CN114094167A - Battery with improved battery capacity - Google Patents
Battery with improved battery capacity Download PDFInfo
- Publication number
- CN114094167A CN114094167A CN202111396648.1A CN202111396648A CN114094167A CN 114094167 A CN114094167 A CN 114094167A CN 202111396648 A CN202111396648 A CN 202111396648A CN 114094167 A CN114094167 A CN 114094167A
- Authority
- CN
- China
- Prior art keywords
- carbonate
- battery
- positive plate
- adhesive tape
- meth
- Prior art date
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- Granted
Links
- 239000002390 adhesive tape Substances 0.000 claims abstract description 48
- 239000012790 adhesive layer Substances 0.000 claims abstract description 28
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 9
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000002000 Electrolyte additive Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001774 Perfluoroether Polymers 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 claims description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- WVCXIIOIWJECBJ-UHFFFAOYSA-N FC(CF)(F)C(C(C(F)(F)F)(F)F)OC(C(C(F)(F)F)(F)F)C(CF)(F)F Chemical group FC(CF)(F)C(C(C(F)(F)F)(F)F)OC(C(C(F)(F)F)(F)F)C(CF)(F)F WVCXIIOIWJECBJ-UHFFFAOYSA-N 0.000 claims description 2
- KAEZJNCYNQVWRB-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] KAEZJNCYNQVWRB-UHFFFAOYSA-K 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052744 lithium Inorganic materials 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 238000001556 precipitation Methods 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- -1 polyethylene terephthalate Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-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
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005912 ethyl carbonate group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
Abstract
The invention provides a battery. The battery can effectively improve the high-temperature performance of the battery cell prepared by the synergistic effect of the positive plate termination adhesive tape and fluoroethylene carbonate in the non-aqueous electrolyte, and simultaneously can solve the problem of lithium precipitation at the edge of the positive plate after the battery cell is circulated, thereby avoiding the problems of failure of high-temperature storage thickness of the battery cell and lithium precipitation in high-temperature circulation caused by the upwarp deformation of the positive plate termination adhesive tape in the high-temperature environment of the battery, easy dissolution of the adhesive layer of the positive plate termination adhesive tape in the electrolyte, easy redox decomposition of the electrolyte at the positive and negative electrode interfaces, and the like.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a high-voltage battery with excellent high-temperature performance.
Background
In recent years, batteries have been widely used in the fields of smart phones, tablet computers, smart wearing, electric tools, electric vehicles, and the like. With the widespread use of batteries, consumer demands for energy density and use environment of batteries are increasing, which requires that batteries have excellent high-temperature safety performance at high voltage.
At present, potential safety hazards exist in the use process of the battery, for example, serious safety accidents easily occur under some extreme use conditions such as continuous high temperature and the like of the battery, and a battery core is deformed and ignited and even explodes. The main reasons for these problems are that the adhesive layer of the battery pole piece termination adhesive tape is easily dissolved in the electrolyte at high temperature and high pressure and loses the cohesiveness, so that the adhesive tape cannot effectively fix the battery pole piece termination adhesive tape, and the battery pole piece is locally deformed and warped or short-circuited to cause safety accidents; on the other hand, the electrolyte is easy to decompose at high temperature and high voltage, and oxidation-reduction decomposition occurs on the surfaces of the positive electrode and the negative electrode to damage an SEI film, so that the impedance of the battery cell is continuously increased, and the performance of the battery cell is deteriorated.
Disclosure of Invention
The invention aims to solve the problems that the high-temperature storage thickness of a battery core is invalid and lithium is separated out in a high-temperature cycle manner due to the warping deformation of a positive plate termination adhesive tape when the conventional battery is used in a high-temperature environment, a glue layer in the positive plate termination adhesive tape is easily soluble in a non-aqueous electrolyte, the non-aqueous electrolyte is easily oxidized, reduced and decomposed on positive and negative electrode interfaces, and the like, and provides a battery which is a high-voltage battery and has excellent high-temperature performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a battery includes a positive electrode sheet, a negative electrode sheet, a nonaqueous electrolytic solution, and a separator;
a positive plate termination adhesive tape is arranged at the paste coating tail part of the positive plate;
the non-aqueous electrolyte comprises a non-aqueous organic solvent, an electrolyte additive and a lithium salt, wherein the electrolyte additive comprises fluoroethylene carbonate;
the area of the positive plate termination adhesive tape is A cm2The fluoroethylene carbonate accounts for B wt%, the width of the positive plate is C cm, and the ratio of A to B is 0.5-5; the ratio of A to C is in the range of 1-3;
the positive plate termination adhesive tape comprises a PET (polyethylene terephthalate) base material and a (methyl) acrylic acid termination adhesive layer coated on the surface of the PET base material.
In the present invention, the (meth) acrylic acid means acrylic acid and/or methacrylic acid.
In the battery, the number of the positive plate termination adhesive tapes is two, namely, one positive plate termination adhesive tape is arranged on each of the two side surfaces of the positive current collector in the positive plate, and the area A of each positive plate termination adhesive tape is the area of the positive plate termination adhesive tape arranged on the surface of one side of the positive current collector in the positive plate. Further, the areas of the positive plate termination tapes arranged on the two side surfaces of the positive current collector in the positive plate are the same.
According to the invention, the ratio of A to B is 0.5, 0.8, 1, 1.2, 1.4, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.5, 5 or any point in the range formed by the two endpoints. When the ratio of A to B is in the range of 0.5-5, the fluoroethylene carbonate in the non-aqueous electrolyte and the positive plate stop adhesive tape can have better synergistic effect; specifically, the fluoroethylene carbonate belongs to a carbonate compound, has larger viscosity, large intermolecular dipole moment and strong polarity, the (methyl) acrylic acid terminated adhesive layer belongs to a carboxylate compound, the different structural species and the different compatibility of the two are poor, when the ratio of A to B is in the range of 0.5-5, the large intermolecular dipole moment and the strong polarity of the fluoroethylene carbonate can strengthen the intermolecular acting force of the (methyl) acrylic acid terminated adhesive layer, can better inhibit the dissolution and dispersion of the (methyl) acrylic acid terminated adhesive layer after soaking in an electrolyte, keep better viscosity and reduce the liquefaction and the flow of the (methyl) acrylic acid terminated adhesive layer, ensure that the (methyl) acrylic acid terminated adhesive layer keeps better viscosity, delay the aging failure of the positive plate terminated adhesive tape, avoid the (methyl) acrylic acid terminated adhesive layer from overflowing the positive plate terminated adhesive tape and covering the surface of a positive active substance to cause hole blockage, the deformation of the battery cell caused by the upwarp of the positive plate stopping adhesive tape after the battery cell is stored at high temperature is improved, and the problems of lithium precipitation at the edge caused by hole blocking and the like in the battery cell circulation process are solved.
According to the invention, the ratio of A to C is 1, 1.2, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.5, 3 or any point in the range of the two endpoints. When the ratio of A to C is in the range of 1-3, the adhesive layer area of the positive plate stopping adhesive tape is more reasonably covered on the surfaces of the coating paste and the hollow foil, so that the influence of the electrolyte on the adhesive layer is reduced.
According to the invention, the paste coating tail part of the positive plate is provided with the positive plate termination adhesive tape, and the positive plate termination adhesive tape can fix the tail part of the battery core and cover burrs of the edge cutting of the positive plate, so that the short circuit of the battery is prevented, and the insulation protection effect is achieved.
According to the invention, the area A of the positive plate termination adhesive tape is 3-120 cm2Between the ranges; illustratively, the area A of the positive electrode tab termination tape is 3cm2、5cm2、10cm2、20cm2、30cm2、40cm2、50cm2、60cm2、70cm2、80cm2、90cm2、100cm2、110cm2、120cm2Or any point in the range defined by any two of the endpoints.
According to the invention, the width C of the positive plate is within the range of 1-120 cm; illustratively, the width C of the positive electrode sheet is 1cm, 3cm, 5cm, 6cm, 8cm, 10cm, 16cm, 20cm, 30cm, 40cm, 50cm, 60cm, 70cm, 80cm, 90cm, 100cm, 110cm, 120cm or any point in the range of the two endpoints.
According to the invention, the thickness of the positive plate termination adhesive tape is 8-20 μm.
According to the invention, the (meth) acrylic stop glue layer comprises a cross-linking modified (meth) acrylic acid and/or a cross-linking modified (meth) acrylate.
According to the invention, the crosslinking agent which crosslinks the modified (meth) acrylic acid and/or crosslinks the modified (meth) acrylate comprises vinylene carbonate.
According to the invention, the (meth) acrylic esters are chosen from (meth) acrylic acid C1-10Alkyl esters illustratively selected from at least one of isooctyl acrylate, n-butyl acrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, and the like.
According to the invention, the vinylene carbonate is present in an amount of 0.5 to 5 wt.%, for example 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 1.2 wt.%, 1.5 wt.%, 1.8 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 3.8 wt.%, 4 wt.%, 4.5 wt.% or 5 wt.%, based on the mass of the cross-linked modified (meth) acrylic acid and/or the cross-linked modified (meth) acrylate.
According to the invention, the (meth) acrylic acid stop glue layer further comprises an auxiliary agent, for example, at least one selected from an antioxidant, an inorganic filler and the like.
According to the invention, the antioxidant is a conventionally used antioxidant suitable for crosslinking-modified (meth) acrylic acid and/or crosslinking-modified (meth) acrylic esters.
According to the invention, the inorganic filler is a conventionally used inorganic filler suitable for crosslinking-modified (meth) acrylic acid and/or crosslinking-modified (meth) acrylic esters.
According to the invention, the mass percentage of the fluoroethylene carbonate is the mass percentage of the fluoroethylene carbonate to the total mass of the nonaqueous electrolyte.
According to the invention, the fluoroethylene carbonate accounts for 5-30 wt%; preferably, the fluoroethylene carbonate accounts for 5-10 wt%. Illustratively, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 12 wt.%, 15 wt.%, 18 wt.%, 20 wt.%, 22 wt.%, 25 wt.%, 28 wt.%, or 30 wt.%.
According to the invention, the electrolyte additive also comprises at least one of 1, 3-propane sultone, 1, 3-propene sultone, fluoroethylene carbonate, ethylene sulfite, ethylene sulfate, lithium dioxalate borate, lithium difluorophosphate, lithium difluorooxalate phosphate and vinyl ethylene carbonate, and the content of the at least one is 0-10 wt% of the total mass of the nonaqueous electrolyte.
According to the invention, the non-aqueous organic solvent is selected from at least one of carbonate, carboxylic ester and fluoroether, wherein the carbonate is selected from one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and methyl propyl carbonate; the carboxylic ester is selected from one or more of ethyl propionate and propyl propionate; the fluoroether is selected from 1,1,2, 3-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether.
According to the invention, the lithium salt is selected from at least one of lithium bistrifluoromethylsulfonyl imide, lithium bisfluorosulfonyl imide and lithium hexafluorophosphate.
According to the invention, the concentration of the lithium salt is 1-2 mol/L.
According to the invention, the positive plate comprises a positive current collector and a positive active material layer coated on one side or two sides of the positive current collector, the positive active material layer comprises a positive active material, a conductive agent and a binder,
the positive active material is selected from lithium cobaltate or lithium cobaltate subjected to doping coating treatment of two or more elements of Al, Mg, Mn, Cr, Ti and Zr, and the chemical formula of the lithium cobaltate subjected to doping coating treatment of two or more elements of Al, Mg, Mn, Cr, Ti and Zr is LixCo1-y1-y2-y3-y4Ay1By2Cy3Dy4O2(ii) a X is more than or equal to 0.95 and less than or equal to 1.05, y1 is more than or equal to 0.01 and less than or equal to 0.1, y2 is more than or equal to 0.1, y3 is more than or equal to 0.1, y4 is more than or equal to 0 and less than or equal to 0.1, and A, B, C, D is selected from two or more elements of Al, Mg, Mn, Cr, Ti and Zr.
According to the present invention, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder,
the negative active material is selected from graphite or a graphite composite material containing 1-12 wt% of SiOx/C or Si/C.
According to the present invention, the charge cut-off voltage of the battery is 4.45V or more.
According to the invention, the battery is a lithium ion battery.
In the present invention, the term "between … … ranges" includes the endpoints, exemplarily "between 0.5 and 5 ranges" and means 0.5 or more and 5 or less.
The invention has the beneficial effects that:
the present invention provides a battery which is a high voltage type battery and has excellent high temperature performance. The inventor of the invention finds that the high-temperature performance of the battery cell prepared by the method can be effectively improved by the synergistic effect of the positive plate termination adhesive tape and fluoroethylene carbonate in the non-aqueous electrolyte, and the problem of lithium precipitation at the edge of the positive plate after the battery cell is circulated can be solved, so that the problems of failure of high-temperature storage thickness of the battery cell, lithium precipitation in high-temperature circulation, easy dissolution of the adhesive layer of the positive plate termination adhesive tape in the electrolyte, easy redox decomposition of the electrolyte at the positive and negative electrode interfaces and the like caused by the upwarp deformation of the positive plate termination adhesive tape when the battery is used in a high-temperature environment are avoided.
In the invention, the fluoroethylene carbonate in the non-aqueous electrolyte and the positive plate termination adhesive tape have a synergistic effect; specifically, the fluoroethylene carbonate belongs to a carbonate compound, has larger viscosity, large intermolecular dipole moment and strong polarity, the (methyl) acrylic acid terminated adhesive layer belongs to a carboxylate compound, the different structural species and the different compatibility of the two are poor, when the ratio of A to B is in the range of 0.5-5, the large intermolecular dipole moment and the strong polarity of the fluoroethylene carbonate can strengthen the intermolecular acting force of the (methyl) acrylic acid terminated adhesive layer, can better inhibit the dissolution and dispersion of the (methyl) acrylic acid terminated adhesive layer after soaking in an electrolyte, keep better viscosity and reduce the liquefaction and the flow of the (methyl) acrylic acid terminated adhesive layer, ensure that the (methyl) acrylic acid terminated adhesive layer keeps better viscosity, delay the aging failure of the positive plate terminated adhesive tape, avoid the (methyl) acrylic acid terminated adhesive layer from overflowing the positive plate terminated adhesive tape and covering the surface of a positive active substance to cause hole blockage, the deformation of the battery cell caused by the upwarp of the positive plate termination adhesive tape after the battery cell is stored at high temperature is improved, and the problems of lithium precipitation at the edge caused by hole plugging in the battery cell circulation process and the like are solved.
Meanwhile, the fluoroethyl carbonate can form firmer SEI films on the surfaces of the positive electrode and the negative electrode, stabilize the interfaces of the positive electrode and the negative electrode under high temperature and high pressure, reduce side reactions and the generation of hydrofluoric acid, avoid the corrosion damage of the hydrofluoric acid to the (methyl) acrylic acid termination adhesive layer, further slow down the aging failure of the (methyl) acrylic acid termination adhesive layer when the positive electrode plate termination adhesive tape is soaked in the non-aqueous electrolyte, avoid the (methyl) acrylic acid termination adhesive layer from overflowing the positive electrode plate termination adhesive tape and covering the surface of a positive electrode active substance to cause hole blockage, improve the deformation of the battery cell caused by the upwarp of the positive electrode plate termination adhesive tape after the battery cell is stored at high temperature, and simultaneously improve the problems of lithium precipitation at the edge caused by the hole blockage in the battery cell circulation process and the like.
Furthermore, the (methyl) acrylic acid termination adhesive layer in the positive termination adhesive tape contains vinylene carbonate which can participate in acrylic acid cross-linking polymerization, so that the acrylic acid termination adhesive layer contains an ethyl carbonate structure branched chain, the acrylic acid termination adhesive layer is more resistant to high temperature and high pressure, the adhesive layer structure is stabilized, and the high-temperature performance of the battery cell is further improved.
Drawings
Fig. 1 is a schematic structural view of a positive electrode sheet according to a preferred embodiment of the present invention.
Fig. 2 is a schematic structural view of a positive electrode sheet according to another preferred embodiment of the present invention.
Fig. 3 is a side view of the positive electrode tab shown in fig. 2.
Reference numerals: 1-the head of the positive plate; 2-the tail part of the positive plate; 3-empty foil area; 4, stopping the adhesive tape on the positive plate; 5, the tail part of the positive plate on one surface; 6, terminating the adhesive tape on the positive plate on one side; 7-the tail part of the positive plate on the other side; 8-the other side positive plate is terminated with adhesive tape.
Detailed Description
In the present invention, the "positive electrode tab terminating tape" refers to a tape provided at the tail of a paste (e.g., a positive electrode active material layer) on the surface of a positive electrode current collector in a positive electrode tab, and the positive electrode tab terminating tape partially covers the paste on the surface of the positive electrode current collector and partially covers the surface of the positive electrode current collector (i.e., a blank foil on the surface of the positive electrode current collector), as specifically shown in fig. 1 to 3.
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Comparative examples 1 to 6 and examples 1 to 6
The lithium ion batteries of comparative examples 1 to 6 and examples 1 to 6 were manufactured in the following manner, differing only in the positive electrode tab terminating tape and the nonaqueous electrolytic solution at the tail of the paste application of the positive electrode tab, as shown in table 1.
(1) Preparation of positive plate
LiCoO as positive electrode active material2Mixing polyvinylidene fluoride (PVDF) serving as a binder and acetylene black serving as a conductive agent according to the weight ratio of 97.2:1.3:1.5, adding N-methylpyrrolidone (NMP), and stirring under the action of a vacuum stirrer until a mixed system becomes uniform and flowable anode slurry; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 9-12 mu m; baking the coated aluminum foil in 5 sections of baking ovens with different temperature gradients, drying the aluminum foil in a baking oven at 120 ℃ for 8 hours, rolling and slitting to obtain the required positive plates with different sizes, wherein the specific width of each plate is shown in table 1.
(2) Preparation of negative plate
Preparing a slurry from an artificial graphite negative electrode material with the mass ratio of 96.5%, a single-walled carbon nanotube (SWCNT) conductive agent with the mass ratio of 0.1%, a conductive carbon black (SP) conductive agent with the mass ratio of 1%, a sodium carboxymethylcellulose (CMC) binder with the mass ratio of 1% and a Styrene Butadiene Rubber (SBR) binder with the mass ratio of 1.4% by a wet process, coating the slurry on the surface of a negative current collector copper foil, drying (the temperature is 85 ℃, the time is 5h), rolling and die cutting to obtain negative electrode sheets with different sizes.
(3) Preparation of non-aqueous electrolyte
In a glove box filled with argon (moisture)<10ppm, oxygen content<1ppm), Ethylene Carbonate (EC), Propylene Carbonate (PC), Propyl Propionate (PP), Ethyl Propionate (EP) were mixed uniformly in a mass ratio of 1:1:3:2, and 13 wt.% of LiPF based on the total mass of the nonaqueous electrolyte solution was slowly added to the mixed solution6And additives (the specific amount and selection of the additives are shown in table 1), and uniformly stirring to obtain the nonaqueous electrolytic solution.
(4) Preparation of separator
Selecting a polyethylene diaphragm with the thickness of 7-9 mu m.
(5) Preparation of positive plate termination adhesive tape
The method comprises the following steps of uniformly stirring 38 parts by weight of isooctyl acrylate, 3 parts by weight of butyl acrylate, 3 parts by weight of vinyl acetate, 3 parts by weight of acrylic acid, 5 parts by weight of isoprene rubber, 1 part by weight of pentaerythritol trimethacrylate, 1 part by weight of azobisisobutyronitrile and 36 parts by weight of ethyl ester at the temperature of 80 ℃ to obtain a mixed solution, then adding a certain part by weight of a crosslinking agent vinylene carbonate into the mixed solution, uniformly stirring at normal temperature, uniformly mixing, and coating the mixed solution on the surface of a PET (polyethylene terephthalate) substrate to obtain the anode plate termination adhesive tape. The positive plate termination adhesive tape comprises a PET (polyethylene terephthalate) base material and a (methyl) acrylic acid termination adhesive layer coated on the surface of the PET base material, wherein the specific dosage of vinylene carbonate in the (methyl) acrylic acid termination adhesive layer is shown in table 1, and the area of the positive plate termination adhesive tape is shown in table 1.
(6) Preparation of lithium ion battery
Winding the prepared positive plate, the diaphragm and the negative plate, and pasting a positive plate termination adhesive tape at the ending part of the positive plate (the areas of the positive plate termination adhesive tapes on the two sides of the positive current collector are the same), so as to obtain a naked battery cell without liquid injection; placing the bare cell in an outer packaging foil, injecting the prepared electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation, shaping, sorting and other processes to obtain the required lithium ion battery.
TABLE 1 lithium ion batteries prepared in comparative examples 1 to 6 and examples 1 to 6
The cells obtained in the above comparative examples and examples were subjected to electrochemical performance tests, as described below:
45 ℃ cycling experiment: the batteries obtained in the above examples and comparative examples were placed at (45. + -. 2) ℃ and left to stand for 2-3 hours, when the body of the battery reaches (45 +/-2) DEG C, the battery is charged according to a constant current of 1C and the cut-off current is 0.05C, the battery is placed for 5 minutes after being fully charged, then the battery is discharged to the cut-off voltage of 3.0V according to a constant current of 0.7C, the highest discharge capacity of the previous 3 cycles is recorded as the initial capacity Q, and when the cycles reach 400 times, the last discharge capacity Q of the battery is recorded1And the disassembly cycle 400T battery records whether the lithium is separated from the battery edge, and the recording result is shown in Table 2.
The calculation formula used therein is as follows: capacity retention (%) ═ Q1/Q×100％。
High temperature storage at 85 ℃ for 6 hours experiment: the cells obtained in the above examples and comparative examples were subjected to a charge-discharge cycle test at a charge-discharge rate of 0.5C for 3 times at room temperature, and then charged to a full charge state at a rate of 0.5C, and the maximum discharge capacity Q of the previous 0.5C cycles was recorded2And battery thickness T1. The fully charged cells were stored at 85 ℃ for 6 hours and the cell thickness T after 6 hours was recorded2And 0.5C discharge capacity Q3And calculating to obtain experimental data such as the thickness change rate, the capacity retention rate and the like of the battery stored at high temperature, and recording the results as shown in table 2.
The calculation formula used therein is as follows:
capacity retention (%) ═ Q3/Q2X is 100%; thickness change rate (%) - (T)2-T1)/T1×100％
Thermal shock test at 130 ℃: the batteries obtained in the above examples and comparative examples were heated at an initial temperature of 25. + -. 3 ℃ by convection or a circulating hot air oven at a temperature change rate of 5. + -. 2 ℃/min, heated to 130. + -. 2 ℃ and held for 60min, and the test was terminated, and the results of the battery state were recorded as shown in Table 2.
TABLE 2 experimental test results of the batteries obtained in comparative examples 1 to 5 and examples 1 to 7
As can be seen from the results of table 2: according to the comparative example and the embodiment, the synergistic effect of the fluoroethylene carbonate and the positive plate termination adhesive tape is added into the electrolyte, so that the prepared battery can effectively improve the high-temperature performance of the battery cell and simultaneously solve the problem of lithium precipitation at the edge of the pole piece after the battery cell is circulated.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A battery includes a positive electrode sheet, a negative electrode sheet, a nonaqueous electrolytic solution, and a separator;
a positive plate termination adhesive tape is arranged at the paste coating tail part of the positive plate;
the non-aqueous electrolyte comprises a non-aqueous organic solvent, an electrolyte additive and a lithium salt, wherein the electrolyte additive comprises fluoroethylene carbonate;
the area of the positive plate termination adhesive tape is A cm2The fluoroethylene carbonate accounts for B wt%, the width of the positive plate is C cm, and the ratio of A to B is 0.5-5; the ratio of A to C is in the range of 1-3;
the positive plate termination adhesive tape comprises a PET base material and a (methyl) acrylic acid termination adhesive layer coated on the surface of the PET base material.
2. The battery according to claim 1, wherein the positive electrode tab termination tape has an area A of 3cm2～120cm2Between the ranges.
3. The battery according to claim 1 or 2, wherein the width C of the positive electrode sheet is in the range of 1cm to 120 cm.
4. A battery according to any one of claims 1 to 3, wherein the fluoroethylene carbonate is present in an amount of 5 to 30 wt.%.
5. The battery according to claim 4, wherein the fluoroethylene carbonate is present in an amount of 5 to 10 wt%.
6. The battery of any of claims 1-5, wherein the (meth) acrylic stop gum layer comprises a cross-linked modified (meth) acrylic acid and/or a cross-linked modified (meth) acrylate, and the cross-linking agent that cross-links the modified (meth) acrylic acid and/or the cross-linked modified (meth) acrylate comprises vinylene carbonate.
7. The battery according to claim 6, wherein the vinylene carbonate content is 0.5-5 wt.% of the mass of the cross-linked modified (meth) acrylic acid and/or the cross-linked modified (meth) acrylate.
8. The battery according to any one of claims 1 to 7, wherein the electrolyte additive further comprises at least one of 1, 3-propane sultone, 1, 3-propene sultone, ethylene sulfite, vinyl sulfate, lithium dioxalate borate, lithium difluorophosphate, lithium difluorooxalate phosphate and vinyl ethylene carbonate, and the content thereof is 0 to 10 wt% of the total mass of the nonaqueous electrolyte.
9. The battery according to any one of claims 1 to 8, wherein the non-aqueous organic solvent is selected from at least one of carbonate, carboxylic ester and fluoroether, wherein the carbonate is selected from one or more combinations of ethylene carbonate, propylene carbonate, fluoroethylene carbonate, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, methylpropyl carbonate; the carboxylic ester is selected from one or more of ethyl propionate and propyl propionate; the fluoroether is selected from 1,1,2, 3-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether.
10. The battery according to any one of claims 1 to 9, wherein the charge cut-off voltage of the battery is 4.45V or more.
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