WO2018099097A1 - 电解液及二次锂电池 - Google Patents
电解液及二次锂电池 Download PDFInfo
- Publication number
- WO2018099097A1 WO2018099097A1 PCT/CN2017/093745 CN2017093745W WO2018099097A1 WO 2018099097 A1 WO2018099097 A1 WO 2018099097A1 CN 2017093745 W CN2017093745 W CN 2017093745W WO 2018099097 A1 WO2018099097 A1 WO 2018099097A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- lithium
- electrolyte
- performance
- fluoroborate
- Prior art date
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003792 electrolyte Substances 0.000 title claims abstract description 36
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- -1 p-ethylphenyl Chemical group 0.000 claims description 36
- 239000008151 electrolyte solution Substances 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- GCMBIWYUVPAPEG-UHFFFAOYSA-N tris(1,1,1,3,3,3-hexafluoropropan-2-yl) borate Chemical compound FC(F)(F)C(C(F)(F)F)OB(OC(C(F)(F)F)C(F)(F)F)OC(C(F)(F)F)C(F)(F)F GCMBIWYUVPAPEG-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- DIEXQJFSUBBIRP-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) borate Chemical compound FC(F)(F)COB(OCC(F)(F)F)OCC(F)(F)F DIEXQJFSUBBIRP-UHFFFAOYSA-N 0.000 claims description 3
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical group CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- DCAYPVUWAIABOU-NJFSPNSNSA-N hexadecane Chemical group CCCCCCCCCCCCCCC[14CH3] DCAYPVUWAIABOU-NJFSPNSNSA-N 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 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 claims 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 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical group CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical group CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- BGHCVCJVXZWKCC-NJFSPNSNSA-N tetradecane Chemical group CCCCCCCCCCCCC[14CH3] BGHCVCJVXZWKCC-NJFSPNSNSA-N 0.000 claims description 2
- IIYFAKIEWZDVMP-NJFSPNSNSA-N tridecane Chemical group CCCCCCCCCCCC[14CH3] IIYFAKIEWZDVMP-NJFSPNSNSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 230000002349 favourable effect Effects 0.000 abstract 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000007747 plating Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 46
- 229910001416 lithium ion Inorganic materials 0.000 description 46
- 230000008021 deposition Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- JLBWCTOQWXSLBS-UHFFFAOYSA-N OBOF Chemical compound OBOF JLBWCTOQWXSLBS-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical class [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical group CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
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- 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
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- 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
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- 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
- H01M10/0568—Liquid materials characterised by the solutes
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- 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
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- 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
Definitions
- the present invention relates to the field of battery technologies, and in particular, to an electrolyte and a secondary lithium battery.
- lithium ion secondary batteries The high energy density, long cycle life, wide operating temperature range and green environmental protection of lithium ion secondary batteries have made it the main energy source for mobile electronic devices.
- people have higher and higher requirements for the charge and discharge rate of lithium ion secondary batteries, that is, lithium ion secondary batteries are required to have a large rate of charge and discharge capability; in addition, their environmental adaptability is also higher.
- current electronic products sometimes need to be used under extreme conditions, such as high temperature or low environment. Generally, lithium ion secondary batteries will deteriorate in extreme conditions compared to conventional environments. very obvious.
- the electrolyte has a significant influence on the charge and discharge rate performance and high and low temperature performance of the lithium ion secondary battery.
- the high-temperature performance can be improved by passivating the positive and negative electrode interfaces by adding a film-forming additive, but the charge-discharge rate performance and the low-temperature discharge performance of the lithium ion secondary battery are seriously deteriorated by simultaneously increasing the interface impedance of the positive and negative electrodes.
- the viscosity of the electrolyte is lowered at a low temperature, and the electrical conductivity is improved.
- the charge and discharge rate performance and the low-temperature discharge performance of the lithium ion secondary battery can be improved, but The high-temperature performance of lithium ion secondary batteries generally deteriorates, and the problem of lithium ion secondary batteries in application cannot be finally solved.
- an object of the present invention is to provide an electrolyte and a secondary lithium battery, which can have excellent high-temperature cycle performance simultaneously when the electrolyte is applied to a secondary lithium battery. High-temperature storage performance, low-temperature discharge performance and large-rate charging performance, and the low-temperature lithium deposition of secondary lithium batteries is also significantly suppressed.
- the present invention provides an electrolyte comprising a lithium salt, an organic solvent, and an additive.
- the additive includes a fluoroborate and lithium difluorophosphate.
- the invention provides a secondary lithium battery comprising an electrolyte according to one aspect of the invention.
- the secondary lithium battery When the electrolyte of the present invention is applied to a secondary lithium battery, the secondary lithium battery can have excellent high-temperature cycle performance, high-temperature storage performance, low-temperature discharge performance, and large-rate charging performance, and low-temperature lithium deposition of the secondary lithium battery. The situation has also been significantly suppressed.
- the electrolytic solution according to the first aspect of the invention includes a lithium salt, an organic solvent, and an additive.
- the additive includes a fluoroborate and lithium difluorophosphate (LiPO 2 F 2 ).
- lithium difluorophosphate can improve high temperature cycle performance, high temperature storage performance, and low temperature discharge performance of the secondary lithium battery because of two oxygen in the lithium difluorophosphate structure
- the atom can cooperate with the transition metal element in the positive electrode active material to improve the stability of the positive electrode active material and reduce the oxidation activity of the electrolyte, thereby effectively improving the high temperature cycle performance of the secondary lithium battery and suppressing the secondary lithium battery. Volume expansion at high temperatures.
- the action of lithium difluorophosphate and the positive electrode is beneficial to reduce the electrochemical reaction resistance of the positive electrode, improve the dynamic performance of the positive electrode, and improve the low-temperature discharge performance of the secondary lithium battery.
- lithium difluorophosphate will reductively decompose in the negative electrode, and the decomposition product covers the surface of the negative electrode, resulting in an increase in the lithium-insertion of the negative electrode, which is not conducive to the large-rate charging performance of the negative electrode, especially when charging in a low-temperature environment, a high lithium-insertion impedance. It is easy to cause precipitation of metallic lithium on the surface of the negative electrode, thereby deteriorating the low-temperature charging performance of the secondary lithium battery.
- an SEI film having a high ionic conductivity can be formed on the surface of the negative electrode, thereby effectively improving the low-temperature charging performance and the large-rate charging performance of the secondary lithium battery.
- the formation mechanism of the SEI film is explained below, but is not limited thereto.
- the fluoroborate is selected from one or more of the compounds represented by Formula 1.
- R 1, R 2, R 3 are each independently selected from carbon atoms in the alkane group having 1 to 20 carbon atoms, and an aryl group having 6 to 16, and R 1, R 2, R 3 At least one of the hydrogen atoms is replaced by a fluorine atom.
- the alkane group having 1 to 20 carbon atoms may be a chain alkane group or a cycloalkane group.
- the alkane group having 1 to 20 carbon atoms may be selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
- n-pentyl isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, decyl, decyl, undecane
- a group a dodecane group, a tridecane group, a tetradecane group, a pentadecane group, a hexadecane group, a heptadecane group, an octadecyl group, a nonadecane group or an eicosyl group.
- the aryl group having 6 to 16 carbon atoms may be selected from the group consisting of a phenyl group, a benzyl group, a biphenyl group, a p-tolyl group, an o-tolyl group, and an m-tolyl group.
- R 1 , R 2 and R 3 are the same.
- the fluoroborate is selected from the group consisting of tris(2,2,2-trifluoroethyl) borate (TTFEB), three (2, 2, 3) One of 3-trifluoropropyl)borate (TTFPB), tris(hexafluoroisopropyl)borate (THFPB), tris(pentafluorophenyl)borate (TPFPBA) or Several.
- the content of the lithium difluorophosphate is 0.1% to 3% of the total mass of the electrolyte.
- the content of the lithium difluorophosphate is less than 0.1% of the total mass of the electrolyte, the reaction of the low-impedance passivation film formed on the surface of the positive electrode is insufficient, and the improvement effect on the performance at high temperature is not obvious;
- the content of lithium difluorophosphate is higher than 3% of the total mass of the electrolyte, the film formation on the surface of the negative electrode is too thick, and the impedance is significantly increased, which is disadvantageous for the performance of the secondary lithium battery. Can improve.
- the content of the fluoroborate is 0.01% to 5% of the total mass of the electrolyte.
- the content of the fluoroborate is less than 0.01% of the total mass of the electrolyte, the modification of the negative electrode SEI film by the fluoroborate is not obvious, and the interface resistance cannot be effectively reduced, and the charging performance at a large rate and the low-temperature lithium deposition are not effective.
- the situation is not significantly improved; when the content of the fluoroborate is more than 5% of the total mass of the electrolyte, the fluoroborate promotes the decomposition of the lithium salt, and the generated PF 5 catalyzes the polymerization of the electrolyte.
- the high-temperature cycle performance and high-temperature storage performance of the secondary lithium battery are deteriorated.
- the lithium salt is one or more selected from the group consisting of LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiTFSI, LiTFS, LiFSI, LiDFOB, LiBOB.
- the organic solvent is selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
- Ethyl methyl carbonate (EMC) ⁇ -butyrolactone (BL), methyl formate (MF), ethyl formate (MA), ethyl acetate (EA), ethyl propionate (EP), propyl propionate (PP), one or more of dimethyl sulfoxide (DMSO), sulfolane (TMSO), dimethyl sulfone (MSM), tetrahydrofuran (THF).
- DMSO dimethyl sulfoxide
- TMSO sulfolane
- MSM dimethyl sulfone
- THF tetrahydrofuran
- a secondary lithium battery according to a second aspect of the invention includes the electrolytic solution according to the first aspect of the invention.
- the secondary lithium battery further includes a positive electrode sheet, a negative electrode sheet, a separator, and a packaging foil.
- the secondary lithium battery may be a lithium ion secondary battery or a lithium metal secondary battery.
- the positive electrode sheet may include a positive electrode current collector and a positive electrode film provided on the positive electrode current collector and containing a positive electrode active material.
- the positive active material may be selected from one or more of lithium cobaltate, lithium iron phosphate, lithium manganate, nickel manganese cobalt ternary material, and nickel cobalt aluminum ternary material.
- the negative electrode sheet may include a negative electrode current collector and an anode negative film provided on the negative electrode current collector and containing the negative electrode active material.
- the negative active material may be selected from graphite and/or silicon.
- the negative electrode sheet may also directly use metallic lithium and alloys thereof.
- the specific kind of the separator is not particularly limited, and may be any separator material used in the prior art, such as polyethylene, polypropylene, and polyposition. Fluoroethylene and their multilayer composite membranes are not limited to these.
- the present application is further illustrated below in conjunction with the embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the application.
- the present invention selects a soft-packed lithium ion secondary battery for related testing.
- the lithium ion secondary batteries of Examples 1-17 and Comparative Examples 1-6 were each prepared in the following manner.
- the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , the binder polyvinylidene fluoride, and the conductive agent acetylene black were mixed at a mass ratio of 97:1:2, and N-methylpyrrolidone (NMP) was added thereto to act in a vacuum mixer.
- NMP N-methylpyrrolidone
- the mixture was stirred until the system was uniformly transparent to obtain a positive electrode slurry; the positive electrode slurry was uniformly coated on a positive electrode current collector aluminum foil having a thickness of 14 ⁇ m; the aluminum foil was dried at room temperature, transferred to an oven at 120 ° C for 1 hour, and then cooled.
- the positive electrode sheets were obtained by pressing and slitting.
- the negative electrode active material artificial graphite, thickener sodium carboxymethyl cellulose (CMC), binder styrene-butadiene rubber emulsion were mixed at a mass ratio of 98:1:1, deionized water was added, and a negative electrode was obtained under the action of a vacuum mixer.
- the slurry was uniformly coated on a negative electrode current collector copper foil having a thickness of 8 ⁇ m; the copper foil was air-dried at room temperature, transferred to an oven at 120 ° C for 1 hour, and then subjected to cold pressing and slitting to obtain a negative electrode sheet.
- a fluoroborate and lithium difluorophosphate were added, and the mixture was uniformly mixed to obtain an electrolytic solution.
- the concentration of LiPF 6 was 1 mol/L.
- the specific types and contents of the fluoroborate and lithium difluorophosphate used in the electrolytic solution are shown in Table 1.
- Table 1 the addition amount of the fluoroborate and lithium difluorophosphate is a mass percentage calculated based on the total mass of the electrolyte.
- a polypropylene having a thickness of 12 ⁇ m was used as the separator.
- the positive electrode sheet, the separator film and the negative electrode sheet are stacked in this order, so that the separator is in a function of isolating between the positive and negative electrode sheets, and then wound into a square bare cell, and then placed in an aluminum plastic film, and then at 80.
- the corresponding electrolyte is injected and sealed, and then subjected to a process of standing, hot-cold pressing, chemical formation, jig, and volume to obtain a finished flexible packaging lithium ion secondary battery.
- the lithium ion secondary battery was allowed to stand at 25 ° C for 30 minutes, then charged at a constant current of 1 C to a voltage of 4.3 V, and then charged at a constant voltage of 4.3 V until the current was 0.05 C. At this time, the lithium ion secondary battery was tested. The volume was recorded as V 0 ; then the fully charged lithium ion secondary battery was placed in an 85 ° C incubator, stored for 10 days, and the volume was measured by the drainage method and recorded as V 1 .
- the volume expansion ratio (%) of the lithium ion secondary battery after storage at 85 ° C for 10 days (V 1 - V 0 ) / V 0 ⁇ 100%.
- the lithium ion secondary battery was allowed to stand at 45 ° C for 30 minutes, then charged at a constant current of 3 C to a voltage of 4.3 V, further charged at a constant voltage of 4.3 V until the current was 0.05 C, allowed to stand for 5 minutes, and then kept constant at 1 C.
- the discharge discharge voltage is 2.8 V, which is a charge and discharge cycle process, and the discharge capacity of this time is the first discharge capacity of the lithium ion secondary battery.
- the lithium ion secondary battery was subjected to 500 cycles of charge/discharge test in accordance with the above method.
- the capacity retention ratio (%) of the lithium ion secondary battery after circulating N times at 45 ° C (discharge capacity after N times of cycle / discharge capacity of first cycle) ⁇ 100%.
- the lithium ion secondary battery was allowed to stand at 25 ° C for 30 minutes, and then discharged at a constant current of 1 C rate. After standing at 2.8 V, it was allowed to stand for 5 min, and then charged to 4.3 V at a constant current of 0.5 C, and allowed to stand for 5 minutes, and then discharged at a constant current of 1 C to 2.8 V to obtain a charging capacity at a charge of 0.5 C rate.
- the lithium ion secondary battery was allowed to stand at 25 ° C for 30 minutes, and then discharged at a constant current of 1 C to 2.8 V, and allowed to stand for 5 minutes, after which the lithium ion secondary batteries were respectively at different magnifications (1C, 3C, 5C).
- the flow was charged to 4.3 V, and allowed to stand for 5 minutes, and then discharged at a constant current of 1 C to 2.8 V to obtain a charging capacity under different charging rates (1C, 3C, 5C).
- Charge capacity ratio (%) of lithium ion secondary battery under different rate charging different charge rate (1C, 3C, 5C) charge capacity under charge / charge capacity at 0.5C rate charge ⁇ 100%.
- the lithium ion secondary battery was allowed to stand at 25 ° C for 30 minutes, then charged at a constant current of 1 C to a voltage of 4.3 V, further charged at a constant voltage of 4.3 V to a current of 0.05 C, and allowed to stand for 5 minutes, and then lithium was
- the ion secondary battery was statically discharged at a different temperature (25 ° C, 0 ° C, -10 ° C) for 4 h, and then discharged at a constant current of 1 C to a voltage of 2.8 V. After the end of the discharge, it was allowed to stand for 5 minutes, and the lithium ion II was recorded. The discharge capacity of the secondary battery.
- the discharge capacity ratio (%) of the lithium ion secondary battery at different temperatures (discharge capacity at 0 ° C, -10 ° C) / (discharge capacity at 25 ° C) ⁇ 100%.
- the lithium ion secondary battery was allowed to stand at 25 ° C for 30 minutes, and then charged at a constant current of 5 C to a voltage of 4.3 V, further charged at a constant voltage of 4.3 V to a current of 0.05 C, and allowed to stand for 5 minutes, and then 1C constant current discharge to a voltage of 2.8V, this is a charge and discharge cycle, the lithium ion secondary battery is cycled 10 times according to the above process, and then charged to a voltage of 4.3V with a constant current of 5C.
- a lithium ion secondary battery charged to 4.3 V was disassembled, and lithium deposition on the surface of the negative electrode was observed.
- the degree of lithium is divided into no lithium, slight lithium, moderate lithium and severe lithium.
- the slight lithium deposition indicates that the lithium deposition region on the surface of the negative electrode is 1/10 or less of the entire region
- the severe lithium deposition indicates that the lithium deposition region on the surface of the negative electrode exceeds 1/3 of the entire region.
- Example 1-17 simultaneously adding lithium difluorophosphate and fluoroborate in the electrolyte, the lithium ion secondary battery has excellent high temperature cycle performance, high temperature storage performance, low temperature discharge performance, large rate charging performance, and lithium The low-temperature lithium deposition of the ion secondary battery is significantly suppressed.
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Abstract
本发明提供一种电解液及二次锂电池。所述电解液包括锂盐、有机溶剂以及添加剂。所述添加剂包括氟代硼酸酯以及二氟磷酸锂。当所述电解液应用到二次锂电池中后，二次锂电池能同时具有优良的高温循环性能、高温存储性能、低温放电性能和大倍率充电性能，且二次锂电池的低温析锂情况也得到明显抑制。
Description
本发明涉及电池技术领域，具体涉及一种电解液及二次锂电池。
锂离子二次电池的高能量密度、长循环寿命、宽工作温度范围及绿色环保已使得其成为目前移动电子设备的主要能源。在用户体验上，人们对锂离子二次电池的充放电速率提出越来越高的要求，即需要锂离子二次电池具有大倍率充放电能力；另外，对其环境适应性也提出了较高的要求，现在的电子产品有时候需要在极端条件下使用，如温度很高或者很低的环境，一般地，相对于常规环境而言，锂离子二次电池在极端条件使用时性能会恶化的非常明显。
电解液作为锂离子二次电池的重要组成部分，对锂离子二次电池的充放电倍率性能、高低温性能有着重大的影响。然而一般情况下，从电解液的角度改善锂离子二次电池的充放电倍率性能、低温放电性能和高温性能存在矛盾。一方面，通过加入成膜添加剂钝化正负极界面可改善高温性能，但由于同时增加了正负极界面阻抗，使得锂离子二次电池的充放电倍率性能和低温放电性能严重恶化。另一方面，优化有机溶剂组成，使电解液低温下的粘度降低，电导率提高，如通过添加大量低粘度的有机溶剂，可以提高锂离子二次电池的充放电倍率性能和低温放电性能，但是锂离子二次电池的高温性能通常会变差，不能最终解决锂离子二次电池在应用中的问题。
发明内容
鉴于背景技术中存在的问题，本发明的目的在于提供一种电解液及二次锂电池，当所述电解液应用到二次锂电池中后，二次锂电池能同时具有优良的高温循环性能、高温存储性能、低温放电性能和大倍率充电性能，且二次锂电池的低温析锂情况也得到明显抑制。
为了达到上述目的，在本发明的一方面，本发明提供了一种电解液，其包括锂盐、有机溶剂以及添加剂。所述添加剂包括氟代硼酸酯以及二氟磷酸锂。
在本发明的另一方面，本发明提供了一种二次锂电池，其包括根据本发明一方面所述的电解液。
相对于现有技术，本发明的有益效果为：
当本发明的电解液应用到二次锂电池中后，二次锂电池能同时具有优良的高温循环性能、高温存储性能、低温放电性能和大倍率充电性能，且二次锂电池的低温析锂情况也得到明显抑制。
下面详细说明根据本发明的电解液及二次锂电池。
首先说明根据本发明第一方面的电解液。
根据本发明第一方面的电解液包括锂盐、有机溶剂以及添加剂。所述添加剂包括氟代硼酸酯以及二氟磷酸锂(LiPO2F2)。
在根据本发明第一方面所述的电解液中，二氟磷酸锂能够改善二次锂电池的高温循环性能、高温存储性能以及低温放电性能，其原因是二氟磷酸锂结构中的两个氧原子可与正极活性材料中的过渡金属元素产生络合作用，改善正极活性材料的稳定性，降低对电解液的氧化活性，从而有效改善二次锂电池的高温循环性能并抑制二次锂电池在高温下的体积膨胀。同时，二氟磷酸锂与正极的作用有利于降低正极电化学反应阻抗，改善正极的动力学性能，提高二次锂电池的低温放电性能。然而，二氟磷酸锂会在负极发生还原分解，分解产物覆盖负极表面，造成负极嵌锂阻抗增大，不利于负极的大倍率充电性能，尤其在低温环境下充电时，较高的嵌锂阻抗容易引起负极表面金属锂析出，从而恶化二次锂电池的低温充电性能。在含有二氟磷酸锂的电解液中引入氟代硼酸酯后，可在负极表面形成离子电导率高的SEI膜，有效改善二次锂电池的低温充电性能和大倍率充电性能。该SEI膜的形成机理解释如下，但并不限于此。氟代硼酸酯能优先在负极表面还原分解，提高SEI膜的稳定性，并抑制有机溶剂的进一步还原分解，而且，氟代硼酸酯是硼基
阴离子受体，可以与F-、O2-、O2
2-等阴离子结合，促进SEI膜中的惰性组分LiF、Li2O、Li2O2等无机盐的溶解，改善SEI膜的组成，有效减小负极界面阻抗，从而改善二次锂电池的低温充电性能和大倍率充电性能。
在根据本发明第一方面所述的电解液中，所述氟代硼酸酯选自式1所示的化合物中的一种或几种。其中，R1、R2、R3各自独立地选自碳原子数为1～20的烷烃基、碳原子数为6～16的芳基中的一种，且R1、R2、R3中的至少一个上有氢原子被氟原子取代。
在根据本发明第一方面所述的电解液中，所述碳原子数为1～20的烷烃基可为链状烷烃基，也可为环烷烃基。具体地，所述碳原子数为1～20的烷烃基可选自甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、环戊基、正己基、异己基、环己基、庚基、环庚基、辛基、环辛基、壬基、癸基、十一烷烃基、十二烷烃基、十三烷烃基、十四烷烃基、十五烷烃基、十六烷烃基、十七烷烃基、十八烷烃基、十九烷烃基、二十烷烃基中的一种。
在根据本发明第一方面所述的电解液中，所述碳原子数为6～16的芳基可选自苯基、苄基、联苯基、对甲苯基、邻甲苯基、间甲苯基、对乙苯基、间乙苯基、邻乙苯基、3,5-二甲苯基、2,6-二甲基苯基、3,5-二乙基苯基、2,6-二乙基苯基、3,5-二异丙苯基、2,6-二异丙苯基、3,5-二正丙苯基、2,6-二正丙苯基、3,5-二正丁苯基、2,6-二正丁苯基、3,5-二异丁苯基、2,6-二异丁苯基、3,5-二叔丁苯基、2,6-二叔丁苯基、三苯甲基、1-萘基、2-萘基中的一种。
在根据本发明第一方面所述的电解液中，R1、R2、R3上均有氢原子被氟原子取代。
在根据本发明第一方面所述的电解液中，优选地，R1、R2、R3相同。
在根据本发明第一方面所述的电解液中，所述氟代硼酸酯选自三(2,2,2-三氟乙基)硼酸酯(TTFEB)、三(2,2,3,3-四氟丙基)硼酸酯(TTFPB)、三(六氟异丙基)硼酸酯(THFPB)、三(五氟苯基)硼酸酯(TPFPBA)中的一种或
几种。
在根据本发明第一方面所述的电解液中，所述二氟磷酸锂的含量为所述电解液总质量的0.1％～3％。当所述二氟磷酸锂的含量低于所述电解液总质量的0.1％时，其在正极表面生成的低阻抗钝化膜的反应不够充分，对高温下性能的改善作用不明显；当所述二氟磷酸锂的含量高于所述电解液总质量的3％时，其在负极表面成膜过厚，阻抗显著增加，反而不利于二次锂电池的性
能的改善。
在根据本发明第一方面所述的电解液中，所述氟代硼酸酯的含量为所述电解液总质量的0.01％～5％。当所述氟代硼酸酯的含量低于电解液总质量的0.01％时，氟代硼酸酯对负极SEI膜的修饰不明显，不能有效降低界面阻抗，对大倍率充电性能和低温析锂情况没有明显改善；当所述氟代硼酸酯的含量高于电解液总质量的5％时，氟代硼酸酯会促进锂盐的分解，生成的PF5会催化电解液的聚合反应，导致二次锂电池的高温循环性能和高温存储性能变差。
在根据本发明第一方面所述的电解液中，所述锂盐选自LiPF6、LiBF4、LiClO4、LiAsF6、LiTFSI、LiTFS、LiFSI、LiDFOB、LiBOB中的一种或几种。
在根据本发明第一方面所述的电解液中，所述有机溶剂选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、γ-丁内酯(BL)、甲酸甲酯(MF)、甲酸乙酯(MA)、乙酸乙酯(EA)、丙酸乙酯(EP)、丙酸丙酯(PP)、二甲基亚砜(DMSO)、环丁砜(TMSO)、二甲基砜(MSM)、四氢呋喃(THF)中的一种或几种。
其次说明根据本发明第二方面的二次锂电池。
根据本发明第二方面的二次锂电池包括根据本发明第一方面所述的电解液。
在根据本发明第二方面所述的二次锂电池中，所述二次锂电池还包括正极片、负极片、隔离膜以及包装箔。
在根据本发明第二方面所述的二次锂电池中，所述二次锂电池可为锂离子二次电池或锂金属二次电池。
在根据本发明第二方面所述的二次锂电池中，所述正极片可包括正极集流体和设置于所述正极集流体上且包含正极活性材料的正极膜片。所述正极活性材料可选自钴酸锂、磷酸铁锂、锰酸锂、镍锰钴三元材料、镍钴铝三元材料中的一种或几种。
在根据本发明第二方面所述的二次锂电池中，所述负极片可包括负极集流体和设置于所述负极集流体上且包含负极活性材料的负极膜片。所述负极活性材料可选自石墨和/或硅。
在根据本发明第二方面所述的二次锂电池中，所述负极片也可直接使用金属锂及其合金。
在根据本发明第二方面所述的二次锂电池中，隔离膜的具体种类并不受到具体的限制，可以是现有技术中使用的任何隔离膜材料，例如聚乙烯、聚丙烯、聚偏氟乙烯以及它们的多层复合膜，但不仅限于这些。
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围，本发明选择了软包锂离子二次电池进行相关的测试。
在实施例和对比例中所使用到的试剂、材料以及仪器如没有特殊的说明，均可商购获得。
实施例1-17以及对比例1-6中的锂离子二次电池均按照下述方法进行制备。
(1)正极片制备
将正极活性材料LiNi0.5Co0.2Mn0.3O2、粘结剂聚偏氟乙烯、导电剂乙炔黑按照质量比97:1:2进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌至体系成均一透明状，获得正极浆料；将正极浆料均匀涂覆于厚度为14μm的正极集流体铝箔上；将铝箔在室温晾干后转移至120℃烘箱干燥1h，然后经过冷压、分切得到正极片。
(2)负极片制备
将负极活性材料人造石墨、增稠剂羧甲基纤维素钠(CMC)、粘结剂丁苯橡胶乳液按照质量比98:1:1进行混合，加入去离子水，在真空搅拌机作用下获得负极浆料；将负极浆料均匀涂覆在厚度为8μm的负极集流体铜箔上；将铜箔在室温晾干后转移至120℃烘箱干燥1h，然后经过冷压、分切得到负极片。
(3)电解液制备
在含水量<10ppm的氩气气氛手套箱中，将EC、EMC、DEC按照质量比为EC:EMC:DEC＝30:50:20进行混合作为有机溶剂，接着将充分干燥的锂盐LiPF6溶解于混合有机溶剂中，之后加入氟代硼酸酯以及二氟磷酸锂，混
合均匀后获得电解液。其中，LiPF6的浓度为1mol/L。电解液中所用到的氟代硼酸酯以及二氟磷酸锂具体种类以及含量如表1所示。在表1中，氟代硼酸酯以及二氟磷酸锂的添加量为基于电解液的总质量计算得到的质量百分数。
(4)隔离膜的制备
以厚度为12μm的聚丙烯作为隔离膜。
(5)锂离子二次电池的制备
将正极片、隔离膜、负极片按顺序叠好，使隔离膜处于正、负极片之间起到隔离的作用，然后卷绕成方形的裸电芯后，装入铝塑膜，然后在80℃下烘烤除水后，注入相应的电解液并封口，之后经过静置、热冷压、化成、夹具、分容等工序，获得成品软包装锂离子二次电池。
表1实施例1-17及对比例1-6的参数
接下来说明锂离子二次电池的测试过程。
(1)锂离子二次电池的高温存储性能测试
在25℃下，将锂离子二次电池静置30分钟，之后以1C恒流充电至电压为4.3V，然后以4.3V恒压充电至电流为0.05C，此时测试锂离子二次电池的体积并记为V0；然后将满充的锂离子二次电池放入85℃恒温箱中，存储10天，采用排水法测试体积并记为V1。
锂离子二次电池85℃存储10天后的体积膨胀率(％)＝(V1-V0)/V0×100％。
(2)锂离子二次电池的高温循环性能测试
在45℃下，将锂离子二次电池静置30分钟，之后以3C恒流充电至电压为4.3V，进一步以4.3V恒压充电至电流为0.05C，静置5分钟，然后以1C恒流放电至电压为2.8V，此为一个充放电循环过程，此次的放电容量为锂离子二次电池的首次放电容量。将锂离子二次电池按照上述方法进行500次循环充电/放电测试。
锂离子二次电池45℃循环N次后的容量保持率(％)＝(循环N次后的放电容量/首次循环的放电容量)×100％。
(3)锂离子二次电池的大倍率充电性能测试
在25℃下，将锂离子二次电池静置30分钟，然后以1C倍率恒流放电
至2.8V，静置5min，之后以0.5C倍率恒流充电至4.3V，并静置5分钟，之后以1C倍率恒流放电至2.8V，得到0.5C倍率充电下的充电容量。
在25℃下，将锂离子二次电池静置30分钟，然后以1C倍率恒流放电至2.8V，静置5min，之后将锂离子二次电池分别以不同倍率(1C、3C、5C)恒流充电至4.3V，并静置5分钟，之后以1C倍率恒流放电至2.8V，得到不同倍率(1C、3C、5C)充电下的充电容量。
锂离子二次电池不同倍率充电下的充电容量比(％)＝不同倍率(1C、3C、5C)充电下的充电容量/0.5C倍率充电下的充电容量×100％。
(4)锂离子二次电池的低温放电性能测试
在25℃下，将锂离子二次电池静置30分钟，之后以1C恒流充电至电压为4.3V，进一步以4.3V恒压充电至电流为0.05C，并静置5分钟，然后将锂离子二次电池分别在不同温度(25℃、0℃、-10℃)下静止4h后，以1C恒流放电至电压为2.8V，放电结束后再静置5分钟，记录此时锂离子二次电池的放电容量。
锂离子二次电池不同温度下的放电容量比(％)＝(0℃、-10℃下的放电容量)/(25℃下的放电容量)×100％。
(5)负极析锂测试
在25℃下，将锂离子二次电池静置30分钟，之后先以5C恒流充电至电压为4.3V，进一步以4.3V恒压充电至电流为0.05C，并静置5分钟，然后以1C恒流放电至电压为2.8V，此为一个充放电循环，将锂离子二次电池按上述过程循环10次，然后以5C恒流充电至电压为4.3V。在干燥房环境中，将充电至4.3V的锂离子二次电池拆解，观察负极表面的析锂情况。其中，析锂程度分为不析锂、轻微析锂、中度析锂以及严重析锂。轻微析锂表示负极表面的析锂区域为整体区域的1/10以下，严重析锂表示负极表面的析锂区域超过整体区域的1/3。
表2实施例1-17和对比例1-6的性能测试结果
从对比例1-2的对比中可以看出，在电解液中加入二氟磷酸锂，锂离子二次电池的高温循环性能和高温存储性能得到显著改善，锂离子二次电池的低温放电性能也有大幅度提高，但是锂离子二次电池的大倍率充电性能和低温析锂情况明显恶化。从对比例1和对比例3的对比中可以看出，在电解液中加入三(六氟异丙基)硼酸酯可显著改善锂离子二次电池的大倍率充电性能和低温析锂情况，但是锂离子二次电池的高温循环性能和高温存储性能恶化。实施例1-17在电解液中同时加入二氟磷酸锂和氟代硼酸酯，锂离子二次电池同时具有优良的高温循环性能、高温存储性能、低温放电性能、大倍率充电性能，且锂离子二次电池的低温析锂情况得到明显抑制。
在对比例4-6中，氟代硼酸酯和/或二氟磷酸锂的含量过高，均会恶化锂离子二次电池的性能。
根据上述说明书的揭示，本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此，本申请并不局限于上面揭示和描述的具体实施方式，对本申请的一些修改和变更也应当落入本申请的权利要求的保护范围内。
Claims (10)
- 一种电解液，包括：锂盐；有机溶剂；以及添加剂；其特征在于，所述添加剂包括氟代硼酸酯以及二氟磷酸锂。
- 根据权利要求1所述的电解液，其特征在于，所述氟代硼酸酯选自式1所示的化合物中的一种或几种；
其中，R1、R2、R3各自独立地选自碳原子数为1～20的烷烃基、碳原子数为6～16的芳基中的一种，且R1、R2、R3中的至少一个上有氢原子被氟原子取代。 - 根据权利要求2所述的电解液，其特征在于，所述碳原子数为1～20的烷烃基选自甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、环戊基、正己基、异己基、环己基、庚基、环庚基、辛基、环辛基、壬基、癸基、十一烷烃基、十二烷烃基、十三烷烃基、十四烷烃基、十五烷烃基、十六烷烃基、十七烷烃基、十八烷烃基、十九烷烃基、二十烷烃基中的一种；所述碳原子数为6～16的芳基选自苯基、苄基、联苯基、对甲苯基、邻甲苯基、间甲苯基、对乙苯基、间乙苯基、邻乙苯基、3,5-二甲苯基、2,6-二甲基苯基、3,5-二乙基苯基、2,6-二乙基苯基、3,5-二异丙苯基、2,6-二异丙苯基、3,5-二正丙苯基、2,6-二正丙苯基、3,5-二正丁苯基、2,6-二正丁苯基、3,5-二异丁苯基、2,6-二异丁苯基、3,5-二叔丁苯基、2,6-二叔丁苯基、三苯甲 基、1-萘基、2-萘基中的一种。
- 根据权利要求1所述的电解液，其特征在于，R1、R2、R3上均有氢原子被氟原子取代。
- 根据权利要求1或4所述的电解液，其特征在于，R1、R2、R3相同。
- 根据权利要求4所述的电解液，其特征在于，所述氟代硼酸酯选自三(2,2,2-三氟乙基)硼酸酯、三(2,2,3,3-四氟丙基)硼酸酯、三(六氟异丙基)硼酸酯、三(五氟苯基)硼酸酯中的一种或几种。
- 根据权利要求1所述的电解液，其特征在于，所述二氟磷酸锂的含量为所述电解液总质量的0.1％～3％；所述氟代硼酸酯的含量为所述电解液总质量的0.01％～5％。
- 根据权利要求1所述的电解液，其特征在于，所述锂盐选自LiPF6、LiBF4、LiClO4、LiAsF6、LiTFSI、LiTFS、LiFSI、LiDFOB、LiBOB中的一种或几种。
- 根据权利要求1所述的电解液，其特征在于，所述有机溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、γ-丁内酯、甲酸甲酯、甲酸乙酯、乙酸乙酯、丙酸乙酯、丙酸丙酯、二甲基亚砜、环丁砜、二甲基砜、四氢呋喃中的一种或几种。
- 一种二次锂电池，其特征在于，包括根据权利要求1-9中任一项所述的电解液。
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| WO2021128093A1 (zh) * | 2019-12-25 | 2021-07-01 | 宁德新能源科技有限公司 | 电化学装置及包含其的电子装置 |
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| CN116259721A (zh) * | 2016-10-13 | 2023-06-13 | 株式会社Lg新能源 | 锂离子二次电池用负极及其制造方法 |
| CN109270150B (zh) * | 2018-09-29 | 2022-11-04 | 东莞东阳光科研发有限公司 | 一种铝电解电容器容量比表征方法及装置 |
| CN111864261A (zh) * | 2019-04-26 | 2020-10-30 | 宁德时代新能源科技股份有限公司 | 电解液及锂离子电池 |
| CN111063883A (zh) * | 2019-12-25 | 2020-04-24 | 宁德新能源科技有限公司 | 电化学装置及包含其的电子装置 |
| CN111276744A (zh) * | 2020-02-12 | 2020-06-12 | 清华大学 | 一种含阴离子受体添加剂的局部高浓度锂金属电池电解液 |
| KR20220020495A (ko) * | 2020-08-12 | 2022-02-21 | 주식회사 엘지에너지솔루션 | 퇴화 셀 제조방법 및 퇴화 셀 평가 방법 |
| CN112240983B (zh) * | 2020-09-22 | 2021-10-26 | 清华大学 | 电池析锂检测方法及其检测装置 |
| CN113359039A (zh) * | 2021-06-23 | 2021-09-07 | 万向一二三股份公司 | 一种锂离子动力电池评估及再利用方法 |
| CN113659200B (zh) * | 2021-06-30 | 2022-12-23 | 厦门海辰储能科技股份有限公司 | 一种改善锂电池高温性能的电解液添加剂、电解液及电化学装置 |
| CN113991180B (zh) * | 2021-11-02 | 2023-04-07 | 惠州锂威新能源科技有限公司 | 一种锂离子电池电解液及锂离子电池 |
| CN114267882A (zh) * | 2021-12-17 | 2022-04-01 | 珠海冠宇电池股份有限公司 | 一种电池 |
| CN114665152A (zh) * | 2022-04-06 | 2022-06-24 | 香河昆仑新能源材料股份有限公司 | 一种含氟代烷基硼酸酯化合物的电解液及由该电解液组成的电池 |
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| KR102164007B1 (ko) * | 2014-04-07 | 2020-10-12 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
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Also Published As
| Publication number | Publication date |
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| CN108123172A (zh) | 2018-06-05 |
| CN108123172B (zh) | 2020-08-28 |
| EP3550657B1 (en) | 2023-06-28 |
| US20190267671A1 (en) | 2019-08-29 |
| EP3550657A1 (en) | 2019-10-09 |
| EP3550657A4 (en) | 2020-08-19 |
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