CN117832584A - Electrochemical device and electronic device - Google Patents
Electrochemical device and electronic device Download PDFInfo
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- CN117832584A CN117832584A CN202211200167.3A CN202211200167A CN117832584A CN 117832584 A CN117832584 A CN 117832584A CN 202211200167 A CN202211200167 A CN 202211200167A CN 117832584 A CN117832584 A CN 117832584A
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- positive electrode
- electrochemical device
- current collector
- lithium
- fluorine
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- 239000003792 electrolyte Substances 0.000 claims abstract description 63
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000011737 fluorine Substances 0.000 claims abstract description 57
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 57
- 239000007774 positive electrode material Substances 0.000 claims abstract description 46
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000011888 foil Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- -1 bis (2-fluoroethyl) ethylene carbonate Chemical compound 0.000 claims description 32
- 239000000654 additive Substances 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims description 14
- 159000000002 lithium salts Chemical class 0.000 claims description 14
- 238000004804 winding Methods 0.000 claims description 13
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000003475 lamination Methods 0.000 claims description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 5
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- SLWDKUKGSGLZNC-UHFFFAOYSA-N C(O)(O)=O.FC(C=CC(F)(F)F)(F)F Chemical compound C(O)(O)=O.FC(C=CC(F)(F)F)(F)F SLWDKUKGSGLZNC-UHFFFAOYSA-N 0.000 claims description 3
- ZBXZQKULYKAQRY-UHFFFAOYSA-N carbonic acid 1,1,4,4-tetrafluorobut-2-ene Chemical compound OC(O)=O.FC(F)C=CC(F)F ZBXZQKULYKAQRY-UHFFFAOYSA-N 0.000 claims description 3
- AWKSWTTXGDTMQV-UHFFFAOYSA-N carbonic acid 1,4-difluorobut-2-ene Chemical compound OC(O)=O.FCC=CCF AWKSWTTXGDTMQV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- 125000005463 sulfonylimide group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 30
- 230000008569 process Effects 0.000 abstract description 21
- 238000013461 design Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 55
- 229910001416 lithium ion Inorganic materials 0.000 description 55
- 230000002159 abnormal effect Effects 0.000 description 34
- 230000005856 abnormality Effects 0.000 description 19
- 239000006227 byproduct Substances 0.000 description 18
- 239000006183 anode active material Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000001105 regulatory effect Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 9
- 239000011267 electrode slurry Substances 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- 238000003825 pressing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- 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 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-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
- 230000004075 alteration Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BVWQQMASDVGFGI-UHFFFAOYSA-N ethene propyl hydrogen carbonate Chemical compound C(CC)OC(O)=O.C=C BVWQQMASDVGFGI-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 238000009461 vacuum packaging Methods 0.000 description 1
Abstract
The application provides an electrochemical device and electron device, electrochemical device include electrode assembly and electrolyte, and the electrolyte includes fluorine-containing compound, and electrode assembly includes positive pole piece, negative pole piece and diaphragm, and the diaphragm sets up between positive pole piece and negative pole piece, and electrode assembly is by positive pole piece, diaphragm and the range upon range of setting of negative pole piece. The positive electrode plate comprises a positive electrode current collector and a positive electrode active material layer, wherein the positive electrode current collector is aluminum foil and further comprises silicon element; the positive electrode current collector comprises a first surface and a second surface which are opposite, the positive electrode current collector is provided with a single-sided area, the first surface of the single-sided area is provided with a positive electrode active material layer, the second surface of the single-sided area is not provided with the positive electrode active material layer, the single-sided area comprises a first part, the second surface of the first part is positioned on the outer surface of the electrode assembly, and the first part is provided with a through hole extending along the direction from the second surface to the first surface. Through the design, the risk of failure of the electrochemical device in the charge-discharge cycle process can be reduced.
Description
Technical Field
The present disclosure relates to the field of electrochemical technology, and in particular, to an electrochemical device and an electronic device.
Background
The electrode assembly in the existing secondary battery (such as a lithium ion battery) mostly has a bare positive electrode current collector (usually aluminum foil is selected), for example, a winding structure of which the positive electrode current collector is terminated, a winding structure of die-cut aluminum tab, or a lamination structure of which the positive electrode single-sided area is terminated. Along with the continuous promotion of lithium ion battery voltage system, the oxidation capability of positive pole piece to electrolyte when full charge also continuously strengthens, in order to reduce the oxidation of positive pole piece to electrolyte, the protection effect to positive pole piece and negative pole piece under the high voltage is often improved through the content of fluorine-containing compound in the continuous increase electrolyte to prior art.
However, fluorine-containing compounds such as fluorine-containing additives and fluorine-containing lithium salts tend to decompose in the electrolyte to produce Lewis acids (e.g., PF 5 ) The reaction of F removal occurs under the action of (C) to produce HF. In this case, after the lithium ion battery is injected, the electrolyte is in contact with the exposed positive electrode current collector, HF in the electrolyte and the positive electrode current collector are easy to react to generate impurities, and the generated impurities diffuse along with the electrolyte in the lithium ion battery and are accumulated in a specific area of the positive electrode plate (for example, the edge position of the positive active material layer arranged in a single-sided area of the positive electrode current collector), so that the positive electrode plate is abnormal, lithium precipitation of the negative electrode plate is affected, and the lithium ion battery is invalid in the charge-discharge cycle. Based on this, how to reduce the risk of failure of the lithium ion battery during the charge-discharge cycle becomes a technical problem to be solved by those skilled in the art.
Disclosure of Invention
An object of the present application is to provide an electrochemical device and an electronic device to reduce the risk of failure of the electrochemical device during charge-discharge cycles.
In the context of the present application, the present application is explained using a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery. The specific technical scheme is as follows:
the first aspect of the present application provides an electrochemical device, which comprises an electrode assembly and an electrolyte, wherein the electrolyte comprises a fluorine-containing compound, the electrode assembly comprises a positive electrode plate, a negative electrode plate and a diaphragm, the diaphragm is arranged between the positive electrode plate and the negative electrode plate, and the electrode assembly is formed by laminating the positive electrode plate, the diaphragm and the negative electrode plate. The positive electrode plate comprises a positive electrode current collector and a positive electrode active material layer, wherein the positive electrode current collector is aluminum foil and further comprises silicon element; the positive electrode current collector comprises a first surface and a second surface which are opposite, the positive electrode current collector is provided with a single-sided area, the first surface of the single-sided area is provided with a positive electrode active material layer, and the second surface of the single-sided area is not provided with the positive electrode active material layer. The single-sided region includes a first portion, a second surface of which is located at an outer surface of the electrode assembly, and the first portion is provided with a through hole extending in a direction from the second surface to the first surface. Through the design, the by-product generated by the reaction of the electrolyte and the positive electrode current collector or the positive electrode active material layer in the injection liquid formation process or the charge-discharge cycle process of the electrochemical device is directly attached to the through hole, can react with the positive electrode plate in situ, and reduces the aggregation risk of the by-product in a specific area or other areas of the positive electrode plate. Therefore, the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle process is reduced.
In one embodiment of the present application, the mass percentage of silicon element in the positive electrode current collector is e.0.03 < e.ltoreq.0.13. The fluorine-containing compound comprises a fluorine-containing additive, wherein the mass percentage of the fluorine-containing additive in the electrolyte is f% which is more than or equal to 0.1 and less than or equal to 40.0. When the electrolyte comprises a fluorine-containing additive and the mass percentage of the fluorine-containing additive in the electrolyte is regulated and controlled within the range, the protection capability of the electrolyte to the negative electrode plate can be enhanced by selecting the positive current collector with the silicon-containing element content range, and a uniform and compact protection film is formed on the surface of the negative electrode plate, so that the cycle performance of an electrochemical device is improved; meanwhile, the content of a byproduct fluorine silicon compound generated by the reaction of HF in the electrolyte and silicon element in the positive electrode current collector is reduced. In this way, the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle is reduced.
In one embodiment of the present application, 0.5.ltoreq.fe.ltoreq.3.6. Preferably, 0.5.ltoreq.fe2.4. And the value of fe is regulated and controlled within the range, and the mass percentage of silicon element in the positive electrode current collector is matched with the mass percentage of fluorine-containing additive in the electrolyte, so that the risk of failure of the electrochemical device in the charge-discharge cycle process is reduced.
In one embodiment of the present application, the cross-sectional area of the through hole is b mm 2 B is more than or equal to 0.1 and less than or equal to 1.0. The sectional area of the through hole is regulated and controlled within the range, so that the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle process is reduced.
In one embodiment of the present application, the number of through holes is plural, calculated as the area of the second surface of the first portion, and the number of through holes per unit area is d/cm 2 D is more than or equal to 2 and less than or equal to 10. Preferably, 6.ltoreq.d.ltoreq.10. The number of through holes in the unit area of the second surface of the first part is regulated and controlled within the range, and the abnormal risk of the positive electrode plate is reduced, so that the failure risk of the electrochemical device in the charge-discharge cycle process is reduced.
In one embodiment of the present application, 0 < f/(db). Ltoreq.100. Preferably, 0 < f/(db) 60. The value f/(db) is regulated and controlled within the range, so that the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle process is further reduced.
In one embodiment of the present application, the fluorine-containing additive includes at least one of fluoroethylene carbonate, bis (fluoromethyl) ethylene carbonate, bis (difluoromethyl) ethylene carbonate, bis (trifluoromethyl) ethylene carbonate, bis (2-fluoroethyl) ethylene carbonate, bis (2, 2-difluoroethyl) ethylene carbonate, bis (2, 2-trifluoroethyl) ethylene carbonate, 2-fluoroethyl methyl ethylene carbonate, 2-difluoroethyl methyl ethylene carbonate, or 2, 2-trifluoroethyl methyl ethylene carbonate. The fluorine-containing additive is more beneficial to weakening the oxidizing capacity of the positive electrode plate to the electrolyte, and uniform and compact protective films are formed on the surfaces of the positive electrode plate and the negative electrode plate to protect the positive electrode plate and the negative electrode plate.
In one embodiment of the present application, the fluorine-containing compound further includes a fluorine-containing lithium salt including at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium bis (trifluoromethane) sulfonimide, lithium difluorosulfonimide, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium perfluorobutyl sulfonate, lithium bissulfonimide, or lithium fluoride. The addition of the fluorine-containing lithium salt is more beneficial to providing high ionic conductivity, so that the transmission rate of lithium ions is faster.
In one embodiment of the present application, the structure of the electrode assembly is a lamination stack; or the structure of the electrode assembly is a winding structure, the positive current collector further comprises a double-sided area, and the double-sided area and the single-sided area are sequentially connected along the winding direction.
In one embodiment of the present application, the through hole is formed by punching in a direction from the second surface to the first surface. In this way, the risk of contact between the burrs and the packaging bag can be reduced, so that the packaging bag is prevented from being pierced by the burrs generated by the through holes, and the packaging performance and the safety performance of the electrochemical device are improved.
In one embodiment of the present application, the electrochemical device further includes a pouch containing the electrode assembly and the electrolyte, and the first portion is connected to the pouch.
A second aspect of the present application provides an electronic device comprising the electrochemical device provided in the first aspect of the present application. Thus, the advantageous effects of the electrochemical device provided in the first aspect of the present application can be obtained.
Of course, not all of the above-described advantages need be achieved simultaneously in practicing any one of the products or methods of the present application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following description will briefly introduce the drawings that are required to be used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other embodiments may also be obtained according to these drawings to those skilled in the art.
FIG. 1 is a schematic view of an electrode assembly according to some embodiments of the present application;
fig. 2 is a schematic cross-sectional structure of the positive electrode tab of the electrode assembly of fig. 1 in the direction of its thickness in an expanded state;
fig. 3 is a schematic structural view of the positive electrode sheet of fig. 2, as viewed in the thickness direction thereof;
fig. 4 is an enlarged view of a dashed box labeled 301 in fig. 3;
FIG. 5 is a schematic view of an electrode assembly according to some embodiments of the present application;
Fig. 6 is a schematic cross-sectional structure of the positive electrode tab of the electrode assembly of fig. 5 in the expanded state in the thickness direction thereof;
FIG. 7 is a schematic structural view of a positive electrode sheet according to some embodiments of the present application;
fig. 8 is a schematic cross-sectional structure of the positive electrode sheet of comparative example 1 in the direction of its thickness in the developed state.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. Based on the embodiments herein, a person of ordinary skill in the art would be able to obtain all other embodiments based on the disclosure herein, which are within the scope of the disclosure herein.
In the specific embodiment of the present application, the present application is explained using a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery.
The electrode assembly in an electrochemical device (such as a lithium ion battery) mostly has a bare positive current collector, and the positive current collector in the prior art generally uses aluminum foil with a silicon element content of 0.06-0.18% by mass, and most of the silicon element exists in the form of silicon dioxide or silicate. Along with the continuous promotion of electrochemical device voltage system, the oxidation capability of positive pole piece to electrolyte also continuously strengthens when full charge, in order to reduce the oxidation of positive pole piece to electrolyte, the prior art often improves the guard action to positive pole piece and negative pole piece under high voltage through increasing the content of fluorine-containing compound in the electrolyte.
However, fluorine-containing compounds, such as fluorine-containing additives and fluorine-containing lithium salts, are prone to decomposition in electrolytes to produce Lewis acids (e.g., PF 5 ) The reaction of F removal occurs under the action of (C) to produce HF. In this case, after the electrochemical device is injected, the electrolyte is in contact with the exposed aluminum foil, HF in the electrolyte may react with components in the aluminum foil, such as silicon dioxide or silicate, to generate a byproduct fluorosilicone compound, which diffuses inside the electrochemical device and gathers in a specific area of the positive electrode sheet (for example, an edge position of a positive electrode active material layer disposed in a single-sided area of the positive electrode current collector), so that the positive electrode sheet is abnormal (for example, a local area has obvious color difference due to an increase in silicon content), abnormal areas of the positive electrode sheet cannot be normally delithiated, lithium ions are extracted from edges of the abnormal areas of the positive electrode sheet, and a lithium intercalation position of the negative electrode sheet corresponding to the edges of the abnormal areas is insufficient, so that lithium precipitation occurs, thereby causing failure of the electrochemical device during a charge-discharge cycle. In order to solve the problem of failure of an electrochemical device during charge-discharge cycles, the present application provides an electrochemical device and an electronic device.
The first aspect of the present application provides an electrochemical device, which comprises an electrode assembly and an electrolyte, wherein the electrolyte comprises a fluorine-containing compound, the electrode assembly comprises a positive electrode plate, a negative electrode plate and a diaphragm, the diaphragm is arranged between the positive electrode plate and the negative electrode plate, and the electrode assembly is formed by laminating the positive electrode plate, the diaphragm and the negative electrode plate. The positive pole piece comprises a positive pole current collector and a positive pole active material layer, wherein the positive pole current collector is aluminum foil and further comprises silicon element. The positive electrode current collector comprises a first surface and a second surface which are opposite, the positive electrode current collector is provided with a single-sided area, the first surface of the single-sided area is provided with a positive electrode active material layer, the second surface of the single-sided area is not provided with the positive electrode active material layer, the single-sided area comprises a first part, the second surface of the first part is positioned on the outer surface of the electrode assembly, and the first part is provided with a through hole extending along the direction from the second surface to the first surface.
It is understood that the single-sided region is a segment of the positive current collector, and thus, the first surface of the single-sided region is the first surface of the positive current collector, and the second surface of the single-sided region is the second surface of the positive current collector. The first portion is one or all of the single-sided regions, i.e., also one of the positive current collector, and therefore the first surface of the first portion is the first surface of the positive current collector and the second surface of the first portion is the second surface of the positive current collector. Unless otherwise specified, the first surface and the second surface have the same area.
The second surface of the first portion, that is, part or all of the second surface of the single-sided region, is disposed on the outer surface of the electrode assembly, so that the possibility that the negative electrode current collector (such as copper foil) is in direct contact with the packaging bag is reduced, the risk that the copper foil is corroded in contact with the aluminum foil in the packaging bag is reduced, and the packaging performance and safety of the electrochemical device are improved. Meanwhile, the first part is a single-sided area which is arranged in the ending area of the electrode assembly, so that the material of the positive electrode active material layer can be saved, and the production cost of the electrochemical device is reduced. The arrangement of the through holes enables the by-products generated by the reaction of the electrolyte and the positive electrode current collector or the positive electrode active material layer to be directly attached to the through holes in the injection and liquefaction process or in the charge-discharge cycle process of the electrochemical device, and the by-products can react with the positive electrode plate in situ, so that the risk of aggregation of the by-products in a specific area or other areas of the positive electrode plate is reduced. Therefore, the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle process is reduced.
Illustratively, in some embodiments of the present application, as shown in fig. 1 to 6, the structure of the electrode assembly 001 is a winding structure, the winding direction is shown as W, the electrode assembly 001 includes a positive electrode tab 100, a negative electrode tab 200, and a separator 300 disposed between the positive electrode tab 100 and the negative electrode tab 200, the positive electrode tab 100 including a positive electrode current collector 10 and a positive electrode active material layer 20 disposed on the positive electrode current collector 10. The positive electrode current collector 10 includes opposite first and second surfaces 10a and 10b, the positive electrode current collector 10 includes a single-sided region 30, the first surface 10a of the single-sided region 30 is provided with the positive electrode active material layer 20, and the second surface 10b of the single-sided region 30 is not provided with the positive electrode active material layer 20. The single-sided region 30 includes a first portion 301, the second surface 10b of the first portion 301 being located at the outer surface of the electrode assembly 001, the first portion 301 being provided with a through hole 50 extending in the direction from the second surface 10b to the first surface 10 a. As shown in fig. 1 to 4, the positive electrode current collector 10 further includes a double-sided region 40, a first double-sided dummy foil region 61, and a second double-sided dummy foil region 62, the portions of the single-sided region 30 other than the first portion 301 being not located at the outer surface of the electrode assembly 001, the second surface 10b of the first portion 301 being located at the outer surface of the electrode assembly 001, the first portion 301 being provided with a through hole 50 extending in the direction from the second surface 10b to the first surface 10 a. The positive electrode current collector in the electrode assembly shown in fig. 5 does not include the second double-sided dummy foil region 62 including the double-sided region 40, the single-sided region 30, and the first double-sided dummy foil region 61, and as shown in fig. 5 and 6, the first portion 301 may be understood as the single-sided region 30, the second surface 10b of the first portion 301 may also be understood as the second surface 10b of the single-sided region 30, that is, the second surface 10b of the single-sided region 30 is located at the outer surface of the electrode assembly 001, and the single-sided region 30 is provided with the through holes 50 extending in the direction from the second surface 10b to the first surface 10 a.
Illustratively, in some embodiments of the present application, the electrode assembly is constructed in a lamination structure, and is formed by stacking a positive electrode sheet, a negative electrode sheet, and a separator between the positive electrode sheet and the negative electrode sheet, both outermost sides of the electrode assembly in a thickness direction are single-sided positive electrode sheets, specifically, as shown in fig. 7, the single-sided positive electrode sheet includes a positive electrode current collector 10, the positive electrode current collector 10 includes opposite first and second surfaces 10a and 10b, the positive electrode current collector 10 includes a single-sided region 30, the first surface 10a of the single-sided region 30 is provided with a positive electrode active material layer 20, and the second surface 10b of the single-sided region 30 is not provided with a positive electrode active material layer 20. The single-sided region 30 includes a first portion 301, the second surface 10b of the first portion 301 being located at the outer surface of the electrode assembly 001, the first portion 301 being provided with a through hole 50 extending in the direction from the second surface 10b to the first surface 10 a. The first portion 301 may be understood as a single-sided region 30, and the second surface 10b of the first portion 301 may be understood as a second surface 10b of the single-sided region 30, i.e., the second surface 10b of the single-sided region 30 is located at an outer surface of the electrode assembly, and the single-sided region 30 is provided with a through hole 50 extending in a direction from the second surface 10b to the first surface 10 a. In general, the positive electrode sheet that is not located at the outer surface of the electrode assembly is a double-sided positive electrode sheet including a positive electrode current collector including opposite first and second surfaces, each of which is provided with a positive electrode active material layer.
The area of the second surface of the first portion is not particularly limited in this application, and may vary according to the size of the area of the first/second surface of the positive electrode current collector, and may be selected according to actual needs by those skilled in the art as long as the object of this application can be achieved. For example, the area of the second surface of the positive electrode current collector is 500mm 2 The second surface of the first portion has an area of 50mm 2 To 2000mm 2 。
In one embodiment of the present application, the mass percentage of silicon element in the positive electrode current collector is e.0.03 < e.ltoreq.0.13. The fluorine-containing compound comprises a fluorine-containing additive, wherein the mass percentage of the fluorine-containing additive in the electrolyte is f% which is more than or equal to 0.1 and less than or equal to 40.0. Preferably, 5.ltoreq.f.ltoreq.25. For example, e has a value of 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, or any value in the range between any two of the foregoing values. For example, f has a value of 0.1, 2.0, 5.0, 10.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, or any value in any range between any two of the foregoing values. The mass percentage content of the silicon element in the positive current collector is regulated and controlled within the range, so that the abnormal production of the positive current collector (such as cold pressing fracture and winding fracture) can be reduced, the strength and the ductility of the positive current collector meet the preparation process requirements, and the positive current collector has good conductivity. When the electrolyte comprises a fluorine-containing additive and the mass percentage of the fluorine-containing additive in the electrolyte is regulated and controlled within the range, the protection capability of the electrolyte to the negative electrode plate can be enhanced by selecting the positive current collector with the silicon-containing element content range, and a uniform and compact protection film is formed on the surface of the negative electrode plate, so that the cycle performance of an electrochemical device is improved; meanwhile, the content of a byproduct fluorine silicon compound generated by the reaction of HF in the electrolyte and silicon element in the positive electrode current collector is reduced. In this way, the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle is reduced.
In one embodiment of the present application, 0.5.ltoreq.fe.ltoreq.3.6. Preferably, 0.5.ltoreq.fe2.4. For example, the value of fe may be 0.5, 1.0, 1.5, 2.0, 2.4, 2.8, 3.2, 3.6 or any value within any two of the foregoing ranges. And the value of fe is regulated and controlled within the range, and the mass percentage of silicon element in the positive electrode current collector is matched with the mass percentage of fluorine-containing additive in the electrolyte, so that the content of a byproduct fluorine-silicon compound generated by the reaction of HF in the electrolyte and the silicon element in the positive electrode current collector is reduced. In this way, the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle is reduced.
In one embodiment of the present application, the cross-sectional area of the through hole is b mm 2 B is more than or equal to 0.1 and less than or equal to 1.0. For example, b has a value of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or any value in any two of the above ranges. The cross-sectional area of the through hole is regulated and controlled in the range, the through hole is not easy to be blocked by the positive electrode slurry, the coating weight of the first part is not easy to be reduced due to leakage into the through hole when the positive electrode slurry is coated, and under the condition that the strength of the first part is not influenced, the size of the through hole can expose positive electrode active material which meets the requirement of in-situ reaction of byproducts. In this way, the by-product generated by the reaction of the electrolyte and the positive electrode current collector or the positive electrode active material layer in the injection formation or in the charge-discharge circulation process of the electrochemical device is directly attached to the through hole, can react with the positive electrode plate in situ, and reduces the risk of aggregation of the by-product in a specific area or other areas of the positive electrode plate. Therefore, the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle process is reduced.
The shape of the through hole is not particularly limited in the present application, and those skilled in the art can select according to actual circumstances as long as the object of the present application can be achieved. For example, the shape of the through hole is a circle, an ellipse, a polygon, or the like, wherein the number of sides of the polygon is any one of 3 to 12. Wherein the shape of the through holeWhen the shape is circular, the radius r of the through hole is adjusted to make the cross section of the through hole be b mm 2 Changes, in particular, b=pi r 2 。
In one embodiment of the present application, the number of through holes is plural, calculated as the area of the second surface of the first portion, and the number of through holes per unit area is d/cm 2 D is more than or equal to 2 and less than or equal to 10. Preferably, 6.ltoreq.d.ltoreq.10. For example, the number of through holes per unit area of the second surface of the first portion is 2, 3, 4, 5, 6, 7, 8, 9 or 10. The number of through holes per unit area of the second surface of the first portion is regulated within the above range, and under the condition that the strength of the first portion is not affected, the number of through holes provided in the first portion can expose the positive electrode active material in an amount required to satisfy the in-situ reaction of the by-product. In this way, the by-product generated by the reaction of the electrolyte and the positive electrode current collector or the positive electrode active material layer in the injection formation or in the charge-discharge circulation process of the electrochemical device is directly attached to the through hole, can react with the positive electrode plate in situ, and reduces the risk of aggregation of the by-product in a specific area or other areas of the positive electrode plate. Therefore, the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle process is reduced.
Illustratively, fig. 4 shows that the first portion 301 is provided with a through-hole 50 extending in the direction from the second surface 10b to the first surface 10a, the through-hole 50 being circular in shape. In the drawings of the present application, the number of through holes 50 is only schematically illustrated, and is not intended to limit the number of through holes.
In the present application, "the number of the through holes" is "a plurality of" is not particularly limited as long as the number of the through holes satisfies that the number of the through holes per unit area of the second surface of the first portion is 2 to 10.
The type of aluminum foil is not particularly limited, and may be any known in the art as long as the object of the present application can be achieved.
The method for regulating and controlling the mass percentage content of the silicon element in the positive electrode current collector is not particularly limited, so long as the purpose of the application can be achieved. For example, the positive electrode current collector is prepared by blending the types of raw materials and the proportions of the raw materials.
In one embodiment of the present application, 0 < f/(db). Ltoreq.100. Preferably, 0 < f/(db) 60. For example, the value of f/(db) is 0.01, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or any value between any two of the above ranges. The value of f/(db) is regulated and controlled within the above range, the area of the through hole arranged in the second surface of the first part is matched with the mass percentage of the fluorine-containing additive in the electrolyte, and the ratio of the total area of the through holes arranged in the first part to the total area of the first part can expose the positive electrode active material meeting the requirement of in-situ reaction of byproducts. In this way, the by-product generated by the reaction of the electrolyte and the positive electrode current collector or the positive electrode active material layer in the injection formation or in the charge-discharge circulation process of the electrochemical device is directly attached to the through hole, can react with the positive electrode plate in situ, and reduces the risk of aggregation of the by-product in a specific area or other areas of the positive electrode plate. Therefore, the risk of abnormality of the positive electrode plate is reduced, and the risk of failure of the electrochemical device in the charge-discharge cycle process is further reduced.
In one embodiment of the present application, the fluorine-containing additive includes at least one of fluoroethylene carbonate (FEC), bis (fluoromethyl) ethylene carbonate (DFEC), bis (difluoromethyl) ethylene carbonate, bis (trifluoromethyl) ethylene carbonate, bis (2-fluoroethyl) ethylene carbonate, bis (2, 2-difluoroethyl) ethylene carbonate, bis (2, 2-trifluoroethyl) ethylene carbonate, 2-fluoroethyl methyl ethylene carbonate, 2-difluoroethyl methyl ethylene carbonate, or 2, 2-trifluoroethyl methyl ethylene carbonate. The fluorine-containing additive is more beneficial to weakening the oxidizing capacity of the positive electrode plate to the electrolyte, and uniform and compact protective films are formed on the surfaces of the positive electrode plate and the negative electrode plate to protect the positive electrode plate and the negative electrode plate.
In one embodiment of the present application, the electrolyte further comprises a fluorine-containing lithium salt, including lithium hexafluorophosphate (LiPF) 6 ) Difluorophosphoric acidLithium (LiPF) 2 ) Lithium bis (trifluoromethane) sulfonimide (LiTFSI), lithium bis (fluorosulfonimide) (LiTSI), lithium tetrafluoroborate (LiBF) 4 ) Lithium difluorooxalato borate (LiBF) 2 (C 2 O 4 ) LiDFOB), lithium hexafluoroantimonate (LiSbF 6 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perfluorobutyl sulfonate (LiC) 4 F 9 SO 3 ) Lithium bissulfonylimide (LiN (C) x F 2x+ 1 SO 2 )(C y F 2y+1 SO 2 ) Wherein x and y are positive integers and x.ltoreq.10, y.ltoreq.10) or at least one of lithium fluoride (LiF). The addition of the fluorine-containing lithium salt is more beneficial to providing high ionic conductivity, so that the transmission rate of lithium ions is faster. Preferably, the fluorine-containing lithium salt comprises LiPF 6 At least one of LiTFSI or LiTSI is more advantageous for reducing the production cost of the electrochemical device.
The content of the fluorine-containing lithium salt in the electrolyte is not particularly limited as long as the object of the present application can be achieved. For example, the content of the fluorine-containing lithium salt in the electrolyte is 8 to 20% by mass.
In one embodiment of the present application, the structure of the electrode assembly is a lamination stack.
In one embodiment of the present application, as shown in fig. 1 and 2, the electrode assembly has a winding structure, and the positive electrode current collector 10 further includes a double-sided region 40, and the double-sided region 40 is sequentially connected with the single-sided region 30 in the winding direction W. The positive electrode active material layer 20 is disposed on both the first surface 10a and the second surface 10b of the double-sided region 40.
In one embodiment of the present application, the through hole is formed by punching in a direction from the second surface to the first surface. The burr that produces when setting up the through-hole is covered by the anodal active material layer that sets up on the first surface, has reduced the risk that exists the burr on the second surface of first part, like this, can reduce the risk that the burr contacted with the wrapping bag to prevent that the wrapping bag from being pricked by the burr that the through-hole produced, thereby improve electrochemical device's packaging performance and security performance.
In one embodiment of the present application, the electrochemical device further includes a pouch containing the electrode assembly and the electrolyte, and the first portion is connected to the pouch. The "contact" in this application may mean direct contact between the second surface of the first portion and the inside of the packing bag near the electrode assembly, or a separator, such as a gummed paper or a separator, is provided between the second surface of the first portion and the inside of the packing bag near the electrode assembly.
The thickness of the positive electrode current collector is not particularly limited as long as the object of the present application can be achieved. For example, the thickness of the positive electrode current collector is 8 μm to 20 μm.
The preparation method of the positive electrode current collector is not particularly limited, and any preparation method known in the art may be used as long as the object of the present application can be achieved.
The present application is not particularly limited in the compaction density after cold pressing of the positive electrode sheet and the negative electrode sheet, as long as the object of the present application can be achieved. For example, the compacted density of the positive electrode sheet and the negative electrode sheet after cold pressing is 3.9g/cm 3 To 4.3g/cm 3 。
The positive electrode active material layer of the present application includes a positive electrode active material. The kind of the positive electrode active material is not particularly limited as long as the object of the present application can be achieved. For example, the positive electrode active material may include lithium nickel cobalt manganese oxide (e.g., common NCM811, NCM622, NCM523, NCM 111), lithium nickel cobalt aluminate, lithium iron phosphate, lithium-rich manganese-based material, lithium cobalt oxide (LiCoO) 2 ) At least one of lithium manganate, lithium iron manganese phosphate, lithium titanate, and the like. In the present application, the positive electrode active material may further contain non-metal elements such as fluorine, phosphorus, boron, chlorine, silicon, sulfur, and the like, which can further improve the stability of the positive electrode active material. Optionally, the positive electrode active material layer further includes a conductive agent and a binder. The kind of the conductive agent and the binder in the positive electrode active material layer is not particularly limited in the present application as long as the object of the present application can be achieved. The mass ratio of the positive electrode active material, the conductive agent, and the binder in the positive electrode active material layer is not particularly limited in this application, and those skilled in the art can select according to actual needs as long as the object of this application can be achieved. For example, a positive electrode active material, a conductive agent, and in the positive electrode active material layerThe mass ratio of the binder is (97.5-97.9) (0.9-1.7) (1.0-2.0).
The thickness of the positive electrode active material layer is not particularly limited as long as the object of the present application can be achieved. For example, the thickness of the positive electrode active material layer is 30 μm to 120 μm.
The negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer arranged on at least one surface of the negative electrode current collector. The above-mentioned "anode active material layer disposed on at least one surface of the anode current collector" means that the anode active material layer may be disposed on one surface of the anode current collector in the thickness direction thereof, or may be disposed on both surfaces of the anode current collector in the thickness direction thereof. The "surface" here may be the entire region of the negative electrode current collector or may be a partial region of the negative electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. The negative electrode current collector is not particularly limited as long as the object of the present application can be achieved. For example, the negative electrode current collector may include copper foil, copper alloy foil, nickel foil, titanium foil, foam nickel, foam copper, or the like. The anode active material layer includes an anode active material. The kind of the negative electrode active material is not particularly limited in the present application, as long as the object of the present application can be achieved. For example, the anode active material may include at least one of natural graphite, artificial graphite, soft carbon, hard carbon, mesophase carbon microspheres, tin-based material, silicon-based material, lithium titanate, transition metal nitride, natural crystalline flake graphite, or the like. Optionally, the anode active material layer further includes at least one of a conductive agent, a stabilizer, and a binder. The kind of the conductive agent, the stabilizer, and the binder in the anode active material layer is not particularly limited as long as the object of the present application can be achieved. The mass ratio of the anode active material, the conductive agent, the stabilizer, and the binder in the anode active material layer is not particularly limited as long as the object of the present application can be achieved. For example, the mass ratio of the anode active material, the conductive agent, the stabilizer, and the binder in the anode active material layer is (97 to 98): 0.5 to 1.5): 1.0 to 1.9.
The thickness of the anode current collector and the anode active material layer is not particularly limited as long as the object of the present application can be achieved. For example, the thickness of the anode current collector is 5 μm to 20 μm, and the thickness of the anode active material layer is 30 μm to 120 μm.
The electrolyte of the present application also includes a nonaqueous solvent. The nonaqueous solvent is not particularly limited as long as the object of the present application can be achieved. For example, the nonaqueous solvent may include, but is not limited to, at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl Propyl Carbonate (MPC), ethylene Propyl Carbonate (EPC), methyl Ethyl Carbonate (MEC), ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, or propyl propionate.
The content of the nonaqueous solvent in the electrolyte is not particularly limited as long as the object of the present application can be achieved. For example, the nonaqueous solvent is 70 to 99% by mass in the electrolyte.
The separator and the packaging bag are not particularly limited in this application, and may be those known in the art as long as the object of the present application can be achieved.
The electrochemical device of the present application is not particularly limited, and may include any device in which an electrochemical reaction occurs. In some embodiments, the electrochemical device may include, but is not limited to: lithium metal secondary batteries, lithium ion secondary batteries, sodium ion secondary batteries, lithium polymer secondary batteries, lithium ion polymer secondary batteries, and the like.
The method of manufacturing the electrochemical device is not particularly limited, and may be a method known in the art as long as the object of the present application can be achieved.
A second aspect of the present application provides an electronic device comprising the electrochemical device provided in the first aspect of the present application. Thus, the advantageous effects of the electrochemical device provided in the first aspect of the present application can be obtained.
The electronic device of the present application is not particularly limited, and may be any electronic device known in the art. In some embodiments, the electronic device may include, but is not limited to: notebook computers, pen-input computers, mobile computers, electronic book players, portable telephones, portable facsimile machines, portable copiers, portable printers, headsets, video recorders, liquid crystal televisions, hand-held cleaners, portable CD-players, mini-compact discs, transceivers, electronic notebooks, calculators, memory cards, portable audio recorders, radios, standby power supplies, motors, automobiles, motorcycles, mopeds, bicycles, lighting fixtures, toys, game machines, watches, electric tools, flash lamps, cameras, household large-sized batteries, lithium ion capacitors, and the like.
Examples
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. The various tests and evaluations were carried out according to the following methods.
Test method and apparatus:
detection of different element contents:
taking the lithium ion batteries of each example and comparative example, dismantling the lithium ion batteries after fully discharging, washing the positive electrode active material layer on the surface of the positive electrode current collector by using N-methyl pyrrolidone, and finally washing the positive electrode current collector by using DMC; and after the cleaning is finished, carrying out an Inductively Coupled Plasma (ICP) spectrometer test on the positive electrode current collector to obtain the contents of aluminum element and silicon element.
And (3) detecting the content of the fluorine-containing additive:
the lithium ion batteries of each example and comparative example were centrifuged to obtain 10mL of an electrolyte. The mass percentage of the fluorine-containing additive in the electrolyte can be obtained by a gas chromatography detection method.
Detecting the abnormality of the positive electrode plate:
and disassembling the lithium ion batteries of each example and the comparative example after fully discharging, and visually observing the positive pole piece to obtain abnormal appearance of the heterochromatic marks, namely, obvious chromatic aberration is formed between part of the positive pole piece and the surrounding area. And performing an X-ray energy spectrum analysis (EDS) test on the positive pole piece in the abnormal region, and judging that the positive pole piece is abnormal if the silicon element content in the abnormal region is more than 2 wt%. If the abnormal appearance of the heterochromatic mark does not appear on the positive electrode plate, the abnormal appearance of the positive electrode plate does not exist, and the EDS test is not carried out on the positive electrode plate.
The problem of failure in the charge-discharge cycle process of the electrochemical device is characterized by the abnormal appearance of the positive electrode sheet and the silicon content of >2wt% in the abnormal region.
Judging whether the positive pole piece is abnormal or not:
in each example or comparative example < preparation of positive electrode sheet >, whether the positive electrode current collector is broken or not and whether the electrode sheet is broken or not is judged in the cold pressing process of the positive electrode sheet.
Example 1
< preparation of Positive electrode sheet >
LiCoO as positive electrode active material 2 Mixing conductive carbon black serving as a conductive agent, polyvinylidene fluoride (PVDF) serving as a binder according to the mass ratio of 96:2:2, adding N-methyl pyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain positive electrode slurry, wherein the solid content of the positive electrode slurry is 70wt%. The positive electrode slurry was uniformly coated on the first surfaces 10a of the both-sided region 40 and the single-sided region 30 of the positive electrode current collector 10 as shown in fig. 6, and then dried at 120 deg.c for 1h. The above steps are repeated on the second surface 10b of the double-sided region 40 of the positive current collector 10, and a positive electrode sheet as shown in fig. 6 is obtained. Drying at 120 ℃ for 1h, and then cold pressing, cutting and cutting to obtain the positive pole piece with the specification of 78mm multiplied by 875 mm. The first surface 10a of the double-sided region 40 has a specification of 78mm×780mm, the first surface 10a of the single-sided region 30 has the same specification as the first surface 10a of the first portion 31, the specification of 78mm×80mm, and the first empty foil region 61 has a specification of 78mm×15mm. The first portion 301 (also understood as the single-sided region 30) is provided with a through hole 50 extending in the direction from the second surface 10b to the first surface 10a, wherein the through hole 50 is circular in shape, and the cross-sectional area bmm of the through hole 50 2 ＝0.13mm 2 Number d/cm of through holes 50 per unit area of the first portion 301 2 =6/cm 2 . The thickness of the positive electrode active material layer 20 was 100 μm, and the thickness of the positive electrode current collector 10 was 12 μm. Mass of silicon element in positive electrode current collector 10The percentage content is m% = 0.08%.
< preparation of negative electrode sheet >
Mixing negative electrode active material graphite, binder styrene-butadiene rubber and thickener sodium carboxymethyl cellulose according to the mass ratio of 97.4:1.4:1.2, adding deionized water, and uniformly stirring under the action of a vacuum stirrer to obtain negative electrode slurry, wherein the solid content of the negative electrode slurry is 75wt%. The negative electrode slurry was uniformly coated on one surface of a negative electrode current collector copper foil having a thickness of 12 μm, and then dried at 120 ℃ for 1 hour to obtain a negative electrode having a coating thickness of 130 μm and a negative electrode active material layer coated on one side. Repeating the steps on the other surface of the negative electrode current collector to obtain the negative electrode plate with the double-sided coating negative electrode active material layer. Drying at 120 ℃ for 1h, and then cold pressing, cutting and cutting to obtain the negative electrode plate with the specification of 74mm multiplied by 867 mm.
< preparation of electrolyte >
At the water content<In a 10ppm argon atmosphere glove box, EC, PC and DEC are mixed according to the mass ratio of 1:1:1 to obtain an organic solvent, and then the fluorine-containing lithium salt LiPF is added into the organic solvent 6 Obtaining the basic electrolyte. And adding fluorine-containing additive FEC into the basic electrolyte to obtain the electrolyte. Fluorine-containing lithium salt LiPF 6 The mass percentage of the fluorine-containing additive FEC in the electrolyte is 13.8 percent, and the mass percentage of the fluorine-containing additive FEC in the electrolyte is f% =20 percent.
< preparation of separator >
A porous polyethylene film having a thickness of 7 μm was used.
< preparation of lithium ion Battery >
And sequentially stacking the positive electrode plate, the diaphragm and the negative electrode plate, so that the diaphragm is positioned between the positive electrode plate and the negative electrode plate to play a role in isolation, and winding to obtain the electrode assembly with the winding structure shown in fig. 5. And then placing the electrode assembly in an aluminum plastic film packaging bag, drying, injecting electrolyte, and carrying out the procedures of vacuum packaging, standing, formation, degassing, trimming and the like to obtain the lithium ion battery.
Examples 2 to 24
The procedure of example 1 was repeated except that the relevant production parameters were adjusted as shown in Table 1.
Comparative example 1
The same procedure as in example 1 was repeated except that in < preparation of positive electrode sheet > the positive electrode current collector was as shown in positive electrode current collector 8 in fig. 8, and the first portion 301, i.e., the single-sided region 30, was not provided with a through hole, and the prepared positive electrode sheet was as shown in fig. 8.
The relevant preparation parameters and performance tests for each example and comparative example are shown in table 1.
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As can be seen from examples 1 to 25 and comparative example 1, examples 1 to 24 apply the positive electrode sheet having the first portion provided with the through hole extending in the direction from the second surface to the first surface to the lithium ion battery, the positive electrode sheet had a reduced risk of abnormal appearance after the lithium ion battery was subjected to the charge and discharge cycle, the Si content of the abnormal region of the positive electrode sheet was less than 2wt%, indicating that the risk of failure of the lithium ion battery during the charge and discharge cycle was reduced, and the positive electrode sheet was made without abnormality. In comparative example 1, the first portion of the positive electrode sheet without the through hole was applied to the lithium ion battery, and the risk of abnormal appearance of the positive electrode sheet failed to be reduced, and the Si content of the abnormal region of the positive electrode sheet was greater than 2wt%, indicating that the risk of failure of the lithium ion battery during the charge-discharge cycle failed to be reduced.
The cross-sectional area of the through hole generally affects the probability of failure of the lithium ion battery during charge and discharge cycles. As can be seen from examples 1 to 5, the cross-sectional area of the through hole of the positive electrode sheet is selected to be in the range of the application, after the lithium ion battery is subjected to charge-discharge cycle, the risk of abnormal appearance of the positive electrode sheet is reduced, the Si content of the abnormal area of the positive electrode sheet is less than 2wt%, which indicates that the risk of failure of the lithium ion battery during the charge-discharge cycle is reduced, and the positive electrode sheet is made to be free from abnormality.
The number of through holes per unit area of the second surface of the first portion generally affects the risk probability of failure of the lithium ion battery during charge and discharge cycles. As can be seen from examples 3, 6 to 9, the lithium ion battery with the number of through holes in the unit area of the second surface of the first portion of the positive electrode sheet within the range of the present application was selected, and after the lithium ion battery was subjected to charge-discharge cycle, the risk of abnormal appearance of the positive electrode sheet was reduced, the Si content in the abnormal region of the positive electrode sheet was less than 2wt%, which indicates that the risk of failure of the lithium ion battery during the charge-discharge cycle was reduced, and the positive electrode sheet was made without abnormality.
The mass percentage e% of silicon element in the positive electrode current collector and the mass percentage f% of fluorine-containing additive in the electrolyte generally affect the risk probability of failure of the lithium ion battery during charge-discharge cycles. From example 3, example 10 to example 17, it can be seen that, by selecting a lithium ion battery with a mass percentage e% of silicon element in the positive electrode current collector and a mass percentage f% of fluorine-containing additive in the electrolyte within the scope of the application, after the lithium ion battery is subjected to charge-discharge cycle, the risk of abnormal appearance of the positive electrode sheet is reduced, the Si content in the abnormal area of the positive electrode sheet is less than 2wt%, which indicates that the risk of failure of the lithium ion battery during the charge-discharge cycle is reduced, and the positive electrode sheet is made without abnormality.
Further, the value of fe also typically affects the risk probability of failure of the lithium ion battery during the charge-discharge cycle. As can be seen from examples 3, 10 to 17, the lithium ion battery with fe value within the scope of the present application is selected, and after the lithium ion battery is subjected to charge-discharge cycle, the risk of having abnormal appearance of the positive electrode sheet is reduced, the Si content in the abnormal region of the positive electrode sheet is less than 2wt%, which indicates that the risk of failure of the lithium ion battery during the charge-discharge cycle is reduced, and the positive electrode sheet is made without abnormality.
The value of f/(db) also typically affects the risk probability of failure of the lithium ion battery during charge and discharge cycles. As can be seen from examples 18 to 22, the use of the lithium ion battery having the value of f/(db) within the range of the present application, after the lithium ion battery is subjected to the charge-discharge cycle, the risk of having an abnormal appearance of the positive electrode sheet is reduced, the Si content of the abnormal region of the positive electrode sheet is less than 2wt%, which indicates that the risk of failure of the lithium ion battery during the charge-discharge cycle is reduced, and the positive electrode sheet is made without abnormality.
The type of fluorine-containing additive also typically affects the risk probability of failure of the lithium ion battery during charge and discharge cycles. As can be seen from examples 3 and 23, the lithium ion battery with the fluorine-containing additive in the scope of the application has the advantages that after the lithium ion battery is subjected to charge-discharge cycle, the risk of abnormal appearance of the positive electrode plate is reduced, the Si content of the abnormal region of the positive electrode plate is less than 2wt%, which indicates that the risk of failure of the lithium ion battery during the charge-discharge cycle is reduced, and the positive electrode plate is made without abnormality.
The type of fluorine-containing lithium salt also typically affects the risk probability of failure of the lithium ion battery during charge and discharge cycles. As can be seen from examples 3 and 24, the lithium ion battery with the type of the fluorine-containing lithium salt in the scope of the application is selected, after the lithium ion battery is subjected to charge-discharge cycle, the risk of abnormal appearance of the positive electrode plate is reduced, the Si content of the abnormal area of the positive electrode plate is less than 2wt%, which indicates that the risk of failure of the lithium ion battery during the charge-discharge cycle is reduced, and the positive electrode plate is made without abnormality.
It should be noted that in this document relational terms such as first and second, and the like are used solely to distinguish one entity from another entity without necessarily requiring or implying any actual such relationship or order between such entities. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modifications, equivalent substitutions, improvements, etc. that are within the spirit and principles of the present application are intended to be included within the scope of the present application.
Claims (16)
1. An electrochemical device comprises an electrode assembly and electrolyte, wherein the electrolyte comprises fluorine-containing compounds, the electrode assembly comprises a positive electrode plate, a negative electrode plate and a diaphragm, the diaphragm is arranged between the positive electrode plate and the negative electrode plate, and the electrode assembly is formed by laminating the positive electrode plate, the diaphragm and the negative electrode plate;
the positive electrode plate comprises a positive electrode current collector and a positive electrode active material layer, wherein the positive electrode current collector is aluminum foil and further comprises silicon element; the positive electrode current collector comprises a first surface and a second surface which are opposite, the positive electrode current collector is provided with a single-sided area, the first surface of the single-sided area is provided with the positive electrode active material layer, the second surface of the single-sided area is not provided with the positive electrode active material layer, the single-sided area comprises a first part, the second surface of the first part is positioned on the outer surface of the electrode assembly, and the first part is provided with a through hole extending along the direction from the second surface to the first surface.
2. The electrochemical device according to claim 1, wherein the silicon element accounts for 0.03< e.ltoreq.0.13 by mass percent in the positive electrode current collector; the fluorine-containing compound comprises a fluorine-containing additive, wherein the mass percentage of the fluorine-containing additive in the electrolyte is f% which is more than or equal to 0.1 and less than or equal to 40.0.
3. The electrochemical device according to claim 2, wherein 0.5.ltoreq.fe.ltoreq.3.6.
4. The electrochemical device according to claim 3, wherein 0.5.ltoreq.fe.ltoreq.2.4.
5. The electrochemical device according to claim 2, wherein a cross-sectional area of the through hole is b mm 2 ，0.1≤b≤1.0。
6. The electrochemical device according to claim 5, wherein 0.5.ltoreq.b.ltoreq.1.0.
7. The electrochemical device according to claim 3, wherein the number of the through holes is plural, the number of the through holes per unit area being d/cm, calculated as the area of the second surface of the first portion 2 ，2≤d≤10。
8. The electrochemical device according to claim 7, wherein 6.ltoreq.d.ltoreq.10.
9. The electrochemical device according to claim 7, wherein 0 < f/(db). Ltoreq.100.
10. The electrochemical device according to claim 9, wherein 0 < f/(db). Ltoreq.60.
11. The electrochemical device of claim 2, wherein the fluorine-containing additive comprises at least one of fluoroethylene carbonate, bis (fluoromethyl) ethylene carbonate, bis (difluoromethyl) ethylene carbonate, bis (trifluoromethyl) ethylene carbonate, bis (2-fluoroethyl) ethylene carbonate, bis (2, 2-difluoroethyl) ethylene carbonate, bis (2, 2-trifluoroethyl) ethylene carbonate, 2-fluoroethyl methyl ethylene carbonate, 2-difluoroethyl methyl ethylene carbonate, or 2, 2-trifluoroethyl methyl ethylene carbonate.
12. The electrochemical device of claim 1, wherein the fluorine-containing compound comprises a fluorine-containing lithium salt comprising at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium bis (trifluoromethane) sulfonimide, lithium bis (fluorosulfonimide), lithium tetrafluoroborate, lithium difluorooxalato borate, lithium hexafluoroantimonate, lithium hexafluoroarsonate, lithium perfluorobutyl sulfonate, lithium bis (sulfonyl imide), or lithium fluoride.
13. The electrochemical device of claim 1, wherein the structure of the electrode assembly is a lamination stack; or,
the structure of the electrode assembly is a winding structure, the positive current collector further comprises a double-sided area, and the double-sided area is sequentially connected with the single-sided area along the winding direction.
14. The electrochemical device according to claim 1, wherein the through hole is formed by punching in a direction from the second surface to the first surface.
15. The electrochemical device of claim 1, wherein the electrochemical device further comprises a pouch containing the electrode assembly and the electrolyte, the first portion interfacing with the pouch.
16. An electronic device comprising the electrochemical device of any one of claims 1 to 15.
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