CN113809398B - Electrolyte additive, electrolyte and sodium secondary battery - Google Patents
Electrolyte additive, electrolyte and sodium secondary battery Download PDFInfo
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- CN113809398B CN113809398B CN202110925903.0A CN202110925903A CN113809398B CN 113809398 B CN113809398 B CN 113809398B CN 202110925903 A CN202110925903 A CN 202110925903A CN 113809398 B CN113809398 B CN 113809398B
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- Prior art keywords
- electrolyte
- sodium
- secondary battery
- carbonate
- borate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 137
- 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 title claims abstract description 67
- 239000011734 sodium Substances 0.000 title claims abstract description 67
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 67
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 54
- -1 fluoro oxalic acid sodium phosphate salt Chemical compound 0.000 claims abstract description 54
- 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 claims abstract description 20
- 239000004327 boric acid Substances 0.000 claims abstract description 13
- 150000002825 nitriles Chemical class 0.000 claims abstract description 13
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 16
- 159000000000 sodium salts Chemical class 0.000 claims description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 9
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 238000007600 charging Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000005678 chain carbonates Chemical class 0.000 claims description 6
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- 229960003351 prussian blue Drugs 0.000 claims description 5
- 239000013225 prussian blue Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 3
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 3
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910020808 NaBF Inorganic materials 0.000 claims description 3
- 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 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- PYMZYVXDCJXPAM-UHFFFAOYSA-N ethane-1,2-diol;propanenitrile Chemical compound CCC#N.CCC#N.OCCO PYMZYVXDCJXPAM-UHFFFAOYSA-N 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 claims description 3
- VCYZVXRKYPKDQB-UHFFFAOYSA-N ethyl 2-fluoroacetate Chemical compound CCOC(=O)CF VCYZVXRKYPKDQB-UHFFFAOYSA-N 0.000 claims description 3
- RUXHZGKZALQIBK-UHFFFAOYSA-N ethyl 3,3-difluoropropanoate Chemical compound CCOC(=O)CC(F)F RUXHZGKZALQIBK-UHFFFAOYSA-N 0.000 claims description 3
- HGWFSORGJISSEQ-UHFFFAOYSA-N ethyl 3-fluoropropanoate Chemical compound CCOC(=O)CCF HGWFSORGJISSEQ-UHFFFAOYSA-N 0.000 claims description 3
- OCJKUQIPRNZDTK-UHFFFAOYSA-N ethyl 4,4,4-trifluoro-3-oxobutanoate Chemical compound CCOC(=O)CC(=O)C(F)(F)F OCJKUQIPRNZDTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 claims description 3
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 3
- GCMBIWYUVPAPEG-UHFFFAOYSA-N tris(1,1,1,3,3,3-hexafluoropropan-2-yl) borate Chemical compound FC(F)(F)C(C(F)(F)F)OB(OC(C(F)(F)F)C(F)(F)F)OC(C(F)(F)F)C(F)(F)F GCMBIWYUVPAPEG-UHFFFAOYSA-N 0.000 claims description 3
- DIEXQJFSUBBIRP-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) borate Chemical compound FC(F)(F)COB(OCC(F)(F)F)OCC(F)(F)F DIEXQJFSUBBIRP-UHFFFAOYSA-N 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000002161 passivation Methods 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 9
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910001415 sodium ion Inorganic materials 0.000 description 36
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 30
- 239000010408 film Substances 0.000 description 30
- 239000008151 electrolyte solution Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229940021013 electrolyte solution Drugs 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical class C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- RFRYDXDIJOVXOP-UHFFFAOYSA-N B([O-])(F)F.[Na+] Chemical compound B([O-])(F)F.[Na+] RFRYDXDIJOVXOP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- AGLXPZYGNMGAFU-UHFFFAOYSA-N B([O-])(O)O.[Na+].C(C(=O)O)(=O)O Chemical compound B([O-])(O)O.[Na+].C(C(=O)O)(=O)O AGLXPZYGNMGAFU-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001373 Na3V2(PO4)2F3 Inorganic materials 0.000 description 1
- 229910020892 NaBOB Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 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
- 150000001638 boron Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
Disclosed herein are an electrolyte additive, an electrolyte, and a sodium secondary battery. The electrolyte additive comprises at least one of oxalic acid sodium borate salt and fluoro oxalic acid sodium phosphate salt, a mixture of polyalcohol nitrile, hydrofluoroether and boric acid ester. The electrolyte contains the electrolyte additive. The sodium secondary battery contains the electrolyte. The electrolyte additive can improve the wettability and high-voltage resistance of the electrolyte, is favorable for generating a passivation film and improving the stability of the passivation film, effectively inhibits the expansion, gas production and excessively fast increase of impedance of the sodium secondary battery, and improves the cycle performance, high-voltage resistance and high-temperature storage performance of the sodium secondary battery, thereby improving the safety performance of the sodium secondary battery and prolonging the service life of the sodium secondary battery.
Description
Technical Field
The application relates to the technical field of sodium secondary batteries, in particular to an electrolyte additive, electrolyte and a sodium secondary battery.
Background
The working principle and structure of the sodium ion battery are consistent with those of a lithium battery, the energy density of the sodium ion battery is close to or exceeds that of a lithium iron phosphate battery, the low-temperature performance, the cycle performance and the rapid charge and discharge performance of the sodium ion battery are superior to those of the lithium ion battery, the global sodium resource content is rich, and the price is lower. In the future, due to serious limitation of lithium resources, sodium ion batteries are more widely applied to energy storage and electric vehicle markets.
The sodium ion battery electrolyte is used as a sodium ion transmission carrier in the battery, can improve or promote various performances of the battery, and is an important component of the sodium ion battery. The diameter of sodium ions is larger than that of lithium ions, and the volume expansion and the capacity decay of the lithium electrode material are larger in the deintercalation process.
Since the sodium ion battery is higher than the lithium ion battery, it is necessary to improve the high-voltage resistance of the electrolyte and prevent decomposition. Compared with the traditional lithium ion battery, the metal sodium in the sodium ion battery has higher chemical activity, so that electrolyte solvent, trace moisture and trace impurities are reacted and decomposed on the surface of the negative electrode, and gas is separated out. The gas generation of the sodium ion battery not only generates gas release during the SEI film generation, but also accelerates organic solvent molecules such as: the decomposition of solvent molecules such as ethylene carbonate causes expansion of the battery, the interface of the battery becomes poor, the impedance is increased, and the rate performance, low-temperature performance, cycle performance, high-temperature storage performance and battery safety of the battery are affected. The existing sodium ion electrolyte severely lags behind the development requirement of the sodium ion battery, and cannot perfectly solve the problems, especially when the charging voltage of the sodium ion battery is increased, the problems are added into the bottleneck of wide application of the sodium ion battery.
By combining the above, a novel sodium ion battery electrolyte is needed to be designed at present, and the stability of a battery interface is improved through an electrolyte additive, so that the problems of swelling, impedance increase, gas production and the like during the circulation of the sodium ion battery can be changed, and the novel sodium ion battery electrolyte is an effective means for preparing a high-performance and long-circulation sodium ion battery.
Disclosure of Invention
The purpose of the present application is to overcome the above-mentioned shortcomings of the prior art, and provide an electrolyte additive, an electrolyte and a sodium secondary battery containing the electrolyte, so as to solve the technical problems of swelling, impedance increase, gas production and the like during circulation of the existing sodium secondary battery.
In order to achieve the object of the above application, in one aspect of the present application, an electrolyte additive is provided. The electrolyte additive comprises at least one of oxalic acid sodium borate salt and fluoro oxalic acid sodium phosphate salt, a mixture of polyalcohol nitrile, hydrofluoroether and boric acid ester.
Further, the mass ratio of at least one of oxalic acid sodium borate salt and fluorooxalic acid sodium phosphate salt, polyalcohol nitrile, hydrofluoroether and boric acid ester is 1-5: 1 to 10:1 to 10:0.5 to 5.
Further, the polyol nitrile includes a molecular structural formula I 1 To I 6 At least one of the indicated polyol nitrile compounds:
wherein R is 1 To R 21 Identical or different being C 1 ～C 10 Is a hydrocarbon group.
Further, the hydrofluoroether includes CF 3 -CHF-CF 2 -O-CH 2 -CF 2 -CHF 2 、CF 3 -CHF-CF 2 -O-CH 2 -CF 3 At least one of them.
Further, the borate ester includes at least one of tris (trifluoroethyl) borate and tris (hexafluoroisopropyl) borate.
Further, the oxalic acid sodium borate salt comprises NaBF 2 C 2 O 4 、NaB(C 2 O 4 ) 2 At least one of them.
Further, the sodium salt of fluorooxalic acid phosphate comprises NaPF 2 (C 2 O 4 ) 2 、NaPF 4 C 2 O 4 At least one of them.
In another aspect of the present application, an electrolyte is provided. The electrolyte comprises a nonaqueous solvent, and further comprises sodium salt dissolved in the nonaqueous solvent and an electrolyte additive.
Further, the mass concentration of at least one of oxalic acid sodium borate and fluorooxalic acid sodium phosphate in the electrolyte is 1-5%.
Further, the mass concentration of the polyol nitrile in the electrolyte is 1-10%.
Further, the mass concentration of the hydrofluoroether in the electrolyte is 1-10%.
Further, the mass concentration of the borate in the electrolyte is 0.5% -5%. Further, the mass concentration of the nonaqueous solvent in the electrolyte is 63% -85%.
Further, the nonaqueous solvent includes at least one of cyclic carbonate, chain carbonate, and fluorocarboxylic acid ester.
Further, the concentration of sodium salt in the electrolyte is 0.3-1.5 mol/L.
Further, the sodium salt includes at least one of sodium hexafluorophosphate, sodium perchlorate, sodium nitrate, sodium phosphate, sodium sulfate, sodium fluoride, sodium tetrafluorooxalate phosphate, sodium tetrafluoroborate, and sodium difluorophosphate.
Further, the electrolyte also contains other additives, and the mass concentration of the other additives in the electrolyte is 1-10%.
Specifically, the cyclic carbonate includes at least one of ethylene carbonate, propylene carbonate, and butylene carbonate.
Specifically, the chain carbonate includes at least one of dimethyl carbonate, methylethyl carbonate, and diethyl carbonate.
Specifically, the fluorocarboxylic acid ester includes at least one of ethyl monofluoroacetate, ethyl difluoroacetate, ethyl trifluoroacetate, ethyl 3-fluoropropionate, ethyl 3, 3-difluoropropionate, ethyl 3, 3-trifluoropropionate, ethyl 4, 4-trifluorobutyrate, and ethyl trifluoroacetoacetate.
Specifically, other additives include at least one of 1, 3-propenolactone, vinylene carbonate, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, vinyl sulfate, ethylene carbonate, ethylene sulfite, 1, 4-butanesulfonolide, fluoroethylene carbonate, bis-fluoroethylene carbonate, ethylene glycol bis-propionitrile ether, fluoroethylene carbonate, tris (trimethylsilane) phosphate, and tris (trimethylsilane) borate.
In yet another aspect of the present application, a sodium secondary battery is provided. The sodium secondary battery comprises a positive plate, a negative plate and electrolyte, wherein the electrolyte is the electrolyte.
Further, the positive electrode active material contained in the positive electrode sheet of the sodium secondary battery includes at least one of sodium-transition metal oxide, sodium-transition metal phosphate, sodium-transition metal sulfate, sodium-transition metal Prussian blue compound, and sodium-transition metal Prussian blue compound.
Further, the negative electrode active material contained in the negative electrode sheet of the sodium secondary battery includes at least one of carbon, alloy, transition metal oxide, and sodium-transition metal phosphate.
Further, the highest charging voltage of the sodium secondary battery is 4.1V to 4.5V.
Compared with the prior art, the application has the following beneficial effects:
according to the electrolyte additive, at least one of oxalic acid sodium borate and fluorooxalic acid sodium phosphate, the polyalcohol nitrile, the hydrofluoroether and the boric acid ester are compounded, so that synergism is achieved among all components, wettability and high-voltage resistance of the electrolyte are improved, electrochemical performance of the electrolyte is effectively improved, generation of a passivation film and stability of the passivation film are facilitated, and expansion, gas production and excessively rapid impedance growth of a sodium secondary battery are effectively inhibited. The cycle performance, the high-voltage resistance and the high-temperature storage performance of the sodium secondary battery are improved, so that the safety performance of the sodium secondary battery is improved, and the service life of the sodium secondary battery is prolonged.
The electrolyte contains the electrolyte additive, so that the electrolyte has high compatibility of all components, uniform dispersion and high stability of a dispersion system. The components of the electrolyte additive can play a role in enhancing the effect in the electrolyte, so that the electrolyte has high wettability and high-voltage resistance, has higher electrochemical performance stability, and is beneficial to passivation film generation and improvement of the stability of the passivation film.
The electrolyte of the sodium secondary battery is the electrolyte, so that the sodium secondary battery does not generate phenomena such as expansion and gas production or has small expansion and gas production in circulation, the excessively rapid increase of impedance is avoided, and the electrolyte is excellent in circulation performance, high-voltage resistance and high-temperature storage performance, so that the sodium secondary battery has high safety performance and long service life.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application in the examples and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass in the specification of the embodiment of the present application may be a mass unit well known in the chemical industry field such as μ g, mg, g, kg.
In one aspect, embodiments of the present application provide an electrolyte additive. The electrolyte additive comprises at least one of oxalic acid sodium borate salt, fluoro oxalic acid sodium phosphate salt, a mixture of polyalcohol nitrile, hydrofluoroether and boric acid ester.
Thus, the electrolyte additive is compounded by at least one of oxalic acid sodium borate and fluorooxalic acid sodium phosphate, the polyalcohol nitrile, the hydrofluoroether and the boric acid ester, so that the components have a synergistic effect, can be uniformly dispersed in the electrolyte, and the dispersion system is stable, thereby effectively improving the wettability and high pressure resistance of the electrolyte, and being beneficial to passivation film generation and passivation film stability.
In the embodiment, the electrolyte additive comprises at least one of oxalic acid sodium borate and fluoro oxalic acid sodium phosphate, and the mass ratio of the polyalcohol nitrile to the hydrofluoroether to the boric acid ester is 1-5: 1 to 10:1 to 10:0.5 to 5. By controlling and optimizing the content proportion of the active components contained in the electrolyte additive, the synergistic effect among the components is improved on the basis of fully playing the roles of the components, so that the physical and electrochemical properties of the electrolyte are further improved, and the generation of a passivation film and the stability of the passivation film are facilitated.
The polyol nitrile contained in the electrolyte additive can improve the compatibility of each component of the electrolyte, plays a role in synergy between other components, and can effectively improve the stability of a passivation film, so that the battery can reduce the generation of gas under high temperature and high pressure conditions, reduce the thickness expansion of a sodium secondary battery, prolong the cycle life of the sodium secondary battery and improve the safety performance of the sodium secondary battery.
In addition, the polyol nitrile may form a relatively effective protective film on the surface of the positive electrode, covering its active site, thereby reducing the reactivity of the positive electrode to the electrolyte. Meanwhile, the polyalcohol nitrile can form extremely strong complexing force with metal atoms on the surface of the positive electrode, and can well inhibit the advantages of dissolution of transition metal and oxidative decomposition of electrolyte, and prevent electrode deterioration, thereby effectively improving the high-voltage resistance of the electrolyte.
In one embodiment, the polyol nitrile includes a compound of formula I 1 To I 6 At least one of the indicated polyol nitrile compounds:
wherein R is 1 To R 21 Identical or different being C 1 ～C 10 Is a hydrocarbon group.
In a specific embodiment, the C 1 ～C 10 The alkyl group of (a) may be, but is not limited to, an alkyl group, a fluoroalkyl group, and the like.
Above I 1 To I 6 The shown polyol nitrile compound can fully play the functions of the polyol nitrile, and the tri-nitrile or tetra-nitrile compound can promote the boron salt in the electrolyte to form a solid electrolyte phase interface film on the surface of the positive electrode, and the film forming impedance is smaller. Meanwhile, the tri-nitrile or tetra-nitrile compound can also form a multi-tooth chelation with a positive electrode interface film (Cathode Electrode Interface, abbreviated as CEI film), so that the stability of the CEI film is improved, and the cycle and storage performance of the sodium ion battery under high voltage are improved.
The hydrofluoroether contained in the electrolyte additive can effectively improve the wettability of the electrolyte in the electrode and the cycle performance of the sodium secondary battery, and can improve the oxidation resistance of the electrolyte. The hydrofluoroether and the polyol nitrile can play a role in synergism, effectively slow down the decomposition of a solvent, improve the cycle performance of a battery, reduce the expansion and gas production of an electrode, improve the high-temperature storage performance of a sodium secondary battery, and delay the attenuation of the electrode in a long cycle process.
In an embodiment, the hydrofluoroether comprises CF 3 -CHF-CF 2 -O-CH 2 -CF 2 -CHF 2 (denoted as F-103), CF 3 -CHF-CF 2 -O-CH 2 -CF 3 (denoted as F-103). The hydrofluoroethers can further improve the wettability and oxidation resistance of the electrolyte to the electrode, thereby improving the stability of the electrolyte and the cycle performance of the sodium secondary battery. More importantly, the synergistic effect with the polyol nitrile can be improved, and the stability of the electrolyte is improved.
The borate contained in the electrolyte additive can play a role in synergy with other components, effectively reduce the content of HF in the electrolyte, slow down the precipitation of transition metal, promote circulation in high voltage of 4.4V or above, accelerate dissolution of NaF due to electron deficiency property, and endow CEI with thin film thickness and low impedance.
In an embodiment, the borate ester comprises at least one of tris (trifluoroethyl) borate, tris (hexafluoroisopropyl) borate. The boric acid ester compounds can further improve the synergistic effect with other components, further reduce transition metal precipitation, improve the cyclicity under high voltage, further accelerate NaF dissolution and reduce CEI membrane impedance.
The oxalic acid sodium borate and/or the fluoro oxalic acid sodium phosphate contained in the electrolyte additive can promote the generation of an SEI film, and particularly when the oxalic acid sodium borate and the fluoro oxalic acid sodium phosphate exist simultaneously, the components of the SEI film can be regulated, and the stability of the SEI film can be improved.
In an embodiment, the sodium oxalate borate salt comprises sodium difluoroborate (NaBF) as shown in the following structural formula 2 C 2 O 4 Abbreviated as NaODFB), boron bisoxalateSodium acid (NaB (C) 2 O 4 ) 2 At least one of NaBOB for short);
the sodium fluorooxalate phosphate salt comprises NaPF as shown in the following structural formula 2 (C 2 O 4 ) 2 、NaPF 4 C 2 O 4 At least one of them.
The oxalic acid sodium borate and/or the fluoro oxalic acid sodium phosphate can further facilitate the generation of SEI films and improve the stability of SEI films.
In addition, the electrolyte additive in the embodiment of the application can be mixed according to the contained components or further according to the component content proportion or directly dissolved according to the proportion.
In another aspect, embodiments of the present application provide an electrode solution. The electrolyte comprises a nonaqueous solvent, sodium salt dissolved in the nonaqueous solvent and electrolyte additives.
The electrolyte additive comprises the electrolyte additive of the embodiment of the application, namely the electrolyte of the embodiment of the application contains sodium salt, at least one of oxalic acid sodium borate and fluorooxalic acid sodium phosphate, and a mixture of polyalcohol nitrile, hydrofluoroether and boric acid ester. Therefore, the electrolyte of the embodiment of the application has high compatibility of each component, can be uniformly dispersed, and has high dispersion stability. The components contained in the electrolyte additive can be fully dispersed in the electrolyte, so that the components contained in the electrolyte additive can fully exert a synergistic effect, the electrolyte of the embodiment of the application is endowed with high electrochemical performance stability, such as high wettability and high voltage resistance, and passivation film generation and stability and conductivity improvement of the passivation film are facilitated.
In the embodiment, the mass concentration of at least one of oxalic acid sodium borate salt and fluoro oxalic acid sodium phosphate salt in the electrolyte is 1% -5%, specifically, may be typical but not limited to 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and the like.
In the examples, the mass concentration of the polyol nitrile contained in the electrolyte is 1% to 10%, and specifically may be typical but not limited to 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 6%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% or the like.
In the embodiment, the mass concentration of the hydrofluoroether contained in the electrolyte is 1% to 10%, specifically, it may be typical but not limited to 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 6%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% or the like.
In the embodiment, the mass concentration of the borate ester in the electrolyte is 0.5% to 5%, specifically, may be typical but not limited to 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
The content of the components contained in the electrolyte additive in the embodiment of the application is adjusted, so that the components can be fully mutually dissolved in a nonaqueous solvent, and the stability of an electrolyte dispersion system is further improved. Meanwhile, the components contained in the electrolyte additive can fully play a role in synergism, so that the wettability and high-pressure resistance of the electrolyte can be improved, and the generation of a passivation film and the improvement of the stability of the passivation film are facilitated.
The nonaqueous solvent contained in the electrolyte in the embodiment of the application constructs a solvent carrier of the electrolyte, and can fully dissolve each component and enable each component to fully play a role, and in the embodiment, the mass concentration of the nonaqueous solvent in the electrolyte is 63% -85%, specifically, typical but not limiting concentrations such as 63%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85% and the like. The concentration of the nonaqueous solvent is regulated, so that the content of the solute in the electrolyte can be indirectly regulated, the effect of each solute is improved, and the physical and electrochemical properties of the electrolyte in the embodiment of the application are improved.
In an embodiment, the nonaqueous solvent includes at least one of a cyclic carbonate, a chain carbonate, and a fluorocarboxylic acid ester. In a specific embodiment, the cyclic carbonate comprises at least one of ethylene carbonate, propylene carbonate, and butylene carbonate. The chain carbonate includes at least one of dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate. The fluorocarboxylic acid ester includes at least one of ethyl monofluoroacetate, ethyl difluoroacetate, ethyl trifluoroacetate, ethyl 3-fluoropropionate, ethyl 3, 3-difluoropropionate, ethyl 3, 3-trifluoropropionate, ethyl 4, 4-trifluorobutyrate and ethyl trifluoroacetoacetate. By selecting and controlling the types of the nonaqueous solvents, the effects of the solutes can be further improved, and the physical and electrochemical properties of the electrolyte in the embodiment of the application can be improved.
The sodium salt contained in the electrolyte of the embodiment of the present application may be a sodium salt contained in a sodium ion electrolyte. In an embodiment, the concentration of the sodium salt in the electrolyte is 0.3 to 1.5mol/L, specifically, it may be a typical but not limited to a molar concentration of 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, etc.
In particular embodiments, the sodium salt comprises at least one of sodium hexafluorophosphate, sodium perchlorate, sodium nitrate, sodium phosphate, sodium sulfate, sodium fluoride, sodium tetrafluorooxalate phosphate, sodium tetrafluoroborate, sodium difluorophosphate.
Through controlling and adjusting the concentration of sodium salt and selecting the type of sodium salt, the electrolyte can play a synergistic effect with the additive in the embodiment of the application, improve the sodium ion conductivity of the electrolyte, improve the stability of electrochemical performance, and facilitate the generation of a passivation film and the improvement of the stability and conductivity of the passivation film.
In the examples, the electrolyte solution further contains other additives. In an embodiment, the mass concentration of other additives in the electrolyte is 1% -10%. By adding other additives into the electrolyte, other corresponding properties of the electrolyte of the embodiment of the application or other synergistic or auxiliary effects with the electrolyte additives of the application are further endowed, thereby further enhancing the effect of the electrolyte additives of the above-referenced application in the electrolyte and thereby further enhancing the above-referenced properties of the electrolyte.
In an embodiment, the other additives include at least one of 1, 3-propenesulfonic acid lactone (PS), vinylene Carbonate (VC), vinyl sulfate (DTD), ethylene carbonate (VEC), ethylene Sulfite (ES), and 1, 4-butanesulfonic acid lactone (BS), fluoroethylene carbonate, bis-fluoroethylene carbonate (DFEC), ethylene glycol bis-propionitrile ether (DENE), fluoroethylene carbonate (FEC), tris (trimethylsilane) phosphate (TMSP), and tris (trimethylsilane) borate (TMSB). The addition of the additives can improve the functions of the electrolyte additives applied in the text above, and further facilitate the generation of the passivation film and improve the stability and conductivity of the passivation film.
In addition, the electrolyte according to the embodiment of the present application may be formulated according to the following electrolyte formulation method.
On the other hand, based on the above-mentioned application example electrolyte, the present embodiment also provides a sodium secondary battery. The sodium secondary battery comprises a positive plate, a negative plate and electrolyte. Of course, the sodium secondary battery also includes other necessary components, such as a separator and the like.
Wherein, the electrolyte is the electrolyte of the embodiment of the application of the text above. Because the electrolyte of the sodium secondary battery is the electrolyte of the embodiment of the application of the text, the sodium secondary battery of the application of the text is particularly endowed with no phenomena such as expansion and gas production or little expansion and gas production in circulation based on the components and the characteristics of the electrolyte of the embodiment of the application of the text, and the sodium secondary battery of the application of the text has high circulation performance and high temperature performance, thereby having high safety performance, high multiplying power and long service life.
In an embodiment, the positive electrode active material contained in the positive electrode sheet of the sodium secondary battery includes at least one of sodium-transition metal oxide, sodium-transition metal phosphate and variants, sodium-transition metal sulfate, sodium-transition metal Prussian blue compound, and sodium-transition metal Prussian blue compound.
In an embodiment, the negative electrode active material contained in the negative electrode sheet of the sodium secondary battery includes at least one of carbon, alloy, transition metal oxide, and sodium-transition metal phosphate.
On the basis that electrolyte contained in the sodium secondary battery is the electrolyte of the embodiment of the application of the text, through optimizing electrode materials contained in the positive plate and the negative plate, the electrochemical stability of the electrolyte can be improved together with the electrolyte, the phenomenon of gas production expansion failure of the sodium secondary battery in circulation is reduced or avoided, the excessively rapid increase of impedance is avoided, the circulation performance, the high-voltage resistance performance and the high-temperature storage performance of the sodium secondary battery are improved, the safety performance of the sodium secondary battery is improved, the service life is prolonged, and meanwhile, the working voltage of the sodium secondary battery can be improved. The maximum charging voltage of the sodium secondary battery of the embodiment of the application reaches 4.1V-4.5V.
The electrolyte additive and the electrolyte are taken as examples of the embodiment of the application, and the application is further described in detail.
1. Electrolyte additive examples:
examples A1 to A7
The present examples A1 to A7 provide electrolyte additives, respectively. The electrolyte additives of this example A1 to example A7 each have a component content ratio as shown in table 1 below.
Comparative examples A1 to A5
The present comparative examples A1 to A5 provide electrolyte additives, respectively. The electrolyte additives of this comparative example A1 to comparative example A5 each have a component content ratio as shown in the following table 1.
2. Electrolyte examples:
examples B1 to B7
The present embodiment B1 to embodiment B7 provide electrolytic solutions, respectively. Each electrolyte contains the following basic components and additive components. Wherein, the types and contents of the basic components contained in each electrolyte of examples B1 to B7 are as follows:
mass ratio EC of Ethylene Carbonate (EC), methyl ethyl carbonate (EMC), propylene Carbonate (PC) EMC: pc=1.5:8:0.5, 0.5wt% vc, 1.5wt% fec, 1 wt% PS, 1.0mol/L sodium hexafluorophosphate (NaPF 6 )。
The additive components contained in each of the electrolytes of examples B1 to B7 are shown in table 1 below, and specifically, the electrolyte of example B1 contains the electrolyte additive of example A1 described above, the electrolyte of example B2 contains the electrolyte additive of example A2 described above, and so on, and the electrolyte of example B7 contains the electrolyte additive of example A7 described above. Wherein the concentrations of the components contained in the electrolyte additive in the electrolyte are shown in table 1, respectively.
The electrolyte of each example was prepared as follows:
mixing Ethylene Carbonate (EC), methyl ethyl carbonate (EMC) and Propylene Carbonate (PC) according to the mass ratio EC: PC=1.5:8:0.5 according to the types and the contents of the components contained in the examples B1 to B7, respectively adding 0.5wt% of VC, 1.5wt% of FEC, 1% wt of PS and the examples A1 to A7 to provide electrolyte additives, and fully mixing and dissolving for later use; then 1mol/L sodium hexafluorophosphate (NaPF) was added 6 ) The electrolyte solutions of the respective examples were prepared after sufficiently mixing and dissolving.
Comparative examples B1 to B5
This comparative example B1 provides an electrolyte, which is the base component contained in example B1. I.e. without the electrolyte additive provided in example A1, compared to the electrolyte in example B1.
Electrolyte average base Components provided in comparative examples B2 to B5
The present comparative examples B2 to B5 each provide an electrolyte. Each electrolyte contains the following basic components and additive components. Wherein the kinds and contents of the basic components contained in each of the electrolytes of comparative examples B2 to B5 are the same as those of example B1, the additive components contained in comparative examples B2 to B5 are shown in table 1 below, specifically, the electrolyte of comparative example B2 contains the electrolyte additive of comparative example A2 described above, and the electrolyte of comparative example B5 contains the electrolyte additive of comparative example A5 described above, wherein the concentrations of the components contained in the electrolyte additive are shown in table 1, respectively.
Table 1 additive levels for each example and comparative example combination
3. Sodium ion battery example:
examples C1 to C7 and comparative examples C1 to C5
The present examples C1 to C7 and comparative examples C1 to C5 provide a sodium ion battery, respectively. The sodium ion batteries are assembled into sodium ion batteries according to the following methods:
1) Preparation of a positive plate:
positive electrode active material Na 3 V 2 (PO 4 ) 2 F 3 Conducting agent Superp and binder PVDF according to the mass ratio of 93:3:4 weighing and then dispersing the materials in N-methyl-2-pyrrolidone (NMP) to obtain positive electrode slurry; coating the positive electrode slurry on a positive electrode aluminum foil current collector, drying by a coating machine, and then carrying out vacuum baking at 85 ℃ for 20 hours, and then carrying out quasi-pressing and slitting to obtain a positive electrode plate of the sodium ion battery;
2) Preparing a negative plate:
hard carbon, a conductive agent Superp and CMC: SBR are mixed according to the mass ratio of 95:2:1.5:1.5, stirring, coating, baking, cold pressing and cutting to obtain the negative electrode plate of the sodium ion battery,
3) Electrolyte solution:
with the electrolytes provided in examples B1 to B7 and comparative examples B1 to B5 as the electrolytes of the respective sodium secondary batteries, respectively, the electrolyte provided in specific example B1 as the electrode solution of the sodium secondary battery in example C1, the electrolyte provided in example B2 as the electrode solution of the sodium secondary battery in example C2, and so on, the electrolyte provided in example B7 as the electrode solution of the sodium secondary battery in example C7, the electrolyte provided in comparative example B1 as the electrode solution of the sodium secondary battery in comparative example C1, and the electrolyte provided in comparative example B5 as the electrode solution of the sodium secondary battery in comparative example C5.
4) Assembling of sodium secondary battery:
winding the positive plate, the negative plate, the electrolyte and the isolating film into a sodium ion battery cell, packaging with an aluminum plastic film, respectively injecting the prepared electrolyte into the battery cells of each embodiment in a glove box with the dew point controlled below-40 ℃, vacuum packaging, standing for 24 hours, and carrying out conventional formation and capacity division according to the following steps: constant-current charging is carried out at 0.05C to 3.4V, constant-current charging is carried out at 0.2C to 3.95V, and secondary vacuum sealing and air extraction are carried out; then charging to 4.1V with constant current of 0.2C, standing for 24 hours at normal temperature, charging with constant voltage of 0.2C and 4.1V, and stopping current of 0.05C to obtain the sodium ion battery for standing.
5) Sodium ion battery performance test:
the sodium ion battery of each example assembled in section 4) was subjected to the following performance tests:
51 High temperature storage performance test):
the initial thickness T0 of the sodium-ion battery of each example assembled in section 4) was measured at room temperature in a state of 4.1V full charge, and then the thickness T1 was measured after the full charge was stored in an oven at 85 ℃ for 4 hours. The thickness expansion ratio= (T1/T0-1) 100%, and the capacity remaining ratio=c1/c0 100% were measured and shown in table 2 below.
52 Normal temperature cycle performance test):
the sodium ion battery of each example assembled in section 4) was charged to 4.1V at constant current of 0.5C at normal temperature and then the constant voltage charging current was reduced to 0.02C, and then discharged to 3.0V at constant current of 0.5C, and the cycle was repeated for 1000 weeks, the weekly discharge capacity was recorded, and the capacity retention rate of the high temperature cycle was calculated as follows: n-week capacity retention = n-week discharge capacity/1-week discharge capacity 100%, the measured results are shown in table 2 below.
53 Normal temperature cycle thickness expansion test):
the thickness of the sodium ion battery of each example assembled in section 4) was measured at room temperature at a voltage of 4.1V before and after the cycle, and the thickness expansion ratio = (T1/T0-1) = (100%, and the measured results are shown in table 2 below.
54 Normal temperature high pressure cycle thickness expansion test):
the sodium ion battery of each example assembled in section 4) was charged to 4.3V at constant current at normal temperature with a current of 0.5C, then the constant voltage 4.3V charging current was reduced to 0.02C, then discharged to 3.0V with a current of 0.5C, and so on for 500 weeks. The thickness was measured at 4.3V before and after the cycle at room temperature, and the thickness expansion ratio= (T1/T0-1) ×100% was measured, and the results are shown in table 2 below.
TABLE 2
From the test results in Table 2, 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 through using the polyalcohol nitrile, the hydrofluoroether, the boric acid ester and the sodium difluoroborate (phosphate), the electrode expansion rate is obviously improved, and after the battery is stored at a circulating temperature and a high temperature, the battery has controllable volume expansion and no obvious gas generation.
The test performance in table 2 of the sodium secondary batteries in comparative example C6 and example C7 shows that the upper limit amount of the electrolyte additive content (example C6) in the embodiment of the present application in the electrolyte has no significant performance difference compared with other embodiments (examples C1 to C5). The addition of the lower limit amount (example C7) at the same time was slightly inferior in comparison with the other examples (examples C1 to C5), but was significantly improved in comparison with comparative example C1.
Since the comparative example C1 contains only the basic electrolyte, that is, no electrolyte additive according to the embodiment of the present application, the cycle performance of the sodium secondary battery in comparative example C1 is significantly low, and at the same time, when the expansion rate of the sodium secondary battery is higher than 8%, significant gas is generated, which causes rapid decay of the cycle life of the sodium secondary battery, and at the same time, the high internal pressure of the sodium secondary battery also easily causes a safety risk of bursting or short circuit.
As can be seen from comparative example C2, oxalic acid sodium borate salt and fluoro oxalic acid sodium phosphate salt can effectively improve the cycle performance of the battery, but the effect of improving the thickness expansion of the battery is not obvious; it can be seen from comparative examples C3 and C4 that the performance was improved except that the high-voltage expansion of the battery was not improved; c5 shows that the polyol nitrile can effectively improve the expansion of the battery, especially the thickness expansion under high voltage, and has no obvious improvement on the cycle performance
Further, in the electrolyte solution contained in the sodium secondary battery of the embodiment C1 to the embodiment C6 and the comparative example C2 to the comparative example C5, at least one of oxalic acid sodium borate salt and fluorooxalic acid sodium phosphate salt contained in the electrolyte solution additive, polyalcohol nitrile, hydrofluoroether, boric acid ester and other components play a role in synergism in the electrolyte solution, so that the electrochemical properties of the electrolyte solution, the electrode and the like are effectively improved, the generation of gas is reduced under the conditions of high temperature and high pressure, the thickness expansion of the sodium secondary battery is reduced, the excessively rapid increase of impedance is avoided, and the electrochemical properties such as the cycle property, the high-voltage resistance property, the high-temperature storage property, the safety property and the like of the sodium secondary battery are improved.
The foregoing description of the preferred embodiment of the present invention is not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (8)
1. An electrolyte, characterized in that: the electrolyte additive comprises a mixture of at least one of oxalic acid sodium borate and fluorooxalic acid sodium phosphate, a polyalcohol nitrile, a hydrofluoroether and a boric acid ester;
the polyol nitrile comprises a molecular structural formula I 1 To I 6 At least one of the indicated polyol nitrile compounds:
Ⅰ 1 Ⅰ 2
Ⅰ 3 Ⅰ 4
Ⅰ 5 Ⅰ 6 ；
wherein R is 1 To R 21 Identical or different being C 1 ~C 10 Alkyl of (a);
the hydrofluoroether comprises CF 3 -CHF-CF 2 -O-CH 2 -CF 2 -CHF 2 、CF 3 -CHF-CF 2 -O-CH 2 -CF 3 At least one of (a) and (b);
the borate ester comprises at least one of tri (trifluoroethyl) borate and tri (hexafluoroisopropyl) borate.
2. The electrolyte of claim 1, wherein: at least one of oxalic acid sodium borate and fluorooxalic acid sodium phosphate, polyalcohol nitrile, hydrofluoroether and boric acid ester with the mass ratio of 1-5: 1-10: 1-10: 0.5 to 5.
3. The electrolyte according to claim 1 or 2, characterized in that: the oxalic acid sodium borate salt comprises NaBF 2 C 2 O 4 、NaB(C 2 O 4 ) 2 At least one of (a) and (b);
the sodium fluorooxalate phosphate comprises NaPF 2 (C 2 O 4 ) 2 、NaPF 4 C 2 O 4 At least one of them.
4. The electrolyte of claim 1, wherein: the mass concentration of at least one of oxalic acid sodium borate and fluorooxalic acid sodium phosphate in the electrolyte is 1% -5%; and/or
The mass concentration of the polyol nitrile in the electrolyte is 1% -10%; and/or
The mass concentration of the hydrofluoroether in the electrolyte is 1% -10%; and/or
The mass concentration of the borate in the electrolyte is 0.5% -5%; and/or
The mass concentration of the nonaqueous solvent in the electrolyte is 63% -85%; and/or
The nonaqueous solvent comprises at least one of cyclic carbonate, chain carbonate and fluorocarboxylic acid ester; and/or
The concentration of the sodium salt in the electrolyte is 0.3-1.5 mol/L; and/or
The sodium salt comprises at least one of sodium hexafluorophosphate, sodium perchlorate, sodium nitrate, sodium phosphate, sodium sulfate, sodium fluoride, sodium tetrafluorooxalate phosphate, sodium tetrafluoroborate and sodium difluorophosphate; and/or
The electrolyte also contains other additives, and the mass concentration of the other additives in the electrolyte is 1% -10%.
5. The electrolyte according to claim 4, wherein: the cyclic carbonate includes at least one of ethylene carbonate, propylene carbonate, and butylene carbonate;
the chain carbonate comprises at least one of dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate;
the fluorocarboxylic acid ester comprises at least one of ethyl monofluoroacetate, ethyl difluoroacetate, ethyl trifluoroacetate, ethyl 3-fluoropropionate, ethyl 3, 3-difluoropropionate, ethyl 3, 3-trifluoropropionate, ethyl 4, 4-trifluorobutyrate and ethyl trifluoroacetoacetate.
6. The electrolyte according to claim 4, wherein: the other additives include at least one of 1, 3-propenolactone, vinylene carbonate, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, vinyl sulfate, ethylene carbonate, ethylene sulfite, 1, 4-butanesulfonolide, fluoroethylene carbonate, bis-fluoroethylene carbonate, ethylene glycol bis-propionitrile ether, fluoroethylene carbonate, tris (trimethylsilane) phosphate, and tris (trimethylsilane) borate.
7. The utility model provides a sodium secondary battery, includes positive plate, negative plate and electrolyte, its characterized in that: the electrolyte comprising the electrolyte of any one of claims 1-6.
8. The sodium secondary battery according to claim 7, wherein: the positive electrode active material contained in the positive electrode sheet of the sodium secondary battery comprises at least one of sodium-transition metal oxide, sodium-transition metal phosphate, sodium-transition metal sulfate and sodium-transition metal Prussian blue compound; and/or
The negative electrode active material contained in the negative electrode sheet of the sodium secondary battery comprises at least one of carbon, alloy, transition metal oxide and sodium-transition metal phosphate; and/or
The highest charging voltage of the sodium secondary battery is 4.1V-4.5V.
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| CN114497744A (en) * | 2022-03-07 | 2022-05-13 | 天津市捷威动力工业有限公司 | Sodium ion electrolyte and application thereof, sodium ion battery and preparation method thereof |
| CN117321061A (en) * | 2022-06-24 | 2023-12-29 | 时代思康新材料有限公司 | Sodium difluoro oxalate borate, and preparation method and application thereof |
| CN118648152A (en) * | 2022-07-11 | 2024-09-13 | 宁德时代新能源科技股份有限公司 | Sodium ion battery electrolyte, sodium ion battery containing same and electricity utilization device |
| CN117913345A (en) * | 2022-10-19 | 2024-04-19 | 深圳新宙邦科技股份有限公司 | Sodium ion secondary battery |
| WO2024086987A1 (en) * | 2022-10-24 | 2024-05-02 | 宁德时代新能源科技股份有限公司 | Mixed additive, electrolyte solution for sodium secondary battery, sodium secondary battery, battery module, battery pack, and electric device |
| CN115663287B (en) * | 2022-12-13 | 2023-04-04 | 湖南法恩莱特新能源科技有限公司 | High-pressure-resistant flame-retardant sodium ion electrolyte, preparation method thereof and sodium ion battery |
| CN118352627A (en) * | 2023-01-16 | 2024-07-16 | 宁德时代新能源科技股份有限公司 | Electrolyte for sodium secondary battery, and electricity using device |
| CN118352642A (en) * | 2023-01-16 | 2024-07-16 | 宁德时代新能源科技股份有限公司 | Electrolyte for sodium secondary battery, and electricity using device |
| WO2024152146A1 (en) * | 2023-01-16 | 2024-07-25 | 宁德时代新能源科技股份有限公司 | Non-aqueous electrolyte, sodium-ion battery containing same, and electrical apparatus |
| CN115799645B (en) * | 2023-02-06 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Electrolyte for sodium secondary battery, sodium secondary battery and electricity utilization device |
| CN117219870B (en) * | 2023-11-09 | 2024-04-16 | 宁德时代新能源科技股份有限公司 | Electrolyte, sodium secondary battery and electricity utilization device |
| CN117219867A (en) * | 2023-11-09 | 2023-12-12 | 宁德时代新能源科技股份有限公司 | Electrolyte, sodium secondary battery and electricity utilization device |
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