CN109755671A - Solve the problems, such as the method that battery anode active substance expands, softens, falling off - Google Patents
Solve the problems, such as the method that battery anode active substance expands, softens, falling off Download PDFInfo
- Publication number
- CN109755671A CN109755671A CN201811303681.3A CN201811303681A CN109755671A CN 109755671 A CN109755671 A CN 109755671A CN 201811303681 A CN201811303681 A CN 201811303681A CN 109755671 A CN109755671 A CN 109755671A
- Authority
- CN
- China
- Prior art keywords
- battery
- electrode
- discharge
- positive
- charge
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 191
- 239000013543 active substance Substances 0.000 title claims abstract description 32
- 238000007600 charging Methods 0.000 claims abstract description 291
- 239000011149 active material Substances 0.000 claims abstract description 93
- 238000003411 electrode reaction Methods 0.000 claims abstract description 76
- 239000007774 positive electrode material Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 26
- 238000002161 passivation Methods 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 239000007772 electrode material Substances 0.000 claims abstract description 17
- 230000003446 memory effect Effects 0.000 claims abstract description 15
- 230000002829 reductive effect Effects 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 288
- 239000011133 lead Substances 0.000 claims description 120
- 230000008569 process Effects 0.000 claims description 107
- 238000003860 storage Methods 0.000 claims description 49
- 239000003795 chemical substances by application Substances 0.000 claims description 42
- 230000008961 swelling Effects 0.000 claims description 42
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 40
- 230000006870 function Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 18
- 230000008602 contraction Effects 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 230000006399 behavior Effects 0.000 claims description 11
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004021 humic acid Substances 0.000 claims description 8
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006183 anode active material Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 239000004117 Lignosulphonate Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 235000019357 lignosulphonate Nutrition 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- 229910001947 lithium oxide Inorganic materials 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 238000007599 discharging Methods 0.000 description 49
- 230000005611 electricity Effects 0.000 description 36
- 239000000463 material Substances 0.000 description 19
- 230000002441 reversible effect Effects 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000011505 plaster Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 230000004087 circulation Effects 0.000 description 13
- 239000011530 conductive current collector Substances 0.000 description 13
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- 239000012530 fluid Substances 0.000 description 11
- 230000002401 inhibitory effect Effects 0.000 description 11
- 238000011017 operating method Methods 0.000 description 11
- 125000002015 acyclic group Chemical group 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000008439 repair process Effects 0.000 description 10
- 230000019635 sulfation Effects 0.000 description 9
- 238000005670 sulfation reaction Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000008771 sex reversal Effects 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 206010011906 Death Diseases 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910000464 lead oxide Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 230000004069 differentiation Effects 0.000 description 4
- 150000002611 lead compounds Chemical class 0.000 description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- -1 plumbous plumbate Chemical compound 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910002640 NiOOH Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052924 anglesite Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940067573 brown iron oxide Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of methods for solving the problems, such as battery anode active substance and expanding, soften, falling off, it include: that the anode of the battery or/and battery group or positive active material is made to carry out battery terminal negative electrode reaction, or metal or 0 chemical valence are reduced by electrochemical reducting reaction, or the battery or/and the progress polarity reversion of the anode or/and cathode of battery group and subsequent charging or charge and discharge is electrically operated；The method, it is also used for solving the other problems of battery, including but not limited to the burn into passivation, salinization of battery, crystallization, electrode active material specific surface area shrink, active material and collector poor contact or/and fall off, early stage capacitance loss, memory effect, active material itself resolution problem, one such or a variety of；The method disclosed in the present can solve the problems such as battery anode active substance expands, softens, falling off, and significantly improve or extend the service life of battery or battery pack.
Description
Technical field
The present invention relates to a kind of method for solving the problems, such as battery malfunction, in particular to a kind of solution battery positive voltage activity
Mass expansion softens, the method for the problem that falls off, and individually or simultaneously solves the method for the other Problem of Failure of battery.
Background technique
Battery, including but not limited to lead-acid accumulator, nickel-iron storage battery, cadmium-nickel storage battery, nickel-hydrogen battery, height
Ferrite battery, lithium-ions battery etc., can cycle charge discharge work, thus substantially reduce society production, life, environmental protection at
This, and the service life of battery is longer, then its economic benefit generated and social benefit are bigger.Battery is caused to use the longevity
There are many reason of life terminates, and important reason such as positive active material expands or/and softens or/and fall off, burn into is passivated, early
Phase capacitance loss, the contraction of cathode specific surface area, active material inactivation, salinization, crystallization, active material contact not with collector
The problems such as good, memory effect, active material itself decompose.
Summary of the invention
The problem to be solved by the invention is to provide a kind of solution battery anode active substances to expand, softens, falls off and ask
The method of topic, to improve or extend the service life of battery or battery pack, alternatively, provide it is a kind of solution or improvement battery or
The positive active material of battery pack expands or/and softens or/and fall off, burn into passivation, early stage capacitance loss, salinization, crystallization
Change, cathode specific surface area are shunk, active material and conductive current collector poor contact, memory effect, active material itself decompose,
One of or various problems, Lai Tigao or the service life for extending battery or battery pack.
The salinization, including but not limited to, sulfation.
The service life includes but is not limited to one of cycle life, float life or a variety of.
The battery or battery pack, that is, battery or battery group.
It is described to solve the above problems, including but not limited to: to the solution of the above problem, reparation, reverse, elimination, improvement, delaying
It solves, inhibit, prevent, avoid.
To solve one of above-mentioned technical problem of the present invention, the present invention provides a kind of solution battery anode active substance is swollen
It is swollen, soften, the method for the problem that falls off, comprising: make the battery or/and battery group anode or positive active material carry out
Battery terminal negative electrode reaction is reduced into metal or 0 chemical valence by electrochemical reducting reaction, alternatively, by the electric power storage
The anode or/and cathode of pond or/and battery group carry out polarity reversion and subsequent charging or charge and discharge is electrically operated, the operation it is total
Cumulative number >=1 time；It is described that anode, cathode progress polarity reversion and subsequent charging or charge and discharge is electrically operated, that is, by positive electricity
Pole, negative electrode carry out polarity reversion, and after polarity reversion, will carry out charging or charge and discharge by the electrode of polarity reversion
Operation.
Total cumulative number refers to, the battery or battery pack it is entire existing for it during or the battery or
Entire period of the battery pack before its end of life and after end of life, all generations are in the battery or battery
With group in total, the always accumulative anode, negative polarity reversion or polarity reversion and subsequent charging or charge and discharge behaviour
The number of work.Each time it is described anode, negative polarity reversion and subsequent charging or charge and discharge it is electrically operated each other can continuously into
Row discontinuously carries out, or part is carried out continuously, the discontinuous progress in part.
The polarity of the battery or battery anode or cathode includes that the positivity of the electrode of battery or battery pack is (just
Polarity matter) or negativity (cathode property), the positivity feature of electrode generally comprise, the electrode reaction occurred on this electrode be anode
Electrode reaction, electrode potential are mutually more high, and the negativity feature of electrode generally comprises, and the electrode reaction occurred on this electrode is negative
Pole electrode reaction, electrode potential are mutually more low.The polarity reversion refers to that the polarity of originally positivity electrode becomes negativity by positivity
Or/and the polarity of original negativity electrode becomes positivity by negativity.
It is described will by polarity reversion electrode carry out charging or charge and discharge it is electrically operated, that is, will polarity reversion before for anode and
Be after polarity reversion cathode electrode charge as cathode or charge and discharge is electrically operated, polarity is inverted before be cathode and polarity is anti-
It is that positive electrode carries out charging as anode or charge and discharge is electrically operated after turning, the former keeps generation battery terminal negative electrode on electrode anti-
It answers, the latter makes that battery positive voltage electrode reaction occurs on electrode.
With by the anode of battery or battery pack, cathode carry out for the first time, the reversion of second polarity and subsequent charging or
For the electrically operated process of charge and discharge, to the positive and negative electrode polarity invert and subsequent charge or charge and discharge it is electrically operated work further
Illustrate, for convenience of description, with original anode (being also labeled as electrode A herein), original cathode (being also labeled as electrode B herein)
Call, when not carried out any anode, negative polarity reversion and subsequent charging or electrically operated charge and discharge described in
Battery or the anode of battery pack, cathode, in this way, when battery or the anode of battery pack, cathode progress first time polarity is anti-
Turn and subsequent charging or charge and discharge it is electrically operated when, operating procedure includes, firstly, by battery or the positive electrode of battery pack, negative electricity
Pole carries out polarity reversion, that is, keeps the polarity of battery or the original anode (electrode A) of battery pack negative by being just inverted to, originally
The polarity of cathode (electrode B) be inverted to just by negative, will be by the electricity of secondary polarity reversion then after secondary polarity reversion
Pole carries out charging or charge and discharge is electrically operated, that is, by original anode (electrode A) as cathode, by original cathode (electrode B) conduct
Anode, to after secondary polarity reversion battery or battery pack carries out charging or charge and discharge is electrically operated, whole process is from the secondary polarity
Charging or the electrically operated completion of charge and discharge after reverse turn operation to the secondary polarity reversion, as 1 polarity reversion and subsequent charging
Or charge and discharge is electrically operated (at this point, completing the reversion of first time polarity and subsequent charging or charge and discharge of the battery or battery pack
It is electrically operated), this anode, the polarity reversion of cathode and subsequent charging or charge and discharge it is electrically operated it is realized include, for
Anode (electrode A) originally, electrode potential by mutually more it is high be transformed into mutually more low, its electrode reaction for being occurred by original
The battery positive voltage electrode reaction come is inverted to battery terminal negative electrode reaction, for original cathode (electrode B), changes phase
Instead.
It is recognised that on the basis of above-mentioned 1 polarity inverts and subsequent charges or charge and discharge is electrically operated, then carry out 1 pole
Sex reversal and subsequent charging or charge and discharge it is electrically operated (this be also the battery or battery pack the reversion of second of polarity and subsequent
Charging or charge and discharge are electrically operated), then in the charging or charge and discharge operating process after the polarity reversion of rear primary (for the second time), filled
Electricity or the positivity electrodes of charge and discharge are then battery or the original anode (electrode A) of battery pack, are electrically charged or the negativity of charge and discharge
Electrode is then battery or the original cathode (electrode B) of battery pack, the polarity reversion of this time (for the second time) anode, cathode
And subsequent charging or charge and discharge it is electrically operated it is realized include that for original anode (electrode A), electrode potential is by mutually more
Low mutually more high, its electrode reaction occurred that is transformed into is inverted to battery by original battery terminal negative electrode reaction
Anode electrode reaction, for original cathode (electrode B), variation is opposite.In this way, for original anode (electrode A), originally
Cathode (electrode B) has carried out altogether 2 (i.e. for the first time, second) polarity reversions and subsequent charging or charge and discharge is electrically operated.
3 times or the polarity reversion greater than 3 times and subsequent charging or charge and discharge are electrically operated, can be at above-mentioned 2 times (for the first time, the
It is secondary) polarity reversion and subsequent charging or charge and discharge it is electrically operated on the basis of repeatedly carry out similar first time or first again or again
Secondary, second polarity reversion and subsequent charging or charge and discharge are electrically operated and realizes, can be according to above-mentioned 2 times (for the first time, for the second time)
Polarity, which inverts and subsequent charges, or charge and discharge is electrically operated analogizes understanding, implements.
Polarity reversion and subsequent charging or charge and discharge are electrically operated, including by the electrode of battery or/and battery group
Polarity reversion is carried out, and after polarity reversion, so that the electrode inverted by the polarity is carried out following electrochemical reaction: making the pole
It is that positive electrode carries out battery terminal negative electrode reaction after polarity reversion or passes through electrochemical reducting reaction before sex reversal
And it is reduced into metal or 0 chemical valence, the preceding electrode for cathode of polarity reversion is made to carry out accumulator positive after polarity reversion
Pole electrode reaction, it is one such or a variety of.
Electric current in polarity reversion and subsequent charging or charge and discharge behaviour includes DC current, pulse current or arteries and veins
The recombination current of punching and direct current.
Polarity reversion and subsequent charging or charge and discharge it is electrically operated in, the charging operations after any polarity reversion
Number is 1 time or more (including 1 time, the same below).
It is described that battery or the positive and negative electrode of battery pack are subjected to polarity reversion and subsequent charging or the electrically operated packet of charge and discharge
It includes, makes the anode, negative polarity reversion and subsequent charging or the electrically operated work with the battery or battery pack of charge and discharge,
Intert each other, be alternately carried out, and make the battery or battery pack at work, at positive, original cathode originally
In one of following three kinds of electrode working conditions: (1) original anode works as anode always, and cathode originally begins
It works eventually as cathode；(2) original anode works as cathode always, cathode originally be used as always anode into
Row work；(3) original anode is worked as anode sometimes, is worked sometimes as cathode, correspondingly, bearing originally
Pole is used as cathode to be worked sometimes, is used as anode to work sometimes；Its described original positive, original cathode is,
Do not carried out it is any it is described anode, negative polarity reversion and subsequent charging or charge and discharge it is electrically operated when, the battery or
Anode, the cathode of battery pack.
In above-mentioned (1), (2), (3) under any operative state, the battery or battery pack its arbitrarily twice
The polarity reversion and subsequent charging of the anode, cathode between work or charge and discharge number of operations are 0 time or more (including 0
It is secondary, the same below).
It is described that battery or the positive and negative electrode of battery pack are subjected to polarity reversion and subsequent charging or the electrically operated packet of charge and discharge
It includes: carrying out twice in succession or continuously the positive and negative electrode polarity of even-times inverts and subsequent charging or charge and discharge are electrically operated, carry out single
Or the reversion of positive and negative electrode polarity and subsequent charging or charge and discharge of continuum method time are electrically operated, it is one such or a variety of.
It is described anode, cathode to be subjected to polarity reversion and subsequent charging or charge and discharge is electrically operated includes, only in battery pack
Some monocell individually carry out positive and negative electrode polarity reversion and subsequent charging or charge and discharge is electrically operated or only right
Certain (i.e. two or more) monocells in battery pack carry out the positive and negative electrode polarity reversion and subsequent charging or
Charge and discharge is electrically operated, or only to the partial electrode in single battery battery carry out positive and negative electrode polarity reversion and subsequent
Charging or charge and discharge are electrically operated.This all referred to as distinguishes operation.The monocell, that is, single battery.
It is described by positive and negative electrode carry out polarity reversion and subsequent charging or charge and discharge it is electrically operated include carry out pulse charge or/
With the operation of electric discharge；The pulse charge or/and electric discharge include positive pulse, negative pulse, positive negative pulse stuffing mixed pulses charging or/and
One of discharge operation is a variety of.
For target and requirement, technique, safety, etc. needs, it is described by anode, cathode carry out polarity reversion and its
Charging or charge and discharge afterwards it is electrically operated can battery or battery pack any charged or working condition (including before work, work
In, work after, stand) under directly initiate, start and carry out, can also the polarity invert and subsequent charge or charge and discharge behaviour
Make before first to battery or battery pack carry out electric discharge or/and charging operations (hereinafter referred to as polarity reversion before electric discharge or/and fill
It is electrically operated), then restart, start and carries out the polarity reversion and subsequent charging or charge and discharge is electrically operated.Latter situation
Including carrying out discharge operation until voltage is reduced to 0V or 0V or more, then again to battery or battery pack before polarity reversion
Carry out polarity reversion.
The polarity of the battery or battery pack inverts, polarity inverts and subsequent charges or charge and discharge is electrically operated, polarity is anti-
Electric discharge or/and charging operations, differentiation operation before turning can be executed by programming.
The battery or the anode of battery pack, cathode carry out charging or charge and discharge behaviour after polarity reversion, polarity reversion
Make or polarity reversion before electric discharge or/and charging operations can according to certain magnitude of physical quantity, quantitative value, chemical magnitude and they
One of changing value, calculated value or the results such as a variety of settings, measurement, signal acquisition, calculating and start or stop or motionless
Make.The magnitude of physical quantity includes voltage value, current value, current density value, charge value, capability value, performance number, time value, temperature
One of angle value, force value, pressure values, density value, shading value, frequency values are a variety of；The quantitative value include accumulated number,
Odd number value, even number value, ratio value, battery or/and battery pack one of charge-discharge cycle time numerical value or a variety of；The chemistry
Magnitude includes the acidity value of battery or/and battery pack.The magnitude of physical quantity, quantitative value, chemical magnitude include battery or/and electricity
Pond group during the charging process, in discharge process, in On The Cycle Working Process, during float duty, open circuit or static condition in
Magnitude of physical quantity, quantitative value, chemical magnitude and other magnitudes of physical quantity relevant to battery or/and battery group, quantitative value, change
Learn magnitude.
It is described to carry out charging by the electrode of polarity reversion or charge and discharge is electrically operated, wherein the charging or charge and discharge
Electricity is generally 0.5 times of the electrode rated capacity or more.
The active material of its anode of the battery or/and cathode is with two or more stable oxidation state
One of the simple substance of element, compound are a variety of.
The element with two or more stable oxidation state includes but is not limited to: lead, iron, copper, nickel, manganese,
Silver, phosphorus, sulphur, chlorine, vanadium, chromium, cobalt, arsenic, selenium, bromine, tin, antimony, tellurium, iodine, tungsten, bismuth are one such or a variety of.
The battery or battery group, including but not limited to: lead-acid accumulator, nickel-iron storage battery, iron-ferrate
Battery, copper-ferrate battery, the battery of cadmium-nickel storage battery or battery pack, it is one such or a variety of.
The ferrate includes but is not limited to: K2FeO4、Na2FeO4、BaFeO4。
It is described to solve the problems, such as that battery anode active substance expands, softens, fall off method, it is also used for individually solving electric power storage
The other problems in pond, or solve the problems, such as battery anode active substance expand, soften, fall off while be also used for solve electric power storage
The other problems in pond, the other problems include but is not limited to: corrosion (including but not limited to electrode, fluid confluence, the collection of battery
Flow-induced corrosion), passivation, early stage capacitance loss, salinization, crystallization, cathode specific surface area shrink, active material and conductive current collector
Poor contact, memory effect, active material itself decompose, one such or various problems.
It is described that battery or the progress polarity reversion of the positive and negative electrode of battery pack and subsequent charging or charge and discharge is electrically operated,
Be further characterized in that, carry out or carried out the positive and negative electrode polarity invert and subsequent charging or the electrically operated battery of charge and discharge or
Its anode of battery pack and cathode are positive and negative anodes current electrode (that is, electrode positive, that cathode is general), the general electricity of positive and negative anodes
Pole can not only be used for anode and use, also can be used as cathode use or certain as anode in the battery or battery pack
Use, it is certain used as cathode, or the battery or battery pack work or use process in, some time makes as anode
Use, some time again used as cathode, it is one such or a variety of；It is described when constituting the anode of battery or battery pack with cathode
Anode, cathode, positive and negative anodes current electrode include but is not limited to: anode or/and cathode, its electrode active material including swelling agent
Or positive and negative anodes current electrode in active matter formula including swelling agent or/and anode or/and cathode, there is identical activity each other
The positive and negative anodes current electrode of substance or identical active matter formula, each other the positive and negative anodes current electrode of equivalence are same each other
Or identical positive and negative anodes current electrode, it is one such or a variety of；The equivalence each other refers to, after electrode is melted into, each other
Function and performance having the same, alternatively, electrode is after by chemical conversion or charge and discharge, each other battery or battery pack work or
In use process, do not consider (exclude, arrange in the case where error component (such as, but not limited to: foozle, measurement error)
Remove, remove the presence or influence of error), there is or show identical function and performance；It is described same or it is identical just
Cathode current electrode refers to that the positive electrode and negative electrode of the battery are in the institutes such as electrode structure, size, formula, material, manufacture technology
(that is, all electrodes are all identical in terms of constituting) identical in terms of thering is electrode to constitute, alternatively, described same or identical
Positive and negative anodes current electrode refers to, those are mutually the same before being carried out chemical conversion or charge and discharge, are being carried out chemical conversion or charge and discharge
Can form the positive and negative anodes current electrode of positive or negative pole later, it is described carried out chemical conversion or charge and discharge before it is mutually the same refer to,
Electrode is by before being melted into, and the electrode or the anode, cathode, in all respects, such as, but not limited to collector, active material are matched
Side and active material quality (such as, but not limited to lead paste formula and lead plaster quality), manufacture technology etc., identical (that is,
It is all identical in all respects), alternatively, not considering that the foozle generated when manufacturing electrode (is excluded, excluded, removing foozle
Presence or influence), carried out chemical conversion or charge and discharge it is electrically operated before, two or more electrodes each other all electrodes constitute,
Manufacture view (such as electrode structure, appearance, size, formula, material, manufacture technology) is identical.
The swelling agent is used to prevent, inhibit, improves electrode specific surface area contraction or electrode active material specific surface area receipts
Contracting.
The swelling agent includes but is not limited to: barium sulfate, calcium sulfate, silica, silicate, humic acid, lignosulphonic acid
The oxide or hydroxide of salt, the oxide of aluminium or hydroxide, titanyl compound or hydroxide, lithium, it is one such
Or it is a variety of.
Mass percentage of the swelling agent in active material or active matter formula is 0.01%-50%.
The active material, including but not limited to: metallic lead, lead plaster, lead powder, lead compound, lead powder mixture, leaded are closed
Object mixture, NiOOH, Ni (OH)2, Fe, Fe (OH)2, FeOOH, ferrate, copper, copper compound, it is one such or more
Kind or they it is one such or it is a variety of with swelling agents, other additives are one such or the mixture of a variety of formation；
The lead plaster includes: dry lead plaster, wet lead plaster；
The lead powder includes but is not limited to: the lead oxide powder with certain oxidizability；
The lead compound includes but is not limited to: lead monoxide, plumbous plumbate, lead orthoplumbate, brown lead oxide, hydrogen-oxygen
Change lead, lead sulfate, basic lead sulphate, ceruse, basic lead carbonate, other lead oxides, other lead hydroxide, Qi Taqian
Salt, it is one such or a variety of；
The lead powder mixture are as follows: the lead powder and other materials, such as additive, the substance after mixing；
The lead compound mixture are as follows: the lead compound and other materials, such as additive, the substance after mixing.
The active matter formula includes but is not limited to: the anode, cathode, before electrode chemical conversion, active matter
The formula of matter.
It is described by battery or the positive and negative electrode of battery pack carry out polarity reversion and subsequent charging or charge and discharge is electrically operated can be with
It automatically or/and is manually realized by a kind of circuit, the circuit has described by battery or/and the anode of battery group
Carry out polarity reversion or polarity reversion and subsequent charging or the electrically operated function of charge and discharge with cathode, the circuit can or it is practical
On battery or/and the anode of battery group, cathode are subjected to polarity reversion or polarity inverts and subsequent charging or charge and discharge
Total cumulative number >=1 time of operation.
The circuit, which is effected or carried out, carries out the anode, negative polarity reversion or pole to battery or/and battery group
Sex reversal and subsequent the electrically operated method of charging or charge and discharge include: to carry out antipole charging, strong to the battery or battery pack
It charges after system electric discharge, reversal connection, it is one such or a variety of.
It charges after the reversal connection, i.e., (charge and discharge electric appliance anode clip or cathode output end and battery terminal negative under reversal connection state
Plate or cathode connection, charge and discharge electric appliance cathode clip or cathode output end and accumulator anode board positive are connect), to battery into
Row charging.
It charges after the reversal connection, including but not limited to, makes the positive and negative electrode of battery that polarity reversion occur.
The charge and discharge electric appliance, i.e. charging or/and discharger.
The circuit realizes that the method for carrying out antipole charging to battery or/and battery group includes but is not limited to pass through
Be connected to the circuit output end on the battery or battery set electrode polarity reversion and the polarity reversion after to institute
Charging or the charge and discharge for stating battery or battery pack progress are electrically operated, to realize the positive and negative electrode polarity of the battery or battery pack
Reversion or polarity reversion and subsequent charging or charge and discharge are electrically operated.
The circuit includes but is not limited to: management circuit, the charging/discharging apparatus of power supply, battery or battery pack, described to fill
Discharge equipment includes but is not limited to: charger, charger, instrument for repairing, tester, charge and discharge electric appliance, battery or battery set management system
System.
The electric power storage for solving the problems, such as the method that battery anode active substance expands, softens, falling off and being applied to of the invention
Pond or/and battery group, including but not limited to: surface plate grating, tubular type, takeup type, bipolar system, horizontal lead cloth, cystosepiment
Grating, pillar have and stablize gap body electric pole type, sintered type, pouch type secondary battery or battery pack, or including but not limited to valve-regulated
Sealed cell or battery group, colloid storage battery or battery group, lead carbon battery battery or battery group, super capacitor
Device-battery (abbreviation superbattery) battery or battery group, or include but is not limited to the battery mixing company of these types
The battery group of mixed type made of connecing and the battery or battery pack of various other types.The full tube type storage battery tool
There are tubular type positive electrode, tubular type negative electrode.
The present invention improves or extends battery or the method for battery pack service life can be applied to battery or battery pack, storage
Chemical conversion work when battery or the circuit or charging/discharging apparatus of battery pack, the reparation of battery or battery pack, regeneration or the manufacturing
Skill.
Unless otherwise indicated, the shape, structure of the battery, construction include but is not limited to the prior art disclosed in,
The shape, structure of well known, general battery, construction, the shape, structure of the disclosure, well known, general battery,
Construction includes but is not limited to: battery includes positive (positive electrode), cathode (negative electrode), electrolyte, diaphragm (or plate), current remittance
Fluid (or row), output terminal, battery case (or shell)；It is inserted with (or being separated with) partition between the anode, cathode, it is same polar
Electrode (or electrode group its electrode), which is all conductively connected, to be conductively connected in fluid confluence (or row) to be formed each other, and positive electrode is connected
Fluid confluence (or row) is conductively connected with battery positive voltage output terminal, connects the fluid confluence (or row) and battery of negative electrode
Negative output terminals are conductively connected, when forming battery group, be conductively connected the output terminal of item and each battery into
Row is conductively connected and forms the series, parallel between each battery；As optional, the positive electrode can be with battery positive voltage output end
Son is conductively connected, and the negative electrode can be conductively connected with battery terminal negative output terminal；The anode, cathode, every
Film (or plate), electrolyte are in battery case (or shell), and electrolyte is in contact with anode, cathode, diaphragm (or plate)；The electrode
Including electrode current collecting body, active material, described collector itself is at least a part of or one end and active material conductive electrical contact
Or combine, alternatively, described collector itself is at least a part of or one end is arranged inside active material or surface, the afflux
At least one of connector (or item) or accumulator output terminal electric conductivity connect between the body other end and fluid confluence or single battery
It connects.
Beneficial effect
The present invention is by carrying out the reversion of positive and negative electrode polarity and subsequent charging or charge and discharge to the battery or battery group
It is electrically operated, it can solve, prevent, inhibiting, repairing, battery or the positive active material of battery group is reversed to expand or/and soften
Or/and fall off, burn into passivation, early stage capacitance loss, salinization, crystallization, cathode specific surface area are shunk, active material and conductive
Collector poor contact, memory effect, active material itself decomposition etc., one such or various problems, caused electric power storage
Pond end of life, to improve or extend the service life of battery or battery group.
For example, for lead-acid accumulator, the electrode reaction of lead-acid accumulator are as follows:
Anode:
Cathode:
As it can be seen that the reaction product after anode, negative discharge is PbSO4, product PbSO4It is converted to respectively again after charged
Positive active material PbO2With negative electrode active material Pb；Using the original anode of lead-acid accumulator as cathode, cathode originally is made
For anode, operation is charged the battery, makes that negative electrode reaction occurs on original anode, anode occurs on cathode originally
Electrode reaction, then the discharging product PbSO of original anode4It can be converted to negative electrode active material Pb, equally, original cathode
Discharging product PbSO4Positive active material PbO can be converted to2, i.e. the polarity of positive and negative electrode can invert, due to electrode reaction equation
(1), the electrode reaction in (2) is reversible, and therefore, the polarity between the original anode of lead-acid accumulator and original cathode is anti-
Turn also to be reversible.In addition, using the original anode of lead-acid accumulator as cathode, original cathode as anode, to battery into
Row charging operations result even in the PbO on original anode2Pb directly on Pb conversion, original cathode is directly to PbO2
Conversion, thus also complete the reversible polarity reversion between lead-acid accumulator original anode and original cathode.
For conventional lead-acid batteries in charge and discharge, anode is with the active matter on the increase electrode of the charge and discharge number of occurrence again
Matter PbO2Combination between particle is gradually relaxed, is disengaged from each other, so that positive active material expands, is loose, softens, falls off；It is negative
Pole with tending to show as being bonded to each other between the active material Pb particle on the increase electrode of the charge and discharge number of occurrence so that
Cathode specific surface area shrinks, is hardened.Using the original anode of lead-acid accumulator as cathode, cathode originally is as anode, to electricity
Pond carries out charging operations, then the original positive active material PbO of lead-acid accumulator2Disengaging between particle can pass through negative electricity
Pole is reacted and is reversed, and equally, the combination between the original negative electrode active material Pb particle of lead-acid accumulator can pass through
Anode electrode reaction is also reversed, i.e., the expansion, softening of active substance for positive electrode of lead-acid accumulator, drop out effects, cathode ratio
Surface area shrinkage effect can be reversed each other by above-mentioned electrode reaction (1) (2), in other words, polarity through the invention
Reversion and subsequent charging or charge and discharge are electrically operated, and the expansion of active substance for positive electrode of lead-acid accumulator softens, falls off, the ratio of cathode
Surface area shrinkage effect is also reversible.
Polarity reversion and subsequent charging or charge and discharge through the invention is electrically operated, selects suitable charge and discharge system (no
Same charge and discharge system generates structure, property of the physics of electrode or electrode active material and chemistry etc. by electrode reaction
Influence, change effect it is also different), by or not by regulating measures such as additives, make activity caused by anode electrode reaction
Material grains be disengaged from each other reacted with negative electrode caused by active material particle be bonded to each other, take a turn for the worse or cancel out each other,
Can substantially improve even be eliminated lead-acid accumulator positive active material expand, soften, falling off, cathode specific surface area contraction ask
Topic, to significantly improve or extend the service life of lead-acid accumulator.Theoretically, if can solve lead-acid accumulator or plumbic acid
The positive active material of battery group expands, softens, falling off, cathode specific surface area is shunk and except positive active material expansion,
Soften, fall off, other than the failure mode that cathode specific surface area is shunk and battery caused by other failure modes for being currently known or
The problem of end of life of battery pack, then the service life of lead-acid accumulator and battery pack is it could even be possible to be intended to infinitely
It is long or extremely long.
In addition, method of the invention or polarity reversion and subsequent charging or charge and discharge are electrically operated, store battery or plumbic acid
Electrochemical reaction process experienced is not limited solely to commonly to work in cycle charge-discharge operation battery in use
Electrochemical reaction process, this make the positive electrode of battery or lead-acid accumulator, negative electrode, electrolyte, collector, fluid confluence,
Liquid/solid interface, solid/liquid/solid interface etc., which have occurred, is conducive to make battery or waste lead-acid accumulators problem to achieve a solution, make
The variation that battery or performances of the lead-acid battery improve, thus can also make battery or lead-acid accumulator corrosion (including but
Be not limited to electrode, fluid confluence, collector corrosion), passivation, sulfation, the contraction of cathode specific surface area, active material and collector
It poor contact or/and falls off, is early stage capacitance loss, one such or a variety of, be resolved, repair, reversing, eliminating, improving,
Alleviate, inhibit, prevent, avoid.
In another example usual positive active material is NiOOH/Ni (OH) for nickel-iron storage battery2, negative electrode active material
For Fe/Fe (OH)2/ FeOOH, due to the NiOOH and Ni (OH) of anode2Density variation between active material easily leads to electrode through following
Dilatancy after ring, soften, fall off, cathode iron electrode is easy to happen passivation, these problems, the side that can provide through the invention
Method carries out the reversion of positive and negative electrode polarity and subsequent charging to the battery or battery group or charge and discharge is electrically operated, realizes solution
Certainly, it repairs, reverse, eliminate, improve, alleviate, inhibit, prevent, avoid.
It is decomposed in another example itself easily occurs for the ferrate in iron-ferrate battery, which can be by this hair
The method realization of bright offer is solved, is repaired, reversing, eliminating, improving, alleviating, inhibiting, preventing, avoiding.
Battery or battery pack, when its positive electrode and negative electrode is electrode positive, that cathode is general, production and recycling have
The characteristics of greater efficiency, lower cost, and of the invention polarity reversion and subsequent charging or and discharge operation are carried out to it
It can be improved or prolong its service life, the technical solution for the electrode for keeping its anode, cathode general is carried out, and makes it have reality
The property used.
Operation distinguished to battery or battery pack, i.e., in battery pack or battery each monocell, part monocell,
It is electrically operated that partial electrode individually carries out the of the invention reversion of positive and negative electrode polarity and subsequent charging or charge and discharge, be conducive to maintenance,
The consistency of capacity each other is adjusted in battery pack between monocell, the service life of battery or battery pack is improved or extend.
In conclusion method of the invention is applied to battery or battery group, the positive-active of battery can solve
Mass expansion or/and softening or/and fall off, burn into passivation, early stage capacitance loss, salinization, crystallization, cathode specific surface area receive
Contracting, active material and conductive current collector poor contact, memory effect, active material itself decompose, one such or a variety of ask
Topic, significantly improves or extends the service life of battery or battery pack.
In addition, positive and negative electrode polarity reversion of the invention and subsequent charging or charge and discharge is electrically operated that battery also can be improved
Active material utilization is to battery capacity, including the capacity in battery initial capacity and use process.
Detailed description of the invention
Fig. 1 is operating discharge capacity and the operating discharge end of 1 lead-acid accumulator cycle charge-discharge of embodiment of the present invention work
Only voltage data figure.
Fig. 2 is operating discharge capacity and the operating discharge end of 3 lead-acid accumulator cycle charge-discharge of embodiment of the present invention work
Only voltage data figure.
Specific embodiment
Below in conjunction with specific embodiment, technology contents of the invention, feature and effect are described in further detail.
Embodiment 1
The present embodiment is related to solving the problems, such as that active substance for positive electrode of lead-acid accumulator expands, softens, falling off or/and raising or prolonging
Method, battery charging and discharging device and the lead-acid accumulator of long lead-acid accumulator service life, the wherein battery charging and discharging of the present embodiment
Device can be to this implementation based on current source circuit, voltage source circuit and the forced charge or/and forced electric discharge function included by it
The positive and negative electrode of example lead-acid accumulator carries out polarity reversion and subsequent charging or charge and discharge is electrically operated.Following the present embodiment owns
The operation carried out to the present embodiment lead-acid accumulator is battery charging and discharging device through this embodiment in addition to illustrating manually
Come what is realized, the present embodiment battery charging and discharging device has the function of executing by setup program for function and work.The present embodiment plumbic acid
Battery, rated capacity are 1.77Ah (2h rate, 25 DEG C), and voltage rating 2V, anode is with existing general commercial anode lead
Anode made from paste formulation (wherein sulfuric acid phase is 4.5wt.% for the content of ball milling lead powder, and does not contain barium sulfate in formula)
Lead plaster is only used as anode when battery works, because referred to herein as positive plate (it is clear for subsequent statement, in the present embodiment also by
It is named as electrode A), negative plate has cathode lead plaster made from existing general commercial cathode lead plaster formula, when battery works only
Used as cathode, because referred to herein as negative plate (it is clear for subsequent statement, be also named as in the present embodiment electrode B 1,
B2), the lead powder that positive and negative electrode lead plaster uses is existing general commercial ball milling lead powder, dry lead plaster on positive plate after solidifying, being dry
Quality is 29.69g, and the sulfuric acid solution density in the present embodiment lead-acid accumulator is 1.27g/cm3, the present embodiment exclude or prevent
Lose the interference of the factors to the present embodiment implementation process and result of implementation such as liquid, open circuit, short circuit, mechanical failure, test failure.
The method that the present embodiment improved or extended lead-acid accumulator service life is, firstly, allowing the present embodiment lead acid storage battery
Pond carries out cycle charge-discharge work, the cycle charge-discharge working system of the present embodiment lead-acid accumulator are as follows: when battery is in charging
When rear state, electric discharge work is carried out to battery with the constant current of 1031mA, upon discharging between reach 36 timesharing in 1 hour and (put
Capacitance is 1649mAh, when being the 93% of rated capacity) or when cell voltage≤1.75V, stop electric discharge, then with
The constant current of 412mA charges the battery, and after measuring cell voltage and reaching 2.65V, be converted into 2.65V constant pressure after
It is continuous to charge to battery, when twice (constant current, constant pressure) charging reach total time 6 hours 24 points, battery charging process terminates, then,
Discharge process above-mentioned is repeated with the constant current of 1031mA again, repeatedly, is cyclically discharged, is charged, discharge, recharge again,
Circulating battery charge and discharge is set to work, cell operating conditions temperature is 25 ± 1 DEG C；Secondly, when positive material(PAM) softening or/and taking off
It falls, sulfation, passivation, early stage capacitance loss, burn into active material and collector poor contact, negative electrode active material compare table
One of area contraction factor a variety of leads to the present embodiment lead-acid accumulator its discharge capacity or electric discharge in above-mentioned work
(for example, what is set in the present embodiment is respectively when time is less than a certain preset capability value or sometime value
900mAh, 1 hour 36 points, 47 points, it is as follows), stop the work of battery, start to carry out at least phase twice in succession to battery
The reversion of positive and negative electrode polarity and subsequent charging or charge and discharge are electrically operated, make the present embodiment lead-acid accumulator after the completion of the operation, work
It is restored or improves as discharge capacity, then, battery is put under its original working system again and continue work；
Then in this way, during the cycle charge-discharge work (abbreviation cycle operation, the same below) of the present embodiment lead-acid accumulator, repeatedly
Ground, interspersed ground are carried out to more phases the same as or similar to the above-mentioned positive and negative electrode polarity reversion twice in succession of the present embodiment and thereafter
Charging or charge and discharge it is electrically operated, to inhibit, prevent, repair, improve, eliminate or reverse the positive active material of lead-acid accumulator
Soften or/and fall off, negative electrode active material specific surface area is shunk, electrode/fluid confluence/collector burn into passivation, early stage capacity damage
One of mistake, sulfation, active material and collector poor contact problem are a variety of, to significantly improve or extend this implementation
The service life of example lead-acid battery.Specifically, through this embodiment battery charging and discharging device and its setting program, execute function, if
Determine and execute to carry out positive plate, the polarity reversion of negative plate and subsequent charging or charge and discharge behaviour to the present embodiment lead-acid accumulator
Make, when carrying out the present embodiment anode plate for lead acid accumulator, cathode reversal of plate polarity reverse turn operation, one is manual operations: by battery
Voltage is down near 0V, then relies on manpower, by the connection of the present embodiment battery charging and discharging device and the present embodiment lead-acid accumulator
State connect from charge and discharge electric appliance anode clip (anode output conductive clamp, the same below) with anode plate for lead acid accumulator (electrode A),
Charge and discharge electric appliance cathode clip (cathode exports conductive clamp, the same below) connect (this with lead-acid battery negative pole plate (electrode B 1, B2)
Kind connection claims just to connect state, the same below), it changes into charge and discharge electric appliance anode clip and lead-acid battery negative pole plate (electrode B 1, B2)
Connection, charge and discharge electric appliance cathode clip connect with anode plate for lead acid accumulator (electrode A) (such connection title reversal connection state, below
Together), or by reversal connection state it changes at state is just connect, then the transformed battery of electrode connection status is carried out charging to battery
Voltage > 0V, to realize the polarity reversion of its electrode of the present embodiment battery；Another kind is battery charging and discharging through this embodiment
Device is automatically brought into operation: when the present embodiment lead-acid accumulator is in and just connects state, the perseverance in battery charging and discharging device through this embodiment
Stream source carries out forced electric discharge to the present embodiment battery and the voltage of battery is made to be transformed into the state of < 0V from the state of >=0V, or
Charge the battery (or forced charge) in cell voltage < 0V and make cell voltage be transformed into from the state of < 0V >=
The state of 0V realizes the polarity reverse turn operation to the present embodiment lead-acid accumulator automatically.When battery, which is in, just connects state,
Battery continues forced electric discharge in cell voltage < 0V so that cell voltage be intended to it is more negative, then at this time battery positive plate (electricity
Pole A) on it is main happens is that in charging process, cell negative plate (electrode B 1, B2) in acid accumulator negative pole lead electrode reaction
It is main happens is that in lead acid battery positive electrode electrode reaction charging process (can refer to electrode reaction equation of the present invention (1), (2),
It is the same below)；And the present embodiment battery is in when just connecing state, battery is forced to charge in cell voltage < 0V, so that battery
Voltage is intended to corrigendum or 0V, then main happens is that acid accumulator negative pole lead electrode is anti-on battery positive plate (electrode A) at this time
It is main happens is that in lead acid battery positive electrode electrode reaction on the discharge process answered, cell negative plate (electrode B 1, B2)
Discharge process；When the present embodiment battery, which is in, just connects state, battery is electrically charged in cell voltage > 0V, so that cell voltage
Be intended to correct, then it is main happens is that filling in lead acid battery positive electrode electrode reaction on battery positive plate (electrode A) at this time
It is main happens is that charging process in acid accumulator negative pole lead electrode reaction on electric process, cell negative plate (electrode B 1, B2).
In this way, the forced electric discharge of battery charging and discharging device, forced charge function and operation are realized to the present embodiment electricity through this embodiment
Charging or charge and discharge after polarity reverse turn operation and the polarity reversion of pond positive and negative electrode is electrically operated.In addition, also utilizing the present embodiment
Charging, discharging function possessed by battery charging and discharging device are come charging, the electric discharge when implementing to the work of the present embodiment lead-acid accumulator
Operation, with realize the present embodiment battery cycle charge-discharge work (below to all operations of the present embodiment lead-acid accumulator and
Measurement in addition to illustrate be it is outer manually, be through this embodiment battery charging and discharging device progress setting program, execute realization).
The method specific implementation process that the present embodiment improved or extended lead-acid accumulator service life is as follows:
By upper, initially set up when the operating discharge capacity of the present embodiment lead-acid accumulator is less than 900mAh, stop this reality
Apply the reversion of positive and negative electrode polarity and subsequent charging that a lead-acid accumulator works and starts to carry out the battery first, second time
Or charge and discharge is electrically operated.According to the present embodiment work the 2nd charge/discharge operation circulation of the present embodiment battery after chemical conversion
Make system and carry out charge-discharge cycle work, occur on the present embodiment battery positive plate when work lead acid battery positive electrode electrode reaction,
Acid accumulator negative pole lead electrode reaction occurs on negative plate, as shown in Figure 1, when work charge-discharge cycle is to the 148th time, this reality
The operating discharge capacity for applying a battery starts obviously to show the phenomenon that gradually declining, on inspection, this is because positive electrode active material
Matter softening, fall off caused by (following operating discharge capacity decline the reason of with this together), when charge-discharge cycle works to the 179th time
When, operating discharge capacity when battery discharge is to 1.75V is down to 899mAh (i.e. residual capacity be rated capacity 50.9%), i.e.,
Reach and starts the trigger condition electrically operated to the progress positive and negative electrode polarity reversion of the present embodiment battery and subsequent charging or charge and discharge
(discharge capacity < 900mAh), at this point, start to carry out the present embodiment battery the reversion of first, second positive and negative electrode polarity and its
Charging or charge and discharge afterwards electrically operated preparation and the formal operation, that is, (cell voltage at this time after the electric discharge of the 179th task
For 1.75V), continue to battery with 1031mA constant current carry out electric discharge 4min and to cell voltage be 0V when, stop electric discharge, then
The polarity reversion of its positive plate, negative plate is carried out to the battery, that is, manually by the present embodiment battery charging and discharging device and the present embodiment
The connection status of lead-acid accumulator connect from charge and discharge electric appliance anode clip with anode plate for lead acid accumulator (electrode A), charge and discharge electric appliance
State that cathode clip was connect with lead-acid battery negative pole plate (electrode B 1, B2) just connect, change at, charge and discharge electric appliance anode clip with
Lead-acid battery negative pole plate (electrode B 1, B2) connection, charge and discharge electric appliance cathode clip are connect with anode plate for lead acid accumulator (electrode A)
Reversal connection state, formed be commonly called as antipole connection, then, with the constant current of 1031mA to the battery after transformation connection status
It charges, so that acid accumulator negative pole lead electrode reaction occurs on the positive plate (electrode A) of the present embodiment lead-acid accumulator
Charging process, the present embodiment lead-acid accumulator negative plate (electrode B 1, B2) on lead acid battery positive electrode electrode reaction occurs
Charging process, when small through 3 15min, cell voltage rise to 1.75V (at this time negative plate or electrode B 1, B2 be positive, positive plate
Or electrode A is negative) after, continuation charges to battery 3 hours with the constant current of 1031mA, and (this process cell voltage rises from 1.75V
At this time it is still negative plate or electrode B 1, B2 are positive, positive plate or electrode A are negative to 2.23V), then, with 1031mA constant current
It discharges battery, so that acid accumulator negative pole lead electrode occurs on the positive plate (electrode A) of the present embodiment lead-acid accumulator
Lead acid battery positive electrode electrode occurs on the discharge process of reaction, the negative plate (electrode B 1, B2) of the present embodiment lead-acid accumulator
The discharge process of reaction, the electric discharge through 24min, to 0V when stop discharging, then, positive and negative electrode pole is carried out to the battery again
Sex reversal, that is, manually by the connection status of battery charging and discharging device and the present embodiment lead-acid accumulator from charge and discharge electric appliance anode clip
It is connect with lead-acid battery negative pole plate (electrode B 1, B2), charge and discharge electric appliance cathode clip and anode plate for lead acid accumulator (electrode A) connect
The reversal connection state connect is changed at charge and discharge electric appliance anode clip is connect with anode plate for lead acid accumulator (electrode A), charge and discharge electric appliance is negative
Pole clip just connects state with what lead-acid battery negative pole plate (electrode B 1, B2) was connect, then, to the battery with the perseverance of 258.4mA
Electric current charges, so that it is anti-that lead acid battery positive electrode electrode occurs on the positive plate (electrode A) of the present embodiment lead-acid accumulator
It is anti-that acid accumulator negative pole lead electrode occurs on the negative plate (electrode B 1, B2) of the charging process, the present embodiment lead-acid accumulator answered
The charging process answered, the charging through 31min, to cell voltage 1.75V when (at this time positive plate or electrode A be positive, negative plate or electricity
B1, B2 are negative for pole), then with 16 hours 35min of 412mA constant current charge, to cell voltage 2.65V, then, then with 2.65V perseverance
Voltage charges to the battery 3 hours, and (this constant current, constant-voltage charge process positive plate or electrode A be positive, negative plate or electrode B 1, B2
Be negative), after the completion of the constant-voltage charge, so far, complete first, second positive and negative electrode polarity reversion to the present embodiment battery and
Thereafter charging or charge and discharge is electrically operated.Then, the battery is reentered under the same charge and discharge cycles working condition and system
Carry out the 180th task electric discharge and later cycle charge discharge work.The result shows that being inverted through first, second positive and negative electrode polarity
And subsequent charging or charge and discharge it is electrically operated after, the battery under the 180th task state discharge capacity rising reaches
1452.5mAh, and to be restored to regular picture capacity 1649mAh (corresponding to put for the discharge capacity under its 181st task state
The electric time be 1 hour 36 points).
Next, make the present embodiment battery continuation run under working system, and will triggering positive and negative electrode polarity reversion and its
The electrically operated condition of charging or charge and discharge afterwards passes through programming change are as follows: as the operating discharge time < of the present embodiment lead-acid accumulator
36 timesharing in 1 hour, stop battery work and start automatically to battery carry out third, the 4th time positive and negative electrode polarity invert and
Thereafter charging or charge and discharge is electrically operated.As shown in Figure 1, operating discharge capacity in the 181-224 times electric discharge-charging work circulation
Reach the regular picture time, 1 hour 36 points (corresponding discharge capacity is 1649mAh), this in the cycle charge discharge course of work
Lead acid battery positive electrode electrode reaction occurs on embodiment battery positive plate (electrode A), occurs on negative plate (electrode B 1, B2)
Acid accumulator negative pole lead electrode reaction, when the work of battery charge-discharge cycle is to the 225th time, the electric discharge ability to work of battery is opened
Begin to decline, discharge time is 35 timesharing in 1 hour (battery discharge final voltage is reduced to 1.75V at this time), therefore, according to setting
Trigger condition and execute program, the present embodiment battery charging and discharging device at this time immediately by the present embodiment battery by working condition from turn
Enter positive plate, the polarity reversion of negative plate and subsequent charging or the electrically operated preparation and implementation phase of charge and discharge, i.e., fills for the 225th time
Putting cycle operation electric discharge terminates, after cell voltage is down to 1.75V, and battery is stopped work, makes the connection of battery Yu charge and discharge electric appliance
State, which is positive, connects state, it may be assumed that the present embodiment battery charging and discharging device output head anode and the present embodiment anode plate for lead acid accumulator (electricity
Pole A) be connected, the present embodiment battery charging and discharging device negative pole of output end and the present embodiment lead-acid battery negative pole plate (electrode B 1,
B2) it is connected, then the present embodiment battery is automatically carried out continuing electric discharge and forced electric discharge with the constant current of 1031mA, and
The forced electric discharge function of battery charging and discharging device through this embodiment, this continues electric discharge and forced electric discharge operation and makes this through 23min
Embodiment cell voltage drops to 0V from 1.75V quickly, and (this process makes the positive plate or electricity of the present embodiment lead-acid accumulator
Occur on the A of pole the discharge process of lead acid battery positive electrode electrode reaction, the negative plate of the present embodiment lead-acid accumulator or electrode B 1,
The discharge process of acid accumulator negative pole lead electrode reaction occurs on B2), then so that cell voltage is dropped to ﹣ from 0V through 36min again
(battery charging and discharging device is measured and the cell voltage that shows, and the same below, this process makes the present embodiment lead acid storage battery by 1.75V
The charging process of acid accumulator negative pole lead electrode reaction, the present embodiment lead-acid accumulator occur on the positive plate or electrode A in pond
The charging process of lead acid battery positive electrode electrode reaction occurs on negative plate or electrode B 1, B2), after reaching ﹣ 1.75V, continue
Keep 1031mA constant current forced electric discharge 3 hours (at this moment measure cell voltage from ﹣ 1.75V and drop to about ﹣ 2.15V, this process
Still make the charging that acid accumulator negative pole lead electrode reaction occurs on the positive plate (electrode A) of the present embodiment lead-acid accumulator
Journey, the present embodiment lead-acid accumulator negative plate (electrode B 1, B2) on occur lead acid battery positive electrode electrode reaction charging
Journey), then, charge and discharge electric appliance then carries out forced charge to the battery with the constant current of 1031mA and (it is time-consuming to measure the charging of this process
23 minutes, cell voltage from about ﹣ 2.15V rises to 0V (this process makes the positive plate or electrode A of the present embodiment lead-acid accumulator
The negative plate or electrode B 1, B2 of the upper discharge process that acid accumulator negative pole lead electrode reaction occurs, the present embodiment lead-acid accumulator
The upper discharge process that lead acid battery positive electrode electrode reaction occurs), after cell voltage reaches 0V, charge and discharge electric appliance automatically continues
It is charged with the constant current of 258.4mA to battery, (this process makes this reality after so that cell voltage is reached 1.75V
Apply charging process, the present embodiment that lead acid battery positive electrode electrode reaction occurs on the positive plate or electrode A of a lead-acid accumulator
The charging process of acid accumulator negative pole lead electrode reaction occurs on the negative plate or electrode B 1, B2 of lead-acid accumulator), then with
The constant current of 412mA continues charging 41 minutes 8 hours to battery, so that measure cell voltage up to 2.65V, then, switches to pair
The battery is charged with 2.65V constant pressure, and this constant-voltage charge is made to keep 3 hours (positive plates during this constant current, constant-voltage charge
Or electrode A is positive, negative plate or electrode B 1, B2 are negative), after the completion of this constant-voltage charge, so far, complete to the present embodiment battery
Third, the reversion of the 4th positive and negative electrode polarity and subsequent charging or charge and discharge it is electrically operated, then the present embodiment battery is rotated back into
It is carried out the 226th time under its original, the same cycle charge discharge working condition and system and the cycle charge-discharge of number works later.
The result shows that after third, the 4th positive and negative electrode polarity reversion and subsequent charging or charge and discharge are electrically operated, the present embodiment battery
In the 228th cycle operation discharge time be restored to 1 hour 36 points, and next until the 239th circulation industrial
Its operating discharge time is all normal in work, be 1 hour 36 points.(the 226th, 227 working cycles are made due to maloperation
Final discharging voltage has been lower than 1.75V, leads to overdischarge).
Next, running the continuation of the present embodiment battery under working system, as shown in Figure 1, when the present embodiment battery exists
When cycle operation is to the 240th time, discharge time is 35 timesharing in 1 hour, and the positive and negative electrode polarity set before triggering again is anti-
Turn and subsequent charging or the electrically operated beginning condition of charge and discharge, thus it is (electric at the end of electric discharge after the electric discharge of the 240th task
Cell voltage is 1.75V), next charge and discharge electric appliance has started to carry out the present embodiment battery into the 5th, the 6th positive plate, cathode
The polarity of plate invert and subsequent charging or charge and discharge it is electrically operated, operating method and process and the present embodiment third, the 4th time just,
Negative polarity reversion and subsequent charging or charge and discharge are electrically operated identical, then, reenter the present embodiment lead-acid accumulator together
Then the 241st time of the present embodiment battery is carried out under preceding cycle charge-discharge working condition and system and the circulation of number is filled later
Electric discharge work.As a result, after the 5th, the 6th reversion of positive and negative electrode polarity and subsequent charging or charge and discharge is electrically operated, this implementation
Example battery discharge time in the 243rd cycle operation be restored to 1 hour 36 points (the 241st, 242 working cycles due to
Maloperation makes final discharging voltage be lower than 1.75V, leads to overdischarge).
Next, running the continuation of the present embodiment battery under working system, and in the charge-discharge cycle mistake for carrying out the 244th time
Cheng Zhong will trigger the beginning condition that the present embodiment battery positive and negative electrode polarity inverts and subsequent charges or charge and discharge is electrically operated and pass through
Programming change are as follows: when discharge time < 45 minutes of the present embodiment battery, stop battery and work and start automatically to this reality
It applies a lead-acid accumulator or its positive and negative pole plate carries out the 7th time, the 8th positive and negative electrode polarity reversion and subsequent charging or fills
Discharge operation.As shown in Figure 1, its discharge performance is begun to decline when the present embodiment battery working cycles are to the 251st time, the 268th
When secondary, the operating discharge time is 42 points (corresponding operating discharge capacity is 721mAh), triggers the positive and negative electrode polarity of setting at this time
Reversion and subsequent charging or the electrically operated beginning condition of charge and discharge, thus after the 268th electric discharge work (at the end of electric discharge
Cell voltage is 1.75V), stop battery work, next charge and discharge electric appliance starts to carry out the present embodiment battery the 7th time, the 8th
Secondary positive plate, the polarity reversion of negative plate and subsequent charging or charge and discharge are electrically operated, operating method and process and the present embodiment
Third, the 4th time positive and negative electrode polarity reversion and subsequent charging or charge and discharge it is electrically operated essentially identical, institute the difference is that,
After cell voltage reaches ﹣ 1.75V, continue to keep 1031mA constant current forced electric discharge 4 hours (rather than 3 hours, this process
Measuring cell voltage is still to drop to about ﹣ 2.15V from ﹣ 1.75V), the 7th time, the polarity of the 8th positive plate, negative plate
After the completion of reversion and subsequent charging or charge and discharge are electrically operated, the present embodiment lead-acid accumulator is made to reenter the same cycle charge discharge
Then the 269th time and the cycle charge-discharge work of number later of the present embodiment battery are carried out under electric working condition and system.Knot
Fruit, after the 7th, the 8th reversion of positive and negative electrode polarity and subsequent charging or charge and discharge is electrically operated, the present embodiment battery is the
In 269 cycle operations discharge time be restored to 1 hour 12 points (discharge capacity 1252mAh), and in the 270th circulation
In work discharge time be restored to 1 hour 36 points, and next until the 290th time cycle charge-discharge work in its work
Make discharge time all and be normal 1 hour 36 points.
As shown in Figure 1, the present embodiment lead-acid accumulator, in next the 270-463 times cycle operation, circulation is filled
Cycle operation of the working condition and system of discharging all with above-mentioned the 1-270 times it is identical, and whenever the present embodiment lead-acid accumulator
The operating discharge time or operating discharge capacity be down to 1 hour 36 points or when 1649mAh or following, i.e., the present embodiment plumbic acid is stored
Battery one phase of progress inverts and subsequent charges similar to above-mentioned polarity twice in succession or charge and discharge is electrically operated, i.e., respectively in its work
Make between discharge the 295th, 296 time, between the 309th, 310 time, between the 324th, 325 time, between the 344th, 345 time, the
369, between 370 times, between the 385th, 386 time, between the 405th, 406 time, between the 425th, 426 time, the 441st, 442 take second place
Between, between the 457th, 458 time, respectively carried out continuous nine, the ten times, it is 11st, 12 time continuous ..., even
Continuous the 27th, 28 time, the polarity reversion and subsequent charging or charge and discharge of totally 10 phases are electrically operated, and make this implementation
The operating discharge time of example lead-acid accumulator or capacity are in each issue of polarity reversion and subsequent charging or charge and discharge twice in succession
Restore in electrically operated subsequent first time or second of operating discharge to 1 hour 36 points or 1649mAh, so that this implementation
Example lead-acid accumulator possesses the ability for continuing to work normally electric discharge.
As shown in Figure 1, after each issue of polarity reversion and subsequent charging or charge and discharge twice in succession is electrically operated in the present embodiment,
The operating discharge time of the present embodiment lead-acid accumulator or capacity are put in the 1st time subsequent either the 2nd task of the operation
Restore in electricity to 1 hour 36 points or 1649mAh, real work of battery is put before this may start with each issue of polarity reverse turn operation
Capacitance declines degree, carries out each polarity reversion and subsequent charging or the electric current in charge and discharge operating process, voltage, charge and discharge
Size, the method for capacitance, number of stages etc. are related.For example, the active material particle on positive plate softens, the degree that falls off is big,
Or the decline of battery real work discharge capacity is more, in the polarity reversion and subsequent charging of the phase that carries out twice in succession
It is mutually also big to the charge volume demand after the 1st polarity reversion of the phase or when charge and discharge behaviour, and filled after the 2nd polarity reversion of the phase
Power consumption is larger to advantageously ensure that battery full charge, therefore, if charge capacity is relatively small after if the phase, the 2nd polarity is inverted
Be likely to result in battery undercharge, will make the present embodiment lead-acid accumulator need through the reversion of polarity twice in succession and its
First time operating discharge and charging process after charging or charge and discharge afterwards is electrically operated supply battery charge amount to continue as it.Example
Such as, it is carried out between the 405th, 406 time of its operating discharge of the present embodiment lead-acid accumulator or between the 441st, 442 time continuous
Polarity reversion twice and subsequent charging or charge and discharge are electrically operated, by the 405th time or the 441st task electric discharge result it is found that the two
The present embodiment lead-acid accumulator operating discharge capacity decline degree be respectively less than between the 179th time, the 405th, 406 time institute into
The capable reversion of polarity twice in succession and subsequent charging or charge and discharge operating process are as follows: (electric at this time after the electric discharge of the 405th task
Cell voltage is 1.75V), keep battery charging and discharging device and the present embodiment battery just connect state under, continue to battery with
1031mA constant current carries out electric discharge and forced electric discharge 132min, when so that cell voltage dropping to 0V from 1.75V, then again under 0V
Drop to -1.75V (during wherein, dropping to 0V from 1.75V, it is main on positive plate or electrode A happens is that lead-acid accumulator just
The discharge process of pole electrode reaction, negative plate or electrode B 1, B2 are upper main happens is that acid accumulator negative pole lead electrode reaction
Discharge process, it is main happens is that acid accumulator negative pole lead electrode on positive plate or electrode A during dropping to -1.75V from 0V
The charging process of reaction, negative plate or electrode B 1, B2 it is upper main happens is that lead acid battery positive electrode electrode reaction charging
Journey), the polarity of negative plate (electrode B 1, B2) is positive when reaching -1.75V, the polarity of positive plate (electrode A) is negative, and then, continues
With the constant current of 1031mA to the battery forced electric discharge 4 hours (this process cell voltage continues to drop to from -1.75V -
2.087V, is still negative plate at this time or electrode B 1, B2 are positive, positive plate or electrode A are negative), then, with 1031mA constant current
Forced charge is carried out to the battery, so that lead-acid storage battery negative occurs on the positive plate (electrode A) of the present embodiment lead-acid accumulator
Lead-acid accumulator is occurring just on the discharge process of pole electrode reaction, the negative plate (electrode B 1, B2) of the present embodiment lead-acid accumulator
The discharge process of pole electrode reaction, the forced charge through 35min, to 0V when stop, then, then to the battery with 258.4mA's
Constant current charges, so that lead acid battery positive electrode electrode occurs on the positive plate (electrode A) of the present embodiment lead-acid accumulator
Acid accumulator negative pole lead electrode occurs in the charging process of reaction, the negative plate (electrode B 1, B2) of the present embodiment lead-acid accumulator
The charging process of reaction, the charging through 1 hour 21min, to cell voltage 1.75V when (positive plate or electrode A are positive and negative at this time
Pole plate or electrode B 1, B2 are negative), then with 412mA constant current charge 14 hours, to cell voltage 2.63V, then, then with 2.65V
Constant voltage to the battery charge 4 hours (this constant current, constant-voltage charge process positive plate or electrode A be positive, negative plate or electrode B 1,
B2 is negative), then, reenters the battery under the same cycle charge-discharge working condition and system and carry out the 406th work
Make electric discharge and the later cycle operation of number.The reversion of polarity twice in succession and subsequent charging carried out between 441st, 442 time
Or charge and discharge it is electrically operated with the 405th, 406 time between it is essentially identical, institute the difference is that, carried out between the 441st, 442 time
Twice in succession polarity reversion and subsequent charging or charge and discharge it is electrically operated in the 1st polarity reversion after forced electric discharge electric current be
1515mA (that is, the forced electric discharge makes the charging process that acid accumulator negative pole lead electrode reaction occurs in positive plate or electrode A, makes
The charging process of lead acid battery positive electrode electrode reaction occurs on negative plate or electrode B 1, B2).
It is considered as non-productive work if defining operating discharge capacity and being lower than the 80% of rated capacity in the present embodiment or disregards
Enter cycle charge-discharge work times (i.e. battery), then the present embodiment lead-acid accumulator is being carried out the first phase or first
The polarity of secondary the present embodiment invert and subsequent charging or charge and discharge it is electrically operated before, as shown in Figure 1, its circulation industrial for effectively working
Make number or service life is that (after 143 circulations, continuously operating discharge capacity is below rated capacity to 145 circulations three times
80%), but through this embodiment positive and negative electrode polarity reversion and subsequent charging or charge and discharge operating method, lead acid storage battery
Pond, battery charging and discharging device after the cycle operation of the present embodiment lead-acid accumulator 463 times, can also continue to work normally,
Effective working cycles number reaches 408 times, increases 181%, continue when not generating collector burn into dehydration according to
Aforesaid operations method can be such that the service life of the present embodiment lead-acid accumulator obtains and continue to extend.
On the one hand as described above, the reversion of positive and negative electrode polarity and subsequent charge and discharge of the present embodiment or charge and discharge is electrically operated makes
The present embodiment lead-acid accumulator positive material(PAM) softening, falling off is enhanced, repairs, reversing so that the present embodiment
It is improved or is restored after the operating discharge capacity operation in lead-acid accumulator cycle operation, another aspect, the present embodiment
Positive and negative electrode polarity reversion and subsequent charge and discharge or charge and discharge it is electrically operated, also necessarily to the present embodiment circulating battery course of work
Middle electrode passivation, early stage capacitance loss, the burn into active material for occurring, slightly occurring or will occur contacts not with collector
The problem of good, cathode specific surface area is shunk has the function of improvement, reparation, reverse, prevention.The present embodiment lead-acid accumulator just
In normal On The Cycle Working Process, (for example, in a manner of providing cycle operation number) periodically or non-periodically, interspersed ground are to this implementation
Example lead-acid accumulator carry out the present embodiment positive and negative electrode polarity reversion and subsequent charge and discharge or charge and discharge it is electrically operated, it will effectively
Improvement, reparation, reverse, prevention positive active material expansion or/and softening or/and fall off, electrode passivation, burn into early stage hold
Loss, sulfation, active material and collector poor contact, cathode specific surface area contraction problem are measured, to improve or extend
The service life of the present embodiment lead-acid accumulator.
In the other embodiment of the present embodiment, by the present embodiment lead-acid accumulator forced electric discharge to cell voltage < 0V
Or the forced electric discharge time after ﹣ 1.75V can also be 5 hours, 10 hours, 20 hours, and cell voltage is made to can achieve ﹣ 2.3V, ﹣
2.65V, ﹣ 2.78V etc., to obtain, stronger positive material(PAM) softening, fall off reversing effect.
In the other embodiment of the present embodiment, the present embodiment is improved to or is extended the side of lead-acid accumulator service life
Method is applied to the present embodiment lead-acid batteries, and the voltage rating of the present embodiment lead-acid batteries is 12V, rated capacity is
12Ah is implemented in operation in method, mainly to making in the setting and execution of the numerical value of voltage, electric current, capacity in operation etc.
Corresponding variation, e.g., after lead-acid batteries forced electric discharge to battery voltage < 0V, makes battery voltage continue to decline
Stop forced electric discharge after to ﹣ 6V, ﹣ 10.5V, ﹣ 13V, ﹣ 15V, forced electric discharge electric current is 0.3 multiplying power, 0.5 multiplying power, 1 multiplying power, 2 times
Rate.
In the other embodiment of the present embodiment, the above-mentioned lead-acid accumulator of the present embodiment includes but is not limited to plane grid
Formula lead-acid accumulator, tube type lead-acid accumulator, full tube type lead-acid accumulator, spirally wound lead acid battery, bipolar system lead acid storage battery
Pond or horizontal lead cloth, pillar, have and stablize gap body electric pole type lead-acid accumulator or valve controlling sealed lead cystosepiment grating
Acid accumulator, gelled lead acid battery, lead carbon battery battery, supercapacitor-lead-acid accumulator (superbattery) battery,
It is one such or a variety of.
In the other embodiment of the present embodiment, the above-mentioned lead-acid accumulator of the present embodiment can be replaced by identical capacity
Other type batteries, other type batteries include but is not limited to: nickel-iron storage battery, iron-ferrate electric power storage
Pond, cadmium-nickel storage battery, one such or a variety of, the present embodiment above method can be applied to other type batteries, can
The maximum value of the absolute value for the voltage for allowing to reach when by charging is turned down, to adapt to different types of battery nominal operation electricity
Pressure.
In the other embodiment of the present embodiment, the present embodiment lead-acid accumulator includes anode, cathode, alternatively, this reality
Applying a lead-acid accumulator positive and negative electrode is positive and negative anodes current electrode, the anode of the present embodiment lead-acid accumulator, cathode, positive and negative
Pole current electrode, including but not limited to, anode or/and cathode, its electrode active material or active material including swelling agent are matched
Positive and negative anodes current electrode or/and anode or/and cathode in side including swelling agent have identical active material or identical each other
The positive and negative anodes current electrode of active matter formula, each other the positive and negative anodes current electrode of equivalence are same or identical each other
Positive and negative anodes current electrode, it is one such or a variety of.The swelling agent is used to prevent, inhibit, improves electrode specific surface area contraction
Or electrode active material specific surface area is shunk, the swelling agent includes but is not limited to: barium sulfate, calcium sulfate, silica, silicic acid
Salt, humic acid, lignosulphonates, aluminum oxide or hydroxide, titanium oxide or hydroxide, oxidate for lithium or hydroxide
Object, it is one such or a variety of.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Embodiment 2
The voltage rating of the present embodiment battery or battery pack is U, rated capacity C2(2h rate, 25 DEG C), C5(5h rate, 25
DEG C) or C20(20h rate, 25 DEG C), wherein U=1.2V, 1.5V, 2V, 4V, 6V, 12V, 24V, 36V, 48V, 60V or 72V, 240V,
360V, 480V, 600V or other voltage values, C2=6.5Ah, 12Ah, 14Ah, 16Ah, 20Ah, 24Ah, 30Ah or 32Ah, or
Person, C5=8.6Ah, 15.9Ah, 18.6Ah, 21.2Ah, 26.5Ah, 31.9Ah, 39.8Ah or 42.5Ah is alternatively, C20=
10.4Ah, 19.2Ah, 22.4Ah, 25.6Ah, 32Ah, 38.4Ah, 48Ah or 51.2Ah.The present embodiment battery or battery pack
Just extremely electrode A 1, A2 ..., An (n=positive integer), and be connected to the output terminal of the present embodiment battery or battery pack
The cathode of A, the present embodiment battery or battery pack be electrode B 1, B2 ..., Bn (n=positive integer), and be connected to the present embodiment
The output terminal B of battery or battery pack.Solve the problems, such as battery anode active substance expand, soften, falling off or/and raising or
The concrete operations for extending the method for the service life of the present embodiment battery or battery pack are, when the present embodiment battery or battery
After group carried out 1 time or more cycle charge-discharge work, due to the present embodiment battery or the cycle charge discharge of battery pack, overcharge
The reasons such as electricity, charge less electricity, high active substance utilization rate, cause the present embodiment battery or the operating discharge capacity of battery pack because just
Pole active mass expansion or/and softening or/and fall off, burn into passivation, early stage capacitance loss, salinization, crystallization, cathode compare table
One of reasons such as area contraction, active material and conductive current collector poor contact, memory effect, active material itself decomposition
Or it is a variety of cause the present embodiment battery or the operating discharge capacity of battery pack to decline, then whenever the present embodiment battery or battery
The operating discharge capacity of group drops to its rated capacity C2、C5Or C2060%, 75%, 80%, 90% or 95% when, Huo Zheben
In the cycle charge discharge course of work of embodiment battery or battery pack charging voltage climbing speed accelerate 10%, 15%, 20%,
When 30% or 50% or when cycle operation reaches certain number, start it is automatic to the present embodiment battery or battery pack or/
Manually carry out a phase twice in succession polarity reversion and subsequent charging or charge and discharge it is electrically operated, that is, operation (1) step: with
One constant current source or/and voltage source carry out antipole charging to the present embodiment battery or battery pack, and the electric current of antipole charging is C2、
C5、0.5C20、0.3C2、3C2Or 5C5One of or the voltage of a variety of or antipole charging be one of 0.5U, U, 1.5U, 2U
Or it is a variety of so that the electrode A 1 of the present embodiment battery or battery pack, A2 ..., the polarity of An is inverted by original positive polarity
At negative polarity, electrode B 1, B2 ..., the polarity of Bn by original negative polarity is inverted to positive polarity (this is the first time of current period
Polarity reversion), then, operates (2) step: charge and discharge being continued to the present embodiment battery or battery pack, charge or discharge
Electric current is C2、C5、0.5C20、0.3C2、3C2Or 5C5One of or a variety of or charge or discharge voltage be 0.5U, U, 1.5U,
One of 2U or a variety of so that the electrode A 1 of the present embodiment battery or battery pack, A2 ..., storage battery negative occurs on An
The charging of pole electrode reaction or/and exoelectrical reaction process, electrode B 1, B2 ..., battery positive voltage electrode reaction occurs on Bn
Charging or/and exoelectrical reaction process, when the electricity to the present embodiment battery or battery pack charge or discharge reaches 4C2、3C5、
0.5C20、0.3C2、3C2Or 5C5When or voltage when reaching 0.6U, U, 1.2U, 2.1U, operate (3) step: then with 3C2、
2.5C5、0.5C20、0.8C2、6C2Or 2C5One of electric current or a variety of pairs of the present embodiment batteries or battery pack carry out antipole
Charging so that the electrode A 1 of this implementations battery or battery pack, A2 ..., on An generation battery terminal negative electrode reaction electric discharge
Process, electrode B 1, B2 ..., the discharge process of battery positive voltage electrode reaction occurs on Bn, until electrode A 1, A2 ... An
Polarity by negative polarity be inverted to positive polarity, electrode B 1, B2 ..., the polarity of Bn negative polarity (this is inverted to by positive polarity
Inverted for second of the polarity of current period), it then operates (4) step: the present embodiment battery or battery pack is continued to charge
Or charge and discharge, charge or discharge electric current are C2、2C5、0.5C20、0.1C2、3C2Or 0.05C5One of or it is a variety of or charging electricity
Pressure is one of 0.7U, 0.9U, 1.1U, 1.7U or a variety of, and charge and discharge are direct current or pulse charge and discharge, so that the present embodiment
The electrode A 1 of battery or battery pack, A2 ..., occur on An battery positive voltage electrode reaction charging or/and discharge process,
Electrode B 1, B2 ..., charging or the/discharge process of battery terminal negative electrode reaction occur on Bn, this process stores the present embodiment
Battery or battery set charge/discharge is charged or/and the electricity of electric discharge is when reaching certain value, such as 6C2、3C5、2C20、8C2、3C2、
0.5C2Or 2C5Or battery or battery voltage be when reaching certain value, such as 0.7U, 0.9U, 1.05U or 1.4U, this implementation
Example battery or battery pack operating discharge capacity or ability to work are restored or improve, and terminate current period twice in succession positive and negative
Polarity reversion and subsequent charging or charge and discharge are electrically operated, then put into the present embodiment battery or battery pack in cycle operation
Go work or use.In this way, it is similar, according to the method for the raising or extension battery or battery pack of the present embodiment, according to need
Want or set, (for example, in a manner of providing cycle operation number) in due course, periodically or non-periodically to the present embodiment battery or
Battery pack is between certain twice cycle operation, and the polarity of progress one phase or more phases twice in succession inverts and subsequent charges or charge and discharge
It is electrically operated, make the present embodiment battery or battery pack in the feelings that battery mistake liquid, short circuit, open circuit, grid mechanical failure etc. is not present
It under condition, effectively improves, repair, reversing, eliminating, inhibiting, preventing positive active material expansion or/and softening or/and fall off, is rotten
Erosion, passivation, early stage capacitance loss, salinization, crystallization, cathode specific surface area is shunk, active material contacts not with conductive current collector
Good, memory effect, active material itself decompose, one such or various problems, thus repeatedly, multiple make the present embodiment
Battery or battery pack operating discharge capacity or ability to work are repaired, restored or are improved, to improve or extend this implementation
The service life of example battery or battery pack.
The present embodiment battery includes but is not limited to lead-acid accumulator, nickel-iron storage battery, iron-ferrate electric power storage
Pond, cadmium-nickel storage battery, it is one such or a variety of.
The present embodiment lead-acid accumulator includes but is not limited to surface plate grating lead-acid accumulator, tube type lead-acid accumulator, complete
Tube type lead-acid accumulator, spirally wound lead acid battery, bipolar lead acid battery, horizontal lead cloth lead-acid accumulator, cystosepiment
Grating lead-acid accumulator, pillar lead-acid accumulator have and stablize gap body electric pole type lead-acid accumulator, valve-controlled sealed lead-acid storage
Battery, gelled lead acid battery, lead carbon battery battery, supercapacitor-lead-acid accumulator (superbattery) formula lead acid storage battery
Pond, it is one such or a variety of.
In the other embodiment of the present embodiment, the present embodiment battery includes anode, cathode, alternatively, the present embodiment
Battery positive and negative electrode is positive and negative anodes current electrode, anode, cathode, the positive and negative anodes current electrode of the present embodiment battery, packet
It includes but is not limited to, include swelling agent in anode or/and cathode, its electrode active material or active matter formula including swelling agent
Positive and negative anodes current electrode or/and anode or/and cathode, there is identical active material or identical active matter formula just each other
Cathode current electrode, each other the positive and negative anodes current electrode of equivalence are each other same or identical positive and negative anodes current electrode,
One of or it is a variety of.The swelling agent for preventing, inhibiting, improving, shrink or electrode active material compares table by electrode specific surface area
Area contraction, the swelling agent includes but is not limited to: barium sulfate, calcium sulfate, silica, silicate, humic acid, lignosulphonic acid
Salt, aluminum oxide or hydroxide, titanium oxide or hydroxide, oxidate for lithium or hydroxide, it is one such or a variety of.
In the other embodiment of the present embodiment, quality of the swelling agent in active material or active matter formula
Percentage composition be 0.01% or more, 0.02% or more, 0.03% or more, 0.05% or more, 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,
It is one such or a variety of.
In the other embodiment of the present embodiment, quality of the swelling agent in active material or active matter formula
Percentage composition is one such or a variety of less than or equal to 5%, 10%, 20%, 30%, 40%, 50%.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Embodiment 3
The present embodiment is related to solving the problems, such as that active substance for positive electrode of lead-acid accumulator expands, softens, falling off or/and raising or prolonging
Method, battery charging and discharging device, lead plaster or the active material of long lead-acid accumulator service life, lead-acid battery electrode and plumbic acid store
Battery, wherein the charge and discharge electrical device of the present embodiment, which has, carries out polarity reversion and subsequent charging for the positive and negative electrode of lead-acid accumulator
Or function and programmable execution function that charge and discharge is electrically operated, when the present embodiment battery charging and discharging device output end and the present embodiment plumbic acid
After battery terminal is connected, after the present embodiment battery charging and discharging device can be by the reversion of the polarity of its output end and polarity reversion
Charging, charging or charge and discharge it is electrically operated and to the present embodiment lead-acid accumulator carry out the reversion of positive and negative electrode polarity, polarity reversion after filling
Electricity or charge and discharge are electrically operated, and the operation that all pairs of batteries of following the present embodiment carry out is this implementation in addition to illustrating manually
What example battery charging and discharging device was realized by its function and work.
The voltage rating of the present embodiment lead-acid accumulator is 2V, and design rated capacity is 821mAh (2h rate, 25 DEG C), this reality
Applying a lead-acid accumulator includes two electrodes, which is positive and negative anodes current electrode (the i.e. general electricity of anode, cathode
Pole), while being also same or identical positive and negative anodes current electrode, that is, do not consider the foozle generated when manufacturing electrode
(presence or influence of excluding, exclude, removing foozle), two panels the present embodiment lead-acid battery electrode is by chemical conversion
Before, each other all electrodes constitute, manufacture view (manufacture by such as electrode structure, appearance, collector, lead paste formula and lead plaster quality
Technique etc.) it is identical, after being melted into, which is then respectively formed anode and cathode, by two electrodes point
It is not defined as electrode A, electrode B, when most starting, electrode A is carried out to the chemical conversion and work of battery as anode, electrode B as cathode
Make, be separated with partition between two electrodes, two plate electrode of the present embodiment includes ball milling lead in lead plaster or active matter formula
Powder, BaSO4(0.8%, mass percent, relative to ball milling lead powder), sulfuric acid, water, staple fiber, the averagely work on every plate electrode
Property material mass be 13.41g, the sulfuric acid solution density in the present embodiment lead-acid accumulator is 1.27g/cm3, the present embodiment row
It removes or prevents and lose the factors such as liquid, open circuit, short circuit, mechanical failure, test failure to the present embodiment implementation process and result of implementation
Interference.
The present embodiment solve the problems, such as active substance for positive electrode of lead-acid accumulator expand, soften, falling off or/and raising or extend lead
The method of acid accumulator service life are as follows: firstly, the present embodiment battery is allowed to carry out cycle charge-discharge work, working system are as follows: when
Battery when state, discharges to battery with the constant current of 371mA after charging, as cell voltage≤1.75V, stops
Electric discharge, then charges to it with the constant current of 222mA, and after measuring cell voltage and reaching 2.65V, be converted into
2.65V constant pressure continue to battery charge, twice (constant current, constant pressure) charging total time be 7 hours 24 points (have removing for specified otherwise
Outside), then, discharge process above-mentioned then with the constant current of 371mA is repeated, discharges, charge repeatedly, make circulating battery work
Make, cell operating conditions temperature is 25 ± 1 DEG C.Secondly, being followed when the present embodiment lead-acid accumulator works in above-mentioned cycle operation
When ring number reaches the numerical value of a certain setting (for example, set in the present embodiment be respectively the 15th time, the 31st time ...), stop
The work of battery starts to carry out battery single positive and negative electrode polarity reversion and subsequent charging or charge and discharge is electrically operated, the behaviour
After the completion of work, the anode before making battery work under original working system and inverting polarity is anti-in polarity
Worked after turning as cathode, the battery cathode before polarity reversion works after polarity reversion as anode, until touching
Hair or the single positive and negative electrode polarity for starting next time invert and subsequent charges or charge and discharge is electrically operated, so repeatedly, interspersedly originally
In embodiment lead-acid accumulator On The Cycle Working Process, to the present embodiment lead-acid accumulator carry out single positive and negative electrode polarity reversion and
Thereafter charging or charge and discharge is electrically operated, makes the electrode A of the present embodiment lead-acid accumulator sometimes as anode work, sometimes as negative
Pole work, corresponding electrode B are used as cathode work, sometimes as anode work sometimes, with solution, improvement, reparation, elimination, inverse
Turn, the positive active material extruding that inhibits or prevent the present embodiment lead-acid accumulator or/and softening or/and fall off, cathode compares table
Area contraction, corrosion (including but not limited to electrode, fluid confluence, collector corrosion), passivation, early stage capacitance loss, sulfation,
Active material with it is one or more in collector poor contact, active material itself resolution problem, make the present embodiment lead acid storage battery
The operating discharge charging ability in pond is improved, is restored, improved or is safeguarded after each operation, is stored to realize and solve plumbic acid
Battery positive electrode active material expands, softens, the problem that falls off or/and raising or extend the present embodiment lead-acid accumulator use the longevity
Life.The On The Cycle Working Process of the present embodiment battery also possessed by the present embodiment battery charging and discharging device charging, discharging function Lai
Implement (to be battery charge and discharge through this embodiment below to all operations of battery and measurement other than illustrating and being manual
Electric appliance carries out program setting, executes realization).
By upper, initially set up when the present embodiment lead-acid accumulator operating discharge number reaches and completes the 15th time, the 31st time
When, stop battery and works and start to carry out battery single positive and negative electrode polarity reversion and subsequent charging or charge and discharge behaviour
Make.As shown in Fig. 2, the electrode condition of the present embodiment battery is A+/B- in the 1-15 times cycle operation, sent out in electrode A at this time
Raw anode electrode reacts, and negative electrode reaction occurs in electrode B, in the 1-15 times cycle operation, the present embodiment battery is put
Capacitance totally tends to reduce, and on inspection, this is primarily due to caused by positive material(PAM) softening, the effect of falling off (with lead
The BaSO of high-content in cream4, high active substance utilization rate, deep discharge it is related, it is similar below), after the 15th electric discharge, electric discharge
Capacity is 942mAh.At this time according to program setting, the present embodiment battery charging and discharging device is automatically stopped the work of battery, to battery into
The preparation and formal operation that row first time single positive and negative electrode polarity inverts and subsequent charges or charge and discharge is electrically operated, that is, the 15th
After task discharges (cell voltage is 1.75V at this time), stops battery work, battery is continued to put with 371mA constant current
Electricity 1 hour, this process makes cell voltage be down to 0.04V, then stops electric discharge, and the polarity for carrying out its positive and negative electrode to the battery is anti-
Turn, i.e., through this embodiment charge and discharge electrical output terminal polarity reversion, by the connection status of charge and discharge electric appliance and lead-acid accumulator from
Charge and discharge electric appliance cathode output end connect with lead-acid battery electrode A, charge and discharge electric appliance cathode output end and lead-acid battery electrode B
Connection, change connect at, charge and discharge electric appliance cathode output end with lead-acid battery electrode A, charge and discharge electric appliance cathode output end and plumbic acid
Battery terminal B connection, after the transformation of this connection status, the cell voltage measured is negative value, then, with the constant current pair of 186mA
The transformed the present embodiment battery of connection status charges, and cell voltage is made to rise to 0V from negative value and then rise to again
(reversion of the present embodiment battery first time polarity occurs for 1.75V, wherein cell voltage rises to 0V process from negative value during this
In, the discharge process of lead acid battery positive electrode electrode reaction occurs in electrode A, acid accumulator negative pole lead electrode occurs in electrode B
The discharge process of reaction, it is anti-that during rising to 1.75V from 0V acid accumulator negative pole lead electrode occurs for cell voltage in electrode A
The charging process of lead acid battery positive electrode electrode reaction occurs in the charging process answered, electrode B), when cell voltage reaches 1.75V
Afterwards, continue to charge to 2.65V to battery with the constant current of 222mA, then charge the battery 4 again with the constant voltage of 2.65V
It 16 points of hour, is then discharged with 371mA constant current battery, until 1.75V, then, then with the constant current of 222mA to battery
It charges, until cell voltage reaches 2.65V and is changed to 2.65V to battery progress constant-voltage charge 5 hours, after charging,
So far, it completes that the first time single positive and negative electrode polarity of the present embodiment battery is inverted and subsequent charged or charge and discharge is electrically operated, this
When battery electrode condition changed into A-/B+ from A+/B-.Then, electrode A is made to be worked as cathode, electrode B is made
It works for anode, so that the battery is reentered the 16th task of progress under the same electric discharge-charging cycle working system and put
Electricity and the later cycle operation of number.The result shows that through the reversion of first time single positive and negative electrode polarity and subsequent charging or charge and discharge
After electrically operated, discharge capacity of the present embodiment battery under the 16th cycle operation state is 888.3mAh.This time polarity reversion
It is in the process afterwards 7031mAh to the charging capacity of battery with this section before battery recovery cycle operation.
Run the continuation of the present embodiment battery under working system, as shown in Fig. 2, in the present embodiment battery the
In 16-31 cycle operation, the electrode condition of the present embodiment battery is A-/B+, and negative electrode reaction occurs in electrode A at this time,
Anode electrode reaction occurs in electrode B, in the 16-31 times cycle operation of the present embodiment battery, discharge capacity is from 888.3mAh
It is changed to 905mAh, wherein it is because logical before this electric discharge that discharge capacity, which increases to 987.6mAh, in the 27th task circulation
Manual intervention is crossed to have carried out an overcharge to battery (i.e. 2.65V constant voltage charging time than under moderate working system more 10 is small
When), the working system of other cycle-indexes is constant.At the end of the 31st cycle operation is discharged, according to program setting, touch at this time
The beginning condition electrically operated to the progress polarity reversion of battery positive and negative electrode and subsequent charging or charge and discharge, therefore, the present embodiment are sent out
Charge and discharge electric appliance has automatically started to carry out battery second of single positive and negative electrode polarity reversion and subsequent charging or charge and discharge behaviour
The preparation and formal operation of work, that is, after the electric discharge of the 31st task (cell voltage is 1.75V at this time), the present embodiment fills
Discharger stops battery work, continues electric discharge 1 hour to battery with 371mA constant current, this process is down to cell voltage
Then 0.02V stops electric discharge, the polarity for carrying out its positive and negative electrode to the battery inverts, i.e., charge and discharge electric appliance exports through this embodiment
(the polarity reversion of charge and discharge electrical output terminal is by the relay circuit contact open and close shape in charge and discharge electric appliance for the polarity reversion at end
State transformation is realized), by the connection status of charge and discharge electric appliance and lead-acid accumulator from charge and discharge electric appliance cathode output end and lead acid storage battery
The connection of pond electrode B, charge and discharge electric appliance cathode output end are connect with lead-acid battery electrode A, are changed into charge and discharge electric appliance cathode output end
It is connect with lead-acid battery electrode A, charge and discharge electric appliance cathode output end is connect with lead-acid battery electrode B, the transformation of this connection status
Afterwards, the cell voltage measured is then negative value fills the transformed the present embodiment battery of connection status with the constant current of 186mA
Electricity 15 minutes, then charged the battery with the constant current of 371mA, so that cell voltage is risen to 0V from negative value and then is risen to again
(second of the polarity reversion of the present embodiment battery occurs for 2.65V, wherein cell voltage rises to 0V process from negative value during this
In, the discharge process of acid accumulator negative pole lead electrode reaction occurs in electrode A, lead acid battery positive electrode electrode occurs in electrode B
The discharge process of reaction, it is anti-that during rising to 2.65V from 0V lead acid battery positive electrode electrode occurs for cell voltage in electrode A
The charging process of acid accumulator negative pole lead electrode reaction occurs in the charging process answered, electrode B), then again with 2.65V constant voltage
It charges 4 hours to battery, then battery is carried out with the constant current of 371mA again to be discharged to 1.75V, then, then with the perseverance of 222mA
Current versus cell carry out charging 7 hours 25 points, then again with 2.65V constant voltage to battery charge 7 hours 25 points, so far, complete
It is to the reversion of second of single positive and negative electrode polarity of the present embodiment battery and subsequent charging or charge and discharge electrically operated, battery at this time
Electrode condition is changed into A+/B- from A-/B+.Then, electrode A is made to be worked as anode, electrode B is carried out as cathode
Work, make the battery reenter under the same electric discharge-charging cycle working system carry out the 32nd task electric discharge and it is secondary later
Several cycle operations.The result shows that after second of single positive and negative electrode polarity reversion and subsequent charging or charge and discharge are electrically operated,
Capacity is 1189mAh when electric discharge of the battery under the 32nd cycle operation state, this should be inverted with polarity after to battery
It is fully charged related, this time polarity reversion after be to total charging capacity of battery between battery recovery cycle operation
6659mAh.Run battery continuation under working system, as shown in Fig. 2, in the 32-45 times cycle operation, this
The electrode condition of embodiment battery is A+/B-, at this time happens is that anode electrode reacts, happens is that bearing in electrode B in electrode A
Pole electrode reaction, discharge capacity of the present embodiment battery in the 32-45 times cycle operation drop to 787mAh from 1189mAh.
In the cycle charge discharge course of work of the present embodiment lead-acid accumulator, repeatedly, repeatedly, interspersedly carry out the present embodiment
It is similar to as described above for the first time or secondary single positive and negative electrode polarity inverts and subsequent charges or charge and discharge is electrically operated, i.e.,
The present embodiment lead-acid accumulator is realized between the 45th, 46 time of working cycles number in its On The Cycle Working Process, the 55th, 56
Between secondary, between the 64th, 65 time, between the 73rd, 74 time, between the 82nd, 83 time, between the 94th, 95 time, the 104th, 105 take second place
Between carry out or carried out third time, the 4th time ..., the reversion of the 9th single positive and negative electrode polarity and subsequent charging
Or charge and discharge is electrically operated.Fig. 2 acceptance of the bid shows the present embodiment lead-acid accumulator and is passing through each secondary single positive and negative electrode polarity of the present embodiment
Before or after reversion and subsequent charging or charge and discharge are electrically operated, in the cycle charge discharge course of work, the polarity shape of electrode A, B
State or polar orientation situation.The present embodiment lead-acid accumulator is at the 46th time and later in the cycle operation system of number, charging side
Method is altered to, and after operating discharge, is then charged with the constant current of 222mA to it, and is reached when measuring cell voltage
After 2.65V, be converted into continuing with 2.65V constant pressure charging to battery, twice (constant current, constant pressure) charging total time be 8 hours 24 points.
As shown in Fig. 2, the operating discharge capacity of the present embodiment lead-acid accumulator all gets a promotion or restores on year-on-year basis.One side
Face is as described above, the reversion of positive and negative electrode polarity and subsequent charge and discharge or charge and discharge of the present embodiment are electrically operated so that the present embodiment lead
The positive active material of acid accumulator expands, softens, falling off is enhanced, repairs, reversing, eliminating, inhibiting, preventing, so that
It is improved or is restored after the operating discharge capacity operation in the present embodiment lead-acid accumulator cycle operation, another aspect,
The reversion of positive and negative electrode polarity and subsequent charge and discharge or charge and discharge of the present embodiment are electrically operated, also necessarily to the present embodiment circulating battery
Occur in the course of work, slight electrode passivation, early stage capacitance loss, burn into active material and the afflux that occurs or will occur
The problem of body poor contact, cathode specific surface area shrink, sulfation is with improvement, reparation, reverse, supression, elimination, prevention
Effect, for example, since electrode A, B alternately and repeatedly carry out charge-discharge cycle work as positive or negative pole, so that as positive work
As when the electrode corrosion problem that generates improved when electrode carries out charge-discharge cycle work as cathode, repaired, reversed, thus
But also the etching problem of the present embodiment lead-acid accumulator in the long-term use is delayed, is improved, is repaired, is reversed, is prevented
Only, in the present embodiment lead-acid accumulator normal circulation course of work, periodically or non-periodically (for example, to provide cycle operation
The mode of number), the positive and negative electrode polarity that interspersedly carries out the present embodiment to the present embodiment lead-acid accumulator inverts and subsequent fills
Electric discharge or charge and discharge are electrically operated, it will it is effective improve, repair, reversing, eliminating, inhibiting, prevention positive material(PAM) softening or/and
It falls off, electrode passivation, burn into early stage capacitance loss, sulfation, active material and collector poor contact, cathode specific surface
Product contraction problem, to improve or extend the service life of the present embodiment lead-acid accumulator.
In the present embodiment, fast charging and discharging pulse current also can be used, pulse voltage carries out the anode of this example, cathode
Polarity reversion and subsequent charging or charge and discharge are electrically operated.
Some experimental datas in the present embodiment show after each single polarity reversion of the present embodiment lead-acid accumulator and its
The degree and the present embodiment of the operating discharge capacity restoration of the present embodiment lead-acid accumulator after charging or charge and discharge afterwards is electrically operated
Normal or charge-discharge cycle compared with high discharge capacity can be continuously kept to work after each operating discharge capacity restoration of lead-acid accumulator
Number (i.e. after the reversion of each single polarity and subsequent charging or charge and discharge it is electrically operated between the present embodiment lead-acid accumulator institute it is normal
Or the charge-discharge cycle number of higher work discharge capacity) and correspondingly each single polarity reversion and subsequent charging or charge and discharge
Electric current employed in operation, voltage, time, charge/discharge capacity, pulse or direct current, the internal resistance of battery, density of electrolyte, electrolysis
The size of liquid degree of saturation, the difference of mode and it is different.
By the specific capacity of existing commercialization power electric lead-acid accumulator battery positive electrode active material under nominal operating conditions
61mAh/g (2h rate, 25 DEG C) is calculated, and the rated capacity of the present embodiment lead-acid battery electrode is 821mAh (according to aforementioned reality
Apply the active material mass average value of single electrode of lead-acid accumulator), if discharge capacity when defining 100% depth of discharge
The judgement continuously terminated three times lower than 80% (657mAh) Shi Zuowei battery of rated capacity or rated capacity according to
According to then as shown in Fig. 2, the discharge capacity attenuation trend line according to the 1-15 times is believed that the present embodiment lead-acid accumulator exists
When without the reversion of the present embodiment positive and negative electrode polarity and subsequent charging or electrically operated charge and discharge, service life substantially will be respectively
For 25 times and 36 times.However in fact, the present embodiment battery through the present embodiment positive and negative electrode polarity invert and subsequent charging or
After charge and discharge is electrically operated, the operating discharge capacity of battery remains on rated capacity after the 111st cycle operation, battery
Service life be raised significantly or extend, further, exclude to make short circuit, open circuit, dehydration, pollution etc. of battery failure because
In the case where element, the present embodiment improves or extends the method for lead-acid accumulator service life, makes making for this example lead-acid accumulator
Bigger raising or extension are obtained on the basis of 111 circulations with the service life.The present embodiment lead-acid battery electrode is as anode
Active material utilization when work is apparently higher than the active material utilization of existing commercial power lead-acid storage battery positive electrode, main
If related with the thickness of the present embodiment electrode, collector construction.
Two plate electrodes of the present embodiment lead acid storage battery are also positive and negative anodes current electrode of equal value each other, because being changed in electrode
Cheng Hou, the two function having the same and performance, but in actual use, polarity inverts and subsequent charges or the electrically operated system of charge and discharge
The variation and difference of the factors such as degree, cycle operation system will lead to the two and difference occur in the performance of function and performance.
The above-mentioned lead-acid accumulator of the present embodiment, including but not limited to surface plate grating lead-acid accumulator, tubalar type lead acid electric power storage
Pond, full tube type lead-acid accumulator, spirally wound lead acid battery, bipolar lead acid battery, horizontal lead cloth lead-acid accumulator, bubble
Foam grid formula lead-acid accumulator, pillar lead-acid accumulator have and stablize gap body electric pole type lead-acid accumulator, valve controlling sealed lead
Acid accumulator, gelled lead acid battery, lead carbon battery battery, supercapacitor-lead-acid accumulator (superbattery) formula plumbic acid
Battery, one such or a variety of, the present embodiment above method is equally applicable for other type lead-acid accumulators.
In the other embodiment of the present embodiment, the above-mentioned lead-acid accumulator of the present embodiment can be replaced by identical capacity
Other type batteries, other type batteries include but is not limited to: nickel-iron storage battery, iron-ferrate electric power storage
Pond, cadmium-nickel storage battery, one such or a variety of, the present embodiment above method can be applied to other type batteries, can
The maximum value of the absolute value for the voltage for allowing to reach when by charging is turned down, to adapt to different types of battery nominal operation electricity
Pressure.
In the other embodiment of the present embodiment, the present embodiment battery includes anode, cathode, alternatively, the present embodiment
Battery positive and negative electrode is positive and negative anodes current electrode, anode, cathode, the positive and negative anodes current electrode of the present embodiment battery, packet
It includes but is not limited to, include swelling agent in anode or/and cathode, its electrode active material or active matter formula including swelling agent
Positive and negative anodes current electrode or/and anode or/and cathode, there is identical active material or identical active matter formula just each other
Cathode current electrode, each other the positive and negative anodes current electrode of equivalence are each other same or identical positive and negative anodes current electrode,
One of or it is a variety of.The swelling agent for preventing, inhibiting, improving, shrink or electrode active material compares table by electrode specific surface area
Area contraction, the swelling agent includes but is not limited to: barium sulfate, calcium sulfate, silica, silicate, humic acid, lignosulphonic acid
Salt, aluminum oxide or hydroxide, titanium oxide or hydroxide, oxidate for lithium or hydroxide, it is one such or a variety of.
In the other embodiment of the present embodiment, the above-mentioned swelling agent of the present embodiment or barium sulfate are in active material or activity
Mass percentage content in material formula be more 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%, it is one such or a variety of.
In the other embodiment of the present embodiment, the above-mentioned swelling agent of the present embodiment or barium sulfate are in active material or activity
Mass percentage content in material formula is less than or equal to 5%, 10%, 20%, 30%, 40%, 50%, it is one such or
It is a variety of.
In the other embodiment of the present embodiment, reduces the percentage composition of barium sulfate in lead plaster, increases on fixed electrode
The mechanical force of lead plaster increases the additive for slowing down active material softening, falling off in lead plaster, and other implementation methods or process are not
Become, so that after each single polarity reversion and subsequent charging or charge and discharge are electrically operated, the operating discharge capacity attenuation of battery
Speed slows down.
In the other embodiment of the present embodiment, the polarity reverse turn operation of the present embodiment battery charging and discharging device output end,
Also the control circuit of battery charging and discharging device circuit manages the thyristor in control electrode sex reversal execution circuit through this embodiment
Polarity reversion of the switching state transformation to realize or by being made of in management control execution circuit transistor, inductance, capacitor
The working condition transformation of circuit is to realize or by the forced electric discharge of management control constant-current source or constant pressure source, forced charge movement
Transformation is to realize.
In the other embodiment of the present embodiment, the present embodiment is improved to or is extended the side of lead-acid accumulator service life
Method is applied to the present embodiment lead-acid batteries, and the voltage rating of the present embodiment lead-acid batteries is 12V, rated capacity is
20Ah is implemented in operation in method, mainly to making in the setting and execution of the numerical value of voltage, electric current, capacity in operation etc.
Corresponding variation e.g. after lead-acid batteries are carried out antipole charging and polarity reversion is caused to occur, makes electricity to battery pack charging
Pond group voltage stops charging after rising to 8V, 10.8V, 13.3V, 15.5V, and charging current is 0.3 multiplying power, 0.5 multiplying power, 1
Multiplying power, 2 multiplying powers.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Embodiment 4
The present embodiment battery or battery pack, including but not limited to surface plate grating battery, tube type storage battery, full tubular type
It is battery, winding type accumulator, bipolar system battery, horizontal lead cloth battery, cystosepiment grating battery, valve controlling sealed
Battery, colloid storage battery, lead carbon battery, supercapacitor-battery, one such or a variety of, the present embodiment battery
Or the voltage rating U of battery pack be 1.2V, 1.5V, 2V, 4V, 6V, 12V, 24V, 36V, 48V, 60V or 72V, 120V, 240V,
Rated capacity (the C of 360V, 480V, 600V or other voltage values, the present embodiment battery or battery pack2, 2 hour rates, 25 DEG C)
For 12Ah, 14Ah, 16Ah, 18Ah, 20Ah, 24Ah, 30Ah, 60Ah, 100Ah, 200Ah or 1000Ah, the present embodiment battery
Or battery pack has output terminal A, B, output terminal A and the present embodiment battery or electrode A 1 in battery pack,
A2 ..., An (n=positive integer) be mutually conductively connected, the electrode in output terminal B and the present embodiment battery or battery pack
B1, B2 ..., Bn (n=positive integer) is mutually conductively connected.Electrode A 1 in the present embodiment battery or battery pack,
A2 ..., An, B1, B2 ..., Bn be positive and negative anodes current electrode (i.e. anode, the general electrode of cathode), can both make
Anode for battery uses or work, and the cathode that also can be used as battery uses or work.The present embodiment battery or battery
Group is in the initial cycle charge-discharge course of work, and the polarity of output terminal A is positive, the polarity of output terminal B is negative, that is,
The present embodiment battery or battery pack in initial On The Cycle Working Process, electrode A 1, A2 ..., An it is upper happens is that
The charge and discharge process of battery positive voltage electrode reaction, electrode B 1, B2 ..., Bn is upper happens is that battery terminal negative electrode is anti-
The charge and discharge process answered.Partition is separated between positive and negative electrode.
The present embodiment solves the problems, such as that battery anode active substance expands, softens, falling off or/and raising or extending this implementation
Example battery or the method for battery pack service life be, when the present embodiment battery or battery pack in the use of its cycle operation or
In work, when working cycles reach certain number or as needed (for example, due to positive active material expands or/and softens or/
With fall off, burn into passivation, early stage capacitance loss, salinization, crystallization, cathode specific surface area are shunk, active material and conductive afflux
Body poor contact, memory effect, active material itself decompose, one such or various problems cause the present embodiment battery or
When battery pack operating discharge capacity declines and is lower than certain capacitance values or after, it is desirable to or need to improve battery or battery pack work
When discharge capacity or raising, extension battery or battery pack service life) between certain twice working cycles, automatic or/and hand
A single positive and negative electrode polarity reversion and subsequent charging dynamicly are carried out to this example battery or battery pack or charge and discharge are grasped
Make, improves, eliminates, reversing, inhibiting, preventing positive active material from expanding or/and softening or/and fall off, burn into passivation, early stage
Capacitance loss, salinization, crystallization, cathode specific surface area shrink, active material and conductive current collector poor contact, memory effect,
Active material itself decomposes, one such or various problems, so that the ability to work of the present embodiment battery or battery pack is extensive
It is multiple or improve, complete secondary positive and negative electrode polarity reversion and subsequent charging or charge and discharge it is electrically operated after, by the present embodiment battery or
Battery pack with after secondary polarity reversion polarization state, put into charge-discharge cycle work again and use or work, until again
Triggering starts to carry out the reversion of positive and negative electrode polarity and subsequent charging or charge and discharge to the present embodiment battery or battery pack again
It is electrically operated, in this way, make the present embodiment battery or battery pack cycle operation and the present embodiment to the present embodiment battery
Battery pack carry out the reversion of positive and negative electrode polarity and subsequent charging or charge and discharge it is electrically operated it is having a rest to each other, interspersed, alternately into
Row occurs, to improve or extend the service life of the present embodiment battery or battery pack.
The reversion of first time single positive and negative electrode polarity and subsequent charging are carried out to the present embodiment battery or battery pack or filled
Discharge operation comprising steps of when the present embodiment battery or battery pack in the On The Cycle Working Process of most initial (this reality during this
It applies a battery or the polarity of battery pack output terminal A is positive, the polarity of output terminal B is negative, that is, electrode A 1,
A2 ..., occur the charge and discharge process of battery positive voltage electrode reaction on An, electrode B 1, B2 ..., store on Bn
The charge and discharge process of battery cathode electrode reaction), when working cycles reach certain certain number, for example, 5 times, 9 times, 20 times or 60
It is secondary, antipole charging is carried out to the present embodiment battery or battery pack, the mode of the antipole charging includes, the single stage, multistage
Section, constant current (such as 0.1C2、0.5C2、1.2C2、6C2), constant pressure (such as U, 1.3U, 2U, 5U), positive pulse, negative pulse it is therein
It is one or more, and finally make the polarity of output terminal A, B of the present embodiment battery or battery pack, thus electrode A 1,
A2 ..., An, B1, B2 ... the polarity of Bn inverts, and, after secondary polarity reversion, to the present embodiment battery
Or battery pack carries out charging or charge and discharge, charging or the modes of charge and discharge include, the single stage, the multistage, constant current (such as
0.15C2、0.4C2、0.8C2、 7C2), constant pressure (such as 0.8U, 1.5U, 2U, 4U), positive pulse, negative pulse it is one such or more
Kind, then, makes the present embodiment battery or battery pack with the polarization state after the secondary polarity reversion, put into cycle operation again
In go to carry out cycle operation, the present embodiment battery or battery pack complete first time single positive and negative electrode polarity reversion and thereafter
Charging or charge and discharge it is electrically operated after in the On The Cycle Working Process that is carried out, the present embodiment battery or battery pack output terminal A's
Polarity is negative, the polarity of output terminal B is positive, that is, electrode A 1, A2 ..., battery terminal negative electrode reaction occurs on An
Charge and discharge process, electrode B 1, B2 ..., the charge and discharge process of battery positive voltage electrode reaction occurs on Bn.
Second of single positive and negative electrode polarity reversion and subsequent charging are carried out to the present embodiment battery or battery pack or filled
Discharge operation comprising steps of invert in above-mentioned first time single positive and negative electrode polarity when the present embodiment battery or battery pack and its
(the present embodiment battery or battery pack output terminal A during this in On The Cycle Working Process after charging or charge and discharge afterwards is electrically operated
Polarity be negative, the polarity of output terminal B is positive, that is, electrode A 1, A2 ..., that battery terminal negative electrode occurs on An is anti-
The charge and discharge process answered, electrode B 1, B2 ..., the charge and discharge process of battery positive voltage electrode reaction occurs on Bn), work
When circulation completes certain certain number, for example, 9 times, 13 times, 20 times or 40 times, the is carried out to the present embodiment battery or battery pack
The mode of the charging of secondary antipole, secondary antipole charging includes, single stage, multistage, constant current (such as 0.2C2、 0.5C2、
1.5C2、3C2), constant pressure (such as U, 1.1U, 2U, 4U), positive pulse, negative pulse it is one such or a variety of, and finally make this reality
Apply the polarity of output terminal A, B of a battery or battery pack, thus electrode A 1, A2 ..., An, B1, B2 ... Bn
Polarity, invert, and, after secondary polarity reversions, charging or charge and discharge are carried out to the present embodiment battery or battery pack, filled
Electricity or the modes of charge and discharge include, single stage, multistage, constant current (such as 0.18C2、0.7C2、2C2、5C2), constant pressure (such as
0.6U, 1.3U, 2.2U, 3U), positive pulse, negative pulse it is one such or a variety of, then, make the present embodiment battery or battery
Group is put into cycle operation again with the polarization state after the secondary polarity reversion and is gone to carry out cycle operation, the present embodiment electric power storage
What pond or battery pack were carried out after second of single positive and negative electrode polarity reversion of completion and subsequent charging or charge and discharge are electrically operated follows
In the ring course of work, the polarity of the present embodiment battery or battery pack output terminal A are positive, the polarity of output terminal B is negative,
That is, electrode A 1, A2 ..., occur the charge and discharge process of battery positive voltage electrode reaction on An, electrode B 1, B2 ...,
The charge and discharge process of battery terminal negative electrode reaction occurs on Bn.
In the cycle charge discharge course of work of the present embodiment battery or battery pack, implement other single positive and negative electrodes
Polarity reversion and subsequent charging or the electrically operated method of charge and discharge and implement above-mentioned the present embodiment for the first time or second of single just,
The method of negative polarity reversion and subsequent charging or charge and discharge is mutually similar.In this way, in the present embodiment battery or battery pack
The present embodiment positive and negative electrode polarity as described above reversion and thereafter repeatedly, repeatedly, interspersedly is carried out in the cycle charge discharge course of work
Charging or charge and discharge it is electrically operated so that the present embodiment battery or the positive active material positive active material of battery pack expansion
Or/and softens or/and fall off, burn into passivation, early stage capacitance loss, salinization, crystallization, the contraction of cathode specific surface area, active matter
Matter and conductive current collector poor contact, memory effect, active material itself decompose, and one such or various problems are changed
It is apt to, repairs, reverses, eliminates, inhibits, prevents, solves, so that the present embodiment battery or the operating discharge of battery pack holds
Amount, service life are improved or are extended.
The present embodiment battery includes but is not limited to: lead-acid accumulator, nickel-iron storage battery, iron-ferrate electric power storage
Pond, cadmium-nickel storage battery, it is one such or a variety of.
The present embodiment lead-acid accumulator includes but is not limited to: surface plate grating lead-acid accumulator, tube type lead-acid accumulator, complete
Tube type lead-acid accumulator, spirally wound lead acid battery, bipolar lead acid battery, horizontal lead cloth lead-acid accumulator, cystosepiment
Grating lead-acid accumulator, pillar lead-acid accumulator have and stablize gap body electric pole type lead-acid accumulator, valve-controlled sealed lead-acid storage
Battery, gelled lead acid battery, lead carbon battery battery, supercapacitor-lead-acid accumulator (superbattery) formula lead acid storage battery
Pond, it is one such or a variety of.
In the other embodiment of the present embodiment, in the present embodiment battery or the On The Cycle Working Process of battery pack,
In order to improve, repair, reverse, solve, prevent because of positive active material expansion or/and soften or/and fall off, burn into is passivated, early
Phase capacitance loss, salinization, crystallization, cathode specific surface area is shunk, active material and conductive current collector poor contact, memory are imitated
Answer, active material itself decompose the problems such as in it is one or more caused by battery or battery pack ability to work decline or use
End-of-life to the present embodiment battery or battery pack more phases, interspersedly carries out the positive and negative electrode polarity of odd times number or even number
Reversion and subsequent charging or charge and discharge are electrically operated, complete each issue of odd times number or even number the reversion of positive and negative electrode polarity and subsequent
After charging or charge and discharge are electrically operated, polarization state after the present embodiment battery or battery pack are inverted with the phase polarity is thrown again
Entering into charge-discharge cycle work and uses or work, the ability to work for obtaining the present embodiment battery or battery pack is restored or is improved,
The positive and negative electrode pole of odd times number or even number is carried out to the present embodiment battery or battery pack until triggering or starting the another phase again
Sex reversal and subsequent charging or charge and discharge are electrically operated.The positive and negative electrode polarity of each issue of odd times number or even number is inverted and subsequent is filled
Any secondary positive and negative electrode polarity reversion and subsequent charging or charge and discharge during electric or charge and discharge is electrically operated is electrically operated aforementioned with the present embodiment
First time the reversion of second single positive and negative electrode polarity and subsequent charging or charge and discharge it is electrically operated similar same.
In the other embodiment of the present embodiment, the anode of the present embodiment battery or battery pack, cathode or say all
Electrode is same or identical positive and negative anodes current electrode, that is, electrode by before being melted into, all electrodes or it is described just
Pole, cathode, each other in all respects, such as, but not limited to collector, active matter formula and active material quality are (such as but unlimited
In lead paste formula and lead plaster quality), manufacture technology etc., it is identical (that is, all identical in all respects), alternatively, not considering
The foozle (exclude, exclude, removing the presence or influence of foozle) generated when manufacturing electrode, the present embodiment battery
Or all electrodes of battery pack are by before being melted into, and constitute each other in all electrodes, manufacture view (such as electrode structure, appearance,
Collector, fluid confluence, active matter formula and quality, other accessories, manufacture technology etc.) it is identical, after being melted into, this
Embodiment battery or each electrode of battery pack are then respectively formed positive or negative pole.
In the other embodiment of the present embodiment, the positive and negative electrode of the present embodiment battery or battery pack or all electricity are said
Pole is positive and negative anodes current electrode of equal value each other, that is, after electrode is melted into, function and performance having the same each other, alternatively,
After electrode is by chemical conversion or charge and discharge, in the work or use process of battery or battery pack, do not consider error component (such as
But be not limited to foozle, measurement error) in the case where (presence or influence of excluding, exclude, removing error), the present embodiment
Each electrode there is or show identical function and performance.
In the other embodiment of the present embodiment, pulse current can be used, pulse voltage replaces direct current, constant voltage
It carries out polarity reversion and subsequent charging in the polarity reversion and subsequent charging or charge and discharge operating procedure of this example or fills
Discharge step or process, to be conducive to improve the present embodiment accumulator pole sex reversal and subsequent charging or charge and discharge is electrically operated
Timeliness, efficiency.
In the other embodiment of the present embodiment, the present embodiment battery includes anode, cathode, alternatively, the present embodiment
Battery positive and negative electrode is positive and negative anodes current electrode, anode, cathode, the positive and negative anodes current electrode of the present embodiment battery, packet
It includes but is not limited to, include swelling agent in anode or/and cathode, its electrode active material or active matter formula including swelling agent
Positive and negative anodes current electrode or/and anode or/and cathode, there is identical active material or identical active matter formula just each other
Cathode current electrode, each other the positive and negative anodes current electrode of equivalence are each other same or identical positive and negative anodes current electrode,
One of or it is a variety of.The swelling agent for preventing, inhibiting, improving, shrink or electrode active material compares table by electrode specific surface area
Area contraction, the swelling agent includes but is not limited to: barium sulfate, calcium sulfate, silica, silicate, humic acid, lignosulphonic acid
Salt, aluminum oxide or hydroxide, titanium oxide or hydroxide, oxidate for lithium or hydroxide, it is one such or a variety of.
In the other embodiment of the present embodiment, the above-mentioned swelling agent of the present embodiment or barium sulfate are in active material or activity
Mass percentage content in material formula 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%, it is one such or a variety of.
In the other embodiment of the present embodiment, the above-mentioned swelling agent of the present embodiment or barium sulfate are in active material or activity
Mass percentage content in material formula is less than or equal to 5%, 10%, 20%, 30%, 40%, 50%, it is one such or
It is a variety of.
In the other embodiment of the present embodiment, the present embodiment battery, positive and negative electrode is the general electricity of positive and negative anodes
Pole, (1) the present embodiment battery are lead-acid accumulator, the anode or/and cathode, positive and negative anodes current electrode or its active material
Or in active matter formula include swelling agent barium sulfate, the barium sulfate it is described anode or/and cathode, positive and negative anodes current electrode or
Mass percentage in its active material or active matter formula is 0.01%, 0.05%, 0.1%, 0.4%, 0.8%,
1.0%, 2.0%, 10%, it is one such or a variety of；Or (2) the present embodiment battery is lead-acid accumulator, the anode
It or/and include swelling agent barium sulfate, titanium dioxide in cathode, positive and negative anodes current electrode or its active material or active matter formula
Silicon, calcium sulfate, the barium sulfate are matched in the anode or/and cathode, positive and negative anodes current electrode or its active material or active material
Mass percentage in side is 0.01%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 10%, therein one
Kind or a variety of, silica, calcium sulfate are in the anode or/and cathode, positive and negative anodes current electrode or its active material or work
Property material formula in mass percentage be 0.03%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%,
10%, it is one such or a variety of；Or (3) the present embodiment battery is nickel-iron storage battery, the positive or/and cathode,
It include swelling agent lithium hydroxide in positive and negative anodes current electrode or its active material or active matter formula, the lithium hydroxide is described
Anode or/and cathode, positive and negative anodes current electrode or its active material or active matter formula in mass percentage be
0.01%, 0.05%, 0.1%, 0.4%, 0.8%, 1.0%, 2.0%, 10%, it is one such or a variety of.
In the other embodiment of the present embodiment, the present embodiment battery, positive and negative electrode is the general electricity of positive and negative anodes
Pole, and there is identical active material or identical active matter formula each other: (1) the present embodiment battery be lead-acid accumulator,
Anode, the active material of cathode or active matter formula are equal are as follows: lead powder or lead oxide powder 100Kg, staple fiber 0.06Kg, acetylene black
0.28Kg, barium sulfate 0.8Kg, sulfuric acid solution (mass percentage of sulfuric acid is 45%) 8.7Kg, water 8.25Kg；Or (2) are originally
Embodiment battery is lead-acid accumulator, and anode, the active material of cathode or active matter formula are equal are as follows: lead powder or lead oxide
Powder 100Kg, lignin 0.16Kg, humic acid 0.2Kg, barium sulfate 0.4Kg, silica 0.06Kg, the sulfuric acid solution (quality of sulfuric acid
Percentage composition is 45%) 8.7Kg, water 8.25Kg；Or (3) the present embodiment battery is iron-ferrate battery, just
Pole, the active material of cathode or active matter formula are equal are as follows: iron powder or brown iron oxide 100Kg, lithium hydroxide 0.2Kg, hydroxide
Barium 0.4Kg, potassium hydroxide solution (mass percentage of potassium hydroxide is 40%) 8Kg, water 8Kg；
Alternatively, further, the present embodiment battery, anode, cathode, positive and negative anodes current electrode not only have each other
Identical active material as described above or identical active matter formula, and before being carried out chemical conversion or charge and discharge, it is mutually the same,
Do not consider the foozle (exclude, exclude, removing the presence or influence of foozle) generated when manufacturing electrode, it is described just
Pole, cathode, positive and negative anodes current electrode carried out chemical conversion or charge and discharge it is electrically operated before, the collector that has or use each other and
Cream technique, smear or powder filling technique, solidification or sintering process and all other electrode are constituted, manufacture view is identical；
In the other embodiment of the present embodiment, the present embodiment battery, positive and negative electrode is the positive and negative of equivalence each other
Pole current electrode, after the electrode is melted into, (such as, but not limited to: first 0.14C is permanent under a certain work charging, discharging condition
Current charge 5 hours, then constant-voltage charge 4 hours, then 0.05C constant-current charge 2 hours, then 0.5C multiplying power discharging, environment temperature were
25 DEG C, C is the rated capacity of battery), the present embodiment battery, anode, cathode, positive and negative anodes current electrode are in the 1st polarity
This 21 times positive discharge capacities shown in the 1st time-the 21 time cycle charging, discharge process after reversion are averaged
Value is 10Ah, then, the polarity of the anode of the battery, cathode is carried out the 2nd reversion, after inverting the 1st polarity
Anode be inverted to cathode, the cathode after inverting the 1st polarity is inverted to anode, then, by the 2nd polarity
It is formed by anode after being formed by cathode, the 2nd polarity reversion after reversion, under identical charging, discharging condition (such as
But it is not limited to: first 0.14C constant-current charge 5 hours, then constant-voltage charge 4 hours, then 0.05C constant-current charge 2 hours, then 0.5C
Multiplying power discharging, environment temperature are 25 DEG C, and C is the rated capacity of battery) cycle charging, electric discharge are carried out, it obtains the present embodiment and stores
Battery, anode, cathode, positive and negative anodes current electrode the 1st time-the 21 time cycle charging, electric discharge after the 2nd polarity inverts
The average value of the capacity of 21 back discharges shown in the process is 10.5Ah, is excluding, is removing manufacture, test etc.
In the case where caused 0.5Ah error (in the case where not considering error component), the anode, cathode, positive and negative anodes are general
Charging or/and discharge performance of the electrode under same polarity are mutually the same, or think, the anode, cathode, positive and negative anodes are logical
Charging or/and discharge performance of the electricity consumption extremely under same polarity are mutually the same, and the discharge capacity average value of 0.5Ah
Difference belongs to nominal error to each other.
The positive charge or/and electric discharge refer to that anode, cathode, positive and negative anodes current electrode are anti-in certain polarity by progress
Before turning, the charging, the electric discharge that carry out or carried out；The reverse charging or/and electric discharge refer to that anode, cathode, positive and negative anodes are general
Electrode is after being carried out certain polarity reversion, the charging, the electric discharge that carry out or carried out.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Embodiment 5
The present embodiment battery group, solve the problems, such as battery anode active substance expand, soften, falling off or/and raising or
The battery set charge/discharge device and positive and negative electrode polarity for extending battery group service life invert and subsequent charge or charge and discharge is electrically operated
Differentiation operating method, wherein the present embodiment battery group includes 7 of equal value battery monocell A, B, C, D, E, F, G, the electricity
The voltage rating of pond group is 12V, and rated capacity is equal to the rated capacity of monocell in battery group, every list in the battery pack
Body battery all has positive and negative electrode circuit input/output terminal independent.
The present embodiment battery set charge/discharge device have to any one single battery in the present embodiment battery group individually into
The reversion of its positive and negative electrode polarity of row and subsequent charging or charge and discharge operating function.
The differentiation operating method that the present embodiment positive and negative electrode polarity inverts and subsequent charges or charge and discharge is electrically operated are as follows: make this
Embodiment battery group carries out charge-discharge cycle work under rated voltage, monocell A, B, C, D, E when work in the battery pack,
F is in cycle operation state, undertakes the task of battery pack, and monocell G is in acyclic working condition, and battery pack is based on single
Battery A, B, C, D, E, F carry out cycle operation, when the operating discharge capacity of battery pack drops to the 80% of battery pack rated capacity
When, the triggering and execution program set in battery set charge/discharge device through this embodiment, for living in battery pack because positive
Property substance softening, fall off caused by the maximum monocell B of capacity attenuation degree it is switched to non-follow by cycle operation state
Ring working condition, and the monocell G with acceptable operation ability by original place in acyclic working condition is switched to cycle operation
State, so that battery pack is based on monocell A, C, D, E, F, G and can continue cycling through work, for being transferred to by former cycle operation state
The monocell B of acyclic working condition individually carries out the reversion of its battery positive and negative electrode polarity and subsequent charging or charge and discharge behaviour
Make, so that the ability to work of monocell B is restored to acceptable operation ability, after the completion of the operation, monocell B is made to be in acyclic
It is working condition, to be switched.
It works when battery pack is based on monocell A, C, D, E, F, G, and its operating discharge capacity drops to battery pack volume
Constant volume 75% when, the triggering that has set in battery set charge/discharge device through this embodiment and program is executed, for battery
In group because of positive material(PAM) softening, fall off caused by the maximum monocell E of capacity attenuation degree by it by working cycles shape
State is switched to acyclic working condition, and the monocell B with acceptable operation ability by original place in acyclic working condition is cut
Cycle operation state is changed to, so that battery pack is based on monocell A, B, C, D, F, G and can continue cycling through work, for being followed by original
The monocell E that ring working condition is transferred to acyclic working condition individually carry out its battery positive and negative electrode polarity reversion and subsequent
Charging or charge and discharge are electrically operated, so that the ability to work of monocell E is restored to acceptable operation ability, battery pack when which carries out
It can work or be in other states in cycle operation, after the completion of the operation, monocell E made to be in acyclic work shape
It is state, to be switched.
Cycle operation is carried out when battery pack is based on monocell A, B, C, D, F, G, and its operating discharge capacity drops to battery
Group rated capacity 65% when, in battery pack because of positive material(PAM) softening, fall off caused by capacity attenuation degree most
Big monocell and the monocell in acyclic working condition carry out similar aforesaid operations, so that battery pack is again based on six
Monocell with acceptable operation ability and carry out charge-discharge cycle work, and make the maximum monocell of capacity attenuation degree then through electricity
After the reversion of pond positive and negative electrode polarity and subsequent charging or charge and discharge are electrically operated, restore acceptable operation ability, be in acyclic work shape
It is state, to be switched.
According to the method described above, alternately, individually (not necessarily in order or average time) to monocell A, B, C, D, E, F
Or G carries out the reversion of positive and negative electrode polarity and subsequent charging or charge and discharge is electrically operated, the service life of the present embodiment battery group obtains
It significantly improves or extends, the service life than conventional accumulators group improves or extends up to 1 times or more.
In the other embodiment of the present embodiment, by the present embodiment above-mentioned monocell A, B, C, D, E, F, G, it is replaced by 7
Only small-scale battery pack (such as 7 specifications be 12V20Ah battery pack) forms the present embodiment battery group and (such as is formed
Voltage rating is the extensive battery pack of 72V), by small-scale battery pack A, B, C, D, E, F, G by similar in above-described embodiment
Method is operated, and so that the service life of the present embodiment battery group is significantly improved or is extended, than conventional accumulators group
Service life improves or extends up to 1 times or more.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Embodiment 6
The present embodiment solve the problems, such as battery anode active substance expand, soften, falling off or/and raising or extend battery
The group battery set charge/discharge device of service life, battery group and solve the problems, such as that battery anode active substance expands, softens, falls off
Or/and improve or extend the reversion of positive and negative electrode polarity and subsequent charging or the electrically operated area of charge and discharge of battery group service life
Divide operating method, wherein the present embodiment battery group includes 6 battery monocell A, B, C, D, E, F of equal value, the battery pack
Voltage rating be 12V, rated capacity be equal to battery group in monocell rated capacity, 12Ah (2h rate, 25 DEG C), the battery
Every monocell in group all has positive and negative electrode circuit input/output terminal independent.
The differentiation operation electrically operated to battery pack progress positive and negative electrode polarity reversion and subsequent charging or charge and discharge are as follows: make
The present embodiment battery group carries out charge-discharge cycle work under rated voltage, when the decline of the present embodiment battery power discharge capacity is (former
It is the same below because including positive material(PAM) softening, falling off or negative terminal surface product is shunk or sulfation) to battery pack rated capacity
75% when, the triggering that has set in battery set charge/discharge device through this embodiment and execute program, battery pack stopped into work
Make, to the heavier one or more rows of discharge capacity decaying in battery pack carry out the reversion of its battery positive and negative electrode polarity and subsequent
Charging or charge and discharge are electrically operated, and operating method is analogous to the relevant operation in the above embodiment of the present invention, keep the one or more single
The ability to work of battery is restored to acceptable operation ability, after the completion of the operation, battery pack is made to be restored to working condition.Whenever this reality
When applying the discharge capacity of a battery pack and dropping to the 75% of rated capacity, aforesaid operations are repeated, the present embodiment battery group is made
Service life is significantly improved or is extended, and the service life than conventional accumulators group is improved or extended up to 1 times or more.
In the other embodiment of the present embodiment, by the present embodiment above-mentioned monocell A, B, C, D, E, F, it is replaced by 6
Small-scale battery pack (such as 6 specifications be 12V12Ah battery pack) forms the present embodiment battery group and (such as forms volume
Constant voltage is the extensive battery pack of 72V), small-scale battery pack A, B, C, D, E, F are operated by above-mentioned similar method,
So that the service life of the present embodiment battery group is significantly improved or is extended, than conventional accumulators group service life improve or
Extend up to 1 times or more.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Embodiment 7
The present embodiment only makes the progress of the partial electrode in the single battery of battery or anti-by the positive and negative electrode polarity is carried out
Turn and subsequent charging or charge and discharge it is electrically operated.Contain 7 anodes, 8 cathode in the present embodiment single battery battery, is using
In the process, wherein there is the problems such as 2 positive electrodes occur active mass expansions, soften, fall off degree heavier and monocell is caused to hold
Degradation is measured, the positive and negative electrode polarity reversion and subsequent charging individually are carried out to 2 plate electrode or charge and discharge is electrically operated, solution
Certainly its active mass expansion, the problems such as softening, falling off, to improve capacity and the service life of the present embodiment monocell, operating method
It is identical or be analogous to operation described in 1-4 of the embodiment of the present invention.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Embodiment 8
The present embodiment solve the problems, such as battery anode active substance expand, soften, falling off or/and raising or extend battery
Or the method for the service life of battery pack, including during the float duty of battery or battery pack, interting ground to this implementation
It is 1 time or 1 time with Shangdi, identical or be analogous to all of above implementation of the present invention that example battery or battery pack, which carry out total cumulative number,
The reversion of positive and negative electrode polarity described in example (i.e. 1-embodiment of embodiment 7) and subsequent charging or charge and discharge are electrically operated, to improve,
It repairs, reverse, eliminating, inhibiting, preventing battery or the positive active material of battery pack from expanding or/and softening or/and fall off, is rotten
Erosion, passivation, early stage capacitance loss, salinization, crystallization, cathode specific surface area is shunk, active material contacts not with conductive current collector
Good, memory effect, active material itself decompose, one such or various problems, make the present embodiment battery or battery pack
Ability to work is restored or improves or prevent decline, and the present embodiment battery or battery pack are then put into floating charge work again
In work, until trigger or start again again to the present embodiment battery or electric power storage group carry out the reversion of positive and negative electrode polarity and
Thereafter charging or charge and discharge is electrically operated.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Embodiment 9
The battery of the present embodiment is nickel-iron storage battery or iron-ferrate battery, and rated capacity is 10Ah (C5,
5h, 25 DEG C), when the present embodiment battery because positive active material expand or/and soften or/and fall off, burn into passivation,
Early stage capacitance loss, salinization, crystallization, cathode specific surface area is shunk, active material and conductive current collector poor contact, memory are imitated
Answer, active material itself decompose, one such or various problems and cause operating discharge capacity decline or the cycle operation longevity
When life terminates, the reversion of positive and negative electrode polarity and subsequent charging or charge and discharge are carried out to the present embodiment battery by charging/discharging apparatus
It is electrically operated, to solve the positive active material expansion of the present embodiment battery or/and softening or/and fall off, burn into passivation, early
Phase capacitance loss, salinization, crystallization, cathode specific surface area is shunk, active material and conductive current collector poor contact, memory are imitated
It answers, active material itself decomposition, one such or various problems, to improve or extend the use longevity of the present embodiment battery
Life.
The step packet electrically operated to the progress positive and negative electrode polarity reversion of the present embodiment battery and subsequent charging or charge and discharge
Include: (1) method to be charged by antipole makes the present embodiment battery that polarity reversion occur, i.e., by positive electrode (nickel electrode or high-speed rail
Hydrochlorate electrode, is defined as electrode A) it is connected with the negative output terminal of the present embodiment charging/discharging apparatus, negative electrode is (iron electrode, fixed
Justice is electrode B) it is connected with the positive output end of the present embodiment charging/discharging apparatus, 1/2C then is carried out to electrode A, B5Electric current fills
Electricity, so that the polarity of final electrode B is positive relative to the polarity of electrode A, the polarity of the polarity comparative electrode B of electrode A is negative, and
After electrode A, the polarity of electrode B invert, the polarization state is kept, with C5Electric current continue charging 5 hours；Then (2)
With C5Electric current this two electrode is carried out being discharged to 0V；Then (3) are by the positive output end of electrode A and the present embodiment charging/discharging apparatus
It is connected, electrode B is connected with the negative output terminal of the present embodiment charging/discharging apparatus, 1/ then is carried out to electrode A, electrode B
2C5Electric current charging, so that the polarity of final electrode B is negative relative to the polarity of electrode A, the polarity of electrode A is relative to electrode B
Polarity is positive, and inverts and subsequent charges by above-mentioned positive and negative electrode polarity or charge and discharge is electrically operated, solves, improves positive-active
Mass expansion or/and softening or/and fall off, burn into passivation, early stage capacitance loss, salinization, crystallization, cathode specific surface area receive
Contracting, active material and conductive current collector poor contact, memory effect, active material itself decompose, one such or a variety of ask
Topic, makes the operating discharge capacity of the present embodiment battery be improved or be restored to normal rated capacity value, so that this
The service life of embodiment battery is improved or is extended.
In the other embodiment of the present embodiment, after completing above-mentioned (1) step, the polarity of electrode A is negative, electrode B
Polarity be positive, under this polarization state, so that the present embodiment battery is put into work charge-discharge cycle and use, this operating method
Also solve, improve positive active material expansion or/and softening or/and fall off, burn into passivation, early stage capacitance loss, salinization,
Crystallization, cathode specific surface area shrink, active material and conductive current collector poor contact, memory effect, active material is from status
Solution, one such or various problems make the operating discharge capacity of the present embodiment battery be improved or be restored to normally
Rated capacity value, so that the service life of the present embodiment battery is improved or extended.
In the other embodiment of the present embodiment, the present embodiment battery includes anode, cathode, alternatively, the present embodiment
Battery positive and negative electrode is positive and negative anodes current electrode, anode, cathode, the positive and negative anodes current electrode of the present embodiment battery, packet
It includes but is not limited to, include swelling agent in anode or/and cathode, its electrode active material or active matter formula including swelling agent
Positive and negative anodes current electrode or/and anode or/and cathode, there is identical active material or identical active matter formula just each other
Cathode current electrode, each other the positive and negative anodes current electrode of equivalence are each other same or identical positive and negative anodes current electrode,
One of or it is a variety of.The swelling agent for preventing, inhibiting, improving, shrink or electrode active material compares table by electrode specific surface area
Area contraction, the swelling agent includes but is not limited to: barium sulfate, calcium sulfate, silica, silicate, humic acid, lignosulphonic acid
The oxide or hydroxide of salt, aluminum oxide or hydroxide, titanyl compound or hydroxide, lithium, it is one such or
It is a variety of.
In the other embodiment of the present embodiment, the above-mentioned swelling agent of the present embodiment is in active material or active matter formula
In mass percentage content be 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%, it is one such or a variety of.
In the other embodiment of the present embodiment, the above-mentioned swelling agent of the present embodiment is in active material or active matter formula
In mass percentage content be less than or equal to 5%, 10%, 20%, 30%, 40%, 50%, it is one such or a variety of.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Embodiment 10
The present embodiment is identical to or including embodiment 1-21, China described in Chinese patent application 201710975570.6
Embodiment 1-21 and 23 described in patent application 201710975698.2, institute in Chinese patent application 201710975569.3
Embodiment 1-3, Chinese patent application described in the embodiment 1-21 stated and 23, Chinese patent application 201810452604.8
Embodiment 1-9 described in 201811297354.1, embodiment 1-10 described in Chinese patent application 201811296518.9.
The present embodiment method makes the service life of battery or battery pack be significantly improved or be extended, and works as depth of discharge
(DOD) when including but is not limited to 1-100%, the present embodiment method makes the service life of battery or battery pack improve or extend
To 1.3 times or more -10 times or more, or/and, cycle life improve or extend 50 times or more -500 times or more, 500 times with
It is -3000 times or more upper, it is one such or a variety of.
Claims (10)
1. a kind of method for solving the problems, such as battery anode active substance and expanding, soften, falling off, which is characterized in that including making
The anode or positive active material for stating battery or/and battery group carry out battery terminal negative electrode reaction, or pass through electrochemistry
Reduction reaction and be reduced into metal or 0 chemical valence.
2. a kind of method for solving the problems, such as battery anode active substance and expanding, soften, falling off, which is characterized in that including by institute
The anode or/and cathode for stating battery or/and battery group carry out polarity reversion and subsequent charging or charge and discharge is electrically operated, the behaviour
Total cumulative number >=1 time made；It is described that anode, cathode progress polarity reversion and subsequent charging or charge and discharge is electrically operated, that is, will
Positive electrode, negative electrode carry out polarity reversion, and after polarity reversion, will be charged or are filled by the electrode of polarity reversion
Discharge operation.
3. solving the problems, such as the method that battery anode active substance expands, softens, falling off according to claim 2, feature
It is, the active material of its anode of the battery or/and cathode is the member with two or more stable oxidation state
Simple substance, one of the compound or a variety of of element；The element with two or more stable oxidation state include but
It is not limited to: lead, iron, copper, nickel, manganese, silver, phosphorus, sulphur, chlorine, vanadium, chromium, cobalt, arsenic, selenium, bromine, tin, antimony, tellurium, iodine, tungsten, bismuth therein one
Kind is a variety of.
4. any one of -3 side for solving the problems, such as battery anode active substance and expanding, soften, falling off according to claim 1
Method, which is characterized in that the battery or battery group, including but not limited to: lead-acid accumulator, nickel-iron storage battery, iron-height
Ferrite battery, copper-ferrate battery, the battery of cadmium-nickel storage battery or battery pack, it is one such or a variety of.
5. solving the problems, such as the method that battery anode active substance expands, softens, falling off according to claim 2, feature
It is, it is described that positive and negative electrode progress polarity reversion and subsequent charging or charge and discharge is electrically operated, including make the positive and negative electrode polarity
Reversion and subsequent the electrically operated work with the battery or battery pack of charging or charge and discharge, intert each other, are alternately carried out, and
Make the battery or battery pack at work, positive, original cathode originally is in following three kinds of electrode working conditions
One of: (1) original anode always as anode work, and cathode originally is used as cathode to work always；(2)
Anode originally works as cathode always, and cathode originally is used as anode to work always；(3) original anode has
Shi Zuowei anode is worked, is used as cathode to work sometimes, and correspondingly, cathode originally is used as cathode to carry out work sometimes
Make, be used as anode to work sometimes；Its described original positive, original cathode is, do not carried out it is any described
When anode, negative polarity reversion and subsequent charging or electrically operated charge and discharge, anode, the cathode of the battery or battery pack.
6. any one of -5 side for solving the problems, such as battery anode active substance and expanding, soften, falling off according to claim 1
Method, which is characterized in that the method is also used for individually solving the other problems of battery, or is solving battery positive voltage activity
Mass expansion, soften, the problem that falls off while be also used for solving the other problems of battery, the other problems include but unlimited
Shunk in the burn into passivation of: battery, salinization, crystallization, cathode specific surface area, active material and collector poor contact or/
With fall off, early stage capacitance loss, memory effect, active material itself resolution problem, it is one such or a variety of.
7. any one of -5 side for solving the problems, such as battery anode active substance and expanding, soften, falling off according to claim 1
Method, which is characterized in that its anode of the battery or battery pack and cathode are positive and negative anodes current electrode, and the positive and negative anodes are general
Electrode can not only be used for anode and use, also can be used as cathode use or certain as just in the battery or battery pack
Pole uses, it is certain used as cathode, or in the battery or battery pack work or use process, some time is as anode
Use, some time again used as cathode, it is one such or a variety of；The anode, cathode, positive and negative anodes current electrode include but not
It is limited to: positive and negative including swelling agent in anode or/and cathode, its electrode active material or active matter formula including swelling agent
Pole current electrode or/and anode or/and cathode, the positive and negative anodes each other with identical active material or identical active matter formula lead to
With electrode, each other of equal value positive and negative anodes current electrode, be each other same or identical positive and negative anodes current electrode, therein one
Kind is a variety of；The swelling agent is used to prevent, inhibit, improves electrode specific surface area contraction or electrode active material specific surface area receipts
Contracting.
8. solving the problems, such as the method that battery anode active substance expands, softens, falling off according to claim 7, feature
Be, the swelling agent includes but is not limited to: barium sulfate, calcium sulfate, silica, silicate, humic acid, lignosulphonates,
The oxide or hydroxide of aluminium, titanyl compound or hydroxide, lithium oxide or hydroxide, it is one such or more
Kind.
9. solving the problems, such as the method that battery anode active substance expands, softens, falling off according to claim 8, feature
It is, mass percentage of the swelling agent in active material or active matter formula is 0.01%-50%.
10. according to claim 1-3,5, any one of 8-9 solution battery anode active substance expands, softens, falls off
The method of problem, which is characterized in that the method is realized by a kind of circuit, is implemented, the circuit have battery or/and
The function that anode, the cathode of battery group carry out polarity reversion or polarity inverts and subsequent charges or charge and discharge is electrically operated, it is described
Total cumulative number that circuit can or actually be effected or carried out the function is >=1 time；Alternatively, the circuit can be to the electric power storage
Pond or battery group charge after carrying out antipole charging, forced electric discharge, reversal connection, one such or a variety of.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017110738627 | 2017-11-05 | ||
| CN201711073862 | 2017-11-05 | ||
| CN201711073858 | 2017-11-05 | ||
| CN2017110738580 | 2017-11-05 | ||
| CN201711073854 | 2017-11-05 | ||
| CN2017110738542 | 2017-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109755671A true CN109755671A (en) | 2019-05-14 |
Family
ID=64998413
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| Application Number | Title | Priority Date | Filing Date |
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| CN202310591927.6A Pending CN116742153A (en) | 2017-11-05 | 2018-11-01 | Method for solving softening and falling-off problems of positive electrode active material of lead-acid storage battery |
| CN202311833984.7A Pending CN117810567A (en) | 2017-11-05 | 2018-11-01 | Method for solving softening and falling-off problems of positive electrode active materials of lead-acid storage battery or battery pack |
| CN201811296518.9A Pending CN109361027A (en) | 2017-11-05 | 2018-11-01 | The method for improving or extending lead-acid accumulator or battery pack service life |
| CN201811297354.1A Pending CN109216805A (en) | 2017-11-05 | 2018-11-01 | A method of it solving the problems, such as active substance for positive electrode of lead-acid accumulator softening, falls off |
| CN202310591562.7A Pending CN117175024A (en) | 2017-11-05 | 2018-11-01 | Method for solving softening and falling-off problems of positive electrode active material of lead-acid storage battery |
| CN201811303681.3A Pending CN109755671A (en) | 2017-11-05 | 2018-11-02 | Solve the problems, such as the method that battery anode active substance expands, softens, falling off |
| CN201811304067.9A Pending CN109755672A (en) | 2017-11-05 | 2018-11-03 | A kind of two-way discharge battery |
| CN201811303777.XA Pending CN109273779A (en) | 2017-11-05 | 2018-11-03 | Long service life head-acid accumulator |
| CN201811303768.0A Pending CN109755577A (en) | 2017-11-05 | 2018-11-03 | Long life accumulator |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310591927.6A Pending CN116742153A (en) | 2017-11-05 | 2018-11-01 | Method for solving softening and falling-off problems of positive electrode active material of lead-acid storage battery |
| CN202311833984.7A Pending CN117810567A (en) | 2017-11-05 | 2018-11-01 | Method for solving softening and falling-off problems of positive electrode active materials of lead-acid storage battery or battery pack |
| CN201811296518.9A Pending CN109361027A (en) | 2017-11-05 | 2018-11-01 | The method for improving or extending lead-acid accumulator or battery pack service life |
| CN201811297354.1A Pending CN109216805A (en) | 2017-11-05 | 2018-11-01 | A method of it solving the problems, such as active substance for positive electrode of lead-acid accumulator softening, falls off |
| CN202310591562.7A Pending CN117175024A (en) | 2017-11-05 | 2018-11-01 | Method for solving softening and falling-off problems of positive electrode active material of lead-acid storage battery |
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| CN201811304067.9A Pending CN109755672A (en) | 2017-11-05 | 2018-11-03 | A kind of two-way discharge battery |
| CN201811303777.XA Pending CN109273779A (en) | 2017-11-05 | 2018-11-03 | Long service life head-acid accumulator |
| CN201811303768.0A Pending CN109755577A (en) | 2017-11-05 | 2018-11-03 | Long life accumulator |
Country Status (2)
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| CN (9) | CN116742153A (en) |
| WO (2) | WO2019086022A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN117810567A (en) | 2024-04-02 |
| CN109216805A (en) | 2019-01-15 |
| CN109273779A (en) | 2019-01-25 |
| CN109755672A (en) | 2019-05-14 |
| CN109755577A (en) | 2019-05-14 |
| CN109361027A (en) | 2019-02-19 |
| CN116742153A (en) | 2023-09-12 |
| WO2019086021A1 (en) | 2019-05-09 |
| WO2019086022A1 (en) | 2019-05-09 |
| CN117175024A (en) | 2023-12-05 |
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