WO2024114206A1 - Lithium-ion battery - Google Patents
Lithium-ion battery Download PDFInfo
- Publication number
- WO2024114206A1 WO2024114206A1 PCT/CN2023/127484 CN2023127484W WO2024114206A1 WO 2024114206 A1 WO2024114206 A1 WO 2024114206A1 CN 2023127484 W CN2023127484 W CN 2023127484W WO 2024114206 A1 WO2024114206 A1 WO 2024114206A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- lithium
- ion battery
- active material
- electrode active
- Prior art date
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 73
- 239000007774 positive electrode material Substances 0.000 claims abstract description 124
- 239000011572 manganese Substances 0.000 claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 49
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 7
- -1 sultone compound Chemical class 0.000 claims description 59
- 229910021645 metal ion Inorganic materials 0.000 claims description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 5
- 229910013716 LiNi Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 4
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 claims description 4
- ZVYSYCLZXICWLH-UHFFFAOYSA-N 1,3-dioxetan-2-one Chemical compound O=C1OCO1 ZVYSYCLZXICWLH-UHFFFAOYSA-N 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 3
- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000008282 halocarbons Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- LLEVMYXEJUDBTA-UHFFFAOYSA-N heptanedinitrile Chemical compound N#CCCCCCC#N LLEVMYXEJUDBTA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 claims description 3
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- UFBCAWKXDJDIOA-UHFFFAOYSA-N tris(triethylsilyl) borate Chemical compound CC[Si](CC)(CC)OB(O[Si](CC)(CC)CC)O[Si](CC)(CC)CC UFBCAWKXDJDIOA-UHFFFAOYSA-N 0.000 claims description 3
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims description 3
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 20
- 230000008859 change Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 10
- 150000005678 chain carbonates Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- 229910021383 artificial graphite Inorganic materials 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 150000003457 sulfones Chemical class 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000011883 electrode binding agent Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 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 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125758 compound 15 Drugs 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CHCLGECDSSWNCP-UHFFFAOYSA-N methoxymethoxyethane Chemical compound CCOCOC CHCLGECDSSWNCP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- LUVQJDCOCWBMEN-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl bis(prop-2-ynyl) phosphate Chemical compound P(=O)(OCC#C)(OCC#C)OC(C(F)(F)F)C(F)(F)F LUVQJDCOCWBMEN-UHFFFAOYSA-N 0.000 description 1
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- MHWAJHABMBTNHS-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C.FC(F)=C(F)F MHWAJHABMBTNHS-UHFFFAOYSA-N 0.000 description 1
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- OSUGFVIHMXAUEN-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2-trichloroethene Chemical group FC(F)=C.ClC=C(Cl)Cl OSUGFVIHMXAUEN-UHFFFAOYSA-N 0.000 description 1
- XLOFNXVVMRAGLZ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2-trifluoroethene Chemical group FC(F)=C.FC=C(F)F XLOFNXVVMRAGLZ-UHFFFAOYSA-N 0.000 description 1
- CIKVTYVSUSJJAA-UHFFFAOYSA-N 1,1-difluoroethene;fluoroethene Chemical group FC=C.FC(F)=C CIKVTYVSUSJJAA-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- HQSLKNLISLWZQH-UHFFFAOYSA-N 1-(2-propoxyethoxy)propane Chemical compound CCCOCCOCCC HQSLKNLISLWZQH-UHFFFAOYSA-N 0.000 description 1
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OSSBKXMASZTOSG-UHFFFAOYSA-N 2-(trifluoromethyl)oxolane Chemical compound FC(F)(F)C1CCCO1 OSSBKXMASZTOSG-UHFFFAOYSA-N 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- NONFLFDSOSZQHR-UHFFFAOYSA-N 3-(trimethylsilyl)propionic acid Chemical compound C[Si](C)(C)CCC(O)=O NONFLFDSOSZQHR-UHFFFAOYSA-N 0.000 description 1
- HKMTZXXNXLVEDX-UHFFFAOYSA-N 4-(2,2,2-trifluoroethyl)hepta-1,6-diyn-4-yl dihydrogen phosphate Chemical compound C(C#C)C(CC(F)(F)F)(OP(O)(O)=O)CC#C HKMTZXXNXLVEDX-UHFFFAOYSA-N 0.000 description 1
- QMGIUYMIMNCOHF-UHFFFAOYSA-N 4-(trifluoromethyl)hepta-1,6-diyn-4-yl dihydrogen phosphate Chemical compound C#CCC(CC#C)(C(F)(F)F)OP(=O)(O)O QMGIUYMIMNCOHF-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000143432 Daldinia concentrica Species 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 229910010820 Li2B10Cl10 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013375 LiC Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- 229910012423 LiSO3F Inorganic materials 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- IZJSTXINDUKPRP-UHFFFAOYSA-N aluminum lead Chemical compound [Al].[Pb] IZJSTXINDUKPRP-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HPZCUDJYOUMWRW-UHFFFAOYSA-N bis(prop-2-ynyl) trifluoromethyl phosphate Chemical compound P(=O)(OCC#C)(OCC#C)OC(F)(F)F HPZCUDJYOUMWRW-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- VCYZVXRKYPKDQB-UHFFFAOYSA-N ethyl 2-fluoroacetate Chemical compound CCOC(=O)CF VCYZVXRKYPKDQB-UHFFFAOYSA-N 0.000 description 1
- GUICUMLKEBGGLD-UHFFFAOYSA-N ethyl bis(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OCC)OCC#C GUICUMLKEBGGLD-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HSAPVOPSUVJVGL-UHFFFAOYSA-N methyl bis(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OC)OCC#C HSAPVOPSUVJVGL-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- AIKFSRURHOARNU-UHFFFAOYSA-N propyl bis(prop-2-ynyl) phosphate Chemical compound CCCOP(=O)(OCC#C)OCC#C AIKFSRURHOARNU-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical group ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- FCTINJHSYHFASK-UHFFFAOYSA-N tris(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OCC#C)OCC#C FCTINJHSYHFASK-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
In order to solve the problem of the dissolving-out of Mn ions due to the valence changes of Mn in existing lithium-ion battery positive electrodes, the present invention provides a lithium-ion battery, comprising a positive electrode, a negative electrode and a non-aqueous electrolyte solution, wherein the positive electrode comprises a positive electrode material layer that contains a positive electrode active material; the positive electrode active material comprises a manganese-containing positive electrode material, and the specific surface area of the positive electrode active material is 0.5-1.5 m2/g; and the non-aqueous electrolyte solution comprises a non-aqueous organic solvent, an additive and a lithium salt, and the additive comprises a compound as represented by structural formula 1: (1). The lithium-ion battery satisfies the following condition: 0.5 ≤ (Vr/Vr*)/Wr ≤ 12, where 0.4 ≤ Vr/Vr* ≤ 1.5, and 0.1 ≤ Wr ≤ 3. The lithium-ion battery provided in the present invention can effectively inhibit the irreversible change of the manganese ion valence of a manganese-containing positive electrode material during the cycling process of a battery, such that the dissolving-out of manganese ions in the manganese-containing positive electrode material is reduced.
Description
本发明属于储能装置技术领域，具体涉及一种锂离子电池。The invention belongs to the technical field of energy storage devices, and in particular relates to a lithium ion battery.
锂离子电池有着工作电压高、能量密度大、安全性能好、自放电小、可快速充电、工作范围宽、使用寿命长等优点，在全球二次电池市场占据主导地位，近年，为实现“碳中和”这一绿色目标，新能源电动汽车迎来了发展的顶峰。在锂离子电池技术中，正极材料是锂离子电压和容量的决定性因素，决定着锂电池容量的天花板，电解液则为锂电池容量达到所需的血液。但无论是高电压体系还是高镍体系，保证正极材料框架的稳定是实现其容量天板的必要条件。宏观上的稳定是由正极活性物质微观结构决定的，比如正极材料中金属离子的价态、正极金属离子与氧的配位状态等，通过对这些微观参数的变化可以表征其正极材料的稳定状态。现阶段正极材料脱嵌锂过程中，当锂脱嵌到一定程度，相态的转变使得正极材料框架不稳定，正极高价态的金属离子容易脱出，例如：含锰基正极的锂离子电池充电过程中，锰的溶出，以Mn2+形式迁移到负极，并在负极沉积造成短路。在高电压及高镍体系，正极材料与电解液间存在较差的兼容性，不利于锂离子的传递。电解液对正极活性物质保护差，使得正极材料的高价态金属离子暴露，暴露的高价态金属离子对电解液有一定的催化作用，引起电解液的催化氧化，进而导致晶格氧缺失，引发Mn离子的溶出，造成正极活性材料的结构坍塌，影响电池性能；同时当Mn的平均价态低于+3.5时，正极活性材料的晶体结构会发生转变由稳定结构转至不稳定结构，使电极的极化作用增强，引起容量衰减，导电性能差等缺点。目前许多研究人员通过往正极活性材料中添加导电剂来强化正极活性材料的导电性能，导电性能得到一定的改善，但是进而引发出一系列问题，导电剂的加入使得正极稳定性变差，Mn离子更易溶出，并且进一步弱化了锂离子的扩散速率，同时正极活性材料与电解液之间的兼容性变得更差，进而使得电池的高低温条件下循环性能和存储性能劣化。Lithium-ion batteries have the advantages of high operating voltage, high energy density, good safety performance, low self-discharge, fast charging, wide operating range, and long service life. They dominate the global secondary battery market. In recent years, in order to achieve the green goal of "carbon neutrality", new energy electric vehicles have reached the peak of development. In lithium-ion battery technology, the positive electrode material is the decisive factor in lithium-ion voltage and capacity, and determines the ceiling of lithium battery capacity. The electrolyte is the blood required for the lithium battery capacity to reach the required level. However, whether it is a high-voltage system or a high-nickel system, ensuring the stability of the positive electrode material framework is a necessary condition for achieving its capacity ceiling. Macroscopic stability is determined by the microstructure of the positive electrode active material, such as the valence state of the metal ions in the positive electrode material, the coordination state of the positive electrode metal ions and oxygen, etc. The stability of the positive electrode material can be characterized by the changes in these microscopic parameters. At present, during the process of lithium deintercalation of positive electrode materials, when lithium is deintercalated to a certain extent, the phase transition makes the framework of the positive electrode material unstable, and the high-valent metal ions of the positive electrode are easily deintercalated. For example, during the charging process of lithium-ion batteries containing manganese-based positive electrodes, manganese is dissolved and migrates to the negative electrode in the form of Mn 2+ , and deposits at the negative electrode to cause a short circuit. In high-voltage and high-nickel systems, there is poor compatibility between the positive electrode material and the electrolyte, which is not conducive to the transfer of lithium ions. The electrolyte has poor protection for the positive electrode active material, which exposes the high-valent metal ions of the positive electrode material. The exposed high-valent metal ions have a certain catalytic effect on the electrolyte, causing catalytic oxidation of the electrolyte, which in turn leads to lattice oxygen deficiency, triggering the dissolution of Mn ions, causing the structural collapse of the positive electrode active material, and affecting the battery performance; at the same time, when the average valence of Mn is lower than +3.5, the crystal structure of the positive electrode active material will change from a stable structure to an unstable structure, which will enhance the polarization of the electrode, causing capacity decay, poor conductivity and other shortcomings. At present, many researchers have enhanced the conductivity of positive electrode active materials by adding conductive agents to them. The conductivity has been improved to a certain extent, but this has led to a series of problems. The addition of conductive agents has made the positive electrode less stable, Mn ions more easily dissolved, and further weakened the diffusion rate of lithium ions. At the same time, the compatibility between the positive electrode active materials and the electrolyte has become worse, which has led to the deterioration of the cycle performance and storage performance of the battery under high and low temperature conditions.
发明内容Summary of the invention
针对现有锂离子电池正极存在Mn的价位变化导致Mn离子溶出的问题，本发明提供了一种锂离子电池。Aiming at the problem that the valence change of Mn in the positive electrode of the existing lithium ion battery leads to the dissolution of Mn ions, the present invention provides a lithium ion battery.
本发明解决上述技术问题所采用的技术方案如下：The technical solution adopted by the present invention to solve the above technical problems is as follows:
本发明提供了一种锂离子电池，包括正极、负极和非水电解液，所述正极包括含有正极活性材料的正极材料层，所述正极活性材料包括含锰正极材料，所述正极活性材料的比表面积为0.5～1.5m2/g，所述非水电解液包括非水有机溶剂、添加剂和锂盐，所述添加剂包括结构式1所示的化合物:
The present invention provides a lithium ion battery, comprising a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the positive electrode comprises a positive electrode material layer containing a positive electrode active material, wherein the positive electrode active material comprises a manganese-containing positive electrode material, and wherein the specific surface area of the positive electrode active material is 0.5 to 1.5 m2 /g; and the non-aqueous electrolyte comprises a non-aqueous organic solvent, an additive and a lithium salt, wherein the additive comprises a compound shown in structural formula 1:
The present invention provides a lithium ion battery, comprising a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the positive electrode comprises a positive electrode material layer containing a positive electrode active material, wherein the positive electrode active material comprises a manganese-containing positive electrode material, and wherein the specific surface area of the positive electrode active material is 0.5 to 1.5 m2 /g; and the non-aqueous electrolyte comprises a non-aqueous organic solvent, an additive and a lithium salt, wherein the additive comprises a compound shown in structural formula 1:
其中，n为0或1，X选自R1、R2各自独立选自H、卤素、未取代或卤素取代的C1-C5的烃基、且X、R1和R2中至少含有一个硫原子；Where n is 0 or 1, and X is selected from R 1 and R 2 are each independently selected from H, halogen, unsubstituted or halogen-substituted C1-C5 hydrocarbon group, and X, R1 and R2 contain at least one sulfur atom;
所述锂离子电池满足以下条件：The lithium-ion battery meets the following conditions:
0.5≤(Vr/Vr*)/Wr≤12，且0.4≤Vr/Vr*≤1.5，0.1≤Wr≤3；0.5≤(Vr/Vr*)/Wr≤12, and 0.4≤Vr/Vr*≤1.5, 0.1≤Wr≤3;
其中，Vr为正极活性材料的微孔比表面积，单位为m2/g；Wherein, Vr is the micropore specific surface area of the positive electrode active material, in m 2 /g;
Vr*为正极活性材料的介孔比表面积，单位为m2/g；Vr* is the mesoporous specific surface area of the positive electrode active material, in m 2 /g;
Wr为非水电解液中结构式1所示化合物的质量百分含量，单位为％。Wr is the mass percentage of the compound represented by structural formula 1 in the non-aqueous electrolyte, in %.
可选的，所述锂离子电池满足以下条件：
1≤(Vr/Vr*)/Wr≤10。Optionally, the lithium-ion battery meets the following conditions:
1≤(Vr/Vr*)/Wr≤10.
1≤(Vr/Vr*)/Wr≤10。Optionally, the lithium-ion battery meets the following conditions:
1≤(Vr/Vr*)/Wr≤10.
可选的，所述正极活性材料的微孔比表面积和介孔比表面积的比值Vr/Vr*为0.5～1.2。Optionally, the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material, Vr/Vr*, is 0.5 to 1.2.
可选的，所述正极活性材料的微孔比表面积Vr为0.2～0.7m2/g。Optionally, the micropore specific surface area Vr of the positive electrode active material is 0.2 to 0.7 m 2 /g.
可选的，所述正极活性材料的介孔比表面积Vr*为0.14～1.4m2/g。Optionally, the mesoporous specific surface area Vr* of the positive electrode active material is 0.14 to 1.4 m 2 /g.
可选的，所述非水电解液中结构式1所示化合物的质量百分含量Wr为0.1％～2％。Optionally, the mass percentage content Wr of the compound represented by structural formula 1 in the non-aqueous electrolyte is 0.1% to 2%.
可选的，所述锂离子电池40～60℃高温循环500周条件下，所述正极活性材料中金属离子Mn的价态比值为0.1≤M2+*/M4+*≤0.4，其中M2+*为Mn2+含量，为M4+*为Mn4+的含量。Optionally, when the lithium-ion battery is cycled at a high temperature of 40 to 60° C. for 500 cycles, the valence ratio of the metal ion Mn in the positive electrode active material is 0.1≤M 2+* /M 4+* ≤0.4, where M 2+* is the Mn 2+ content, and M 4+* is the Mn 4+ content.
可选的，所述结构式1所示的化合物包括以下化合物中的至少一种：
Optionally, the compound represented by structural formula 1 includes at least one of the following compounds:
Optionally, the compound represented by structural formula 1 includes at least one of the following compounds:
可选的，所述含锰正极材料选自LiNixCoyMnzL(1-x-y-z)O2中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Cu、V或Fe，0<x≤1，0≤y≤1，0<z≤1，0<x+y+z≤1。
Optionally, the manganese-containing positive electrode material is selected from at least one of LiNi x Co y Mn z L (1-xyz) O 2 , wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Cu, V or Fe, 0<x≤1, 0≤y≤1, 0<z≤1, 0<x+y+z≤1.
可选的，所述添加剂还包括磺酸内酯类化合物、环状碳酸酯类化合物、磷酸酯类化合物、硼酸酯类化合物和腈类化合物中的至少一种；Optionally, the additive further comprises at least one of a sultone compound, a cyclic carbonate compound, a phosphate compound, a borate compound and a nitrile compound;
以所述非水电解液的总质量为100％计，所述添加剂的添加量为0.01％～30％；Based on the total mass of the non-aqueous electrolyte being 100%, the additive is added in an amount of 0.01% to 30%;
所述磺酸内酯类化合物选自1,3-丙烷磺酸内酯、1,4-丁烷磺酸内酯、1,3-丙烯磺酸内酯、中的至少一种；The sultone compound is selected from 1,3-propane sultone, 1,4-butane sultone, 1,3-propylene sultone, At least one of;
所述环状碳酸酯类化合物选自碳酸亚乙烯酯、碳酸乙烯亚乙酯、亚甲基碳酸乙烯酯、氟代碳酸乙烯酯、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯或结构式2所示化合物中的至少一种：
The cyclic carbonate compound is selected from at least one of vinylene carbonate, ethylene carbonate, methylene carbonate, fluoroethylene carbonate, trifluoromethylethylene carbonate, bisfluoroethylene carbonate or the compound shown in Structural Formula 2:
The cyclic carbonate compound is selected from at least one of vinylene carbonate, ethylene carbonate, methylene carbonate, fluoroethylene carbonate, trifluoromethylethylene carbonate, bisfluoroethylene carbonate or the compound shown in Structural Formula 2:
所述结构式2中，R21、R22、R23、R24、R25、R26各自独立地选自氢原子、卤素原子、C1-C5基团中的一种；In the structural formula 2, R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are each independently selected from a hydrogen atom, a halogen atom, and a C1-C5 group;
所述磷酸酯类化合物选自三(三甲基硅烷)磷酸酯、三(三甲基硅烷)亚磷酸酯或结构式3所示化合物中的至少一种：
The phosphate compound is selected from at least one of tris(trimethylsilyl)phosphate, tris(trimethylsilyl)phosphite or the compound shown in structural formula 3:
The phosphate compound is selected from at least one of tris(trimethylsilyl)phosphate, tris(trimethylsilyl)phosphite or the compound shown in structural formula 3:
所述结构式3中，R31、R32、R33各自独立的选自C1-C5的饱和烃基、不饱和烃基、卤代烃基、-Si(CmH2m+1)3，m为1～3的自然数，且R31、R32、R33中至少有一个为不饱和烃基；In the structural formula 3, R 31 , R 32 , and R 33 are each independently selected from a C1-C5 saturated hydrocarbon group, an unsaturated hydrocarbon group, a halogenated hydrocarbon group, and -Si(C m H 2m+1 ) 3 , m is a natural number of 1 to 3, and at least one of R 31 , R 32 , and R 33 is an unsaturated hydrocarbon group;
所述硼酸酯类化合物选自三(三甲基硅烷)硼酸酯和三(三乙基硅烷)硼酸酯中的至少一种；The borate compound is selected from at least one of tris(trimethylsilyl)borate and tris(triethylsilyl)borate;
所述腈类化合物选自丁二腈、戊二腈、乙二醇双(丙腈)醚、己烷三腈、己二腈、庚二腈、辛二腈、壬二腈、癸二腈中的至少一种。The nitrile compound is selected from at least one of succinonitrile, glutaronitrile, ethylene glycol bis(propionitrile) ether, hexanetrinitrile, adiponitrile, pimelonitrile, suberonitrile, azelaic acid dinitrile and sebacononitrile.
根据本发明提供的锂离子电池，结构式1所示的化合物能够在正极表面分解形成界面膜，
该界面膜能够起到隔离正极活性材料和非水电解液的作用，以减少非水电解液在正极活性材料表面的分解，同时，发明人发现，在调控正极活性材料的比表面积的情况下，所述正极活性材料表面形成的界面膜质量与所述正极活性材料的微孔比表面积和介孔比表面积的比值以及非水电解液中结构式1所示的化合物的含量相关，通过选择具有特定范围的微孔比表面积和介孔比表面积的比值的正极活性材料，配合结构式1所示化合物的含量调整，使其满足条件0.5≤(Vr/Vr*)/Wr≤12，能够有效抑制含锰正极材料在电池循环过程中的锰离子价位的不可逆改变，进而减少含锰正极材料中锰离子溶出，推测是由于在该微孔比表面积和介孔比表面积的比值范围和结构式1所示的化合物的含量下，结构式1所示的化合物形成的界面膜具有与含锰正极材料表面锰元素更好的配合效果，在正极活性材料及电解质相界面形成特定的网状导电界面，作为特殊的锂离子传输通道，有利于锂离子的脱附和传递，同时使得金属锰离子与O之间的配位保持六配位，维持正极活性材料的立体结构。According to the lithium ion battery provided by the present invention, the compound represented by structural formula 1 can be decomposed on the surface of the positive electrode to form an interface film. The interface film can play a role in isolating the positive electrode active material and the non-aqueous electrolyte to reduce the decomposition of the non-aqueous electrolyte on the surface of the positive electrode active material. At the same time, the inventors found that when the specific surface area of the positive electrode active material is regulated, the quality of the interface film formed on the surface of the positive electrode active material is related to the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material and the content of the compound shown in structural formula 1 in the non-aqueous electrolyte. By selecting a positive electrode active material with a specific range of the ratio of the micropore specific surface area to the mesopore specific surface area, and adjusting the content of the compound shown in structural formula 1, the condition 0.5≤(Vr/Vr*)/Wr≤1 is satisfied. 2. It can effectively inhibit the irreversible change of the valence of manganese ions in the manganese-containing positive electrode material during the battery cycle, thereby reducing the dissolution of manganese ions in the manganese-containing positive electrode material. It is speculated that the interface film formed by the compound shown in structural formula 1 has a better coordination effect with the manganese element on the surface of the manganese-containing positive electrode material under the ratio range of the micropore specific surface area to the mesopore specific surface area and the content of the compound shown in structural formula 1, and forms a specific mesh conductive interface at the interface between the positive electrode active material and the electrolyte phase, which serves as a special lithium ion transmission channel, is conducive to the desorption and transfer of lithium ions, and at the same time, the coordination between the metal manganese ion and O is maintained at six coordination, maintaining the three-dimensional structure of the positive electrode active material.
为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
本发明实施例提供了一种锂离子电池，包括正极、负极和非水电解液，所述正极包括含有正极活性材料的正极材料层，所述正极活性材料包括含锰正极材料，所述正极活性材料的比表面积为0.5～1.5m2/g，所述非水电解液包括非水有机溶剂、添加剂和锂盐，所述添加剂包括结构式1所示的化合物：
The embodiment of the present invention provides a lithium ion battery, comprising a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the positive electrode comprises a positive electrode material layer containing a positive electrode active material, wherein the positive electrode active material comprises a manganese-containing positive electrode material, and wherein the specific surface area of the positive electrode active material is 0.5 to 1.5 m 2 /g; and the non-aqueous electrolyte comprises a non-aqueous organic solvent, an additive and a lithium salt, wherein the additive comprises a compound shown in structural formula 1:
The embodiment of the present invention provides a lithium ion battery, comprising a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the positive electrode comprises a positive electrode material layer containing a positive electrode active material, wherein the positive electrode active material comprises a manganese-containing positive electrode material, and wherein the specific surface area of the positive electrode active material is 0.5 to 1.5 m 2 /g; and the non-aqueous electrolyte comprises a non-aqueous organic solvent, an additive and a lithium salt, wherein the additive comprises a compound shown in structural formula 1:
其中，n为0或1，X选自R1、R2各自独立选自H、卤素、未取代或卤素取代的C1-C5的烃基、且X、R1和R2中至少含有一个硫原子；Where n is 0 or 1, and X is selected from R 1 and R 2 are each independently selected from H, halogen, unsubstituted or halogen-substituted C1-C5 hydrocarbon group, and X, R1 and R2 contain at least one sulfur atom;
所述锂离子电池满足以下条件：The lithium-ion battery meets the following conditions:
0.5≤(Vr/Vr*)/Wr≤12，且0.4≤Vr/Vr*≤1.5，0.1≤Wr≤3；
0.5≤(Vr/Vr*)/Wr≤12, and 0.4≤Vr/Vr*≤1.5, 0.1≤Wr≤3;
其中，Vr为正极活性材料的微孔比表面积，单位为m2/g；Wherein, Vr is the micropore specific surface area of the positive electrode active material, in m 2 /g;
Vr*为正极活性材料的介孔比表面积，单位为m2/g；Vr* is the mesoporous specific surface area of the positive electrode active material, in m 2 /g;
Wr为非水电解液中结构式1所示化合物的质量百分含量，单位为％。Wr is the mass percentage of the compound represented by structural formula 1 in the non-aqueous electrolyte, in %.
发明人发现，在调控正极活性材料的比表面积的情况下，所述正极活性材料表面形成的界面膜质量与所述正极活性材料的微孔比表面积和介孔比表面积的比值以及非水电解液中结构式1所示的化合物的含量相关，通过选择具有特定范围的微孔比表面积和介孔比表面积的比值的正极活性材料，配合结构式1所示化合物的含量调整，使其满足条件0.5≤(Vr/Vr*)/Wr≤12，能够有效抑制含锰正极材料在电池循环过程中的锰离子价位的不可逆改变，进而减少含锰正极材料中锰离子溶出，推测是由于在该微孔比表面积和介孔比表面积的比值范围和结构式1所示的化合物的含量下，结构式1所示的化合物形成的界面膜具有与含锰正极材料表面锰元素更好的配合效果，在正极活性材料及电解质相界面形成特定的网状导电界面，作为特殊的锂离子传输通道，有利于锂离子的脱附和传递，同时使得金属锰离子与O之间的配位保持六配位，维持正极活性材料的立体结构。The inventors found that, in the case of regulating the specific surface area of the positive electrode active material, the quality of the interfacial film formed on the surface of the positive electrode active material is related to the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material and the content of the compound represented by structural formula 1 in the non-aqueous electrolyte. By selecting a positive electrode active material having a ratio of the micropore specific surface area to the mesopore specific surface area in a specific range and adjusting the content of the compound represented by structural formula 1 to satisfy the condition 0.5≤(Vr/Vr*)/Wr≤12, the manganese ionization of the manganese-containing positive electrode material during the battery cycle can be effectively suppressed. The irreversible change of the sub-valence position reduces the dissolution of manganese ions in the manganese-containing positive electrode material. It is speculated that the interface film formed by the compound shown in structural formula 1 has a better coordination effect with the manganese element on the surface of the manganese-containing positive electrode material under the ratio range of the micropore specific surface area to the mesopore specific surface area and the content of the compound shown in structural formula 1, and forms a specific mesh conductive interface at the interface between the positive electrode active material and the electrolyte phase, which serves as a special lithium ion transmission channel, is conducive to the desorption and transfer of lithium ions, and at the same time keeps the coordination between the metal manganese ion and O six-coordinated, maintaining the three-dimensional structure of the positive electrode active material.
在优选的实施例中，所述锂离子电池满足以下条件：
1≤(Vr/Vr*)/Wr≤10。In a preferred embodiment, the lithium-ion battery meets the following conditions:
1≤(Vr/Vr*)/Wr≤10.
1≤(Vr/Vr*)/Wr≤10。In a preferred embodiment, the lithium-ion battery meets the following conditions:
1≤(Vr/Vr*)/Wr≤10.
通过以上关系式的进一步限定，能够综合正极活性材料的微孔比表面积Vr、正极活性材料的介孔比表面积Vr*和非水电解液中结构式1所示化合物的质量百分含量Wr对于含锰正极材料中锰离子溶出的影响，并在含锰正极材料表面形成稳定的界面膜；主要作用有：一、可以减少极化作用带来的冲击；二、作为正极锰金属离子溶出的屏障，减少正极锰金属离子的溶出；三、通过界面协同效应强化正极活性材料的结构，同时弱化正极活性材料与非水电解液间的界面阻抗，使锂电池具有良好的倍率性能、高温存储性能和高温循环性能。Through further limitation of the above relationship, the influence of the micropore specific surface area Vr of the positive electrode active material, the mesopore specific surface area Vr* of the positive electrode active material and the mass percentage Wr of the compound shown in the structural formula 1 in the non-aqueous electrolyte on the dissolution of manganese ions in the manganese-containing positive electrode material can be comprehensively considered, and a stable interface film can be formed on the surface of the manganese-containing positive electrode material; the main functions are: 1. It can reduce the impact caused by polarization; 2. It serves as a barrier to the dissolution of positive electrode manganese metal ions, reducing the dissolution of positive electrode manganese metal ions; 3. It strengthens the structure of the positive electrode active material through the interface synergistic effect, and at the same time weakens the interface impedance between the positive electrode active material and the non-aqueous electrolyte, so that the lithium battery has good rate performance, high temperature storage performance and high temperature cycle performance.
在本发明的描述中，“微孔”指代孔径小于2nm的孔，“介孔”指代孔径大于等于2nm的孔，优选为2～50nm的孔。In the description of the present invention, "micropore" refers to a pore with a pore diameter less than 2 nm, and "mesopore" refers to a pore with a pore diameter greater than or equal to 2 nm, preferably a pore with a pore diameter of 2 to 50 nm.
术语“微孔比表面积”、术语“介孔比表面积”以及术语“正极活性材料的比表面积”可通过氮吸附BET比表面积方法进行测量。The term “micropore specific surface area”, the term “mesopore specific surface area”, and the term “specific surface area of the positive electrode active material” may be measured by a nitrogen adsorption BET specific surface area method.
在一些实施例中，所述正极活性材料的微孔比表面积和介孔比表面积的比值Vr/Vr*为0.4、0.45、0.5、0.6、0.7、0.8、0.9、1.0、1.1或1.2。In some embodiments, the ratio of the micropore specific surface area to the mesopore specific surface area of the cathode active material, Vr/Vr*, is 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 or 1.2.
在优选的实施例中，所述正极活性材料的微孔比表面积和介孔比表面积的比值Vr/Vr*为0.5～1.2。In a preferred embodiment, the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material Vr/Vr* is 0.5 to 1.2.
所述正极活性材料的微孔比表面积和介孔比表面积的比值Vr/Vr*的大小会影响非水电解液对于正极材料层的浸润效果，同时影响正极活性材料中的保液量，在进行初次化成的时候，正极活性材料中的保液量与形成的界面膜厚度相关，而形成的界面膜厚度过高时，会堵塞部分微孔，减小正极活性材料与非水电解液的实际接触面积，影响非水电解液与正极活性材料之间的锂离子脱嵌；形成的界面膜厚度过低时，会导致非水电解液在正极活性材料表面的副反应严重，同时难以抑制锰离子的溶出；在本发明的电池体系中，当正极活性材料的微孔比表面积和介孔比表面积的比值Vr/Vr*处于上述范围时，利于生成厚度合适且离子电导率较好
的界面膜，有效抑制锰离子的价位变化同时避免对于电池阻抗的影响。The size of the ratio Vr/Vr* of the micropore specific surface area and the mesopore specific surface area of the positive electrode active material will affect the wetting effect of the non-aqueous electrolyte on the positive electrode material layer, and at the same time affect the liquid retention amount in the positive electrode active material. During the initial formation, the liquid retention amount in the positive electrode active material is related to the thickness of the formed interface film. When the thickness of the formed interface film is too high, some micropores will be blocked, reducing the actual contact area between the positive electrode active material and the non-aqueous electrolyte, affecting the lithium ion deintercalation between the non-aqueous electrolyte and the positive electrode active material; when the thickness of the formed interface film is too low, it will cause serious side reactions of the non-aqueous electrolyte on the surface of the positive electrode active material, and it will be difficult to inhibit the dissolution of manganese ions; in the battery system of the present invention, when the ratio Vr/Vr* of the micropore specific surface area and the mesopore specific surface area of the positive electrode active material is within the above range, it is conducive to the generation of a suitable thickness and good ionic conductivity. The interface film can effectively inhibit the price change of manganese ions while avoiding the impact on battery impedance.
在一些实施例中，所述正极活性材料的微孔比表面积Vr为0.2～0.7m2/g。In some embodiments, the micropore specific surface area Vr of the positive electrode active material is 0.2 to 0.7 m 2 /g.
在一些实施例中，所述正极活性材料的微孔比表面积Vr可以为0.2m2/g、0.4m2/g、0.5m2/g、0.6m2/g、0.7m2/g。In some embodiments, the micropore specific surface area Vr of the positive electrode active material may be 0.2 m 2 /g, 0.4 m 2 /g, 0.5 m 2 /g, 0.6 m 2 /g, or 0.7 m 2 /g.
在一些实施例中，所述正极活性材料的介孔比表面积Vr*为0.14～1.4m2/g。In some embodiments, the mesoporous specific surface area Vr* of the positive electrode active material is 0.14 to 1.4 m 2 /g.
在一些实施例中，所述正极活性材料的介孔比表面积Vr*可以为0.14m2/g、0.16m2/g、0.2m2/g、0.3m2/g、0.4m2/g、0.5m2/g、0.6m2/g、0.7m2/g、0.8m2/g、0.9m2/g、1m2/g、1.1m2/g、1.2m2/g、1.3m2/g或1.4m2/g。In some embodiments, the mesoporous specific surface area Vr* of the cathode active material may be 0.14 , 0.16 , 0.2 , 0.3 , 0.4 , 0.5 , 0.6, 0.7 , 0.8, 0.9, 1 , 1.1, 1.2 , 1.3 or 1.4 m2 /g.
在一些实施例中，所述非水电解液中结构式1所示化合物的质量百分含量Wr可以为0.1％、0.2％、0.4％、0.5％、0.7％、0.8％、0.9％、1.0％、1.1％、1.3％、1.5％、1.8％、2.0％、2.3％、2.5％、2.7％、2.8％、2.9％或3.0％In some embodiments, the mass percentage content Wr of the compound represented by structural formula 1 in the non-aqueous electrolyte may be 0.1%, 0.2%, 0.4%, 0.5%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.3%, 1.5%, 1.8%, 2.0%, 2.3%, 2.5%, 2.7%, 2.8%, 2.9% or 3.0%.
在优选的实施例中，所述非水电解液中结构式1所示化合物的质量百分含量Wr为0.1％～2％。In a preferred embodiment, the mass percentage content Wr of the compound represented by structural formula 1 in the non-aqueous electrolyte is 0.1% to 2%.
在上述质量百分含量范围内的结构式1所示化合物，能够在含锰正极材料表面发生分解，形成一种特殊的界面膜，该界面膜与特定比表面积正极活性材料通过界面协同作用强化含锰正极材料的稳定性，同时强化锂离子传输通道，含锰正极材料中无论是高电压还是高镍体系，其特点是Mn离子容易溶出，结构式1所示的化合物在含锰正极材料与非水电解液之间形成金属离子(除锂离子外)的屏障，可以对锰离子起到络合作用，抑制锰离子从正极的溶出及在负极的沉积；屏蔽与非水电解液的接触，进而减少副反应的发生和非水电解液的损失，从而显著改善电池的高温循环性能，结构式1所示的化合物弱化正极材料与电解质间的界面阻抗，实现对正极材料和负极材料的保护，同时可以明显降低高温条件下电池的气胀作用，从而改善电池的高温存储性能和高温循环性能。The compound shown in the structural formula 1 within the above-mentioned mass percentage range can decompose on the surface of the manganese-containing positive electrode material to form a special interface film. The interface film and the positive electrode active material with a specific specific surface area can enhance the stability of the manganese-containing positive electrode material through interface synergy, and at the same time enhance the lithium ion transmission channel. The manganese-containing positive electrode material, whether it is a high voltage or high nickel system, is characterized in that Mn ions are easily dissolved. The compound shown in the structural formula 1 forms a barrier of metal ions (except lithium ions) between the manganese-containing positive electrode material and the non-aqueous electrolyte, which can complex the manganese ions and inhibit the dissolution of manganese ions from the positive electrode and the deposition of manganese ions on the negative electrode; shield the contact with the non-aqueous electrolyte, thereby reducing the occurrence of side reactions and the loss of the non-aqueous electrolyte, thereby significantly improving the high-temperature cycle performance of the battery. The compound shown in the structural formula 1 weakens the interface impedance between the positive electrode material and the electrolyte, realizes the protection of the positive electrode material and the negative electrode material, and can significantly reduce the expansion effect of the battery under high temperature conditions, thereby improving the high-temperature storage performance and high-temperature cycle performance of the battery.
在一些实施例，所述锂离子电池40～60℃高温循环500周条件下，所述正极活性材料中金属离子Mn的价态比值为0.1≤M2+*/M4+*≤0.4，其中M2+*为Mn2+含量，为M4+*为Mn4+的含量。In some embodiments, when the lithium-ion battery is cycled at a high temperature of 40 to 60° C. for 500 cycles, the valence ratio of the metal ion Mn in the positive electrode active material is 0.1≤M 2+* /M 4+* ≤0.4, where M 2+* is the Mn 2+ content, and M 4+* is the Mn 4+ content.
所述正极活性材料中金属离子Mn的价态比值可通过以下方法测试得到：The valence ratio of the metal ion Mn in the positive electrode active material can be obtained by testing using the following method:
通过X射线光电子能谱仪(XPS)测试正极片，具有顶值为653.1～653.7eV的峰代表Mn2+所对应的2p1/2峰，该峰的峰面积大小对应Mn2+含量，具有顶值为653.8～654.2eV的峰代表Mn4+的所对应的2p1/2峰，该峰的峰面积大小对应Mn4+含量，通过两种峰面积的比值计算出所述正极活性材料中金属离子Mn的价态比值。The positive electrode sheet was tested by an X-ray photoelectron spectrometer (XPS). The peak with a top value of 653.1-653.7 eV represented the 2p1/2 peak corresponding to Mn 2+ , and the peak area of the peak corresponded to the Mn 2+ content. The peak with a top value of 653.8-654.2 eV represented the 2p1/2 peak corresponding to Mn 4+ , and the peak area of the peak corresponded to the Mn 4+ content. The valence ratio of the metal ion Mn in the positive electrode active material was calculated by the ratio of the two peak areas.
在一些实施例中，所述结构式1所示的化合物包括以下化合物中的至少一种：
In some embodiments, the compound represented by structural formula 1 includes at least one of the following compounds:
In some embodiments, the compound represented by structural formula 1 includes at least one of the following compounds:
需要说明的是，以上仅是本发明优选的化合物，并不代表对于本发明的限制。It should be noted that the above are only preferred compounds of the present invention and do not represent limitations on the present invention.
本领域技术人员在知晓结构式1所示的化合物的结构式的情况下，根据化学合成领域的公知常识可以知晓上述化合物的制备方法。例如：化合物15可通过以下方法制成：A person skilled in the art, knowing the structural formula of the compound shown in Structural Formula 1, can know the preparation method of the above compound according to the common knowledge in the field of chemical synthesis. For example, Compound 15 can be prepared by the following method:
将山梨醇、碳酸二甲酯、甲醇碱性物质催化剂氢氧化钾以及DMF等有机溶剂置于反应容器中，在加热条件下进行反应数小时后，加入一定量的草酸调节pH至中性，过滤、重结晶后即可得到中间产物1，接着将中间产物1、碳酸酯、二氯亚砜等在高温条件下发生酯化反应得到中间产物2，再使用高碘酸钠等氧化剂将中间产物2氧化即可得到化合物15。Sorbitol, dimethyl carbonate, methanol, alkaline substance catalyst potassium hydroxide and organic solvent such as DMF are placed in a reaction container, and reacted under heating conditions for several hours. Then, a certain amount of oxalic acid is added to adjust the pH to neutral. After filtering and recrystallization, intermediate product 1 can be obtained. Then, intermediate product 1, carbonate, dichlorothionyl, etc. are subjected to esterification reaction under high temperature conditions to obtain intermediate product 2. Then, intermediate product 2 is oxidized using an oxidant such as sodium periodate to obtain compound 15.
在一些实施例中，所述锂离子电池为软包电池或硬壳电池。In some embodiments, the lithium-ion battery is a soft-pack battery or a hard-shell battery.
在一些实施例中，所述含锰正极材料选自LiNixCoyMnzL(1-x-y-z)O2中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Cu、V或Fe，0<x≤1，0≤y≤1，0<z≤1，0<x+y+z≤1。In some embodiments, the manganese-containing positive electrode material is selected from at least one of LiNi x Co y Mn z L (1-xyz) O 2 , wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Cu, V or Fe, 0<x≤1, 0≤y≤1, 0<z≤1, 0<x+y+z≤1.
在一些实施例中，所述正极材料层还包括有正极粘结剂，所述正极粘结剂包括聚偏氟乙烯、偏氟乙烯的共聚物、聚四氟乙烯、偏氟乙烯-六氟丙烯的共聚物、四氟乙烯-六氟丙烯的共聚物、四氟乙烯-全氟烷基乙烯基醚的共聚物、乙烯-四氟乙烯的共聚物、偏氟乙烯-四氟乙烯的共聚物、偏氟乙烯-三氟乙烯的共聚物、偏氟乙烯-三氯乙烯的共聚物、偏氟乙烯-氟代乙烯的共聚物、偏氟乙烯-六氟丙烯-四氟乙烯的共聚物、热塑性聚酰亚胺、聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚甲基丙烯酸甲酯等热塑性树脂；丙烯酸类树脂；羟甲基纤维素钠；丁腈橡胶、聚丁橡胶、乙烯-丙烯橡胶、苯乙烯-丁二烯-苯乙烯嵌段共聚物或其氢化物、乙烯-丙烯-二烯三元共聚物、聚乙酸乙烯酯、间规-1,2-聚丁二烯、乙烯-乙烯乙酸酯中的至少一种。In some embodiments, the positive electrode material layer also includes a positive electrode binder, and the positive electrode binder includes polyvinylidene fluoride, a copolymer of vinylidene fluoride, polytetrafluoroethylene, a copolymer of vinylidene fluoride-hexafluoropropylene, a copolymer of tetrafluoroethylene-hexafluoropropylene, a copolymer of tetrafluoroethylene-perfluoroalkyl vinyl ether, a copolymer of ethylene-tetrafluoroethylene, a copolymer of vinylidene fluoride-tetrafluoroethylene, a copolymer of vinylidene fluoride-trifluoroethylene, a copolymer of vinylidene fluoride-trichloroethylene, a copolymer of vinylidene fluoride-fluoroethylene, a copolymer of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene, a thermoplastic polyimide, polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate and other thermoplastic resins; acrylic resin; sodium hydroxymethyl cellulose; at least one of nitrile rubber, polybutadiene rubber, ethylene-propylene rubber, styrene-butadiene-styrene block copolymer or its hydride, ethylene-propylene-diene terpolymer, polyvinyl acetate, syndiotactic-1,2-polybutadiene, and ethylene-vinyl acetate.
在一些实施例中，所述正极材料层还包括正极导电剂，所述正极导电剂包括导电炭黑、导电碳球、导电石墨、导电碳纤维、碳纳米管、石墨烯或还原氧化石墨烯中的至少一种。In some embodiments, the positive electrode material layer further includes a positive electrode conductive agent, and the positive electrode conductive agent includes at least one of conductive carbon black, conductive carbon balls, conductive graphite, conductive carbon fibers, carbon nanotubes, graphene, or reduced graphene oxide.
在一些实施例中，所述正极集流体选自可传导电子的金属材料，优选的，所述正极集流体包括Al、Ni、锡、铜、不锈钢的至少一种，在更优选的实施例中，所述正极集流体选自铝箔。In some embodiments, the positive electrode current collector is selected from a metal material that can conduct electrons. Preferably, the positive electrode current collector includes at least one of Al, Ni, tin, copper, and stainless steel. In a more preferred embodiment, the positive electrode current collector is selected from aluminum foil.
在一些实施例中，所述负极包括负极材料层，所述负极材料层包括负极活性材料。In some embodiments, the negative electrode includes a negative electrode material layer, and the negative electrode material layer includes a negative electrode active material.
在优选实施例中，所述负极活性材料包括碳基负极、硅基负极、锡基负极、锂负极中的至少一种。其中碳基负极可包括石墨、硬碳、软碳、石墨烯、中间相碳微球等；硅基负极可包括硅材料、硅的氧化物、硅碳复合材料以及硅合金材料等；锡基负极可包括锡、锡碳、锡氧、锡金属化合物；锂负极可包括金属锂或锂合金。锂合金具体可以是锂硅合金、锂钠合金、锂钾合金、锂铝合金、锂锡合金和锂铟合金中的至少一种。In a preferred embodiment, the negative electrode active material includes at least one of a carbon-based negative electrode, a silicon-based negative electrode, a tin-based negative electrode, and a lithium negative electrode. The carbon-based negative electrode may include graphite, hard carbon, soft carbon, graphene, mesophase carbon microspheres, etc.; the silicon-based negative electrode may include silicon materials, silicon oxides, silicon-carbon composite materials, and silicon alloy materials, etc.; the tin-based negative electrode may include tin, tin carbon, tin oxygen, and tin metal compounds; the lithium negative electrode may include metallic lithium or a lithium alloy. The lithium alloy may specifically be at least one of a lithium silicon alloy, a lithium sodium alloy, a lithium potassium alloy, a lithium aluminum alloy, a lithium tin alloy, and a lithium indium alloy.
在一些实施例中，所述负极材料层还包括有负极粘结剂和负极导电剂，所述负极活性材料、所述负极粘结剂和所述负极导电剂共混得到所述负极材料层。In some embodiments, the negative electrode material layer further includes a negative electrode binder and a negative electrode conductive agent, and the negative electrode active material, the negative electrode binder and the negative electrode conductive agent are blended to obtain the negative electrode material layer.
所述负极粘接剂和负极导电剂的可选择范围分别与所述正极粘结剂和正极导电剂相同，在此不再赘述。
The selectable ranges of the negative electrode binder and the negative electrode conductor are the same as those of the positive electrode binder and the positive electrode conductor, respectively, and will not be described in detail here.
在一些实施例中，所述负极还包括负极集流体，所述负极材料层形成于所述负极集流体的表面。In some embodiments, the negative electrode further includes a negative electrode current collector, and the negative electrode material layer is formed on a surface of the negative electrode current collector.
所述负极集流体选自可传导电子的金属材料，优选的，所述负极集流体包括Al、Ni、锡、铜、不锈钢的至少一种，在更优选的实施例中，所述负极集流体选自铜箔。The negative electrode current collector is selected from metal materials that can conduct electrons. Preferably, the negative electrode current collector includes at least one of Al, Ni, tin, copper, and stainless steel. In a more preferred embodiment, the negative electrode current collector is selected from copper foil.
在一些实施例中，所述锂盐包括LiPF6、LiBOB、LiDFOB、LiPO2F2、LiBF4、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO2F)2、LiClO4、LiAlCl4、LiCF3SO3、Li2B10Cl10、LiSO3F、LiTOP、LiDODFP、LiOTF和低级脂肪族羧酸锂盐中的至少一种。In some embodiments, the lithium salt includes at least one of LiPF6 , LiBOB, LiDFOB, LiPO2F2 , LiBF4 , LiSbF6 , LiAsF6 , LiN( SO2CF3 ) 2 , LiN(SO2C2F5) 2 , LiC ( SO2CF3 ) 3 , LiN( SO2F ) 2 , LiClO4 , LiAlCl4 , LiCF3SO3 , Li2B10Cl10 , LiSO3F , LiTOP, LiDODFP, LiOTF and a lower aliphatic carboxylic acid lithium salt.
在一些实施例中，所述非水电解液中，所述锂盐的浓度为0.1mol/L～8mol/L。在优选实施例中，所述非水电解液中，所述锂盐的浓度为0.5mol/L～2.5mol/L。具体的，所述非水电解液中，所述锂盐的浓度可以为0.5mol/L、1mol/L、1.5mol/L、2mol/L、2.5mol/L。In some embodiments, the concentration of the lithium salt in the non-aqueous electrolyte is 0.1 mol/L to 8 mol/L. In a preferred embodiment, the concentration of the lithium salt in the non-aqueous electrolyte is 0.5 mol/L to 2.5 mol/L. Specifically, the concentration of the lithium salt in the non-aqueous electrolyte may be 0.5 mol/L, 1 mol/L, 1.5 mol/L, 2 mol/L, or 2.5 mol/L.
在一些实施例中，所述非水有机溶剂包括醚类溶剂、腈类溶剂、碳酸酯类溶剂和羧酸酯类溶剂中的至少一种。In some embodiments, the non-aqueous organic solvent includes at least one of an ether solvent, a nitrile solvent, a carbonate solvent, and a carboxylate solvent.
在一些实施例中，醚类溶剂包括环状醚或链状醚，优选为碳原子数3～10的链状醚及碳原子数3～6的环状醚，环状醚具体可以但不限于是1,3-二氧戊烷(DOL)、1,4-二氧惡烷(DX)、冠醚、四氢呋喃(THF)、2-甲基四氢呋喃(2-CH3-THF)，2-三氟甲基四氢呋喃(2-CF3-THF)中的至少一种；所述链状醚具体可以但不限于是二甲氧基甲烷、二乙氧基甲烷、乙氧基甲氧基甲烷、乙二醇二正丙基醚、乙二醇二正丁基醚、二乙二醇二甲基醚。由于链状醚与锂离子的溶剂化能力高、可提高离子解离性，因此特别优选粘性低、可赋予高离子电导率的二甲氧基甲烷、二乙氧基甲烷、乙氧基甲氧基甲烷。醚类化合物可以单独使用一种，也可以以任意的组合及比率组合使用两种以上。醚类化合物的含量没有特殊限制，在不显著破坏本发明高压实锂离子电池效果的范围内是任意的，在非水溶剂体积比为100％中通常体积比为1％以上、优选体积比为2％以上、更优选体积比为3％以上，另外，通常体积比为30％以下、优选体积比为25％以下、更优选体积比为20％以下。在将两种以上醚类化合物组合使用的情况下，使醚类化合物的总量满足上述范围即可。醚类化合物的含量在上述的优选范围内时，易于确保由链状醚的锂离子离解度的提高和粘度降低所带来的离子电导率的改善效果。另外，负极活性材料为碳基材料的情况下，可抑制因链状醚与锂离子共同发生共嵌入的现象，因此能够使输入输出特性、充放电速率特性达到适当的范围。In some embodiments, the ether solvent includes a cyclic ether or a chain ether, preferably a chain ether with 3 to 10 carbon atoms and a cyclic ether with 3 to 6 carbon atoms. The cyclic ether may be, but is not limited to, at least one of 1,3-dioxolane (DOL), 1,4-dioxolane (DX), crown ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH 3 -THF), and 2-trifluoromethyltetrahydrofuran (2-CF 3 -THF); the chain ether may be, but is not limited to, dimethoxymethane, diethoxymethane, ethoxymethoxymethane, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, and diethylene glycol dimethyl ether. Since the chain ether has a high solvation ability with lithium ions and can improve ion dissociation, dimethoxymethane, diethoxymethane, and ethoxymethoxymethane, which have low viscosity and can impart high ionic conductivity, are particularly preferred. The ether compound may be used alone or in any combination and ratio. The content of the ether compound is not particularly limited and is arbitrary within the range that does not significantly damage the effect of the high-density lithium-ion battery of the present invention. The volume ratio is usually 1% or more, preferably 2% or more, and more preferably 3% or more in the non-aqueous solvent volume ratio of 100%. In addition, the volume ratio is usually 30% or less, preferably 25% or less, and more preferably 20% or less. When two or more ether compounds are used in combination, the total amount of the ether compounds can be made to meet the above range. When the content of the ether compound is within the above preferred range, it is easy to ensure the improvement effect of ion conductivity brought about by the increase in lithium ion dissociation degree and the decrease in viscosity of the chain ether. In addition, when the negative electrode active material is a carbon-based material, the phenomenon of co-embedding of chain ethers and lithium ions can be suppressed, so that the input-output characteristics and charge-discharge rate characteristics can reach an appropriate range.
在一些实施例中，腈类溶剂具体可以但不限于是乙腈、戊二腈、丙二腈中的至少一种。In some embodiments, the nitrile solvent may specifically be but is not limited to at least one of acetonitrile, glutaronitrile, and malononitrile.
在一些实施例中，碳酸酯类溶剂包括环状碳酸酯或链状碳酸酯，环状碳酸酯具体可以但不限于是碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、γ-丁内酯(GBL)、碳酸亚丁酯(BC)中的至少一种；链状碳酸酯具体可以但不限于是碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)中的至少一种。环状碳酸酯的含量没有特殊限制，在不显著破坏本发明锂离子电池效果的范围内是任意的，但在单独使用一种的情况下其含量的下限相对于非水电解液的溶剂总量来说，通常体积比为3％以上、优选体积比为5％以上。通过设定该范围，可避免由于非水电解液的介电常数降低而导致电导率降低，易于使非水电解质电池的大电流放电特性、相对于负极的稳定性、循环特性达到良好的范围。另外，上限通常体积比为90％以下、优选体积比为85％以下、更优选体积比为80％以下。通过设定该范
围，可提高非水电解液的氧化/还原耐性，从而有助于提高高温保存时的稳定性。链状碳酸酯的含量没有特殊限定，相对于非水电解液的溶剂总量，通常为体积比为15％以上、优选体积比为20％以上、更优选体积比为25％以上。另外，通常体积比为90％以下、优选体积比为85％以下、更优选体积比为80％以下。通过使链状碳酸酯的含量在上述范围，容易使非水电解液的粘度达到适当范围，抑制离子电导率的降低，进而有助于使非水电解质电池的输出特性达到良好的范围。在组合使用两种以上链状碳酸酯的情况下，使链状碳酸酯的总量满足上述范围即可。In some embodiments, the carbonate solvent includes a cyclic carbonate or a chain carbonate. The cyclic carbonate may be, but is not limited to, at least one of ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (GBL), and butylene carbonate (BC); the chain carbonate may be, but is not limited to, at least one of dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and dipropyl carbonate (DPC). There is no special restriction on the content of the cyclic carbonate, and it is arbitrary within the range that does not significantly damage the effect of the lithium ion battery of the present invention. However, when one is used alone, the lower limit of its content is usually 3% or more by volume, preferably 5% or more by volume, relative to the total amount of solvent in the non-aqueous electrolyte. By setting this range, the decrease in conductivity due to the decrease in the dielectric constant of the non-aqueous electrolyte can be avoided, and it is easy to make the large current discharge characteristics, stability relative to the negative electrode, and cycle characteristics of the non-aqueous electrolyte battery reach a good range. In addition, the upper limit is usually 90% or less by volume, preferably 85% or less by volume, and more preferably 80% or less by volume. By setting this range The content of the linear carbonate is not particularly limited, and is generally 15% or more by volume, preferably 20% or more by volume, and more preferably 25% or more by volume relative to the total amount of solvent in the nonaqueous electrolyte. In addition, the volume ratio is generally 90% or less, preferably 85% or less by volume, and more preferably 80% or less by volume. By making the content of the linear carbonate in the above range, it is easy to make the viscosity of the nonaqueous electrolyte reach an appropriate range, suppress the reduction of ionic conductivity, and then help to make the output characteristics of the nonaqueous electrolyte battery reach a good range. When two or more linear carbonates are used in combination, the total amount of the linear carbonates can be satisfied in the above range.
在一些实施例中，还可优选使用具有氟原子的链状碳酸酯类(以下简称为“氟化链状碳酸酯”)。氟化链状碳酸酯所具有的氟原子的个数只要为1以上则没有特殊限制，但通常为6以下、优选4以下。氟化链状碳酸酯具有多个氟原子的情况下，这些氟原子相互可以键合于同一个碳上，也可以键合于不同的碳上。作为氟化链状碳酸酯，可列举，氟化碳酸二甲酯衍生物、氟化碳酸甲乙酯衍生物、氟化碳酸二乙酯衍生物等。In certain embodiments, it is also possible to preferably use chain carbonates with fluorine atoms (hereinafter referred to as "fluorinated chain carbonates"). The number of fluorine atoms possessed by the fluorinated chain carbonate is not particularly limited as long as it is more than 1, but is generally less than 6, preferably less than 4. When the fluorinated chain carbonate has a plurality of fluorine atoms, these fluorine atoms can be bonded to the same carbon or to different carbons. As the fluorinated chain carbonate, fluorinated dimethyl carbonate derivatives, fluorinated ethyl methyl carbonate derivatives, fluorinated diethyl carbonate derivatives, etc. can be listed.
羧酸酯类溶剂包括环状羧酸酯和/或链状碳酸酯。作为环状羧酸酯的例子，可以列举如：γ-丁内酯、γ-戊内酯、δ-戊内酯中的至少一种。作为链状碳酸酯的例子，可以列举如：乙酸甲酯(MA)、乙酸乙酯(EA)、乙酸丙酯(EP)、乙酸丁酯、丙酸丙酯(PP)、丙酸丁酯中的至少一种。The carboxylate solvent includes cyclic carboxylate and/or chain carbonate. Examples of cyclic carboxylate include at least one of γ-butyrolactone, γ-valerolactone, and δ-valerolactone. Examples of chain carbonate include at least one of methyl acetate (MA), ethyl acetate (EA), propyl acetate (EP), butyl acetate, propyl propionate (PP), and butyl propionate.
在一些实施例中，砜类溶剂包括环状砜和链状砜，优选地，在为环状砜的情况下，通常为碳原子数3～6、优选碳原子数3～5，在为链状砜的情况下，通常为碳原子数2～6、优选碳原子数2～5的化合物。砜类溶剂的含量没有特殊限制，在不显著破坏本发明锂离子电池效果的范围内是任意的，相对于非水电解液的溶剂总量，通常体积比为0.3％以上、优选体积比为0.5％以上、更优选体积比为1％以上，另外，通常体积比为40％以下、优选体积比为35％以下、更优选体积比为30％以下。在组合使用两种以上砜类溶剂的情况下，使砜类溶剂的总量满足上述范围即可。砜类溶剂的含量在上述范围内时，倾向于获得高温保存稳定性优异的非水电解液。In some embodiments, the sulfone solvent includes a cyclic sulfone and a chain sulfone. Preferably, in the case of a cyclic sulfone, it is usually a compound with 3 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and in the case of a chain sulfone, it is usually a compound with 2 to 6 carbon atoms, preferably 2 to 5 carbon atoms. The content of the sulfone solvent is not particularly limited and is arbitrary within the range that does not significantly damage the effect of the lithium ion battery of the present invention. Relative to the total amount of solvent in the non-aqueous electrolyte, the volume ratio is usually 0.3% or more, preferably 0.5% or more, and more preferably 1% or more. In addition, the volume ratio is usually 40% or less, preferably 35% or less, and more preferably 30% or less. In the case of using two or more sulfone solvents in combination, the total amount of the sulfone solvents can meet the above range. When the content of the sulfone solvent is within the above range, a non-aqueous electrolyte with excellent high temperature storage stability tends to be obtained.
在优选的实施例终，所述非水有机溶剂包括碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸丙烯酯、乙酸丁酯、γ-丁内酯、丙酸丙酯、丙酸乙酯、丁酸乙酯、乙酸甲酯、乙酸乙酯、氟代乙酸乙酯和氟醚中的至少一种。In a preferred embodiment, the non-aqueous organic solvent includes at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, butyl acetate, γ-butyrolactone, propyl propionate, ethyl propionate, ethyl butyrate, methyl acetate, ethyl acetate, ethyl fluoroacetate and fluoroether.
在优选的实施例中，所述非水有机溶剂为环状碳酸酯和链状碳酸酯的混合物。In a preferred embodiment, the non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate.
在一些实施例中，所述添加剂还包括磺酸内酯类化合物、环状碳酸酯类化合物、磷酸酯类化合物、硼酸酯类化合物和腈类化合物中的至少一种；In some embodiments, the additive further comprises at least one of a sultone compound, a cyclic carbonate compound, a phosphate compound, a borate compound, and a nitrile compound;
优选的，以所述非水电解液的总质量为100％计，所述添加剂的含量为0.01％～30％。Preferably, based on the total mass of the non-aqueous electrolyte being 100%, the content of the additive is 0.01% to 30%.
在一些实施例中，所述磺酸内酯类化合物选自1,3-丙烷磺酸内酯、1,4-丁烷磺酸内酯、1,3-丙烯磺酸内酯中的至少一种；In some embodiments, the sultone compound is selected from at least one of 1,3-propane sultone, 1,4-butane sultone, and 1,3-propene sultone;
所述环状碳酸酯类化合物选自碳酸亚乙烯酯、碳酸乙烯亚乙酯、亚甲基碳酸乙烯酯、氟代碳酸乙烯酯、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯或结构式2所示化合物中的至少一种：
The cyclic carbonate compound is selected from at least one of vinylene carbonate, ethylene carbonate, methylene carbonate, fluoroethylene carbonate, trifluoromethylethylene carbonate, bisfluoroethylene carbonate or the compound shown in Structural Formula 2:
The cyclic carbonate compound is selected from at least one of vinylene carbonate, ethylene carbonate, methylene carbonate, fluoroethylene carbonate, trifluoromethylethylene carbonate, bisfluoroethylene carbonate or the compound shown in Structural Formula 2:
所述结构式2中，R21、R22、R23、R24、R25、R26各自独立地选自氢原子、卤素原子、C1-C5基团中的一种；In the structural formula 2, R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are each independently selected from a hydrogen atom, a halogen atom, and a C1-C5 group;
所述磷酸酯类化合物选自三(三甲基硅烷)磷酸酯、三(三甲基硅烷)亚磷酸酯或结构式3所示化合物中的至少一种：
The phosphate compound is selected from at least one of tris(trimethylsilyl)phosphate, tris(trimethylsilyl)phosphite or the compound shown in structural formula 3:
The phosphate compound is selected from at least one of tris(trimethylsilyl)phosphate, tris(trimethylsilyl)phosphite or the compound shown in structural formula 3:
所述结构式3中，R31、R32、R33各自独立的选自C1-C5的饱和烃基、不饱和烃基、卤代烃基、-Si(CmH2m+1)3，m为1～3的自然数，且R31、R32、R33中至少有一个为不饱和烃基；In the structural formula 3, R 31 , R 32 , and R 33 are each independently selected from a C1-C5 saturated hydrocarbon group, an unsaturated hydrocarbon group, a halogenated hydrocarbon group, and -Si(C m H 2m+1 ) 3 , m is a natural number of 1 to 3, and at least one of R 31 , R 32 , and R 33 is an unsaturated hydrocarbon group;
在优选的实施例中，所述结构式3所示的磷酸酯类化合物可为磷酸三炔丙酯、二炔丙基甲基磷酸酯、二炔丙基乙基磷酸酯、二炔丙基丙基磷酸酯、二炔丙基三氟甲基磷酸酯、二炔丙基-2,2,2-三氟乙基磷酸酯、二炔丙基-3,3,3-三氟丙基磷酸酯、二炔丙基六氟异丙基磷酸酯、磷酸三烯丙酯、二烯丙基甲基磷酸酯、二烯丙基乙基磷酸酯、二烯丙基丙基磷酸酯、二烯丙基三氟甲基磷酸酯、二烯丙基-2,2,2-三氟乙基磷酸酯、二烯丙基-3,3,3-三氟丙基磷酸酯、二烯丙基六氟异丙基磷酸酯中的至少一种；In a preferred embodiment, the phosphate compound shown in the structural formula 3 may be at least one of tripropargyl phosphate, dipropargyl methyl phosphate, dipropargyl ethyl phosphate, dipropargyl propyl phosphate, dipropargyl trifluoromethyl phosphate, dipropargyl-2,2,2-trifluoroethyl phosphate, dipropargyl-3,3,3-trifluoropropyl phosphate, dipropargyl hexafluoroisopropyl phosphate, triallyl phosphate, diallyl methyl phosphate, diallyl ethyl phosphate, diallyl propyl phosphate, diallyl trifluoromethyl phosphate, diallyl-2,2,2-trifluoroethyl phosphate, diallyl-3,3,3-trifluoropropyl phosphate, and diallyl hexafluoroisopropyl phosphate;
所述硼酸酯类化合物选自三(三甲基硅烷)硼酸酯和三(三乙基硅烷)硼酸酯中的至少一种；The borate compound is selected from at least one of tris(trimethylsilyl)borate and tris(triethylsilyl)borate;
所述腈类化合物选自丁二腈、戊二腈、乙二醇双(丙腈)醚、己烷三腈、己二腈、庚二腈、辛二腈、壬二腈、癸二腈中的至少一种。The nitrile compound is selected from at least one of succinonitrile, glutaronitrile, ethylene glycol bis(propionitrile) ether, hexanetrinitrile, adiponitrile, pimelonitrile, suberonitrile, azelaic acid dinitrile and sebacononitrile.
在另一些实施例中，所述添加剂还可包括其它能改善电池性能的添加剂：例如，提升电池安全性能的添加剂，具体如氟代磷酸酯、环磷腈等阻燃添加剂，或叔戊基苯、叔丁基苯等防过充添加剂。In other embodiments, the additives may also include other additives that can improve battery performance: for example, additives that enhance battery safety performance, such as flame retardant additives such as fluorophosphates and cyclophosphazenes, or overcharge prevention additives such as tert-amylbenzene and tert-butylbenzene.
需要说明的是，除非特殊说明，一般情况下，所述添加剂中任意一种可选物质在非水电
解液中的含量为10％以下，优选的，含量为0.1-5％，更优选的，含量为0.1％～2％。具体的，所述添加剂中任意一种可选物质的含量可以为0.05％、0.08％、0.1％、0.5％、0.8％、1％、1.2％、1.5％、1.8％、2％、2.2％、2.5％、2.8％、3％、3.2％、3.5％、3.8％、4％、4.5％、5％、5.5％、6％、6.5％、7％、7.5％、7.8％、8％、8.5％、9％、9.5％、10％。It should be noted that, unless otherwise specified, generally, any one of the optional substances in the additives is The content in the solution is less than 10%, preferably, the content is 0.1-5%, and more preferably, the content is 0.1% to 2%. Specifically, the content of any one of the optional substances in the additive can be 0.05%, 0.08%, 0.1%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 7.8%, 8%, 8.5%, 9%, 9.5%, 10%.
在一些实施例中，当添加剂选自氟代碳酸乙烯酯时，以所述非水电解液的总质量为100％计，所述氟代碳酸乙烯酯的含量为0.05％～30％。In some embodiments, when the additive is selected from fluoroethylene carbonate, the content of the fluoroethylene carbonate is 0.05% to 30% based on the total mass of the non-aqueous electrolyte as 100%.
在一些实施例中，所述锂离子电池中还包括有隔膜，所述隔膜位于所述正极和所述负极之间。In some embodiments, the lithium-ion battery further includes a separator, and the separator is located between the positive electrode and the negative electrode.
所述隔膜可为现有常规隔膜，可以是陶瓷隔膜、聚合物隔膜、无纺布、无机-有机复合隔膜等，所述聚合物隔膜选自聚烯烃类、聚酰胺类、聚砜类、聚磷腈类、聚醚砜类、聚醚醚酮类、聚醚酰胺类和聚丙烯腈类中的一种或几种，包括但不限于单层PP(聚丙烯)、单层PE(聚乙烯)、双层PP/PE、双层PP/PP和三层PP/PE/PP等隔膜。The diaphragm may be an existing conventional diaphragm, such as a ceramic diaphragm, a polymer diaphragm, a non-woven fabric, an inorganic-organic composite diaphragm, etc. The polymer diaphragm is selected from one or more of polyolefins, polyamides, polysulfones, polyphosphazenes, polyethersulfones, polyetheretherketones, polyetheramides and polyacrylonitrile, including but not limited to single-layer PP (polypropylene), single-layer PE (polyethylene), double-layer PP/PE, double-layer PP/PP and three-layer PP/PE/PP diaphragms.
在优选的实施例，所述隔膜包括基材隔膜和表面涂层，表面涂层为无机颗粒或有机凝胶或二者混合物且涂覆在基材隔膜至少一侧表面。In a preferred embodiment, the separator includes a substrate separator and a surface coating, wherein the surface coating is inorganic particles or organic gel or a mixture of the two and is coated on at least one side of the substrate separator.
以下通过实施例对本发明进行进一步的说明。The present invention is further described below by way of examples.
以下实施例和对比例涉及的化合物如下表所示：The compounds involved in the following examples and comparative examples are shown in the following table:
表1
Table 1
Table 1
表2实施例和对比例各参数设计
Table 2 Parameter design of embodiments and comparative examples
Table 2 Parameter design of embodiments and comparative examples
实施例1Example 1
本实施例用于说明本发明公开的锂离子电池及其制备方法，包括以下操作步骤：This embodiment is used to illustrate the lithium ion battery and the preparation method thereof disclosed in the present invention, and includes the following steps:
1)电解液的制备1) Preparation of electrolyte
将碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)按质量比为EC:DEC:EMC＝1:1:1进行混合，然后加入六氟磷酸锂(LiPF6)至摩尔浓度为1mol/L，再加入添加剂混合均匀，添加剂种类及含量如表2所示。Ethylene carbonate (EC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC) were mixed at a mass ratio of EC:DEC:EMC=1:1:1, and then lithium hexafluorophosphate (LiPF 6 ) was added to a molar concentration of 1 mol/L, and then additives were added and mixed evenly. The types and contents of the additives are shown in Table 2.
2)正极片的制备2) Preparation of positive electrode
按93:4:3的质量比混合正极活性材料、导电剂和粘结剂聚偏二氟乙烯(PVDF)，其中，正极活性材料的种类及比表面积以及正极活性材料的微孔比表面积和介孔比表面积的比值如表2所示，然后将它们分散在N-甲基-2-吡咯烷酮(NMP)中，得到正极浆料。将浆料均匀涂布在铝箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上铝制引出线后得到正极片，极片的厚度在120-150μm。The positive electrode active material, the conductive agent and the binder polyvinylidene fluoride (PVDF) are mixed in a mass ratio of 93:4:3, wherein the type and specific surface area of the positive electrode active material and the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material are shown in Table 2, and then they are dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode slurry. The slurry is evenly coated on both sides of the aluminum foil, dried, rolled and vacuum dried, and welded with an aluminum lead wire using an ultrasonic welder to obtain a positive electrode sheet, the thickness of which is 120-150μm.
3)负极片的制备3) Preparation of negative electrode
按94:1:2.5:2.5的质量比混合负极活性材料人造石墨、导电碳黑Super-P、粘结剂丁苯橡胶(SBR)和羧甲基纤维素(CMC)，然后将它们分散在去离子水中，得到负极浆料。将浆料涂布在铜箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上镍制引出线后得到负极片，极片的厚度在120-150μm。The negative electrode active material artificial graphite, conductive carbon black Super-P, binder styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) are mixed in a mass ratio of 94:1:2.5:2.5, and then dispersed in deionized water to obtain negative electrode slurry. The slurry is coated on both sides of the copper foil, dried, rolled and vacuum dried, and the nickel lead wire is welded with an ultrasonic welder to obtain the negative electrode sheet, the thickness of which is 120-150μm.
4)电芯的制备
4) Preparation of battery cells
在正极片和负极片之间放置厚度为20μm的三层隔离膜，然后将正极片、负极片和隔膜组成的三明治结构进行卷绕，再将卷绕体压扁后放入铝箔包装袋，在75℃下真空烘烤48h，得到待注液的电芯。A three-layer separator with a thickness of 20 μm is placed between the positive electrode sheet and the negative electrode sheet, and then the sandwich structure consisting of the positive electrode sheet, the negative electrode sheet and the separator is wound. The wound body is flattened and placed in an aluminum foil packaging bag, and vacuum-baked at 75°C for 48 hours to obtain a battery cell to be injected with liquid.
5)电芯的注液和化成5) Battery filling and formation
在露点控制在-40℃以下的手套箱中，将上述制备的电解液注入电芯中，经真空封装，静置24h。然后按以下步骤进行首次充电的常规化成：0.05C恒流充电180min,0.1C恒流充电至100min，0.2C恒流充电至3.95V，二次真空封口，然后进一步以0.2C的电流恒流充电至4.4V，常温搁置12h后，以0.2C的电流恒流放电至3.0V。In a glove box with a dew point controlled below -40°C, the prepared electrolyte was injected into the battery cell, vacuum packaged, and left to stand for 24 hours. Then, the conventional formation of the first charge was carried out according to the following steps: 0.05C constant current charging for 180 minutes, 0.1C constant current charging to 100 minutes, 0.2C constant current charging to 3.95V, secondary vacuum sealing, and then further charging to 4.4V at 0.2C constant current, leaving at room temperature for 12 hours, and then discharging to 3.0V at 0.2C constant current.
实施例2～28Embodiments 2 to 28
实施例2～28用于说明本发明公开的锂离子电池及其制备方法，包括实施例1中大部分操作步骤，其不同之处在于：Examples 2 to 28 are used to illustrate the lithium ion battery and the preparation method thereof disclosed in the present invention, and include most of the operation steps in Example 1, except that:
采用表2中实施例2～28所示的添加剂及含量、正极活性材料的种类、比表面积以及正极活性材料的微孔比表面积和介孔比表面积比值。The additives and contents, the types and specific surface areas of the positive electrode active materials, and the ratios of the micropore specific surface area and the mesopore specific surface area of the positive electrode active materials shown in Examples 2 to 28 in Table 2 were used.
对比例1～8Comparative Examples 1 to 8
对比例1～8用于对比说明本发明公开的锂离子电池及其制备方法，包括实施例1中大部分操作步骤，其不同之处在于：Comparative Examples 1 to 8 are used to compare and illustrate the lithium ion battery and the preparation method thereof disclosed in the present invention, and include most of the operation steps in Example 1, except that:
采用表2中对比例1～8所示的添加剂及含量、正极活性材料的种类、比表面积以及正极活性材料的微孔比表面积和介孔比表面积比值。The additives and contents, types and specific surface areas of the positive electrode active materials, and the ratios of the micropore specific surface area and the mesopore specific surface area of the positive electrode active materials shown in Comparative Examples 1 to 8 in Table 2 were used.
性能测试Performance Testing
对上述制备得到的锂离子电池进行如下性能测试：The lithium-ion battery prepared above was subjected to the following performance tests:
一、高温循环性能测试1. High temperature cycle performance test
将锂离子电池置于恒温45℃的烘箱中，以1C的电流恒流充电至4.4V(LiNi0.5Co0.2Mn0.3O2/人造石墨电池)或4.4V(0.4Li2MnO3·0.6LiNiO2/人造石墨电池)或4.8V(LiNi0.4Mn0.6O2/人造石墨电池)，再恒压充电至电流下降至0.02C，然后以1C的电流恒流放电至3.0V，如此循环，记录第1次的放电容量和最后一次的放电容量。The lithium-ion battery was placed in an oven at a constant temperature of 45°C, and charged at a constant current of 1C to 4.4V (LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery) or 4.4V (0.4Li 2 MnO 3 ·0.6LiNiO 2 /artificial graphite battery) or 4.8V (LiNi 0.4 Mn 0.6 O 2 /artificial graphite battery), then charged at a constant voltage until the current dropped to 0.02C, and then discharged at a constant current of 1C to 3.0V, and this cycle was repeated, and the first discharge capacity and the last discharge capacity were recorded.
按下式计算高温循环的容量保持率：The capacity retention rate of high temperature cycle is calculated as follows:
容量保持率(％)＝最后一次的放电容量/第1次的放电容量×100％。Capacity retention rate (%) = last discharge capacity/first discharge capacity×100%.
二、高温储存性能测试2. High temperature storage performance test
将化成后的锂离子电池在常温下用1C恒流恒压充至4.4V(LiNi0.5Co0.2Mn0.3O2/人造石墨电池)或4.4V(0.4Li2MnO3·0.6LiNiO2/人造石墨电池)或4.8V(LiNi0.4Mn0.6O2/人造石墨电池)，测量电池初始放电容量及初始电池厚度，然后在60℃环境中储存30天后，以1C放电至3V，测量电池的保持容量和恢复容量及储存后电池厚度。计算公式如下：The formed lithium-ion battery was charged to 4.4V (LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery) or 4.4V (0.4Li 2 MnO 3 ·0.6LiNiO 2 /artificial graphite battery) or 4.8V (LiNi 0.4 Mn 0.6 O 2 /artificial graphite battery) at room temperature with 1C constant current and constant voltage, and the initial discharge capacity and initial battery thickness of the battery were measured. Then, after being stored in a 60°C environment for 30 days, the battery was discharged to 3V at 1C, and the battery retention capacity and recovery capacity as well as the battery thickness after storage were measured. The calculation formula is as follows:
电池容量保持率(％)＝保持容量/初始容量×100％；Battery capacity retention rate (%) = retention capacity/initial capacity × 100%;
电池容量恢复率(％)＝恢复容量/初始容量×100％；
Battery capacity recovery rate (%) = recovery capacity/initial capacity × 100%;
厚度膨胀率(％)＝(储存后电池厚度-初始电池厚度)/初始电池厚度×100％。Thickness expansion ratio (%) = (battery thickness after storage - initial battery thickness) / initial battery thickness × 100%.
三、锰离子溶出检测3. Manganese ion dissolution test
取循环后电池中的电解液，通过电感耦合等离子体发射光谱仪(ICP-OES)检测出电解液中Mn元素的含量(ppm)。The electrolyte in the battery after the cycle was taken, and the content (ppm) of Mn element in the electrolyte was detected by inductively coupled plasma optical emission spectrometry (ICP-OES).
四、正极活性材料中金属离子Mn的价态比值检测4. Detection of valence ratio of metal ion Mn in positive electrode active materials
锂离子电池在40～60℃高温循环500周后，对电池进行拆解，取出正极片并清洗，通过X射线光电子能谱仪(XPS)测试正极片，具有顶值为653.1～653.7eV的峰代表Mn2+所对应的2p1/2峰，该峰的峰面积大小对应Mn2+含量，具有顶值为653.8～654.2eV的峰代表Mn4+的所对应的2p1/2峰，该峰的峰面积大小对应Mn4+含量，通过两种峰面积的比值计算出所述正极活性材料中金属离子Mn的价态比值。After the lithium-ion battery was cycled at a high temperature of 40 to 60° C. for 500 weeks, the battery was disassembled, the positive electrode sheet was taken out and cleaned, and the positive electrode sheet was tested by an X-ray photoelectron spectrometer (XPS). The peak with a top value of 653.1 to 653.7 eV represents the 2p1/2 peak corresponding to Mn 2+ , and the peak area of the peak corresponds to the Mn 2+ content. The peak with a top value of 653.8 to 654.2 eV represents the 2p1/2 peak corresponding to Mn 4+ , and the peak area of the peak corresponds to the Mn 4+ content. The valence ratio of the metal ion Mn in the positive electrode active material is calculated by the ratio of the two peak areas.
(1)实施例1～17和对比例1～4得到的测试结果填入表3。(1) The test results obtained in Examples 1 to 17 and Comparative Examples 1 to 4 are entered in Table 3.
表3
table 3
table 3
由实施例1～17和对比例1～4的测试结果可知，在采用的正极活性材料类型相同的情况下，正极活性材料的微孔比表面积和介孔比表面积的比值Vr/Vr*和非水电解液中结构式1所示化合物的质量百分含量Wr满足预设关系0.5≤(Vr/Vr*)/Wr≤12，且0.4≤Vr/Vr*≤1.5，0.1≤Wr≤3时，锂离子电池同时具有优异的高温循环性能和高温存储性能，推测是由于在该微孔比表面积和介孔比表面积的比值范围和结构式1所示的化合物的含量下，结构式1所示的化合物形成的界面膜具有与含锰正极材料表面锰元素更好的配合效果，在正极活性材料及电解质相界面形成特定的网状导电界面，作为特殊的锂离子传输通道，有利于锂离子的脱附和传递，同时使得金属锰离子与O之间的配位保持六配位，维持正极活性材料的立体结构，进而抑制了含锰正极材料中锰离子的溶出，避免在电池循环过程中的锰离子价位的不可逆改变。It can be seen from the test results of Examples 1 to 17 and Comparative Examples 1 to 4 that, when the type of positive electrode active material used is the same, the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material Vr/Vr* and the mass percentage content Wr of the compound represented by structural formula 1 in the non-aqueous electrolyte satisfy the preset relationship of 0.5≤(Vr/Vr*)/Wr≤12, and 0.4≤Vr/Vr*≤1.5, 0.1≤Wr≤3, the lithium ion battery has excellent high temperature cycle performance and high temperature storage performance at the same time, which is presumably due to the fact that the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material Vr/Vr* and the mass percentage content Wr of the compound represented by structural formula 1 in the non-aqueous electrolyte satisfy the preset relationship of 0.5≤(Vr/Vr*)/Wr≤12, and 0.4≤Vr/Vr*≤1.5, 0.1≤Wr≤3. Under the ratio range of the area and the content of the compound shown in Structural Formula 1, the interfacial film formed by the compound shown in Structural Formula 1 has a better coordination effect with the manganese element on the surface of the manganese-containing positive electrode material, and forms a specific mesh conductive interface at the interface between the positive electrode active material and the electrolyte phase, which serves as a special lithium ion transmission channel, is conducive to the desorption and transfer of lithium ions, and at the same time, the coordination between the metal manganese ions and O is maintained at six coordination, maintaining the three-dimensional structure of the positive electrode active material, thereby inhibiting the dissolution of manganese ions in the manganese-containing positive electrode material, and avoiding the irreversible change of the manganese ion valence during the battery cycle.
由实施例1～17的测试结果可知，当正极活性材料的微孔比表面积和介孔比表面积的比值Vr/Vr*和非水电解液中结构式1所示化合物的质量百分含量Wr满足进一步满足1≤(Vr/Vr*)/Wr≤10，且0.5≤Vr/Vr*≤1.2，0.1≤Wr≤2时，锂离子二次电池具有最佳的高温循环容量保持率和高温存储容量保持率、容量恢复率和较低的厚度膨胀率，推测此时得到的界面膜能够更加有效地减少极化作用带来的冲击，抑制正极锰金属离子的溶出。It can be seen from the test results of Examples 1 to 17 that when the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material Vr/Vr* and the mass percentage content Wr of the compound represented by structural formula 1 in the non-aqueous electrolyte further satisfy 1≤(Vr/Vr*)/Wr≤10, and 0.5≤Vr/Vr*≤1.2, 0.1≤Wr≤2, the lithium-ion secondary battery has the best high-temperature cycle capacity retention rate and high-temperature storage capacity retention rate, capacity recovery rate and lower thickness expansion rate. It is speculated that the interface film obtained at this time can more effectively reduce the impact caused by polarization and inhibit the dissolution of manganese metal ions in the positive electrode.
由对比例1～4的测试结果可知，当(Vr/Vr*)/Wr值大于或小于本电池体系的限定条件时，均会导致结构式1所示的化合物形成的界面膜稳定性的下降，进而导致了锰离子的价位变化和溶出，进一步地引发了锂离子电池的性能劣化。It can be seen from the test results of Comparative Examples 1 to 4 that when the (Vr/Vr*)/Wr value is greater than or less than the limiting conditions of the present battery system, the stability of the interfacial film formed by the compound shown in Structural Formula 1 will decrease, which will lead to changes in the valence and dissolution of manganese ions, further causing the performance degradation of the lithium-ion battery.
(2)实施例4、实施例18～22得到的测试结果填入表4。(2) The test results obtained in Example 4 and Examples 18 to 22 are entered in Table 4.
表4
Table 4
Table 4
由实施例4、实施例18～22的测试结果可知，在本发明提供的锂离子电池体系中，对于不同的结构式1所示的化合物，当正极活性材料的微孔比表面积和介孔比表面积的比值Vr/Vr*和非水电解液中结构式1所示化合物的质量百分含量Wr满足预设关系0.5≤(Vr/Vr*)/Wr≤12时，其起到的作用相似，均对于锂离子电池的高温循环性能和高温存储性能具有一定的改善作用，说明本发明提供的关系式适用于不同的结构式1所示的化合物。It can be seen from the test results of Example 4 and Examples 18 to 22 that in the lithium-ion battery system provided by the present invention, for different compounds represented by structural formula 1, when the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material Vr/Vr* and the mass percentage content Wr of the compound represented by structural formula 1 in the non-aqueous electrolyte satisfy the preset relationship 0.5≤(Vr/Vr*)/Wr≤12, the effects they play are similar, and both have a certain improvement effect on the high-temperature cycle performance and high-temperature storage performance of the lithium-ion battery, indicating that the relationship provided by the present invention is applicable to different compounds represented by structural formula 1.
(3)实施例4、实施例23～26得到的测试结果填入表5。(3) The test results obtained in Example 4 and Examples 23 to 26 are entered in Table 5.
表5
table 5
table 5
由实施例4、实施例18～22的测试结果可知，在本发明提供的锂离子电池体系中，在非水电解液中加入上述的添加剂VC(碳酸乙烯酯)、FEC(氟代碳酸乙烯酯)、PS(1,3-丙烷磺内酯)或TMSP(三(三甲基硅烷)磷酸酯)，能够进一步提高电池的高温循环性能和高温存储性能，推测是由于结构式1所示的化合物与上述的添加剂共同参与了电极表面钝化膜的成型，得到一种热稳定性能优异的钝化膜，进而有效抑制了锰离子的溶出，降低了电极表面电解液的反应，提高了电池的电化学性能。From the test results of Example 4 and Examples 18 to 22, it can be seen that in the lithium ion battery system provided by the present invention, adding the above-mentioned additives VC (ethylene carbonate), FEC (fluoroethylene carbonate), PS (1,3-propane sultone) or TMSP (tris(trimethylsilyl) phosphate) to the non-aqueous electrolyte can further improve the high temperature cycle performance and high temperature storage performance of the battery. It is speculated that this is because the compound shown in Structural Formula 1 and the above-mentioned additives jointly participate in the formation of the passivation film on the electrode surface, thereby obtaining a passivation film with excellent thermal stability, thereby effectively inhibiting the dissolution of manganese ions, reducing the reaction of the electrolyte on the electrode surface, and improving the electrochemical performance of the battery.
(4)实施例27～28和对比例5～8得到的测试结果填入表6。(4) The test results obtained from Examples 27 to 28 and Comparative Examples 5 to 8 are entered in Table 6.
表6
Table 6
Table 6
由实施例27～28和对比例5～8的测试结果可知，采用其他含锰材料作为正极活性材料，
当正极活性材料的微孔比表面积和介孔比表面积的比值Vr/Vr*和非水电解液中结构式1所示化合物的质量百分含量Wr满足预设关系0.5≤(Vr/Vr*)/Wr≤12，且0.4≤Vr/Vr*≤1.5，0.1≤Wr≤3时，电池同样具有较好的高温循环性能和高温存储性能，且对于锰离子的溶出抑制效果明显，说明本发明提供的关系式对于采用不同的含锰正极材料的锂离子电池高温性能均具有普适性的提高。From the test results of Examples 27 to 28 and Comparative Examples 5 to 8, it can be seen that other manganese-containing materials are used as positive electrode active materials. When the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material Vr/Vr* and the mass percentage content Wr of the compound represented by structural formula 1 in the non-aqueous electrolyte satisfy the preset relationship 0.5≤(Vr/Vr*)/Wr≤12, and 0.4≤Vr/Vr*≤1.5, 0.1≤Wr≤3, the battery also has good high-temperature cycle performance and high-temperature storage performance, and has a significant effect on inhibiting the dissolution of manganese ions, indicating that the relationship provided by the present invention has a universal improvement in the high-temperature performance of lithium-ion batteries using different manganese-containing positive electrode materials.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims (16)
- 一种锂离子电池，其特征在于，包括正极、负极和非水电解液，所述正极包括含有正极活性材料的正极材料层，所述正极活性材料包括含锰正极材料，所述正极活性材料的比表面积为0.5～1.5m2/g，所述非水电解液包括非水有机溶剂、添加剂和锂盐，所述添加剂包括结构式1所示的化合物：
A lithium-ion battery, characterized in that it comprises a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the positive electrode comprises a positive electrode material layer containing a positive electrode active material, the positive electrode active material comprises a manganese-containing positive electrode material, the specific surface area of the positive electrode active material is 0.5 to 1.5 m 2 /g, and the non-aqueous electrolyte comprises a non-aqueous organic solvent, an additive and a lithium salt, wherein the additive comprises a compound shown in structural formula 1:
其中，n为0或1，X选自R1、R2各自独立选自H、卤素、未取代或卤素取代的C1-C5的烃基、且X、R1和R2中至少含有一个硫原子；Where n is 0 or 1, and X is selected from R 1 and R 2 are each independently selected from H, halogen, unsubstituted or halogen-substituted C1-C5 hydrocarbon group, and X, R1 and R2 contain at least one sulfur atom;所述锂离子电池满足以下条件：The lithium-ion battery meets the following conditions:0.5≤(Vr/Vr*)/Wr≤12，且0.4≤Vr/Vr*≤1.5，0.1≤Wr≤3；0.5≤(Vr/Vr*)/Wr≤12, and 0.4≤Vr/Vr*≤1.5, 0.1≤Wr≤3;其中，Vr/Vr*为正极活性材料的微孔比表面积与介孔比表面积的比值；Wherein, Vr/Vr* is the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material;Wr为非水电解液中结构式1所示化合物的质量百分含量，单位为％。Wr is the mass percentage of the compound represented by structural formula 1 in the non-aqueous electrolyte, in %. - 根据权利要求1所述的锂离子电池，其特征在于，所述锂离子电池满足以下条件：
1≤(Vr/Vr*)/Wr≤10。The lithium-ion battery according to claim 1, characterized in that the lithium-ion battery meets the following conditions:
1≤(Vr/Vr*)/Wr≤10. - 根据权利要求1所述的锂离子电池，其特征在于，所述正极活性材料的微孔比表面积与介孔比表面积的比值Vr/Vr*为0.5～1.2。The lithium-ion battery according to claim 1, characterized in that the ratio of the micropore specific surface area to the mesopore specific surface area of the positive electrode active material Vr/Vr* is 0.5 to 1.2.
- 根据权利要求1所述的锂离子电池，其特征在于，所述正极活性材料的微孔比表面积Vr为0.2～0.7m2/g。The lithium-ion battery according to claim 1, characterized in that the micropore specific surface area Vr of the positive electrode active material is 0.2 to 0.7 m 2 /g.
- 根据权利要求1所述的锂离子电池，其特征在于，所述正极活性材料的介孔比表面积Vr*为0.14～1.4m2/g。 The lithium-ion battery according to claim 1, characterized in that the mesoporous specific surface area Vr* of the positive electrode active material is 0.14 to 1.4 m 2 /g.
- 根据权利要求1所述的锂离子电池，其特征在于，所述非水电解液中结构式1所示化合物的质量百分含量Wr为0.1％～2％。The lithium-ion battery according to claim 1, characterized in that the mass percentage Wr of the compound represented by structural formula 1 in the non-aqueous electrolyte is 0.1% to 2%.
- 根据权利要求1所述的锂离子电池，其特征在于，所述锂离子电池40～60℃高温循环500周条件下，所述正极活性材料中金属离子Mn的价态比值为0.1≤M2+*/M4+*≤0.4，其中M2+*为Mn2+含量，为M4+*为Mn4+的含量。The lithium-ion battery according to claim 1 is characterized in that, under the condition of 500 cycles of high temperature of 40-60° C. for the lithium-ion battery, the valence ratio of the metal ion Mn in the positive electrode active material is 0.1≤M 2+* /M 4+* ≤0.4, wherein M 2+* is the Mn 2+ content, and M 4+* is the Mn 4+ content.
- 根据权利要求1所述的锂离子电池，其特征在于，所述结构式1所示的化合物包括以下化合物中的至少一种：
The lithium-ion battery according to claim 1, characterized in that the compound represented by structural formula 1 comprises at least one of the following compounds:
- 根据权利要求1所述的锂离子电池，其特征在于，所述含锰正极材料选自LiNixCoyMnzL(1-x-y-z)O2中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Cu、V或Fe，0<x≤1，0≤y≤1，0<z≤1，0<x+y+z≤1。The lithium-ion battery according to claim 1, characterized in that the manganese-containing positive electrode material is selected from at least one of LiNi x Co y Mn z L (1-xyz) O 2 , wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Cu, V or Fe, 0<x≤1, 0≤y≤1, 0<z≤1, 0<x+y+z≤1.
- 根据权利要求1所述的锂离子电池，其特征在于，所述添加剂还包括磺酸内酯类化合物、环状碳酸酯类化合物、磷酸酯类化合物、硼酸酯类化合物和腈类化合物中的至少一种。The lithium-ion battery according to claim 1, characterized in that the additive further comprises at least one of a sultone compound, a cyclic carbonate compound, a phosphate compound, a borate compound and a nitrile compound.
- 根据权利要求10所述的锂离子电池，其特征在于，以所述非水电解液的总质量为100％计，所述添加剂的添加量为0.01％～30％。The lithium-ion battery according to claim 10, characterized in that, based on the total mass of the non-aqueous electrolyte being 100%, the amount of the additive added is 0.01% to 30%.
- 根据权利要求10所述的锂离子电池，其特征在于，所述磺酸内酯类化合物选自1,3-丙烷磺酸内酯、1,4-丁烷磺酸内酯、1,3-丙烯磺酸内酯、中的至少一种。The lithium-ion battery according to claim 10, characterized in that the sultone compound is selected from 1,3-propane sultone, 1,4-butane sultone, 1,3-propylene sultone, At least one of .
- 根据权利要求10所述的锂离子电池，其特征在于，所述环状碳酸酯类化合物选自碳酸亚乙烯酯、碳酸乙烯亚乙酯、亚甲基碳酸乙烯酯、氟代碳酸乙烯酯、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯或结构式2所示化合物中的至少一种：
The lithium-ion battery according to claim 10, characterized in that the cyclic carbonate compound is selected from at least one of vinylene carbonate, ethylene carbonate, methylene carbonate, fluoroethylene carbonate, trifluoromethylethylene carbonate, bisfluoroethylene carbonate or the compound shown in structural formula 2:
所述结构式2中，R21、R22、R23、R24、R25、R26各自独立地选自氢原子、卤素原子、C1-C5基团中的一种。In the structural formula 2, R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are each independently selected from a hydrogen atom, a halogen atom, and a C1-C5 group. - 根据权利要求10所述的锂离子电池，其特征在于，所述磷酸酯类化合物选自三(三甲基硅烷)磷酸酯、三(三甲基硅烷)亚磷酸酯或结构式3所示化合物中的至少一种：
The lithium-ion battery according to claim 10, characterized in that the phosphate compound is selected from at least one of tris(trimethylsilyl)phosphate, tris(trimethylsilyl)phosphite or the compound shown in structural formula 3:
所述结构式3中，R31、R32、R33各自独立的选自C1-C5的饱和烃基、不饱和烃基、卤代烃基、-Si(CmH2m+1)3，m为1～3的自然数，且R31、R32、R33中至少有一个为不饱和烃基。In the structural formula 3, R 31 , R 32 and R 33 are independently selected from C1-C5 saturated hydrocarbon groups, unsaturated hydrocarbon groups, halogenated hydrocarbon groups, and -Si(C m H 2m+1 ) 3 , m is a natural number of 1 to 3, and at least one of R 31 , R 32 and R 33 is an unsaturated hydrocarbon group. - 根据权利要求10所述的锂离子电池，其特征在于，所述硼酸酯类化合物选自三(三甲基硅烷)硼酸酯和三(三乙基硅烷)硼酸酯中的至少一种。The lithium-ion battery according to claim 10, characterized in that the borate compound is selected from at least one of tris(trimethylsilyl)borate and tris(triethylsilyl)borate.
- 根据权利要求10所述的锂离子电池，其特征在于，所述腈类化合物选自丁二腈、戊二腈、乙二醇双(丙腈)醚、己烷三腈、己二腈、庚二腈、辛二腈、壬二腈、癸二腈中的至少一种。 The lithium-ion battery according to claim 10, characterized in that the nitrile compound is selected from at least one of succinonitrile, glutaronitrile, ethylene glycol bis(propionitrile) ether, hexanetrinitrile, adiponitrile, pimelonitrile, suberonitrile, azelaic acid dinitrile, and sebacononitrile.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211501148.4 | 2022-11-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024114206A1 true WO2024114206A1 (en) | 2024-06-06 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102301670B1 (en) | Lithium secondary battery with improved high temperature storage property | |
| KR102164001B1 (en) | Rechargeable lithium battery | |
| WO2009122908A1 (en) | Nonaqueous electrolyte for lithium battery and lithium battery using same | |
| CN114497692B (en) | Secondary battery | |
| KR102563223B1 (en) | Electrolytes and electrochemical devices | |
| KR20140114227A (en) | Electrode active material for lithium secondary battery, electrode for lithium secondary battery including the same, and lithium secondary battery comprising the same | |
| KR20150015086A (en) | Anode Active Material with Improved Wetting Properties and Lithium Secondary Battery Having the Same | |
| CN115117452B (en) | Lithium ion battery | |
| CN115020814B (en) | Lithium ion battery | |
| WO2024104100A1 (en) | Lithium-ion battery | |
| KR20180029306A (en) | Positive Electrode Active Material for Lithium Secondary Battery Comprising High-voltage Lithium Cobalt Oxide Particle and Method of Manufacturing the Same | |
| KR20150027003A (en) | The Cathode Electrodes For Secondary Battery and the Secondary Battery Comprising the Same | |
| WO2023246279A1 (en) | Lithium secondary battery | |
| WO2024037187A1 (en) | Lithium-ion battery | |
| WO2023241428A1 (en) | Lithium ion battery | |
| WO2024032171A1 (en) | Lithium-ion battery | |
| JP2022528246A (en) | Non-aqueous electrolyte solution additive for lithium secondary batteries, non-aqueous electrolyte solution for lithium secondary batteries and lithium secondary batteries containing this | |
| WO2023016412A1 (en) | Non-aqueous electrolyte solution and battery | |
| WO2023005505A1 (en) | Lithium ion battery | |
| CN110970663A (en) | Non-aqueous electrolyte and lithium ion battery | |
| WO2022218145A1 (en) | Non-aqueous electrolyte and lithium-ion battery | |
| CN116325270A (en) | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same | |
| WO2022042374A1 (en) | Lithium ion battery non-aqueous electrolyte solution and lithium ion battery | |
| WO2024114206A1 (en) | Lithium-ion battery | |
| JP2018092704A (en) | Lithium secondary battery |