CN114497776B - Method for forming lithium ion battery and lithium ion battery - Google Patents
Method for forming lithium ion battery and lithium ion battery Download PDFInfo
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- CN114497776B CN114497776B CN202210023401.3A CN202210023401A CN114497776B CN 114497776 B CN114497776 B CN 114497776B CN 202210023401 A CN202210023401 A CN 202210023401A CN 114497776 B CN114497776 B CN 114497776B
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- ion battery
- lithium ion
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- constant voltage
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000007600 charging Methods 0.000 claims abstract description 66
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 39
- 238000010280 constant potential charging Methods 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 238000002347 injection Methods 0.000 claims abstract description 10
- 239000007924 injection Substances 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 230000005654 stationary process Effects 0.000 claims abstract description 3
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 230000000284 resting effect Effects 0.000 claims 3
- 150000003949 imides Chemical class 0.000 claims 2
- 238000005755 formation reaction Methods 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 28
- 239000010410 layer Substances 0.000 description 20
- 150000002500 ions Chemical class 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
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- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
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- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 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
- H01M10/42—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a method for forming a lithium ion battery and the lithium ion battery, and the method for forming the lithium ion battery comprises the following steps: a first standing step, namely performing first standing treatment on the lithium ion battery subjected to the liquid injection sealing so as to diffuse the electrolyte; a first charging step for performing a first constant voltage charging process and a pulse current charging process on the lithium ion battery after the first stationary process, so as to decompose lithium salt in the electrolyte; a second charging step for performing a second constant voltage charging process on the lithium ion battery after the pulse current charging process, so as to decompose the organic solvent in the electrolyte; a second standing step for performing a second standing treatment on the lithium ion battery subjected to the second constant voltage charging treatment to age the solid electrolyte interface film; and a vacuum exhaust step, which is used for carrying out vacuum exhaust treatment on the lithium ion battery subjected to the second standing treatment and packaging to obtain the formed lithium ion battery.
Description
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a method for forming a lithium ion battery and the lithium ion battery.
Background
The birth of lithium ion batteries quickly changes the life style of human beings due to the characteristics of high energy density, long cycle life, no memory and the like, and is widely applied to 3C digital products, new energy automobiles and large-scale energy storage which is about to be exploded and increased.
When the lithium ion battery works, a layer of solid electrolyte interface film is generated at the electrode interface of the negative electrode under the drive of voltage, and the solid electrolyte interface film has good electronic insulation property and can conduct ions rapidly. However, this solid electrolyte interface film needs to consume lithium ions on the positive electrode side at the time of production, and therefore, the initial coulombic efficiency, initial energy density, and cycle life of the battery are largely dependent on the initial characteristics of the solid electrolyte interface on the negative electrode surface. In order to improve the initial characteristics of the solid electrolyte interface of the lithium ion battery, the lithium ion battery is usually initialized, namely, the solid electrolyte interface film with high ion conductivity and high ploidy and corrosion resistance is constructed through a formation process.
In the prior art, a lithium ion battery is usually initialized by adopting a mode of combining voltage and current, but as nucleation and growth mechanisms of a lithium ion battery solid electrolyte interface film are not clear in the prior art, lithium salt and solvolysis potential in battery electrolyte are difficult to find, so that formation time and formation temperature are difficult to match, and structures and components of the solid electrolyte interface film are difficult to be obviously related to voltage, current and temperature signals, the formation method is generally difficult to realize controllable formation and accurate formation of the solid electrolyte interface film.
Disclosure of Invention
In view of this, the present application provides a method for forming a lithium ion battery and a lithium ion battery capable of achieving precise control of the composition of a solid electrolyte interface film while having high ion conductivity and long cycle life.
A first aspect of the application provides a method for forming a lithium ion battery, comprising:
a first standing step, namely performing first standing treatment on the lithium ion battery subjected to the liquid injection sealing so as to diffuse the electrolyte;
A first charging step for performing a first constant voltage charging process and a pulse current charging process on the lithium ion battery after the first stationary process, so as to decompose lithium salt in the electrolyte;
a second charging step for performing a second constant voltage charging process on the lithium ion battery after the pulse current charging process, so as to decompose the organic solvent in the electrolyte;
a second standing step for performing a second standing treatment on the lithium ion battery subjected to the second constant voltage charging treatment to age the solid electrolyte interface film;
And a vacuum exhaust step, which is used for carrying out vacuum exhaust treatment on the lithium ion battery subjected to the second standing treatment and packaging to obtain the formed lithium ion battery.
According to any embodiment of the first aspect of the present application, the first stationary treatment comprises:
The lithium ion battery after the liquid injection and sealing is kept stand for 6 to 12 hours, preferably 7 to 11 hours at the first temperature,
Wherein the first temperature is 40-55deg.C, preferably 42-52deg.C.
According to any one of the embodiments of the first aspect of the present application, the first constant voltage charging process includes:
the lithium ion battery after the first standing treatment is charged for 0.5 to 48 hours, preferably 1 to 45 hours at the second temperature,
Wherein the second temperature is-10 ℃ to 0 ℃, preferably-9 ℃ to-1 ℃; and/or
The voltage of the constant voltage charge is 1.2 to 1.8V, preferably 1.3 to 1.7V.
According to any embodiment of the first aspect of the present application, the pulse current charging process includes:
the lithium ion battery after the first constant voltage charging treatment is charged by pulse current at a third temperature,
Wherein the third temperature is-10 ℃ to 0 ℃, preferably-9 ℃ to-1 ℃; and/or
The current charged by the pulse current is 0.01-0.1C, preferably 0.02-0.08C; and/or
The number of pulse current charging is 2 to 10, preferably 3 to 8; and/or
The single charging time of the pulse current charging is 0.1 to 10s, preferably 0.5 to 8s.
According to any one of the embodiments of the first aspect of the present application, the second constant voltage charging process includes:
The lithium ion battery after pulse current charging treatment is charged for 0.5 to 48 hours, preferably 1 to 45 hours at a fourth temperature,
Wherein the fourth temperature is-10 ℃ to 0 ℃, preferably-9 ℃ to-1 ℃; and/or
The voltage of the constant voltage charge is 2.2 to 3.0V, preferably 2.3 to 2.8V.
According to any embodiment of the first aspect of the present application, the second standing treatment includes:
the lithium ion battery after the second constant voltage charging treatment is kept stand for 1 to 24 hours, preferably 5 to 20 hours at a fifth temperature,
Wherein the fifth temperature is 40-60 ℃, preferably 45-55 ℃.
According to any one of the embodiments of the first aspect of the present application, the vacuum degree of the vacuum evacuation treatment is 0.1 to 0.8MPa, preferably 0.2 to 0.7MPa; and/or
The time for the vacuum evacuation treatment is 3 to 20 seconds, preferably 5 to 18 seconds.
In a second aspect, the application provides a lithium ion battery made by the method of the first aspect of the application.
According to any one of the embodiments of the second aspect of the present application, the positive electrode active material of the lithium ion battery is lithium iron phosphate; and/or
The negative active material of the lithium ion battery comprises one or more of graphite, silicon carbon, lithium carbon and lithium; and/or
The lithium salt in the lithium ion battery electrolyte comprises one or more of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide and lithium tetrafluoroborate; and/or
The organic solvent in the lithium ion battery electrolyte comprises one or more of ethylene carbonate, fluoroethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate.
Compared with the prior art, the application has at least the following beneficial effects:
The method for forming the lithium ion battery is simple to operate, the structure and the components of the solid electrolyte interface film are obviously related to voltage, current and temperature signals by controlling the whole process in limited steps and reasonably regulating and matching key parameters in each step, so that the component accuracy and the control of the solid electrolyte interface film of the lithium ion battery are realized, the stability of the solid electrolyte interface film is improved, and the high ion conductivity of the battery electrode interface and the long cycle life of the battery are also considered. In addition, the method can obviously reduce lithium ion consumption in the process of forming the solid electrolyte interface film of the lithium ion battery by controlling the reaction parameters in the formation step in a proper range, thereby being beneficial to improving the first coulombic efficiency of the battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and other drawings may be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a transmission electron microscope image of a solid electrolyte interface film of a lithium ion battery according to an embodiment of the present application.
Fig. 2 is a schematic diagram of a pulse current charging process of a lithium ion battery according to an embodiment of the present application.
Fig. 3 is a diagram showing a change in the potential of the positive electrode and the negative electrode in the first charging process of the lithium ion battery according to the embodiment of the application.
Detailed Description
In order to make the application object, technical scheme and beneficial technical effects of the application clearer, the application is further described in detail with reference to the following embodiments. It should be understood that the examples described in this specification are for the purpose of illustrating the application only and are not intended to limit the application.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, and the meaning of "multiple" in "one or more" is two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In the various examples, the list is merely a representative group and should not be construed as exhaustive.
An embodiment of a first aspect of the present application provides a method for forming a lithium ion battery, comprising:
s10, performing first standing treatment on the lithium ion battery subjected to the liquid injection sealing to diffuse electrolyte;
S20, a first charging step, which is used for carrying out a first constant voltage charging treatment and a pulse current charging treatment on the lithium ion battery after the first standing treatment so as to decompose lithium salt in the electrolyte;
S30, a second charging step, namely performing a second constant voltage charging treatment on the lithium ion battery subjected to the pulse current charging treatment so as to decompose an organic solvent in the electrolyte;
S40, a second standing step, namely performing second standing treatment on the lithium ion battery subjected to the second constant voltage charging treatment so as to age the solid electrolyte interface film;
And S50, performing vacuum exhaust treatment on the lithium ion battery subjected to the second standing treatment, and packaging to obtain the formed lithium ion battery.
The method for forming the lithium ion battery in the embodiment of the application is simple to operate, the structure and the components of the solid electrolyte interface film are obviously associated with voltage, current and temperature signals by controlling the whole process in limited steps and reasonably regulating and matching key parameters in each formation step, so that the component accuracy and the control of the solid electrolyte interface film of the lithium ion battery are realized, the solid electrolyte interface film which is mainly composed of inorganic components with high ion conductivity and is assisted by high-toughness organic components is constructed, the stability of the solid electrolyte interface film is improved, and the high ion conductivity of the electrode interface of the battery and the long cycle life of the battery are also considered. In addition, the method reduces thermodynamic corrosion and electrochemical side reaction at the interface by controlling the reaction parameters in the formation step within a proper range, and can remarkably reduce lithium ion consumption in the formation process of the solid electrolyte interface film of the lithium ion battery, thereby being beneficial to improving the first coulombic efficiency of the battery.
In some embodiments, in step S10, the first standing process includes: the lithium ion battery after the liquid injection and sealing is kept stand for 6 to 12 hours, preferably 7 to 11 hours, for example, 8 hours, 9 hours, 10 hours and the like at the first temperature.
In some embodiments, the first temperature is 40 ℃ to 55 ℃, preferably 42 ℃ to 52 ℃, e.g., may be 44 ℃, 46 ℃, 48 ℃,50 ℃, etc.
In the embodiment of the application, the lithium ion battery after the liquid injection and sealing refers to the lithium ion battery after the electrolyte is injected and sealing is performed. In the embodiment of the application, the lithium ion battery after the liquid injection and sealing is kept stand for 6-12 hours at the temperature of 40-55 ℃, so that the injected electrolyte is favorable for fully diffusing in the lithium ion battery, the occurrence of the subsequent formation reaction is facilitated, the constructed electrode interface has a layered structure after the formation is finished, the inner layer is mainly inorganic matters (lithium fluoride, lithium carbonate, lithium oxide and the like), and the outer layer is mainly organic matters (ester lithium, alkyl lithium and the like).
In some embodiments, in step S20, the first constant voltage charging process includes: the lithium ion battery after the first standing treatment is charged at a constant voltage at the second temperature for 0.5 to 48 hours, preferably 1 to 45 hours, and for example, 2 hours, 5 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, and the like can be used.
In some embodiments, the second temperature is-10 ℃ to 0 ℃, preferably-9 ℃ to-1 ℃, e.g., can be-8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, and so on.
In some embodiments, the voltage of the constant voltage charge is 1.2 to 1.8V, preferably 1.3 to 1.7V, for example, 1.4V, 1.5V, 1.6V, and the like.
In the embodiment of the application, the lithium ion battery subjected to the first standing treatment is subjected to constant voltage charging for 0.5-48 hours at the temperature of minus 10-0 ℃, and meanwhile, the voltage value of the constant voltage charging is controlled within a proper range matched with the temperature and time parameters, so that the decomposition potential of lithium salt in electrolyte is favorably achieved, and the decomposition of the lithium salt is controlled to generate inorganic matters containing lithium ions, so that the inorganic matters containing lithium ions are partially aggregated at the negative electrode plate, and the formation of an inorganic solid electrolyte interface film is favorably realized.
As a specific example, taking lithium salt in the electrolyte as lithium difluoroacetimide as an example, when the charging voltage is 1.5V, the decomposition reaction process of lithium difluoroacetimide in the electrolyte is as shown in the following formula (1):
in the formula (1), at a charging voltage of 1.5V, lithium difluoroacetimide takes electrons to generate inorganic substances such as lithium fluoride, lithium nitride, lithium sulfide, lithium oxide and the like, and the generated inorganic substances are partially accumulated near the negative electrode plate, so that the inorganic solid electrolyte interface film is formed advantageously.
In some embodiments, in step S30, the pulse current charging process includes: and carrying out pulse current charging on the lithium ion battery subjected to the first constant voltage charging treatment at a third temperature.
In some embodiments, the third temperature is-10 ℃ to 0 ℃, preferably-9 ℃ to-1 ℃, e.g., can be-8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, and so on.
In some embodiments, the pulsed current charges at a current of 0.01 to 0.1C, preferably 0.02 to 0.08C, for example, may be 0.03C, 0.04C, 0.05C, 0.06C, 0.07C, and the like.
In some embodiments, the number of pulse current charges is 2 to 10 times, preferably 3 to 8 times, for example, 4 times, 5 times, 6 times, 7 times, etc.
In some embodiments, the single charge time for pulsed current charging is 0.1 to 10s, preferably 0.5 to 8s, and may be, for example, 1s, 2s, 3s, 4s, 5s, 6s, 7s, etc.
In some embodiments, taking a pulse current charging current of 0.01C as an example, when the single charging time of the pulse current is 5s and the number of times of charging is 2, the current change during charging is shown in fig. 2.
In the embodiment of the application, the lithium ion battery subjected to the first constant voltage charging treatment is subjected to pulse current charging treatment, and the current value and the charging times of the pulse current charging are controlled within the proper ranges matched with the temperature and time parameter items, so that the lithium salt in the electrolyte is controlled to be fully decomposed, and the formation of the solid electrolyte interface film is facilitated.
In some embodiments, in step S40, the second constant voltage charging process includes: the lithium ion battery after the pulse current charging treatment is charged at a constant voltage at the fourth temperature for 0.5 to 48 hours, preferably 1 to 45 hours, and for example, 2 hours, 5 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, and the like can be used.
In some embodiments, the fourth temperature is-10 ℃ to 0 ℃, preferably-9 ℃ to-1 ℃, e.g., can be-8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, and so on.
In some embodiments, the voltage of the constant voltage charge is 2.2 to 3.0V, preferably 2.3 to 2.8V, for example, 2.4V, 2.5V, 2.6V, 2.7V, and so on.
In the embodiment of the application, the lithium ion battery subjected to pulse current charging treatment is subjected to constant voltage charging for 0.5-48 hours at the temperature of minus 10-0 ℃, and meanwhile, the voltage value of the constant voltage charging is controlled within a proper range matched with the temperature and time parameters, so that the decomposition potential of an organic solvent in the electrolyte is favorably achieved, and organic solvent molecules in the electrolyte are controlled to decompose, so that lithium-containing organic substances are formed after decomposition, and the lithium-containing organic substances are partially aggregated at a negative electrode plate, so that the formation of an organic solid electrolyte interface film is favorably realized.
As a specific example, taking an organic solvent in an electrolyte as ethylene carbonate as an example, when the charging voltage is 2.5V, the decomposition reaction process of fluoroethylene carbonate in the electrolyte is as shown in the following formula (2):
In the formula (2), at a charging voltage of 2.5V, fluoroethylene carbonate undergoes a decomposition reaction to produce a lithium-containing organic substance, which is partially deposited near the negative electrode sheet, thereby facilitating the formation of an organic solid electrolyte interfacial film.
In some embodiments, in step S50, the second standing process includes: the lithium ion battery after the second constant voltage charging treatment is left at the fifth temperature for 1 to 24 hours, preferably 5 to 20 hours, and may be 6 hours, 9 hours, 12 hours, 15 hours, 18 hours, or the like, for example.
In some embodiments, the fifth temperature is 40 ℃ to 60 ℃, preferably 45 ℃ to 55 ℃, e.g., 43 ℃, 47 ℃, 49 ℃, 51 ℃, 53 ℃, and so on.
In the embodiment of the application, the lithium ion battery subjected to the second constant voltage charging treatment is kept stand for 1-5 hours at the temperature of 40-60 ℃, and the aging of the solid electrolyte interface film is facilitated and the stability of the solid electrolyte interface film is improved through the thermodynamic spontaneous reaction at high temperature, so that the organic-inorganic composite solid electrolyte interface film with high flexibility as shown in figure 1 is obtained.
In some embodiments, the vacuum degree of the vacuum evacuation treatment is 0.1 to 0.8MPa, preferably 0.2 to 0.7MPa, and may be, for example, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, or the like.
In some embodiments, the time for the vacuum evacuation treatment is 3 to 20s, preferably 5 to 18s, and may be, for example, 7s, 9s, 11s, 13s, 15s, 17s, and so on.
In the embodiment of the application, the vacuum degree and the time of the vacuum exhaust treatment are controlled within proper ranges, so that the gas generated in the formation process is completely exhausted, and the overall performance of the solid electrolyte interface film and the lithium ion battery is not affected.
In some embodiments, the method of the embodiment of the application can obtain an organic-inorganic interweaved composite solid electrolyte interface film, the structure of which is shown in fig. 1, and the interface film has high ion conductivity and high flexibility, which is beneficial to improving the first coulombic efficiency of a lithium ion battery.
A second aspect of embodiments of the present application provides a lithium ion battery made by the method of the first aspect of the present application.
In some embodiments, a lithium ion battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
In some embodiments, the positive electrode tab includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material.
In some embodiments, the positive electrode active material includes at least lithium iron phosphate, and may also include other positive electrode active materials conventional in the art, such as lithium cobaltate, nickel cobalt manganese, nickel cobalt aluminum, and the like.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as a positive electrode active material, a conductive agent, a binder and any other components, in a solvent to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
In some embodiments, the negative electrode tab includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, the negative electrode film layer including a negative electrode active material.
In some embodiments, the negative active material of the lithium ion battery includes one or more of graphite, silicon carbon, lithium carbon, and lithium.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining a negative electrode plate after the procedures of drying, cold pressing and the like.
In some embodiments, the electrolyte of the lithium ion battery employs an electrolyte solution. The electrolyte includes a lithium salt and an organic solvent.
In some embodiments, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, and lithium tetrafluoroborate.
In some embodiments, the organic solvent comprises one or more of ethylene carbonate, fluoroethylene carbonate, dimethyl carbonate, ethylmethyl carbonate, and diethyl carbonate.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
In some embodiments, a separator is also included in the lithium ion battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used.
In some embodiments, the material of the isolation film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In the embodiment of the application, the lithium ion battery prepared by selecting a proper positive electrode active material, a proper negative electrode active material, a proper lithium salt and a proper organic solvent and matching with the method of the first aspect of the application is provided with the organic-inorganic composite solid electrolyte interface film, and the solid electrolyte interface film has higher stability, thereby being beneficial to improving the ion conductivity, the first coulombic efficiency and the cycle life of the lithium ion battery.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
After the lithium ion battery is injected with liquid and sealed: (1) standing at a high temperature of 40 ℃ for 1.0h; (2) Charging at-10deg.C under constant voltage of 1.2V for 0.5 hr; (3) Charging at-10deg.C with pulse current of 0.01C for 0.1s for 2 times; (4) Charging at-10deg.C under constant voltage of 2.2V for 0.5 hr; (5) standing at a high temperature of 40 ℃ for 1.0h; (6) The generated gas was discharged at a vacuum degree of 0.1MPa for 3s, and the battery was packaged again.
The lithium ion battery is a full battery with a lithium iron phosphate anode matched with a graphite cathode; the anode solid electrolyte interface film obtained after the formation has an organic-inorganic interweaved structure.
Example 2
After the lithium ion battery is injected with liquid and sealed: (1) standing at a high temperature of 55 ℃ for 5.0h; (2) charging at a constant voltage of 1.8V at a low temperature of 0 ℃ for 48 hours; (3) Charging at 0deg.C with pulse current of 0.1C for 10s and pulse times of 10 times; (4) charging at a constant voltage of 3.0V at a low temperature of 0 ℃ for 48 hours; (5) standing at a high temperature of 60 ℃ for 5.0h; (6) The generated gas was discharged at a vacuum degree of 0.8MPa for 20s, and the battery was packaged again.
The lithium ion battery is a full battery with a lithium iron phosphate anode matched with a silicon-carbon cathode; the anode solid electrolyte interface film obtained after the formation has an organic-inorganic interweaved structure.
Example 3
After the lithium ion battery is injected with liquid and sealed: (1) standing at a high temperature of 45 ℃ for 2.5h; (2) charging at a constant voltage of 1.6V at a low temperature of-5 ℃ for 2 hours; (3) Charging at-5deg.C with pulse current of 0.05C for 5s for 4 times; (4) charging at a constant voltage of 2.6V at a low temperature of-5 ℃ for 24 hours; (5) standing at a high temperature of 50 ℃ for 24.0h; (6) The generated gas was discharged at a vacuum degree of 0.3MPa for 5s, and the battery was packaged again.
The lithium ion battery is a full battery with a lithium iron phosphate anode matched with a lithium carbon cathode; the anode solid electrolyte interface film obtained after the formation has an organic-inorganic layered structure.
Example 4
After the lithium ion battery is injected with liquid and sealed: (1) standing for 4 hours at a high temperature of 49 ℃; (2) charging at a constant voltage of 1.4V at a low temperature of 0 ℃ for 4.5 hours; (3) Charging at-10deg.C with pulse current of 0.02C for 1s for 5 times; (4) Charging at-10deg.C under constant voltage of 2.4V for 8.5 hr; (5) standing at a high temperature of 45 ℃ for 10.0h; (6) The generated gas was discharged at a vacuum degree of 0.2MPa for 15s, and the battery was packaged again.
The lithium ion battery is a full battery with a lithium iron phosphate anode matched with a graphite cathode; the anode solid electrolyte interface film obtained after the formation has an organic-inorganic interweaved structure.
Example 5
After the lithium ion battery is injected with liquid and sealed: (1) standing for 4 hours at a high temperature of 53 ℃; (2) charging at a constant voltage of 1.5V at a low temperature of 0 ℃ for 0.5h; (3) Charging at-8deg.C with pulse current of 0.08C for 6s and pulse times of 7 times; (4) Charging at-10deg.C under constant voltage of 2.5V for 0.5 hr; (5) standing at a high temperature of 40 ℃ for 1.0h; (6) The generated gas was discharged at a vacuum degree of 0.6MPa, the time period was 13s, and the battery was packaged again.
The lithium ion battery is a full battery with a lithium iron phosphate anode matched with a silicon-carbon cathode; the anode solid electrolyte interface film obtained after the formation has an organic-inorganic layered structure.
Comparative example 1
The composition of the lithium ion battery was the same as in example 1, except that: the formation of the lithium ion battery is performed by using other formation processes in the prior art which cannot realize the precise and controllable components of the solid electrolyte interface film. For example, after the lithium ion battery is sealed by filling liquid: (1) standing at a low temperature of 50 ℃ for 24 hours; (2) charged to 3.5V at 25 ℃ with a constant current of 0.01C; (3) charging at 25 ℃ with a constant voltage of 3.5V; (4) standing at 40 ℃ for 12.0h; (5) The generated gas was discharged at a vacuum degree of 0.1MPa and the battery was packaged again. The anode solid electrolyte interface film obtained after the formation has an unordered and disordered structure.
Test part
The performance test was conducted in relation to examples 1 to 5 and comparative example 1, and the test results are shown in table 1 below.
TABLE 1
(1) First coulombic efficiency and cycle performance test of lithium ion battery
After the lithium ion secondary batteries of examples 1 to 5 and comparative example 1 were completed in the methods and schemes described in examples 1 to 5 and comparative example 1 at 25 ℃ under normal pressure, the batteries were charged to 3.65V at a constant current of 0.1C rate, then charged to a constant voltage of 0.05C, left standing for 5min, and the charge capacity at that time was recorded, i.e., the first charge capacity; then constant-current discharge is carried out to 2.5V at the rate of 0.1C, and then standing is carried out for 5min, wherein the discharge capacity is recorded at the moment, namely the first discharge capacity, as the first cycle of charge-discharge process. The secondary battery is charged to 3.65V according to the constant current of 0.3C multiplying power, then is charged to the current of 0.05C at constant voltage, is kept stand for 5min, records the charging capacity at the moment, is discharged to 2.5V at the constant current of 0.3C multiplying power, is kept stand for 5min, records the discharge capacity at the moment in the second and subsequent cycles, and is subjected to the charge-discharge test for 2-300 cycles according to the method, and records the charge-discharge capacity at each time.
First coulombic efficiency (%) = first discharge capacity/first charge capacity x 100% of the battery, where first charge capacity is the total capacity of the battery that can be charged at a rate of 0.1C (1c=1 hour charge/discharge Chi Eding charge), and first discharge capacity is the total capacity of the battery that can be discharged at a rate of 0.1C.
Capacity retention rate (%) =300 th discharge capacity/first discharge capacity×100%
As can be seen from comparative analysis examples 1 to 5 and comparative example 1, the method for forming a lithium ion battery provided by the application realizes that the structure and components of the solid electrolyte interface film are obviously related to voltage, current and temperature signals by reasonably regulating and matching key parameters in each formation step, thereby realizing accurate and controllable components of the solid electrolyte interface film of the lithium ion battery. The lithium ion battery obtained by the formation method has obviously improved initial coulombic efficiency and cycle performance, which indicates that the formation method can reduce lithium ion consumption in the formation process of the lithium ion battery solid electrolyte interface film, and is beneficial to improving ion conductivity of battery electrode interface and cycle life of the battery.
While the application has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the application. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (12)
1. A method for forming a lithium ion battery, comprising:
a first standing step, namely performing first standing treatment on the lithium ion battery subjected to the liquid injection sealing so as to diffuse the electrolyte;
A first charging step for performing a first constant voltage charging process and a pulse current charging process on the lithium ion battery after the first stationary process, so as to decompose lithium salt in the electrolyte;
the first constant voltage charging process includes:
the lithium ion battery after the first standing treatment is charged for 0.5 to 48 hours at a constant voltage at a second temperature,
Wherein the second temperature is-10-0 ℃;
the voltage of the constant voltage charge is 1.2-1.8V;
the pulse current charging process includes:
The lithium ion battery after the first constant voltage charging treatment is charged by pulse current at a third temperature,
Wherein the third temperature is-10-0 ℃;
the current of the pulse current charging is 0.01-0.1C;
the pulse current is charged for 2-10 times;
the single charging time of the pulse current charging is 0.1-10 s;
A second charging step, which is used for carrying out a second constant voltage charging treatment on the lithium ion battery after the pulse current charging treatment so as to decompose the organic solvent in the electrolyte;
the second constant voltage charging process includes:
The lithium ion battery after the pulse current charging treatment is charged for 0.5 to 48 hours at a constant voltage at a fourth temperature,
Wherein the fourth temperature is-10-0 ℃;
the voltage of the constant voltage charge is 2.2-3.0V;
A second standing step for performing a second standing treatment on the lithium ion battery subjected to the second constant voltage charging treatment, so as to age the solid electrolyte interface film;
And a vacuum exhaust step, which is used for carrying out vacuum exhaust treatment and packaging on the lithium ion battery subjected to the second standing treatment to obtain the formed lithium ion battery.
2. The method of claim 1, wherein the first resting process comprises:
Standing the lithium ion battery after the liquid injection sealing at a first temperature for 6-12 h,
Wherein the first temperature is 40-55 ℃.
3. The method of claim 2, wherein the lithium ion battery after the liquid injection sealing is kept stand for 7 to 11 hours at a first temperature,
Wherein the first temperature is 42-52 ℃.
4. The method according to claim 1, wherein the lithium ion battery after the first stationary treatment is charged at a constant voltage at a second temperature for 1 to 45 hours,
Wherein the second temperature is-9 ℃ to-1 ℃; and/or
The voltage of the constant voltage charge is 1.3-1.7V.
5. The method of claim 1, wherein the pulsed current charging process comprises:
The lithium ion battery after the first constant voltage charging treatment is charged by pulse current at a third temperature,
Wherein the third temperature is-9 ℃ to-1 ℃; and/or
The current of the pulse current charging is 0.02-0.08 ℃; and/or
The pulse current is charged for 3-8 times; and/or
The single charging time of the pulse current charging is 0.5-8 s.
6. The method of claim 1, wherein the second constant voltage charging process comprises:
The lithium ion battery after the pulse current charging treatment is charged for 1 to 45 hours at a constant voltage at a fourth temperature,
Wherein the fourth temperature is-9 ℃ to-1 ℃; and/or
The voltage of the constant voltage charge is 2.3-2.8V.
7. The method of claim 1, wherein the second resting process comprises:
standing the lithium ion battery subjected to the second constant voltage charging treatment for 1-24 hours at a fifth temperature,
Wherein the fifth temperature is 40-60 ℃.
8. The method of claim 7, wherein the second resting process comprises:
Standing the lithium ion battery subjected to the second constant voltage charging treatment for 5-20 h at a fifth temperature,
Wherein the fifth temperature is 45-55 ℃.
9. The method according to claim 1, wherein the vacuum degree of the vacuum evacuation treatment is 0.1 to 0.8MPa; and/or
The time of the vacuum exhaust treatment is 3-20 s.
10. The method according to claim 9, wherein the vacuum degree of the vacuum evacuation treatment is 0.2 to 0.7MPa; and/or
The time of the vacuum exhaust treatment is 5-18 s.
11. A lithium ion battery made by the method of any one of claims 1-10.
12. The lithium-ion battery of claim 11, wherein the positive electrode active material of the lithium-ion battery is lithium iron phosphate; and/or
The negative active material of the lithium ion battery comprises one or more of graphite, silicon carbon, lithium carbon and lithium; and/or
The lithium salt in the lithium ion battery electrolyte comprises one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonyl imide and lithium tetrafluoroborate; and/or
The organic solvent in the lithium ion battery electrolyte comprises one or more of ethylene carbonate, fluoroethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate.
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| CN109616711A (en) * | 2018-12-18 | 2019-04-12 | 国联汽车动力电池研究院有限责任公司 | A kind of pulse formation method for lithium ion battery |
| CN110661049A (en) * | 2019-08-21 | 2020-01-07 | 中国电力科学研究院有限公司 | Formation method and device for improving cycle stability of lithium ion battery |
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