WO2023236031A1 - 非水电解液、其制备方法、以及包含其的二次电池及用电装置 - Google Patents
非水电解液、其制备方法、以及包含其的二次电池及用电装置 Download PDFInfo
- Publication number
- WO2023236031A1 WO2023236031A1 PCT/CN2022/097310 CN2022097310W WO2023236031A1 WO 2023236031 A1 WO2023236031 A1 WO 2023236031A1 CN 2022097310 W CN2022097310 W CN 2022097310W WO 2023236031 A1 WO2023236031 A1 WO 2023236031A1
- Authority
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- WIPO (PCT)
- Prior art keywords
- aqueous electrolyte
- anion
- optionally
- lithium
- secondary battery
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 253
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001450 anions Chemical class 0.000 claims abstract description 163
- 150000001768 cations Chemical class 0.000 claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 45
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 29
- -1 tetrafluoroborate Chemical compound 0.000 claims description 126
- 239000000654 additive Substances 0.000 claims description 49
- 229910003002 lithium salt Inorganic materials 0.000 claims description 43
- 230000000996 additive effect Effects 0.000 claims description 41
- 159000000002 lithium salts Chemical class 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 34
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- UBQYURCVBFRUQT-UHFFFAOYSA-N N-benzoyl-Ferrioxamine B Chemical compound CC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCN UBQYURCVBFRUQT-UHFFFAOYSA-N 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- 230000009467 reduction Effects 0.000 claims description 19
- VHSLGFZDYCMVHY-UHFFFAOYSA-N boric acid;oxalyl difluoride Chemical compound OB(O)O.FC(=O)C(F)=O VHSLGFZDYCMVHY-UHFFFAOYSA-N 0.000 claims description 17
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 16
- 150000002170 ethers Chemical class 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 150000003949 imides Chemical class 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 7
- WMQHRXUKAYSPPK-UHFFFAOYSA-N 1,1,1-trifluoro-3-(octylthio)acetone Chemical compound CCCCCCCCSCC(=O)C(F)(F)F WMQHRXUKAYSPPK-UHFFFAOYSA-N 0.000 claims description 6
- 229910017008 AsF 6 Inorganic materials 0.000 claims description 6
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 6
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 6
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- XLDXZSVHMLAQMY-UHFFFAOYSA-N lithium;dioxalooxyborinate Chemical compound [Li+].OC(=O)C(=O)OB([O-])OC(=O)C(O)=O XLDXZSVHMLAQMY-UHFFFAOYSA-N 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
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- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical group 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
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- 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
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 4
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 abstract 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 abstract 1
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- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical class [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
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- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
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- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 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
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 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
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
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- 239000011702 manganese sulphate Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
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- 150000003891 oxalate salts Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0045—Room temperature molten salts comprising at least one organic ion
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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 application belongs to the field of battery technology, and specifically relates to a non-aqueous electrolyte, its preparation method, a secondary battery and an electrical device containing the same.
- the inventor of this application unexpectedly discovered during the research process that when the mass concentration of the first cation D1 ppm and the mass concentration of the first anion D2 ppm in the non-aqueous electrolyte satisfy D1 from 0.5 to 870 and D1/D2 from 0.02 to 2 Not only will the first cation not deteriorate the electrochemical performance of the secondary battery, but under the synergistic effect of the first cation and the first anion, the non-aqueous electrolyte of the present application can also enable the secondary battery to have good cycle performance and safety performance and dynamic performance.
- the difference between the standard reduction potential of Men + and the standard reduction potential of Li + is more than 1.0V.
- Men + represents Ni 2+ , Co 2+ , Mn 2+ , and Al 3+ and at least one of Fe 2+ . This can better ensure that Men + are reduced before lithium ions, thereby better reducing the irreversible consumption of active lithium ions during the formation of the SEI film and improving the capacity retention rate of the secondary battery.
- D1 ranges from 100 to 870, optionally from 200 to 870.
- the secondary battery can simultaneously achieve high capacity retention rate, low volume expansion rate and good dynamic performance.
- D1/D2 is 0.3 to 2, optionally 0.3 to 1.2. At this time, it is beneficial to give full play to the synergistic effect between the first cation and the first anion, so that the secondary battery can take into account good cycle performance, safety performance and dynamic performance at the same time.
- D2 ranges from 1 to 3000, optionally from 100 to 2000.
- the secondary battery can simultaneously achieve high capacity retention rate, low volume expansion rate and good dynamic performance.
- the non-aqueous electrolyte solution further contains a second anion, and the second anion is a tetrafluoroborate anion BF 4 - .
- the mass concentration of the second anion in the non-aqueous electrolyte is D3 ppm. Based on the total mass of the non-aqueous electrolyte, D3 is optionally 1 to 3000, more optionally 1 to 2000. This can improve the high-temperature stability and low-temperature performance of the secondary battery.
- D2/D3 is 0.4 to 20, more optionally 1 to 10. This helps to give full play to the synergistic effect between BF 4 - and DFOB - , which can not only broaden the electrochemical window of the non-aqueous electrolyte, but also form a stable and low-resistance SEI film on the surface of the negative active material.
- the non-aqueous electrolyte further contains a third anion
- the third anion includes perchlorate anion ClO 4 - and bistrifluoromethanesulfonyl imide anion N (SO 2 CF 3 ) At least one of 2 - , NO 3 - and SO 4 2- , optionally including at least one of NO 3 - and SO 4 2- .
- the mass concentration of the third anion in the non-aqueous electrolyte is D4 ppm. Based on the total mass of the non-aqueous electrolyte, D4 is optionally 1 to 3000, more optionally 1 to 2000.
- the third anion helps to make the non-aqueous electrolyte have higher thermal stability, thereby improving the high-temperature stability of the secondary battery; the third anion also helps DFOB - become a free ion, reducing the association of anions and cations, This can give full play to the improvement effect of DFOB on the capacity retention rate and dynamic performance of secondary batteries.
- the mass concentration of the third anion in the non-aqueous electrolyte is D4 ppm, optionally, D2/D4 is 0.4 to 20, more optionally 0.8 to 5. At this time, it helps to give full play to the synergistic effect between the first anion and the third anion, which not only improves the thermal stability of the non-aqueous electrolyte, but also forms a stable and low-resistance SEI film on the surface of the negative active material. .
- the non-aqueous electrolyte further contains a fourth anion, and the fourth anion includes hexafluorophosphate anion PF 6 - and bisfluorosulfonyl imide anion N (SO 2 F) 2 - or a combination thereof.
- the mass percentage of the fourth anion in the non-aqueous electrolyte is 8% to 20%, more optionally 9% to 15%, based on the non-aqueous electrolyte. Total mass of water electrolyte.
- the fourth anion includes both hexafluorophosphate anion PF 6 - and bisfluorosulfonylimide anion N(SO 2 F) 2 - , and more optionally , the mass ratio ⁇ of the hexafluorophosphate anion PF 6 - and the bisfluorosulfonylimide anion N(SO 2 F) 2 - is 0.2 to 3, more preferably 0.5 to 1.5. Therefore, the non-aqueous electrolyte is not easily hydrolyzed, can also achieve higher thermal stability, and at the same time, can help form an interface film with lower impedance.
- the non-aqueous electrolyte further contains a fifth anion
- the fifth anion includes dioxaloborate anion BOB - , hexafluoroarsenate anion AsF 6 - , and triflate anion
- This serves to further improve the interfacial properties of the positive electrode and/or the negative electrode, or to improve the ionic conductivity or thermal stability of the non-aqueous electrolyte.
- the mass percentage of the fifth anion in the non-aqueous electrolyte is below 2%, more optionally below 0.5%, based on the Total mass meter.
- the fifth anion includes a difluorophosphate anion PO2F2- .
- the mass ratio ⁇ of the difluorophosphate anion PO 2 F 2 - and the fourth anion is 0.01 to 0.15, more optionally 0.01 to 0.1. This can increase the ionic conductivity of the non-aqueous electrolyte, improve the properties of the positive electrode interface film and/or the negative electrode interface film, and help to construct a stable and low-impedance positive electrode interface film and/or negative electrode interface film, thereby effectively reducing non-conducting The decomposition of water electrolyte further improves the kinetic performance and safety performance of secondary batteries.
- the non-aqueous solvent includes a cyclic carbonate compound and a chain carbonate compound
- the mass percentage of the cyclic carbonate compound in the non-aqueous electrolyte is E1
- the mass percentage of the chain carbonate compound is E1.
- the mass percentage of the ester compound is E2, based on the total mass of the non-aqueous electrolyte.
- E1 is 5% to 40%, optionally 10% to 30%
- E2 is 40% to 85%, which can be
- the selected land is 60% to 80%. At this time, it helps the non-aqueous electrolyte to have appropriate viscosity and ionic conductivity, which is beneficial to the transport of lithium ions.
- the non-aqueous solvent also includes ether compounds, and the ether compounds include tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxcyclopentane, and ethylene glycol monomethyl ether. , at least one of ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethoxymethane and diglyme. Ether compounds help the non-aqueous electrolyte to have appropriate viscosity and/or ionic conductivity, which in turn facilitates the transport of lithium ions.
- the mass percentage of ether compounds in the non-aqueous electrolyte is E3. Based on the total mass of the non-aqueous electrolyte, optionally, E3 is 0.1% to 40%. , more optionally 0.5% to 20%.
- the non-aqueous electrolyte solution further contains a first additive, and the first additive is fluorinated ethylene carbonate. This can effectively improve the cycle performance of the secondary battery.
- the mass concentration of the first additive in the non-aqueous electrolyte is D5 ppm, based on the total mass of the non-aqueous electrolyte, optionally, D5 is 1 to 30,000, more preferably The land selection is from 100 to 20000.
- the mass concentration of the first additive in the non-aqueous electrolyte is D5 ppm, optionally, D5/D2 is 5 to 500, more optionally 5 to 100. This can give full play to the synergistic effect between FEC and DFOB - , which will not only not significantly increase the gas production of the secondary battery, but also further improve the cycle performance of the secondary battery.
- the non-aqueous electrolyte further contains a second additive
- the second additive includes vinylene carbonate, lithium oxalate, vinyl sulfate, and 1,3-propanesultone. At least one.
- the second additive helps to further improve the interface properties of the positive electrode and/or the negative electrode, thereby further improving at least one of cycle performance, safety performance and kinetic performance of the secondary battery.
- the mass percentage of the second additive in the non-aqueous electrolyte is below 5%, more optionally below 2.5%, based on the weight of the non-aqueous electrolyte. Total mass meter.
- the second aspect of the application provides a method for preparing a non-aqueous electrolyte, which includes the following steps: uniformly mixing a non-aqueous solvent, lithium salt, soluble Me salt, soluble difluoroxalate borate and optional additives to obtain a non-aqueous electrolyte.
- Electrolyte, Me represents a metal element other than lithium element, wherein the non-aqueous electrolyte contains a non-aqueous solvent and lithium ions, a first cation and a first anion dissolved therein, and the first cation is other than lithium ion.
- Metal cation M n+ , n represents the valence of the metal cation
- the first anion is difluoroxaloborate anion DFOB -
- the mass concentration of the first cation in the non-aqueous electrolyte is D1 ppm
- the non-aqueous electrolyte The mass concentration of the first anion in is D2 ppm, both are based on the total mass of the non-aqueous electrolyte
- the non-aqueous electrolyte satisfies: D1 is 0.5 to 870 and D1/D2 is 0.02 to 2.
- the difference between the standard reduction potential of Men + and the standard reduction potential of Li + is more than 1.0V.
- Men + represents Ni 2+ , Co 2+ , Mn 2+ , and Al 3+ and at least one of Fe 2+ .
- the soluble difluoroxalate borate includes at least one of Me(DFOB) n and LiDFOB. This helps to adjust the mass concentration of metal cations and first anions in the non-aqueous electrolyte solution within a required range.
- the lithium salt includes a first lithium salt, the first lithium salt includes lithium hexafluorophosphate, lithium bisfluorosulfonyl imide, or a combination thereof, optionally, the lithium salt further includes a third lithium salt.
- Dilithium salt the second lithium salt includes lithium dioxaloborate, lithium tetrafluoroborate, lithium bistrifluoromethanesulfonimide, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, At least one of lithium fluorophosphate, lithium difluorodioxalate phosphate, and lithium tetrafluorooxalate phosphate. This helps to adjust the mass concentration of metal cations and different anions in the non-aqueous electrolyte within a desired range.
- the additive includes at least one of a first additive and a second additive
- the first additive is fluoroethylene carbonate
- the second additive includes vinylene carbonate, oxalic acid At least one of lithium, vinyl sulfate, and 1,3-propanesultone.
- a third aspect of the application provides a secondary battery, including a positive electrode plate, a negative electrode plate and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is the non-aqueous electrolyte of the first aspect of the application or adopts the non-aqueous electrolyte of the first aspect of the application.
- the non-aqueous electrolyte obtained by the two preparation methods.
- 0 ⁇ d ⁇ 0.50 and 0 ⁇ e ⁇ 0.50 optionally, 0 ⁇ d ⁇ 0.30 and 0 ⁇ e ⁇ 0.10.
- FIG. 5 is an exploded schematic view of the embodiment of the battery pack shown in FIG. 4 .
- Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
- the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
- step (c) means that step (c) may be added to the method in any order.
- the method may include steps (a), (b) and (c). , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
- condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
- Non-aqueous electrolyte is one of the key factors affecting the performance of secondary batteries.
- the most widely used non-aqueous electrolyte system currently commercially is a mixed carbonate solution of lithium hexafluorophosphate.
- lithium hexafluorophosphate has poor thermal stability in high temperature environments. It decomposes at higher temperatures to form LiF and PF 5 .
- LiF will increase the interface resistance; PF 5 has strong Lewis acidity, which will interact with the lone pair of electrons on the oxygen atoms in the solvent molecules to cause the solvent to decompose; in addition, PF 5 has a high resistance to trace amounts of moisture in the non-aqueous electrolyte. Sensitivity, HF will be generated when contacting water, thereby increasing the acidity of the non-aqueous electrolyte, which will easily corrode the positive active material and the positive current collector, causing the transition metal ions in the positive active material to dissolve, and the structural stability of the positive active material to deteriorate. This affects the service life of the secondary battery.
- the first aspect of the present application provides a non-aqueous electrolyte solution.
- the inventor of this application unexpectedly discovered during the research process that when the mass concentration of the first cation D1 ppm and the mass concentration of the first anion D2 ppm in the non-aqueous electrolyte satisfy D1 from 0.5 to 870 and D1/D2 from 0.02 to 2 Not only will the first cation not deteriorate the electrochemical performance of the secondary battery, but under the synergistic effect of the first cation and the first anion, the non-aqueous electrolyte of the present application can also enable the secondary battery to have good cycle performance and safety performance and dynamic performance.
- the mechanism is not yet clear, the inventor of the present application speculates that the possible reasons include at least the following points.
- the metal cation Me n+ is electrochemically more active than lithium ions, so it will be reduced prior to lithium ions, thereby reducing the irreversible consumption of active lithium ions during the formation of the SEI film and improving the capacity retention rate of secondary batteries. .
- the metal cation M n+ formed by the reduction of the metal cation Me n+ at the negative electrode has good electronic conductivity, so it can promote the transfer of electrons and promote the formation of a thicker SEI film on the surface of the negative electrode active material, thereby reducing the interaction between the negative electrode active material and non-conducting materials.
- the interfacial side reaction between water and electrolyte improves the capacity retention rate of the secondary battery and reduces the volume expansion rate of the secondary battery.
- difluoroxalate borate anion DFOB - contains an oxalate group, which will be oxidized to form carbon dioxide gas when heated. Therefore, when the secondary battery is in an abuse state such as overcharge or short circuit, the carbon dioxide gas generated will cause the battery to The internal pressure increases, which can quickly open the battery safety valve to prevent the secondary battery from catching fire or even exploding, thus improving the safety performance of the secondary battery.
- the mass concentration of the first cation in the non-aqueous electrolyte is D1 ppm, and D1 is 0.5 to 870.
- D1 is within a suitable range, the secondary battery can simultaneously achieve high capacity retention rate, low volume expansion rate and good dynamic performance.
- the mass concentration of the first cation is too low, it has little improvement effect and cannot be reduced to form a metal element at the negative electrode to increase electronic conductivity and reduce the irreversible consumption of active lithium ions, thereby failing to effectively improve the performance of the secondary battery. Capacity retention rate and reduced volume expansion rate of secondary batteries.
- the SEI film on the surface of the negative active material is too thick, and the dynamic performance of the secondary battery is poor; at the same time, when the mass concentration of the first cation is too high, its negative effect on the SEI film will be greater than Its improvement effect on the SEI film. At this time, too much metal element will catalyze the decomposition of the SEI film. In this process, on the one hand, more gas will be produced, causing the secondary battery to expand, affecting the safety performance of the secondary battery. On the other hand, On the one hand, the by-products produced by decomposition deposited on the surface of the SEI film will hinder the transmission of lithium ions and increase the impedance of the secondary battery.
- D1 can be 1 to 870, 1 to 800, 1 to 700, 1 to 600, 1 to 500, 10 to 870, 10 to 800, 10 to 700, 10 to 600, 10 to 500, 50 to 870 , 50 to 800, 50 to 700, 50 to 600, 50 to 500, 100 to 870, 100 to 800, 100 to 700, 100 to 600, 100 to 500, 200 to 870, 200 to 800, 200 to 700, 200 to 600, 200 to 500, 300 to 870, 300 to 800, 300 to 700, 300 to 600 or 300 to 500.
- D1/D2 is 0.1 to 2, 0.1 to 1.8, 0.1 to 1.6, 0.1 to 1.4, 0.1 to 1.2, 0.1 to 1, 0.1 to 0.9, 0.1 to 0.8, 0.1 to 0.7, 0.1 to 0.6, 0.2 to 2, 0.2 to 1.8, 0.2 to 1.6, 0.2 to 1.4, 0.2 to 1.2, 0.2 to 1, 0.2 to 0.9, 0.2 to 0.8, 0.2 to 0.7, 0.2 to 0.6, 0.3 to 2, 0.3 to 1.8, 0.3 to 1.6, 0.3 to 1.4, 0.3 to 1.2, 0.3 to 1, 0.3 to 0.9, 0.3 to 0.8, 0.3 to 0.7, 0.3 to 0.6, 0.5 to 2, 0.5 to 1.8, 0.5 to 1.6, 0.5 to 1.4,
- the mass concentration of the first anion in the non-aqueous electrolyte is D2 ppm, optionally, D2 is 1 to 3000.
- D2 is within a suitable range, the secondary battery can simultaneously achieve high capacity retention rate, low volume expansion rate and good dynamic performance.
- D2 is 10 to 3000, 10 to 2500, 10 to 2000, 10 to 1500, 10 to 1000, 100 to 3000, 100 to 2500, 100 to 2000, 100 to 1500, 100 to 1000, 200 to 3000 , 200 to 2500, 200 to 2000, 200 to 1500, 200 to 1000, 500 to 3000, 500 to 2500, 500 to 2000, 500 to 1500 or 500 to 1000.
- the metal cation Me n+ represents a metal cation other than lithium ion, and n represents the valence of the metal cation.
- the Me element represents at least one of a transition metal element and a fifth to seventh main group metal element, and n represents 1, 2, 3, 4, 5 or 6.
- the difference between the Me n+ standard reduction potential (vs. standard hydrogen electrode potential) and the Li + standard reduction potential (vs. standard hydrogen electrode potential, that is -3.04V) is more than 1.0V.
- Me represents at least one of Ni, Co, Mn, Al and Fe. More optionally, Men + represents at least one of Ni 2+ , Co 2+ , Mn 2+ , Al 3+ and Fe 2+ .
- BF 4- can improve the high-temperature stability and low-temperature performance of secondary batteries and broaden the electrochemical window of non-aqueous electrolyte.
- the ionic conductivity of BF 4- is low, and a high content is not conducive to the formation of a stable surface on the surface of the negative active material . SEI membrane. Therefore, its content should not be too high.
- D3 is 1 to 2500, 1 to 2000, 1 to 1500, 1 to 1000, 1 to 500, 50 to 3000, 50 to 2500, 50 to 2000, 50 to 1500, 50 to 1000, 50 to 500 , 100 to 3000, 100 to 2500, 100 to 2000, 100 to 1500, 100 to 1000, 100 to 500, 200 to 3000, 200 to 2500, 200 to 2000, 200 to 1500, 200 to 1000 or 200 to 500.
- the mass concentration of the first anion D2 ppm and the mass concentration of the second anion D3 ppm also satisfy: D2/D3 is 0.4 to 20.
- D2/D3 is 0.4 to 20.
- the inventor further studied and found that when D2/D3 is within a suitable range, it helps to give full play to the synergistic effect between BF 4 - and DFOB - , thereby not only broadening the electrochemical window of the non-aqueous electrolyte, but also A stable and low-resistance SEI film can be formed on the surface of the negative active material.
- D2/D3 may be 0.5 to 20, 0.5 to 15, 0.5 to 10, 0.5 to 8, 0.5 to 6, 0.5 to 4, 0.5 to 2, 0.8 to 15, 0.8 to 10, 0.8 to 8, 0.8 to 6, 0.8 to 4, 0.8 to 2, 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 4 or 1 to 2.
- the non-aqueous electrolyte may also contain a third anion, the third anion includes perchlorate anion ClO 4 - , bistrifluoromethanesulfonyl imide anion N (SO 2 CF 3 ) 2 - (abbreviated as TFSI - ), at least one of NO 3 - and SO 4 2- , more optionally including at least one of NO 3 - and SO 4 2- .
- the mass concentration of the third anion in the non-aqueous electrolyte is D4 ppm, and optionally, D4 is 1 to 3000 based on the total mass of the non-aqueous electrolyte.
- D4 is 1 to 2500, 1 to 2000, 1 to 1500, 1 to 1000, 1 to 500, 50 to 3000, 50 to 2500, 50 to 2000, 50 to 1500, 50 to 1000, 50 to 500 , 100 to 3000, 100 to 2500, 100 to 2000, 100 to 1500, 100 to 1000, 100 to 500, 200 to 3000, 200 to 2500, 200 to 2000, 200 to 1500, 200 to 1000 or 200 to 500.
- the mass concentration D2 ppm of the first anion and the mass concentration D4 ppm of the third anion also satisfy: D2/D4 is 0.4 to 20.
- D2/D4 is 0.4 to 20.
- the inventor further studied and found that when D2/D4 is within a suitable range, it helps to give full play to the synergistic effect between the first anion and the third anion, thereby not only improving the thermal stability of the non-aqueous electrolyte, but also It can also form a stable and low-resistance SEI film on the surface of the negative active material.
- D2/D4 may be 0.5 to 20, 0.5 to 15, 0.5 to 10, 0.5 to 8, 0.5 to 6, 0.5 to 5, 0.5 to 4, 0.5 to 3, 0.5 to 2, 0.8 to 15, 0.8 to 10, 0.8 to 8, 0.8 to 6, 0.8 to 5, 0.8 to 4, 0.8 to 3 or 0.8 to 2.
- the non-aqueous electrolyte solution may contain both the above-mentioned second anion and the third anion.
- the mass concentration of the second anion in the non-aqueous electrolyte is D3 ppm
- the mass concentration of the third anion in the non-aqueous electrolyte is D4 ppm, both based on the total mass of the non-aqueous electrolyte, optionally , D3 ranges from 1 to 3000, D4 ranges from 1 to 3000.
- the non-aqueous electrolyte solution satisfies: D2/D3 is 0.4 to 20 and D2/D4 is 0.4 to 20.
- the non-aqueous electrolyte may also contain a fourth anion, the fourth anion includes hexafluorophosphate anion PF 6 - , bisfluorosulfonylimide anion N(SO 2 F) 2 - (abbreviated as FSI - ) or a combination thereof.
- the mass percentage of the fourth anion in the non-aqueous electrolyte is 8% to 20%, more optionally 9% to 18%, further optionally 9% to 15%, based on the The total mass of the non-aqueous electrolyte.
- the non-aqueous electrolyte of the present application uses the compound formed by the fourth anion and lithium ions as the main lithium salt. That is, the present application can use lithium hexafluorophosphate and/or lithium bisfluorosulfonyl imide as the main lithium salt. Lithium hexafluorophosphate has the characteristics of high ionic conductivity and resistance to corrosion of the cathode current collector. As the main lithium salt, it can improve the ionic conductivity and thermal stability of the entire non-aqueous electrolyte.
- the fourth anion includes hexafluorophosphate anion PF 6 - , that is, lithium hexafluorophosphate (LiPF 6 ) can be used as the main lithium salt in this application.
- the fourth anion includes bisfluorosulfonimide anion N(SO 2 F) 2 - , that is, lithium bisfluorosulfonimide (LiFSI) can be used as the main lithium salt in this application.
- LiFSI lithium bisfluorosulfonimide
- the fourth anion includes both hexafluorophosphate anion PF 6 - and bisfluorosulfonimide anion N(SO 2 F) 2 - , that is, the present application can use lithium hexafluorophosphate (LiPF 6 ) and bis Lithium fluorosulfonyl imide (LiFSI) serves as the main lithium salt.
- the mass ratio ⁇ of the hexafluorophosphate anion PF 6 - and the bisfluorosulfonylimide anion N(SO 2 F) 2 - is 0.2 to 3, more optionally 0.3 to 2, 0.4 to 1.8 Or 0.5 to 1.5. Therefore, the non-aqueous electrolyte is not easily hydrolyzed, can also achieve higher thermal stability, and at the same time, can help form an interface film with lower impedance.
- the non-aqueous electrolyte may also contain a fifth anion, and the fifth anion includes dioxaloborate anion BOB - , hexafluoroarsenate anion AsF 6 - , and trifluoromethanesulfonate At least one of the acid anion CF 3 SO 3 - , the difluorophosphate anion PO 2 F 2 - , the difluorodioxalate phosphate anion DODFP - and the tetrafluoroxalate phosphate anion OTFP - .
- the mass percentage of the fifth anion in the non-aqueous electrolyte is below 2%, more optionally below 0.5%, based on the total mass of the non-aqueous electrolyte.
- the fifth anion includes difluorophosphate anion PO 2 F 2 - , thereby improving the ionic conductivity of the non-aqueous electrolyte and improving the positive electrode interface film and/or the negative electrode interface film. properties, and helps to construct a stable and low-resistance positive electrode interface film and/or negative electrode interface film, thereby effectively reducing the decomposition of non-aqueous electrolyte and further improving the kinetic performance and safety performance of secondary batteries.
- the mass ratio ⁇ of the difluorophosphate anion PO 2 F 2 - and the fourth anion is 0.01 to 0.15, more optionally 0.01 to 0.1.
- the non-aqueous electrolyte solution may also contain a first additive, and the first additive is fluoroethylene carbonate (FEC).
- FEC fluoroethylene carbonate
- the mass concentration of the first additive in the non-aqueous electrolyte is D5 ppm, based on the total mass of the non-aqueous electrolyte, optionally, D5 is 1 to 30,000.
- the non-aqueous electrolyte When the non-aqueous electrolyte further contains FEC, it is beneficial to give full play to the improvement effect of FEC on the cycle performance and energy density of the secondary battery.
- FEC has a high dielectric constant. Therefore, when the non-aqueous electrolyte contains FEC, it helps DFOB - in the non-aqueous electrolyte to become free ions and reduces the association of anions and cations, thus enabling DFOB - to be fully utilized. Improvement of secondary battery capacity retention and kinetic properties.
- HF will be formed when FEC decomposes, which will destroy the structural stability of the cathode active material, increase the gas production of the secondary battery, and worsen the storage performance of the secondary battery. Therefore, its content should not be too high.
- D5 is 1 to 25000, 1 to 20000, 1 to 15000, 1 to 10000, 1 to 8000, 1 to 5000, 1 to 2000, 100 to 25000, 100 to 20000, 100 to 15000, 100 to 10000 , 100 to 8000, 100 to 5000 or 100 to 2000.
- the non-aqueous electrolyte solution may also contain a second additive, the second additive includes vinylene carbonate (VC), lithium oxalate, vinyl sulfate (DTD), 1,3 -At least one of propanesultone (PS).
- the second additive helps to further improve the interface properties of the positive electrode and/or the negative electrode, thereby further improving at least one of cycle performance, safety performance and kinetic performance of the secondary battery.
- the mass percentage of the second additive in the non-aqueous electrolyte is below 5%, more optionally below 2.5%, based on the total mass of the non-aqueous electrolyte.
- the non-aqueous electrolyte may also contain the above-mentioned first additive and second additive at the same time, thereby helping to further improve the interfacial properties of the positive electrode and/or the negative electrode, thereby further improving the secondary Battery cycle performance, safety performance and kinetic performance.
- the non-aqueous solvent includes cyclic carbonate compounds and chain carbonate compounds.
- the cyclic carbonate compound can increase the ionic conductivity of the non-aqueous electrolyte due to its high dielectric constant, and the chain carbonate compound can reduce the viscosity of the non-aqueous electrolyte due to its small viscosity. Therefore, when the non-aqueous solvent includes a cyclic carbonate compound and a chain carbonate compound, it helps the non-aqueous electrolyte to have appropriate viscosity and ionic conductivity, which is beneficial to the transport of lithium ions.
- the cyclic carbonate compound may include at least one of ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC).
- chain carbonate compounds may include ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), and At least one of ethyl propyl carbonate (EPC).
- the non-aqueous solvent may also include other solvents besides cyclic carbonate compounds and chain carbonate compounds.
- it may also include at least one of carboxylate compounds, sulfone compounds, and ether compounds.
- carboxylate compounds may include methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate ( At least one of EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB) and 1,4-butyrolactone (GBL).
- the sulfone compound may include at least one of sulfolane (SF), dimethyl sulfone (MSM), methyl ethyl sulfone (EMS), and diethyl sulfone (ESE).
- ether compounds include tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,3-dioxolane (DOL), ethylene glycol monomethyl ether, ethylene glycol dimethyl ether (DME), tetraethyl At least one of glycol dimethyl ether, dimethoxymethane (DMM) and diglyme (DG).
- each component in the non-aqueous electrolyte solution for example, the first cation, the first anion, the second anion, the third anion, the fourth anion, the fifth anion, the first additive, the second additive, etc.
- Its content can be determined according to methods known in the art. For example, gas chromatography-mass spectrometry (GC-MS), ion chromatography (IC), liquid chromatography (LC), nuclear magnetic resonance spectroscopy (NMR), and inductively coupled plasma optical emission spectrometry (ICP-OES) can be used. ) is measured.
- GC-MS gas chromatography-mass spectrometry
- IC ion chromatography
- LC liquid chromatography
- NMR nuclear magnetic resonance spectroscopy
- ICP-OES inductively coupled plasma optical emission spectrometry
- a second aspect of the present application provides a method for preparing a non-aqueous electrolyte solution.
- the non-aqueous electrolyte solution of the first aspect of the present application can be obtained by the method of preparing the non-aqueous electrolyte solution of the second aspect of the present application.
- the preparation method of the non-aqueous electrolyte includes the following steps: Mix the non-aqueous solvent, lithium salt, soluble Me salt, soluble difluoroxalate borate and optional additives evenly to obtain a non-aqueous electrolyte, where Me represents lithium Elements other than metallic elements.
- the soluble Me salt a compound containing Me n+ and soluble in the non-aqueous electrolyte solution can be used.
- the soluble Me salts include Me(DFOB) n , Me(BF 4 ) n , Me(ClO 4 ) n , Me[N(SO 2 CF 3 ) 2 ] n , Me (NO 3 ) n , Me(SO 4 ) n/2 , Me(PF 6 ) n , Me[N(SO 2 F) 2 ] n , Me(BOB) n , Me(AsF 6 ) n , Me(CF At least one of 3 SO 3 ) n , Me(PO 2 F 2 ) n , Me(DODFP) n and Me(OTFP) n .
- the soluble difluoroxalate borate includes at least one of Me(DFOB) n and LiDFOB. This helps to adjust the mass concentration of metal cations and first anions in the non-aqueous electrolyte solution within a desired range.
- the lithium salt includes a first lithium salt including lithium hexafluorophosphate (LiPF 6 ), lithium bisfluorosulfonyl imide (LiFSI), or a combination thereof.
- the first lithium salt serves as the main lithium salt, and its mass percentage in the non-aqueous electrolyte solution can be 8% to 20%, optionally 9% to 18%, and more optionally 9% to 15%. %, based on the total mass of the non-aqueous electrolyte solution.
- the first lithium salt includes lithium hexafluorophosphate (LiPF 6 ).
- the first lithium salt includes both lithium hexafluorophosphate (LiPF 6 ) and lithium bisfluorosulfonimide (LiFSI).
- the mass ratio of lithium hexafluorophosphate and lithium bisfluorosulfonimide is 0.2 to 3, more optionally 0.3 to 2, 0.4 to 1.8 or 0.5 to 1.5. Therefore, the non-aqueous electrolyte is not easily hydrolyzed, can also achieve higher thermal stability, and at the same time, can help form an interface film with lower impedance.
- the lithium salt may also include a second lithium salt, the second lithium salt including lithium dioxaloborate (LiBOB), lithium tetrafluoroborate (LiBF 4 ), bistrifluoromethane Lithium sulfonylimide (LiTFSI), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiTFS), lithium difluorophosphate (LiPO 2 F 2 ), difluorophosphate At least one of lithium fluorodioxalate phosphate (LiDODFP) and lithium tetrafluorooxalate phosphate (LiOTFP).
- LiBOB lithium dioxaloborate
- LiBF 4 lithium tetrafluoroborate
- LiTFSI bistrifluoromethane Lithium sulfonylimide
- LiClO 4 lithium perchlorate
- the second lithium salt can further improve the interface properties of the positive electrode and/or the negative electrode, or improve the ionic conductivity or thermal stability of the non-aqueous electrolyte.
- the mass percentage of the second lithium salt in the non-aqueous electrolyte solution is below 2%, more optionally below 0.5%, based on the total mass of the non-aqueous electrolyte solution.
- the additive includes at least one of a first additive that is fluoroethylene carbonate (FEC) and a second additive that includes vinylene carbonate (VC ), at least one of lithium oxalate, vinyl sulfate (DTD), and 1,3-propanesultone (PS).
- FEC fluoroethylene carbonate
- VC vinylene carbonate
- DTD vinyl sulfate
- PS 1,3-propanesultone
- each raw material in the non-aqueous electrolyte helps to adjust the dissociation degree of lithium salt, soluble Me salt, and soluble difluoroxalate borate in the non-aqueous electrolyte, and helps to obtain A non-aqueous electrolyte solution that satisfies the required mass concentration of metal cations and anions (eg, first anion, second anion, third anion, fourth anion, fifth anion).
- the types and specific contents of each component in the non-aqueous electrolyte solution thus obtained are the same as the non-aqueous electrolyte solution described in the first aspect of the embodiment of the present application.
- the electrode assembly includes a positive electrode piece, a negative electrode piece and an isolation film.
- the isolation film is set between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows lithium ions to pass through.
- the positive electrode sheet includes a positive current collector and a positive electrode film layer disposed on at least one surface of the positive current collector and including a positive active material.
- the positive electrode current collector has two surfaces opposite in its thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
- the cathode film layer includes a cathode active material
- the cathode active material may be a cathode active material known in the art for secondary batteries.
- the cathode active material may include at least one of a lithium transition metal oxide, an olivine-structured lithium-containing phosphate, and their respective modified compounds.
- lithium transition metal oxides may include lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium At least one of nickel cobalt aluminum oxides and their respective modified compounds.
- lithium-containing phosphates with an olivine structure may include lithium iron phosphate, composites of lithium iron phosphate and carbon, lithium manganese phosphate, composites of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and lithium iron manganese phosphate and carbon. At least one of the composite materials and their respective modifying compounds. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
- the layered material with the molecular formula Li a Ni b Co c Mn d Al e M f O g A h is optionally modified by M cation doping, A anion doping or simultaneous doping of M cations and A anions. properties, the crystal structure of the layered material obtained after doping is more stable, and can further improve the electrochemical performance of secondary batteries, such as cycle performance, kinetic performance, etc.
- M is selected from at least one of Si, Ti, Mo, V, Ge, Se, Zr, Nb, Ru, Pd, Sb, Ce, Te, and W.
- A is selected from at least one of F, N, P, and S.
- A is selected from F.
- the crystal structure of Li a Ni b Co c Mn d Al e M f O g A h is more stable, thus enabling the secondary battery to have better cycle performance and kinetic performance.
- 0 ⁇ b ⁇ 0.98 In some embodiments, 0 ⁇ b ⁇ 0.98. Alternatively, 0.50 ⁇ b ⁇ 0.98, 0.55 ⁇ b ⁇ 0.98, 0.60 ⁇ b ⁇ 0.98, 0.65 ⁇ b ⁇ 0.98, 0.70 ⁇ b ⁇ 0.98, 0.75 ⁇ b ⁇ 0.98 or 0.80 ⁇ b ⁇ 0.98.
- c 0.
- 0 ⁇ c ⁇ 0.20 In some embodiments, 0 ⁇ c ⁇ 0.15, 0 ⁇ c ⁇ 0.10, 0 ⁇ c ⁇ 0.09, 0 ⁇ c ⁇ 0.08, 0 ⁇ c ⁇ 0.07, 0 ⁇ c ⁇ 0.06, 0 ⁇ c ⁇ 0.05, 0 ⁇ c ⁇ 0.04, 0 ⁇ c ⁇ 0.03, 0 ⁇ c ⁇ 0.02 or 0 ⁇ c ⁇ 0.01.
- Cobalt is less abundant in the earth's crust, difficult to mine, and expensive. Therefore, low-cobalt or cobalt-free has become an inevitable development trend for cathode active materials. However, cobalt contributes greatly to the lithium ion diffusion rate of the cathode active material.
- DFOB- in the non-aqueous electrolyte can form a low-resistance protective film on the surface of the cathode active material, and the B atoms in DFOB- can easily combine with the O atoms in the cathode active material. , reducing the charge transfer resistance of the cathode active material, thereby reducing the diffusion resistance of lithium ions in the bulk phase of the cathode active material.
- the crystal structure of the low-cobalt or cobalt-free cathode active material is more stable, it can greatly reduce the change in structural properties, chemical properties or electrochemical properties of the cathode active material due to excessive delithiation on the surface of the low-cobalt or cobalt-free cathode active material.
- the probability of problems such as instability, for example, irreversible distortion of the cathode active material and increased lattice defects.
- d 0 and 0 ⁇ e ⁇ 0.50.
- e 0 and 0 ⁇ d ⁇ 0.50.
- Li a Ni b Co c Mn d Al e M f O g A h can be prepared according to conventional methods in the art.
- An exemplary preparation method is as follows: a lithium source, a nickel source, a cobalt source, a manganese source, an aluminum source, an M element precursor, and an A element precursor are mixed and then sintered.
- the sintering atmosphere may be an oxygen-containing atmosphere, such as an air atmosphere or an oxygen atmosphere.
- the O2 concentration of the sintering atmosphere is, for example, 70% to 100%.
- the sintering temperature and sintering time can be adjusted according to actual conditions.
- the M element precursor includes, but is not limited to, at least one of an oxide of the M element, a nitric acid compound, a carbonic acid compound, a hydroxide compound, and an acetic acid compound.
- precursors of element A include, but are not limited to, ammonium fluoride, lithium fluoride, hydrogen fluoride, ammonium chloride, lithium chloride, hydrogen chloride, ammonium nitrate, ammonium nitrite, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, phosphoric acid , at least one of ammonium sulfate, ammonium bisulfate, ammonium bisulfite, ammonium sulfite, ammonium bisulfide, hydrogen sulfide, lithium sulfide, ammonium sulfide and elemental sulfur.
- the mass percentage of the layered material with the molecular formula Li a Ni b Co c Mn d Ale M f O g A h is 80% to 99%.
- the mass percentage of the layered material with the molecular formula Li a Ni b Co c Mn d Al e M f O g A h can be 80%, 81%, 82%, 83%, 84%, 85%, 86 %, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or any range above.
- the mass percentage of the layered material with the molecular formula Li a Ni b Co c Mn d Al e M f O g A h is 85% to 99%, 90% to 99%, 95% to 99%, 80% to 98%, 85% to 98%, 90% to 98%, 95% to 98%, 80% to 97%, 85% to 97%, 90% to 97% or 95% to 97%.
- the positive electrode film layer optionally further includes a positive electrode binder.
- the positive electrode binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene -At least one of propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
- the mass percentage of the cathode binder is less than 5% based on the total mass of the cathode film layer.
- the positive electrode film layer is usually formed by coating the positive electrode slurry on the positive electrode current collector, drying, and cold pressing.
- the positive electrode slurry is usually formed by dispersing the positive electrode active material, optional conductive agent, optional binder and any other components in a solvent and stirring evenly.
- the solvent may be N-methylpyrrolidone (NMP), but is not limited thereto.
- the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector and including a negative electrode active material.
- the negative electrode current collector has two surfaces opposite in its thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
- the negative active material may be a negative active material known in the art for secondary batteries.
- the negative active material includes but is not limited to at least one of natural graphite, artificial graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, and lithium titanate.
- the silicon-based material may include at least one of elemental silicon, silicon oxide, silicon-carbon composite, silicon-nitride composite, and silicon alloy material.
- the tin-based material may include at least one of elemental tin, tin oxide, and tin alloy materials.
- the present application is not limited to these materials, and other conventionally known materials that can be used as negative electrode active materials for secondary batteries can also be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
- the negative electrode film layer optionally further includes a negative electrode conductive agent.
- a negative electrode conductive agent may include superconducting carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphite At least one of alkenes and carbon nanofibers.
- the mass percentage of the negative electrode conductive agent is less than 5%.
- the negative electrode current collector may be a metal foil or a composite current collector.
- the metal foil copper foil can be used.
- the composite current collector may include a polymer material base layer and a metal material layer formed on at least one surface of the polymer material base layer.
- the metal material may be selected from at least one of copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy.
- the polymer material base layer may include polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE) etc.
- the isolation film is disposed between the positive electrode piece and the negative electrode piece, and mainly plays a role in preventing short circuit between the positive electrode and the negative electrode, and at the same time allows lithium ions to pass through.
- the material of the isolation membrane may include at least one of fiberglass, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
- the isolation film may be a single-layer film or a multi-layer composite film. When the isolation film is a multi-layer composite film, the materials of each layer may be the same or different.
- the positive electrode piece, the isolation film and the negative electrode piece can be made into an electrode assembly through a winding process or a lamination process.
- the secondary battery may include an outer packaging.
- the outer packaging can be used to package the above-mentioned electrode assembly and the non-aqueous electrolyte.
- the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
- the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
- the soft bag may be made of plastic, such as at least one of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), and the like.
- This application has no particular limitation on the shape of the secondary battery, which can be cylindrical, square or any other shape. As shown in FIG. 1 , a square-structured secondary battery 5 is shown as an example.
- the outer package may include a housing 51 and a cover 53 .
- the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose to form a receiving cavity.
- the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 is used to cover the opening to close the accommodation cavity.
- the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
- the electrode assembly 52 is packaged in the containing cavity.
- the non-aqueous electrolyte soaks into the electrode assembly 52 .
- the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and can be adjusted according to needs.
- the positive electrode sheet, the separator, the negative electrode sheet, and the non-aqueous electrolyte may be assembled to form a secondary battery.
- the positive electrode sheet, isolation film, and negative electrode sheet can be formed into an electrode assembly through a winding process or a lamination process.
- the electrode assembly is placed in an outer package, dried, and then injected with non-aqueous electrolyte. After vacuum packaging, static Through processes such as placement, formation, and shaping, secondary batteries are obtained.
- the secondary batteries according to the present application can be assembled into battery modules.
- the number of secondary batteries contained in the battery module can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
- FIG. 3 is a schematic diagram of the battery module 4 as an example.
- a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
- the plurality of secondary batteries 5 can be fixed by fasteners.
- the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
- the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
- the battery pack 1 may include a battery box and a plurality of battery modules 4 arranged in the battery box.
- the battery box includes an upper box 2 and a lower box 3 .
- the upper box 2 is used to cover the lower box 3 and form a closed space for accommodating the battery module 4 .
- Multiple battery modules 4 can be arranged in the battery box in any manner.
- a fourth aspect of the present application also provides an electrical device, which includes at least one of a secondary battery, a battery module or a battery pack of the present application.
- the secondary battery, battery module or battery pack may be used as a power source for the electrical device or as an energy storage unit for the electrical device.
- the electrical device may be, but is not limited to, mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric Golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
- the power-consuming device can select a secondary battery, a battery module or a battery pack according to its usage requirements.
- FIG. 6 is a schematic diagram of an electrical device as an example.
- the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
- battery packs or battery modules can be used.
- the power-consuming device may be a mobile phone, a tablet computer, a laptop computer, etc.
- the electrical device is usually required to be light and thin, and secondary batteries can be used as power sources.
- a porous polyethylene (PE) film is used as the isolation membrane.
- Electrode assembly Stack and wind the positive electrode sheet, isolation film, and negative electrode sheet in order to obtain the electrode assembly; put the electrode assembly into the outer packaging, add the above-mentioned non-aqueous electrolyte, and then go through the processes of packaging, standing, forming, aging, etc. , get the secondary battery.
- Test of metal cations After the secondary battery prepared above is fully charged, take out 10ml of free electrolyte from the liquid injection port, and use the inductively coupled plasma atomic emission spectrometry method of Thermo Fisher Scientific company model ICAP-7400 for testing. According to the test As a result, the mass concentration of the first cation in the non-aqueous electrolyte solution was calculated to be D1 ppm.
- Deuterated reagents are prepared according to the following steps: dry deuterated dimethyl sulfoxide (DMSO-d6), deuterated acetonitrile and trifluoromethylbenzene with 4A molecular sieves at a temperature above 25°C for more than 3 days to ensure that all reagents are The water content is less than 3ppm.
- the moisture testing instrument can be the 831KF Coulomb moisture tester of Swiss Metrohm Co., Ltd. Then, in a glove box filled with nitrogen, take 10 ml of dried DMSO-d6 and 300 ⁇ l of dried internal standard trifluoromethylbenzene and mix them evenly to obtain the first solution.
- the secondary battery At 25°C, charge the secondary battery to 4.3V with a constant current of 1C, and continue charging with a constant voltage until the current is 0.05C. At this time, the secondary battery is fully charged; discharge the secondary battery with a constant current of 0.5C and adjust When the secondary battery reaches 50% SOC, the voltage of the secondary battery at this time is recorded as U 1 ; the secondary battery is discharged with a constant current of 4C I 1 for 30 seconds, using a 0.1 second sampling point, and the voltage at the end of the discharge is recorded as U 2 .
- the initial DC internal resistance of the secondary battery is represented by the discharge DC internal resistance of the secondary battery at 50% SOC.
- the initial DC internal resistance of the secondary battery (m ⁇ ) (U 1 -U 2 )/I 1 .
- Table 2 gives the test results of Examples 1 to 36 and Comparative Examples 1 to 4.
- non-aqueous electrolyte further contains the first additive and/or the second additive of the present application, it will help to further improve the cycle performance, kinetic performance and storage of the secondary battery. At least one of the properties.
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Abstract
Description
Claims (18)
- 一种非水电解液,含有非水溶剂以及溶解于其中的锂离子、第一阳离子和第一阴离子,其中,所述第一阳离子为锂离子以外的金属阳离子Me n+,n表示金属阳离子的化合价,所述第一阴离子为二氟草酸硼酸根阴离子DFOB -,所述非水电解液中第一阳离子的质量浓度为D1 ppm,所述非水电解液中第一阴离子的质量浓度为D2 ppm,均基于所述非水电解液的总质量计,并且所述非水电解液满足:D1为0.5至870和D1/D2为0.02至2。
- 根据权利要求1所述的非水电解液,其中,Me n+标准还原电势与Li +标准还原电势的差值在1.0V以上,可选地,Me n+表示Ni 2+、Co 2+、Mn 2+、Al 3+和Fe 2+中的至少一种。
- 根据权利要求1或2所述的非水电解液,其中,D1为100至870,可选地为200至870;和/或,D1/D2为0.3至2,可选地为0.3至1.2;和/或,D2为1至3000,可选地为100至2000。
- 根据权利要求1-3中任一项所述的非水电解液,其中,所述非水电解液还含有第二阴离子,所述第二阴离子为四氟硼酸根阴离子BF 4 -,所述非水电解液中第二阴离子的质量浓度为D3 ppm,基于所述非水电解液的总质量计,可选地,D3为1至3000,更可选地为1至2000;和/或,可选地,D2/D3为0.4至20,更可选地为1至10。
- 根据权利要求1-4中任一项所述的非水电解液,其中,所述非水电解液还含有第三阴离子,所述第三阴离子包括高氯酸根阴离子ClO 4 -、双三氟甲磺酰亚胺根阴离子N(SO 2CF 3) 2 -、NO 3 -和SO 4 2-中的至少一种,可选地包括NO 3 -和SO 4 2-中的至少一种,所述非水电解液中第三阴离子的质量浓度为D4 ppm,基于所述非水电解液的总质量计,可选地,D4为1至3000,更可选地为1至2000;和/或,可选地,D2/D4为0.4至20,更可选地为0.8至5。
- 根据权利要求1-5中任一项所述的非水电解液,其中,所述非水电解液还含有第四阴离子,所述第四阴离子包括六氟磷酸根阴离子PF 6 -、双氟磺酰亚胺根阴离子N(SO 2F) 2 -或其组合,可选地,所述非水电解液中第四阴离子的质量百分含量为8%至20%,更可选地为9%至15%,基于所述非水电解液的总质量计,可选地,所述第四阴离子同时包括六氟磷酸根阴离子PF 6 -和双氟磺酰亚胺根阴离子N(SO 2F) 2 -,更可选地,六氟磷酸根阴离子PF 6 -和双氟磺酰亚胺根阴离子N(SO 2F) 2 -的质量比α为0.2至3,更可选地为0.5至1.5。
- 根据权利要求6所述的非水电解液,其中,所述非水电解液还含有第五阴离子,所述第五阴离子包括二草酸硼酸根阴离子BOB -、六氟砷酸根阴离子AsF 6 -、三氟甲磺酸根阴离子CF 3SO 3 -、二氟磷酸根阴离子PO 2F 2 -、二氟二草酸磷酸根阴离子DODFP -和四氟草酸磷酸根阴离子OTFP -中的至少一种,可选地,所述非水电解液中第五阴离子的质量百分含量在2%以下,更可选地在0.5%以下,基于所述非水电解液的总质量计。
- 根据权利要求7所述的非水电解液,其中,所述第五阴离子包括二氟磷酸根阴离子PO 2F 2 -,可选地,二氟磷酸根阴离子PO 2F 2 -和第四阴离子的质量比β为0.01至0.15,更可选地为0.01至0.1。
- 根据权利要求1-8中任一项所述的非水电解液,其中,所述非水溶剂包括环状碳酸酯化合物和链状碳酸酯化合物,所述非水电解液中环状碳酸酯化合物的质量百分含量为E1,链状碳酸酯化合物的质量百分含量为E2,均基于所述非水电解液的总质量计,E1为5%至40%,可选地为10%至30%;E2为40%至85%,可选地为60%至80%。
- 根据权利要求9所述的非水电解液,其中,所述非水溶剂还包括醚类化合物,所述醚类化合物包括四氢呋喃、2-甲基四氢呋喃、1,3-二氧环戊烷、乙二醇单甲醚、乙二醇二甲醚、四乙二醇二甲醚、二甲氧基甲烷和二甘醇二甲醚中的至少一种,所述非水电解液中醚类化合物的质量百分含量为E3,基于所述非水电解液的总质量计,可选地,E3为0.1%至40%,更可选地为0.5%至20%。
- 根据权利要求1-10中任一项所述的非水电解液,其中,所述非水电解液还含有第一添加剂,所述第一添加剂为氟代碳酸乙烯酯,所述非水电解液中第一添加剂的质量浓度为D5 ppm,基于所述非水电解液的总质量计,可选地,D5为1至30000,更可选地为100至20000;和/或,可选地,D5/D2为5至500,更可选地为5至100。
- 根据权利要求1-11中任一项所述的非水电解液,其中,所述非水电解液还含有第二添加剂,所述第二添加剂包括碳酸亚乙烯酯、草酸锂、硫酸乙烯酯、1,3-丙磺酸内酯中的至少一种,可选地,所述非水电解液中第二添加剂的质量百分含量在5%以下,更可选地在2.5%以下,基于所述非水电解液的总质量计。
- 一种非水电解液的制备方法,包括如下步骤:将非水溶剂、锂盐、可溶性Me盐、可溶性二氟草酸硼酸盐以及可选的添加剂混合均匀,得到非水电解液,Me表示锂元素以外的金属元素,其中,所述非水电解液含有非水溶剂以及溶解于其中的锂离子、第一阳离子和第一阴离子,所述第一阳离子为锂离子以外的金属阳离子Me n+,n表示金属阳离子的化合价,所述第一阴离子为二氟草酸硼酸根阴离子DFOB -,所述非水电解液中第一阳离子的质量浓度为D1 ppm,所述非水电解液中第一阴离子的质量浓度为D2 ppm,均基于所述非水电解液的总质量计,并且所述非水电解液满足:D1为0.5至870和D1/D2为0.02至2。
- 根据权利要求13所述的制备方法,其中,Me n+标准还原电势与Li +标准还原电势的差值在1.0V以上,可选地,Me n+表示Ni 2+、Co 2+、Mn 2+、Al 3+和Fe 2+中的至少一种。
- 根据权利要求13或14所述的制备方法,其中,所述可溶性Me盐包括Me(DFOB) n、Me(BF 4) n、Me(ClO 4) n、Me[N(SO 2CF 3) 2] n、Me(NO 3) n、Me(SO 4) n/2、Me(PF 6) n、Me[N(SO 2F) 2] n、Me(BOB) n、Me(AsF 6) n、Me(CF 3SO 3) n、Me(PO 2F 2) n、Me(DODFP) n和Me(OTFP) n中的至少一种;和/或,所述可溶性二氟草酸硼酸盐包括Me(DFOB) n、LiDFOB中的至少一种;和/或,所述非水溶剂包括环状碳酸酯化合物和链状碳酸酯化合物,可选地,所述非水溶剂同时包括环状碳酸酯化合物、链状碳酸酯化合物和醚类化合物;和/或,所述锂盐包括第一锂盐,所述第一锂盐包括六氟磷酸锂、双氟磺酰亚胺锂或其组合,可选地,所述锂盐还包括第二锂盐,所述第二锂盐包括二草酸硼酸锂、四氟硼酸锂、双三氟甲烷磺酰亚胺锂、高氯酸锂、六氟砷酸锂、三氟甲磺酸锂、二氟磷酸锂、二氟二草酸磷酸锂和四氟草酸磷酸锂中的至少一种;和/或,所述添加剂包括第一添加剂和第二添加剂中的至少一种,所述第一添加剂为氟代碳酸乙烯酯,所述第二添加剂包括碳酸亚乙烯酯、草酸锂、硫酸乙烯酯、1,3-丙磺酸内酯中的至少一种。
- 一种二次电池,包括正极极片、负极极片以及非水电解液,其中,所述非水电解液为根据权利要求1-12中任一项所述的非水电解液或采用权利要求13-15中任一项所述的制备方法得到的非水电解液。
- 根据权利要求15或16所述的二次电池,其中,所述正极极片包括分子式为Li aNi bCo cMn dAl eM fO gA h的层状材料,M表示过渡金属位掺杂阳离子,A表示氧位掺杂阴离子,0.8≤a≤1.2,0≤b≤1,0≤c≤1,0≤d≤1,0≤e≤1,0≤f≤0.2,0≤g≤2,0≤h≤2,b+c+d+e+f=1,g+h=2,可选地,Li aNi bCo cMn dAl eM fO gA h满足如下条件(1)至(8)中的至少一者:(1)M选自Si、Ti、Mo、V、Ge、Se、Zr、Nb、Ru、Pd、Sb、Ce、Te和W中的至少一种;(2)A选自F、N、P和S中的至少一种,可选地,A选自F;(3)0<b<0.98,可选地,0.50≤b<0.98;(4)c=0;(5)0<c≤0.20,可选地,0<c≤0.10;(6)d=0并且0<e<0.50,可选地,d=0并且0<e≤0.10;(7)e=0并且0<d<0.50,可选地,e=0并且0<d≤0.10;(8)0<d<0.50并且0<e<0.50,可选地,0<d≤0.30并且0<e≤0.10。
- 一种用电装置,包括权利要求16或17所述的二次电池。
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US20060204846A1 (en) * | 2005-03-11 | 2006-09-14 | Takuya Sunagawa | Lithium secondary battery |
CN101663790A (zh) * | 2007-04-20 | 2010-03-03 | 三菱化学株式会社 | 非水电解液以及使用该非水电解液的非水电解质二次电池 |
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CN106797021A (zh) * | 2014-10-09 | 2017-05-31 | 宝马股份公司 | 基于碱金属、尤其是基于锂的蓄能器的添加剂 |
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CN113906604A (zh) * | 2019-06-04 | 2022-01-07 | 三菱化学株式会社 | 非水电解液及非水电解质电池 |
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US20060204846A1 (en) * | 2005-03-11 | 2006-09-14 | Takuya Sunagawa | Lithium secondary battery |
CN101663790A (zh) * | 2007-04-20 | 2010-03-03 | 三菱化学株式会社 | 非水电解液以及使用该非水电解液的非水电解质二次电池 |
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CN113906604A (zh) * | 2019-06-04 | 2022-01-07 | 三菱化学株式会社 | 非水电解液及非水电解质电池 |
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