CN116826169A - Sodium ion battery electrolyte additive, electrolyte and battery - Google Patents
Sodium ion battery electrolyte additive, electrolyte and battery Download PDFInfo
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- CN116826169A CN116826169A CN202310756981.1A CN202310756981A CN116826169A CN 116826169 A CN116826169 A CN 116826169A CN 202310756981 A CN202310756981 A CN 202310756981A CN 116826169 A CN116826169 A CN 116826169A
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- Prior art keywords
- sodium
- electrolyte
- ion battery
- additive
- sodium ion
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 80
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003792 electrolyte Substances 0.000 title claims abstract description 69
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 54
- -1 ester compounds Chemical class 0.000 claims abstract description 112
- 239000000654 additive Substances 0.000 claims abstract description 77
- 230000000996 additive effect Effects 0.000 claims abstract description 70
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 64
- 239000011734 sodium Substances 0.000 claims abstract description 64
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 64
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 58
- 239000011593 sulfur Substances 0.000 claims abstract description 58
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 43
- 239000010452 phosphate Substances 0.000 claims description 43
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 28
- OJOUOVMLFBIHRQ-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.[Na+] 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.[Na+] OJOUOVMLFBIHRQ-UHFFFAOYSA-M 0.000 claims description 28
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 23
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 13
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- 150000002596 lactones Chemical class 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 4
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 claims 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000002427 irreversible effect Effects 0.000 abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000011356 non-aqueous organic solvent Substances 0.000 description 5
- 150000003463 sulfur Chemical class 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 125000002619 bicyclic group Chemical group 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SEZQTBVSXGHPFP-UHFFFAOYSA-N B([O-])([O-])[O-].[Na+].C(C(=O)O)(=O)O.[Na+].[Na+] Chemical compound B([O-])([O-])[O-].[Na+].C(C(=O)O)(=O)O.[Na+].[Na+] SEZQTBVSXGHPFP-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910021201 NaFSI Inorganic materials 0.000 description 2
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 2
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- JJFDUEREVQNQCH-UHFFFAOYSA-N B([O-])([O-])[O-].[Na+].C(C(=O)F)(=O)F.[Na+].[Na+] Chemical compound B([O-])([O-])[O-].[Na+].C(C(=O)F)(=O)F.[Na+].[Na+] JJFDUEREVQNQCH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- JVZGJLAPJLXQKT-UHFFFAOYSA-N lithium iron(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Mn+2].[Li+].[Ni+2] JVZGJLAPJLXQKT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- OPUAWDUYWRUIIL-UHFFFAOYSA-L methanedisulfonate Chemical compound [O-]S(=O)(=O)CS([O-])(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-L 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LTPKTTHIQCHIPA-UHFFFAOYSA-M sodium 2-hydroxy-2-oxoacetate phosphoric acid Chemical compound C(C(=O)O)(=O)[O-].[Na+].P(=O)(O)(O)O LTPKTTHIQCHIPA-UHFFFAOYSA-M 0.000 description 1
- FJPWIJZUVYYHQE-UHFFFAOYSA-N sodium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Na+] FJPWIJZUVYYHQE-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical class [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- JGFYQVQAXANWJU-UHFFFAOYSA-M sodium fluoroacetate Chemical compound [Na+].[O-]C(=O)CF JGFYQVQAXANWJU-UHFFFAOYSA-M 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZQDZSGHAIZKNHJ-UHFFFAOYSA-N trisodium difluoro oxalate borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-].FOC(=O)C(=O)OF ZQDZSGHAIZKNHJ-UHFFFAOYSA-N 0.000 description 1
- UWPVVEKAGIPLGQ-UHFFFAOYSA-K trisodium dihydrogen phosphate oxalate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.[O-]C(=O)C([O-])=O UWPVVEKAGIPLGQ-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The application discloses a sodium ion battery electrolyte additive, electrolyte and a battery, and aims to provide an additive which is added into the sodium ion battery electrolyte and can form a sulfur/phosphorus/carbonate base composite SEI film; the additive has low solubility in electrolyte and high stability, can effectively solve the problems of large irreversible capacity loss and low first coulombic efficiency of the prior sodium ion battery, can remarkably improve the cycle performance and high-temperature performance of the sodium ion battery, and can remarkably improve the gas production problem; the sodium ion battery electrolyte additive comprises at least one of sodium fluooxalate and at least one of sulfur-containing ester compounds; the electrolyte comprises a nonaqueous solvent, sodium salt and an electrolyte additive; the application relates to the field of new energy.
Description
Technical Field
The application relates to the field of new energy, in particular to a battery electrolyte additive, electrolyte and a battery.
Background
Sodium ion batteries are expected to become substitutes for lithium ion batteries in the future by virtue of low cost, abundant raw material sources and the like. However, the SEI film of the sodium ion battery has higher solubility than that of the SEI film of the lithium ion battery, and the instability in the charge and discharge process can generate continuous side reaction, so that irreversible capacity loss is caused, even electrolyte is exhausted, the sodium ion battery is not as stable as the lithium ion battery, and the practical application of the sodium ion battery is severely restricted.
For this reason, researchers have often added some additives to the electrolyte of sodium ion batteries to improve the stability of lithium ion batteries, such as:
CN202110925903.0 discloses an electrolyte additive, an electrolyte and a sodium secondary battery, wherein the electrolyte additive comprises a mixture of at least one of oxalic acid sodium borate salt and fluorooxalic acid sodium phosphate salt, a polyalcohol nitrile, hydrofluoroether and boric acid ester; the electrolyte additive has complex components, and can achieve the purposes of improving the wettability and high voltage resistance of the electrolyte, improving the electrochemical performance of the electrolyte, generating a passivation film and improving the stability of the passivation film only when the mass concentration of the electrolyte additive in the electrolyte is 10 percent by compounding oxalic acid sodium borate or fluoro oxalic acid sodium phosphate with polyalcohol nitrile, hydrofluoroether and boric acid ester.
CN202111054821.X discloses an electrolyte for forming sulfate-based SEI film, and preparation and application thereof; the electrolyte contains fluorine-containing sodium salt and a solvent, and the solvent comprises: a sulfur-containing ester organic compound and a non-aqueous organic solvent containing an ether bond. The mass fraction of the non-aqueous organic solvent containing ether bond is 80-99.5 wt%, and the organic solvent contains sulfur estersThe mass fraction of (2) is 0.1-20wt%; the non-aqueous organic solvent containing ether bond is selected from any one or more of cyclic ethers and chain ethers; the sulfur-containing ester organic matter is selected from one or more of vinyl sulfate (DTD) and Propylene Sulfite (PS); the fluorine-containing sodium salt comprises sodium hexafluorophosphate (NaPF) 6 ) Sodium difluorooxalato borate (NaDFOB), sodium trifluoromethane sulfonate (NaCF) 3 SO 3 ) One or more of sodium bis (trifluoromethanesulfonyl imide) (NaTFSI) and sodium bis (fluorosulfonyl imide) (NaFSI); because the technology adopts bis (trifluoromethanesulfonyl imide) sodium (NaTFSI) and bis (fluorosulfonyl imide) sodium (NaFSI), the technology is easy to cause corrosion of an aluminum foil current collector, and certain performance deterioration is brought to the battery.
CN202210214690.5 discloses a sodium ion electrolyte and its application, a sodium ion battery and its preparation method, the sodium ion electrolyte comprises tetrafluoro oxalic acid sodium phosphate additive, non-aqueous solvent and sodium salt dissolved in the non-aqueous solvent. Although the technology indicates that when the electrolyte is applied to a battery, sodium tetrafluorooxalate phosphate can form a low-impedance, compact and thermally stable SEI film on the surface of the negative electrode of the battery, and the SEI film has the characteristic of low impedance, and even in an ultralow-temperature environment, the transmission resistance of sodium ions is small, so that the low-temperature output capacity and the low-temperature cycle life of the battery are improved. Meanwhile, the SEI film has excellent thermal stability, and can prolong the cycle life of a battery at an ultrahigh temperature, but when the additive is singly used, even if the additive amount of sodium tetrafluorooxalate phosphate accounts for 5% of that of a sodium ion electrolyte, the capacity retention rate of the additive is only 86.3% after 1500 weeks of circulation at 55 ℃, and the result is not ideal. Even when sodium tetrafluorooxalate phosphate is adopted as a main film forming agent and fluoroethylene carbonate or vinylene carbonate is adopted as an auxiliary film forming agent, and the content of the auxiliary film forming agent is not more than that of the main film forming agent, the capacity retention rate of the auxiliary film forming agent is improved to 90.8-92.8% after the auxiliary film forming agent is circulated at 55 ℃ for 1500 weeks, but the formed interface film still has higher solubility in electrolyte and insufficient stability, so that the problems of large irreversible capacity loss, low initial coulomb efficiency and poor circulation performance of the existing sodium ion battery are caused.
Disclosure of Invention
In view of the shortcomings of the prior art, a first object of the present application is to provide an additive that can be added to a sodium ion battery electrolyte to form a sulfur/phosphorus/carbonate-based composite SEI film.
A second object of the present application is to provide an electrolyte to which the above-described additive capable of forming a sulfur/phosphorus/carbonate-based composite SEI film is added.
The third object of the application is to provide a battery containing the electrolyte, which can effectively solve the problems of large irreversible capacity loss and low first coulombic efficiency of the prior sodium ion battery, can remarkably improve the cycle performance and high-temperature performance of the sodium ion battery, and can remarkably improve the gas production problem.
In order to achieve the above object, a first technical solution provided by the present application is as follows:
a sodium ion battery electrolyte additive comprises at least one of sodium fluooxalate and at least one of sulfur-containing ester compounds.
Further, the mass ratio of the sodium fluooxalate phosphate to the sulfur-containing ester compound of the sodium ion battery electrolyte additive is 0.1-3: 3 to 0.1; the mass ratio of the preferred sodium fluooxalate phosphate to the sulfur-containing ester compound is 1-3: 3 to 1; the mass ratio of the preferred sodium fluooxalate phosphate to the sulfur-containing ester compound is 1.5-3: 3 to 1.5; in some embodiments the proportions are: 1:1.5, 0.1:1.5, 3:1.5, 1:0.1, 1:3.
further, the sodium fluooxalate phosphate comprises at least one of sodium difluorooxalate phosphate and sodium tetrafluorooxalate phosphate.
Further, the sulfur-containing ester compound comprises at least one of vinyl sulfate, propylene sulfite, ethylene sulfite, methylene methane disulfonate, 1, 3-propylene sultone, propylene sulfate, pentaerythritol dicyclo sulfate, 1, 4-butyl sultone and 2, 4-butyl sultone.
Further, the sulfur-containing ester compound is one or a combination of more of 1, 3-propylene sultone, pentaerythritol dicyclo sulfate, 1, 4-butyl sultone and 2, 4-butyl sultone; the mass ratio of the sodium fluooxalate phosphate to the thioester compound is 0.1-2: 2 to 0.1; the preferred ratio of the sodium fluooxalate phosphate to the thioester compound is 1.5:1 or 1:1.5.
the second technical scheme provided by the application is a sodium ion battery electrolyte which comprises a nonaqueous solvent, sodium salt dissolved in the nonaqueous solvent and the electrolyte additive in the first technical scheme.
More preferably, in the sodium ion battery electrolyte, the mass concentration of the electrolyte additive in the electrolyte is 0.2% -6.0%; more preferably, the mass concentration of the electrolyte additive in the electrolyte is 1% -5.0%; more preferred electrolyte additives have a mass concentration in the electrolyte of 2% to 4.0%; in some embodiments the electrolyte additive is present in the electrolyte at a mass concentration of 2.5%, 1.6%, 4.5%, 1.1%, 4%, 4.5%.
More preferably, in the sodium ion battery electrolyte, the mass of the nonaqueous solvent accounts for 82-85.4% of the total mass of the electrolyte; the mass of the non-aqueous solvent which is more preferable accounts for 84 to 84.9 percent of the total mass of the electrolyte; the mass of the non-aqueous solvent is 82-82.5% of the total mass of the electrolyte; in some embodiments the mass of nonaqueous solvent comprises 82%, 82.5%, 84%, 84.9%, 85.4%, 85.5% of the total mass of the electrolyte.
More preferably, in the sodium ion battery electrolyte, the mass of the sodium salt accounts for 5-25% of the total mass of the electrolyte; more preferably, the sodium salt accounts for 13.5% of the total mass of the electrolyte.
More preferably, the nonaqueous solvent is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, vinylene carbonate, methyl formate, ethyl formate, methyl acetate, ethyl propionate, ethyl butyrate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dimethyl sulfoxide, sulfolane, and dimethyl sulfone.
More preferably, the electrolyte salt of the sodium ion battery electrolyte at least comprises at least one of sodium hexafluorophosphate, sodium difluorophosphate, sodium tetrafluoroborate, sodium difluorosulfimide, sodium bistrifluoromethylsulfonimide, sodium dioxalate borate, sodium difluorooxalate borate and sodium perchlorate.
The third technical scheme provided by the application is a sodium ion battery, comprising the sodium ion battery electrolyte of the second technical scheme.
One of the above technical solutions of the present application has at least one of the following advantages or beneficial effects:
1. the technical scheme provided by the application combines two additives of fluorooxalate and sulfur-containing ester to form the SEI film taking sulfur/phosphorus/fluorine salts as main components, and the sulfur/phosphorus/fluorine salts composite components thereof reduce the solubility of the SEI film and improve the stability of the SEI film through the structure interlocking effect, so that the problems of large irreversible capacity loss and low first coulombic efficiency of the existing sodium ion battery can be effectively solved.
2. According to the technical scheme provided by the application, the SEI film is more stable, and fewer side reactions are caused at the interface of the negative electrode, so that the cycle performance and the high-temperature performance of the sodium ion battery can be obviously improved, and the gas production problem can be obviously improved.
3. The sulfur/phosphorus/fluorine salt-containing SEI film provided by the technical scheme of the application has a wider electrochemical window, and forms a stable and complete SEI film on the surface of the electrode along with the progress of charge-discharge reaction, thereby reducing side reaction between electrolyte and the negative electrode, guaranteeing the cycling stability of the electrode, effectively improving the compatibility of the electrolyte to the negative electrode, and improving the high-temperature characteristic and the safety performance of the battery.
Detailed Description
The technical solutions provided by the present application will be clearly and completely described in the following embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without undue burden are within the scope of the application
Example 1
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass of 1.5:1 sodium tetrafluorooxalate phosphate (NaTFOP) and 1, 3-propenesulfonic acid lactone (PST).
Example 2
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5 sodium tetrafluorooxalate phosphate (NaTFOP) and 1, 3-propenesulfonic acid lactone (PST).
Example 3
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5 sodium tetrafluorooxalate phosphate (NaTFOP) and 1, 4-butanesulfonic acid lactone (1, 4-BS).
Example 4
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass of 1.5:1 sodium tetrafluorooxalate phosphate (NaTFOP) and 1, 4-butanesulfonic acid lactone (1, 4-BS).
Example 5
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5 sodium tetrafluorooxalate phosphate (NaTFOP) and 2, 4-butanesulfonic acid lactone (2, 4-BS).
Example 6
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass of 1.5:1 sodium tetrafluorooxalate phosphate (NaTFOP) and 2, 4-butanesulfonic acid lactone (2, 4-BS).
Example 7
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5 sodium tetrafluorooxalate phosphate (NaTFOP) and pentaerythritol bicyclic sulfate (DTS)
Example 8
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.1 sodium tetrafluorooxalate phosphate (NaTFOP) and pentaerythritol bicyclic sulfate (DTS).
Example 9
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5 sodium tetrafluorooxalate phosphate (NaTFOP) and vinyl sulfate (DTD).
Example 10
The sodium ion battery electrolyte additive provided by the embodiment consists of sodium tetrafluorooxalate phosphate (NaTFOP) and Propylene Sulfite (PS) in a mass ratio of 1:1.5.
Example 11
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass of 0.1:1.5 sodium tetrafluorooxalate phosphate (NaTFOP) and Propylene Sulfite (PS).
Example 12
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5 sodium tetrafluorooxalate phosphate (NaTFOP) and Propylene Sulfite (PS).
Example 13
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 0.1 sodium tetrafluorooxalate phosphate (NaTFOP) and Propylene Sulfite (PS).
Example 14
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 3 sodium tetrafluorooxalate phosphate (NaTFOP) and Propylene Sulfite (PS).
Example 15
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5 sodium difluorooxalate phosphate (NaDFOP) and Propylene Sulfite (PS).
Example 16
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5 sodium difluorooxalate phosphate (NaDFOP) and 1, 3-propenesulfonic acid lactone (PST).
Example 17
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5 sodium difluorooxalate phosphate (NaDFOP) and pentaerythritol biscyclosulfate (DTS).
Example 18
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluoxalate phosphate additive is sodium tetrafluorooxalate phosphate (NaTFOP); the sulfur-containing ester compound additive consists of 1, 3-Propylene Sultone (PST) and vinyl sulfate (DTD) in equal mass ratio.
Example 19
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluoxalate phosphate additive is sodium tetrafluorooxalate phosphate (NaTFOP); the sulfur-containing ester compound additive consists of 1, 4-butanesulfonic acid lactone (1, 4-BS) and vinyl sulfate (DTD) in equal mass ratio.
Example 20
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluoxalate phosphate additive is sodium tetrafluorooxalate phosphate (NaTFOP); the sulfur-containing ester compound additive consists of 2, 4-butanesulfonic acid lactone (2, 4-BS) and vinyl sulfate (DTD) in equal mass ratio.
Example 21
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluoxalate phosphate additive is sodium tetrafluorooxalate phosphate (NaTFOP); the sulfur-containing ester compound additive consists of pentaerythritol dicyclic sulfate (DTS) and vinyl sulfate (DTD) in equal mass ratio.
Example 22
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluoxalate phosphate additive is sodium fluoxalate phosphate (NaTFOP); the sulfur-containing ester compound additive consists of 1, 3-Propylene Sultone (PST) and vinyl sulfate (DTD) in equal mass ratio.
Example 23
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluoxalate phosphate additive is sodium fluoxalate phosphate (NaTFOP); the sulfur-containing ester compound additive consists of 1, 4-butanesulfonic acid lactone (1, 4-BS) and vinyl sulfate (DTD) in equal mass ratio.
Example 24
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluoxalate phosphate additive is sodium fluoxalate phosphate (NaTFOP); the sulfur-containing ester compound additive consists of 2, 4-butanesulfonic acid lactone (2, 4-BS) and vinyl sulfate (DTD) in equal mass ratio.
Example 25
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluoxalate phosphate additive is sodium fluoxalate phosphate (NaTFOP); the sulfur-containing ester compound additive consists of pentaerythritol dicyclic sulfate (DTS) and vinyl sulfate (DTD) in equal mass ratio.
Example 26
The electrolyte additive for the sodium ion battery provided by the embodiment comprises the following components in percentage by mass: 1.5, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluooxalate phosphate additive consists of sodium tetrafluorooxalate phosphate (NaTFOP) and sodium difluorooxalate phosphate (NaDFOP) in equal mass ratio; the sulfur-containing ester compound additive consists of Propylene Sulfite (PS) and vinyl sulfate (DTD) in equal mass ratio.
Example 27
The sodium ion battery electrolyte additive provided by the embodiment comprises the following components in percentage by mass: 2, a sodium fluooxalate phosphate additive and a sulfur-containing ester compound additive; the sodium fluooxalate phosphate additive consists of sodium tetrafluorooxalate phosphate (NaTFOP) and sodium difluorooxalate phosphate (NaDFOP) in equal mass ratio; the sulfur-containing ester compound additive consists of Propylene Sulfite (PS) and vinyl sulfate (DTD) in equal mass ratio.
The sodium ion battery electrolyte additives in examples 1-27 are referenced in table 1;
table 1 additive formulation
Example 28
The electrolyte of the sodium ion battery provided in this embodiment takes sodium hexafluorophosphate accounting for 13.5% of the total mass of the electrolyte as sodium salt, takes a mixture of ethylene carbonate, propylene carbonate, methyl ethyl carbonate and dimethyl carbonate as a nonaqueous organic solvent (wherein the mass ratio of ethylene carbonate, propylene carbonate, methyl ethyl carbonate and dimethyl carbonate is 1:2:5:2), accounts for 84% of the total mass of the electrolyte, and accounts for 2.5% of the total mass of the electrolyte, the electrolyte additive of the sodium ion battery provided in embodiment 1; specifically, the sodium fluooxalate phosphate additive NaTFOP and the sulfur-containing ester compound additive PS respectively account for 1.0% and 1.5% of the total mass of the electrolyte.
A sodium ion battery prepared by the method of:
1) Lithium nickel iron manganese oxide (NaNi) as a positive electrode active material 1/3 Fe 1/3 Mn 1/3 O 2 ) Maleic acid, a conductive agent Super-P, a conductive agent CNT and an adhesive PVDF according to the mass ratio of 96:1.5:0.5:2.0 dissolving in N-methyl pyrrolidone solvent, mixing to obtain positive electrode slurry, coating the positive electrode slurry on aluminum foil of a current collector, oven drying, cold pressing, trimming, cutting, stripping, welding tab, and making into positive electrode sheet of lithium secondary battery.
2) Preparation of negative electrode sheet of lithium secondary battery
The method comprises the following steps of (1) mixing hard carbon serving as a cathode active material, super-P serving as a conductive agent, CMC serving as a thickening agent and SBR serving as a binding agent according to a mass ratio of 96.5:1.0:1.0:1.5, dissolving the mixture in deionized water serving as a solvent, uniformly mixing to prepare negative electrode slurry, uniformly coating the negative electrode slurry on aluminum foil serving as a current collector, drying, carrying out cold pressing, trimming, cutting, slitting, welding lugs, and preparing the negative electrode plate of the sodium ion battery meeting the requirements.
3) Preparation of sodium ion batteries
The positive plate, the negative plate and the isolating film of the sodium ion battery prepared by the process are manufactured into a battery core through a winding process, an aluminum-plastic composite film outer package is adopted, electrolyte is injected after vacuum drying, and the soft package sodium ion battery with the capacity of 1000mA.h is manufactured through processes of formation, aging, capacity division and the like.
Examples 29 to 54 are identical to example 27 in terms of other components and contents, the process being different in terms of the types and amounts of additives, and the specific formulation table being referred to in Table 2;
TABLE 2 electrolyte formulation table
Remarks: the nonaqueous organic solvents in the above tables are all: ethylene carbonate, propylene carbonate, methyl ethyl carbonate and dimethyl carbonate according to a mass ratio of 1:2:5:2, and a mixture of the same.
Comparative example 1
The process was identical to the other components and contents of example 28, except that: the electrolyte solvent content was 86.5% without any additives.
Comparative example 2
The process was identical to the other components and contents of example 28, except that: the electrolyte contains 85.5 percent of solvent, and the sodium fluooxalate phosphate additive NaTFOP contains 1.0 percent and does not contain PS.
Comparative example 3
The process was identical to the other components and contents of example 28, except that: the electrolyte contains 85 percent of solvent, 1.5 percent of sulfur-containing ester compound additive PS and no NaTFOP.
Comparative example 4
The process was identical to the other components and contents of example 28, except that: the content of the electrolyte solvent is 85%, and the additive is 1% of sodium difluoro oxalate borate; the content of Ps in the thioester additive is 1.5%.
Comparative example 5
The process was identical to the other components and contents of example 28, except that: the content of the electrolyte solvent is 85%, and the additive is 1% of sodium difluorosulfimide; the PS content of the thioester additive was 1.5%.
Comparative example 6
The process was identical to the other components and contents of example 28, except that: the electrolyte contains 85% of solvent, and the additive is sodium tetrafluorooxalate phosphate NaTFOP 1%, and vinylene carbonate 1.5%.
Comparative example 7
The process was identical to the other components and contents of example 28, except that: the electrolyte contains 85% of solvent, and the additive is sodium tetrafluorooxalate phosphate NaTFOP 1% and fluoroethylene carbonate 1.5%.
Comparative example 8
The process was identical to the other components and contents of example 28, except that: the electrolyte contains 85% of solvent, and the additive is sodium difluoro oxalate phosphate NaDFOP 1%, and vinylene carbonate 1.5%.
Comparative example 9
The process was identical to the other components and contents of example 28, except that: the electrolyte contains 85% of solvent, and the additive is sodium difluorooxalate phosphate NaDFOP 1%, fluoroethylene carbonate 1.5%.
In order to demonstrate the effects of the technical proposal provided by the application, the battery performance test provided by the application is given below
The sodium ion batteries in the examples and the comparative examples were subjected to tests of normal temperature, high temperature cycle and high temperature storage performance, and specific test conditions are as follows, and the test results are shown in table 1:
and (3) normal temperature cyclic test: the battery is subjected to charge-discharge cycle test at room temperature of 25 ℃ in a charge-discharge multiplying power voltage range of 2.0-4.0V at 1 ℃.
High temperature cycle test: the battery is subjected to charge-discharge cycle test at 45 ℃ in a charge-discharge multiplying power voltage range of 1C/1C of 2.0-4.0V.
High temperature storage test: the battery was cycled 3 times at room temperature of 25 ℃ with a charge-discharge rate of 1C and then charged to a full-charge state, and after being stored at a high temperature of 55 ℃ for 7 days, the thickness test and the 1C discharge residual capacity test were performed.
Table 3 shows the test results of examples 28 to 54 and comparative examples 1 to 9
Analysis of results:
first part
From the data in table 3, it can be seen that the combined electrolyte additive provided by the embodiment of the application effectively improves the cycle performance of the sodium secondary battery by the combined use of the sodium fluooxalate phosphate and the sulfur-containing ester compound, and the gas expansion rate of the battery is obviously improved.
It is seen from examples 28 to 52 that when the nonaqueous electrolyte contains both the sodium fluooxalate and the sulfur-containing ester compound, the cycle capacity retention rate, the high-temperature cycle capacity retention rate and the high-temperature capacity recovery rate of the battery have significant advantages, and when the content of the sodium fluooxalate and the sulfur-containing ester compound is 1% and 1.5% or 1.5% and 1%, respectively, the performance advantages of the battery are more significant.
According to the embodiments 36 and 45-52, when the nonaqueous electrolyte contains two additives of sodium fluooxalate and a sulfur-containing ester compound, particularly after the sulfur-containing ester compound is compounded with other sulfur-containing ester compounds by adopting vinyl sulfate, the cycle capacity retention rate, the high-temperature cycle capacity retention rate and the high-temperature capacity recovery rate of the battery are obviously higher than those of the battery prepared by singly compounding only the vinyl sulfate and the sodium fluooxalate, and the possible reasons are that the instability of the vinyl sulfate is caused, and the instability of the vinyl sulfate is greatly improved by the combination of the vinyl sulfate, propylene sulfite, ethylene sulfite, methane disulfonate, 1, 3-propylene sultone, propylene sulfate, pentaerythritol dicyano-sulfate, 1, 4-butanesulfonolide or 2, 4-butanesulfonolide.
It can be seen from examples 53 and 54 that when the nonaqueous electrolyte contains two additives, namely sodium fluooxalate phosphate and a sulfur-containing ester compound, and the sodium fluooxalate phosphate is sodium difluorooxalate phosphate and sodium tetrafluorooxalate phosphate, and the sulfur-containing ester compound is propylene sulfite and vinyl sulfate, the content of the sodium fluooxalate phosphate and the sulfur-containing ester is 1wt%, and the content of the sodium fluooxalate phosphate and the sulfur-containing ester is 2wt%, and the battery cycle capacity retention rate, the high-temperature cycle capacity retention rate and the high-temperature capacity recovery rate data are basically consistent, which indicates that further increase of the content of the additives cannot significantly improve the battery performance.
It is seen from example 28 and comparative example 1 that when the non-aqueous electrolyte is free of the sodium oxalate phosphate additive and the sulfur-containing ester compound additive, the cycle performance, capacity storage and recovery performance of the battery are significantly reduced, and the problem of gassing of the battery is deteriorated.
As can be seen from examples 28 and comparative example 2, when only the sodium fluorooxalate phosphate additive was present in the nonaqueous electrolyte without the sulfur-containing ester compound additive, the cycle performance of the battery was significantly reduced, both the capacity storage and recovery performance were remarkably deteriorated, and the problem of gas generation of the battery was deteriorated.
It is seen from examples 28 and comparative example 3 that when only the sulfur-containing ester compound additive and no sodium fluorooxalate phosphate additive were present in the nonaqueous electrolyte, the cycle performance, capacity storage and recovery performance of the battery were significantly lowered, and the problem of gas generation of the battery was deteriorated.
It is seen from examples 28 and comparative example 4 that when sodium difluorooxalato borate and PS were added to the nonaqueous electrolytic solution, the cycle performance, capacity storage and recovery performance of the battery were significantly reduced, and the problem of gas generation of the battery was deteriorated.
It can be seen from examples 28 and comparative example 5 that when sodium bisfluorosulfonyl imide is used in the nonaqueous electrolyte instead of sodium fluoroacetate additive, the cycle performance, capacity storage and recovery performance of the battery are significantly reduced, and the problem of gas generation of the battery is deteriorated.
It can be seen from examples 28 to 44 and comparative examples 6 to 10 that the performance of the electrolyte using the sulfur-containing ester compound is far superior to that of the electrolyte using the substitution additive such as Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), etc., which may be due to the following reasons: the compound such as sulfur can be combined with sodium fluooxalate phosphate to form SEI film with sulfur/phosphorus/fluorine salt as main component, and the compound component of sulfur/phosphorus/fluorine salt reduces SEI film solubility and improves SEI film stability through structure interlocking effect. And the VC or FEC is adopted, so that the effect is not caused.
Second part
As can be seen from examples 28 to 54, when the sulfur-containing ester compound is one of 1, 3-propenesulfonic acid lactone, pentaerythritol dicyclo sulfate, 1, 4-butanesulfonic acid lactone and 2, 4-butanesulfonic acid lactone, or when the vinyl sulfate is combined with one of 1, 3-propenesulfonic acid lactone, pentaerythritol dicyclo sulfate, 1, 4-butanesulfonic acid lactone and 2, 4-butanesulfonic acid lactone, the sulfur-containing ester compound is compounded with sodium fluoxalate phosphate, and the effect is obvious, and the performance of the battery is obviously superior to that of the vinyl sulfate due to the fact that the battery is singly used; the application preferably adopts one or more of sodium fluooxalate phosphate, 1, 3-propylene sultone, pentaerythritol dicyclo sulfate, 1, 4-butyl sultone and 2, 4-butyl sultone for compound use, or is combined with sodium fluooxalate phosphate after vinyl sulfate is compounded with one of 1, 3-propylene sultone, pentaerythritol dicyclo sulfate, 1, 4-butyl sultone and 2, 4-butyl sultone.
In conclusion, the lithium/sodium ion battery prepared by utilizing the ionic liquid electrolyte provided by the application has high capacity retention rate and good electrochemical performance.
Claims (10)
1. The sodium ion battery electrolyte additive is characterized by comprising at least one of sodium fluooxalate and at least one of sulfur-containing ester compounds.
2. The sodium ion battery electrolyte additive according to claim 1, wherein the mass ratio of the sodium fluoxalate phosphate to the sulfur-containing ester compound is 0.1-3:3-0.1.
3. The sodium ion battery electrolyte additive of claim 1, wherein the sodium fluorooxalate phosphate comprises at least one of sodium difluorooxalate phosphate and sodium tetrafluorooxalate phosphate.
4. The sodium ion battery electrolyte additive of claim 1, wherein the sulfur-containing ester compound comprises at least one of vinyl sulfate, propylene sulfite, ethylene sulfite, methylene methane disulfonate, 1, 3-propenolactone, propylene sulfate, pentaerythritol bicyclosulfate, 1, 4-butanesulfonate, and 2, 4-butanesulfonate.
5. The sodium ion battery electrolyte additive according to claim 4, wherein the sulfur-containing ester compound is one or more of 1, 3-propenesulfonic acid lactone, pentaerythritol double-ring sulfate, 1, 4-butanesulfonic acid lactone and 2, 4-butanesulfonic acid lactone; the mass ratio of the sodium fluooxalate phosphate to the thioester compound is 0.1-2:2-0.1.
6. The additive for sodium ion battery electrolyte according to claim 4, wherein the sulfur-containing ester compound is at least one of ethylene sulfate, propylene sulfite, ethylene sulfite, methylene methane disulfonate, 1, 3-propylene sultone, propylene sulfate, pentaerythritol dicyclo sulfate, 1, 4-butyl sultone and 2, 4-butyl sultone.
7. A sodium ion battery electrolyte comprising a non-aqueous solvent, a sodium salt dissolved in the non-aqueous solvent, and the electrolyte additive of any one of claims 1-6.
8. The sodium ion battery electrolyte according to claim 7, wherein the mass concentration of the electrolyte additive in the electrolyte is 0.2% -6.0%; and/or the number of the groups of groups,
the mass of the nonaqueous solvent accounts for 82-85.4% of the total mass of the electrolyte; the mass of the sodium salt accounts for 5-25% of the total mass of the electrolyte.
9. The electrolyte for sodium ion battery according to claim 7, wherein the nonaqueous solvent is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, vinylene carbonate, methyl formate, ethyl formate, methyl acetate, ethyl propionate, ethyl butyrate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dimethyl sulfoxide, sulfolane, and dimethyl sulfone; and/or the number of the groups of groups,
the sodium salt is at least one selected from sodium hexafluorophosphate, sodium difluorophosphate, sodium tetrafluoroborate, sodium bisfluorosulfonyl imide, sodium bistrifluoromethylsulfonyl imide, sodium bisoxalato borate, sodium difluorooxalato borate and sodium perchlorate.
10. A sodium ion battery comprising the sodium ion battery electrolyte of claim 7.
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