or / and negative, positive and negative pass The mass percentage of the electrode or the active substance or active substance thereof is 0.03%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 10%, one or more of them; or (3) The storage battery of the embodiment is an iron-nickel storage battery, and the positive electrode or/and the negative electrode, the positive and negative electrode common electrode or the active material or active material formulation thereof include a swelling agent lithium hydroxide in the positive electrode. Or / and the negative electrode, the positive and negative electrode common electrode or the content of the active substance or active substance in the content of 0.01%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 10%, wherein One or more.
在本实施例的其它实施方式中，本实施例蓄电池，其正、负极均为正负极通用电极，且彼此具有相同活性物质或相同活性物质配方：(1)本实施例蓄电池为铅酸蓄电池，其正极、负极的活性物质或活性物质配方均为：铅粉或氧化铅粉100Kg、短纤维0.06Kg、乙炔黑0.28Kg、硫酸钡0.8Kg、硫酸溶液(硫酸的质量百分含量为45％)8.7Kg、水8.25Kg；或者(2)本实施例蓄电池为铅酸蓄电池，其正极、负极的活性物质或活性物质配方均为：铅粉或氧化铅粉100Kg、木素0.16Kg、腐殖酸0.2Kg、硫酸钡0.4Kg、二氧化硅0.06Kg、硫酸溶液(硫酸的质量百分含量为45％)8.7Kg、水8.25Kg；或者(3)本实施例蓄电池为铁-高铁酸盐蓄电池，其正极、负极的活性物质或活性物质配方均为：铁粉或氧化铁粉100Kg、氢氧化锂0.2Kg、氢氧化钡0.4Kg、氢氧化钾溶液(氢氧化钾的质量百分含量为40％)8Kg、水8Kg；In other embodiments of the present embodiment, the battery of the embodiment has positive and negative electrodes which are positive and negative common electrodes, and have the same active substance or the same active substance formula as each other: (1) The battery of the embodiment is a lead-acid battery. The active material or active substance formula of the positive electrode and the negative electrode are: lead powder or lead oxide powder 100Kg, short fiber 0.06Kg, acetylene black 0.28Kg, barium sulfate 0.8Kg, sulfuric acid solution (sulfuric acid content is 45%) 8.7Kg, water 8.25Kg; or (2) The battery of this embodiment is a lead-acid battery, and the active material or active substance of the positive electrode and the negative electrode are: lead powder or lead oxide powder 100Kg, lignin 0.16Kg, humic Acid 0.2Kg, barium sulfate 0.4Kg, silica 0.06Kg, sulfuric acid solution (45% by mass of sulfuric acid) 8.7Kg, water 8.25Kg; or (3) Battery of this embodiment is iron-ferrate battery The active material or active substance formula of the positive electrode and the negative electrode are: iron powder or iron oxide powder 100Kg, lithium hydroxide 0.2Kg, barium hydroxide 0.4Kg, potassium hydroxide solution (potassium hydroxide mass percentage is 40 %) 8Kg, water 8Kg;
或者，进一步的，本实施例蓄电池，其正极、负极、正负极通用电极，不仅彼此具有如上所述的相同活性物质或相同活性物质配方，且在被进行化成或充放电之前，彼此相同，即，电极被化成之前，所述所有电极或所述正极、负极、正负极通用电极，彼此在各方面，例如但不限于集流体、活性物质配方和活性物质质量(例如但不限于铅膏配方和铅膏质量)、制做工艺等方面，完全相同(即，在各方面都相同)，或者，不考虑制造电极时产生的制造误差(即刨除、排除、去掉制造误差的存在或影响)，所述正极、负极、正负极通用电极在被进行化成或充放电操作之前，彼此具有或采用的集流体、和膏工艺、涂片或灌粉工艺、固化或烧结工艺以及所有其它电极构成、制造方面完全相同。Or, further, the positive electrode, the negative electrode, and the positive and negative electrode common electrodes of the battery of the present embodiment not only have the same active substance or the same active substance formulation as described above, but are identical to each other before being chemicalized or charged and discharged. That is, before the electrode is formed, all of the electrodes or the positive electrode, the negative electrode, the positive and negative electrode common electrodes are in various aspects, such as but not limited to a current collector, an active substance formulation, and an active substance mass (such as but not limited to a lead paste). The formulation and the quality of the lead paste), the manufacturing process, etc. are identical (ie, the same in all respects), or, regardless of the manufacturing error (ie, the removal or elimination, the removal of the manufacturing error or the influence) caused by the manufacture of the electrode. The positive electrode, the negative electrode, the positive and negative electrode common electrodes have a current collector or a paste process, a smear or powder filling process, a curing or sintering process, and all other electrodes formed before or after being subjected to a chemical formation or charge and discharge operation. And manufacturing is exactly the same.
在本实施例的其它实施方式中，本实施例蓄电池，其正、负极均为彼此等价的正负极通用电极，所述电极被化成后，在某一工作充电、放电条件下(例如但不限于：先0.14C恒流充电5小时，再恒压充电4小时，再0.05C恒流充电2小时，然后0.5C倍率放电，环境温度为25℃，C为蓄电池的额定容量)，本实施例蓄电池、正极、负极、正负极通用电极在第1次极性反转后的第1次－第21次的循环充电、放电过程中所表现出的该21次正向放电容量的平均值为10Ah，然后，将该蓄电池的正极、负极的极性进行第2次反转，使所述第1次极性反转后的正极被反转成负极，使所述第1次极性反转后的负极被反转成正极，然后，将该第2次极性反转后所形成的负极、该第2次极性反转后所形成的正极，在相同的充电、放电条件下(例如但不限于：先0.14C恒流充电5小时，再恒压充电4小时，再0.05C恒流充电2小时，然后0.5C倍率放电，环境温度为25℃，C为蓄电池的额定容量)进行循环充电、放电，获得本实施例蓄电池、正极、负极、正负极通用电极在该第2次极性反转后第1次－第21次的循环充电、放电过程中所表现出的该21次反向放电的容量的平均值为10.5Ah，在排除、去掉制造、测试等所引起的0.5Ah误差的情况下(即不考虑误差因素的情况下)，所述正极、负极、正负极通用电极在同一种极性下的充电或/和放电性能彼此相同，或者认为，所述正极、负极、正负极通用电极其在同一种极性下的充电或/和放电性能彼此相同，而0.5Ah的放电容量平均值的差值属于彼此间的正常误差。In other embodiments of the present embodiment, in the battery of the embodiment, the positive and negative electrodes are positive and negative common electrodes equivalent to each other, and the electrodes are formed into a working charging and discharging condition (for example, Not limited to: first 0.14C constant current charging for 5 hours, then constant voltage charging for 4 hours, then 0.05C constant current charging for 2 hours, then 0.5C rate discharge, ambient temperature is 25 ° C, C is the rated capacity of the battery), this implementation The average value of the 21 positive discharge capacities exhibited by the battery, the positive electrode, the negative electrode, and the positive and negative electrode common electrodes during the first to the 21st cycle charge and discharge after the first polarity inversion. When it is 10 Ah, the polarity of the positive electrode and the negative electrode of the battery is reversed for the second time, and the positive electrode after the first polarity inversion is inverted to the negative electrode, and the first polarity is reversed. The turned-off negative electrode is inverted into a positive electrode, and then the negative electrode formed by inverting the second polarity and the positive electrode formed after the second polarity is inverted are subjected to the same charging and discharging conditions ( For example, but not limited to: first 0.14C constant current charging for 5 hours, then constant voltage charging for 4 hours, then 0 .05C constant current charging for 2 hours, then 0.5C rate discharge, ambient temperature is 25 ° C, C is the rated capacity of the battery) for cyclic charging and discharging, obtaining the battery, positive electrode, negative electrode, positive and negative electrode common electrode of the present embodiment The average value of the 21st reverse discharge capacities exhibited during the first to the 21st cycle charging and discharging after the second polarity inversion is 10.5 Ah, and the manufacturing and testing are excluded or removed. In the case of a 0.5Ah error (ie, without considering the error factor), the positive, negative, positive and negative common electrodes have the same charge or/and discharge performance under the same polarity, or The positive electrode, the negative electrode, the positive and negative electrode common electrodes have the same charging or/and discharging performance under the same polarity, and the difference in the average value of the discharge capacity of 0.5 Ah belongs to a normal error between each other.
所述正向充电或/和放电，是指正极、负极、正负极通用电极在被进行某次极性反转之前，进行或被进行的充电、放电；所述反向充电或/和放电，是指正极、负极、正负极通用电极在被进行该某次极性反转之后，进行或被进行的充电、放电。The forward charging or/and discharging refers to charging and discharging performed or performed before the positive polarity, the negative electrode, and the positive and negative electrode common electrodes are subjected to a certain polarity inversion; the reverse charging or/and discharging It refers to charging and discharging that are performed or performed after the positive polarity, the negative electrode, and the positive and negative electrode common electrodes are subjected to the polarity reversal.
本实施例方法使蓄电池或电池组的使用寿命获得显著提高或延长，当放电深度(DOD)包括但不限于1-100％时，本实施例方法使蓄电池或电池组的使用寿命提高或延长至1.3倍以上－10倍以上，或/和，循环寿命提高或延长了50次以上－500次以上、500次以上－3000次以上，其中的一种或多种。The method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack. When the depth of discharge (DOD) includes but is not limited to 1-100%, the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
实施例5Example 5
本实施例解决蓄电池正极活性物质膨胀、软化、脱落问题或/和提高或延长蓄电池或电池组的使用寿命的方法，包括在蓄电池或电池组的浮充工作过程中，穿插地对本实施例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4)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、防止蓄电池或电池组的正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题，使本实施例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蓄电池或蓄电池组进行正、负极极性反转及其后的充电或充放电操作。The present embodiment solves the problem that the positive electrode active material expands, softens, falls off, or/and increases or prolongs the service life of the battery or the battery pack, including interspersed with the battery of the embodiment or during the floating operation of the battery or the battery pack. The polarity of the positive and negative polarities described in the above or all of the above embodiments of the present invention (i.e., the first embodiment to the fourth embodiment) are the same or similar to the total cumulative number of times of the battery pack. Charging or charging and discharging operations to improve, repair, reverse, eliminate, inhibit, prevent expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization of the positive active material of the battery or battery pack Reducing or reducing or reducing the working capacity of the battery or the battery pack of the present embodiment by one or more problems, such as shrinkage of the specific surface area of the negative electrode, poor contact of the active material with the conductive current collector, memory effect, and decomposition of the active material itself. Drop, and then put the battery or battery pack of this embodiment into the floating charge work until it is triggered again or start this implementation again. For example, the battery or the battery pack performs positive and negative polarity inversion and subsequent charging or charging and discharging operations.
本实施例方法使蓄电池或电池组的使用寿命获得显著提高或延长，当放电深度(DOD)包括但不限于1-100％时，本实施例方法使蓄电池或电池组的使用寿命提高或延长至1.3倍以上－10倍以上，或/和，循环寿命提高或延长了50次以上－500次以上、500次以上－3000次以上，其中的一种或多种。The method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack. When the depth of discharge (DOD) includes but is not limited to 1-100%, the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
实施例6Example 6
本实施例的蓄电池为铁-镍蓄电池或铁－高铁酸盐蓄电池，额定容量为10Ah(C 5，5h，25℃)，当本实施例的蓄电池因为正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题而导致工作放电容量下降或者循环工作寿命终止时，通过充放电设备对本实施例蓄电池进行正、负极极性反转及其后的充电或充放电操作，来解决本实施例蓄电池的正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题，以提高或延长本实施例蓄电池的使用寿命。 The battery of this embodiment is an iron-nickel battery or an iron-ferrate battery, and has a rated capacity of 10 Ah (C 5, 5 h, 25 ° C). When the battery of this embodiment is expanded or/and softened or/and Shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact of active material with conductive current collector, memory effect, decomposition of active material itself, one or more problems leading to work When the discharge capacity is decreased or the cycle working life is terminated, the positive and negative polarity inversion and subsequent charging or charging and discharging operations of the battery of the embodiment are performed by the charging and discharging device to solve the expansion or/and the positive active material of the battery of the embodiment. Softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact of active material with conductive current collector, memory effect, decomposition of active substance itself, one or more The problem is to increase or lengthen the service life of the battery of this embodiment.
对本实施例蓄电池进行正、负极极性反转及其后的充电或充放电操作的步骤包括：(1)通过反极充电的方法，使本实施例蓄电池发生极性反转，即将正电极(镍电极或高铁酸盐电极，定义为电极A)与本实施例充放电设备的负输出端相连接、将负电极(铁电极、定义为电极B)与本实施例充放电设备的正输出端相连接，然后对电极A、B进行1/2C 5电流充电，使得最终电极B的极性相对于电极A的极性为正、电极A的极性相对电极B的极性为负，且当电极A、电极B的极性发生反转后，保持该极性状态，以C 5的电流继续充电5小时；然后(2)以C 5的电流对此两电极进行放电至0V；然后(3)将电极A与本实施例充放电设备的正输出端相连接、将电极B与本实施例充放电设备的负输出端相连接，然后对电极A、电极B进行1/2C 5电流充电，使得最终电极B的极性相对于电极A的极性为负、电极A的极性相对于电极B的极性为正，经过上述正、负极极性反转及其后的充电或充放电操作，解决、改善了正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题，使本实施例蓄电池的工作放电容量得到提高或恢复到正常的 额定容量值，从而使得本实施例蓄电池的使用寿命获得提高或延长。 The steps of performing the positive and negative polarity inversion and the subsequent charging or charging and discharging operations on the battery of the embodiment include: (1) the polarity reversal of the battery of the embodiment is performed by the method of reverse polarity charging, that is, the positive electrode ( A nickel electrode or a ferrate electrode is defined as an electrode A) connected to the negative output end of the charge and discharge device of the present embodiment, and a negative electrode (iron electrode, defined as electrode B) and a positive output terminal of the charge and discharge device of the embodiment. Connected, and then 1/2C 5 current charging of electrodes A, B, so that the polarity of the final electrode B is positive with respect to the polarity of the electrode A, the polarity of the electrode A is negative with respect to the polarity of the electrode B, and After the polarity of the electrode A and the electrode B are reversed, the polarity state is maintained, and the current of C 5 is continuously charged for 5 hours; then (2) the two electrodes are discharged to 0 V with a current of C 5 ; then (3) The electrode A is connected to the positive output end of the charging and discharging device of the embodiment, the electrode B is connected to the negative output end of the charging and discharging device of the embodiment, and then the electrode A and the electrode B are charged with 1/2 C 5 current. The polarity of the final electrode B is made negative with respect to the polarity of the electrode A, and the electrode A The polarity is positive with respect to the polarity of the electrode B, and the positive or negative polarity inversion and subsequent charging or charging and discharging operations solve and improve the expansion or/and softening or/and shedding and corrosion of the positive active material. Passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact of active material with conductive current collector, memory effect, decomposition of active material itself, one or more problems of the battery of this embodiment The working discharge capacity is increased or restored to a normal rated capacity value, thereby increasing or prolonging the service life of the battery of this embodiment.
在本实施例的其它实施方式中，完成上述第(1)步骤后，电极A的极性为负、电极B的极性为正，在此极性状态下，使本实施例蓄电池投入到工作中充放循环使用，此操作方法也解决、改善了正极活性物质膨胀或/和软化或/和脱落、腐蚀、钝化、早期容量损失、盐化、结晶化、负极比表面积收缩、活性物质与导电集流体接触不良、记忆效应、活性物质自身分解，其中的一种或多种问题，使本实施例蓄电池的工作放电容量得到提高或恢复到正常的额定容量值，从而使得本实施例蓄电池的使用寿命获得提高或延长。In other embodiments of the present embodiment, after the step (1) is completed, the polarity of the electrode A is negative, and the polarity of the electrode B is positive. In this polarity state, the battery of the embodiment is put into operation. In the middle of charge and discharge cycle, this method also solves and improves the expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative surface area shrinkage, active substance and The contact current of the conductive current collector, the memory effect, and the decomposition of the active material itself, one or more problems, the working discharge capacity of the battery of the embodiment is improved or restored to a normal rated capacity value, thereby making the battery of the embodiment The service life is increased or extended.
在本实施例的其它实施方式中，本实施例蓄电池包括正极、负极，或者，本实施例蓄电池正、负电极均为正负极通用电极，本实施例蓄电池的正极、负极、正负极通用电极，包括但不限于，包括膨胀剂的正极或/和负极、其电极活性物质或活性物质配方中包括膨胀剂的正负极通用电极或/和正极或/和负极、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、彼此为同一种的或相同的正负极通用电极，其中的一种或多种。所述膨胀剂用来防止、抑制、改善电极比表面积收缩或电极活性物质比表面积收缩，所述膨胀剂包括但不限于：硫酸钡、硫酸钙、二氧化硅、硅酸盐、腐殖酸、木素磺酸盐、铝氧化物或氢氧化物、钛的氧化物或氢氧化物、锂的氧化物或氢氧化物，其中的一种或多种。In other embodiments of the present embodiment, the battery of the embodiment includes a positive electrode and a negative electrode, or the positive and negative electrodes of the battery in this embodiment are both positive and negative common electrodes, and the positive electrode, the negative electrode, the positive and negative electrodes of the battery of the embodiment are generally used. Electrode, including but not limited to, a positive electrode or/and a negative electrode including a swelling agent, a positive electrode active electrode or an active electrode or a negative electrode including an expansion agent in an electrode active material or an active material formulation, and/or a positive electrode or/and a negative electrode, having the same active substance or The positive and negative electrode common electrodes of the same active material formulation, the positive and negative electrode common electrodes of the same active substance, and the positive and negative common electrodes of the same or the same, one or more of them. The expansion agent is used to prevent, inhibit, and improve the specific surface area shrinkage of the electrode or the specific surface area shrinkage of the electrode active material, including but not limited to: barium sulfate, calcium sulfate, silicon dioxide, silicate, humic acid, Lignosulfonate, aluminum oxide or hydroxide, titanium oxide or hydroxide, lithium oxide or hydroxide, one or more of them.
在本实施例的其它实施方式中，本实施例上述膨胀剂在活性物质或活性物质配方中的质量百分比含量大于或等于0.01％、0.02％、0.03％、0.05％、0.08％、0.10％、0.2％、0.3％、0.4％、0.5％、0.6％、0.8％、1％、2％、3％、4％，其中的一种或多种。In other embodiments of the present embodiment, the mass percentage of the above-mentioned expansion agent in the active substance or active substance formulation of the present embodiment is greater than or equal to 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.10%, 0.2. %, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, one or more of them.
在本实施例的其它实施方式中，本实施例上述膨胀剂在活性物质或活性物质配方中的质量百分比含量小于或等于5％、10％、20％、30％、40％、50％，其中的一种或多种。In other embodiments of the present embodiment, the mass percentage of the above-mentioned expansion agent in the active substance or active substance formulation of the present embodiment is less than or equal to 5%, 10%, 20%, 30%, 40%, 50%, wherein One or more.
本实施例方法使蓄电池或电池组的使用寿命获得显著提高或延长，当放电深度(DOD)包括但不限于1-100％时，本实施例方法使蓄电池的使用寿命提高或延长至1.3倍以上－10倍以上，或/和，循环寿命提高或延长了50次以上－500次以上、500次以上－3000次以上，其中的一种或多种。The method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack. When the depth of discharge (DOD) includes but is not limited to 1-100%, the method of the embodiment increases or extends the service life of the battery to 1.3 times or more. -10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.
实施例7Example 7
本实施例相同于或包括中国专利申请201710975570.6中所述的实施例1-21、中国专利申请201710975698.2中所述的实施例1-21及23、中国专利申请201710975569.3中所述的实施例1-21及23、中国专利申请201810452604.8中所述的实施例1-3、中国专利申请201811297354.1中所述的实施例1-9、中国专利申请201811296518.9中所述的实施例1-10。The present embodiment is the same as or includes the embodiments 1-21 and 23 described in the Chinese Patent Application No. 201710975570.6, and the examples 1-21 and 23 described in the Chinese Patent Application No. 201710975568.2. And Examples 1-10 described in Examples 1-3 of the Chinese Patent Application No. 201810452604.8, Examples 1-9 described in Chinese Patent Application No. 201811297354.1, and Chinese Patent Application No. 201811296518.9.
本实施例方法使蓄电池或电池组的使用寿命获得显著提高或延长，当放电深度(DOD)包括但不限于1-100％时，本实施例方法使蓄电池或电池组的使用寿命提高或延长至1.3倍以上－10倍以上，或/和，循环寿命提高或延长了50次以上－500次以上、500次以上－3000次以上，其中的一种或多种。The method of the embodiment provides a significant increase or extension of the service life of the battery or the battery pack. When the depth of discharge (DOD) includes but is not limited to 1-100%, the method of the embodiment increases or extends the service life of the battery or the battery pack to 1.3 times or more and 10 times or more, or / and, the cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, one or more of them.

Claims (10)

  1. 一种解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，其特征在于，包括使所述蓄电池或/和蓄电池组的正极或正极活性物质进行蓄电池负极电极反应，或通过电化学还原反应而被还原成金属或0化合价。A method for solving the problem of expansion, softening and shedding of a positive electrode active material of a battery, characterized in that it comprises reacting a positive electrode or a positive electrode active material of the battery or/and a battery pack with a negative electrode of a battery or by an electrochemical reduction reaction Reduced to metal or 0 valence.
  2. 一种解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，其特征在于，包括将所述蓄电池或/和蓄电池组的正极或/和负极进行极性反转及其后的充电或充放电操作，该操作的总累计次数≥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。A method for solving the problem of expansion, softening and falling off of a positive electrode active material of a battery, characterized in that it comprises performing polarity reversal of the positive or/and negative electrode of the battery or/and battery group and subsequent charging or charging and discharging operations The total cumulative number of operations is ≥1 times; the polarity is reversed and the subsequent charging or charging and discharging operations are performed, that is, the polarity of the positive electrode and the negative electrode are reversed, and at the pole After the polarity is reversed, the electrode that has undergone the polarity inversion is charged or charged and discharged.
  3. 根据权利要求2所述解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，其特征在于，所述蓄电池其正极或/和负极的活性物质为具有二种或二种以上稳定氧化价态的元素的单质、化合物中的一种或多种；所述具有二种或二种以上稳定氧化价态的元素包括但不限于：铅、铁、铜、镍、锰、银、磷、硫、氯、钒、铬、钴、砷、硒、溴、锡、锑、碲、碘、钨、铋其中的一种或多种。A method for solving the problem of expansion, softening, and shedding of a positive electrode active material of a battery according to claim 2, wherein the active material of the positive electrode or/and the negative electrode of the battery is an element having two or more stable oxidation valence states. One or more of a simple substance or a compound; the element having two or more stable oxidation valence states includes, but is not limited to, lead, iron, copper, nickel, manganese, silver, phosphorus, sulfur, chlorine, One or more of vanadium, chromium, cobalt, arsenic, selenium, bromine, tin, antimony, bismuth, iodine, tungsten, and antimony.
  4. 根据权利要求1－3任一项所述解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，其特征在于，所述蓄电池或蓄电池组，包括但不限于：铅酸蓄电池、铁-镍蓄电池、铁-高铁酸盐电池、铜-高铁酸盐电池、镉-镍蓄电池的电池或电池组，其中的一种或多种。The method for solving the problem of expansion, softening, and falling off of a positive electrode active material of a battery according to any one of claims 1 to 3, wherein the battery or battery pack includes, but is not limited to, a lead-acid battery, an iron-nickel battery, One or more of an iron-ferrate battery, a copper-ferrate battery, a battery or a battery of a cadmium-nickel battery.
  5. 根据权利要求2所述解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，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蓄电池或电池组的工作，彼此穿插、交替地进行，并使所述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，所述蓄电池或电池组的正极、负极。A method for solving the problem of expansion, softening, and shedding of a positive electrode active material of a battery according to claim 2, wherein said positive or negative polarity is reversed and subsequent charging or charging and discharging operations are performed, including said positive The reverse polarity polarity inversion and subsequent charging or charging and discharging operations and the operation of the battery or the battery pack are interspersed and alternately performed, and when the battery or the battery pack is in operation, its original positive electrode and original The negative electrode is in one of the following three electrode operating states: (1) 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 (3) The original positive electrode may operate as a positive electrode or 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 The negative electrode is charged or charged and discharged without being subjected to any of the positive and negative polarity inversions The positive electrode and the negative electrode of the battery or the battery pack.
  6. 根据权利要求1-5任一项所述解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，其特征在于，所述方法也用于单独地解决蓄电池的其他问题，或在解决蓄电池正极活性物质膨胀、软化、脱落问题的同时也用于解决蓄电池的其他问题，所述其他问题包括但不限于：蓄电池的腐蚀、钝化、盐化、结晶化、负极比表面积收缩、活性物质与集流体接触不良或/和脱落、早期容量损失、记忆效应、活性物质自身分解问题，其中的一种或多种。A method for solving the problem of expansion, softening, and shedding of a positive electrode active material of a battery according to any one of claims 1 to 5, characterized in that the method is also used to solve other problems of the battery alone or to solve the positive electrode active material of the battery. The problems of expansion, softening and shedding are also used to solve other problems of the battery, including but not limited to: corrosion, passivation, salinization, crystallization of the battery, shrinkage of the specific surface area of the anode, contact of the active material with the current collector. Poor or / and shedding, early capacity loss, memory effect, active substance decomposition, one or more of them.
  7. 根据权利要求1-5任一项所述解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，其特征在于，所述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；所述正极、负极、正负极通用电极包括但不限于：包括膨胀剂的正极或/和负极、 其电极活性物质或活性物质配方中包括膨胀剂的正负极通用电极或/和正极或/和负极、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、彼此为同一种的或相同的正负极通用电极，其中的一种或多种；所述膨胀剂用来防止、抑制、改善电极比表面积收缩或电极活性物质比表面积收缩。The method for solving the problem of expansion, softening, and shedding of a positive electrode active material of a battery according to any one of claims 1 to 5, wherein the positive electrode and the negative electrode of the battery or the battery are both positive and negative common electrodes, and the positive electrode a negative electrode common electrode in which the battery or the battery pack can be used as a positive electrode or a negative electrode, or used as a positive electrode, some as a negative electrode, or used or used in the battery or battery pack. In the process, when used as a positive electrode at a time, and sometimes used as a negative electrode, one or more of them; the positive electrode, the negative electrode, the positive and negative electrode common electrodes include, but are not limited to, a positive electrode or/and a negative electrode including a swelling agent, The electrode active material or active material formulation includes positive and negative electrode common electrodes of the expansion agent or/and a positive electrode or/and a negative electrode, positive and negative electrode common electrodes having the same active substance or the same active substance formula, and equivalent positive and negative a very common electrode, one or more of the same or the same positive and negative electrode of the same type; the expansion agent is used to prevent, suppress, change Good electrode specific surface area shrinkage or electrode active material specific surface area shrinkage.
  8. 根据权利要求7所述解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，其特征在于，所述膨胀剂包括但不限于：硫酸钡、硫酸钙、二氧化硅、硅酸盐、腐殖酸、木素磺酸盐、铝的氧化物或氢氧化物、钛的氧化物或氢氧化物、锂的氧化物或氢氧化物，其中的一种或多种。The method for solving the problem of expansion, softening and shedding of a positive electrode active material of a battery according to claim 7, wherein the expansion agent comprises, but not limited to, barium sulfate, calcium sulfate, silica, silicate, humic acid. , one or more of a lignosulfonate, an oxide or hydroxide of aluminum, an oxide or hydroxide of titanium, an oxide or hydroxide of lithium.
  9. 根据权利要求8所述解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，其特征在于，所述膨胀剂在活性物质或活性物质配方中的质量百分含量为0.01％-50％。The method for solving the problem of expansion, softening, and shedding of a positive electrode active material of a battery according to claim 8, wherein the expansion agent has a mass percentage of 0.01% to 50% in the active material or active substance formulation.
  10. 根据权利要求1－3、5、8－9任一项所述解决蓄电池正极活性物质膨胀、软化、脱落问题的方法，其特征在于，所述方法通过一种电路实现、实施，所述电路具有将蓄电池或/和蓄电池组的正极、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；或者，所述电路能对所述蓄电池或蓄电池组进行反极充电、强制放电、反接后充电，其中的一种或多种。The method for solving the problem of expansion, softening, and shedding of a positive electrode active material of a battery according to any one of claims 1-3, 5, and 8-9, wherein the method is implemented and implemented by a circuit having The function of performing polarity reversal or polarity inversion and subsequent charging or charging and discharging operations on the positive and negative electrodes of the battery or/and the battery pack, the total cumulative number of times the circuit can or actually implement or implement the function is ≥ 1 time; or, the circuit can perform reverse polarity charging, forced discharging, reverse charging and charging, or one or more of the battery or battery pack.
PCT/CN2018/113859 2017-11-05 2018-11-03 Method for solving problems of expanding, softening, and falling-off of positive electrode active substance of storage battery WO2019086021A1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CN201711073862 2017-11-05
CN201711073862.7 2017-11-05
CN201711073854 2017-11-05
CN201711073858 2017-11-05
CN201711073858.0 2017-11-05
CN201711073854.2 2017-11-05

Publications (1)

Publication Number Publication Date
WO2019086021A1 true WO2019086021A1 (en) 2019-05-09

Family

ID=64998413

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/CN2018/113860 WO2019086022A1 (en) 2017-11-05 2018-11-03 Long-life storage battery
PCT/CN2018/113859 WO2019086021A1 (en) 2017-11-05 2018-11-03 Method for solving problems of expanding, softening, and falling-off of positive electrode active substance of storage battery

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/113860 WO2019086022A1 (en) 2017-11-05 2018-11-03 Long-life storage battery

Country Status (2)

Country Link
CN (9) CN117810567A (en)
WO (2) WO2019086022A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220057564A (en) * 2019-09-03 2022-05-09 다라믹 엘엘씨 Improved lead acid battery separator incorporating carbon, and improved battery, system, vehicle, and related methods
CN110649228B (en) * 2019-11-26 2020-03-10 湖南丰日电源电气股份有限公司 Storage battery polar plate
CN111146408B (en) * 2020-02-11 2022-11-29 河南创力新能源科技股份有限公司 Preparation method of iron-nickel battery cathode
CN112103573B (en) * 2020-08-07 2021-10-22 天能电池集团股份有限公司 Method for determining acid absorption saturation of valve-controlled lead storage battery
CN113422047B (en) * 2021-05-20 2022-10-28 风帆有限责任公司 Lead storage battery capable of being started normally in low-charge state
CN114597354B (en) * 2022-02-25 2024-08-30 天能电池集团股份有限公司 Positive electrode lead paste of lead storage battery, preparation method of positive electrode lead paste and lead storage battery

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1874049A (en) * 2006-06-16 2006-12-06 果崇贤 Method for prolonging service life of accumulator
CN101150211A (en) * 2007-10-13 2008-03-26 胡松柏 Forward and reverse charging and activation method for lead acid accumulator jar
CN102082305A (en) * 2010-12-21 2011-06-01 无锡市霄鹰环境科技有限公司 Ionic lead-acid cell repair protection solution
CN103633389A (en) * 2013-11-26 2014-03-12 河南超威电源有限公司 Lead-acid storage battery container formation process
CN107732338A (en) * 2016-10-27 2018-02-23 杨春晓 The method for improving or extending lead-acid accumulator or battery pack service life
CN107742748A (en) * 2016-10-27 2018-02-27 杨春晓 Lead-acid accumulator or battery pack with the long life
CN107768752A (en) * 2016-10-27 2018-03-06 杨春晓 Raising extends lead-acid accumulator or the device of battery pack service life
CN108011133A (en) * 2016-10-27 2018-05-08 杨春晓 Raising extends lead-acid accumulator or the circuit of battery pack service life

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1525590A (en) * 2003-02-24 2004-09-01 昆明倍特瑞电化学有限公司 Method for preparing positive and negative electrode interchanged storage cell
CN1265496C (en) * 2003-11-27 2006-07-19 苏州市安珀电器有限公司 Waste lead-acid battery repairing machine
CN100570944C (en) * 2006-11-23 2009-12-16 常易宸 A kind of method of reviver acid accumulator
CN100495807C (en) * 2007-07-24 2009-06-03 卧龙电气集团股份有限公司 Recovery method for abnormal capacity loss of storage battery
CN201149885Y (en) * 2007-12-18 2008-11-12 焦义初 Positive-negative ion accumulator repairing instrument
CN101459258A (en) * 2009-01-06 2009-06-17 江苏优德电源科技有限公司 Internal chemical synthetic reverse charging chemical process for lead acid battery
CN102306799B (en) * 2010-03-24 2014-12-10 衡阳瑞达电源有限公司 Deep cycle-resistant lead-acid storage battery plate and manufacturing method
CN102013530B (en) * 2010-11-05 2013-09-04 江西省电力科学研究院 Antipole repair method for irreversible vulcanization of 2V high-capacity lead-acid storage battery cathode
CN103782442A (en) * 2011-09-01 2014-05-07 新神户电机株式会社 Lead storage cell
CN102593529B (en) * 2012-02-24 2014-08-27 中南大学 Variable-polarity lead-acid battery and using method thereof
CN103909827A (en) * 2013-12-31 2014-07-09 崔玲 Intelligent electric vehicle instrument
JP6333595B2 (en) * 2014-03-26 2018-05-30 古河電池株式会社 Storage battery system operation method and storage battery system operation device
CN105098263A (en) * 2014-05-14 2015-11-25 上海欧顿医药科技有限公司 Method for detecting, balancing and restoring six-block lead-acid storage battery
JP6299417B2 (en) * 2014-05-19 2018-03-28 Tdk株式会社 Secondary battery charge / discharge control system
CN107017436A (en) * 2016-01-28 2017-08-04 杨春晓 Lead-acid accumulator and lead-acid batteries
CN106129357B (en) * 2016-07-14 2019-02-12 安徽轰达电源有限公司 Deep glue-type spy consolidates lead carbon battery lead plaster
CN108649287A (en) * 2017-05-26 2018-10-12 杨春晓 A kind of lead-acid accumulator or battery pack
CN108550936A (en) * 2017-11-05 2018-09-18 杨春晓 A kind of lead-acid batteries

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1874049A (en) * 2006-06-16 2006-12-06 果崇贤 Method for prolonging service life of accumulator
CN101150211A (en) * 2007-10-13 2008-03-26 胡松柏 Forward and reverse charging and activation method for lead acid accumulator jar
CN102082305A (en) * 2010-12-21 2011-06-01 无锡市霄鹰环境科技有限公司 Ionic lead-acid cell repair protection solution
CN103633389A (en) * 2013-11-26 2014-03-12 河南超威电源有限公司 Lead-acid storage battery container formation process
CN107732338A (en) * 2016-10-27 2018-02-23 杨春晓 The method for improving or extending lead-acid accumulator or battery pack service life
CN107742748A (en) * 2016-10-27 2018-02-27 杨春晓 Lead-acid accumulator or battery pack with the long life
CN107768752A (en) * 2016-10-27 2018-03-06 杨春晓 Raising extends lead-acid accumulator or the device of battery pack service life
CN108011133A (en) * 2016-10-27 2018-05-08 杨春晓 Raising extends lead-acid accumulator or the circuit of battery pack service life

Also Published As

Publication number Publication date
CN109755672A (en) 2019-05-14
CN117810567A (en) 2024-04-02
CN116742153A (en) 2023-09-12
CN117175024A (en) 2023-12-05
CN109273779A (en) 2019-01-25
CN109216805A (en) 2019-01-15
CN109755671A (en) 2019-05-14
CN109755577A (en) 2019-05-14
WO2019086022A1 (en) 2019-05-09
CN109361027A (en) 2019-02-19

Similar Documents

Publication Publication Date Title
WO2019086021A1 (en) Method for solving problems of expanding, softening, and falling-off of positive electrode active substance of storage battery
CN102593529B (en) Variable-polarity lead-acid battery and using method thereof
CN101599559A (en) Desulphurization recovery technology for battery
CN107732338A (en) The method for improving or extending lead-acid accumulator or battery pack service life
CN113178574B (en) Positive pole lead plaster of lead-acid storage battery and bipolar horizontal storage battery containing positive pole lead plaster
JP2001028263A (en) Lead-acid battery formation method
JP4140277B2 (en) Control valve type lead acid battery
WO2018166409A1 (en) Lead-acid battery or battery pack with long service life
JP2008071717A (en) Method of chemical conversion of lead-acid battery
CN201629386U (en) On-line restoration device for lead-acid storage battery
CN107768752A (en) Raising extends lead-acid accumulator or the device of battery pack service life
WO2018166407A1 (en) Method for improving or prolonging service life of lead-acid storage battery or battery pack
WO2018166408A1 (en) Device for improving or prolonging service life of lead-acid battery or battery pack
JP2002289168A (en) Control valve type lead storage battery
CN108649287A (en) A kind of lead-acid accumulator or battery pack
JP2003346890A (en) Valve regulated lead-acid battery and its manufacturing method
JP4742424B2 (en) Control valve type lead acid battery
CN101728531A (en) Anode material of nickel-hydrogen power battery and preparation method thereof
JP4999309B2 (en) Alkaline storage battery
JP2546665B2 (en) Alkaline battery
JP2001351695A (en) Recharging method of plural alkali water solution secondary cells for backup use connected in parallel
CN108565507A (en) The method for enhancing, safeguarding ability to work after lead-acid accumulator or battery pack storage life, storage
JP2975673B2 (en) Method for producing cadmium negative electrode plate
MATSUMOTO et al. Trends in secondary batteries for portable electronic equipment
JPH0810590B2 (en) Method for manufacturing sealed lead acid battery and electrode plate for sealed lead acid battery

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18872483

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 17/08/2020)

122 Ep: pct application non-entry in european phase

Ref document number: 18872483

Country of ref document: EP

Kind code of ref document: A1