CN113809398A - Electrolyte additive, electrolyte and sodium secondary battery - Google Patents
Electrolyte additive, electrolyte and sodium secondary battery Download PDFInfo
- Publication number
- CN113809398A CN113809398A CN202110925903.0A CN202110925903A CN113809398A CN 113809398 A CN113809398 A CN 113809398A CN 202110925903 A CN202110925903 A CN 202110925903A CN 113809398 A CN113809398 A CN 113809398A
- Authority
- CN
- China
- Prior art keywords
- sodium
- electrolyte
- secondary battery
- carbonate
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 144
- 239000011734 sodium Substances 0.000 title claims abstract description 108
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 108
- 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 107
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 56
- -1 polyol nitriles Chemical class 0.000 claims abstract description 61
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims description 22
- 159000000000 sodium salts Chemical class 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 13
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003125 aqueous solvent Substances 0.000 claims description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000005678 chain carbonates Chemical class 0.000 claims description 6
- 238000007600 charging Methods 0.000 claims description 6
- 150000005676 cyclic carbonates Chemical class 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
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 4
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 4
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 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
- 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
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910019396 NaPF4 Inorganic materials 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
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 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
- FMDMKDPUFQNVSH-UHFFFAOYSA-N ethyl 3,3,3-trifluoropropanoate Chemical compound CCOC(=O)CC(F)(F)F FMDMKDPUFQNVSH-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
- PSRZMXNNQTWAGB-UHFFFAOYSA-N ethyl 4,4,4-trifluorobutanoate Chemical compound CCOC(=O)CCC(F)(F)F PSRZMXNNQTWAGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 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
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 14
- 238000003860 storage Methods 0.000 abstract description 11
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 229910001415 sodium ion Inorganic materials 0.000 description 38
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 30
- 230000002195 synergetic effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000670 limiting effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-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
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229960003351 prussian blue Drugs 0.000 description 4
- 239000013225 prussian blue Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 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 compound 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 3
- 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
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 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
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012528 membrane Substances 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
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CLODVVCTNPJPIG-UHFFFAOYSA-J 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+].[Na+].[Na+].[Na+] Chemical compound 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+].[Na+].[Na+].[Na+] CLODVVCTNPJPIG-UHFFFAOYSA-J 0.000 description 1
- 229910001373 Na3V2(PO4)2F3 Inorganic materials 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910020892 NaBOB Inorganic materials 0.000 description 1
- 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 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
- 230000009172 bursting Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 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
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 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
- 238000004519 manufacturing process Methods 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
- 230000036961 partial effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 235000021317 phosphate Nutrition 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
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 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
- 238000009461 vacuum packaging 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
The application discloses an electrolyte additive, an electrolyte and a sodium secondary battery. The electrolyte additive comprises a mixture of at least one of sodium oxalato borate salt, sodium fluorooxalato phosphate salt, polyol nitriles, hydrofluoroethers, and borate esters. The electrolyte contains the electrolyte additive of the present application. The sodium secondary battery contains the electrolyte of the present application. The electrolyte additive can improve the wettability and the high-voltage resistance of electrolyte, is favorable for generating a passivation film and improving the stability of the passivation film, effectively inhibits the expansion, gas generation and impedance of the sodium secondary battery from excessively increasing, and improves the cycle performance, the high-voltage resistance and the high-temperature storage performance of the sodium secondary battery, thereby also 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, and the sodium ion battery has rich global sodium resource content and lower price. The sodium ion battery is severely limited by lithium resources in the future, and can be more widely applied to the markets of energy storage and electric vehicles.
The electrolyte of the sodium ion battery 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 the sodium ions is larger than that of the lithium ions, and the sodium ions have the problems of larger volume expansion, easier capacity attenuation and the like in the de-intercalation process compared with the lithium electrode material.
Since the sodium ion battery is higher than the lithium ion battery, it is necessary to improve the high pressure resistance of the electrolyte to prevent decomposition. Compared with the traditional lithium ion battery, the metal sodium in the sodium ion battery has higher chemical activity, so that an electrolyte solvent, trace moisture and trace impurities are violently reacted and decomposed on the surface of a negative electrode to separate out gas. Gas generated from the sodium ion battery not only generates gas release during the generation of the SEI film, but also accelerates organic solvent molecules such as: the decomposition of solvent molecules such as ethylene carbonate and the like causes battery expansion, battery interface deterioration and impedance increase, and battery rate performance, low-temperature performance, cycle performance, high-temperature storage performance and battery safety are influenced. The current sodium ion electrolyte seriously lags the development requirement of the sodium ion battery, and the problem cannot be perfectly solved, especially when the charging voltage of the sodium ion battery is increased, the problem is more added to the bottleneck of the wide application of the sodium ion battery.
In summary, it is necessary to design a novel sodium ion battery electrolyte, and the stability of the battery interface is improved by the electrolyte additive, so that the problems of swelling, impedance increase, gas generation and the like of the sodium ion battery during the circulation period can be solved, and the method is an effective means for preparing the high-performance long-circulation sodium ion battery.
Disclosure of Invention
The present application is directed to overcome the above-mentioned deficiencies in the prior art, and provides an electrolyte additive, an electrolyte and a sodium secondary battery containing the electrolyte, so as to solve the technical problems of large expansion, increased impedance, gas generation and the like during the cycle of the conventional sodium secondary battery.
To achieve the above object, according to one aspect of the present application, there is provided an electrolyte additive. The electrolyte additive comprises a mixture of at least one of sodium oxalato borate salt, sodium fluorooxalato phosphate salt, polyol nitriles, hydrofluoroethers, and borate esters.
Further, the mass ratio of at least one of sodium oxalatoborate and sodium fluorooxalatophosphate, polyol nitrile, hydrofluoroether and boric acid ester is 1-5: 1-10: 1-10: 0.5 to 5.
Further, the polyol nitriles include the molecular structural formula I1To I6At least one of the polyol nitrile compounds:
wherein R is1To R21Identical or different is C1～C10Alkyl group of (1).
Further, hydrofluoroethers include CF3-CHF-CF2-O-CH2-CF2-CHF2、CF3-CHF-CF2-O-CH2-CF3At least one of (1).
Further, the borate ester includes at least one of tris (trifluoroethyl) borate ester, tris (hexafluoroisopropyl) borate ester.
Further, the sodium oxalato borate salt includes NaBF2C2O4、NaB(C2O4)2At least one of (1).
Further, the sodium fluorooxalate phosphate salt includes NaPF2(C2O4)2、NaPF4C2O4At least one of (1).
In another aspect of the present application, an electrolyte is provided. The electrolyte comprises a non-aqueous solvent, and also comprises a sodium salt dissolved in the non-aqueous solvent and the electrolyte additive.
Further, the mass concentration of at least one of the sodium oxalato borate salt and the sodium fluorooxalato phosphate salt in the electrolyte is 1-5%.
Further, the mass concentration of the polyol nitrile in the electrolyte is 1-10%.
Furthermore, 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% to 85%.
The nonaqueous solvent further includes at least one of a cyclic carbonate, a chain carbonate, and a fluorocarboxylic acid ester.
Furthermore, the concentration of the 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.
Furthermore, 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, ethyl methyl 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, 3-trifluoropropionate, ethyl 4,4, 4-trifluorobutyrate, and ethyl trifluoroacetoacetate.
Specifically, the other additive includes at least one of 1, 3-propylene sultone, vinylene carbonate, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, vinyl sulfate, vinyl ethylene carbonate, ethylene sulfite, 1, 4-butanesultone, fluoroethylene carbonate, difluoroethylene carbonate, ethylene glycol dipropionitrile 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, and 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 a sodium-transition metal oxide, a sodium-transition metal phosphate and a variant thereof, a sodium-transition metal sulfate, a sodium-transition metal prussian blue-based compound, and a sodium-transition metal prussian blue-based compound.
Further, the negative electrode active material contained in the negative electrode sheet of the sodium secondary battery includes at least one of carbon species, alloy species, transition metal oxides, and sodium-transition metal phosphates.
Further, the maximum charge voltage of the sodium secondary battery is 4.1V to 4.5V.
Compared with the prior art, the method has the following beneficial effects:
according to the electrolyte additive, at least one of sodium oxalato borate salt and fluoro sodium oxalato phosphate salt, polyol nitrile, hydrofluoroether and boric acid ester are compounded, so that the components have a synergistic effect, the wettability and high pressure resistance of the electrolyte are improved, the electrochemical performance of the electrolyte is effectively improved, a passivation film is favorably generated, the stability of the passivation film is favorably improved, and the expansion, gas production and impedance over-quick increase 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 contained electrolyte additive has the advantages that each component can play a synergistic effect in the electrolyte, the electrolyte is endowed with high wettability and high pressure resistance, the electrochemical performance stability is high, and the generation of a passive film and the stability of the passive film are facilitated.
The electrolyte of the sodium secondary battery is the electrolyte, so that the sodium secondary battery does not expand or generate gas or has small expansion and gas generation in circulation, the impedance is prevented from being excessively rapidly increased, and the circulation performance, the high-voltage resistance and the high-temperature storage performance of the sodium secondary battery are excellent, so that the sodium secondary battery has high safety performance and long service life.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, 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 merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (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, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application 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 weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
In one aspect, an electrolyte additive is provided in embodiments herein. The electrolyte additive of the embodiment of the application comprises a mixture of at least one of sodium oxalato borate salt and sodium fluorooxalato phosphate salt, polyalcohol nitriles, hydrofluoroether and boric acid ester.
Therefore, the electrolyte additive is compounded by at least one of sodium oxalato borate salt and sodium fluorooxalate phosphate salt, the polyol nitrile, the hydrofluoroether and the boric acid ester, so that the components have a synergistic effect, the components can be uniformly dispersed in the electrolyte, and a dispersion system is stable, so that the wettability and the high-pressure resistance of the electrolyte are effectively improved, and the electrolyte additive is beneficial to generating a passivation film and improving the stability of the passivation film.
In the embodiment, the electrolyte additive in the embodiment of the application contains at least one of sodium oxalato borate salt and sodium fluorooxalato phosphate salt, polyol nitrile, hydrofluoroether and boric acid ester in a mass ratio of 1-5: 1-10: 1-10: 0.5 to 5. By controlling and optimizing the content ratio of the active components contained in the electrolyte additive, the synergistic effect among the components is improved on the basis of fully playing the role of each component, so that the physical and electrochemical properties of the electrolyte are further improved, and the generation of a passive film and the stability of the passive film are facilitated.
The polyalcohol nitrile contained in the electrolyte additive can improve the compatibility of each component of the electrolyte, has a synergistic effect with other components, and can effectively improve the stability of a passive film, so that the generation of gas is reduced, the thickness expansion of a sodium secondary battery is reduced, the cycle life of the sodium secondary battery is prolonged, and the safety performance of the sodium secondary battery is improved.
In addition, the polyol nitrile can form a relatively effective protective film on the surface of the positive electrode to cover the active site, so that the reactivity of the positive electrode to the electrolyte is reduced. Meanwhile, the polyalcohol nitrile can form strong complexing force with metal atoms on the surface of the anode, can well inhibit the advantages of transition metal dissolution and electrolyte oxidative decomposition, and prevent the deterioration of an electrode, thereby effectively improving the high pressure resistance of the electrolyte.
In one embodiment, the polyol nitriles comprise the molecular structure I1To I6At least one of the polyol nitrile compounds:
wherein R is1To R21Identical or different is C1～C10Alkyl group of (1).
In a specific embodiment, the C1～C10The alkyl group of (a) may be, but is not limited to, an alkyl group, a fluoroalkyl group, or the like.
Above I1To I6The polyol nitrile compound can fully exert the functions of the polyol nitrile, and the trinitrile or tetranitrile compound can promote the boron salt in the electrolyte to form a solid electrolyte phase interface film on the surface of the positive electrode, so that the film forming resistance is lower. Meanwhile, the trinitrile or tetranitrile compound can form a multidentate chelation effect with a Cathode Electrode Interface (CEI film for short) to improve the stability of the CEI film, so that the cycle and storage performance of the sodium-ion battery under high voltage are improved.
The hydrofluoroether contained in the electrolyte additive disclosed by the embodiment of the application can effectively improve the wettability of the electrolyte in an electrode and the cycle performance of a 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 the battery, reduce the expansion and gas generation of the electrode, improve the high-temperature storage performance of the sodium secondary battery, and delay the attenuation of the electrode in a long cycle process.
In embodiments, the hydrofluoroether comprises CF3-CHF-CF2-O-CH2-CF2-CHF2(denoted F-103), CF3-CHF-CF2-O-CH2-CF3(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 between the electrolyte and the polyol nitrile can be improved, and the stability of the electrolyte is improved.
Boric acid ester contained in the electrolyte additive can play a synergistic role with other components, the content of HF in the electrolyte is effectively reduced, the precipitation of transition metal is slowed down, the circulation is promoted in high voltage of 4.4V or above, the NaF dissolution is accelerated due to the electron-deficient property, and the CEI film is endowed with thin thickness and low impedance.
In an embodiment, the borate ester includes at least one of tris (trifluoroethyl) borate ester, tris (hexafluoroisopropyl) borate ester. The borate compounds can further improve the effect of synergistic effect with other components, further reduce the precipitation of transition metals, improve the cyclicity under high voltage, further accelerate the dissolution of NaF and reduce the resistance of CEI films.
The sodium oxalato borate salt and/or the sodium fluorooxalato phosphate salt contained in the electrolyte additive can promote the generation of the SEI film, and especially when the sodium oxalato borate salt and the sodium fluorooxalato phosphate salt exist simultaneously, the components of the SEI film can be adjusted, and the stability of the SEI film can be improved.
In the examples, the sodium oxalato salt includes sodium difluorooxalato (NaBF) represented by the following structural formula2C2O4NaODFB for short), sodium bisoxalato (NaB (C)2O4)2NaBOB for short);
the fluoro oxalic acid sodium phosphate comprises NaPF shown in the following structural formula2(C2O4)2、NaPF4C2O4At least one of (1).
The sodium oxalato borate salt and/or the sodium fluorooxalato phosphate salt can further facilitate the generation of the SEI film and improve the stability of the SEI film.
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 in proportion or directly dissolved according to the proportion.
In another aspect, an embodiment of the present application provides an electrode solution. The electrolyte of the embodiment of the application comprises a non-aqueous solvent, and also comprises a sodium salt and an electrolyte additive dissolved in the non-aqueous solvent.
The electrolyte additive contained in the electrolyte of the embodiment of the present application includes the electrolyte additive of the embodiment of the present application, that is, the electrolyte of the embodiment of the present application contains a mixture including at least one of sodium oxalato borate salt, sodium fluorooxalato phosphate salt, polyol nitrile, hydrofluoroether, and borate in addition to the sodium salt. 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 provided by the embodiment of the invention has high electrochemical performance stability, such as high wettability and high pressure resistance, and the electrolyte is beneficial to generation of a passivation film and improvement of stability and conductivity of the passivation film.
In the examples of the present application, the mass concentration of at least one of the sodium oxalato borate salt and the sodium fluorooxalato phosphate salt contained in the electrolyte solution of the examples is 1% to 5%, and specifically, may be a typical but non-limiting concentration such as 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 solution is 1% to 10%, and may be a typical, but not limiting, concentration such as 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%.
In the examples, the mass concentration of the hydrofluoroether in the electrolyte is 1% to 10%, and may be a typical but non-limiting concentration such as 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%.
In the examples, the boric acid ester may be present in the electrolyte at a concentration of 0.5% to 5% by mass, specifically, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% by mass, which is typical but not limiting.
The content of the components contained in the electrolyte additive of the embodiment of the application in the electrolyte is adjusted, so that the components can be fully mutually dissolved in the non-aqueous solvent, and the stability of the electrolyte dispersion system is further improved. Meanwhile, each component contained in the electrolyte additive provided by the embodiment of the application can fully play a synergistic role, so that the wettability and the high-voltage resistance of the electrolyte provided by the embodiment of the application are improved, and the electrolyte additive is favorable for generating a passivation film and improving the stability of the passivation film.
The nonaqueous solvent contained in the electrolyte solution of the embodiments of the present application constitutes a solvent carrier of the electrolyte solution, and can sufficiently dissolve each component and make each component sufficiently function, and in the embodiments, the mass concentration of the nonaqueous solvent in the electrolyte solution is 63% to 85%, and specifically, may be a typical but non-limiting concentration such as 63%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, and the like. By adjusting the concentration of the non-aqueous solvent, the content of the solute in the electrolyte can be indirectly adjusted, so that the effect of each solute is improved, and the physical and electrochemical performances 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 includes at least one of ethylene carbonate, propylene carbonate, and butylene carbonate. The chain carbonate includes at least one of dimethyl carbonate, ethyl methyl 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, 3-trifluoropropionate, ethyl 4,4, 4-trifluorobutyrate, and ethyl trifluoroacetate. By selecting and controlling the kind of the nonaqueous solvent, the effect of each solute can be further improved, and the physical and electrochemical properties of the electrolyte solution of the embodiment of the present application, such as those described above, can be improved.
The sodium salt contained in the electrolyte of the embodiment of the application can be the sodium salt contained in the sodium ion electrolyte. In an embodiment, the concentration of the sodium salt in the electrolyte is 0.3 to 1.5mol/L, and specifically may be a typical but non-limiting molar concentration such as 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, and the like.
In specific embodiments, the sodium salt comprises at least one of sodium hexafluorophosphate, sodium perchlorate, sodium nitrate, sodium phosphate, sodium sulfate, sodium fluoride, sodium tetrafluorooxalate, sodium tetrafluoroborate, and sodium difluorophosphate.
Through controlling and adjusting the concentration of the sodium salt and selecting the type of the sodium salt, the electrolyte can play a role in synergy with the additives in the embodiments of the application, so that the conductivity of sodium ions of the electrolyte in the embodiments of the application is improved, the stability of electrochemical properties is improved, and the electrolyte is beneficial to generating a passivation film and improving the stability and conductivity of the passivation film.
In addition to the above electrolyte examples, in the examples, the electrode solution of the embodiments of the present application further contains other additives. In the embodiment, the mass concentration of other additives in the electrolyte is 1-10%. By adding other additives into the electrolyte, corresponding other performances of the electrolyte in the embodiment of the application are further endowed, or other synergistic effects or auxiliary effects with the electrolyte additive in the application are further improved, so that the effect of the electrolyte additive in the application in the electrolyte is further improved, and the performances of the electrolyte are further improved.
In an embodiment, the other additive includes at least one of 1, 3-Propylene Sultone (PS), Vinylene Carbonate (VC), vinyl sulfate (DTD), Vinyl Ethylene Carbonate (VEC), Ethylene Sulfite (ES), and 1, 4-Butane Sultone (BS), fluoroethylene carbonate, difluoroethylene carbonate (DFEC), ethylene glycol dipropionitrile ether (done), fluoroethylene carbonate (FEC), tris (trimethylsilane) phosphate (TMSP), and tris (trimethylsilane) borate (TMSB). The addition of the additives can improve the function of the electrolyte additive applied in the above text, and is further beneficial to the generation of a passivation film and the improvement of the stability and the conductivity of the passivation film.
The electrolyte solution of the examples of the present application can be prepared by the following electrolyte solution preparation method.
On the other hand, based on the electrolyte of the examples of the above-mentioned application, the present example also provides a sodium secondary battery. The sodium secondary battery of the embodiment of the application comprises a positive plate, a negative plate and electrolyte. Of course, the sodium secondary battery includes necessary other components such as a separator and the like.
The electrolyte is the electrolyte of the embodiment of the above text application. The electrolyte of the sodium secondary battery in the embodiment of the application is the electrolyte in the embodiment of the application, and based on the components and the characteristics of the electrolyte in the embodiment of the application, the sodium secondary battery in the embodiment of the application is particularly endowed with no phenomena of expansion, gas generation and the like or small expansion and gas generation in the cycle, and has high cycle performance and high-temperature performance, thereby having high safety performance and rate multiplication 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 a sodium-transition metal oxide, a sodium-transition metal phosphate and a sodium-transition metal variant, a sodium-transition metal sulfate, a sodium-transition metal prussian blue-based compound, and a sodium-transition metal prussian blue-based 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 species, alloy species, transition metal oxide, and sodium-transition metal phosphate.
On the basis that the electrolyte contained in the sodium secondary battery is the electrolyte of the embodiment of the above text application, by optimizing the electrode materials contained in the positive plate and the negative plate, the electrolyte can be mixed with the electrolyte, the electrochemical stability of the electrolyte is improved, the phenomenon of bad gas expansion of the sodium secondary battery in circulation is reduced or avoided, and the impedance is prevented from increasing too fast, 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, the service life is prolonged, and the working voltage of the sodium secondary battery can be improved. The maximum charging voltage of the sodium secondary battery in the embodiment of the invention reaches 4.1V-4.5V.
The present application will now be described in further detail with reference to examples of electrolyte additives and electrolytes in the examples of the present application.
1. Electrolyte additive examples:
example A1 to example A7
Electrolyte additives were provided in examples A1 through A7, respectively. The electrolyte additive of this example a1 to example a7 contained the components in the proportions indicated in table 1 below.
Comparative examples A1 to A5
Electrolyte additives are provided in comparative examples a1 through a5, respectively. The electrolyte additives of this comparative example a1 to comparative example a5 contained the components in the content ratios to the components, respectively, as shown in table 1 below.
2. Electrolyte example:
example B1 to example B7
Examples B1 to B7 each provide an electrolyte. Each electrolyte contains the following base component and additive component. The types and contents of the basic components contained in each of the electrolytes of examples B1 to B7 were as follows:
ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and Propylene Carbonate (PC) in a mass ratio of EMC: PC ═ 1.5:8:0.5, 0.5 wt% VC, 1.5 wt% FEC, 1 wt% PS and 1.0mol/L sodium hexafluorophosphate (NaPF)6)。
The additive components contained in the electrolytes of examples B1 to B7 are shown in Table 1 below, specifically, the electrolyte of example B1 contains the additive of the electrolyte of example A1, the electrolyte of example B2 contains the additive of the electrolyte of example A2, and so on, and the electrolyte of example B7 contains the additive of the electrolyte of example A7. Wherein, the concentrations of the components contained in the electrolyte additive in the electrolyte are respectively shown in table 1.
The electrolyte of each example was prepared as follows:
mixing Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and Propylene Carbonate (PC) according to the types and the content of the components contained in the embodiments B1 to B7 respectively according to the mass ratio EC: EMC: PC of 1.5:8:0.5, adding 0.5 wt% of VC, 1.5 wt% of FEC, 1 wt% of PS and the electrolyte additives provided in the embodiments A1 to A7 respectively, and fully mixing and dissolving the mixture for standby; then adding 1mol/L hexafluorophosphoric acidSodium (NaPF)6) The electrolytes of the respective examples were prepared after being sufficiently mixed and dissolved.
Comparative examples B1 to B5
Comparative example B1 provides an electrolyte that is the base component for example B1. That is, the electrolyte additive provided in example A1 was absent as compared to the electrolyte of example B1.
Comparative examples B2 to B5 provide electrolyte homogeneous base components
Comparative examples B2 to B5 provide electrolytes, respectively. Each electrolyte contains the following base component and additive component. The types and the contents of the basic components contained in 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 the following Table 1, specifically, the electrolyte of comparative example B2 contains the additive of the electrolyte of comparative example A2, and the like, and the electrolyte of comparative example B5 contains the additive of the electrolyte of comparative example A5, wherein the concentrations of the components contained in the electrolyte additive in the electrolyte are respectively shown in Table 1.
TABLE 1 contents of additive combinations for the examples and comparative examples
3. Sodium ion battery examples:
examples C1 to C7 and comparative examples C1 to C5
The present example C1 to example C7 and the comparative example C1 to comparative example C5 each provide a sodium ion battery. The sodium ion batteries are assembled into the sodium ion battery by the following methods:
1) preparing a positive plate:
positive electrode active material Na3V2(PO4)2F3The conductive agent Superp and the binder PVDF are mixed according to the mass ratio of 93: 3: 4, weighing, and then dispersing them 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 thenAfter vacuum baking for 20 hours at 85 ℃, carrying out standard pressing and splitting to obtain a positive plate of the sodium ion battery;
2) preparing a negative plate:
mixing hard carbon, a conductive agent Superp, CMC and SBR according to a mass ratio of 95: 2: weighing at a ratio of 1.5:1.5, stirring, coating, baking, cold pressing, and cutting to obtain the negative plate of the sodium-ion battery,
3) electrolyte solution:
the electrolyte provided by the examples B1 to B7 and the electrolyte provided by the comparative examples B1 to B5 are respectively used as the electrolyte of each sodium secondary battery, the electrolyte provided by the specific example B1 is used as the electrode solution of the sodium secondary battery in the example C1, the electrolyte provided by the example B2 is used as the electrode solution of the sodium secondary battery in the example C2, and the like, the electrolyte provided by the example B7 is used as the electrode solution of the sodium secondary battery in the example C7, the electrolyte provided by the comparative example B1 is used as the electrode solution of the sodium secondary battery in the comparative example C1, and the electrolyte provided by the comparative example B5 is used as the electrode solution of the sodium secondary battery in the comparative example C5.
4) Assembling the sodium secondary battery:
winding the positive plate, the negative plate, the electrolyte and the isolating membrane into a sodium ion battery cell, packaging the sodium ion battery cell by using an aluminum plastic membrane, respectively injecting the prepared electrolyte into the battery cells of each embodiment in a glove box with the dew point controlled below-40 ℃, carrying out vacuum packaging, standing for 24 hours, and then carrying out conventional formation and partial volume according to the following steps: charging to 3.4V at constant current of 0.05C and 3.95V at constant current of 0.2C, and vacuum sealing and pumping for the second time; and further charging to 4.1V at a constant current of 0.2C, standing at normal temperature for 24h, and then charging at a constant voltage of 0.2C and 4.1V at a cut-off current of 0.05C to obtain the sodium ion battery for standing.
5) Sodium ion battery performance test:
the sodium ion batteries of the examples assembled in section 4) were subjected to the following performance tests:
51) and (3) testing the high-temperature storage performance:
the sodium ion battery of each example assembled in section 4) was measured for its initial thickness T0 at room temperature in a state of 4.1V at full charge, and then its thickness T1 was measured after storage in an oven at 85 ℃ for 4h at full charge. The thickness expansion rate was (T1/T0-1) × 100%, and the remaining capacity rate was C1/C0 × 100%, and the measurement results are shown in table 2 below.
52) And (3) testing the normal-temperature cycle performance:
the sodium ion battery in each embodiment assembled in section 4) was charged at a constant current of 0.5C to 4.1V at normal temperature and then the constant voltage charging current was decreased to 0.02C, and then discharged at a constant current of 0.5C to 3.0V, and the cycle was repeated for 1000 weeks, the discharge capacity per week was recorded, and the capacity retention ratio in the high temperature cycle was calculated according to the following formula: the n-cycle capacity retention rate is 100% of the n-cycle discharge capacity/1-cycle discharge capacity, and the measurement results are shown in table 2 below.
53) Normal temperature cycle thickness expansion test:
the sodium ion battery of each example assembled in section 4) was measured for thickness at a voltage of 4.1V before and after the cycle at room temperature, and the thickness expansion rate was (T1/T0-1) × 100%, and the measurement results were as shown in table 2 below.
54) Normal temperature high pressure cycle thickness expansion test:
the sodium ion battery in each example assembled in section 4) was charged to 4.3V at a constant current of 0.5C at normal temperature, then the constant voltage 4.3V charge current was decreased to 0.02C, and then discharged to 3.0V at a constant current of 0.5C, and this was repeated for 500 weeks. The thickness was measured at room temperature before and after the cycle at a voltage of 4.3V, and the thickness expansion rate was 100% (T1/T0-1), and the results were shown in table 2 below.
TABLE 2
As can be seen from the test results in table 2: the combined electrolyte additive provided by the embodiment of the application effectively improves the cycle performance of the sodium secondary battery through the use of polyol nitrile, hydrofluoroether, boric acid ester and sodium difluoro oxalate (phosphorus) acid, the electrode expansion rate is obviously improved, and after the circulation and high-temperature storage, the battery has controllable volume expansion and no obvious gas is generated.
As can be seen from the performance tests in table 2 for the sodium secondary batteries of comparative example C6 and example C7, the upper limit amount of the electrolyte additive of the examples of this application (example C6) in the electrolyte is not significantly different from the performance of the other examples (example C1 to example C5). The simultaneous addition of the lower amount (example C7) gave slightly poorer performance than the other examples (example C1 to example C5), but a clear improvement over comparative example C1.
In comparative example C1, the cycle performance of the sodium secondary battery in comparative example C1 was significantly lower because only the base electrolyte was contained, i.e., the electrolyte additive of the examples of the present application was not contained, and the expansion rate of the sodium secondary battery was higher than 8%, which resulted in significant gas generation, causing rapid decay of the cycle life of the sodium secondary battery, and the high internal pressure of the sodium secondary battery also easily caused a safety risk of bursting or short-circuiting.
It can be seen from comparative example C2 that sodium oxalato borate salt and sodium fluorooxalato phosphate salt can effectively improve the cycle performance of the battery, but the expansion effect for improving the thickness of the battery is not obvious; as can be seen from comparative examples C3 and C4, the other properties were improved except that the cell high voltage swelling was not improved; c5 it can be seen that the polyol nitriles are effective in improving the swelling, especially the thickness swelling at high voltage, of the battery without significantly improving the cycle performance
By further comparing examples C1 to C6 and comparative examples C2 to C5, in the electrolyte contained in the sodium secondary battery of examples C1 to C6, at least one of sodium oxalato borate and sodium fluorooxalato phosphate, polyol nitrile, hydrofluoroether, borate and other components contained in the electrolyte additive of the examples play a role in synergism in the electrolyte, so that the electrochemical properties of the electrolyte, an electrode and the like are effectively improved, the battery can reduce gas generation under high-temperature and high-pressure conditions, the thickness expansion of the sodium secondary battery is reduced, the too rapid increase of impedance is avoided, and the electrochemical properties such as the cycle performance, the high-voltage resistance, the high-temperature storage performance, the safety performance and the like of the sodium secondary battery are improved.
The present invention is not intended to be limited to the particular embodiments shown and described, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed.
Claims (10)
1. An electrolyte additive, characterized in that: comprises a mixture of at least one of sodium oxalato borate salt and sodium fluorooxalato phosphate salt, polyalcohol nitriles, hydrofluoroethers and boric acid esters.
2. The electrolyte additive of claim 1 wherein: the mass ratio of at least one of the sodium oxalatoborate salt and the sodium fluorooxalatophosphate salt to the polyol nitrile to the hydrofluoroether to the boric acid ester is 1-5: 1-10: 1-10: 0.5 to 5.
3. The electrolyte additive according to claim 1 or 2, wherein: the polyol nitrile comprises a molecular structural formula I1To I6At least one of the polyol nitrile compounds:
wherein R is1To R21Identical or different is C1～C10Alkyl groups of (a);
and/or
The hydrofluoroether comprises CF3-CHF-CF2-O-CH2-CF2-CHF2、CF3-CHF-CF2-O-CH2-CF3At least one of;
and/or
The borate ester comprises at least one of tri (trifluoroethyl) borate ester and tri (hexafluoroisopropyl) borate ester.
4. The electrolyte additive according to claim 1 or 2, wherein: the sodium oxalato borate salt comprises NaBF2C2O4、NaB(C2O4)2At least one of;
said fluorineSodium salt of sodium oxalato phosphate includes NaPF2(C2O4)2、NaPF4C2O4At least one of (1).
5. An electrolyte comprising a nonaqueous solvent, further comprising a sodium salt dissolved in the nonaqueous solvent and the electrolyte additive according to any one of claims 1 to 4.
6. The electrolyte of claim 5, wherein: at least one of the sodium oxalato borate salt and the sodium fluorooxalato phosphate salt is 1 to 5 percent of the mass concentration in the electrolyte; and/or
The mass concentration of the polyalcohol 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 boric acid ester in the electrolyte is 0.5-5%; and/or
The mass concentration of the non-aqueous solvent in the electrolyte is 63-85%; and/or
The non-aqueous solvent comprises at least one of cyclic carbonate, chain carbonate and fluorocarboxylate; 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 tetrafluoro oxalate 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%.
7. The electrolyte of claim 6, wherein: the cyclic carbonate comprises at least one of ethylene carbonate, propylene carbonate and butylene carbonate;
the chain carbonate comprises at least one of dimethyl carbonate, ethyl methyl 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, 3-trifluoropropionate, ethyl 4,4, 4-trifluorobutyrate and ethyl trifluoroacetoacetate.
8. The electrolyte of claim 6, wherein: the other additive includes at least one of 1, 3-propylene sultone, vinylene carbonate, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, vinyl sulfate, vinyl ethylene carbonate, ethylene sulfite, 1, 4-butanesultone, fluoroethylene carbonate, difluoroethylene carbonate, ethylene glycol dipropionitrile ether, fluoroethylene carbonate, tris (trimethylsilane) phosphate and tris (trimethylsilane) borate.
9. A sodium secondary battery comprises a positive plate, a negative plate and electrolyte, and is characterized in that: the electrolyte comprises the electrolyte of any one of claims 5 to 7.
10. The sodium secondary battery according to claim 9, characterized in that: 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 and variants, sodium-transition metal sulfate, sodium-transition metal prussian blue compounds and sodium-transition metal prussian blue compounds; 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 maximum charging voltage of the sodium secondary battery is 4.1V-4.5V.
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