WO2019086022A1 - Long-life storage battery - Google Patents

Long-life storage battery Download PDF

Info

Publication number
WO2019086022A1
WO2019086022A1 PCT/CN2018/113860 CN2018113860W WO2019086022A1 WO 2019086022 A1 WO2019086022 A1 WO 2019086022A1 CN 2018113860 W CN2018113860 W CN 2018113860W WO 2019086022 A1 WO2019086022 A1 WO 2019086022A1
Authority
WO
WIPO (PCT)
Prior art keywords
battery
electrode
positive
charging
lead
Prior art date
Application number
PCT/CN2018/113860
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 WO2019086022A1 publication Critical patent/WO2019086022A1/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
    • H01M10/06—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
    • 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 battery, in particular to a long-life battery.
  • the battery can be recharged and discharged, which can greatly reduce the production, living and environmental protection costs of the society.
  • the technical problem to be solved by the present invention is to provide a long-life battery which has a long life because it can or advantageously helps to overcome and solve some battery problems, including but not Limited to positive electrode active material expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salting, crystallization, negative electrode specific surface area shrinkage, poor contact of active material with conductive current collector, memory effect, active substance Decomposition by itself, one or more of these problems.
  • the salinization includes, but is not limited to, sulfation.
  • the life including but not limited to, the service life, including but not limited to: cycle life, float life, storage or storage life, one or more of them.
  • 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 long-life battery comprising a positive electrode and a negative electrode, wherein the positive and negative electrodes of the battery or battery pack are positive and negative common electrodes, and the positive and negative electrode common electrodes are In the battery or 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.
  • the positive electrode, the negative electrode, the positive and negative electrode common electrodes include, but are not limited to, positive and negative electrode common electrodes having the same active substance or the same active substance formula, and each other The same or the same positive and negative electrode common electrode, the positive and negative electrode common electrode of each other, the electrode active material or the positive and negative electrode of the active material formulation including the expansion agent or/and the positive electrode or/and the negative electrode, One or more of them; or the battery or battery pack includes a swelling agent in its positive or/and negative electrode;
  • 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 active material of the positive electrode or/and the negative electrode of the battery is one or more of a simple substance or a compound having two or more kinds of stable oxidation valence states; the two or more stable oxidation valences are Elements of the state include, but are not limited to: lead, iron, copper, nickel, manganese, silver, phosphorus, sulfur, chlorine, vanadium, chromium, cobalt, arsenic, selenium, bromine, tin, antimony, bismuth, iodine, tungsten, antimony. One or more.
  • the battery 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 or more of which.
  • 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 number of all the battery cells in the battery pack includes, but is not limited to, ⁇ N+1, and the N is equal to the rated voltage value of the battery pack divided by the rated voltage value of the battery cells in the battery pack.
  • the material of the current collector of the positive electrode or/and the negative electrode and the positive and negative electrode common electrode of the battery includes, but is not limited to, lead, lead alloy, composite material whose surface layer is lead or lead alloy, one or more of which are The composite material whose surface layer is lead or lead alloy has a surface layer/core structure or a surface layer/transition layer/core structure.
  • the core material is one or more of a metal or/and an alloy thereof or/and a compound thereof, a conductive plastic, a plastic, a conductive ceramic, a carbon material, a glass, a silica, and the transition layer material is One or more of a core material, a surface layer material; the metal or/and alloy thereof or/and compounds thereof include, but are not limited to, aluminum, copper, lead, titanium, tin, or/and alloys thereof and/or One or more of its compounds, including but not limited to: one or more of carbon black, activated carbon, graphite, carbon fiber, foamed carbon, carbon nanotubes, graphene.
  • the battery performs or is subjected to a charge or charge/discharge operation of the battery or/and the battery pack positive and negative polarity inversion, and the total cumulative number of times the battery performs or is performed is ⁇ 1 times.
  • the positive and negative polarity inversion and subsequent charging or charging and discharging operations that is, the positive electrode and the negative electrode are reversed in polarity, and after the polarity is reversed, the electrode undergoing the polarity inversion is performed. Charging or charging and discharging operations.
  • the battery includes a circuit having a function of performing polarity reversal of the positive and negative electrodes of the battery and subsequent charging or charging and discharging operations; or the circuit can reverse the battery or the battery pack One or more of charging, forced discharging, and reverse charging.
  • the battery and the storage battery of the present invention are subjected to or subjected to charging or charging and discharging operations of the positive electrode and the negative electrode of the battery or/and the battery pack, and the battery positive active material is expanded or/and softened or/and peeled off, corroded and blunt.
  • early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact between active material and conductive current collector, memory effect, decomposition of active material itself, one or more problems can be overcome, solved, and thus the battery Has a long life.
  • 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 common electrodes for the positive electrode and the negative electrode (ie, the positive and negative electrode for common use), the production, recovery efficiency, yield, production and recovery costs are reduced, and the battery of the present invention is ensured to have a good work. Performance, including life and capacity.
  • Fig. 1 is a graph showing the working discharge capacity and the working discharge termination voltage data of a lead-acid battery in a cycle charge and discharge operation according to a second 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 pack in the cycle charging and discharging operation of the third embodiment of the present invention.
  • Embodiment 3 is a single positive and negative polarity reversal and subsequent charging or charging and discharging operation of the lead-acid battery pack according to Embodiment 3 of the present invention during the 23-28th cycle charging and discharging operation process and during the process. Current and voltage data plots.
  • FIG. 4 is a schematic view showing the surface layer/core structure of a lead-acid battery or a battery-group electrode current-collecting composite material having a long service life according to Embodiment 7 of the present invention.
  • Fig. 5 is a schematic view showing the surface layer/transition layer/core structure of a lead-acid battery or a battery electrode current collector composite material having a long service life according to Embodiment 7 of the present invention.
  • the long-life battery includes a positive electrode and a negative electrode
  • the positive electrode and the negative electrode of the battery or the battery pack are both positive and negative common electrodes (electrodes for the positive electrode and the negative electrode), and the positive and negative electrode common electrodes are
  • the battery or battery pack it can be used either as a positive electrode or as a negative electrode, or as a positive electrode, some as a negative electrode, or as a positive electrode during operation or use of the battery or battery pack.
  • the positive electrode, the negative electrode, the positive and negative electrode common electrodes include, but are not limited to, positive and negative electrode common electrodes having the same active substance or the same active substance formula, The positive and negative electrode common electrodes of the same or the same, the positive and negative electrode common electrodes which are equivalent to each other, the positive electrode and the negative electrode of the electrode active material or the active material formulation including the expansion agent, and/or the positive electrode or/and the negative electrode One or more of them;
  • the battery or the battery pack includes a swelling agent in the positive electrode or/and the negative electrode.
  • 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 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 same or the same positive and negative common electrode means that the positive electrode and the negative electrode of the battery are identical in terms of electrode structure, size, formulation, material, manufacturing process and the like (ie, all electrode compositions)
  • the same or the same, the same or the same positive and negative electrode for the positive and negative electrodes means that those which are identical to each other before being formed or charged and discharged, can form a positive electrode or a negative electrode after being formed or charged and discharged.
  • the negative electrode common electrode, which is identical to each other before being formed or charged and discharged means that 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 activity before the electrode is formed.
  • the quality of the substance (such as but not limited to the quality of the lead paste and the quality of the lead paste), the manufacturing process, etc. are identical (ie, the same in all respects), or the manufacturing error (ie, removal, elimination) is not considered when manufacturing the electrode.
  • the manufacturing error ie, removal, elimination
  • two or more electrodes are constructed and manufactured with respect to each other before being subjected to a charge or charge and discharge operation ( Electrode structure, shape, size, formulation, material, making process, etc.) are identical.
  • each other means that the electrodes have the same function and performance after being formed, or the electrodes are not affected by the error factor during the operation or use of the battery or the battery pack after being formed or charged and discharged (for example, but not limited to: manufacturing error, measurement error) (ie, erasing, eliminating, eliminating the presence or influence of errors), having or exhibiting the same function and performance.
  • 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 of the positive electrode or/and the negative electrode of the battery is one or more of a simple substance or a compound having two or more kinds of stable oxidation valence states; the two or more stable oxidation valences are Elements of the state include, but are not limited to: lead, iron, copper, nickel, manganese, silver, phosphorus, sulfur, chlorine, vanadium, chromium, cobalt, arsenic, selenium, bromine, tin, antimony, bismuth, iodine, tungsten, antimony. One or more.
  • the battery 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 or more of which.
  • the ferrate includes, but is not limited to, K 2 FeO 4 , Na 2 FeO 4 , BaFeO 4 .
  • the number of all battery cells in the battery pack includes, but is not limited to, ⁇ N+1, and the N is equal to the rated voltage value of the battery pack divided by the rated voltage value of the battery cells in the battery pack.
  • the material of the current collector of the positive electrode or/and the negative electrode and the positive and negative electrode common electrode of the battery includes, but is not limited to, lead, lead alloy, composite material whose surface layer is lead or lead alloy, one or more of which are The composite material whose surface layer is lead or lead alloy has a surface layer/core structure or a surface layer/transition layer/core structure.
  • the core material is one or more of a metal or/and an alloy thereof or/and a compound thereof, a conductive plastic, a plastic, a conductive ceramic, a carbon material, a glass, a silica, and the transition layer material is One or more of a core material, a surface layer material; the metal or/and alloy thereof or/and compounds thereof include, but are not limited to, aluminum, copper, lead, titanium, tin, or/and alloys thereof and/or One or more of its compounds, including but not limited to: one or more of carbon black, activated carbon, graphite, carbon fiber, foamed carbon, carbon nanotubes, graphene.
  • the battery performs or is subjected to a charge or charge/discharge operation of the battery or/and the battery pack positive and negative polarity inversion, and the total cumulative number of times the battery performs or is performed is ⁇ 1 times.
  • the positive and negative polarity inversion and subsequent charging or charging and discharging operations that is, the positive electrode and the negative electrode are reversed in polarity, and after the polarity is reversed, the electrode undergoing the polarity inversion is performed. Charging or charging and discharging operations.
  • the reverse polarity of the positive electrode and the negative electrode and subsequent charging or charging and discharging operations include, but are not limited to, causing the positive electrode or the positive electrode active material of the battery or/and the battery pack to react with the battery negative electrode or by electrochemical reduction reaction. It is reduced to metal or 0 valence.
  • 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 (electrical 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 electrodes of the battery or the battery pack and the subsequent charging or charging and discharging operations include: inverting the polarity of the positive electrode and the negative electrode, and subsequent charging or charging and discharging operations and 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
  • 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 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 reverse polarity of the positive electrode and the negative electrode and subsequent charging or charging and discharging operations include, but are not limited to, solving the problem of expansion, softening, and falling off of the positive electrode active material of the battery, or are also used to solve other problems of the battery separately, or are solved.
  • the problem of expansion, softening and shedding of the positive electrode active material of the battery is also used to solve other problems of the battery, including but not limited to: corrosion of the battery (including but not limited to electrodes, sinks, current collector corrosion), passivation Early capacity loss, salinization, crystallization, shrinkage of the 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, one or more problems.
  • 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 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 and discharging operations of the positive electrode, the negative polarity, or the polarity reversal of the battery or/and the battery pack including but not limited to: the battery or the battery
  • the group performs reverse polarity charging, forced discharging, reverse charging and charging, one or more of them.
  • 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 battery pack includes, but is not limited to, a planar grid type, a tubular type, a wound type, a bipolar type, a horizontal lead cloth type, a foam grid type, a column type, a stable gap body electrode type, Sintered, pouch battery or battery pack, or including 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 (super battery) battery or battery Groups, or hybrid battery packs including, but not limited to, these types of batteries, and other various types of batteries or battery packs.
  • the full tubular battery has a tubular positive electrode and a tubular negative electrode.
  • 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 battery or the battery is subjected to or is subjected to a charging or charging/discharging operation method of the positive or negative polarity of the battery or/and the battery pack, and the life or the service life of the battery or the battery pack is significantly improved or extended.
  • the depth of discharge (DOD) includes, but is not limited to, 1-100%
  • the life or the service life of the battery or the battery pack in the present embodiment is increased or extended to 1.3 times or more by the battery, operation, and method in the present embodiment.
  • -10 times or more, or / and, the life or 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 includes a positive electrode and a negative electrode.
  • the positive and negative electrodes of the battery in this embodiment are positive and negative common electrodes.
  • the positive electrode, the negative electrode, and the positive and negative common electrodes of the battery of the embodiment include, but are not limited to, the same as each other.
  • 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, one or more of which.
  • the mass percentage of the barium sulfate or the swelling agent in the active material or the active material formulation in the present embodiment is 0.01% or more, 0.02% or more, 0.03% or more, 0.05% or more, and 0.08. % or more, 0.1% or more, 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, 3% or more, one or more of them .
  • the mass percentage of the expansion agent in the active substance or active substance formulation is not more than or equal to 5%, 10%, 20%, 30%, 40%, 50%, wherein One or more.
  • 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 active material or active substance formulation of the lead-acid battery of the present embodiment includes but is not limited to one or two of the following: positive electrode: lead powder or lead oxide powder 100Kg, barium sulfate 1.0Kg, short fiber 0.06Kg, sulfuric acid solution (45wt.%) 8.3Kg, water 8.25Kg; negative electrode: lead powder or lead oxide powder 100Kg, barium sulfate 0.6Kg, acetylene black 0.3Kg, sulfuric acid solution (45wt.%) 9.0Kg, water 8.25Kg;
  • the iron-ferrate battery active material or active substance formulation of the present embodiment includes but is not limited to one or two of the following: negative electrode: iron powder or iron oxide powder 100Kg, activated carbon 0.5Kg, lithium hydroxide 0.9Kg; positive electrode: high iron 100 kg of acid hydrate and 0.9 kg of lithium hydroxide.
  • the shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
  • the specific operation of the method for improving or prolonging the service life of the battery or the battery pack of the embodiment is that, after the battery or the battery pack of the embodiment has been subjected to the cyclic charge and discharge operation for more than one time, the battery or the battery pack is cycled according to the embodiment.
  • the charging and discharging, overcharging, undercharging, high active material utilization rate and the like cause the working discharge capacity of the battery or the battery pack of the present embodiment to be softened or/and detached, sulfated, passivated, and early capacity loss due to the positive active material.
  • Performing one or two consecutive polarity inversions and/or subsequent charging or charging and discharging operations that is, operating step (1): using a constant current source or/and a voltage source for the battery of the embodiment or The battery pack is subjected to reverse polarity charging, and the current of the reverse polarity charging is one or more of C 2 , C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or the voltage charged by the reverse pole is 0.5U.
  • step (2) is operated: for the battery of this embodiment
  • the charging or discharging current is one or more of C 2 , C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or the charging or discharging voltage is 0.5U, U One or more of 1.5U and 2U, such that the charging or/and discharge reaction of the negative electrode of the battery occurs on the electrodes A1, A2, ..., An of the battery or the battery of the present embodiment.
  • step (4) is operated: for the battery or battery of this embodiment
  • the group continues to charge or charge and discharge, and the charging or discharging current is one of C 2 , 2C 5 , 0.5C 20 , 0.1C 2 , 3C 2 , or 0.05C 5 or
  • a plurality of or charging voltages are one or more of 0.7U, 0.9U, 1.1U, and 1.7U, and the charging and discharging are DC or pulse charging and discharging, so that the electrodes A1, A2, ..
  • charging or / and discharging process of the battery positive electrode reaction occurs on the An
  • charging or / discharging process of the battery negative electrode reaction occurs on the electrodes B1, B2, ..., Bn
  • the process charging the battery or the battery pack of the embodiment When the amount of charge or/and discharge discharged by the discharge reaches 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, for example 0.7U, 0.9U, 1.05U or 1.4U, the working discharge capacity or working capacity of the battery or battery pack in this embodiment is restored or improved, improved, and the positive and negative polarity reversal and subsequent charging are repeated twice in this period.
  • a certain value such as 6C 2 , 3C 5 , 2C 20 , 8C 2 , 3C 2 , 0.5C 2 , or 2C 5
  • the battery or battery voltage reaches a
  • 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.
  • the battery, the operation and the method of the embodiment can significantly improve or prolong the life or the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
  • the embodiment relates to a lead-acid battery, a lead paste, a lead-acid battery electrode, a method for improving or prolonging the service life of a lead-acid battery, and a battery charge and discharge device.
  • the charge and discharge device of the embodiment has a positive and negative electrodes of a lead-acid battery.
  • the polarity inversion and the function of the subsequent charging or charging and discharging operation, the battery charger and the discharger of the present embodiment can be charged, charged or charged and discharged after the polarity inversion and polarity inversion at the output end thereof.
  • the lead-acid battery performs the charging or charging/discharging operation after the polarity of the battery is reversed, the polarity is reversed, and the polarity is reversed. All the operations on the battery in this embodiment are charged and discharged in this embodiment except for the manual operation. Electrical appliances are realized through their functions and work.
  • the lead-acid battery of the present embodiment has a rated voltage of 2V and a designed rated capacity of 821mAh (2h rate, 25°C).
  • the lead-acid battery of the embodiment includes two electrodes, and the two electrodes are positive and negative common electrodes (ie, positive electrode).
  • 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.
  • spacer electrodes have AGM separator, a lead, or lead paste
  • the two electrode paste formulations of the present embodiment comprises a ball lead powder, BaSO 4 (0.8%, by mass percentage, with respect to the ball mill lead powder), sulfur , Water, short fibers, the average mass of the active material on each electrode sheet 13.41 g, density of the solution of sulfuric acid in the lead-acid battery of the present embodiment is the embodiment of 1.27g / cm 3, the present embodiment eliminates or prevents fluid loss, open, short Factors such as mechanical damage, test failure, etc. interfere with the implementation process and implementation results of this embodiment.
  • the shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
  • the method for improving or prolonging the service life of the lead-acid battery in the embodiment is as follows: Firstly, the battery of the embodiment is subjected to cyclic charging and discharging work, and the working system is: when the battery is in the state of charging, the battery is discharged with a constant current of 371 mA.
  • the discharge is stopped, then it is charged with a constant current of 222mA, and when the measured battery voltage reaches 2.65V, it is converted to continue charging the battery with a constant voltage of 2.65V, twice (constant current) , constant voltage)
  • the total charging time is 7 hours and 24 minutes (except for special instructions), and then repeat the above discharge process with a constant current of 371 mA, so that the battery is cycled and discharged, and the battery operating environment temperature is 25 ⁇ 1 ° C.
  • the number of working cycles of the lead-acid battery of the embodiment reaches a certain set value in the above cyclic operation (for example, the 15th, 31st, ..., respectively, set in the embodiment), the battery is stopped.
  • the work begins with a single positive and negative polarity reversal of the battery and subsequent charging or charging and discharging operations. After the operation is completed, the battery is operated under the original working system and the polarity is reversed. The positive electrode of the battery operates as a negative electrode after the polarity is reversed, and the negative electrode of the battery before the polarity reversal operates as a positive electrode after the polarity is reversed until the next positive or negative polarity reversal of the next positive or negative polarity is started. Subsequent charging or charging and discharging operation, in the cycle operation of the lead-acid battery of the embodiment, the single-time positive and negative polarity reversal and the subsequent charging or charging are performed on the lead-acid battery of the embodiment.
  • the electrode A of the lead-acid battery of the present embodiment sometimes operates as a positive electrode and sometimes as a negative electrode, and the corresponding electrode B sometimes operates as a negative electrode and sometimes as a positive electrode to improve and repair.
  • One or more of the problem of poor contact causes the working discharge charging capability of the battery of the embodiment to be improved, restored, improved or maintained after each operation, thereby achieving an increase or extension of the service life of the lead-acid battery of the embodiment.
  • the cycle operation process of the battery of the embodiment is also implemented by the charging and discharging functions of the battery charger and discharger of the embodiment (hereinafter all the operations and measurements of the battery are charged and discharged by the battery of the embodiment except that the manual is specifically described.
  • the appliance is programmed and implemented.
  • the electrode state of the battery of the present 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 polarity reversal of its positive and negative poles, that is, the polarity of the output end of the charge and discharge device is reversed by the present embodiment (the polarity reversal at the output end of the charge and discharge device is through the contact of the relay circuit in the charger/discharger,
  • the state of connection between the charge and discharge device and the lead-acid battery is connected from the positive output end of the charge and discharge device to the lead-acid battery electrode A, and the negative output end of the charge and discharge device is connected to the lead-acid battery electrode B, and is changed into
  • the negative output end of the charge and discharge device is connected to the lead acid battery electrode A, and the positive and negative output end of the charge and discharge device is connected with the lead acid battery electrode B.
  • the battery of this embodiment after the connection state conversion is charged with a constant current of 186 mA, so that the battery voltage rises from a negative value to 0 V and then rises to 1.75 V (the first polarity reversal of the battery of this embodiment occurs in this process).
  • the discharge process of the lead-acid battery positive electrode reaction occurs on the electrode A
  • the discharge process of the lead-acid battery negative electrode reaction occurs on the electrode B
  • the battery voltage rises from 0V to 1.75V the battery voltage rises from 0V to 1.75V.
  • the charging process of the negative electrode reaction of the lead-acid battery on the electrode A and the charging process of the positive electrode reaction of the lead-acid battery on the electrode B occur.
  • the battery voltage reaches 1.75V
  • the battery is continuously charged to 2.65 with a constant current of 222 mA. V, then charge the battery for 4 hours and 16 minutes with a constant voltage of 2.65V, then discharge the battery to a constant current of 371mA to 1.75V, and then charge the battery with a constant current of 222mA until the battery voltage reaches 2.65V was changed to 2.25V to charge the battery for 5 hours.
  • the first single positive and negative polarity of the battery of this embodiment is completed.
  • the discharge capacity of the battery of this embodiment in the 16th cycle operation state is 888.3 mAh after the first single positive and negative polarity inversion and subsequent charging or charging and discharging operations.
  • the charging capacity of the battery during this polarity reversal and before the battery recovery cycle is 7031 mAh.
  • the battery of the embodiment is continuously operated under the working system.
  • the electrode state of the battery of the embodiment is A-/B+, and the electrode at this time.
  • a negative electrode reaction occurs on A
  • 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 is operated as a positive electrode
  • the electrode B is operated as a negative electrode
  • the battery is re-entered into the same discharge-charge cycle operation system to perform the 32nd operation discharge and the subsequent number of cycles.
  • the results show that after the second single positive and negative polarity inversion and subsequent charging or charging and discharging operations, the battery has a discharge capacity of 1189 mAh in the 32nd cycle operation state, which should be opposite to the polarity. After the turn, the battery is fully charged.
  • the total charge capacity of the battery between the polarity reversal and the battery recovery cycle is 6659 mAh.
  • the battery is continuously operated under the working system. As shown in FIG.
  • the electrode state of the battery of this embodiment is A+/B-, and at this time, the positive electrode is generated on the electrode A.
  • the negative electrode reaction occurred on the electrode B.
  • the discharge capacity of the battery in the 32-45 cycle of the present example was reduced from 1189 mAh to 787 mAh.
  • the present embodiment is repeated, repeated, and interspersed, for example, the single positive and negative polarity reversal similar to the first or second time described above.
  • the charging or charging and discharging operation that is, between the 45th, 46th, 55th, 56th, 64th, and 65th times of the working cycle of the lead-acid battery of the embodiment in the cycle work process thereof , between the 73rd, 74th, the 82nd, the 83rd, the 94th, the 95th, the 104th, the 105th, or the third, fourth, bib .
  • the ninth single positive and negative polar polarity reversal and subsequent charging or charging and discharging operations. 1 shows the electrode of the lead-acid battery of the present embodiment during the cycle charging and discharging operation before or after the single positive and negative polarity inversion and the subsequent charging or charging and discharging operations of the present embodiment.
  • the charging method is changed to, after the end of the working discharge, the battery is charged with a constant current of 222 mA, and when the measured battery voltage reaches 2.65 V, , converted to a constant voltage of 2.65V to continue charging the battery, the total time of two (constant current, constant voltage) charging is 8 hours and 24 minutes.
  • the working discharge capacity of the lead-acid battery of the present embodiment is improved or restored year by year.
  • the positive and negative polarity inversion of the present embodiment and the subsequent charge and discharge or charge and discharge operations cause the positive active material of the lead-acid battery of the present embodiment to be softened and peeled off, improved, repaired, reversed, eliminated, Suppressing and preventing, so that the working discharge capacity in the cycle operation of the lead-acid battery of the embodiment is improved or restored after the operation, and on the other hand, the polarity of the positive and negative poles of the embodiment is reversed and then charged or discharged or charged.
  • the discharge operation also has the problems of electrode passivation, early capacity loss, corrosion, poor contact of active material and current collector, shrinkage of specific surface area of the anode, and sulfation which occur during the cycle operation of the battery of the present embodiment.
  • the cycle work is improved, repaired, reversed, thereby also making the lead-acid battery of the embodiment During the period of use, the corrosion problem is delayed, improved, repaired, reversed, and prevented.
  • the lead-acid battery in this embodiment In the normal cycle of the lead-acid battery in this embodiment, it is periodically or irregularly (for example, in the manner of specifying the number of cycles) and interspersed.
  • Performing the positive and negative polarity inversion and the subsequent charge, discharge or charge and discharge operations of the present embodiment for the lead-acid battery of the present embodiment will effectively improve, repair, reverse, eliminate, suppress, and prevent the softening of the positive active material or/or And the shedding, electrode passivation, corrosion, early capacity loss, sulfation, poor contact between the active material and the current collector, and the specific surface area shrinkage of the anode, thereby increasing or prolonging the service life of the lead-acid battery of the present embodiment.
  • the positive and negative polarity inversion of the present example and the subsequent charging or charging and discharging operations can also be performed using the rapid charge and discharge pulse current and the pulse voltage.
  • Some experimental data in this embodiment indicate the degree of recovery of the working discharge capacity of the lead-acid battery of the present embodiment after the single polarity inversion of the lead-acid battery of the present embodiment and the charging or charging and discharging operation thereafter.
  • the number of times that the lead-acid battery can continuously maintain the normal or high discharge capacity of the charge 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 battery of the 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 this embodiment makes the example
  • the service life of lead-acid batteries continues to increase or increase over the 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 pulse current and the pulse voltage may be used instead of the direct current and the constant voltage to perform the polarity inversion in the two consecutive polarity inversions of the present example and the subsequent charging or charging and discharging operation steps. Subsequent charging or charging and discharging steps or processes are advantageous for improving the aging and energy efficiency of the battery polarity inversion and subsequent charging or charging and discharging operations 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 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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
  • the lead-acid battery pack of this embodiment is a full-tube lead-acid battery pack with a rated voltage of 4V and a rated capacity of 539mAh (C 3.5 , 3.5h rate, 25° C.) connected in series by two identical tubular-type lead-acid batteries.
  • Each of the electrodes of the full-tube lead-acid battery is a tubular electrode, and the tubular electrodes are positive and negative common electrodes (ie, electrodes common to the positive electrode and the negative electrode), and the tubular positive and negative
  • the extremely common electrode is the same in the electrode structure and active material formulation.
  • each of the full-tube lead-acid batteries includes three tubular positive and negative common electrodes.
  • the six tubular positive and negative electrodes of the lead battery pack of the present embodiment are generally used.
  • the electrodes are named as electrodes A1, A2, A3, A4, B1, and B2, respectively.
  • the six electrodes are arranged in each of the full-tube lead-acid batteries in the lead-acid battery pack of the present embodiment: the electrode B1 is sandwiched between electricity.
  • the mass of the active material in the A4 casing is 5.8g
  • the mass of the active material in the sleeve of the electrode B1 or B2 is 5.5g
  • the active substances in the electrodes A1, A2, A3, A4, B1, B2 are all ball-milled.
  • Powder, barium sulfate (0.8wt% relative to ball-milled lead powder) the two output terminals of the lead-acid battery of this embodiment are respectively named as battery terminals A, B, wherein the battery terminal A is connected to the electrode A1 or A2 or A3 or A4, the battery terminal B is connected to the electrode B1 or B2.
  • the electrodes A1, A2, A3, and A4 are cycled as the positive electrode ( That is, during the cyclic working process, the electrodes A1, A2, A3, and A4 are charged and discharged during the reaction of the positive electrode of the lead-acid battery), and the electrodes B1 and B2 are used as the negative electrode for the cyclic operation (that is, the electrodes B1 and B2 occur during the cyclic operation).
  • the charging and discharging process of the negative electrode of the lead-acid battery that is, the polarity of the terminal A of the battery pack is positive, and the polarity of the terminal B of the battery pack is negative, which is expressed as A+/B- (same reason, when the battery pack When the polarity of terminal A is negative and the polarity of battery terminal B is positive, It is expressed as A-/B+), and the separators of the positive and negative tube electrodes are separated by a separator.
  • the density of the sulfuric acid solution of the electrolyte used in the lead-acid battery group of the present embodiment is 1.27 g/cm 3 , and the present embodiment excludes or prevents the loss. Factors such as liquid, open circuit, short circuit, mechanical damage, test failure, etc. interfere with the implementation process and implementation results of this embodiment.
  • the shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
  • the method for improving or prolonging the service life of the lead-acid battery pack of the embodiment is that, when the lead-acid battery pack of the embodiment is circulated to a certain number of times or the working discharge charging capability is softened or/and detached from the positive active material, the ratio of the negative electrode is increased. Automatic or / and manual when one or more of surface area shrinkage, current collector or sink corrosion, passivation, early capacity loss, sulfation, poor contact of active material and current collector, etc. Performing a single polarity inversion and subsequent charging or charging and discharging operations on the positive and negative electrodes of the lead-acid battery pack of the present embodiment to improve, repair, reverse, prevent, suppress, and eliminate the softening and negative electrode ratio of the positive active material.
  • the lead-acid battery pack of the embodiment is re-introduced into the cyclic charging and discharging operation by the polarity state of the electrode after the polarity is reversed, until the next positive and negative polarity is started. Reverse and subsequent charging or charging and discharging operations.
  • the lead acid battery pack of the embodiment is re-introduced into the cyclic charging and discharging operation by the electrode polarity state after the polarity inversion.
  • Cycling operation for example, if the electrodes A1, A2, A3, and A4 of the lead-acid battery pack of the present embodiment are operated as a positive electrode before the polarity is reversed (that is, the electrodes A1, A2, and A3 during the cycle operation) On the A4, the charge and discharge process of the positive electrode reaction of the lead-acid battery occurs), after the polarity is reversed, the electrodes A1, A2, A3, and A4 are used as the negative electrode for the charge and discharge cycle (ie, the electrode A1 during the cycle operation).
  • the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs.
  • the corresponding electrodes B1 and B2 are cycled as the negative electrode before the polarity is reversed (that is, the electrode B1 during the cycle operation).
  • the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on B2), and the cycle is performed as the positive electrode after the polarity reversal (that is, the charging of the positive electrode of the lead-acid battery occurs on the electrodes B1 and B2 during the cyclic operation).
  • the electrodes A1, A2, A3, A4 or the electrodes B1, B2 during the cyclic operation before the polarity inversion are reversed
  • the electrodes A1, A2, A3, A4 Or the polar states or polar directions of the electrodes B1 and B2 during the cyclic operation after the polarity inversion are reversed.
  • Triggering or starting the triggering of any polarity reversal and subsequent charging or charging and discharging operations on the positive and negative poles of the lead-acid battery pack of the embodiment may be manual triggering or the arrival of the program according to a preset trigger condition.
  • the automatic triggering, the triggering condition may be one or more of a certain number of cyclic charging and discharging operations or cumulative times, a charging amount, a discharging amount, a charging and discharging rate, a current variation amount, a voltage variation amount, or the like, or a calculated value thereof.
  • the circulating charge and discharge working system adopted in the lead-acid battery pack of the present embodiment is: discharging discharge to 3.5V at a current of 0.283 C 3.5 during working discharge, and then performing constant current charging to 5.95 V or time 9 at a current of 0.338 C 3.5 . After 24 hours, then constant voltage charging was carried out for 3 hours with a voltage of 5.3 V, and then the previous working discharge process was repeated, and the cycle of the lead-acid battery pack of this example was cyclically charged and discharged.
  • the lead-acid battery pack of the embodiment is in the process of circulation Between the sixth and seventh times of the number of work cycles, between the 17th and 18th, between the 25th and 26th, between the 33rd and 34th, between the 41st and the 42nd, and 56th. Between 57 times or in sequence, the first, second, ..., the sixth single positive and negative polar polarity reversal and subsequent charging or charging and discharging operations are performed. Or the method or process of performing positive or negative polarity inversion and subsequent charging or charging and discharging operations is as follows:
  • the positive and negative output terminals of the battery pack are connected in reverse polarity, that is, the positive output end of the charge and discharge device is connected to the negative output terminal (battery terminal B) of the lead-acid battery pack of the embodiment, and the negative output of the charge and discharge device
  • the terminal is connected to the positive output terminal (battery terminal A) of the lead-acid battery pack of the embodiment, and after the reverse pole is connected, the charge and discharge device measures the voltage of the lead-acid battery pack of the embodiment to be -5.53V, and then, the implementation
  • the lead-acid battery pack is charged at a current of 458 mA in the state of the reverse pole connection, so that the voltages of the positive and negative output terminals of the lead-acid battery pack of the present embodiment (the measured values of the charge and discharge device, the same in the present embodiment) From -5.53V When it reaches 0V and then rises to 5.8V, in this process, the first polarity reversal occurs in the lead-acid battery
  • the main occurrence of A4 is the charging process of the negative electrode reaction of lead-acid battery.
  • the main charging process on the electrodes B1 and B2 is the charging process of the positive electrode of the lead-acid battery.
  • the output of the charging and discharging device and the lead-acid battery of this embodiment are maintained.
  • the lead-acid battery pack of this embodiment is discharged at 152.7 mA for 14 minutes to 3.5 V, and then charged at a constant current of 229 mA for 8 hours to 5.72 V, and then, 152.7mA discharge for 2 minutes to 4.5V, and then charged at a constant current of 114mA for 3 hours to 5.5V, and then put the lead-acid battery pack of the embodiment into the seventh working discharge process of the cycle, for the seventh time. Even thereafter Work to cycle 17 times.
  • the polarity of the battery terminal A is negative
  • the polarity of the electrode pool terminal B is positive, as shown in FIG.
  • the positive and negative output terminals of the battery pack are connected in reverse polarity at that time, that is, the positive output end of the charging and discharging device is connected to the negative output terminal (battery group terminal A) of the lead-acid battery group of the embodiment, and the charging and discharging device The negative output terminal is connected to the positive output terminal (battery pack terminal B) of the lead-acid battery pack of the present embodiment.
  • the charge and discharge device measures the voltage of the lead-acid battery pack of the embodiment to be -4.54V.
  • the lead-acid battery pack of the present embodiment is charged at a current of 459 mA in the state of the reverse pole connection, so that the output voltage of the lead-acid battery pack of the present embodiment (the measured value of the charge and discharge device, the same in the present embodiment) From -4.54V to 0V It rises to 5.8V for 4 hours and 30 minutes.
  • the lead-acid battery pack of this embodiment has a second polarity reversal, that is, during the process of rising from -4.54V to 0V, electrodes A1, A2, and A3.
  • A4 is the discharge process of the negative electrode of lead-acid battery, the discharge process of the positive electrode of lead-acid battery on the electrodes B1 and B2, and the electrode A1 during the process of 0V rising to 5.8V.
  • A2, A3, and A4 mainly occur in the charging process of the positive electrode of the lead-acid battery.
  • the charging process of the negative electrode of the lead-acid battery occurs mainly on the electrodes B1 and B2.
  • the output of the charging and discharging device is maintained and the embodiment is
  • the lead-acid battery pack of this embodiment is discharged at 152.7 mA for 17 minutes to 3.5 V, and then charged at a constant current of 229 mA for 8 hours to 5.41 V, and then And then discharge at 152.7mA for 2 minutes to 4.23V, and then charge at a constant current of 114mA for 3 hours to 5.26V, and then put the lead-acid battery of the embodiment into the 18th working discharge process in the cycle work, get on 18 and thereafter until the first cycle for 25 times.
  • the polarity of the battery terminal A is positive, and the polarity of the electrode bank terminal B is negative, as shown in FIG. 2, that is, in the process.
  • the charging and discharging process of the positive electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, A3, and A4, and the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on the electrodes B1 and B2, that is, the battery terminals A, B and the electrode
  • the polarity state or polarity direction of A1, A2, A3, A4, B1, B2 is returned to the state at which the lead-acid battery pack of the present embodiment is most initially cycled.
  • the single positive and negative polarity inversions similar to the first or second time of the present embodiment as described above are repeated, repeated, and interspersed as described above.
  • the charging or charging and discharging operation that is, the lead-acid battery pack of the embodiment is realized between the 25th and 26th, the 33rd and 34th, the 41st and the 42nd, and the 56th of the working cycle. 57th, ..., X, X+1 times or the third, fourth, fifth, sixth, ...., Y
  • the secondary positive and negative polarity inversions and subsequent charging or charging and discharging operations (X, Y are positive integers).
  • FIG. 2 is a diagram showing the battery pack terminal A in the cycle operation process of the lead-acid battery pack of the embodiment before or after the single charge and charge polarity reversal and subsequent charging or charging and discharging operations.
  • the polarity state or polarity direction of B, FIG. 3 shows the 23-28th cycle charge and discharge operation process of the lead-acid battery pack of the embodiment and the third single positive and negative poles interposed during the process.
  • the polarity reversal of the negative electrode and the subsequent charging or charging and discharging operations are basically the same, except that after the steps of "discharging at 152.7 mA for 2 minutes and then charging at 114 mA constant current for 3 hours" are completed after the operation. Then, the battery was discharged at a current of 153 mA for 2 hours and 58 minutes, and then the lead-acid battery pack of the present embodiment was put into the 26th cycle.
  • the working discharge capacity of the lead-acid battery pack of the present embodiment is improved or restored year by year, and after inspection, this is checked.
  • the positive and negative polarity inversion of the present embodiment and the subsequent charge and discharge or charge and discharge operations of the present embodiment cause the positive active material of the lead-acid battery of the present embodiment to soften or/and fall off, electrode passivation, early capacity loss, and corrosion.
  • One or more of the problems of poor contact between the active material and the current collector and shrinkage of the specific surface area of the negative electrode are improved, repaired, reversed, suppressed, eliminated, and prevented.
  • the irregularity of the polarity of the positive and negative electrodes of the present embodiment and the subsequent charge and discharge or charge and discharge operations of the lead-acid battery pack of the present embodiment may be performed intermittently (for example, in a manner of specifying the number of cycles). Effectively improve, repair, reverse, eliminate, inhibit, prevent softening or/and shedding, passivation, corrosion, early capacity loss, sulfation, active substances and sets of positive active materials
  • the problem of poor contact between the body and the specific surface area of the negative electrode increases or prolongs the service life of the lead-acid battery pack of the present embodiment.
  • the electrodes A1, A2, A3, A4, B1, and B2 are alternately alternately charged or discharged as a positive electrode or a negative electrode
  • the cycle work makes the corrosion problem of the electrode generated as the positive electrode work improve, repair and reverse when the electrode is used as the negative electrode for the charge and discharge cycle, thereby also delaying the corrosion problem of the lead-acid battery pack of the present embodiment during long-term use.
  • the method for improving or prolonging the service life of the lead-acid battery pack is such that the service life of the lead-acid battery pack of the present example continues to be greatly improved or extended based on the existing effective number of cycles.
  • the positive and negative polarity inversion of the present example and the subsequent charging or charging and discharging operations can also be performed using the rapid charge and discharge pulse current and the pulse voltage.
  • Some experimental data in this embodiment indicate the degree of recovery of the working discharge capacity of the lead-acid battery pack of the present embodiment after the single polarity inversion and the subsequent charging or charging and discharging operation of the lead-acid battery pack of this embodiment.
  • the number of times of charging and discharging cycles in which the lead-acid battery pack of the present embodiment can continuously maintain normal or high discharge capacity after each working discharge capacity is restored ie, charging or charging and discharging after each single polarity inversion
  • the number of charge and discharge cycles in which the lead-acid battery pack of the present embodiment operates normally or has a higher discharge capacity, and the current used in each single polarity inversion and subsequent charge or charge and discharge operations The voltage, time, charge and discharge capacity, pulse or DC, internal resistance of the battery or battery pack, electrolyte density, and the degree of electrolyte saturation vary.
  • the positive, negative or all electrodes of the full-tube lead-acid battery pack of the present embodiment are the same or the same tubular positive and negative common electrodes, that is, the electrode is not considered.
  • Manufacturing error ie, eliminating, eliminating, eliminating the existence or influence of manufacturing error
  • all the electrodes or all tubular electrodes of the full-tube lead-acid battery of the present embodiment are formed on all the electrodes before being formed,
  • the manufacturing aspects (such as electrode structure, shape, conductive core, casing, fluid pool, active material formulation and quality, manufacturing process, etc.) are identical.
  • each of the full-tube lead-acid battery packs of this embodiment The tubular electrodes are respectively formed into a positive electrode or a negative electrode.
  • the positive, negative or all electrodes of the full-tube lead-acid battery pack of the present embodiment are tubular positive and negative common electrodes equivalent to each other, that is, the electrodes are formed or charged. After discharge, in the case of the operation or use of the lead-acid battery pack, regardless of the error (such as but not limited to: manufacturing error, measurement error) (ie, removing, eliminating, eliminating the existence or influence of manufacturing error), Each of the tubular electrodes of the examples have or exhibit the same function and performance.
  • the above-described full-tube lead-acid battery of the present embodiment can be replaced with other types of lead-acid batteries or battery packs having the same capacity and the same formula, the other types of lead-acid batteries or battery packs.
  • the above method of the present embodiment can be applied to the other types of lead-acid batteries or battery packs, and the voltage, current and other parameters can be applied according to the rated working voltage and rated capacity of the battery or the battery pack. Appropriately and correspondingly varying the size, for example when charging
  • 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 pulse current and the pulse voltage may be used instead of the direct current and the constant voltage to perform the polarity inversion in the two consecutive polarity inversions of the present example and the subsequent charging or charging and discharging operation steps. Subsequent charging or charging and discharging steps or processes are advantageous for improving the aging and energy efficiency of the battery polarity inversion and subsequent charging or charging and discharging operations 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 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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
  • 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 the battery pack of the embodiment has output terminals A, B, the output terminal A and the 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 battery includes a positive electrode and a negative electrode.
  • the positive and negative electrodes of the battery in this embodiment are positive and negative common electrodes.
  • the positive electrode, the negative electrode, and the positive and negative common electrodes of the battery of the embodiment include, but are not limited to, the same as each other.
  • 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 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 shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
  • the positive and negative electrodes are positive and negative common electrodes
  • (1) the battery in this embodiment is a lead-acid battery
  • the positive electrode and/or the negative electrode are positive and negative.
  • the extremely common 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%, 3%, 4%, 10%, one or more of them; or (2) the battery of the present 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, calcium sulfate, and the barium sulfate is in the positive electrode or/and the negative electrode, positive and negative
  • a swelling agent lithium hydroxide having a mass percentage of 0.01%, 0.05%, 0.1%, 0.4% in the positive electrode or/and the negative electrode, the positive and negative electrode common electrode or the active material or active substance formulation thereof , 0.8%, 1.0%, 2.0%, 3%, 10%, one or more of them.
  • 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 lead.
  • the acid battery has the active material or active substance formula of the positive electrode and the negative electrode: 100Kg of lead powder or lead oxide powder, 0.06Kg of short fiber, 0.28Kg of acetylene black, 0.8Kg of barium sulfate, and sulfuric acid solution (mass percentage of sulfuric acid 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 example
  • 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 are identical;
  • 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 reversed are charged and discharged in the same manner as described above.
  • the charging, and/or discharging performance of the positive electrode, the negative electrode, and the positive and negative electrode common electrodes are the same under the same polarity. Or it is considered that the positive electrode, the negative electrode, the positive and negative electrode common electrodes have the same charging and/or discharging performance under the same polarity, and the difference in the average value of the discharge capacity of 0.5 Ah belongs to the normal error between each other. It is 5% and 4.76% of the average of the forward and reverse discharge capacities.
  • the battery of the embodiment has a rated voltage of 2V or 1.47V, and the positive and negative electrodes are positive and negative common electrodes equivalent to each other, and after the electrodes are formed, in a certain regulation Under charging and discharging conditions (such as but not limited to: first 0.5C constant current charging to 2.47V or 1.8V, then constant voltage charging for 3 hours, then 0.5C rate discharge, ambient temperature is 25 ° C, C is the rated capacity of the battery)
  • the average value is 20 Ah, and then the polarity of the positive electrode and the negative electrode of the battery is reversed for the twelfth time, and the positive electrode after the eleventh polarity inversion is inverted to the negative electrode, so that the eleventh time is made.
  • the negative electrode after the polarity inversion is reversed to the positive electrode, and then the negative electrode formed by inverting the 12th polarity and the positive electrode formed after the 12th polarity is inverted are the same as the above-described specifications.
  • Under charging and discharging conditions (such as but not limited to: first 0.5C constant current charging to 2.47V or 1.
  • the charge, and/or discharge performance of the positive electrode, the negative electrode, and the positive and negative electrode common electrodes are the same as each other 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 3 Ah belongs to the normal error between each other, and the error is positive and negative.
  • the average value of the discharge capacity was 15% and 17.6%.
  • 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 for 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 in the use or work of the circulating work, the working cycle reaches a certain number of times or as needed (for example, due to Expansion or/and softening or/and shedding of the positive active material, corrosion, passivation, early capacity loss, salinization, crystallization, shrinkage of the 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,
  • One or more of the problems cause the battery or battery pack of the present embodiment to decrease in operating discharge capacity and below or below a certain capacity value, and it is desirable or necessary to increase the working discharge capacity of the battery or the battery pack or to increase or extend the use of the battery or the battery pack.
  • the battery or battery pack of this example is automatically or/and manually subjected to a single positive and negative polarity reversal and subsequent charging or charging and discharging operations, improving, eliminating, and reversing. , inhibiting, preventing expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss of the positive active material , 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 material itself, one or more problems, such that the working capacity of the battery or the battery pack of the present embodiment is restored Or, after completing the positive or negative polarity inversion and subsequent charging or charging and discharging operations, the battery or the battery pack of the embodiment is re-introduced to the charging and discharging state by the polarity state after the polarity is reversed.
  • 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, charge or discharge mode includes a single phase, multiple phase, constant current (e.g. 0.15C 2, 0.4C 2, 0.8C 2 , 7C 2), constant One or more of a voltage (for example, 0.8U, 1.5U, 2U, 4U), a positive pulse, and a negative pulse, and then, in the polarity state of the battery or the battery pack of this embodiment after the polarity is reversed, Re-input into the cycle work to perform the cycle 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,
  • the polarity of the battery or battery pack output terminal A is negative
  • the polarity of the output terminal B is positive, that is, the charging and discharging process of the battery negative electrode reaction occurs on the electrodes
  • 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 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, during the operation or use of the battery or battery pack, regardless of the error (such as but not limited to: manufacturing error, measurement error) (ie, removal, exclusion, The presence or influence of the error is removed), and the electrodes of this embodiment have or exhibit the same function and performance.
  • the pulse current and the pulse voltage may be used instead of the direct current and the constant voltage to perform the polarity inversion in the two consecutive polarity inversions of the present example and the subsequent charging or charging and discharging operation steps. Subsequent charging or charging and discharging steps or processes are advantageous for improving the aging and energy efficiency of the battery polarity inversion and subsequent charging or charging and discharging operations of the present embodiment.
  • the battery, the operation and the method of the embodiment can significantly improve or prolong the life or the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
  • the battery of the embodiment, the method for improving or prolonging the service life of the battery or the battery pack includes the total cumulative number of times of the battery or the battery pack of the embodiment in the floating charging operation of the battery or the battery pack is 1 or 1 times.
  • the fluid contact failure, the memory effect, the decomposition of the active substance itself, one or more problems, the working capacity of the battery or the battery pack of the embodiment is restored or increased or prevented, and then the battery or the battery pack of the embodiment is re-applied. Put it into the floating
  • the battery, the operation and the method of the embodiment can significantly improve or prolong the life or the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
  • the battery of this embodiment is an iron-nickel battery or an iron-ferrate battery, and the rated capacity is 10 Ah (C 5, 5 h, 25 ° C).
  • the battery in this embodiment includes a positive electrode and a negative electrode, or, in this embodiment, the battery is positive and negative.
  • the electrodes are common electrodes for positive and negative electrodes.
  • the positive electrode, the negative electrode, and the positive and negative electrode of the battery of the present embodiment include, but are not limited to, a positive electrode or/and a negative electrode including a swelling agent, and an electrode active material or an active material formulation including expansion.
  • 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, an oxide or hydroxide of aluminum, an oxide or hydroxide of titanium, an oxide or hydroxide of lithium, 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 shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
  • the battery of the present embodiment expands or/and softens and/or falls off, corrosion, passivation, early capacity loss, salinization, crystallization, specific surface area shrinkage of the positive electrode active material, poor contact of the active material with the conductive current collector, memory
  • the effect, the active material itself decomposes, and one or more problems cause the working discharge capacity to decrease or the cycle working life to be terminated, and the positive and negative polarity inversion and subsequent charging of the battery of the embodiment are performed by the charging and discharging device.
  • 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, the operation and the method of the embodiment can significantly improve or prolong the life or the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
  • the long-life lead-acid battery of the present embodiment is the same as or similar to the lead-acid battery described in Embodiment 1-6 of the present invention except for the electrode current collector material.
  • the materials of the long-life lead-acid battery or the battery electrode collector of the present embodiment include, but are not limited to, lead, lead alloy, composite materials whose surface layer is lead or lead alloy, one or more of them.
  • the composite material whose surface layer is lead or lead alloy in this embodiment has a surface layer/core structure, as shown in FIG. 4, or a surface layer/transition layer/core structure, as shown in FIG.
  • the material of the long-life lead-acid battery or the battery electrode current collector of the present embodiment is a composite material having a surface layer/core structure. As shown in FIG. 4, the surface layer material 15 is lead, and the core material 16 is copper.
  • the material of the long-life lead-acid battery or the battery electrode current collector of the present embodiment is a composite material having a surface layer/core structure, as shown in FIG. 4, the surface layer material. 15 is a lead-bismuth alloy, and the core material 16 is aluminum.
  • the material of the long-life lead-acid battery electrode current collector of the embodiment is a composite material having a surface layer/transition layer/core structure, as shown in FIG. 5, the surface layer material 15 is Lead, the transition layer material 17 is tin, and the core material 16 is aluminum.
  • the material of the long-life lead-acid battery or the battery electrode current collector of the embodiment is a composite material having a surface layer/transition layer/core structure, as shown in FIG. 5, the surface layer
  • the material 15 is a lead-calcium-tin-aluminum alloy
  • the transition layer material 17 is a tin dioxide/titanium composite material
  • the core material 16 is a conductive plastic.
  • the lead-acid battery or the battery pack of the present embodiment becomes a lead-acid battery having a long life or a long service life by performing a positive or negative polarity reversal of the positive and negative polarities and subsequent charging or charging and discharging operations of the total cumulative number of times ⁇ 1 times or
  • the battery pack, the operation is the same or similar to the operation and method described in Embodiment 1-6 of the present invention.
  • the battery, the operation and the method of the embodiment can significantly improve or prolong the life or the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
  • the operation and method of the battery of the present embodiment for improving or prolonging the life of the battery or the battery pack are the same as or include the embodiments 1-21 and 23 described in the embodiment 1-21 and the Chinese patent application 201710975698.2 described in the Chinese Patent Application No. 201710975570.6.
  • the battery, the operation and the method of the embodiment can significantly improve or prolong the life or the service life of the battery or the battery pack.
  • the depth of discharge (DOD) includes but is not limited to 1-100%
  • the battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.

Abstract

Disclosed is a long-life storage battery. The positive electrode and the negative electrode of the storage battery are both general-purpose electrodes for positive and negative electrodes, and the positive electrode, the negative electrode and the general-purpose electrodes for positive and negative electrodes include, but are not limited to: one or more of general-purpose electrodes, having the same active substance or the same active substance formulation, for positive and negative electrodes, general-purpose electrodes, which are of the same type or identical, for positive and negative electrodes, general-purpose electrodes, which are equivalent to each other, for positive and negative electrodes, and general-purpose electrodes for positive and negative electrodes or/and positive electrodes or/and negative electrodes, the electrode active substance or the active substance formulation of which comprises an expanding agent; or, the positive electrode and/or the negative electrode of the storage battery comprises an expanding agent. The storage battery has a long life.

Description

长寿命蓄电池Long life battery 技术领域Technical field
本发明涉及一种蓄电池，特别涉及一种长寿命蓄电池。The invention relates to a battery, in particular to a long-life battery.
背景技术Background technique
蓄电池，可循环充放，可大大降低社会的生产、生活、环保成本，蓄电池的寿命或使用寿命越长，则其产生的经济效益和社会效益就越大。导致蓄电池寿命或使用寿命终止的原因很多，重要的原因包括但不限于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。The battery can be recharged and discharged, which can greatly reduce the production, living and environmental protection costs of the society. The longer the life or service life of the battery, the greater the economic and social benefits it generates. There are many reasons for the end of battery life or end of life. Important reasons include, but are not limited to, expansion or/and softening and/or shedding of positive active materials, corrosion, passivation, loss of early capacity, shrinkage of specific surface area of the anode, and deactivation of active substances. , salinization, crystallization, poor contact between active materials and current collectors, memory effects, decomposition of active substances, etc.
发明内容Summary of the invention
本发明所要解决的技术问题是提供一种长寿命蓄电池，所述长寿命蓄电池，因为可以或有利于、有助于克服、解决一些蓄电池问题，从而具有长寿命，所述蓄电池问题，包括但不限于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。The technical problem to be solved by the present invention is to provide a long-life battery which has a long life because it can or advantageously helps to overcome and solve some battery problems, including but not Limited to positive electrode active material expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salting, crystallization, negative electrode specific surface area shrinkage, poor contact of active material with conductive current collector, memory effect, active substance Decomposition by itself, one or more of these problems.
所述盐化，包括但不限于，硫酸盐化。The salinization includes, but is not limited to, sulfation.
所述寿命，包括但不限于使用寿命，所述使用寿命包括但不限于：循环寿命、浮充寿命、贮存或存储寿命，其中的一种或多种。The life, including but not limited to, the service life, including but not limited to: cycle life, float life, storage or storage life, one or more of them.
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.
为解决上述技术问题，本发明提供了一种长寿命蓄电池，包括正极、负极，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：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、彼此为同一种的或相同的正负极通用电极、彼此等价的正负极通用电极、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，其中的一种或多种；或者，所述蓄电池或电池组其正极或/和负极中包括膨胀剂；In order to solve the above technical problem, the present invention provides a long-life battery comprising a positive electrode and a negative electrode, wherein the positive and negative electrodes of the battery or battery pack are positive and negative common electrodes, and the positive and negative electrode common electrodes are In the battery or 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 of which; the positive electrode, the negative electrode, the positive and negative electrode common electrodes include, but are not limited to, positive and negative electrode common electrodes having the same active substance or the same active substance formula, and each other The same or the same positive and negative electrode common electrode, the positive and negative electrode common electrode of each other, the electrode active material or the positive and negative electrode of the active material formulation including the expansion agent or/and the positive electrode or/and the negative electrode, One or more of them; or the battery or battery pack includes a swelling agent in its positive or/and negative electrode;
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。The active material of the positive electrode or/and the negative electrode of the battery is one or more of a simple substance or a compound having two or more kinds of stable oxidation valence states; the two or more stable oxidation valences are Elements of the state include, but are not limited to: lead, iron, copper, nickel, manganese, silver, phosphorus, sulfur, chlorine, vanadium, chromium, cobalt, arsenic, selenium, bromine, tin, antimony, bismuth, iodine, tungsten, antimony. One or more.
所述蓄电池，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 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 or more of which.
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.
所述蓄电池在蓄电池组中的所有单电池个数包括但不限于：≥N+1，所述N等于所述蓄电池组的额定电压数值除以所述蓄电池组中单电池的额定电压数值。The number of all the battery cells in the battery pack includes, but is not limited to, ≥ N+1, and the N is equal to the rated voltage value of the battery pack divided by the rated voltage value of the battery cells in the battery pack.
所述蓄电池的正极或/和负极、正负极通用电极的集流体的材料包括但不限于：铅、铅合金、表面层为铅或铅合金的复合型材料，其中的一种或多种，所述表面层为铅或铅合金的复合型材料具有表面层/芯体结构或表面层/过渡层/芯体结构。The material of the current collector of the positive electrode or/and the negative electrode and the positive and negative electrode common electrode of the battery includes, but is not limited to, lead, lead alloy, composite material whose surface layer is lead or lead alloy, one or more of which are The composite material whose surface layer is lead or lead alloy has a surface layer/core structure or a surface layer/transition layer/core structure.
所述芯体材料为金属或/和其合金或/和其化合物、导电塑料、塑料、导电陶瓷、碳材料、玻璃、二氧化硅其中的一种或多种，所述过渡层材料为所述芯体材料、表面层材料中的一种或多种；所述金属或/和其合金或/和其化合物包括但不限于：铝、铜、铅、钛、锡或/和其合金或/和其化合物中的一种或多种，所述碳材料包括但不限于：碳黑、活性碳、石墨、碳纤维、泡沫碳、碳纳米管、石墨烯中的一种或多种。The core material is one or more of a metal or/and an alloy thereof or/and a compound thereof, a conductive plastic, a plastic, a conductive ceramic, a carbon material, a glass, a silica, and the transition layer material is One or more of a core material, a surface layer material; the metal or/and alloy thereof or/and compounds thereof include, but are not limited to, aluminum, copper, lead, titanium, tin, or/and alloys thereof and/or One or more of its compounds, including but not limited to: one or more of carbon black, activated carbon, graphite, carbon fiber, foamed carbon, carbon nanotubes, graphene.
所述蓄电池进行或被进行蓄电池或/和蓄电池组正极、负极极性反转及其后的充电或充放电操作，所述蓄电池进行或被进行该操作的总累计次数为≥1次，所述正极、负极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。The battery performs or is subjected to a charge or charge/discharge operation of the battery or/and the battery pack positive and negative polarity inversion, and the total cumulative number of times the battery performs or is performed is ≥1 times. The positive and negative polarity inversion and subsequent charging or charging and discharging operations, that is, the positive electrode and the negative electrode are reversed in polarity, and after the polarity is reversed, the electrode undergoing the polarity inversion is performed. Charging or charging and discharging operations.
所述蓄电池包括一种电路，所述电路具有将蓄电池的正极、负极进行极性反转及其后的充电或充放电操作的功能；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 battery includes a circuit having a function of performing polarity reversal of the positive and negative electrodes of the battery and subsequent charging or charging and discharging operations; or the circuit can reverse the battery or the battery pack One or more of charging, forced discharging, and reverse charging.
有益效果Beneficial effect
本发明蓄电池、蓄电池进行或被进行蓄电池或/和蓄电池组正极、负极极性反转及其后的充电或充放电操作，使蓄电池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，得以克服、解决，从而蓄电池具有长寿命。The battery and the storage battery of the present invention are subjected to or subjected to charging or charging and discharging operations of the positive electrode and the negative electrode of the battery or/and the battery pack, and the battery positive active material is expanded or/and softened or/and peeled off, corroded and blunt. , early capacity loss, salinization, crystallization, negative surface area shrinkage, poor contact between active material and conductive current collector, memory effect, decomposition of active material itself, one or more problems, can be overcome, solved, and thus the battery Has a long life.
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 PCTCN2018113860-appb-000001
positive electrode:
Figure PCTCN2018113860-appb-000001
负极：
Figure PCTCN2018113860-appb-000002
negative electrode:
Figure PCTCN2018113860-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，当其正极与负极为正极、负极通用的电极时(即正负极通用电极)，会明显提高生产、回收效率、良率，降低生产、回收成本，以及保证本发明蓄电池具有良好的工作性能，包括寿命、容量。When the positive electrode and the negative electrode are common electrodes for the positive electrode and the negative electrode (ie, the positive and negative electrode for common use), the production, recovery efficiency, yield, production and recovery costs are reduced, and the battery of the present invention is ensured to have a good work. Performance, including life and capacity.
附图说明DRAWINGS
图1是本发明实施例2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 a cycle charge and discharge operation according to a second embodiment of the present invention.
图2是本发明实施例3铅酸蓄电池组循环充放电工作的工作放电容量及工作放电终止电压数据图。2 is a data diagram showing the working discharge capacity and the working discharge termination voltage of the lead-acid battery pack in the cycle charging and discharging operation of the third embodiment of the present invention.
图3是本发明实施例3铅酸蓄电池组在其第23－28次循环充放电工作过程期间及该过程期间穿插的单次正、负极极性反转及其后的充电或充放电操作过程中的电流、电压数据图。3 is a single positive and negative polarity reversal and subsequent charging or charging and discharging operation of the lead-acid battery pack according to Embodiment 3 of the present invention during the 23-28th cycle charging and discharging operation process and during the process. Current and voltage data plots.
图4是本发明实施例7具有长使用寿命的铅酸蓄电池或电池组电极集流体复合型材料表面层/芯体结构示意图。4 is a schematic view showing the surface layer/core structure of a lead-acid battery or a battery-group electrode current-collecting composite material having a long service life according to Embodiment 7 of the present invention.
图5是本发明实施例7具有长使用寿命的铅酸蓄电池或电池组电极集流体复合型材料表面层/过渡层/芯体结构示意图。Fig. 5 is a schematic view showing the surface layer/transition layer/core structure of a lead-acid battery or a battery electrode current collector composite material having a long service life according to Embodiment 7 of the present invention.
图中附图标记说明如下：The reference numerals in the figure are as follows:
15：表面层材料15: surface layer material
16：芯体材料16: core material
17：过渡层材料17: Transition layer material
具体实施方式Detailed ways
本实施方式中，长寿命蓄电池，包括正极、负极，所述蓄电池或电池组其正极和负极均为正负极通用电极(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；所述正极、负极、正负极通用电极包括但不限于：彼此具有相同活性物质或相同活性物质配方的正负极通用电极、彼此为同一种的或相同的正负极通用电极、彼此等价的正负极通用电极、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，其中的一种或多种；In the present embodiment, the long-life battery includes a positive electrode and a negative electrode, and the positive electrode and the negative electrode of the battery or the battery pack are both positive and negative common electrodes (electrodes for the positive electrode and the negative electrode), and the positive and negative electrode common electrodes are In the battery or battery pack, it can be used either as a positive electrode or as a negative electrode, or as a positive electrode, some as a negative electrode, or as a positive electrode during operation or use of the battery or battery pack. The positive electrode, the negative electrode, the positive and negative electrode common electrodes include, but are not limited to, positive and negative electrode common electrodes having the same active substance or the same active substance formula, The positive and negative electrode common electrodes of the same or the same, the positive and negative electrode common electrodes which are equivalent to each other, the positive electrode and the negative electrode of the electrode active material or the active material formulation including the expansion agent, and/or the positive electrode or/and the negative electrode One or more of them;
或者，本实施方式中，所述蓄电池或电池组其正极或/和负极中包括膨胀剂。Alternatively, in the embodiment, the battery or the battery pack includes a swelling agent in the positive electrode or/and the negative electrode.
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。The same or the same positive and negative common electrode means that the positive electrode and the negative electrode of the battery are identical in terms of electrode structure, size, formulation, material, manufacturing process and the like (ie, all electrode compositions) The same or the same, the same or the same positive and negative electrode for the positive and negative electrodes means that those which are identical to each other before being formed or charged and discharged, can form a positive electrode or a negative electrode after being formed or charged and discharged. The negative electrode common electrode, which is identical to each other before being formed or charged and discharged, means that 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 activity before the electrode is formed. The quality of the substance (such as but not limited to the quality of the lead paste and the quality of the lead paste), the manufacturing process, etc. are identical (ie, the same in all respects), or the manufacturing error (ie, removal, elimination) is not considered when manufacturing the electrode. To remove the existence or influence of manufacturing errors, two or more electrodes are constructed and manufactured with respect to each other before being subjected to a charge or charge and discharge operation ( Electrode structure, shape, size, formulation, material, making process, etc.) are identical.
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。The equivalent of each other means that the electrodes have the same function and performance after being formed, or the electrodes are not affected by the error factor during the operation or use of the battery or the battery pack after being formed or charged and discharged ( For example, but not limited to: manufacturing error, measurement error) (ie, erasing, eliminating, eliminating the presence or influence of errors), having or exhibiting the same function and performance.
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。The active material of the positive electrode or/and the negative electrode of the battery is one or more of a simple substance or a compound having two or more kinds of stable oxidation valence states; the two or more stable oxidation valences are Elements of the state include, but are not limited to: lead, iron, copper, nickel, manganese, silver, phosphorus, sulfur, chlorine, vanadium, chromium, cobalt, arsenic, selenium, bromine, tin, antimony, bismuth, iodine, tungsten, antimony. One or more.
所述蓄电池，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 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 or more of which.
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 .
所述蓄电池在蓄电池组中的所有单电池个数包括但不限于：≥N+1，所述N等于所述蓄电池组 的额定电压数值除以所述蓄电池组中单电池的额定电压数值。The number of all battery cells in the battery pack includes, but is not limited to, ≥ N+1, and the N is equal to the rated voltage value of the battery pack divided by the rated voltage value of the battery cells in the battery pack.
所述蓄电池的正极或/和负极、正负极通用电极的集流体的材料包括但不限于：铅、铅合金、表面层为铅或铅合金的复合型材料，其中的一种或多种，所述表面层为铅或铅合金的复合型材料具有表面层/芯体结构或表面层/过渡层/芯体结构。The material of the current collector of the positive electrode or/and the negative electrode and the positive and negative electrode common electrode of the battery includes, but is not limited to, lead, lead alloy, composite material whose surface layer is lead or lead alloy, one or more of which are The composite material whose surface layer is lead or lead alloy has a surface layer/core structure or a surface layer/transition layer/core structure.
所述芯体材料为金属或/和其合金或/和其化合物、导电塑料、塑料、导电陶瓷、碳材料、玻璃、二氧化硅其中的一种或多种，所述过渡层材料为所述芯体材料、表面层材料中的一种或多种；所述金属或/和其合金或/和其化合物包括但不限于：铝、铜、铅、钛、锡或/和其合金或/和其化合物中的一种或多种，所述碳材料包括但不限于：碳黑、活性碳、石墨、碳纤维、泡沫碳、碳纳米管、石墨烯中的一种或多种。The core material is one or more of a metal or/and an alloy thereof or/and a compound thereof, a conductive plastic, a plastic, a conductive ceramic, a carbon material, a glass, a silica, and the transition layer material is One or more of a core material, a surface layer material; the metal or/and alloy thereof or/and compounds thereof include, but are not limited to, aluminum, copper, lead, titanium, tin, or/and alloys thereof and/or One or more of its compounds, including but not limited to: one or more of carbon black, activated carbon, graphite, carbon fiber, foamed carbon, carbon nanotubes, graphene.
所述蓄电池进行或被进行蓄电池或/和蓄电池组正极、负极极性反转及其后的充电或充放电操作，所述蓄电池进行或被进行该操作的总累计次数为≥1次，所述正极、负极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。The battery performs or is subjected to a charge or charge/discharge operation of the battery or/and the battery pack positive and negative polarity inversion, and the total cumulative number of times the battery performs or is performed is ≥1 times. The positive and negative polarity inversion and subsequent charging or charging and discharging operations, that is, the positive electrode and the negative electrode are reversed in polarity, and after the polarity is reversed, the electrode undergoing the polarity inversion is performed. Charging or charging and discharging operations.
所述正极、负极极性反转及其后的充电或充放电操作包括但不限于：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。The reverse polarity of the positive electrode and the negative electrode and subsequent charging or charging and discharging operations include, but are not limited to, causing the positive electrode or the positive electrode active material of the battery or/and the battery pack to react with the battery negative electrode or by electrochemical reduction reaction. It is reduced to metal or 0 valence.
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 (electrical 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 electrodes of the battery or the battery pack and the subsequent charging or charging and discharging operations include: inverting the polarity of the positive electrode and the negative electrode, and subsequent charging or charging and discharging operations and 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.
所述正极、负极极性反转及其后的充电或充放电操作包括但不限于，解决蓄电池正极活性物质膨胀、软化、脱落问题，或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 reverse polarity of the positive electrode and the negative electrode and subsequent charging or charging and discharging operations include, but are not limited to, solving the problem of expansion, softening, and falling off of the positive electrode active material of the battery, or are also used to solve other problems of the battery separately, or are solved. The problem of expansion, softening and shedding of the positive electrode active material of the battery is also used to solve other problems of the battery, including but not limited to: corrosion of the battery (including but not limited to electrodes, sinks, current collector corrosion), passivation Early capacity loss, salinization, crystallization, shrinkage of the 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, one or more problems.
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.
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但不限于：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 and discharging operations of the positive electrode, the negative polarity, or the polarity reversal of the battery or/and the battery pack, including but not limited to: the battery or the battery The group performs reverse polarity charging, forced discharging, reverse charging and charging, one or more of them.
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.
所述蓄电池或/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 battery pack includes, but is not limited to, a planar grid type, a tubular type, a wound type, a bipolar type, a horizontal lead cloth type, a foam grid type, a column type, a stable gap body electrode type, Sintered, pouch battery or battery pack, or including 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 (super battery) battery or battery Groups, or hybrid battery packs including, but not limited to, these types of batteries, and other various types of batteries or battery packs. The full tubular battery has a tubular positive electrode and a tubular negative electrode.
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.
本实施方式中蓄电池、蓄电池进行或被进行蓄电池或/和蓄电池组正极、负极极性反转及其后的充电或充放电操作方法使蓄电池或电池组的寿命或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，通过本实施方式中的蓄电池、操作、方法，本实施方式中的蓄电池或电池组的寿命或使用寿命被提高或延长至1.3倍以上－10倍以上，或/和，寿命或循环寿命被提高或延长了50次以上－500次以上、500次以上－3000次以上，其中的一种或多种。In the embodiment, the battery or the battery is subjected to or is subjected to a charging or charging/discharging operation method of the positive or negative polarity of the battery or/and the battery pack, and the life or the service life of the battery or the battery pack is significantly improved or extended. When the depth of discharge (DOD) includes, but is not limited to, 1-100%, the life or the service life of the battery or the battery pack in the present embodiment is increased or extended to 1.3 times or more by the battery, operation, and method in the present embodiment. -10 times or more, or / and, the life or 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.
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＝2V、4V、6V、12V、24V、36V、48V、60V或72V、240V、360V、480V、600V，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。 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=2V , 4V, 6V, 12V, 24V, 36V, 48V, 60V or 72V, 240V, 360V, 480V, 600V, C 2 = 6.5Ah, 12Ah, 14Ah, 16Ah, 20Ah, 24Ah, 30Ah or 32Ah, 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 C20 = 10.4 Ah, 19.2 Ah, 22.4 Ah, 25.6 Ah, 32 Ah, 38.4 Ah, 48 Ah or 51.2 Ah. 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.
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，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、彼此为同一种的或相同的正负极通用电极、彼此等价的正负极通用电极、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、包括膨胀剂的正极或/和负极，其中的一种或多种。In this embodiment, the battery includes a positive electrode and a negative electrode. Alternatively, the positive and negative electrodes of the battery in this embodiment are positive and negative common electrodes. The positive electrode, the negative electrode, and the positive and negative common electrodes of the battery of the embodiment include, but are not limited to, the same as each other. Positive and negative electrode common electrodes of the active substance or the same active substance formula, positive and negative common electrodes of the same or the same, mutually equivalent positive and negative electrode common electrodes, electrode active materials or active substance formulations including expansion agents One or more of a positive and negative electrode of the common electrode or / and a positive electrode or / and a negative electrode, a positive electrode or / and a negative electrode including a swelling agent.
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，其中的一种或多种。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, one or more of which.
在本实施例的其它实施方式中，本实施例上述硫酸钡或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、3％以上，其中的一种或多种。In other embodiments of the present embodiment, the mass percentage of the barium sulfate or the swelling agent in the active material or the active material formulation in the present embodiment is 0.01% or more, 0.02% or more, 0.03% or more, 0.05% or more, and 0.08. % or more, 0.1% or more, 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, 3% 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不超过或等于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 not more than or equal to 5%, 10%, 20%, 30%, 40%, 50%, wherein One or more.
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.
本实施例铅酸蓄电池活性物质或活性物质配方包括但不限于如下一种或两种：正极：铅粉或氧化铅粉100Kg、硫酸钡1.0Kg、短纤维0.06Kg、、硫酸溶液(45wt.％)8.3Kg、水8.25Kg；负极：铅粉或氧化铅粉100Kg、硫酸钡0.6Kg、乙炔黑0.3Kg、硫酸溶液(45wt.％)9.0Kg、水8.25Kg；The active material or active substance formulation of the lead-acid battery of the present embodiment includes but is not limited to one or two of the following: positive electrode: lead powder or lead oxide powder 100Kg, barium sulfate 1.0Kg, short fiber 0.06Kg, sulfuric acid solution (45wt.%) 8.3Kg, water 8.25Kg; negative electrode: lead powder or lead oxide powder 100Kg, barium sulfate 0.6Kg, acetylene black 0.3Kg, sulfuric acid solution (45wt.%) 9.0Kg, water 8.25Kg;
本实施例铁－高铁酸盐蓄电池活性物质或活性物质配方包括但不限于如下一种或两种：负极：铁粉或氧化铁粉100Kg、活性碳0.5Kg、氢氧化锂0.9Kg；正极：高铁酸钡100kg、氢氧化锂0.9Kg。The iron-ferrate battery active material or active substance formulation of the present embodiment includes but is not limited to one or two of the following: negative electrode: iron powder or iron oxide powder 100Kg, activated carbon 0.5Kg, lithium hydroxide 0.9Kg; positive electrode: high iron 100 kg of acid hydrate and 0.9 kg of lithium hydroxide.
在本实施例的实施方式中，除本实施例指出的、说明的以外，本实施例蓄电池的形状、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。In the embodiment of the present embodiment, the shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
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软化或/和脱落、硫酸盐化、钝化、早期容量损失、活性物质与集流体接触不良、负极活性物质比表面 积收缩等原因中的一种或多种导致本实施例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上发生酸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、改善，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、预防正极活性物质软化或/和脱落、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩等问题，从而反复的、多次的使本实施例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 specific operation of the method for improving or prolonging the service life of the battery or the battery pack of the embodiment is that, after the battery or the battery pack of the embodiment has been subjected to the cyclic charge and discharge operation for more than one time, the battery or the battery pack is cycled according to the embodiment. The charging and discharging, overcharging, undercharging, high active material utilization rate and the like cause the working discharge capacity of the battery or the battery pack of the present embodiment to be softened or/and detached, sulfated, passivated, and early capacity loss due to the positive active material. One or more of the reasons for poor contact between the active material and the current collector, shrinkage of the specific surface area of the negative electrode active material, etc., cause the working discharge capacity of the battery or the battery pack of the present embodiment to decrease, and the working discharge of the battery or the battery pack of this embodiment When the capacity drops to 60%, 75%, 80%, 90% or 95% of its rated capacity C 2 , C 5 or C 20 , or the rate of increase of the charging voltage during the cyclic charging and discharging operation of the battery or battery pack of this embodiment When the speed is increased by 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 started. Performing one or two consecutive polarity inversions and/or subsequent charging or charging and discharging operations, that is, operating step (1): using a constant current source or/and a voltage source for the battery of the embodiment or The battery pack is subjected to reverse polarity charging, and the current of the reverse polarity charging is one or more of C 2 , C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or the voltage charged by the reverse pole is 0.5U. One or more of U, 1.5U, and 2U, such that the polarity of the electrodes A1, A2, ..., An of the battery or battery pack of the present embodiment is reversed from the original positive polarity to the negative polarity, and the electrode B1 The polarity of B, B, ..., Bn is reversed from the original negative polarity to positive polarity (this is the first polarity reversal of this period), and then, step (2) is operated: for the battery of this embodiment Or the battery pack continues to charge and discharge, the charging or discharging current is one or more of C 2 , C 5 , 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or the charging or discharging voltage is 0.5U, U One or more of 1.5U and 2U, such that the charging or/and discharge reaction of the negative electrode of the battery occurs on the electrodes A1, A2, ..., An of the battery or the battery of the present embodiment. Drive electrodes B1, B2, ..., the positive electrode reaction of the battery charging and / or discharging reaction occurs on Bn, when the present embodiment the battery or battery charge or discharge the charge reaches 4C 2, 3C 5, 0.5C 20 , 0.3C 2 , 3C 2 , or 5C 5 or when the voltage reaches 0.6U, U, 1.2U, 2.1U, then operate step (3): to 3C 2 , 2.5C 5 , 0.5C 20 , 0.8C 2 The battery or the battery pack of the embodiment is reversely charged by one or more of the 6C 2 or 2C 5 currents, so that the acid battery negative electrode occurs on the electrodes A1, A2, ..., An of the battery or the battery pack of the present embodiment. The discharge process of the electrode reaction, the discharge process of the battery positive electrode reaction occurs on the electrodes B1, B2, ..., Bn until the polarity of the electrodes A1, A2, ... An is reversed to the positive polarity, the electrode The polarity of B1, B2, ..., Bn is reversed from positive polarity to negative polarity (this is the second polarity reversal of this period), and then step (4) is operated: for the battery or battery of this embodiment The group continues to charge or charge and discharge, and the charging or discharging current is one of C 2 , 2C 5 , 0.5C 20 , 0.1C 2 , 3C 2 , or 0.05C 5 or A plurality of or charging voltages are one or more of 0.7U, 0.9U, 1.1U, and 1.7U, and the charging and discharging are DC or pulse charging and discharging, so that the electrodes A1, A2, .. of the battery or the battery of the present embodiment. , charging or / and discharging process of the battery positive electrode reaction occurs on the An, charging or / discharging process of the battery negative electrode reaction occurs on the electrodes B1, B2, ..., Bn, the process charging the battery or the battery pack of the embodiment When the amount of charge or/and discharge discharged by the discharge reaches 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, for example 0.7U, 0.9U, 1.05U or 1.4U, the working discharge capacity or working capacity of the battery or battery pack in this embodiment is restored or improved, improved, and the positive and negative polarity reversal and subsequent charging are repeated twice in this period. Or charge and discharge operation, and then put the battery or battery pack of the embodiment into a cycle work 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 softening or/and shedding of positive active materials, electrode passivation, corrosion, early capacity loss, sulphation, active substances in the event of mechanical breakage or grid damage. The problem of poor contact with the current collector and shrinkage of the specific surface area of the negative electrode, thereby repeatedly, repeatedly, repairing, restoring or improving the working discharge capacity or working capacity of the battery or the battery pack of the embodiment, thereby improving or extending the battery of the embodiment or The life of the battery pack.
本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或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，本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或使用寿命提高或延长至1.3倍以上－10倍以上，或/和，寿命或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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or 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 battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
实施例2Example 2
本实施例涉及铅酸蓄电池、铅膏、铅酸蓄电池电极、提高或延长铅酸蓄电池使用寿命的方法、电池充放电器，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，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电池正、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 lead-acid battery, a lead paste, a lead-acid battery electrode, a method for improving or prolonging the service life of a lead-acid battery, and a battery charge and discharge device. The charge and discharge device of the embodiment has a positive and negative electrodes of a lead-acid battery. The polarity inversion and the function of the subsequent charging or charging and discharging operation, the battery charger and the discharger of the present embodiment can be charged, charged or charged and discharged after the polarity inversion and polarity inversion at the output end thereof. The lead-acid battery performs the charging or charging/discharging operation after the polarity of the battery is reversed, the polarity is reversed, and the polarity is reversed. All the operations on the battery in this embodiment are charged and discharged in this embodiment except for the manual operation. Electrical appliances are realized through their functions and work.
本实施例铅酸蓄电池的额定电压为2V，设计额定容量为821mAh(2h率，25℃)，本实施例铅酸蓄电池包括两片电极，该两片电极均为正负极通用电极(即正极、负极通用的电极)，同时也是同一种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，该两片电极则分别被形成正极和负极，将该两片电极分别定义为电极A、电极B，最开始时，将电极A作为正极、电极B作为负极进行电池的化成和工作，该两片电极之间隔有AGM隔板，本实施例的该两片电极的铅膏或铅膏配方中包括球磨铅粉、BaSO 4(0.8％，质量百分比，相对于球磨铅粉)、硫酸、水、短纤维，平均每片电极上的活性物质质量为13.41g，本实施例铅酸蓄电池中的硫酸溶液密度为1.27g/cm 3，本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。 The lead-acid battery of the present embodiment has a rated voltage of 2V and a designed rated capacity of 821mAh (2h rate, 25°C). The lead-acid battery of the embodiment includes two electrodes, and the two electrodes are positive and negative common electrodes (ie, positive electrode). 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. spacer electrodes have AGM separator, a lead, or lead paste the two electrode paste formulations of the present embodiment comprises a ball lead powder, BaSO 4 (0.8%, by mass percentage, with respect to the ball mill lead powder), sulfur , Water, short fibers, the average mass of the active material on each electrode sheet 13.41 g, density of the solution of sulfuric acid in the lead-acid battery of the present embodiment is the embodiment of 1.27g / cm 3, the present embodiment eliminates or prevents fluid loss, open, short Factors such as mechanical damage, test failure, etc. interfere with the implementation process and implementation results of this embodiment.
在本实施例的实施方式中，除本实施例指出的、说明的以外，本实施例蓄电池的形状、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。In the embodiment of the present embodiment, the shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
本实施例提高或延长铅酸蓄电池使用寿命的方法为：首先，让本实施例电池进行循环充放电工作，工作制度为：当电池处于充电后状态时，以371mA的恒电流对电池进行放电，当电池电压≤1.75V时，停止放电，接着以222mA的恒电流对其进行充电，并当测得电池电压达到2.65V后，转换成以2.65V恒压继续对电池充电，两次(恒流、恒压)充电总时间为7小时24分(有特殊说明的除外),然后，再以371mA的恒电流重复前述的放电过程，如此反复放电、充电，使电池循环工作，电池工作环境温度为25±1℃。其次，当本实施例铅酸蓄电池在上述循环工作中工作循环次数达到某一设定的数值时(例如，本实施例中设定的分别为第15次、第31次、…)，停止电池的工作，开始对电 池进行一次单次正、负极极性反转及其后的充电或充放电操作，该操作完成后，使电池在原来的工作制度下继续工作、并且使极性反转前的电池正极在极性反转后作为负极进行工作、极性反转前的电池负极在极性反转后作为正极进行工作，直到触发或开始下次的单次正、负极极性反转及其后的充电或充放电操作，如此多次、穿插地在本实施例铅酸蓄电池循环工作过程中，对本实施例铅酸蓄电池进行单次正、负极极性反转及其后的充电或充放电操作，使本实施例铅酸蓄电池的电极A有时作为正极工作、有时作为负极工作，相应的电极B有时作为负极工作、有时作为正极工作，以改善、修复、消除、逆转、抑制或防止本实施电池的正极活性物质软化或/和脱落、负极比表面积收缩、电极/集流体/汇流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良问题中一种或多种，使本实施例电池的工作放电充电能力在每次该操作后得到改善、恢复、提高或维护，从而实现提高或延长本实施例铅酸蓄电池的使用寿命。本实施例电池的循环工作过程也由本实施例电池充放电器所具有的充电、放电功能来实施(以下对电池的所有操作及测量除了特别说明是手动外，均为通过本实施例电池充放电器进行程序设定、执行实现)。The method for improving or prolonging the service life of the lead-acid battery in the embodiment is as follows: Firstly, the battery of the embodiment is subjected to cyclic charging and discharging work, and the working system is: when the battery is in the state of charging, the battery is discharged with a constant current of 371 mA. When the battery voltage is ≤1.75V, the discharge is stopped, then it is charged with a constant current of 222mA, and when the measured battery voltage reaches 2.65V, it is converted to continue charging the battery with a constant voltage of 2.65V, twice (constant current) , constant voltage) The total charging time is 7 hours and 24 minutes (except for special instructions), and then repeat the above discharge process with a constant current of 371 mA, so that the battery is cycled and discharged, and the battery operating environment temperature is 25 ± 1 ° C. 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 improve and repair. Eliminating, reversing, inhibiting or preventing softening or/and shedding of the positive active material of the battery of the present embodiment, shrinkage of the specific surface area of the negative electrode, electrode/catch/concentration corrosion, passivation, early capacity loss, sulfation, active material and current collector One or more of the problem of poor contact causes the working discharge charging capability of the battery of the embodiment to be improved, restored, improved or maintained after each operation, thereby achieving an increase or extension of the service life of the lead-acid battery of the embodiment. The cycle operation process of the battery of the embodiment is also implemented by the charging and discharging functions of the battery charger and discharger of the embodiment (hereinafter all the operations and measurements of the battery are charged and discharged by the battery of the embodiment except that the manual is specifically described. The appliance is programmed and implemented.
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1所示，在第1-15次循环工作中，本实施例电池的电极状态为A+/B-，此时电极A上发生正极电极反应，电极B上发生负极电极反应，在第1-15次循环工作中，本实施例电池的放电容量总体趋向降低，经检查，这主要是因为正极活性物质软化、脱落作用而引起的(与铅膏中高含量的BaSO 4、高活性物质利用率、深度放电有关，以下类同)，在第15次放电后，放电容量为942mAh。此时根据程序设定，本实施例电池充放电器自动停止电池的工作，对电池进行第一次单次正、负极极性反转及其后的充电或充放电操作的准备和正式操作，即，在第15次工作放电结束后(此时电池电压为1.75V)，停止电池工作，对电池继续以371mA恒电流放电1小时，此过程使电池电压降至0.04V，然后停止放电，对该电池进行其正、负极的极性反转，即通过本实施例充放电器输出端的极性反转(充放电器输出端的极性反转是通过充放电器内的继电器电路触点开、闭状态变换实现的)，将充放电器与铅酸蓄电池的连接状态从充放电器正极输出端与铅酸蓄电池电极A连接、充放电器负极输出端与铅酸蓄电池电极B连接，改换成，充放电器负极输出端与铅酸蓄电池电极A连接、充放电器正极输出端与铅酸蓄电池电极B连接，此连接状态变换后，测得的电池电压为负值，然后，以186mA的恒电流对连接状态变换后的本实施例电池进行充电，使电池电压从负值上升至0V然后再上升到1.75V(此过程中发生本实施例电池第一次极性反转，其中电池电压从负值上升至0V过程中，电极A上发生铅酸蓄电池正极电极反应的放电过程、电极B上发生铅酸蓄电池负极电极反应的放电过程，电池电压从0V上升至1.75V的过程中电极A上发生铅酸蓄电池负极电极反应的充电过程、电极B上发生铅酸蓄电池正极电极反应的充电过程)，当电池电压达到1.75V后，继续以222mA的恒电流对电池充电至2.65V，然后再以2.65V的恒电压对电池进行充电4小时16分，然后以371mA恒电流对电池进行放电，至1.75V，然后，再以222mA的恒电流对电池进行充电，直至电池电压达到2.65V改成以2.65V 对电池进行恒压充电5小时，充电结束后，至此，完成对本实施例电池的第一次单次正、负极极性反转及其后的充电或充放电操作，此时电池的电极状态已从A+/B-被改换成A-/B+。然后，使电极A作为负极进行工作、电极B作为正极进行工作，使该电池重新进入同前的放电-充电循环工作制度下进行第16次工作放电及之后次数的循环工作。结果表明，经第一次单次正、负极极性反转及其后的充电或充放电操作后，本实施例电池在第16次循环工作状态下的放电容量为888.3mAh。此次极性反转后与电池恢复循环工作前这段过程中对电池的充电容量为7031mAh。 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. 1, in the 1st-15th cycle operation, the electrode state of the battery of the present 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 polarity reversal of its positive and negative poles, that is, the polarity of the output end of the charge and discharge device is reversed by the present embodiment (the polarity reversal at the output end of the charge and discharge device is through the contact of the relay circuit in the charger/discharger, The state of connection between the charge and discharge device and the lead-acid battery is connected from the positive output end of the charge and discharge device to the lead-acid battery electrode A, and the negative output end of the charge and discharge device is connected to the lead-acid battery electrode B, and is changed into The negative output end of the charge and discharge device is connected to the lead acid battery electrode A, and the positive and negative output end of the charge and discharge device is connected with the lead acid battery electrode B. After the connection state is changed, the measured battery voltage is negative, The battery of this embodiment after the connection state conversion is charged with a constant current of 186 mA, so that the battery voltage rises from a negative value to 0 V and then rises to 1.75 V (the first polarity reversal of the battery of this embodiment occurs in this process). In the process in which the battery voltage rises from a negative value to 0V, the discharge process of the lead-acid battery positive electrode reaction occurs on the electrode A, and the discharge process of the lead-acid battery negative electrode reaction occurs on the electrode B, and the battery voltage rises from 0V to 1.75V. During the process, the charging process of the negative electrode reaction of the lead-acid battery on the electrode A and the charging process of the positive electrode reaction of the lead-acid battery on the electrode B occur. When the battery voltage reaches 1.75V, the battery is continuously charged to 2.65 with a constant current of 222 mA. V, then charge the battery for 4 hours and 16 minutes with a constant voltage of 2.65V, then discharge the battery to a constant current of 371mA to 1.75V, and then charge the battery with a constant current of 222mA until the battery voltage reaches 2.65V was changed to 2.25V to charge the battery for 5 hours. After the charging is completed, the first single positive and negative polarity of the battery of this embodiment is completed. After charging or charging and discharging and transfer operations, this time from the state of the battery electrodes A + / B- is a switch from 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1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1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. 1 , 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 is operated as a positive electrode, and the electrode B is operated as a negative electrode, and the battery is re-entered into the same discharge-charge cycle operation system to perform the 32nd operation discharge and the subsequent number of cycles. The results show that after the second single positive and negative polarity inversion and subsequent charging or charging and discharging operations, the battery has a discharge capacity of 1189 mAh in the 32nd cycle operation state, which should be opposite to the polarity. After the turn, the battery is fully charged. The total charge capacity of the battery between the polarity reversal and the battery recovery cycle is 6659 mAh. Next, the battery is continuously operated under the working system. As shown in FIG. 1, 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1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. 1 shows the electrode of the lead-acid battery of the present embodiment during the cycle charging and discharging operation before or after the single positive and negative polarity inversion and the subsequent charging or charging and discharging operations of the present embodiment. The 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1所示，本实施例铅酸蓄电池的工作放电容量都同比地得到提升或恢复。一方面如上所述，本实施例的正、负极极性反转及其后的充放电或充放电操作使得本实施例铅酸蓄电池的正极活性物质软化、脱落被改善、修复、逆转、消除、抑制、防止，从而使得本实施例铅酸蓄电池循环工作中的工作放电容量该操作之后获得提高或恢复，另一方面，本实施例的正、负极极性反转及其后的充放电或充放电操作，也必然对本实施例电池循环工作过程中发生、轻微发生或将要发生的电极钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极比表面积收缩、硫酸盐化的问题具有改善、修复、逆转、抑止、消除、预防的作用，例如，由于电极A、B反复交替地作为正极或负极进行充放循环工作，使得作为正极工作时产生的电极腐蚀问题在电极作为负极进行充放循环工作时得到改善、修复、逆转，从而也使得本实施例铅酸蓄电池在长期使用过程中的腐蚀问题得到延缓、改善、修复、逆转、防止，在本实施例铅酸蓄电池正常循环工作过程中，定期或不定期的(例如，以规定循环工作次数的方式)、穿插地对本实施例铅酸蓄电池进行本实施例的正、负极极性反转及其后的充放电或充放电操作，将会有效的改善、修复、逆转、消除、抑制、预防正极活性物质软化或/和脱落、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩问题，从而提高或延长本实施例铅酸蓄电池的使用寿命。As shown in FIG. 1, 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 softened and peeled off, improved, repaired, reversed, eliminated, Suppressing and preventing, so that the working discharge capacity in the cycle operation of the lead-acid battery of the embodiment is improved or restored after the operation, and on the other hand, the polarity of the positive and negative poles of the embodiment is reversed and then charged or discharged or charged. The discharge operation also has the problems of electrode passivation, early capacity loss, corrosion, poor contact of active material and current collector, shrinkage of specific surface area of the anode, and sulfation which occur during the cycle operation of the battery of the present embodiment. The effect of improving, repairing, reversing, suppressing, eliminating, and preventing, for example, since the electrodes A and B are repeatedly alternately used as a positive electrode or a negative electrode for charging and discharging cycles, the problem of electrode corrosion generated when the positive electrode is operated is charged at the electrode as a negative electrode. The cycle work is improved, repaired, reversed, thereby also making the lead-acid battery of the embodiment During the period of use, the corrosion problem is delayed, improved, repaired, reversed, and prevented. In the normal cycle of the lead-acid battery in this embodiment, it is periodically or irregularly (for example, in the manner of specifying the number of cycles) and interspersed. Performing the positive and negative polarity inversion and the subsequent charge, discharge or charge and discharge operations of the present embodiment for the lead-acid battery of the present embodiment will effectively improve, repair, reverse, eliminate, suppress, and prevent the softening of the positive active material or/or And the shedding, electrode passivation, corrosion, early capacity loss, sulfation, poor contact between the active material and the current collector, and the specific surface area shrinkage of the anode, thereby increasing or prolonging the service life of the lead-acid battery of the present embodiment.
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1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，另外，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次循环的基础上继续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. 1 , according to the 1-15th discharge capacity attenuation trend line, it can be considered that the lead-acid battery of the 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. In addition, 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 this embodiment makes the example The service life of lead-acid batteries continues to increase or increase over the 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，可以使用脉冲电流、脉冲电压代替直流电、恒电压进行本实例的连续两次极性反转及其后的充电或充放电操作步骤中的极性反转及其后的充电或充放电步骤或过程，从而有利于提高本实施例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 pulse current and the pulse voltage may be used instead of the direct current and the constant voltage to perform the polarity inversion in the two consecutive polarity inversions of the present example and the subsequent charging or charging and discharging operation steps. Subsequent charging or charging and discharging steps or processes are advantageous for improving the aging and energy efficiency of the battery polarity inversion and subsequent charging or charging and discharging operations of the present 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，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.
本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或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，本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或使用寿命提高或延长至1.3倍以上－10倍以上，或/和，寿命或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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or 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 battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
实施例3Example 3
本实施例铅酸蓄电池组为全管式铅酸蓄电池组，额定电压为4V，额定容量为539mAh(C 3.5，3.5h率，25℃)由两只彼此相同的的全管式铅酸蓄电池串联而成，每只全管式铅酸蓄电池的所有电极均为管式电极，且该些管式电极均为正负极通用电极(即正极、负极通用的电极)，且该些管式正负极通用电极在电极结构和活性物质配方上相同，每个管式正负极通用电极的套管内直径为6.3mm,，套管高度为75mm(包括管塞)，套管内铅-钙合金导电骨芯直径为2.5mm，每只全管式铅酸蓄电池包括3个管式正负极通用电极，为了便于本实施例的后续说明，将本实施例铅蓄电池组的6个管式 正负极通用电极分别命名为电极A1、A2、A3、A4、B1、B2，这6个电极在本实施例铅酸蓄电池组中的每只全管式铅酸蓄电池中排布方式为：电极B1夹在电A1、A2之间或电极B2夹在电极A3、A4之间，电极A1或A2或A3或A4套管中活性物质的质量为均为5.8g，电极B1或B2套管中的活性物质质量均为5.5g，电极A1、A2、A3、A4、B1、B2中的活性物质均由球磨铅粉、硫酸钡(相对于球磨铅粉为0.8wt％)构成，将本实施例铅酸蓄电池组的两个输出端子分别命名为电池组端子A、B，其中电池组端子A连接于电极A1或A2或A3或A4，电池组端子B连接于电极B1或B2，本实施例铅酸蓄电池组在其最初始的循环充放电工作过程中，电极A1、A2、A3、A4作为正极进行循环工作(即循环工作过程中电极A1、A2、A3、A4上发生的是铅酸蓄电池正极电极反应的充放电过程)、电极B1、B2作为负极进行循环工作(即循环工作过程中电极B1、B2上发生的是铅酸蓄电池负极电极反应的充放电过程)，即此时电池组端子A的极性为正、电池组端子B的极性为负，表示为A+/B－(同理，当电池组端子A的极性为负、电池组端子B的极性为正时，表示为A－/B+)，正、负管式电极之间隔有隔板，本实施例铅酸蓄电池组使用的电解液硫酸溶液的密度为1.27g/cm 3，本实施例排除或防止了失液、断路、短路、机械损坏、测试故障等因素对本实施例实施过程及实施结果的干扰。 The lead-acid battery pack of this embodiment is a full-tube lead-acid battery pack with a rated voltage of 4V and a rated capacity of 539mAh (C 3.5 , 3.5h rate, 25° C.) connected in series by two identical tubular-type lead-acid batteries. Each of the electrodes of the full-tube lead-acid battery is a tubular electrode, and the tubular electrodes are positive and negative common electrodes (ie, electrodes common to the positive electrode and the negative electrode), and the tubular positive and negative The extremely common electrode is the same in the electrode structure and active material formulation. The inner diameter of the sleeve of each positive and negative electrode of the tube is 6.3mm, the height of the sleeve is 75mm (including the plug), and the lead-calcium alloy conductive bone in the sleeve The core diameter is 2.5 mm, and each of the full-tube lead-acid batteries includes three tubular positive and negative common electrodes. To facilitate the subsequent description of the embodiment, the six tubular positive and negative electrodes of the lead battery pack of the present embodiment are generally used. The electrodes are named as electrodes A1, A2, A3, A4, B1, and B2, respectively. The six electrodes are arranged in each of the full-tube lead-acid batteries in the lead-acid battery pack of the present embodiment: the electrode B1 is sandwiched between electricity. Between A1, A2 or electrode B2 is sandwiched between electrodes A3 and A4, and electrode A1 or A2 or A3 The mass of the active material in the A4 casing is 5.8g, the mass of the active material in the sleeve of the electrode B1 or B2 is 5.5g, and the active substances in the electrodes A1, A2, A3, A4, B1, B2 are all ball-milled. Powder, barium sulfate (0.8wt% relative to ball-milled lead powder), the two output terminals of the lead-acid battery of this embodiment are respectively named as battery terminals A, B, wherein the battery terminal A is connected to the electrode A1 or A2 or A3 or A4, the battery terminal B is connected to the electrode B1 or B2. In the lead-acid battery pack of the embodiment, during the initial cycle charging and discharging operation, the electrodes A1, A2, A3, and A4 are cycled as the positive electrode ( That is, during the cyclic working process, the electrodes A1, A2, A3, and A4 are charged and discharged during the reaction of the positive electrode of the lead-acid battery), and the electrodes B1 and B2 are used as the negative electrode for the cyclic operation (that is, the electrodes B1 and B2 occur during the cyclic operation). The charging and discharging process of the negative electrode of the lead-acid battery), that is, the polarity of the terminal A of the battery pack is positive, and the polarity of the terminal B of the battery pack is negative, which is expressed as A+/B- (same reason, when the battery pack When the polarity of terminal A is negative and the polarity of battery terminal B is positive, It is expressed as A-/B+), and the separators of the positive and negative tube electrodes are separated by a separator. The density of the sulfuric acid solution of the electrolyte used in the lead-acid battery group of the present embodiment is 1.27 g/cm 3 , and the present embodiment excludes or prevents the loss. Factors such as liquid, open circuit, short circuit, mechanical damage, test failure, etc. interfere with the implementation process and implementation results of this embodiment.
在本实施例的实施方式中，除本实施例指出的、说明的以外，本实施例蓄电池的形状、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。In the embodiment of the present embodiment, the shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
提高或延长本实施例铅酸蓄电池组的使用寿命的方法为，每当本实施例铅酸蓄电池组循环工作到某一定次数时或工作放电充电能力由于正极活性物质软化或/和脱落、负极比表面积收缩、集流体或汇流体腐蚀、钝化、早期容量损失、硫酸盐化、活性物质与集流体接触不良等问题中的一种或多种而下降到一定程度时，即自动或/和手动地对本实施例铅酸蓄电池组的正、负极进行一次单次极性反转及其后的充电或充放电操作，以改善、修复、逆转、防止、抑制、消除由于正极活性物质软化、负极比表面积收缩、电极钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良其中的一种或多种原因造成的工作放电容量或工作能力下降、使用寿命终止的问题，使本实施例铅酸蓄电池组的工作放电容量或工作能力恢复或提高，然后在该次极性反转及其后的充电或充放电操作后，使本实施例铅酸蓄电池组以该次极性反转后的电极极性状态重新投入循环充放电工作中去进行循环工作，直到开始下次正、负极极性反转及其后的充电或充放电操作。所述在该次极性反转及其后的充电或充放电操作后，使本实施例铅酸蓄电池组以该次极性反转后的电极极性状态重新投入循环充放电工作中去进行循环工作，例如，若本实施例铅酸蓄电池组的电极A1、A2、A3、A4在该次极性反转前是作为正极进行循环工作(即在循环工作过程中电极A1、A2、A3、A4上发生铅酸蓄电池正极电极反应的充放电过程)，则在该次极性反转后，电极A1、A2、A3、A4是作为负极进行充放循环工作(即在循环工作过程中电极A1、A2、A3、A4上发生铅酸蓄电池负极电极反应的充放电过程)，相应的电极B1、B2若在该次极性反转前是作为负极进行循环工作(即循环工作过程中电极B1、B2上发生铅酸蓄电池负极电极反应的充放电过程)，则在该次极性反转后是作为正极进行循环工作(即 循环工作过程中电极B1、B2上发生铅酸蓄电池正极电极反应的充放电过程)，同理，若电极A1、A2、A3、A4或电极B1、B2在该次极性反转前的循环工作过程中的极性状态或极性方向反之，则，电极A1、A2、A3、A4或电极B1、B2在该次极性反转后的循环工作过程中的极性状态或极性方向亦反之。触发或开始对本实施例铅酸蓄电池组的正、负极进行任意一次极性反转及其后的充电或充放电操作的触发方式，可以是手动触发或程序根据预设定的触发条件的到达情况而自动触发，触发条件可以是一定的循环充放电工作次数或累计次数、充电量、放电量、充放电速率、电流变化量、电压变化量等中的一种或多种或它们的计算值。The method for improving or prolonging the service life of the lead-acid battery pack of the embodiment is that, when the lead-acid battery pack of the embodiment is circulated to a certain number of times or the working discharge charging capability is softened or/and detached from the positive active material, the ratio of the negative electrode is increased. Automatic or / and manual when one or more of surface area shrinkage, current collector or sink corrosion, passivation, early capacity loss, sulfation, poor contact of active material and current collector, etc. Performing a single polarity inversion and subsequent charging or charging and discharging operations on the positive and negative electrodes of the lead-acid battery pack of the present embodiment to improve, repair, reverse, prevent, suppress, and eliminate the softening and negative electrode ratio of the positive active material. Surface area shrinkage, electrode passivation, corrosion, early capacity loss, sulphation, poor contact of active material and current collector, one or more causes of reduced working discharge capacity or working capacity, end of service life, The operating discharge capacity or working capacity of the lead-acid battery pack is restored or improved, and then the polarity reversal and After the charging or charging and discharging operation, the lead-acid battery pack of the embodiment is re-introduced into the cyclic charging and discharging operation by the polarity state of the electrode after the polarity is reversed, until the next positive and negative polarity is started. Reverse and subsequent charging or charging and discharging operations. After the polarity inversion and subsequent charging or charging and discharging operations, the lead acid battery pack of the embodiment is re-introduced into the cyclic charging and discharging operation by the electrode polarity state after the polarity inversion. Cycling operation, for example, if the electrodes A1, A2, A3, and A4 of the lead-acid battery pack of the present embodiment are operated as a positive electrode before the polarity is reversed (that is, the electrodes A1, A2, and A3 during the cycle operation) On the A4, the charge and discharge process of the positive electrode reaction of the lead-acid battery occurs), after the polarity is reversed, the electrodes A1, A2, A3, and A4 are used as the negative electrode for the charge and discharge cycle (ie, the electrode A1 during the cycle operation). On the A2, A3, and A4, the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs. The corresponding electrodes B1 and B2 are cycled as the negative electrode before the polarity is reversed (that is, the electrode B1 during the cycle operation). The charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on B2), and the cycle is performed as the positive electrode after the polarity reversal (that is, the charging of the positive electrode of the lead-acid battery occurs on the electrodes B1 and B2 during the cyclic operation). Discharge process) Similarly, if the polarity state or polarity direction of the electrodes A1, A2, A3, A4 or the electrodes B1, B2 during the cyclic operation before the polarity inversion is reversed, the electrodes A1, A2, A3, A4 Or the polar states or polar directions of the electrodes B1 and B2 during the cyclic operation after the polarity inversion are reversed. Triggering or starting the triggering of any polarity reversal and subsequent charging or charging and discharging operations on the positive and negative poles of the lead-acid battery pack of the embodiment may be manual triggering or the arrival of the program according to a preset trigger condition. The automatic triggering, the triggering condition may be one or more of a certain number of cyclic charging and discharging operations or cumulative times, a charging amount, a discharging amount, a charging and discharging rate, a current variation amount, a voltage variation amount, or the like, or a calculated value thereof.
本实施铅酸蓄电池组采用的循环充放电工作制度为：工作放电时，以0.283C 3.5的电流进行放电至3.5V，然后，以0.338C 3.5的电流进行恒流充电至5.95V或时间为9小时24分，然后再以5.3V的电压进行恒压充电3小时，然后再重复之前的工作放电过程，如此反复、循环，使本实施例铅酸蓄电池组循环充放工作。 The circulating charge and discharge working system adopted in the lead-acid battery pack of the present embodiment is: discharging discharge to 3.5V at a current of 0.283 C 3.5 during working discharge, and then performing constant current charging to 5.95 V or time 9 at a current of 0.338 C 3.5 . After 24 hours, then constant voltage charging was carried out for 3 hours with a voltage of 5.3 V, and then the previous working discharge process was repeated, and the cycle of the lead-acid battery pack of this example was cyclically charged and discharged.
本实施例铅酸蓄电池组循环工作和本实施例提高或延长本实施例铅酸蓄电池组使用寿命的方法实施的部分结果，如图2所示，本实施例铅酸蓄电池组在循环工作过程中，在其工作循环次数的第6、7次之间、第17、18次之间、第25、26次之间、第33、34次之间、第41、42次之间、第56、57次之间进行或被进行了依次为第一次、第二次、.....、第六次的单次正、负极极性反转及其后的充电或充放电操作，所进行或被进行的正、负极极性反转及其后的充电或充放电操作的方法或过程如下：Part of the result of the method for implementing the cycle operation of the lead-acid battery pack of the present embodiment and the method for improving or prolonging the service life of the lead-acid battery pack of the embodiment, as shown in FIG. 2, the lead-acid battery pack of the embodiment is in the process of circulation Between the sixth and seventh times of the number of work cycles, between the 17th and 18th, between the 25th and 26th, between the 33rd and 34th, between the 41st and the 42nd, and 56th. Between 57 times or in sequence, the first, second, ..., the sixth single positive and negative polar polarity reversal and subsequent charging or charging and discharging operations are performed. Or the method or process of performing positive or negative polarity inversion and subsequent charging or charging and discharging operations is as follows:
对于第一次单次正、负极极性反转及其后的充电或充放电操作：当本实施例铅酸蓄电池组处于完成第6次循环工作后的充电状态下时，此时，电极A1、A2、A3、A4的极性为正，电极B1、B2的极性为负，停止本实施例铅酸蓄电池组的循环工作，将充放电设备的正、负输出端与本实施例铅酸蓄电池组此时的正、负极输出端子进行反极连接，即，充放电设备的正输出端与本实施例铅酸蓄电池组的负极输出端子(电池组端子B)连接，充放电设备的负输出端与本实施例铅酸蓄电池组的正极输出端子(电池组端子A)相连接，反极连接后，充放电设备测得本实施例铅酸蓄电池组的电压为－5.53V，然后，对本实施例铅酸蓄电池组以458mA的电流在该反极连接的状态下进行充电，使得本实施例铅酸蓄电池组的正、负极输出端的电压(充放电设备测得值，本实施例中以下同)从－5.53V上升到0V再上升到5.8V，此过程中本实施例铅酸蓄电池组发生了第一次极性反转，即，从-5.53V上升到0V的过程中，电极A1、A2、A3、A4上主要发生的是铅酸蓄电池正极电极反应的放电过程、电极B1、B2上主要发生的是铅酸蓄电池负极电极反应的放电过程，而在0V上升到5.8V的过程中，电极A1、A2、A3、A4上主要发生的是铅酸蓄电池负极电极反应的充电过程，电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的充电过程，在保持充放电设备输出端与本实施例铅酸蓄电池组输出端子的连接状态不变的情况下，再以152.7mA对本实施例铅酸蓄电池组进行放电14分钟至3.5V，然后再以229mA的电流恒流充电8小时至5.72V，然后，再以152.7mA放电2分钟至4.5V,然后，再以114mA恒流充电3小时至5.5V，然后将本实施例铅酸蓄电池组投入到循环工作的第7次工作放电 过程中去，进行第7次乃至其后直到第17次的循环工作。本实施例铅酸蓄电池组在第7－17次的循环工作中，电池组端子A的极性为负、电极池组端子B的极性为正，如图2所示，即，此过程中，电极A1、A2、A3、A4上发生铅酸蓄电池负极电极反应的充放电过程，电极B1、B2上发生铅酸蓄电池正极电极反应的充放电过程。For the first single positive and negative polarity reversal and subsequent charging or charging and discharging operations: when the lead-acid battery pack of the embodiment is in the charging state after the completion of the sixth cycle operation, at this time, the electrode A1 The polarities of A2, A3, and A4 are positive, and the polarities of the electrodes B1 and B2 are negative. The cycle of the lead-acid battery pack of this embodiment is stopped, and the positive and negative outputs of the charge and discharge device are combined with the lead acid of this embodiment. The positive and negative output terminals of the battery pack are connected in reverse polarity, that is, the positive output end of the charge and discharge device is connected to the negative output terminal (battery terminal B) of the lead-acid battery pack of the embodiment, and the negative output of the charge and discharge device The terminal is connected to the positive output terminal (battery terminal A) of the lead-acid battery pack of the embodiment, and after the reverse pole is connected, the charge and discharge device measures the voltage of the lead-acid battery pack of the embodiment to be -5.53V, and then, the implementation The lead-acid battery pack is charged at a current of 458 mA in the state of the reverse pole connection, so that the voltages of the positive and negative output terminals of the lead-acid battery pack of the present embodiment (the measured values of the charge and discharge device, the same in the present embodiment) From -5.53V When it reaches 0V and then rises to 5.8V, in this process, the first polarity reversal occurs in the lead-acid battery pack of this embodiment, that is, in the process of rising from -5.53V to 0V, the electrodes A1, A2, A3, A4 The main occurrence is the discharge process of the positive electrode of the lead-acid battery, the discharge process of the negative electrode of the lead-acid battery on the electrodes B1 and B2, and the electrodes A1, A2 and A3 during the process of 0V rising to 5.8V. The main occurrence of A4 is the charging process of the negative electrode reaction of lead-acid battery. The main charging process on the electrodes B1 and B2 is the charging process of the positive electrode of the lead-acid battery. The output of the charging and discharging device and the lead-acid battery of this embodiment are maintained. When the connection state of the group output terminals is unchanged, the lead-acid battery pack of this embodiment is discharged at 152.7 mA for 14 minutes to 3.5 V, and then charged at a constant current of 229 mA for 8 hours to 5.72 V, and then, 152.7mA discharge for 2 minutes to 4.5V, and then charged at a constant current of 114mA for 3 hours to 5.5V, and then put the lead-acid battery pack of the embodiment into the seventh working discharge process of the cycle, for the seventh time. Even thereafter Work to cycle 17 times. In the lead-acid battery pack of this embodiment, in the 7th to 17th cycle operation, the polarity of the battery terminal A is negative, and the polarity of the electrode pool terminal B is positive, as shown in FIG. 2, that is, in the process. On the electrodes A1, A2, A3, and A4, the charge and discharge process of the negative electrode reaction of the lead-acid battery occurs, and the charge and discharge processes of the positive electrode of the lead-acid battery occur on the electrodes B1 and B2.
对于第二次单次正、负极极性反转及其后的充电或充放电操作：当本实施例铅酸蓄电池组处于完成第17次循环工作后的充电状态下时，此时，电极A1、A2、A3、A4的极性为负，电极B1、B2的极性为正，停止本实施例铅酸蓄电池组的循环工作，将充放电设备的正、负输出端与本实施例铅酸蓄电池组此时的正、负极输出端子进行反极连接，即，充放电设备的正输出端与本实施例铅酸蓄电池组此时的负输出端子(电池组端子A)连接，充放电设备的负输出端与本实施例铅酸蓄电池组此时的正输出端子(电池组端子B)相连接，反极连接后，充放电设备测得本实施例铅酸蓄电池组的电压为－4.54V，然后，对本实施例铅酸蓄电池组以459mA的电流在该反极连接的状态下进行充电，使得本实施例铅酸蓄电池组的输出电压(充放电设备测得值，本实施例中以下同)从－4.54V上升到0V再上升到5.8V，历时4小时30分钟，此过程中本实施例铅酸蓄电池组发生了第二次极性反转，即，从-4.54V上升到0V的过程中，电极A1、A2、A3、A4上主要发生的是铅酸蓄电池负极电极反应的放电过程、电极B1、B2上主要发生的是铅酸蓄电池正极电极反应的放电过程，而在0V上升到5.8V的过程中，电极A1、A2、A3、A4上主要发生的是铅酸蓄电池正极电极反应的充电过程，电极B1、B2上主要发生的是铅酸蓄电池负极电极反应的充电过程，在保持充放电设备输出端与本实施例铅酸蓄电池组输出端子的连接状态不变的情况下，再以152.7mA对本实施例铅酸蓄电池组进行放电17分钟至3.5V，然后再以229mA的电流恒流充电8小时至5.41V，然后，再以152.7mA放电2分钟至4.23V,然后，再以114mA恒流充电3小时至5.26V，然后将本实施例铅酸蓄电池组投入到循环工作中的第18次工作放电过程中去，进行第18次以及其后直到第25次的循环工作。本实施例铅酸蓄电池组在第18－25次的循环工作中，电池组端子A的极性为正、电极池组端子B的极性为负，如图2所示，即，此过程中，电极A1、A2、A3、A4上发生铅酸蓄电池正极电极反应的充放电过程，电极B1、B2上发生铅酸蓄电池负极电极反应的充放电过程，也即，电池组端子A、B以及电极A1、A2、A3、A4、B1、B2的极性状态或极性方向返回到了本实施例铅酸蓄电池组最初始进行循环工作时的状态。For the second single positive and negative polarity reversal and subsequent charging or charging and discharging operations: when the lead-acid battery pack of the embodiment is in the charging state after the completion of the 17th cycle operation, at this time, the electrode A1 The polarity of A2, A3, and A4 is negative, and the polarity of the electrodes B1 and B2 is positive. The cycle of the lead-acid battery pack of this embodiment is stopped, and the positive and negative outputs of the charge and discharge device are combined with the lead acid of this embodiment. The positive and negative output terminals of the battery pack are connected in reverse polarity at that time, that is, the positive output end of the charging and discharging device is connected to the negative output terminal (battery group terminal A) of the lead-acid battery group of the embodiment, and the charging and discharging device The negative output terminal is connected to the positive output terminal (battery pack terminal B) of the lead-acid battery pack of the present embodiment. After the reverse pole is connected, the charge and discharge device measures the voltage of the lead-acid battery pack of the embodiment to be -4.54V. Then, the lead-acid battery pack of the present embodiment is charged at a current of 459 mA in the state of the reverse pole connection, so that the output voltage of the lead-acid battery pack of the present embodiment (the measured value of the charge and discharge device, the same in the present embodiment) From -4.54V to 0V It rises to 5.8V for 4 hours and 30 minutes. During this process, the lead-acid battery pack of this embodiment has a second polarity reversal, that is, during the process of rising from -4.54V to 0V, electrodes A1, A2, and A3. The main occurrence of A4 is the discharge process of the negative electrode of lead-acid battery, the discharge process of the positive electrode of lead-acid battery on the electrodes B1 and B2, and the electrode A1 during the process of 0V rising to 5.8V. A2, A3, and A4 mainly occur in the charging process of the positive electrode of the lead-acid battery. The charging process of the negative electrode of the lead-acid battery occurs mainly on the electrodes B1 and B2. The output of the charging and discharging device is maintained and the embodiment is When the connection state of the lead-acid battery pack output terminal is unchanged, the lead-acid battery pack of this embodiment is discharged at 152.7 mA for 17 minutes to 3.5 V, and then charged at a constant current of 229 mA for 8 hours to 5.41 V, and then And then discharge at 152.7mA for 2 minutes to 4.23V, and then charge at a constant current of 114mA for 3 hours to 5.26V, and then put the lead-acid battery of the embodiment into the 18th working discharge process in the cycle work, get on 18 and thereafter until the first cycle for 25 times. In the 18-25th cycle of the lead-acid battery pack of this embodiment, the polarity of the battery terminal A is positive, and the polarity of the electrode bank terminal B is negative, as shown in FIG. 2, that is, in the process. The charging and discharging process of the positive electrode reaction of the lead-acid battery occurs on the electrodes A1, A2, A3, and A4, and the charging and discharging process of the negative electrode reaction of the lead-acid battery occurs on the electrodes B1 and B2, that is, the battery terminals A, B and the electrode The polarity state or polarity direction of A1, A2, A3, A4, B1, B2 is returned to the state at which the lead-acid battery pack of the present embodiment is most initially cycled.
在本实施例铅酸蓄电池组的循环工作过程中，反复、多次、穿插地进行如上所述类似于本实施例第一次或第二次的单次正、负极极性反转及其后的充电或充放电操作，即实现了本实施例铅酸蓄电池组在其工作循环次数的第25、26次之间、第33、34次之间、第41、42次之间、第56、57次之间、......、第X、X+1次之间进行或被进行的第三次、第四次、第五次、第六次、.....、第Y次的单次正、负极极性反转及其后的充电或充放电操作(X、Y为正整数)。图2中标示出了本实施例铅酸蓄电池组在经过各次单次正、负极极性反转及其后的充电或充放电操作之前或之后，在循环工作过程中，电池组端子A、B的极性状态或极性方向情况，图3中示出了本实施例铅酸蓄电池组第23－28次循环充放电工作过程及该过程期间穿插进行的第三次单次正、负极极性反转及其后的充电或 充放电操作过程中的电流、电压变化情况，第三次单次正、负极极性反转及其后的充电或充放电操作过程与第一次单次正、负极极性反转及其后的充电或充放电操作过程基本相同，所不同之处在于，在操作后期的“以152.7mA放电2分钟、再以114mA恒流充电3小时”的步骤完成后，再以153mA的电流放电2小时58分钟，然后才将本实施例铅酸蓄电池组投入到第26次循环工作中去。During the cyclic operation of the lead-acid battery pack of the present embodiment, the single positive and negative polarity inversions similar to the first or second time of the present embodiment as described above are repeated, repeated, and interspersed as described above. The charging or charging and discharging operation, that is, the lead-acid battery pack of the embodiment is realized between the 25th and 26th, the 33rd and 34th, the 41st and the 42nd, and the 56th of the working cycle. 57th, ..., X, X+1 times or the third, fourth, fifth, sixth, ...., Y The secondary positive and negative polarity inversions and subsequent charging or charging and discharging operations (X, Y are positive integers). FIG. 2 is a diagram showing the battery pack terminal A in the cycle operation process of the lead-acid battery pack of the embodiment before or after the single charge and charge polarity reversal and subsequent charging or charging and discharging operations. The polarity state or polarity direction of B, FIG. 3 shows the 23-28th cycle charge and discharge operation process of the lead-acid battery pack of the embodiment and the third single positive and negative poles interposed during the process. Sexual reversal and subsequent changes in current and voltage during charging or charging and discharging operations, the third single positive and negative polarity reversal and subsequent charging or charging and discharging operations and the first single positive The polarity reversal of the negative electrode and the subsequent charging or charging and discharging operations are basically the same, except that after the steps of "discharging at 152.7 mA for 2 minutes and then charging at 114 mA constant current for 3 hours" are completed after the operation. Then, the battery was discharged at a current of 153 mA for 2 hours and 58 minutes, and then the lead-acid battery pack of the present embodiment was put into the 26th cycle.
如图2所示，完成每次单次极性反转及其后的充电或充放电操作用后，本实施例铅酸蓄电池组的工作放电容量都同比地得到提升或恢复，经检查，这是由于本实施例的正、负极极性反转及其后的充放电或充放电操作使得本实施例铅酸蓄电池组的正极活性物质软化或/和脱落、电极钝化、早期容量损失、腐蚀、活性物质与集流体接触不良、负极比表面积收缩的问题中的一种或多种得到改善、修复、逆转、抑止、消除、预防，在本实施例铅酸蓄电池组正常循环工作过程中，定期或不定期的(例如，以规定循环工作次数的方式)、穿插地对本实施例铅酸蓄电池组进行本实施例的正、负极极性反转及其后的充放电或充放电操作，将会有效的改善、修复、逆转、消除、抑制、预防正极活性物质软化或/和脱落、钝化、腐蚀、早期容量损失、硫酸盐化、活性物质与集流体接触不良、负极比表面积收缩问题，从而提高或延长本实施例铅酸蓄电池组的使用寿命，例如，由于电极A1、A2、A3、A4、B1、B2反复交替的作为正极或负极进行充放循环工作，使得作为正极工作时产生的电极腐蚀问题在电极作为负极进行充放循环工作时得到改善、修复、逆转，从而也使得本实施例铅酸蓄电池组在长期使用过程中的腐蚀问题得到延缓、改善、修复、逆转、防止，从而也有利于大大提高或延长本实施例铅酸蓄电池组的使用寿命，因此，在排除使电池失效的短路、断路、失水、污染等因素的情况下，本实施例提高或延长铅酸蓄电池组使用寿命的方法，使本实例铅酸蓄电池组的使用寿命在现有的有效循环次数基础上继续获得更大的提高或延长。As shown in FIG. 2, after each single polarity inversion and subsequent charging or charging and discharging operations are completed, the working discharge capacity of the lead-acid battery pack of the present embodiment is improved or restored year by year, and after inspection, this is checked. The positive and negative polarity inversion of the present embodiment and the subsequent charge and discharge or charge and discharge operations of the present embodiment cause the positive active material of the lead-acid battery of the present embodiment to soften or/and fall off, electrode passivation, early capacity loss, and corrosion. One or more of the problems of poor contact between the active material and the current collector and shrinkage of the specific surface area of the negative electrode are improved, repaired, reversed, suppressed, eliminated, and prevented. In the normal cycle work of the lead-acid battery pack of the present embodiment, periodically Or the irregularity of the polarity of the positive and negative electrodes of the present embodiment and the subsequent charge and discharge or charge and discharge operations of the lead-acid battery pack of the present embodiment may be performed intermittently (for example, in a manner of specifying the number of cycles). Effectively improve, repair, reverse, eliminate, inhibit, prevent softening or/and shedding, passivation, corrosion, early capacity loss, sulfation, active substances and sets of positive active materials The problem of poor contact between the body and the specific surface area of the negative electrode increases or prolongs the service life of the lead-acid battery pack of the present embodiment. For example, since the electrodes A1, A2, A3, A4, B1, and B2 are alternately alternately charged or discharged as a positive electrode or a negative electrode The cycle work makes the corrosion problem of the electrode generated as the positive electrode work improve, repair and reverse when the electrode is used as the negative electrode for the charge and discharge cycle, thereby also delaying the corrosion problem of the lead-acid battery pack of the present embodiment during long-term use. , improving, repairing, reversing, preventing, and thus also greatly improving or prolonging the service life of the lead-acid battery pack of the embodiment, and therefore, in the case of eliminating short-circuit, open circuit, water loss, pollution, etc., which cause battery failure, In this embodiment, the method for improving or prolonging the service life of the lead-acid battery pack is such that the service life of the lead-acid battery pack of the present example continues to be greatly improved or extended based on the existing effective number of cycles.
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组每次单次极性反转后及其后的充电或充放电操作后本实施例铅酸蓄电池组的工作放电容量恢复的程度以及本实施例铅酸蓄电池组每次工作放电容量恢复后可连续保持正常或较高放电容量的充放循环工作的次数(即每次单次极性反转后及其后的充电或充放电操作之间本实施例铅酸蓄电池组所正常工作或较高放电容量的充放循环次数)与相应地每次单次极性反转及其后的充电或充放电操作中所采用的电流、电压、时间、充放电容量、脉冲或直流、电池或电池组的内阻、电解液密度、电解液饱和程度的大小、方式的不同而不同。Some experimental data in this embodiment indicate the degree of recovery of the working discharge capacity of the lead-acid battery pack of the present embodiment after the single polarity inversion and the subsequent charging or charging and discharging operation of the lead-acid battery pack of this embodiment. And the number of times of charging and discharging cycles in which the lead-acid battery pack of the present embodiment can continuously maintain normal or high discharge capacity after each working discharge capacity is restored (ie, charging or charging and discharging after each single polarity inversion) The number of charge and discharge cycles in which the lead-acid battery pack of the present embodiment operates normally or has a higher discharge capacity, and the current used in each single polarity inversion and subsequent charge or charge and discharge operations, The voltage, time, charge and discharge capacity, pulse or DC, internal resistance of the battery or battery pack, electrolyte density, and the degree of electrolyte saturation vary.
在本实施例的其它实施方式中，本实施例全管式铅酸蓄电池组的正、负极或说所有电极均为同一种的或相同的管式正负极通用电极，即，不考虑制造电极时产生的制造误差(即刨除、排除、去掉制造误差的存在或影响)，本实施例全管式铅酸蓄电池组的所有电极或说所有管式电极在被化成之前，彼此在所有电极构成、制造方面(如电极结构、造形、导电骨芯、套管、汇流体、活性物质配方和质量、制做工艺等)完全相同，在被化成之后，本实施例全管式铅酸蓄电池组的各管式电极则 分别被形成正极或负极。In other embodiments of the present embodiment, the positive, negative or all electrodes of the full-tube lead-acid battery pack of the present embodiment are the same or the same tubular positive and negative common electrodes, that is, the electrode is not considered. Manufacturing error (ie, eliminating, eliminating, eliminating the existence or influence of manufacturing error) generated, all the electrodes or all tubular electrodes of the full-tube lead-acid battery of the present embodiment are formed on all the electrodes before being formed, The manufacturing aspects (such as electrode structure, shape, conductive core, casing, fluid pool, active material formulation and quality, manufacturing process, etc.) are identical. After being formed, each of the full-tube lead-acid battery packs of this embodiment The tubular electrodes are respectively formed into a positive electrode or a negative electrode.
在本实施例的其它实施方式中，本实施例全管式铅酸蓄电池组的正、负极或说所有电极均为彼此等价的管式正负极通用电极，即，在电极被化成或充放电之后，在铅酸蓄电池组的工作或使用过程中，不考虑误差(例如但不限于：制造误差、测量误差)因素的情况下(即刨除、排除、去掉制造误差的存在或影响)，本实施例的各管式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 full-tube lead-acid battery pack of the present embodiment are tubular positive and negative common electrodes equivalent to each other, that is, the electrodes are formed or charged. After discharge, in the case of the operation or use of the lead-acid battery pack, regardless of the error (such as but not limited to: manufacturing error, measurement error) (ie, removing, eliminating, eliminating the existence or influence of manufacturing error), Each of the tubular electrodes of the examples have or exhibit the same function and performance.
在本实施例的其它实施方式中，本实施例上述全管式铅酸蓄电池可被替代为具有相同容量、相同配方的其它类型铅酸蓄电池或电池组，所述其它类型铅酸蓄电池或电池组包括但不限于：平面板栅式铅酸蓄电池、管式铅酸蓄电池、其它结构的全管式铅酸蓄电池、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)蓄电池或电池组，其中的一种或多种，本实施例的上述方法可被应用于该其它类型铅酸蓄电池或电池组，被应用时电压、电流等参数可根据电池或电池组的额定工作电压、额定容量适当地、相应地变化大小，例如对单个电池充电时，使电池电压不超过电池额定工作电压的1.5倍。In other embodiments of the present embodiment, the above-described full-tube lead-acid battery of the present embodiment can be replaced with other types of lead-acid batteries or battery packs having the same capacity and the same formula, the other types of lead-acid batteries or battery packs. Including but not limited to: flat grid type lead-acid batteries, tubular lead-acid batteries, all-tube full-tube lead-acid batteries, wound lead-acid batteries, bipolar lead-acid batteries, or horizontal lead cloth, foam Grid, column, lead-acid battery with stable gap body, or valve-regulated sealed lead-acid battery, colloidal lead-acid battery, lead carbon battery, supercapacitor-lead battery (super battery) battery or battery pack One or more of the above methods, the above method of the present embodiment can be applied to the other types of lead-acid batteries or battery packs, and the voltage, current and other parameters can be applied according to the rated working voltage and rated capacity of the battery or the battery pack. Appropriately and correspondingly varying the size, for example when charging a single battery, the battery voltage does not exceed 1.5 times the rated operating voltage of the battery.
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，可以使用脉冲电流、脉冲电压代替直流电、恒电压进行本实例的连续两次极性反转及其后的充电或充放电操作步骤中的极性反转及其后的充电或充放电步骤或过程，从而有利于提高本实施例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 pulse current and the pulse voltage may be used instead of the direct current and the constant voltage to perform the polarity inversion in the two consecutive polarity inversions of the present example and the subsequent charging or charging and discharging operation steps. Subsequent charging or charging and discharging steps or processes are advantageous for improving the aging and energy efficiency of the battery polarity inversion and subsequent charging or charging and discharging operations of the present 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，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.
本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或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，本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或使用寿命提高或延长至1.3倍以上－10倍以上，或/和，寿命或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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or 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 battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
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 the battery pack of the embodiment has output terminals A, B, the output terminal A and the 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，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、彼此为同一种的或相同的正负极通用电极、彼此等价的正负极通用电极、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、包括膨胀剂的正极或/和负极，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 this embodiment, the battery includes a positive electrode and a negative electrode. Alternatively, the positive and negative electrodes of the battery in this embodiment are positive and negative common electrodes. The positive electrode, the negative electrode, and the positive and negative common electrodes of the battery of the embodiment include, but are not limited to, the same as each other. Positive and negative electrode common electrodes of the active substance or the same active substance formula, positive and negative common electrodes of the same or the same, mutually equivalent positive and negative electrode common electrodes, electrode active materials or active substance formulations including expansion agents One or more of a positive and negative electrode of the common electrode or / and a positive electrode or / and a negative electrode, a positive electrode or / and a negative electrode including a swelling agent. 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.
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.
在本实施例的实施方式中，除本实施例指出的、说明的以外，本实施例蓄电池的形状、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。In the embodiment of the present embodiment, the shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
在本实施例的一种实施方式中，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％、3％、4％、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％、3％、4％、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％、3％、4％、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％、3％、10％，其中的一种或多种。In an embodiment 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 and/or the negative electrode are positive and negative. The extremely common 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%, 3%, 4%, 10%, one or more of them; or (2) the battery of the present 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, calcium sulfate, and the barium sulfate is in the positive electrode or/and the negative electrode, positive and negative The mass percentage of the extremely common electrode or its active substance or active substance formulation is 0.01%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 3%, 4%, 10%, of which One or more of the silica, calcium sulfate in the positive electrode Or / and the negative electrode, positive and negative electrode common electrode or its active substance or active substance formula in the mass percentage of 0.03%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 3%, 4 %, 10%, one or more of them; or (3) The battery of the embodiment is an iron-nickel battery, and the positive electrode or/and the negative electrode, the positive and negative electrode, or the active material or active substance thereof are included in the formulation. a swelling agent lithium hydroxide having a mass percentage of 0.01%, 0.05%, 0.1%, 0.4% in the positive electrode or/and the negative electrode, the positive and negative electrode common electrode or the active material or active substance formulation thereof , 0.8%, 1.0%, 2.0%, 3%, 10%, one or more of them.
在本实施例的另一种实施方式中，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 another embodiment 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 lead. The acid battery has the active material or active substance formula of the positive electrode and the negative electrode: 100Kg of lead powder or lead oxide powder, 0.06Kg of short fiber, 0.28Kg of acetylene black, 0.8Kg of barium sulfate, and sulfuric acid solution (mass percentage of sulfuric acid 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 example is iron-ferric acid Salt battery, its active material or active substance formulation of positive electrode and negative electrode are: iron powder or iron oxide powder 100Kg, lithium hydroxide 0.2Kg, barium hydroxide 0.4Kg, potassium hydroxide solution (mass percentage of potassium hydroxide) 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 are identical;
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，在相同于上述的工作充电、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)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，误差为正、反向放电容量平均值的5％、4.76％。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 reversed are charged and discharged in the same manner as described above. Under conditions (such as but not limited to: first constant current charging for 0.14C for 5 hours, then constant voltage charging 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), cyclic charging and discharging, obtaining the battery, positive electrode, negative electrode, positive and negative electrodes of this embodiment The average value of the 21st reverse discharge capacity exhibited by the common electrode during the first to the 21st cycle charge and discharge after the second polarity inversion is 10.5 Ah, and is removed and removed. In the case of 0.5Ah error caused by testing, etc. (ie, without considering the error factor), the charging, and/or discharging performance of the positive electrode, the negative electrode, and the positive and negative electrode common electrodes are the same under the same polarity. Or it is considered that the positive electrode, the negative electrode, the positive and negative electrode common electrodes have the same charging and/or discharging performance under the same polarity, and the difference in the average value of the discharge capacity of 0.5 Ah belongs to the normal error between each other. It is 5% and 4.76% of the average of the forward and reverse discharge capacities.
在本实施例的其它实施方式中，本实施例蓄电池，额定电压为2V或1.47V，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，在某一规定充电、放电条件下(例如但不限于：先0.5C恒流充电至2.47V或1.8V，再恒压充电3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11次极性反转后的第1次－第24次的循环充电、放电过程中所表现出的该24次正向放电容量的平均值为20Ah，然后，将该蓄电池的正极、负极的极性进行第12次反转，使所述第11次极性反转后的正极被反转成负极，使所述第11次极性反转后的负极被反转成正极，然后，将该第12次极性反转后所形成的负极、该 第12次极性反转后所形成的正极，在相同于上述的规定充电、放电条件下(例如但不限于：先0.5C恒流充电至2.47V或1.8V，再恒压充电3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12次极性反转后第1次－第24次的循环充电、放电过程中所表现出的该24次反向放电的容量的平均值为17Ah，在排除、去掉制造、测试等所引起的3Ah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3Ah的放电容量平均值的差值属于彼此间的正常误差，误差为正、反向放电容量平均值的15％、17.6％。In other embodiments of the present embodiment, the battery of the embodiment has a rated voltage of 2V or 1.47V, and the positive and negative electrodes are positive and negative common electrodes equivalent to each other, and after the electrodes are formed, in a certain regulation Under charging and discharging conditions (such as but not limited to: first 0.5C constant current charging to 2.47V or 1.8V, then constant voltage charging for 3 hours, then 0.5C rate discharge, ambient temperature is 25 ° C, C is the rated capacity of the battery) The 24th forward discharge capacity exhibited by the battery, the positive electrode, the negative electrode, and the positive and negative electrode common electrodes in the first to the 24th cycle charging and discharging after the 11th polarity reversal in this embodiment The average value is 20 Ah, and then the polarity of the positive electrode and the negative electrode of the battery is reversed for the twelfth time, and the positive electrode after the eleventh polarity inversion is inverted to the negative electrode, so that the eleventh time is made. The negative electrode after the polarity inversion is reversed to the positive electrode, and then the negative electrode formed by inverting the 12th polarity and the positive electrode formed after the 12th polarity is inverted are the same as the above-described specifications. Under charging and discharging conditions (such as but not limited to: first 0.5C constant current charging to 2.47V or 1. 8V, then constant voltage charging for 3 hours, then 0.5C rate discharge, ambient temperature is 25 ° C, C is the rated capacity of the battery), cyclic charging and discharging, obtaining the battery, positive electrode, negative electrode, positive and negative electrode common electrode of this embodiment The average value of the capacity of the 24 reverse discharges exhibited during the first to 24th cycle charging and discharging after the 12th polarity inversion is 17 Ah, and the manufacturing, testing, etc. are excluded or removed. In the case of the 3Ah error caused (ie, without considering the error factor), the charge, and/or discharge performance of the positive electrode, the negative electrode, and the positive and negative electrode common electrodes are the same as each other 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 3 Ah belongs to the normal error between each other, and the error is positive and negative. The average value of the discharge capacity was 15% and 17.6%.
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 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 in the use or work of the circulating work, the working cycle reaches a certain number of times or as needed (for example, due to Expansion or/and softening or/and shedding of the positive active material, corrosion, passivation, early capacity loss, salinization, crystallization, shrinkage of the 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, One or more of the problems cause the battery or battery pack of the present embodiment to decrease in operating discharge capacity and below or below a certain capacity value, and it is desirable or necessary to increase the working discharge capacity of the battery or the battery pack or to increase or extend the use of the battery or the battery pack. During the life cycle, the battery or battery pack of this example is automatically or/and manually subjected to a single positive and negative polarity reversal and subsequent charging or charging and discharging operations, improving, eliminating, and reversing. , inhibiting, preventing expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss of the positive active material , 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 material itself, one or more problems, such that the working capacity of the battery or the battery pack of the present embodiment is restored Or, after completing the positive or negative polarity inversion and subsequent charging or charging and discharging operations, the battery or the battery pack of the embodiment is re-introduced to the charging and discharging state by the polarity state after the polarity is reversed. Use or work in the cycle work until the battery or battery pack of this embodiment is again triggered to perform positive or negative polarity reversal and subsequent charging or charging and discharging operations, so that the battery or battery pack of the embodiment is The cyclic operation and the positive or negative polarity inversion of the battery or the battery pack of the present embodiment and the subsequent charging or charging and discharging operations are intermittently, interspersed, alternately performed or occur, thereby improving or extending the present embodiment. The service life of a battery or battery pack.
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 the present embodiment, the battery or battery charge or discharge, charge or discharge mode includes a single phase, multiple phase, constant current (e.g. 0.15C 2, 0.4C 2, 0.8C 2 , 7C 2), constant One or more of a voltage (for example, 0.8U, 1.5U, 2U, 4U), a positive pulse, and a negative pulse, and then, in the polarity state of the battery or the battery pack of this embodiment after the polarity is reversed, Re-input into the cycle work to perform the cycle 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 process of the battery negative electrode reaction occurs on the electrodes A1, A2, ..., An. The charging and discharging process of the battery positive electrode reaction occurs 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.
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(例如但不限于：制造误差、测量误差)因素的情况下(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, during the operation or use of the battery or battery pack, regardless of the error (such as but not limited to: manufacturing error, measurement error) (ie, removal, exclusion, The presence or influence of the error is removed), and 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连续两次极性反转及其后的充电或充放电操作步骤中的极性反转及其后的充电或充放电步骤或过程，从而有利于提高本实施例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 pulse current and the pulse voltage may be used instead of the direct current and the constant voltage to perform the polarity inversion in the two consecutive polarity inversions of the present example and the subsequent charging or charging and discharging operation steps. Subsequent charging or charging and discharging steps or processes are advantageous for improving the aging and energy efficiency of the battery polarity inversion and subsequent charging or charging and discharging operations of the present embodiment.
本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或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，本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或使用寿命提高或延长至1.3倍以上－10倍以上，或/和，寿命或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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or 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 battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
实施例5Example 5
本实施例蓄电池、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组进行正、负极极性反转及其后的充电或充放电操作。The battery of the embodiment, the method for improving or prolonging the service life of the battery or the battery pack, includes the total cumulative number of times of the battery or the battery pack of the embodiment in the floating charging operation of the battery or the battery pack is 1 or 1 times. The positive or negative polarity inversion and the subsequent charging or charging and discharging operations described above, in the same or similar to all of the above embodiments of the present invention (ie, Embodiment 1 to Embodiment 4), to improve, repair, Reversing, eliminating, suppressing, preventing expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative specific surface area shrinkage, active material and conductive set of the positive electrode active material of the battery or battery The fluid contact failure, the memory effect, the decomposition of the active substance itself, one or more problems, the working capacity of the battery or the battery pack of the embodiment is restored or increased or prevented, and then the battery or the battery pack of the embodiment is re-applied. Put it into the floating charge work until it triggers again or starts to reverse the polarity of the positive and negative poles of the battery or the power storage group of this embodiment again. After charging or charging and discharging operations.
本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或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，本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或使用寿命提高或延长至1.3倍以上－10倍以上，或/和，寿命或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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or 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 battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
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℃)，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 battery of this embodiment is an iron-nickel battery or an iron-ferrate battery, and the rated capacity is 10 Ah (C 5, 5 h, 25 ° C). The battery in this embodiment includes a positive electrode and a negative electrode, or, in this embodiment, the battery is positive and negative. The electrodes are common electrodes for positive and negative electrodes. The positive electrode, the negative electrode, and the positive and negative electrode of the battery of the present embodiment include, but are not limited to, a positive electrode or/and a negative electrode including a swelling agent, and an electrode active material or an active material formulation including expansion. Positive and negative electrode common electrode of the agent or / and positive electrode or / and negative electrode, positive and negative electrode common electrodes having the same active substance or the same active substance formula, mutually equivalent positive and negative electrode common electrodes, the same or the same as each other Positive and negative common electrodes, 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, an oxide or hydroxide of aluminum, an oxide or hydroxide of titanium, an oxide or hydroxide of lithium, 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.
在本实施例的实施方式中，除本实施例指出的、说明的以外，本实施例蓄电池的形状、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。In the embodiment of the present embodiment, the shape, structure, and configuration of the battery of the present embodiment include, but are not limited to, the shape of a general, general battery disclosed in the prior art, except for the description and description of the embodiment. Structure, structure.
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。When the battery of the present embodiment expands or/and softens and/or falls off, corrosion, passivation, early capacity loss, salinization, crystallization, specific surface area shrinkage of the positive electrode active material, poor contact of the active material with the conductive current collector, memory The effect, the active material itself decomposes, and one or more problems cause the working discharge capacity to decrease or the cycle working life to be terminated, and the positive and negative polarity inversion and subsequent charging of the battery of the embodiment are performed by the charging and discharging device. Charge and discharge operation to solve the expansion or/and softening or/and shedding, corrosion, passivation, early capacity loss, salinization, crystallization, negative specific surface area shrinkage, active material and conductive current collector of the positive active material of the battery of the present embodiment One or more of the problems of poor contact, memory effect, decomposition of the active substance itself, to increase or prolong 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.
本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或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，本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或使用寿命提高或延长至1.3倍以上－10倍以上，或/和，寿命或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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or 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 battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
实施例7Example 7
本实施例长寿命铅酸蓄电池，除电极集流体材料外，其它方面相同或类同于本发明实施例1-6所述的铅酸蓄电池。The long-life lead-acid battery of the present embodiment is the same as or similar to the lead-acid battery described in Embodiment 1-6 of the present invention except for the electrode current collector material.
本实施例长寿命铅酸蓄电池或电池组电极集流体的材料包括但不限于：铅、铅合金、表面层为铅或铅合金的复合型材料，其中的一种或多种。The materials of the long-life lead-acid battery or the battery electrode collector of the present embodiment include, but are not limited to, lead, lead alloy, composite materials whose surface layer is lead or lead alloy, one or more of them.
本实施例表面层为铅或铅合金的复合型材料具有表面层/芯体结构，如图4所示，或表面层/过渡层/芯体结构，如图5所示。The composite material whose surface layer is lead or lead alloy in this embodiment has a surface layer/core structure, as shown in FIG. 4, or a surface layer/transition layer/core structure, as shown in FIG.
本实施例长寿命铅酸蓄电池或电池组电极集流体的材料为具有表面层/芯体结构的的复合型材料，如图4所示，表面层材料15为铅，芯体材料16为铜。The material of the long-life lead-acid battery or the battery electrode current collector of the present embodiment is a composite material having a surface layer/core structure. As shown in FIG. 4, the surface layer material 15 is lead, and the core material 16 is copper.
在本实施例的其它实施方式中，本实施例长寿命的铅酸蓄电池或电池组电极集流体的材料为具有表面层/芯体结构的的复合型材料，如图4所示，表面层材料15为铅-锑合金，芯体材料16为铝。In other embodiments of the present embodiment, the material of the long-life lead-acid battery or the battery electrode current collector of the present embodiment is a composite material having a surface layer/core structure, as shown in FIG. 4, the surface layer material. 15 is a lead-bismuth alloy, and the core material 16 is aluminum.
在本实施例的其它实施方式中，本实施例长寿命铅酸蓄电池电极集流体的材料为具有表面层/过渡层/芯体结构的复合型材料，如图5所示，表面层材料15为铅，过渡层材料17为锡，芯体材料16为铝。In other embodiments of the present embodiment, the material of the long-life lead-acid battery electrode current collector of the embodiment is a composite material having a surface layer/transition layer/core structure, as shown in FIG. 5, the surface layer material 15 is Lead, the transition layer material 17 is tin, and the core material 16 is aluminum.
在本实施例的其它实施方式中，本实施例长寿命铅酸蓄电池或电池组电极集流体的材料为具有表面层/过渡层/芯体结构的复合型材料，如图5所示，表面层材料15为铅-钙-锡-铝合金，过渡层材料17为二氧化锡/钛复合材料，芯体材料16为导电塑料。In other embodiments of the present embodiment, the material of the long-life lead-acid battery or the battery electrode current collector of the embodiment is a composite material having a surface layer/transition layer/core structure, as shown in FIG. 5, the surface layer The material 15 is a lead-calcium-tin-aluminum alloy, the transition layer material 17 is a tin dioxide/titanium composite material, and the core material 16 is a conductive plastic.
本实施例铅酸蓄电池或电池组通过进行或被进行总累计次数≥1次的正极、负极极性反转及其后的充电或充放电操作成为具有长寿命或长使用寿命的铅酸蓄电池或电池组，所述操作，相同或类同于本发明实施例1-6所述的操作、方法。The lead-acid battery or the battery pack of the present embodiment becomes a lead-acid battery having a long life or a long service life by performing a positive or negative polarity reversal of the positive and negative polarities and subsequent charging or charging and discharging operations of the total cumulative number of times ≥1 times or The battery pack, the operation, is the same or similar to the operation and method described in Embodiment 1-6 of the present invention.
本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或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，本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或使用寿命提高或延长至1.3倍以上－10倍以上，或/和，寿命或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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or 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 battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.
实施例8Example 8
本实施例蓄电池、提高或延长蓄电池或电池组寿命的操作、方法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 operation and method of the battery of the present embodiment for improving or prolonging the life of the battery or the battery pack are the same as or include the embodiments 1-21 and 23 described in the embodiment 1-21 and the Chinese patent application 201710975698.2 described in the Chinese Patent Application No. 201710975570.6. Examples 1 to 21 and 23, as described in Chinese Patent Application No. 1,910, 756, 056, and Examples 1 to 1-3, Chinese Patent Application No. 201811297354.1, and Chinese Patent Application No. 201811296518.9 Examples 1-10 described.
本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或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，本实施例蓄电池、操作、方法使蓄电池或电池组的寿命或使用寿命提高或延长至1.3倍以上－10倍以上，或/和，寿命或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 battery, the operation and the method of the embodiment can significantly improve or prolong the life or 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 battery, the operation and the method of the embodiment make the battery Or the life or service life of the battery pack is increased or extended to 1.3 times or more and 10 times or more, or / and the life or cycle life is increased or extended by 50 times or more - 500 times or more, 500 times or more - 3000 times or more, of which One or more.

Claims (10)

  1. 一种长寿命蓄电池，包括正极、负极，其特征在于，所述蓄电池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：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、彼此为同一种的或相同的正负极通用电极、彼此等价的正负极通用电极、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，其中的一种或多种；或者，所述蓄电池其正极或/和负极中包括膨胀剂；A long-life battery includes a positive electrode and a negative electrode, wherein the positive electrode and the negative electrode of the battery are both positive and negative common electrodes, and the positive and negative electrode common electrodes are used as positive electrodes in the battery. It can also be used 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 some time during the operation or use of the battery, 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, positive and negative electrode common electrodes having the same active substance or the same active substance formula, mutually the same or the same positive and negative electrode common electrodes, and the like. a positive electrode and a negative electrode of a positive electrode, an electrode active material or an active material formulation comprising a positive electrode and a negative electrode of a bulking agent or/and a positive electrode or/and a negative electrode, one or more of which; or, the positive electrode of the battery Or / and the negative electrode include a swelling agent;
    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.
  2. 根据权利要求1所述长寿命蓄电池，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。The long-life battery according to claim 1, wherein the active material of the positive electrode or/and the negative electrode of the 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, One or more of bromine, tin, antimony, bismuth, iodine, tungsten, and antimony.
  3. 根据权利要求2所述长寿命蓄电池，其特征在于，所述蓄电池，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 long-life battery according to claim 2, wherein the battery includes, but is not limited to, a lead-acid battery, an iron-nickel battery, an iron-ferrate battery, a copper-ferrate battery, and a cadmium-nickel battery. One or more of the batteries or battery packs.
  4. 根据权利要求1所述长寿命蓄电池，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 long-life battery according to claim 1, wherein the expansion agent includes, but is not limited to, barium sulfate, calcium sulfate, silica, silicate, humic acid, lignosulfonate, and oxidation of aluminum. Or one or more of a hydroxide or hydroxide, an oxide or hydroxide of lithium, or an oxide or hydroxide of lithium.
  5. 根据权利要求1所述长寿命蓄电池，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 long-life battery according to claim 1, wherein the expansion agent is present in an amount of from 0.01% to 50% by mass in the active substance or active substance formulation.
  6. 根据权利要求1所述长寿命蓄电池，其特征在于，所述蓄电池在蓄电池组中的所有单电池个数包括但不限于：≥N+1，所述N等于所述蓄电池组的额定电压数值除以所述蓄电池组中单电池的额定电压数值。The long-life battery according to claim 1, wherein the number of all the battery cells in the battery pack includes, but is not limited to, ≥ N+1, and the N is equal to the rated voltage value of the battery pack. The rated voltage value of the single battery in the battery pack.
  7. 根据权利要求1所述长寿命蓄电池，其特征在于，所述蓄电池的正极或/和负极、正负极通用电极的集流体的材料包括但不限于：铅、铅合金、表面层为铅或铅合金的复合型材料，其中的一种或多种，所述表面层为铅或铅合金的复合型材料具有表面层/芯体结构或表面层/过渡层/芯体结构。The long-life battery according to claim 1, wherein materials of the current collectors of the positive electrode or/and the negative electrode and the positive and negative electrode common electrodes of the battery include, but are not limited to, lead, lead alloy, and lead layer or lead layer. A composite material of an alloy, one or more of which the composite material having a surface layer of lead or lead alloy has a surface layer/core structure or a surface layer/transition layer/core structure.
  8. 根据权利要求7所述长寿命蓄电池，其特征在于，所述芯体材料为金属或/和其合金或/和其化合物、导电塑料、塑料、导电陶瓷、碳材料、玻璃、二氧化硅其中的一种或多种，所述过渡层材料为所述芯体材料、表面层材料中的一种或多种；所述金属或/和其合金或/和其化合物包括但不限于：铝、铜、铅、钛、锡或/和其合金或/和其化合物中的一种或多种，所述碳材料包括但不限于：碳黑、活性碳、石墨、碳纤维、泡沫碳、碳纳米管、石墨烯中的一种或多种。The long-life battery according to claim 7, wherein the core material is metal or/and an alloy thereof or/and a compound thereof, a conductive plastic, a plastic, a conductive ceramic, a carbon material, a glass, or a silica. One or more, the transition layer material is one or more of the core material and the surface layer material; the metal or/and its alloy or/and its compounds include but are not limited to: aluminum, copper One or more of lead, titanium, tin or/and alloys thereof and/or compounds thereof, including but not limited to: carbon black, activated carbon, graphite, carbon fiber, foamed carbon, carbon nanotubes, One or more of graphene.
  9. 根据权利要求1所述长寿命蓄电池，其特征在于，所述蓄电池进行或被进行蓄电池或/和蓄电池组正极、负极极性反转及其后的充电或充放电操作，所述蓄电池进行或被进行该操作的总累计 次数为≥1次，所述正极、负极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。The long-life battery according to claim 1, wherein said battery is subjected to or is subjected to charging or charging and discharging operations of a battery or/and a battery pack positive electrode and a negative electrode polarity, and said battery is performed or The total number of times of performing the operation is ≥1 times, the polarity of the positive and negative electrodes is reversed, and the subsequent charging or charging and discharging operations, that is, the polarity of the positive electrode and the negative electrode are reversed, and at the polarity After the inversion, the electrode that has undergone the polarity inversion is subjected to a charging or charging and discharging operation.
  10. 根据权利要求1或9所述长寿命蓄电池，其特征在于，所述蓄电池包括一种电路，所述电路具有将蓄电池的正极、负极进行极性反转及其后的充电或充放电操作的功能；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。A long-life battery according to claim 1 or 9, wherein said battery includes a circuit having a function of performing polarity inversion of a positive electrode and a negative electrode of the battery and subsequent charging or charging and discharging operations. 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/CN2018/113860 2017-11-05 2018-11-03 Long-life storage battery WO2019086022A1 (en)

Applications Claiming Priority (6)

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

Publications (1)

Publication Number Publication Date
WO2019086022A1 true WO2019086022A1 (en) 2019-05-09

Family

ID=64998413

Family Applications (2)

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

Family Applications Before (1)

Application Number Title Priority Date Filing Date
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

Country Status (2)

Country Link
CN (9) CN109216805A (en)
WO (2) WO2019086021A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115136378A (en) * 2019-09-03 2022-09-30 达拉米克有限责任公司 Improved carbonaceous lead acid battery separators and improved batteries, systems, vehicles, 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
CN114597354A (en) * 2022-02-25 2022-06-07 天能电池集团股份有限公司 Lead storage battery positive electrode lead paste and preparation method thereof, and lead storage battery

Citations (6)

* 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
CN106129357A (en) * 2016-07-14 2016-11-16 安徽轰达电源有限公司 The solid lead carbon battery lead plaster of deep glue-type spy
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
CN108649287A (en) * 2017-05-26 2018-10-12 杨春晓 A kind of lead-acid accumulator or battery pack

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 Method for recovering improper capacity loss 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
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
CN102082305B (en) * 2010-12-21 2013-08-21 无锡市霄鹰环境科技有限公司 Ionic lead-acid cell repair protection solution
CN102593529B (en) * 2012-02-24 2014-08-27 中南大学 Variable-polarity lead-acid battery and using method thereof
CN103633389B (en) * 2013-11-26 2015-12-09 河南超威电源有限公司 A kind of container formation process for lead acid storage battery
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
CN108011133A (en) * 2016-10-27 2018-05-08 杨春晓 Raising extends lead-acid accumulator or the circuit of battery pack service life
CN108520984A (en) * 2017-11-05 2018-09-11 杨春晓 There are the lead-acid batteries of conversion circuit

Patent Citations (6)

* 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
CN106129357A (en) * 2016-07-14 2016-11-16 安徽轰达电源有限公司 The solid lead carbon battery lead plaster of deep glue-type spy
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
CN108649287A (en) * 2017-05-26 2018-10-12 杨春晓 A kind of lead-acid accumulator or battery pack

Also Published As

Publication number Publication date
CN109273779A (en) 2019-01-25
CN109755577A (en) 2019-05-14
CN109755672A (en) 2019-05-14
CN116742153A (en) 2023-09-12
CN117175024A (en) 2023-12-05
WO2019086021A1 (en) 2019-05-09
CN117810567A (en) 2024-04-02
CN109755671A (en) 2019-05-14
CN109216805A (en) 2019-01-15
CN109361027A (en) 2019-02-19

Similar Documents

Publication Publication Date Title
WO2019086022A1 (en) Long-life storage battery
CN107732338A (en) The method for improving or extending lead-acid accumulator or battery pack service life
WO2012129974A1 (en) Fast charging method for rechargeable battery
CN101752615B (en) Desulphurized high-frequency pulse activating instrument for battery recovery, activating agent and recovery process
CN109659638A (en) A kind of power type lead storage battery high current chemical synthesis technology
CN107742748A (en) Lead-acid accumulator or battery pack with the long life
JP3396696B2 (en) Rechargeable battery
CN113178574B (en) Positive pole lead plaster of lead-acid storage battery and bipolar horizontal storage battery containing positive pole lead plaster
WO2018166409A1 (en) Lead-acid battery or battery pack with long service life
CN107768752A (en) Raising extends lead-acid accumulator or the device of battery pack service life
JP2008071717A (en) Method of chemical conversion of lead-acid battery
WO2018166407A1 (en) Method for improving or prolonging service life of lead-acid storage battery or battery pack
Insinga et al. Performance of lead-acid batteries with nanostructured electrodes at different temperature
CN108649287A (en) A kind of lead-acid accumulator or battery pack
CN108321375B (en) In-situ doped nano molybdenum-based material, preparation method and application
WO2018166408A1 (en) Device for improving or prolonging service life of lead-acid battery or battery pack
JP2004327299A (en) Sealed lead-acid storage battery
CN101728531A (en) Anode material of nickel-hydrogen power battery and preparation method thereof
CN215496791U (en) Long-life zinc electrode and zinc-air secondary battery
JP4742424B2 (en) Control valve type lead acid battery
JPH0355758A (en) Nickel-zinc storage battery and manufacture thereof
JP4999309B2 (en) Alkaline storage battery
JPH0810590B2 (en) Method for manufacturing sealed lead acid battery and electrode plate for sealed lead acid battery
JPH0732012B2 (en) Manufacturing method of sealed lead-acid battery
JPH01154460A (en) Manufacture of cadmium electrode for 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: 18872949

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: 18872949

Country of ref document: EP

Kind code of ref document: A1