CN117154230A - Electrolyte and lithium ion battery thereof - Google Patents
Electrolyte and lithium ion battery thereof Download PDFInfo
- Publication number
- CN117154230A CN117154230A CN202311349419.3A CN202311349419A CN117154230A CN 117154230 A CN117154230 A CN 117154230A CN 202311349419 A CN202311349419 A CN 202311349419A CN 117154230 A CN117154230 A CN 117154230A
- Authority
- CN
- China
- Prior art keywords
- lithium
- electrolyte
- ion battery
- lithium ion
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 57
- 239000003792 electrolyte Substances 0.000 title claims abstract description 30
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 20
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 13
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 10
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910021437 lithium-transition metal oxide Chemical class 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
- 239000010450 olivine Substances 0.000 claims description 3
- 229910052609 olivine Inorganic materials 0.000 claims description 3
- WXVUCMFEGJUVTN-UHFFFAOYSA-N phenyl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CC=C1 WXVUCMFEGJUVTN-UHFFFAOYSA-N 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 3
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 claims description 2
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- OWNSEPXOQWKTKG-UHFFFAOYSA-M lithium;methanesulfonate Chemical compound [Li+].CS([O-])(=O)=O OWNSEPXOQWKTKG-UHFFFAOYSA-M 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- RIZZXCJMFIGMON-UHFFFAOYSA-N prop-2-ynyl acetate Chemical compound CC(=O)OCC#C RIZZXCJMFIGMON-UHFFFAOYSA-N 0.000 claims description 2
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims 1
- VWEYDBUEGDKEHC-UHFFFAOYSA-N 3-methyloxathiolane 2,2-dioxide Chemical compound CC1CCOS1(=O)=O VWEYDBUEGDKEHC-UHFFFAOYSA-N 0.000 claims 1
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 claims 1
- BAPGOVYLNIGTOU-UHFFFAOYSA-N C=COS(=O)(=O)OS(=O)(=O)O Chemical compound C=COS(=O)(=O)OS(=O)(=O)O BAPGOVYLNIGTOU-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- ACNASVKDYHUAHH-UHFFFAOYSA-N ethene silane Chemical compound [SiH4].C=C.C=C.C=C.C=C ACNASVKDYHUAHH-UHFFFAOYSA-N 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002596 lactones Chemical class 0.000 claims 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims 1
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 abstract description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-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
- 239000002000 Electrolyte additive Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 239000006256 anode slurry Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 229940126214 compound 3 Drugs 0.000 description 2
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- 150000003983 crown ethers Chemical class 0.000 description 2
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- OSSBKXMASZTOSG-UHFFFAOYSA-N 2-(trifluoromethyl)oxolane Chemical compound FC(F)(F)C1CCCO1 OSSBKXMASZTOSG-UHFFFAOYSA-N 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 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
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- CHCLGECDSSWNCP-UHFFFAOYSA-N methoxymethoxyethane Chemical compound CCOCOC CHCLGECDSSWNCP-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
The application provides an electrolyte and a lithium ion battery thereof. Comprises lithium salt, nonaqueous solvent and additive, wherein the additive comprises a compound A shown as a structural formula I, and R is 1 ～R 5 Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C6 hydrocarbyl groups, n being taken from an integer greater than zero. The electrolyte provided by the application not only can ensure the high-temperature performance of the lithium ion battery, but also can give consideration to the low-temperature performance of the lithium ion battery, and especially has good low-temperature performance at-20 ℃.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to an electrolyte and a lithium ion battery thereof.
Background
A lithium ion battery is a secondary battery that operates mainly by means of lithium ions moving between a positive electrode and a negative electrode. During charge and discharge, li + To-and-fro intercalation and deintercalation between two electrodes: during charging, li + De-intercalation from the positive electrode, and intercalation into the negative electrode through the electrolyte, wherein the negative electrode is in a lithium-rich state; the opposite is true when discharging.
The lithium ion battery has the advantages of high working voltage, high energy density, environmental friendliness and the like, is widely applied to the fields of 3C consumer batteries, power batteries and energy storage batteries, and has wide application prospects in the fields of aerospace, national defense and military industry and the like.
With the continuous progress of technology, various mobile devices such as aircrafts, ships, vehicles, mobile communication devices and the like are usually operated in high-temperature environments and also in severe cold environments, and therefore, lithium ion batteries with excellent high-low temperature performance are required, so that the development of lithium ion batteries capable of achieving both high-low temperature performance is a relatively hot problem at home and abroad.
Generally, a battery with good performance at normal temperature can only have good low-temperature performance or good high-temperature performance, and is difficult to have good high-temperature performance and low-temperature performance, wherein the main reason is that the liquid temperature window of the lithium ion battery electrolyte is narrow, and the heat stability and the electrochemical stability at high and low temperatures cannot be achieved. In order to solve the application problem of the lithium ion battery under the high and low temperature conditions, the application temperature range of the lithium ion battery is further widened, and various methods are adopted to improve the application temperature range of the lithium ion battery, for example, chinese patent 202010900795.7 discloses that a compound with a cyclic pyrocarbonate structure and thiophene functional groups is adopted as an electrolyte additive to realize that the lithium ion battery not only has high temperature performance, but also has good low temperature performance at-10 ℃, however, the compound has an anhydride structure outside a ring, which easily forms an excessively thick interfacial polymerization layer, thereby preventing the low temperature performance of the lithium ion battery from being further improved, in other words, the compound cannot realize that the lithium ion battery has good low temperature performance at lower temperature conditions (such as-20 ℃) when being used as the electrolyte additive.
Therefore, it is necessary to develop an electrolyte solution capable of simultaneously achieving high and low temperature performance and further improving the low temperature performance of a lithium ion battery, and a lithium ion battery comprising the electrolyte solution.
Disclosure of Invention
The application aims to provide an electrolyte and a lithium ion battery thereof, wherein the electrolyte not only can ensure the high-temperature performance of the lithium ion battery, but also can give consideration to the low-temperature performance of the lithium ion battery, and particularly has good low-temperature performance at-20 ℃.
To achieve the above object, in one aspect, the present application provides an electrolyte comprising a lithium salt, a nonaqueous solvent, and an additive comprising a compound a represented by structural formula i:
wherein R is 1 ～R 5 Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C6 hydrocarbyl groups, n being taken from an integer greater than zero.
Compared with the prior art, the electrolyte comprises lithium salt, a nonaqueous solvent and an additive, wherein the additive comprises a compound A, the compound A has relatively higher oxidation potential and can be adsorbed on the surface of an electrode to form a thinner adsorption layer, the adsorption layer is not easy to crystallize at low temperature, and a lithium ion transmission channel at low temperature can be maintained, so that the lithium ion battery is improvedLow temperature performance at-20 ℃. In addition, the compound A of the application contains SO 3 - And N + The zwitterionic structure of the (B) can form an interface with better heat stability and fewer electron channels in the negative electrode reaction of the lithium ion battery, and meanwhile, SO in the compound A 3 - And N + The structure can be combined with positive and negative ions in lithium salt respectively, and improves the thermal stability of the lithium salt, so that the damage of a decomposition product of the lithium salt to an SEI interface at high temperature is inhibited, and further the high-temperature storage and high-temperature cycle performance of the lithium ion battery are improved.
As a preferred technical scheme, R 1 ～R 3 Each independently selected from substituted or unsubstituted C1-C6 hydrocarbyl radicals, R 4 ～R 5 Each independently selected from hydrogen or halogen, 0 < n.ltoreq.5.
As a preferred technical scheme, R 1 ～R 3 Each independently selected from substituted or unsubstituted C1-C3 alkyl, R 4 ～R 5 Each independently selected from hydrogen or fluorine atoms, 0 < n.ltoreq.3.
As a preferred technical scheme, the compound a is at least one of the following compounds 1 to 6:
as a preferred embodiment, the amount of the compound a is 0.1% to 5%, specifically but not limited to 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 1.5%, 2.0%, 2.2%, 2.5%, 3.0%, 3.2%, 3.5%, 3.8%, 4.0%, 4.2%, 4.5%, 4.8%, 5.0%, based on 100% of the total mass of the lithium salt, the nonaqueous solvent and the additive, and the amount of the compound a is preferably 0.1 to 3.0%.
As a preferred embodiment, the lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium bis (fluorosulfonyl) imide (LiLSI), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium methylsulfonate (LiCH) 3 SO 3 ) TrifluoroLithium methylsulfonate (LiCF) 3 SO 3 ) Lithium fluorosulfonate (LiSO) 3 F) Lithium dioxalate borate (C) 4 BLiO 8 ) Lithium difluorooxalato borate (C) 2 BF 2 LiO 4 ) Lithium difluorophosphate (LiPO) 2 F 2 ) Lithium difluorobis (oxalato) phosphate (LiDFOP), lithium chloroborane (LiBCl) 4 ) At least one of lithium tetraphenyl borate (LiCHB).
As a preferred technical scheme, the total mass of the lithium salt, the nonaqueous solvent and the additive is 100%, the lithium salt is 5% -25%, further, the lithium salt is 6% -20%, more preferably, the mass fraction of the lithium salt is 8% -18%, and particularly but not limited to 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%.
As a preferred technical scheme, the nonaqueous solvent is at least one selected from carbonic acid esters, carboxylic acid esters and ether compounds.
In particular, the carbonates include, but are not limited to, cyclic carbonates and chain carbonates, wherein the cyclic carbonates may be, but are not limited to, ethylene Carbonate (EC), propylene Carbonate (PCA), butylene Carbonate (BC), vinylene Carbonate (VC), or derivatives thereof; chain carbonates include, but are not limited to, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), propylene Carbonate (PC).
In particular, the carboxylic acid esters include, but are not limited to, cyclic carboxylic acid esters, chain carboxylic acid esters, which may be, but are not limited to, particularly gamma-butyrolactone (GBL), gamma-valerolactone (GVL), delta-valerolactone (DVL); chain carboxylic acid esters include, but are not limited to, methyl Acetate (MA), ethyl Acetate (EA), propyl acetate (EP), butyl Acetate (BA), propyl Propionate (PP), butyl Propionate (PRB).
In particular, the ether compounds include, but are not limited to, cyclic ethers or chain ethers, which may include, but are not limited to, in particular at least one of 1, 3-Dioxolane (DOL), 1, 4-Dioxane (DX), crown Ether (CE), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH 3-THF), 2-trifluoromethyl tetrahydrofuran (2-CF 3-THF); the chain ethers may specifically include, but are not limited to, dimethoxymethane (DMM), diethoxymethane (DEM), ethoxymethoxymethane (MEM), ethylene glycol di-n-butyl Ether (EDB), diethylene glycol dimethyl ether (DEGME).
As a preferred technical scheme, the additive further comprises an auxiliary agent, wherein the auxiliary agent is selected from Vinylene Carbonate (VC), vinylene carbonate (VEC), fluoroethylene carbonate (FEC), ethylene Sulfite (ES), 1, 3-propane sultone (1, 3-PS), 1, 3-Propylene Sultone (PST), 1, 4-butane sultone (1, 4-BS), ethylene sulfate (DTD), succinic Anhydride (SA), maleic Anhydride (MA), 2-methyl maleic anhydride (DMMA), methyl carboxylic acid-2-propynyl ester (cam), tetraethyl silane (TVSI), triallyl isocyanurate (TAIC), hexamethylene Diisocynonate (HDI), phenanthroline (O-PHEN), terephthal-diisocyanate (PPDI), 2, 4-Toluene Diisocyanate (TDI), N-phenyl bis (trifluoromethanesulfonyl) imine, bis (ethylene sulfate) (BIDTD), phenyl methane sulfonate (DBCO), triallyl phosphate (TAP), tripropyl phosphate (TPP), 2,4-BS (tms), and trimethylsilane (tmm), at least one of trimethylsilane (tmm), and trimethylsilane (tmm). Illustratively, the auxiliary agent is fluoroethylene carbonate (FEC), and for example, the auxiliary agent is a mixed solvent of Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC).
As a preferred technical solution, the auxiliary agent is 0.1% -5%, specifically but not limited to 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.2%, 2.5%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5% and the auxiliary agent is preferably 0.2% -2% based on the total of the mass of the lithium salt, the nonaqueous solvent and the additive is 100%.
The application also provides a lithium ion battery which comprises a positive electrode, a negative electrode and the electrolyte, and has good high-temperature storage performance, high-temperature cycle performance, low-temperature performance, and low-temperature performance at-20 ℃ in particular.
As a preferred embodiment, the positive electrode includes a positive electrode active material selected from at least one of lithium-containing phosphates of olivine structure and modified compounds thereof, and lithium transition metal oxides and modified compounds thereof. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery positive electrode active material may be used. These positive electrode active materials may be used alone or in combination of two or more.
In particular, examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO 4 (also referred to as LFP for short)), a composite of lithium iron phosphate and carbon, a composite of lithium manganese phosphate (e.g., liMnPO 4), a composite of lithium manganese phosphate and carbon, a composite of lithium manganese phosphate, lithium manganese phosphate and carbon.
In particular, examples of the lithium transition metal oxide may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g. LiNiO) 2 ) Lithium manganese oxide (e.g. LiMnO 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, and lithium nickel cobalt manganese oxide.
As a preferred technical scheme, the positive electrode active material of the application is lithium nickel cobalt manganese oxide, and the chemical formula of the lithium nickel cobalt manganese oxide is LiNi x Co y Mn (1-x-y) M z O 2 Wherein 0.6.ltoreq.x<0.9，x+y<1，0≤z<0.08, M is at least one of Al, mg, zr and Ti. As an example, x=0.8, y=0.1, m is Zr, and z=0.03.
As a preferred embodiment, the negative electrode includes a negative electrode active material including at least one of a carbon-based negative electrode, a silicon-based negative electrode, a tin-based negative electrode, and a lithium negative electrode.
Specifically, wherein the carbon-based negative electrode may include graphite, hard carbon, soft carbon, graphene, mesophase carbon microspheres, and the like; the silicon-based anode may include a silicon material, an oxide of silicon, a silicon-carbon composite material, a silicon alloy material, or the like; 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.
Detailed Description
For a better description of the objects, technical solutions and advantageous effects of the present application, the present application will be further described with reference to specific examples. The specific conditions not specified in examples and comparative examples may be carried out under the conventional conditions or the conditions recommended by the manufacturer, and the reagents or instruments used are conventional products available commercially without specifying the manufacturer.
Example 1
(1) Preparation of electrolyte
In a glove box (O) 2 ＜1ppm，H 2 O < 1 ppm), uniformly mixing Ethylene Carbonate (EC), propylene Carbonate (PC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) according to a mass ratio of 2:1:5:2, taking the obtained mixed solvent as an organic solvent, and adding the compound 1 to obtain a mixed solution. Sealing and packaging the mixed solution, freezing for 2 hr in a quick freezing chamber (-4deg.C), taking out, and placing in a glove box (O) filled with nitrogen 2 ＜1ppm，H 2 O is less than 1 ppm), slowly adding lithium hexafluorophosphate into the mixed solution, and uniformly mixing to obtain the electrolyte.
(2) Preparation of positive plate
Ternary material LiNi 0.8 Co 0.1 Mn 0.1 Zr 0.03 O 2 Uniformly mixing a conductive agent SuperP, an adhesive PVDF and a Carbon Nano Tube (CNT) according to a mass ratio of 96.5:1.5:1:1 to prepare lithium ion battery anode slurry with certain viscosity, and coating the lithium ion battery anode slurry on an aluminum foil for a current collector, wherein the coating amount is 324g/m 2 Drying at 85 ℃ and then cold pressing; then trimming, cutting pieces, splitting, drying at 85 ℃ for 4 hours under vacuum condition after splitting, and welding the tab to prepare the lithium ion battery positive plate meeting the requirements.
(3) Preparing a negative plate:
mixing artificial graphite and silicon according to a mass ratio of 90:10, preparing slurry with a conductive agent SuperP, a thickener CMC and an adhesive SBR (styrene butadiene rubber emulsion) according to a mass ratio of 95:1.5:1.0:2.5, uniformly mixing, coating the mixed slurry on two sides of a copper foil, drying, and rolling to obtain a negative plate, thus preparing the lithium ion battery negative plate meeting the requirements
(4) Preparation of a lithium ion battery:
the positive plate, the negative plate and the diaphragm prepared according to the process are manufactured into a lithium ion battery with the thickness of 4.7mm, the width of 55mm and the length of 60mm through a lamination process, and the lithium ion battery is baked for 10 hours at the temperature of 75 ℃ in vacuum and injected with the electrolyte. After 24h of standing, charging to 4.45V with a constant current of 0.lC (180 mA), and then charging to a current falling to 0.05C (90 mA) with a constant voltage of 4.45V; then discharging to 3.0V at 0.2C (180 mA), repeating the charge and discharge for 2 times, and finally charging the battery to 3.8V at 0.2C (180 mA) to finish the manufacturing of the lithium ion battery.
The composition and content of the electrolytes of examples 1 to 19 and comparative examples 1 to 4 are shown in table 1, and the preparation processes of the lithium ion battery electrolytes, the positive electrode sheet, the negative electrode sheet and the lithium ion battery of examples 2 to 19 and comparative examples 1 to 4 are the same as example 1.
Table 1 composition of electrolytes of examples and comparative examples
The lithium ion batteries produced in examples 1 to 19 and comparative examples 1 to 4 were subjected to a high-temperature storage performance test, a high-temperature cycle performance test, a normal-temperature cycle performance test, and a low-temperature performance test under the following conditions, and the results are shown in table 2.
High temperature storage performance test：
Lithium ion batteries were charged and discharged at 0.5C/0.5C once (the discharge capacity of the battery was recorded as C) at normal temperature (25 ℃ C.) 0 ) The upper limit voltage was 4.4V, and then the battery was charged to 4.4V under constant current and constant voltage of 0.5C, and the measurement was madeCell thickness (thickness noted as D) 0 ) The method comprises the steps of carrying out a first treatment on the surface of the The cell was placed in an oven at 60 ℃ for 30D, taken out and the cell thickness was measured (thickness noted as D 1 ) The method comprises the steps of carrying out a first treatment on the surface of the The cell was placed in a 25 ℃ environment and subjected to 0.5C discharge (discharge capacity recorded as C 1 ) The method comprises the steps of carrying out a first treatment on the surface of the The lithium ion battery is continuously charged and discharged at the normal temperature (25 ℃) for 0.5C/0.5C once (the discharge capacity of the battery is recorded as C) 2 ) The upper limit voltage was 4.4V, and the capacity retention rate, the capacity recovery rate, and the thickness expansion rate were calculated.
Capacity retention= (C 1 /C 0 )*100％
Capacity recovery rate= (C 2 /C 0 )*100％
Thickness expansion ratio= (D 1 /D 0 )*100％
Normal temperature cycle performance test：
The lithium ion battery is charged and discharged at the normal temperature (25 ℃) at 1.0C/1.0C (the discharge capacity of the battery is C) 0 ) The upper limit voltage was 4.4V, and then charging and discharging at 1.0C/1.0C was performed for 500 weeks under normal temperature conditions (the discharge capacity of the battery was C) 1 ) The capacity retention rate was calculated.
Capacity retention= (C 1 /C 0 )*100％
High temperature cycle test：
The lithium ion battery is charged and discharged at 1.0C/1.0C once under the condition of overhigh temperature (45 ℃) (the discharge capacity of the battery is C) 0 ) The upper limit voltage was 4.4V, and then charging and discharging at 1.0C/1.0C was performed for 400 weeks under normal temperature conditions (the battery discharge capacity was C) 1 ) The capacity retention rate was calculated.
Capacity retention= (C 1 /C 0 )*100％
Low temperature performance test：
At normal temperature (25deg.C), the lithium ion battery is charged and discharged once at 0.5C/0.5 (the cut-off voltage of the battery is 3.0V, and the discharge capacity is C) 0 ) The upper limit voltage was 4.4V (off current 0.05C). Then the battery was charged to 4.4V (off-current 0.05C) at normal temperature (25 ℃ C.) and then transferred to-20 ℃ CAfter the mixture was left for 4 hours, 0.5C was discharged to 3.0V, and the discharge capacity was C 1 The capacity retention rate was calculated.
Capacity retention= (C 1 /C 0 )*100％
Table 2 lithium ion battery performance test results
As can be seen from table 2, compared with comparative examples 1 to 4, examples 1 to 19, in which the additive compound a having a specific structure according to the present application was used in the electrolyte, have not only good high-temperature storage and high-temperature cycle properties, but also good low-temperature properties at-20 ℃, probably because the compound a has a relatively high oxidation potential, can be adsorbed on the electrode surface to form a thin adsorption layer, which is not easily crystallized at low temperature, can maintain a lithium ion transport channel at low temperature, and further improve the low-temperature properties of the lithium ion battery at-20 ℃. In addition, the compound A of the application is SO-containing 3 - And N + The zwitterionic structure of the (B) can form an interface with better heat stability and fewer electron channels in the negative electrode reaction of the lithium ion battery, and meanwhile, SO in the compound A 3 - And N + The structure can be combined with positive and negative ions in lithium salt respectively, and the lithium salt adopts LiPF 6 For example, SO in Compound A 3 - And N + The structure can be respectively with Li + And PF (physical filter) 6 - Binding, improving LiPF 6 The heat stability of lithium hexafluoroate at high temperature is inhibited from damaging SEI interface, and further the high-temperature storage and high-temperature cycle performance of the lithium ion battery are improved. More specifically, the mechanism of action of the additive compound a of the present application may be: SO3 - Can regulate and control the solvation core-shell structure of lithium ions, reduce the desolvation energy barrier of the lithium ions, and further reduce the lithium ionsThe sub-transmission resistance improves the lithium ion transmission rate, and the low-temperature performance of the battery is improved. N (N) + Can be combined with PF 6 - Coordination to enhance PF 6 - The gas production of the battery at high temperature is reduced, and the high-temperature performance of the battery is improved.
As can be seen from comparison of examples 1-6, compound 3 and compound 4 have superior combination of properties, possibly due to the introduction of fluorine, so that more fluoride is generated at the electrode interface, and the fluoride effectively passivates the electrode activity, so that the side reaction of the electrolyte is inhibited. The performance of the compound 4 is superior to that of the compound 3, and the side chain ethyl is probably high in stability, the thickness of the formed inorganic SEI is moderate, and the high-temperature and low-temperature characteristics of the battery are exerted.
Comparing example 7 with examples 13-19, it is evident that the addition of the additive based on the additive of the present application can further improve the high temperature storage performance, high temperature cycle performance, low temperature performance of the lithium ion battery, and lower expansion rate.
As is clear from the comparison of examples 13 to 19, when VC/FEC mixed auxiliary agent is used in the electrolyte, the high temperature performance and low temperature performance of the lithium ion battery are greatly improved, and the expansion ratio is further improved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present application can be modified or substituted without departing from the spirit and scope of the technical solution of the present application.
Claims (10)
1. An electrolyte comprising a lithium salt, a nonaqueous solvent and an additive, wherein the additive comprises a compound a represented by structural formula i:
wherein R is 1 ～R 5 Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C6 hydrocarbyl groups, n being taken from an integer greater than zero.
2. The electrolyte according to claim 1, wherein R 1 ～R 3 Each independently selected from substituted or unsubstituted C1-C6 hydrocarbyl radicals, R 4 ～R 5 Each independently selected from hydrogen or halogen, 0 < n.ltoreq.5.
3. The electrolyte according to claim 1, wherein the compound a is selected from at least one of the following compounds 1 to 6:
4. the electrolyte according to claim 1, wherein the compound a is 0.1 to 5% based on 100% of the sum of the mass of the lithium salt, the nonaqueous solvent and the additive.
5. The electrolyte of claim 1, wherein the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethylsulfonyl imide, lithium methylsulfonate, lithium trifluoromethylsulfonate, lithium fluorosulfonate, lithium dioxaborate, lithium difluorooxalato borate, lithium difluorophosphate, lithium difluorobis-oxalato phosphate, lithium chloroborane, and lithium tetraphenyl borate.
6. The electrolyte according to claim 1, wherein the lithium salt is 5 to 25% based on 100% of the sum of the mass of the lithium salt, the nonaqueous solvent and the additive.
7. The electrolyte of claim 1, wherein the nonaqueous solvent is selected from at least one of carbonate, carboxylate, and ether compounds.
8. The electrolyte of claim 1 wherein the additive further comprises an auxiliary agent selected from at least one of vinylene carbonate, fluoroethylene carbonate, ethylene sulfite, 1, 3-propane sultone, 1, 3-propenesulfonic acid lactone, 1, 4-butane sultone, ethylene sulfate, succinic anhydride, maleic anhydride, 2-methyl maleic anhydride, methyl carboxylic acid-2-propynyl ester, tetraethylene silane, triallyl isocyanurate, hexamethylene diiso-nitrile, phenanthroline, terephthal-isocyanate, 2, 4-toluene diisocyanate, N-phenyl bis (trifluoromethanesulfonyl) imide, phenyl methanesulfonate, vinyl disulfate, phenyl methanesulfonate, triallyl phosphate, tripropyl phosphate, 2, 4-butane sultone, isocyanatoethyl methacrylate, methylene methane disulfonate, tris (trimethylsilane) borate, and tris (trimethylsilane) phosphate.
9. A lithium ion battery comprising a positive electrode and a negative electrode, further comprising the electrolyte of any one of claims 1 to 8.
10. The lithium ion battery of claim 9, wherein the positive electrode comprises a positive electrode active material selected from at least one of olivine structured lithium-containing phosphates and their modified compounds and lithium transition metal oxides and their modified compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311349419.3A CN117154230A (en) | 2023-10-18 | 2023-10-18 | Electrolyte and lithium ion battery thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202311349419.3A CN117154230A (en) | 2023-10-18 | 2023-10-18 | Electrolyte and lithium ion battery thereof |
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| CN202311349419.3A Pending CN117154230A (en) | 2023-10-18 | 2023-10-18 | Electrolyte and lithium ion battery thereof |
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