CN116706230B - High-voltage electrolyte for lithium battery - Google Patents
High-voltage electrolyte for lithium battery Download PDFInfo
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- CN116706230B CN116706230B CN202210178118.8A CN202210178118A CN116706230B CN 116706230 B CN116706230 B CN 116706230B CN 202210178118 A CN202210178118 A CN 202210178118A CN 116706230 B CN116706230 B CN 116706230B
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- electrolyte
- lithium
- lithium battery
- voltage
- additive
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 145
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 61
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 68
- 239000001301 oxygen Substances 0.000 claims abstract description 68
- 239000000654 additive Substances 0.000 claims abstract description 43
- 230000000996 additive effect Effects 0.000 claims abstract description 42
- 230000002000 scavenging effect Effects 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 21
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 28
- -1 oxygen radicals Chemical class 0.000 claims description 27
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 25
- BPYKTIZUTYGOLE-IFADSCNNSA-N Bilirubin Chemical compound N1C(=O)C(C)=C(C=C)\C1=C\C1=C(C)C(CCC(O)=O)=C(CC2=C(C(C)=C(\C=C/3C(=C(C=C)C(=O)N\3)C)N2)CCC(O)=O)N1 BPYKTIZUTYGOLE-IFADSCNNSA-N 0.000 claims description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 13
- OYULCCKKLJPNPU-DIFFPNOSSA-N (2s,3r)-2-(9h-fluoren-9-ylmethoxycarbonylamino)-3-hydroxybutanoic acid Chemical compound C1=CC=C2C(COC(=O)N[C@@H]([C@H](O)C)C(O)=O)C3=CC=CC=C3C2=C1 OYULCCKKLJPNPU-DIFFPNOSSA-N 0.000 claims description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 9
- AHYFYYVVAXRMKB-QGZVFWFLSA-N (2r)-3-(1h-indol-3-yl)-2-(phenylmethoxycarbonylamino)propanoic acid Chemical compound N([C@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)OCC1=CC=CC=C1 AHYFYYVVAXRMKB-QGZVFWFLSA-N 0.000 claims description 8
- IZWMZVDEYOKQCG-UHFFFAOYSA-N 1-(2,4-dimethoxyphenyl)-n-[(2,4-dimethoxyphenyl)methyl]methanamine Chemical compound COC1=CC(OC)=CC=C1CNCC1=CC=C(OC)C=C1OC IZWMZVDEYOKQCG-UHFFFAOYSA-N 0.000 claims description 8
- SRLROPAFMUDDRC-INIZCTEOSA-N ethyl N-benzoyl-L-tyrosinate Chemical compound C([C@@H](C(=O)OCC)NC(=O)C=1C=CC=CC=1)C1=CC=C(O)C=C1 SRLROPAFMUDDRC-INIZCTEOSA-N 0.000 claims description 8
- 239000004072 C09CA03 - Valsartan Substances 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 7
- 229960004699 valsartan Drugs 0.000 claims description 7
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- ZCUFFSHMOAEEIL-UHFFFAOYSA-N 6-methoxy-7-phenylmethoxy-1h-quinazolin-4-one Chemical compound COC1=CC2=C(O)N=CN=C2C=C1OCC1=CC=CC=C1 ZCUFFSHMOAEEIL-UHFFFAOYSA-N 0.000 claims description 5
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 5
- 229940017219 methyl propionate Drugs 0.000 claims description 5
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 claims description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- RNNKPNPLIMFSDY-QFIPXVFZSA-N (2s)-3-(2-chlorophenyl)-2-(9h-fluoren-9-ylmethoxycarbonylamino)propanoic acid Chemical compound C([C@@H](C(=O)O)NC(=O)OCC1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1Cl RNNKPNPLIMFSDY-QFIPXVFZSA-N 0.000 claims description 2
- VOEUMFXKYRCDKK-UHFFFAOYSA-N FS(=N)F.FS(=N)F.[Li] Chemical compound FS(=N)F.FS(=N)F.[Li] VOEUMFXKYRCDKK-UHFFFAOYSA-N 0.000 claims description 2
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 2
- CLDYDTBRUJPBGU-UHFFFAOYSA-N butyl 2,2,2-trifluoroacetate Chemical compound CCCCOC(=O)C(F)(F)F CLDYDTBRUJPBGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- SJSNUMAYCRRIOM-QFIPXVFZSA-N valsartan Chemical compound C1=CC(CN(C(=O)CCCC)[C@@H](C(C)C)C(O)=O)=CC=C1C1=CC=CC=C1C1=NN=N[N]1 SJSNUMAYCRRIOM-QFIPXVFZSA-N 0.000 claims 2
- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 claims 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 229910001412 inorganic anion Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 50
- 150000003254 radicals Chemical class 0.000 abstract description 27
- 230000007760 free radical scavenging Effects 0.000 abstract description 14
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 230000001681 protective effect Effects 0.000 abstract description 5
- 235000002639 sodium chloride Nutrition 0.000 abstract description 5
- 239000007784 solid electrolyte Substances 0.000 abstract description 5
- 239000011029 spinel Substances 0.000 abstract description 5
- 229910052596 spinel Inorganic materials 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 239000011780 sodium chloride Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002931 mesocarbon microbead Substances 0.000 description 13
- 229910012820 LiCoO Inorganic materials 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 229910013870 LiPF 6 Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 6
- ACWBQPMHZXGDFX-QFIPXVFZSA-N valsartan Chemical compound C1=CC(CN(C(=O)CCCC)[C@@H](C(C)C)C(O)=O)=CC=C1C1=CC=CC=C1C1=NN=NN1 ACWBQPMHZXGDFX-QFIPXVFZSA-N 0.000 description 6
- 239000002000 Electrolyte additive Substances 0.000 description 5
- 229910013553 LiNO Inorganic materials 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- 229910013075 LiBF Inorganic materials 0.000 description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 description 3
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical group [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- VWVRASTUFJRTHW-UHFFFAOYSA-N 2-[3-(azetidin-3-yloxy)-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound O=C(CN1C=C(C(OC2CNC2)=N1)C1=CN=C(NC2CC3=C(C2)C=CC=C3)N=C1)N1CCC2=C(C1)N=NN2 VWVRASTUFJRTHW-UHFFFAOYSA-N 0.000 description 2
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 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
- DEAZEWBZYSWFCA-UHFFFAOYSA-N C(O)(=O)F.C(O)(=O)F.C(O)(=O)F.C=CC Chemical compound C(O)(=O)F.C(O)(=O)F.C(O)(=O)F.C=CC DEAZEWBZYSWFCA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- BTQLZQAVGBUMOG-UHFFFAOYSA-N n-silylacetamide Chemical compound CC(=O)N[SiH3] BTQLZQAVGBUMOG-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a high-voltage electrolyte for a lithium battery, and belongs to the technical field of lithium battery electrolytes. The lithium battery electrolyte comprises an organic solvent, lithium salt and a compound capable of scavenging oxygen free radicals as an additive. The compound is used as an additive of the electrolyte of the high-voltage lithium battery, can effectively inhibit the phase change of a positive electrode material to spinel and rock salt phases, forms a thin, compact and protective solid electrolyte interface on the surface of the positive electrode, inhibits the release of oxygen from the surface of the positive electrode, avoids the decomposition of the electrolyte, and improves the cycle stability and the coulombic efficiency of the battery. According to the invention, the organic solvent, the lithium salt and the oxygen free radical scavenging additive in the electrolyte of the high-voltage lithium battery are specifically combined, and the proportion and the concentration are further optimized, so that the electrolyte provided by the invention has excellent compatibility with the anode and the cathode, and meanwhile, the cycle performance and the coulombic efficiency of the lithium battery are obviously improved.
Description
Technical Field
The invention belongs to the technical field of lithium battery electrolyte, and particularly relates to high-voltage electrolyte for a lithium battery.
Background
Due to the development of new energy devices such as electric automobiles, the requirements for electrochemical energy storage are continuously increased, which promotes people to urgently develop lithium ion batteries with high energy density, the energy density of the lithium ion batteries is greatly dependent on the positive electrode material, and the development of electrode materials such as ternary materials NCM and lithium cobaltate LiCoO is greatly promoted 2 Lithium-rich manganese layered oxides LRLOs, etc., but when the battery is charged to 4.4V and above, chemical degradation of the electrolyte, i.e., decomposition of the electrolyte caused by active oxygen (e.g., singlet oxygen) and free radical attack at the positive electrode/electrolyte interface, readily occurs in the layered oxide positive electrode. Wherein the active oxygen substance is derived from the layered positive electrode material and released when phase transition (conversion into disordered spinel phase or rock salt phase) occurs, and the free radical is due to electrolysisThe solvent in the liquid is generated by electrochemical oxidation-reduction reaction, etc. These highly Reactive Oxygen Species (ROS) produce CO and CO 2 And the like, and reacts with carbonate-based electrolytes (e.g., dimethyl carbonate, ethylene carbonate, etc.), resulting in decomposition thereof. Therefore, there is a need to explore new high voltage resistant lithium ion battery electrolyte systems to inhibit oxygen evolution, reduce phase changes of the positive electrode, reduce sustained decomposition of the electrolyte, and achieve excellent battery performance.
Currently, for application to high voltage ternary materials NCM, lithium cobalt oxide LiCoO 2 Many studies on high-voltage electrolyte additives for positive electrode materials have been made, but there are significant disadvantages. The literature "Li GJ, liao YH, li ZF, et al, construction a Low-Impedance Interface on a High-Voltage LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cathode with 2,4,6-Triphenyl Boroxine as a Film-Forming Electrolyte Additive for Li-Ion Batteries.ACS applied materials&Interface, 2020,12 (33): 37013-37026. It is proposed to add 5%2,4, 6-triphenylboroxine electrolyte additive (TPBX) to a commercial electrolyte and after 200 cycles at a charge cut-off voltage of 4.35V,1C rate, the TPBX containing electrode provides a capacity of about 135mAh of only 78% of the initial discharge capacity. The literature "Qin Z, hong B, dut B, et al, tributyl borate as a novel electrolyte additive to improve high voltage stability of lithium cobalt oxide in carbonate-based electrolyte. Electrolyte Acta,2018,276:412-416," proposes that the addition of 0.5% tributyl borate (TBB) to a carbonate-based electrolyte has only 85.2% capacity retention after 120 cycles at 0.5C in the 3.0-4.4V voltage range. Although these additives can form a protective layer on the positive electrode to inhibit the decomposition of part of the electrolyte, the effect of scavenging oxygen free radicals in the electrolyte cannot be achieved, and the long-cycle stability of the battery still cannot meet the current requirements.
Therefore, a new electrolyte with high pressure resistance and excellent performance of delaying the capacity fade time, wherein the electrolyte is not easy to decompose by active oxygen and oxygen free radicals, so that the coulomb efficiency can be improved, is needed to be explored.
Disclosure of Invention
Aiming at a series of problems that the high-voltage resistance performance is poor, active oxygen and oxygen free radicals are easy to cause electrolyte decomposition, the coulomb efficiency is low, the capacity attenuation is fast and the like in the current commercial electrolyte, the invention aims to provide an electrolyte additive capable of removing oxygen free radicals, which is used for a high-voltage lithium battery, and the high-voltage electrolyte system has good compatibility with a high-voltage positive electrode, can remove oxygen free radicals generated by decomposition in the electrolyte, and greatly improves the cycle life and the coulomb efficiency of the lithium ion battery under the high-voltage condition.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides application of a compound capable of removing oxygen free radicals, which is used AS an additive of lithium battery electrolyte, wherein the compound capable of removing oxygen free radicals is melanin-1, chromene AS-BO, bilirubin, N-benzyloxycarbonyl-D-tryptophan, N-benzoyl-L-tyrosine ethyl ester, bis (2, 4-dimethoxybenzyl) amine, fmoc-L-threonine, valsartan, 6-methoxy-7-benzyloxyquinazolin-4-one or FMOC-L-2-chloroaniline.
The invention provides an additive for high-voltage lithium battery electrolyte, which comprises at least one compound capable of removing oxygen free radicals, wherein the compound capable of removing oxygen free radicals is melanin-1, chromene AS-BO, bilirubin, N-carbobenzoxy-D-tryptophan, N-benzoyl-L-tyrosine ethyl ester, bis (2, 4-dimethoxybenzyl) amine, fmoc-L-threonine, valsartan, 6-methoxy-7-benzyloxy quinazoline-4-ketone or FMOC-L-2-chloroaniline.
The invention also provides a high-voltage electrolyte for the lithium battery, which comprises an organic solvent, lithium salt and the additive.
Specifically, the organic solvent includes two or more of carbonate such as diethyl carbonate (DEC), propylene Carbonate (PC), ethylene Carbonate (EC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), γ -butyrolactone (GBL), γ -valerolactone (GVL), methylpropyl carbonate (MPC), propylpropionate (PP), ethylpropionate (EP), methyl Propionate (MP), propylene Trifluorocarbonate (TFPC), butyltrifluoroacetate (TFAEt), ethyl trifluoroacetate (DFAE), fluorinated ethylene carbonate (ETFA), ethyl Difluoroacetate (EDFA), and fluorinated carbonate.
Preferably, the organic solvent is EC and DMC in a volume ratio of 1:1.
Preferably, the organic solvents are EC and MPC in a volume ratio of 1:1.
Preferably, the organic solvents are EC and EMC in a volume ratio of 3:7.
Preferably, the organic solvents are EC and GBL in a volume ratio of 3:7.
Preferably, the organic solvents are EC and ETFA in a volume ratio of 2:8.
Preferably, the organic solvents are EC, DMC and DEC in a volume ratio of 1:1:1.
Preferably, the organic solvents are EC, MP and EMC in a volume ratio of 1:1:1.
Preferably, the organic solvents are EC, DMC and GBL in a volume ratio of 6:2:2.
Preferably, the organic solvents are EC, DMC and ETFA in a volume ratio of 6:2:2.
Preferably, the organic solvents are EC, EMC and DFAE in a volume ratio of 5:3:2.
The lithium salt comprises lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium nitrate (LiNO) 3 ) Lithium difluorooxalato borate (LiDFOB), bisoxalato borate (LiBOB), lithium bisdifluorosulfimide (LiSSI), lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) and lithium difluorophosphate (LiPO) 2 F 2 ) At least one of an inorganic anionic lithium salt and an organic anionic lithium salt.
Preferably, the lithium salts are LiDFOB and LiBF 4 The molar ratio is 2:1.
Preferably, the lithium salts are LiDFOB and LiNO 3 The molar ratio is 3:1.
Preferably, the lithium salt is LiFSI and LiBOB in a molar ratio of 1:1.
Preferably, the lithium salt is LiTFSI and LiBOB in a molar ratio of 1:1.
Preferably, the lithium salts are LiFSI and LiBF 4 Molar (mol)The ratio is 2:1.
Preferably, the concentration of the lithium salt is 0.1-3.0mol/L, and the additive accounts for 0.1-10% of the total mass of the electrolyte.
LiNi can be made by using the high-voltage electrolyte added with the oxygen radical scavenging additive of the invention 0.8 Co 0.1 Mn 0.1 O 2 The MCMB button cell has almost no attenuation of 200 cycles of capacity in the voltage range of 2.8-4.4V, and the average coulomb efficiency is as high as 99.9%; liNi 0.8 Co 0.1 Mn 0.1 O 2 The Li button cell has 92% capacity retention rate after 150 circles of circulation in the voltage range of 2.8-4.4V, and the average coulomb efficiency is as high as 99.9%; assembled LiCoO 2 The Li button cell has 94% capacity retention rate after 200 circles of circulation in the voltage range of 3.0-4.6V, and the average coulomb efficiency is as high as 99.9%, which is superior to the performance of the current high-voltage electrolyte.
The compound capable of scavenging oxygen free radicals in the invention contains-NH-chemical bond, and the compound can be decomposed to form a thin, compact and protective solid electrolyte interface in the charge and discharge process of the battery as an additive of the electrolyte, so that the phase change of the positive electrode material from a layered structure to spinel and rock salt phases is effectively inhibited, the release of oxygen from the positive electrode surface is inhibited, and the decomposition of the electrolyte can be effectively avoided, and therefore, the electrolyte added with the compound capable of scavenging oxygen free radicals in the invention can meet the requirements of a high-voltage lithium battery.
The invention also provides a lithium battery, which comprises an anode active material and a cathode active material, and further comprises the high-voltage electrolyte for the lithium battery.
Preferably, the positive electrode active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 Or LiCoO 2 The negative electrode active material is a Mesophase Carbon Microsphere (MCMB) or a metallic lithium sheet.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides an application of a compound capable of scavenging oxygen free radicals, which is used as an additive of high-voltage lithium battery electrolyte, can effectively inhibit the phase transition of a positive electrode material to spinel and rock salt phases, form a thin, compact and protective solid electrolyte interface on the surface of the positive electrode, inhibit the release of oxygen from the surface of the positive electrode, avoid the decomposition of the electrolyte, and improve the cycle stability and coulomb efficiency of the battery.
(2) According to the invention, the organic solvent, the lithium salt and the oxygen free radical scavenging additive in the electrolyte of the high-voltage lithium battery are specifically combined, and the proportion and the concentration are further optimized, so that the electrolyte provided by the invention has excellent compatibility with the anode and the cathode, and meanwhile, the cycle performance and the coulombic efficiency of the lithium battery are obviously improved.
(3) The high-voltage electrolyte for the lithium battery belongs to an electrolyte system with good film forming performance, good multiplying power performance, wide electrochemical window and capability of scavenging oxygen free radicals, and has wide application prospect in the lithium battery.
Drawings
FIG. 1 is a structural diagram of melanin-1.
FIG. 2 is a structural formula of the chromene AS-BO.
FIG. 3 is a bilirubin structural formula diagram.
FIG. 4 is a structural diagram of N-benzyloxycarbonyl-D-tryptophan.
FIG. 5 is a structural diagram of N-benzoyl-L-tyrosine ethyl ester.
FIG. 6 is a diagram of the structural formula of bis (2, 4-dimethoxybenzyl) amine.
FIG. 7 is a diagram showing Fmoc-L-threonine.
Fig. 8 is a valsartan structural formula diagram.
FIG. 9 is a graphic representation of the structural formula of 6-methoxy-7-benzyloxyquinazolin-4-one.
FIG. 10 is a structural diagram of FMOC-L-2-phenylalanine.
FIG. 11 shows the electrolyte prepared in example 1 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in MCMB cell.
FIG. 12 shows the electrolyte prepared in example 2 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in MCMB cell.
FIG. 13 is an embodiment ofThe electrolyte prepared in example 3 was in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in Li battery.
FIG. 14 shows the electrolyte prepared in example 4 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in Li battery.
FIG. 15 shows the electrolyte prepared in example 5 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in Li battery.
FIG. 16 shows the electrolyte prepared in example 6 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in Li battery.
FIG. 17 shows LiCoO of the electrolyte prepared in example 7 2 Cycle life graph in Li battery.
FIG. 18 shows LiCoO of the electrolyte prepared in example 8 2 Charge-discharge curve in Li battery.
FIG. 19 shows LiCoO of the electrolyte prepared in example 9 2 Cycle life graph in MCMB cell.
FIG. 20 shows LiCoO of the electrolyte prepared in example 10 2 Cycle life graph in Li battery.
FIG. 21 shows a commercial electrolyte solution in LiNi prepared in comparative example 1 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in MCMB cell.
FIG. 22 shows a commercial electrolyte solution in LiNi prepared in comparative example 2 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in Li battery.
FIG. 23 is a modified commercial ester-based electrolyte in LiCoO as formulated in comparative example 3 2 Cycle life graph in Li battery.
Detailed Description
Example 1
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
an amount of LiPF 6 Slowly getDissolving in EC and DMC at a volume ratio of 1:1, and slowly adding oxygen free radical scavenging additive melanin-1 (CAS number: 29512-49-0, formula shown in figure 1) to obtain LiPF 6 The concentration of the additive is 0.5mol/L, so that the additive melanin-1 for removing oxygen free radicals accounts for 0.2 percent of the total mass of the electrolyte, and the high-voltage electrolyte which is used for lithium batteries and contains the compound capable of removing oxygen free radicals is obtained after the mixture is uniformly mixed until the mixture is completely dissolved.
FIG. 11 shows the electrolyte prepared in example 1 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in MCMB cell. As can be seen from fig. 11, the above electrolyte was almost free from capacity decay after 200 cycles at a charge cut-off voltage of 4.4V, and the average coulomb efficiency was close to 100%. And the commercial ester-based electrolyte has a capacity retention of less than 80% and an average coulombic efficiency of less than 99% after being cycled for 61 cycles under the condition.
Example 2
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
and slowly dissolving a certain amount of LiDFOB in EC and MPC with the volume ratio of 1:1, slowly adding an oxygen free radical scavenging additive, namely, parachromol AS-BO (CAS number: 132-68-3, with the structural formula shown in figure 2), enabling the concentration of LiDFOB to be 0.1mol/L, enabling high-voltage additive, namely, acetamido silane, to account for 0.1% of the total mass of the electrolyte, and stirring until the electrolyte is completely dissolved, thus obtaining the high-voltage electrolyte which is used for the lithium battery and contains the compound capable of scavenging oxygen free radicals.
FIG. 12 shows the electrolyte prepared in example 2 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in MCMB cell. As can be seen from fig. 12, liNi 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material can be charged and discharged in high efficiency and reversibility in the high-voltage electrolyte. Even under the high charge cut-off voltage of 4.4V, the discharge specific capacity decay is not obvious with the increase of the cycle number, which shows that the electrolyte is specific to LiNi 0.8 Co 0.1 Mn 0.1 O 2 High compatibility of positive electrode material, scavenging oxygen free radical, and inhibiting chemical generation of electrolyteAbility to degrade.
Example 3
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
and slowly dissolving a certain amount of LiFeSI in EC and EMC with the volume ratio of 3:7, then slowly adding an oxygen free radical scavenging additive bilirubin (CAS number: 635-65-4, the structural formula is shown in figure 3) to ensure that the concentration of LiFeSI is 1mol/L, and uniformly mixing until the oxygen free radical scavenging additive bilirubin accounts for 0.5% of the total mass of the electrolyte, thereby obtaining the high-voltage electrolyte which is used for the lithium battery and contains the compound capable of scavenging oxygen free radicals.
FIG. 13 shows the electrolyte prepared in example 3 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in Li battery. As can be seen from fig. 13, the above electrolyte still has 84% of the initial capacity after 150 cycles at a charge cut-off voltage of 4.4V, and the average coulombic efficiency is as high as 99.9%.
Example 4
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
and slowly dissolving a certain amount of LiTFSI in EC and GBL with the volume ratio of 3:7, then slowly adding an oxygen free radical scavenging additive N-benzyloxycarbonyl-D-tryptophan (CAS number: 2279-15-4, the structural formula is shown in figure 4), enabling the concentration of LiTFSI to be 1.5mol/L, enabling the oxygen free radical scavenging additive N-benzyloxycarbonyl-D-tryptophan to account for 1% of the total mass of the electrolyte, and uniformly mixing until the electrolyte is completely dissolved, thus obtaining the high-voltage electrolyte which is used for the lithium battery and contains the compound capable of scavenging oxygen free radicals.
FIG. 14 shows the electrolyte prepared in example 4 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in Li battery. As can be seen from fig. 14, the above electrolyte was improved significantly compared with a commercial electrolyte in that the capacity retention rate was 91% after 150 cycles of the electrolyte at a charge cut-off voltage of 4.4V. Indicating that the additive can be decomposed to form thin, compact and protective materials during the charge and discharge cycle of the batteryA solid electrolyte interface.
Example 5
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
and slowly dissolving a certain amount of LiBOB in EC and ETFA with the volume ratio of 2:8, slowly adding an oxygen free radical scavenging additive N-benzoyl-L-tyrosine ethyl ester (CAS number: 3483-82-7, the structural formula is shown in figure 5), enabling the concentration of the LiBOB to be 0.5mol/L, enabling the oxygen free radical scavenging additive N-benzoyl-L-tyrosine ethyl ester to account for 2% of the total mass of the electrolyte, and uniformly mixing until the electrolyte is completely dissolved, thus obtaining the high-voltage electrolyte which is used for the lithium battery and contains the compound capable of scavenging oxygen free radicals.
FIG. 15 shows the electrolyte prepared in example 5 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in Li battery. As can be seen from fig. 15, liNi 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material can be charged and discharged in high efficiency and reversibility in the high-voltage electrolyte. Even at a charge cutoff voltage of 4.4V high, the increase in polarization is significantly smaller than that of the commercial electrolyte with the increase in the number of cycles, inhibiting oxygen release from the positive electrode surface.
Example 6
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
the molar ratio of LiDFOB to LiBF is 2:1 4 Slowly dissolving in EC, DMC and DEC at volume ratio of 1:1:1, and slowly adding oxygen scavenging free radical additive bis (2, 4-dimethoxybenzyl) amine (CAS number: 20781-23-1, structure formula shown in figure 6) to obtain LiDFOB and LiBF 4 The concentration of the electrolyte is 3mol/L, so that the oxygen free radical scavenging additive bis (2, 4-dimethoxy benzyl) amine accounts for 3 percent of the total mass of the electrolyte, and the electrolyte is uniformly mixed until the electrolyte is completely dissolved, thus obtaining the high-voltage electrolyte which is used for the lithium battery and contains the compound capable of scavenging oxygen free radicals.
FIG. 16 shows the electrolyte prepared in example 6 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in Li cell. As can be seen from fig. 16, the capacity retention rate was 92% after the above electrolyte was circulated for 150 cycles at a charge cut-off voltage of 4.4V, and the additive effectively inhibited the phase transition of the positive electrode material to the spinel or halite phase.
Example 7
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
the molar ratio of LiDFOB to LiNO is 3:1 3 Slowly dissolving in EC, MP and EMC at volume ratio of 1:1:1, and slowly adding oxygen scavenging free radical additive Fmoc-L-threonine (CAS number: 73731-37-0, formula shown in FIG. 7) to obtain LiDFOB and LiNO 3 The concentration of the Fmoc-L-threonine which is an oxygen free radical scavenging additive accounts for 5% of the total mass of the electrolyte, and the high-voltage electrolyte for the lithium battery is obtained after the Fmoc-L-threonine is uniformly mixed until the Fmoc-L-threonine is completely dissolved.
FIG. 17 shows LiCoO of the electrolyte prepared in example 7 2 Cycle life graph in Li battery. As can be seen from FIG. 17, the electrolyte still has 83% capacity retention rate after 150 cycles at a charge cut-off voltage of 4.6V, and the average coulomb efficiency is as high as 99.9% or more. Compared with the traditional commercial ester-based electrolyte, the circulation capacity retention rate and the coulombic efficiency are greatly improved.
Example 8
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
slowly dissolving LiSI and LiBOB with the mol ratio of 1:1 in EC, DMC and GBL with the volume ratio of 6:2:2, then slowly adding valsartan (CAS number: 137862-53-4, the structural formula is shown in figure 8) which is an oxygen free radical scavenging additive, so that the concentration of LiSI and LiBOB is 1mol/L, and uniformly mixing to completely dissolve the valsartan which is a high voltage additive and accounts for 8% of the total mass of the electrolyte, thus obtaining the high voltage electrolyte for the lithium battery.
FIG. 18 shows LiCoO of the electrolyte prepared in example 8 2 Charge-discharge curve in Li battery. As can be seen from fig. 18, liCoO 2 The positive electrode material appears in the high-voltage electrolyteObvious charge-discharge platform and high reversibility. At a charge cutoff voltage of 4.6V, the decay amplitude of the specific discharge capacity is smaller with the progress of the cycle, indicating the excellent high-voltage resistance of the electrolyte.
Example 9
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
slowly dissolving LiTFSI and LiBOB with the mol ratio of 1:1 in EC, DMC and ETFA with the volume ratio of 6:2:2, slowly adding a scavenging oxygen free radical additive 6-methoxy-7-benzyloxy quinazoline-4-ketone (CAS number: 179688-01-8, the structural formula is shown in figure 9), enabling the concentration of LiTFSI and LiBOB to be 2mol/L, enabling the scavenging oxygen free radical additive 6-methoxy-7-benzyloxy quinazoline-4-ketone to account for 10% of the total mass of the electrolyte, and uniformly mixing until the components are completely dissolved, thus obtaining the high-voltage electrolyte for the lithium battery.
FIG. 19 shows LiCoO of the electrolyte prepared in example 9 2 Cycle life graph in MCMB cell. As can be seen from FIG. 19, the electrolyte still has 83% capacity retention after 200 cycles of charge cut-off voltage of 4.6V, and the average coulomb efficiency is as high as 99.9% or more. The additive can effectively remove oxygen free radicals in the electrolyte and effectively avoid the decomposition of the electrolyte.
Example 10
A high-voltage electrolyte for lithium batteries containing a compound capable of scavenging oxygen radicals is prepared by the following steps:
LiFSI and LiBF in a molar ratio of 2:1 4 Slowly dissolving in EC, EMC and DFAE at volume ratio of 5:3:2, and slowly adding oxygen scavenging free radical additive FMOC-L-2-phenylalanine (CAS number: 198560-41-7, formula shown in figure 10) to obtain LiDFOB and LiNO 3 The concentration of the catalyst is 2.5mol/L, so that the oxygen free radical scavenging additive FMOC-L-2-phenylalanine accounts for 1% of the total mass of the electrolyte, and the electrolyte is uniformly mixed until the electrolyte is completely dissolved, thus obtaining the high-voltage electrolyte for the lithium battery.
FIG. 20 shows LiCoO of the electrolyte prepared in example 10 2 Circulation in Li cellRing life graph. As can be seen from FIG. 20, the electrolyte still has 94% capacity retention rate after 200 cycles of charging cut-off voltage of 4.6V, and the average coulomb efficiency is as high as 99.8% or more. This demonstrates that the additive is capable of decomposing during the charge and discharge cycles of the battery to form a dense, protective solid electrolyte interface that inhibits oxygen release from the positive electrode surface.
Comparative example 1
An amount of LiPF 6 Slowly dissolve in EC and DMC in a volume ratio of 1:1 to make lithium salt LiPF 6 The concentration of (C) was 1.5mol/L. Stirring until the electrolyte is completely dissolved, and obtaining the commercial ester-based electrolyte of the lithium ion battery.
FIG. 21 shows the electrolyte prepared in comparative example 1 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in MCMB cell. As can be seen from fig. 21, the above electrolyte has a specific discharge capacity of only 98.5mAh/g after 200 cycles, a capacity retention of only 54%, and an average coulombic efficiency of 99.5%, which is greatly reduced in comparison with the high-voltage electrolyte of the present invention and cycle performance.
Comparative example 2
An amount of LiPF 6 Slowly dissolving in EC, DMC and DEC in a volume ratio of 1:1:1 to obtain lithium salt LiPF 6 The concentration of (C) was 1mol/L. Stirring until the electrolyte is completely dissolved, and obtaining the commercial ester-based electrolyte of the lithium ion battery.
FIG. 22 shows the electrolyte prepared in comparative example 2 in LiNi 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in Li battery. As can be seen from fig. 22, liNi 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material is not obvious in a charge-discharge platform along with the increase of the circulation times in the commercial ester-based electrolyte, the polarization is rapidly increased, and the reversible capacity is rapidly attenuated.
Comparative example 3
An amount of LiPF 6 Slowly dissolving in EC and DEC with volume ratio of 3:7, slowly adding additive Vinylene Carbonate (VC) to obtain lithium salt LiPF 6 The concentration of (2) mol/L, so that the additive VC occupies electricity2% of the total mass of the solution. Stirring until the electrolyte is completely dissolved, and obtaining the commercial ester-based electrolyte modified by the lithium ion battery.
FIG. 23 is a LiCoO showing the electrolyte prepared in comparative example 3 2 Cycle life graph in Li battery. As can be seen from FIG. 23, liCoO was performed under the condition that the charge cutoff voltage was as high as 4.6V 2 The capacity of the Li battery decays rapidly, the capacity after 150 cycles is only 73% of the initial capacity, and in addition, the coulomb efficiency is low, and the application requirements of the high-voltage lithium battery cannot be met.
LiNi in examples and comparative examples 0.8 Co 0.1 Mn 0.1 O 2 /Li、LiNi 0.8 Co 0.1 Mn 0.1 O 2 MCMB and LiCoO 2 Manufacturing and testing of Li button cell:
(1) Positive pole piece: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 Or LiCoO 2 Adding binder polyvinylidene fluoride (PVDF) and conductive carbon black into N-methyl pyrrolidone (NMP) according to a ratio of 9:0.5:0.5, uniformly mixing to obtain slurry, uniformly coating the slurry on an aluminum foil current collector, drying at 110 ℃, and cutting into wafers with a diameter of 12.0 mm by a sheet punching machine;
(2) Li negative electrode: a metal lithium sheet with the thickness of 400 micrometers and the diameter of 16.0 millimeters is adopted;
graphite negative pole piece: adding MCMB, binder lithiated polyacrylic acid (LiPAA) and conductive carbon black into deionized water according to the ratio of 8:1:1, uniformly mixing to obtain slurry, uniformly coating the slurry on a copper foil current collector, and drying at 90 ℃, wherein a negative pole piece is a wafer with the diameter of 14.0 mm;
(3) Electrolyte solution: the electrolytes prepared in examples 1 to 10 and comparative examples 1 to 3;
(4) A diaphragm: cutting a Polyethylene (PE) single-layer diaphragm wafer with the diameter of 19.0 mm by adopting a sheet punching machine;
(5) And (3) battery assembly: in glove box (O) 2 <0.1ppm，H 2 O<0.1 ppm), button lithium ion batteries were assembled in the order of positive electrode case-positive electrode sheet-Polyethylene (PE) single-layer diaphragm disc-negative electrode disc-stainless steel sheet-spring sheet-negative electrode case, and the examples were added1-10 and comparative examples 1-3, and finally packaging to obtain a test cell;
(6) And (3) battery testing: the electrolytes in examples 1 to 10 and comparative examples 1 to 3 correspond to batteries 1 to 13, lini 0.8 Co 0.1 Mn 0.1 O 2 /Li(2.8-4.4V)、LiNi 0.8 Co 0.1 Mn 0.1 O 2 MCMB (2.8-4.4V) and LiCoO 2 The Li (3-4.6V) button half cell is activated for 2 circles at the multiplying power of 0.1C at the room temperature (25 ℃) and then is subjected to the multiplying power long cycle of 0.5C; the test results are shown in FIGS. 11-23, and the results and conclusions are set forth in each example and comparative example, respectively.
Claims (9)
1. Use of a compound capable of scavenging oxygen radicals, characterized in that the compound capable of scavenging oxygen radicals is used AS an additive for lithium battery electrolytes, the compound capable of scavenging oxygen radicals being melanin-1, chromen AS-BO, bilirubin, N-benzyloxycarbonyl-D-tryptophan, N-benzoyl-L-tyrosine ethyl ester, bis (2, 4-dimethoxybenzyl) amine, fmoc-L-threonine, valsartan, 6-methoxy-7-benzyloxyquinazolin-4-one or Fmoc-L-2-chloroaniline.
2. An additive for high voltage lithium battery electrolytes, characterized in that it comprises at least one compound capable of scavenging oxygen radicals, said compound capable of scavenging oxygen radicals being melanin-1, chromene AS-BO, bilirubin, N-benzyloxycarbonyl-D-tryptophan, N-benzoyl-L-tyrosine ethyl ester, bis (2, 4-dimethoxybenzyl) amine, fmoc-L-threonine, valsartan, 6-methoxy-7-benzyloxyquinazolin-4-one or Fmoc-L-2-chlorophenylalanine.
3. A high voltage electrolyte for a lithium battery comprising an organic solvent, a lithium salt, and the additive of claim 2.
4. The high-voltage electrolyte for lithium batteries according to claim 3, wherein the organic solvent comprises two or more of diethyl carbonate, propylene carbonate, ethylene carbonate, dimethyl carbonate, methylethyl carbonate, gamma-butyrolactone, gamma-valerolactone, methylpropyl carbonate, propyl propionate, ethyl propionate, methyl propionate, trifluoropropylene carbonate, butyl trifluoroacetate, ethyl trifluoroacetate, fluoroethylene carbonate, ethyl difluoroacetate and other carbonates, and fluorocarbonates.
5. The high-voltage electrolyte for a lithium battery according to claim 3, wherein the lithium salt comprises at least one of inorganic anion lithium salts and organic anion lithium salts such as lithium tetrafluoroborate, lithium hexafluorophosphate, lithium nitrate, lithium difluorooxalato borate, boric acid bisoxalato borate, lithium bisdifluorosulfimide, lithium perchlorate, lithium bistrifluoromethylsulfonimide and lithium difluorophosphate.
6. The high-voltage electrolyte for lithium batteries according to claim 3, wherein the concentration of said lithium salt is 0.1 to 3.0mol/L.
7. A high voltage electrolyte for a lithium battery according to claim 3, wherein the additive is 0.1% -10% of the total mass of the electrolyte.
8. A lithium battery comprising a positive electrode active material and a negative electrode active material, characterized by further comprising the high-voltage electrolyte for a lithium battery according to any one of claims 3 to 7.
9. The lithium battery of claim 8, wherein the positive electrode active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 Or LiCoO 2 The negative electrode active material is mesophase carbon microsphere or metal lithium sheet.
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