CN117199532A - Sodium ion battery and electrolyte thereof - Google Patents
Sodium ion battery and electrolyte thereof Download PDFInfo
- Publication number
- CN117199532A CN117199532A CN202311473062.XA CN202311473062A CN117199532A CN 117199532 A CN117199532 A CN 117199532A CN 202311473062 A CN202311473062 A CN 202311473062A CN 117199532 A CN117199532 A CN 117199532A
- Authority
- CN
- China
- Prior art keywords
- additive
- ion battery
- sodium ion
- electrolyte
- sodium
- 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
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 96
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003792 electrolyte Substances 0.000 title claims abstract description 56
- 239000000654 additive Substances 0.000 claims abstract description 91
- 230000000996 additive effect Effects 0.000 claims abstract description 90
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- -1 fluoro phosphorus lithium salt Chemical group 0.000 claims abstract description 5
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 5
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 159000000000 sodium salts Chemical class 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021385 hard carbon Inorganic materials 0.000 claims description 6
- 229910021384 soft carbon Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229920001774 Perfluoroether Polymers 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 claims description 3
- MZIYQMVHASXABC-UHFFFAOYSA-N tetrakis(ethenyl)stannane Chemical compound C=C[Sn](C=C)(C=C)C=C MZIYQMVHASXABC-UHFFFAOYSA-N 0.000 claims description 3
- AKRQMTFHUVDMIL-UHFFFAOYSA-N tetrakis(prop-2-enyl)silane Chemical compound C=CC[Si](CC=C)(CC=C)CC=C AKRQMTFHUVDMIL-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910020808 NaBF Inorganic materials 0.000 claims description 2
- 229910021201 NaFSI Inorganic materials 0.000 claims description 2
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- UDLNYNSUFIHIKN-UHFFFAOYSA-N bis(ethenyl)-diethylsilane Chemical compound CC[Si](CC)(C=C)C=C UDLNYNSUFIHIKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 claims description 2
- LRBLIVYQOCFXPX-UHFFFAOYSA-N dimethyl-bis(2-phenylethynyl)silane Chemical compound C=1C=CC=CC=1C#C[Si](C)(C)C#CC1=CC=CC=C1 LRBLIVYQOCFXPX-UHFFFAOYSA-N 0.000 claims description 2
- HBWGDHDXAMFADB-UHFFFAOYSA-N ethenyl(triethyl)silane Chemical compound CC[Si](CC)(CC)C=C HBWGDHDXAMFADB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- AJZHXCZXGCOWPH-UHFFFAOYSA-M lithium difluorophosphoryl sulfate Chemical compound S(=O)(=O)(OP(=O)(F)F)[O-].[Li+] AJZHXCZXGCOWPH-UHFFFAOYSA-M 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 2
- XJPKDRJZNZMJQM-UHFFFAOYSA-N tetrakis(prop-2-enyl)stannane Chemical compound C=CC[Sn](CC=C)(CC=C)CC=C XJPKDRJZNZMJQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- FWSPXZXVNVQHIF-UHFFFAOYSA-N triethyl(ethynyl)silane Chemical compound CC[Si](CC)(CC)C#C FWSPXZXVNVQHIF-UHFFFAOYSA-N 0.000 claims description 2
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical compound C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 2
- PHQRTSONTITQSI-UHFFFAOYSA-N tris(ethenyl)-ethylsilane Chemical compound CC[Si](C=C)(C=C)C=C PHQRTSONTITQSI-UHFFFAOYSA-N 0.000 claims description 2
- FUJPAQRDHMJPBB-UHFFFAOYSA-N tris(ethenyl)-phenylsilane Chemical compound C=C[Si](C=C)(C=C)C1=CC=CC=C1 FUJPAQRDHMJPBB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 13
- 230000000977 initiatory effect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- BWUZCLFBFFQLLM-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-yl hydrogen carbonate Chemical compound FC(F)(F)C(C)OC(O)=O BWUZCLFBFFQLLM-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- PFJLHSIZFYNAHH-UHFFFAOYSA-N 2,2-difluoroethyl acetate Chemical compound CC(=O)OCC(F)F PFJLHSIZFYNAHH-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- QUQSORXWLOUIIW-UHFFFAOYSA-N F[P] Chemical group F[P] QUQSORXWLOUIIW-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
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- 229910021260 NaFe Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WFSRWJJESXWWSH-UHFFFAOYSA-N [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] WFSRWJJESXWWSH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
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- VCYZVXRKYPKDQB-UHFFFAOYSA-N ethyl 2-fluoroacetate Chemical compound CCOC(=O)CF VCYZVXRKYPKDQB-UHFFFAOYSA-N 0.000 description 1
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- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 description 1
- JMKJCPUVEMZGEC-UHFFFAOYSA-N methyl 2,2,3,3,3-pentafluoropropanoate Chemical compound COC(=O)C(F)(F)C(F)(F)F JMKJCPUVEMZGEC-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
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- YSYBYIDPNZPQLJ-UHFFFAOYSA-N methyl trifluoromethyl carbonate Chemical compound COC(=O)OC(F)(F)F YSYBYIDPNZPQLJ-UHFFFAOYSA-N 0.000 description 1
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- CDXJNCAVPFGVNL-UHFFFAOYSA-N propyl 2,2,2-trifluoroacetate Chemical compound CCCOC(=O)C(F)(F)F CDXJNCAVPFGVNL-UHFFFAOYSA-N 0.000 description 1
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- 150000003385 sodium Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of sodium ion batteries, and discloses a sodium ion battery with excellent initial effect, normal temperature and high temperature circulation and high temperature storage performance and electrolyte thereof. Wherein, a sodium ion battery electrolyte comprises: additive A, additive B and additive C; wherein the additive A is silicon or tin compound containing carbon-carbon unsaturated bond, the additive B is fluoro phosphorus lithium salt, and the additive C is boron sodium salt with high film-forming potential.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a sodium ion battery and electrolyte thereof.
Background
The lithium ion battery is widely applied to the fields of mobile electronic equipment, electric automobiles, unmanned aerial vehicles and the like due to the characteristics of high energy density, long service life, no memory effect and the like. With the continuous development of products powered by lithium ion batteries, higher demands are being placed on the energy density, lifetime, and fast charge performance of lithium ion batteries.
However, lithium has limited reserves on the earth, and high cost and low cost, and can restrict the long-term application of the lithium battery. The main element sodium in the sodium ion battery is abundant in the earth, and sodium carbonate which is one of the raw materials is low in price, so that the sodium ion battery is hopeful to replace the lithium ion battery in the near future.
The layered oxide material is an ideal positive electrode material of a sodium ion battery due to high compaction density, high gram capacity and high platform voltage, and is also a positive electrode material with wide research and application in the current industry. However, the layered oxide material is easy to generate phase change under high voltage and high temperature, particles are generated to be broken, oxygen is released and metal ions are dissolved out, meanwhile, the positive electrode material shows strong oxidizing property, side reaction with the electrolyte and the interface of the positive electrode and the negative electrode is further enhanced, in addition, the solubility of the interfacial film component containing sodium ions on the surfaces of the positive electrode and the negative electrode in the electrolyte is higher under high temperature, the interfacial film component can be dissolved into the electrolyte, the interfacial film is damaged, the electrolyte and the active sodium ions are required to be continuously consumed for repairing, and finally the first effect, the high-temperature cycle and the high-temperature storage life of the sodium ion battery are deteriorated.
In order to solve the problems, the conventional method is to dope and coat the positive electrode active material of the sodium ion battery to stabilize the structure of the positive electrode active material and inhibit the oxidative decomposition of the electrolyte on the surface of the positive electrode, but the intercalation and deintercalation of sodium ions on the surface of the positive electrode are hindered, and the low-temperature discharge performance of the sodium ion battery is affected.
Disclosure of Invention
Based on the above-described studies, an object of the present invention is to provide a sodium ion battery having excellent initial efficiency, normal and high temperature cycle and high temperature storage properties, and an electrolyte thereof.
The invention adopts the following technical scheme:
a sodium ion battery electrolyte, the electrolyte comprising: additive A, additive B and additive C; wherein the additive A is silicon or tin compound containing carbon-carbon unsaturated bond, the additive B is fluoro phosphorus lithium salt, and the additive C is boron sodium salt with high film-forming potential.
As a preferred aspect, the additive a is at least one selected from the group consisting of tetravinylsilane, ethyltrivinylsilane, diethyldivinylsilane, triethylvinylsilane, tetraallylsilane, tetravinyltin, tetraallyltin, phenyltrivinylsilane, triethylethynyl silane, dimethyl bis (phenylethynyl) silane, trimethylethynyl silane; the additive a content is 0.3% to 3%, for example 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8% or 3%.
It is noted that any numerical value in this disclosure includes all values of the lower value and the upper value that increment by one unit from the lower value to the upper value, and that there is at least two units of space between any lower value and any higher value.
For example, the additive A is described as having a content of 0.3% to 3%, further 0.311% to 2.99%, further 0.46% to 2.1%, for purposes of illustrating the non-explicitly recited values such as 0.301%, 1.113%, 1.115%, 1.127%, 2.129%, 2.132%, 2.636% and the like.
As described above, the exemplary range in interval units of 0.001 does not exclude increases in interval in appropriate units, e.g., in numerical units of 0.01, 0.02, 0.03, 0.04, 0.05, etc. These are merely examples that are intended to be explicitly recited in this description, and all possible combinations of values recited between the lowest value and the highest value are believed to be explicitly stated in the description in a similar manner.
Unless otherwise indicated, all ranges include endpoints and all numbers between endpoints. "about" or "approximately" as used with a range is applicable to both endpoints of the range. Thus, "about 20 to 30" is intended to cover "about 20 to about 30," including at least the indicated endpoints.
Other descriptions of the numerical ranges presented herein are not repeated with reference to the above description.
As a preferred aspect, the additive B is selected from one or more of lithium monofluorophosphate, lithium difluorophosphate, lithium difluorophosphoryloxy sulfonate, lithium disulfonate difluorophosphate, lithium difluorodioxalate phosphate, lithium tetrafluorooxalate phosphate; the additive B content is 0.2% to 1%, for example 0.2%, 0.3%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1.0%. As a preferred aspect, the additive C is selected from at least one of sodium difluorooxalato borate and sodium dioxaato borate; the content of the additive C is 0.2-1%, for example 0.2%, 0.3%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%.
As a preferred aspect, the organic solvent of the electrolyte is selected from at least one of carbonate solvents, fluorocarbonate solvents, carboxylate solvents, fluorocarboxylate solvents, ether solvents, and fluoroether solvents.
Preferably, the carbonate solvent comprises any one or a combination of at least two of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate or methyl propyl carbonate.
Preferably, the fluorocarbonate solvent includes any one or a combination of at least two of fluoroethylene carbonate, bis-fluoroethylene carbonate, methyltrifluoromethyl carbonate, methyltrifluoroethyl carbonate and bis (2, 2-trifluoroethyl) carbonate.
Preferably, the carboxylate solvent comprises any one or a combination of at least two of methyl formate, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate or ethyl butyrate.
Preferably, the fluorocarboxylate solvent comprises any one or a combination of at least two of ethyl fluoroacetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, 2-trifluoroethyl difluoroacetate, methyl pentafluoropropionate or 2, 2-difluoroethyl acetate.
Preferably, the ether solvent comprises any one or a combination of at least two of tetrahydrofuran, 1, 3-dioxane, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
Preferably, the method comprises the steps of, the fluoroether solvent comprises bis (2, 2-trifluoroethyl) ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether or 1, 2-tetrafluoroethyl-any one or a combination of at least two of 2, 3-tetrafluoropropyl ether.
In a preferred aspect, the sodium salt of the electrolyte is NaPF 6 、NaFSI、NaTFSI、NaBF 4 、NaClO 4 、NaAsF 6 And NaSbF 6 Any one or more of the following.
Preferably, the mass fraction of the sodium salt in the electrolyte is 5% -20%, for example 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.
Further preferably, the mass fraction of the sodium salt in the electrolyte is 8% -18%, for example 8%, 10%, 12%, 14%, 16% or 18%.
A sodium ion battery, the sodium ion battery comprising: the positive electrode plate, the negative electrode plate, the isolating film and the electrolyte of any one of the above.
In a preferred aspect, the positive electrode of the sodium ion battery is a layered oxide, and has a structural formula of NaM x O y M is one or more of iron, copper, nickel, cobalt and manganese, and the value range of x and y is as follows: x is more than or equal to 0.8 and less than or equal to 1.5, and y is more than or equal to 1.5 and less than or equal to 2.5.
Preferably, the active material of the positive electrode is NaFe 0.5 Mn 0.5 O 2 、NaNi 0.3 Fe 0.4 Mn 0.3 O 2 、NaNi 0.33 Fe 0.34 Mn 0.33 O 2 、NaNi 0.25 Fe 0.5 Mn 0.25 O 2 、NaNi 0.2 Cu 0.1 Fe 0.4 Mn 0.3 O 2 、NaNi 0.25 Fe 0.4 Co 0.1 Mn 0.25 O 2 、NaNi 0.5 Fe 0.4 Mn 0.4 O 2.4 Or NaNi 0.4 Fe 0.2 Mn 0.3 O 1.8 One or a combination of at least two of the foregoing. As a preferred aspect, the negative electrode in the negative electrode plate of the sodium ion batteryThe polar material is one or a combination of at least two of hard carbon, soft carbon, expanded graphite, titanium-based material, alloy material or organic material.
As a preferred aspect, the negative electrode material in the negative electrode sheet of the sodium ion battery is at least one of hard carbon and soft carbon.
The beneficial effects are that:
the invention provides a sodium ion battery and an electrolyte thereof, wherein the electrolyte comprises an additive A, an additive B and an additive C; wherein the additive A is silicon or tin compound containing carbon-carbon unsaturated bond, the additive B is fluoro phosphorus-containing lithium salt, and the additive C is boron-containing sodium salt with high film-forming potential.
The additive A is a silicon or tin compound containing carbon-carbon unsaturated bonds, and has lower LUMO energy level (the lowest energy level orbit of unoccupied electrons) and higher HOMO energy level (the highest energy level orbit of occupied electrons) compared with a solvent, so that a film forming reaction can be preferentially carried out on the surfaces of the positive electrode and the negative electrode to form a compact interface film, side reactions between the positive electrode and the negative electrode and the electrolyte are inhibited, and in addition, the silicon or tin on the additive A is positive and tetravalent, so that the additive A has better oxidation-reduction stability. The additive B is fluoro-substituted phosphorus-containing lithium salt, an interfacial film rich in lithium phosphate compounds is formed on the surfaces of the positive electrode and the negative electrode, the lithium phosphate compounds have good ion conducting capacity and high oxidation resistance stability, the direct current internal resistance of the sodium ion battery can be reduced, the high-temperature oxidation resistance can be improved, meanwhile, the consumption of active sodium ions can be reduced, the first effect is improved, in addition, the interfacial film rich in lithium salt compounds has lower solubility in electrolyte at high temperature, has higher thermal stability, the dissolution and repair of the interfacial film on the surfaces of the positive electrode and the negative electrode at high temperature can be further inhibited, and the occurrence of side reactions and the consumption of active sodium ions are inhibited. The additive C is boron-containing sodium salt with high film forming potential, the film forming potential of the additive C is more than 1.2V, film forming reaction can be carried out before sodium ions are stored in a hard carbon/soft carbon slope area, insertion and extraction of sodium ions are facilitated, meanwhile, boron on the additive C can be combined with oxygen on a positive electrode lamellar compound, the activity of oxygen is reduced, the positive electrode material is stabilized, meanwhile, the occurrence of oxygen release can be restrained, in addition, the additive C contains sodium ions, and compared with a solvent, the film forming of the additive C consumes less active sodium ions, so that the first effect is improved.
The additive A, the additive B and the additive C are combined, so that the advantages of the additive A, the additive B and the additive C can be combined, and films can be formed on the surfaces of the positive electrode and the negative electrode preferentially to generate an interfacial film with a loose structure of a sodium-containing compound and a compact stable structure of a lithium-containing compound, thereby ensuring lower impedance of a battery, improving interface stability and reducing side reaction; meanwhile, carbon-carbon unsaturated bonds of the additive A can be combined with oxygen of the positive electrode material through double bond polymerization, so that the stability of the surface of the positive electrode can be improved, the additive B and the additive C respectively contain lithium ions and sodium ions, the consumption of active sodium ions in the positive and negative electrode film forming process can be reduced, and the first effect is improved.
Finally, the sodium ion battery and the electrolyte thereof provided by the invention have excellent initial effect, normal temperature and high temperature circulation and high temperature storage performance.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, shall fall within the scope of the invention.
The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention. In the following examples and comparative examples, reagents, materials and instruments used are commercially available unless otherwise specified.
In the examples and comparative examples of the present invention, the additive materials used to make the sodium ion battery electrolyte are as follows:
additive A: tetravinylsilane, tetraallylsilane, tetravinyltin;
additive B: lithium monofluorophosphate, lithium difluorodioxalate phosphate;
additive C, sodium difluorooxalato borate and sodium dioxaato borate;
organic solvent: propylene Carbonate (PC), ethylene Carbonate (EC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC);
sodium salt: naPF (NaPF) 6 。
According to the invention, the electrolyte is prepared by the following preparation methods in sequence:
firstly, slowly adding sodium salt into a mixed solution of PC, EC, DMC and EMC in a glove box, cooling to room temperature in a container, adding an additive, and uniformly mixing to obtain the electrolyte. The mass ratio of EC, DMC and EMC in the electrolyte solvent is 1:1:2:2, the mass fraction of sodium salt in the electrolyte is 14%, and the names and mass fractions (content) of the additives in the electrolyte are shown in the following table 1.
Table 1: names and proportions of the respective additive components in the electrolytes in examples 1 to 9
According to the preparation method, the electrolyte is prepared according to the following preparation methods in sequence:
firstly, slowly adding sodium salt into a mixed solution of PC, EC, DMC and EMC in a glove box, cooling to room temperature in a container, adding an additive, and uniformly mixing to obtain the electrolyte. The mass ratio of EC, DMC and EMC in the electrolyte solvent is 1:1:2:2, the mass fraction of sodium salt in the electrolyte is 14%, and the names and mass fraction (content) of each additive in the electrolyte are shown in the following table 2.
Table 2: names and proportions of the respective additive components in the electrolytes of comparative examples 1 to 6
Preparation of sodium ion battery:
the electrolytes obtained in examples and comparative examples were respectively applied to sodium ion batteries prepared by the following steps:
(1) Preparation of the Positive electrode
Positive electrode material sodium nickel iron manganese oxide NaNi 0.33 Fe 0.34 Mn 0.33 O 2 The mass ratio of the binding agent polyvinylidene fluoride to the conductive carbon black is fixed at 96:2:2, the anode material sodium ferronickel manganate, the binding agent and the conductive agent are mixed according to the respective proportion requirements, N-methyl pyrrolidone (NMP) is added, and then the mixture is stirred to prepare anode slurry, wherein the mass fraction of NMP in the anode slurry is 28%.
Uniformly coating the anode slurry on an aluminum foil, wherein the coating surface density is 30mg/cm 2 And (3) airing the coated aluminum foil at room temperature, transferring to a baking oven at 120 ℃ for drying for 1h, then carrying out cold pressing, trimming, cutting pieces and slitting, drying for 4h under a vacuum condition at 110 ℃, and welding the tab to prepare the positive electrode of the sodium ion secondary battery meeting the requirements.
(2) Preparation of negative electrode
And (3) dissolving hard carbon, thickener sodium carboxymethyl cellulose (CMC), binder styrene-butadiene rubber emulsion (SBR) and conductive carbon black in solvent deionized water according to a mass ratio of 94:1:2:3, and uniformly mixing to prepare negative electrode slurry, wherein the mass fraction of deionized water in the negative electrode slurry is 46%.
Uniformly coating the negative electrode slurry on a current collector copper foil, wherein the coating surface density is 14mg/cm 2 And then drying at 85 ℃, cold pressing, trimming, cutting pieces and splitting, then drying at 100 ℃ under vacuum for 4 hours, and welding the tab to prepare the negative electrode of the sodium ion secondary battery meeting the requirements.
(3) Preparation of sodium ion batteries
Winding the corresponding positive electrode, negative electrode and isolating film (PE film+3μm ceramic coating) into a bare cell, then filling the bare cell into an aluminum plastic film, baking at 90 ℃ to remove water, filling electrolyte, sealing, standing, hot-cold pressing, forming, exhausting, separating volume and the like to obtain the sodium ion battery.
The electrolyte and the sodium ion battery obtained above are tested, including the following performance tests:
(1) Sodium ion battery initial efficiency test
The first efficiency test flow is included in the formation and capacity separation flow. Standing the sodium ion battery at 25deg.C for 30 min, constant-current charging to 4.0V at 0.5C rate, constant-voltage charging to 0.05C at 4.0V, and recording the total capacity of the battery as C 0 The method comprises the steps of carrying out a first treatment on the surface of the Then standing for 30 minutes, then discharging to 1.5V at constant current with 0.5C multiplying power, and recording the total capacity of discharged to be D 0 。
Sodium ion battery initial effect (%) =d 0 /C 0 。
(2) 25 ℃ cycle performance test of sodium ion battery
The sodium ion battery is kept stand for 30 minutes at 25 ℃, then is charged to 4.0V at constant current with 0.5C multiplying power, then is charged to 0.05C at constant voltage with 4.0V, and is kept stand for 5 minutes, then is discharged to 1.5V at constant current with 0.5C multiplying power, and the discharge capacity is the first discharge capacity C of the sodium ion battery after a charge-discharge cycle process 1 The method comprises the steps of carrying out a first treatment on the surface of the Then 1000 charge-discharge cycles are carried out, and the discharge capacity of the 1000 th cycle is recorded as C 1000 。
Capacity retention (%) =c after 1000 cycles of sodium ion battery at 25 ℃ 1000 /C 1 。
(3) Sodium ion battery 45 ℃ high temperature cycle performance test
The sodium ion battery is kept stand for 30 minutes at 45 ℃, then is charged to 4.0V at constant current with 0.5C multiplying power, then is charged to 0.05C at constant voltage with 4.0V, and is kept stand for 5 minutes, then is discharged to 1.5V at constant current with 0.5C multiplying power, and the discharge capacity is the first discharge capacity C of the sodium ion battery after a charge-discharge cycle process 1 The method comprises the steps of carrying out a first treatment on the surface of the Then 500 charge-discharge cycles are carried out, and the discharge capacity of 500 th cycle is recorded as C 500 。
Capacity retention (%) =c after 500 cycles of sodium ion battery at 45 ℃ 500 /C 1 。
(4) Sodium ion battery 60 ℃ high temperature storage test
Firstly, standing the sodium ion battery at 25 ℃ for 30 minutes; charging to 4.0V at a constant current of 0.5C, further charging to a current of 0.5C at a constant voltage of 4.0V; then at 0Constant current of 5C discharged 1.5V to sodium ion battery, at this time, the discharge capacity was recorded as C 0s The method comprises the steps of carrying out a first treatment on the surface of the Charging to 4.0V with constant current of 0.5C, and further charging to 0.5C with constant voltage of 4.0V; finally, the volume of the battery is tested by a drainage method, wherein the volume is V before storage 0 . Then the sodium ion battery is stored for 30 days at 60 ℃, after the storage is finished, the sodium ion secondary battery is placed in an environment of 25 ℃, and the volume of the battery is tested by adopting a drainage method, wherein the volume is V after the storage 30 . Then discharging the sodium ion battery at 1.5V with a constant current of 0.5C; then charging the sodium ion secondary battery to 4.0V with a constant current of 0.5C, and further charging the sodium ion secondary battery to a constant voltage of 4.0V until the current is 0.5C; then, the sodium ion secondary battery was discharged to 1.5V with a constant current of 0.5C, at which time the discharge capacity was noted as C 30s 。
Storage capacity recovery rate (%) =c after 30 days of sodium ion storage 30S /C 0S ；
Volume expansion rate (%) = (V) of sodium ion battery after 30 days storage 30 -V 0 )/V 0 。
The performance test data of the sodium ion batteries of the inventive examples and comparative examples are shown in table 3.
Table 3: test results of sodium ion cell
As can be seen from comparative examples 1,3, 5 and 2 in table 3, the combination properties of the sodium ion battery in which the additive a, the additive B and the additive C are combined are very remarkable, and it is presumed that the combination properties of the sodium ion battery are remarkably improved mainly by combining the advantages of film formation compactness and thermal stability of the additive a, the improvement of the stabilizing effect and oxidation resistance of the additive B on the interface film, and the suppression of the active sodium ion consumption, the suppression of the oxidizing property of the positive electrode surface, particularly the oxygen release, and the suppression of the active sodium ion consumption, as compared with the additive a and the additive B alone, the additive B alone and the additive C alone in any two combinations.
As can be seen from comparative examples 1 to 2 and examples 1 to 3 in Table 3, all the performances of the sodium ion battery are obviously improved when the content of the additive A in the electrolyte is increased, but all the performances of the sodium ion battery are deteriorated to different degrees when the content of the additive A is excessive. It is presumed that the film forming resistance of the additive a is large, and when the additive is excessive, the interface film formed at the positive and negative electrodes is excessively large and thick, which hinders the transmission of sodium ions at the positive and negative electrode surfaces, and may deteriorate the performance of the sodium ion battery.
As can be seen from comparative examples 3-4, examples 2 and examples 4-5 in Table 3, when the content of the additive B in the electrolyte is increased, the initial effect, the cycle and the storage performance of the sodium ion battery are improved to a certain extent, and when the content of the additive B is increased excessively, various performances of the sodium ion battery are also improved to different extents. It is supposed that the solubility of the additive B in the electrolyte is low, the additive B is not sufficiently dissolved in the electrolyte when the content is too high, and film formation on the surfaces of the positive and negative electrodes cannot be effectively performed.
It can be seen from comparative examples 5 to 6, example 2 and examples 6 to 7 in table 3 that the initial effect, cycle and storage performance of the sodium ion battery are also improved to some extent when the content of the additive C in the electrolyte increases, but when the content of the additive C is excessive, various performances of the sodium ion battery are also deteriorated to different extents, particularly the normal temperature cycle is remarkably deteriorated. It is presumed that, on the one hand, the interfacial resistance of the additive C is large to hinder the transport of sodium ions, and on the other hand, the additive C also has a low solubility to exert no effect, and further, the additive C is an alkaline additive, and if it is excessive, it acts as a catalyst to decompose an electrolyte to produce gas or to lose capacity of a battery.
From examples 2 and 8-9 in table 3, it can be seen that different sodium ion battery improvement effects can be obtained by different types and content combinations of the additive a, the additive B and the additive C, and the research and development personnel can adjust and control according to specific performance requirements.
The applicant states that the sodium-ion battery electrolyte and the sodium-ion battery of the present invention are described by the above examples, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Any numerical value recited herein includes all values of the lower and upper values that are incremented by one unit from the lower value to the upper value, as long as there is a separation of at least two units between any lower value and any higher value. For example, if it is stated that the number of components or the value of a process variable (e.g., temperature, pressure, time, etc.) is from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, then the purpose is to explicitly list such values as 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc. in this specification as well. For values less than 1, one unit is suitably considered to be 0.0001, 0.001, 0.01, 0.1. These are merely examples that are intended to be explicitly recited in this description, and all possible combinations of values recited between the lowest value and the highest value are believed to be explicitly stated in the description in a similar manner.
Unless otherwise indicated, all ranges include endpoints and all numbers between endpoints. "about" or "approximately" as used with a range is applicable to both endpoints of the range. Thus, "about 20 to 30" is intended to cover "about 20 to about 30," including at least the indicated endpoints.
All articles and references, including patent applications and publications, disclosed herein are incorporated by reference for all purposes. The term "consisting essentially of …" describing a combination shall include the identified element, ingredient, component or step as well as other elements, ingredients, components or steps that do not substantially affect the essential novel features of the combination. The use of the terms "comprises" or "comprising" to describe combinations of elements, components, or steps herein also contemplates embodiments consisting essentially of such elements, components, or steps. By using the term "may" herein, it is intended that any attribute described as "may" be included is optional.
Multiple elements, components, parts or steps can be provided by a single integrated element, component, part or step. Alternatively, a single integrated element, component, part or step may be divided into separate plural elements, components, parts or steps. The disclosure of "a" or "an" to describe an element, component, section or step is not intended to exclude other elements, components, sections or steps.
Many embodiments and many applications other than the examples provided will be apparent to those of skill in the art upon reading the above description. The scope of the present teachings should, therefore, be determined not with reference to the above description, but instead should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated herein by reference for the purpose of completeness. The omission of any aspect of the subject matter disclosed herein in the preceding claims is not intended to forego such subject matter, nor should the inventors regard such subject matter as not be considered to be part of the disclosed subject matter.
Claims (10)
1. A sodium ion battery electrolyte, the electrolyte comprising: additive A, additive B and additive C; wherein the additive A is silicon or tin compound containing carbon-carbon unsaturated bond, the additive B is fluoro phosphorus lithium salt, and the additive C is boron sodium salt with high film-forming potential.
2. The sodium ion battery electrolyte of claim 1, wherein the additive a is selected from at least one of tetravinyl silane, ethyltrivinyl silane, diethyl divinyl silane, triethyl vinyl silane, tetraallyl silane, tetravinyl tin, tetraallyl tin, phenyltrivinyl silane, triethyl (ethynyl) silane, dimethyl bis (phenylethynyl) silane, trimethylethynyl silane; the content of the additive A is 0.3-3%.
3. The sodium ion battery electrolyte of claim 1, wherein the additive B is selected from one or more of lithium monofluorophosphate, lithium difluorophosphate, lithium difluorophosphoryloxy sulfonate, lithium disulfonate difluorophosphate, lithium difluorodioxalate phosphate, lithium tetrafluorooxalate phosphate; the content of the additive B is 0.2-1%.
4. The sodium ion battery electrolyte of claim 1, wherein the additive C is selected from at least one of sodium difluorooxalato borate and sodium dioxaato borate; the content of the additive C is 0.2-1%.
5. The sodium ion battery electrolyte of claim 1, wherein the organic solvent of the electrolyte is selected from at least one of carbonate solvents, fluorocarbonate solvents, carboxylate solvents, fluorocarboxylate solvents, ether solvents, and fluoroether solvents.
6. The sodium ion battery electrolyte of claim 1, wherein the sodium salt of the electrolyte is NaPF 6 、NaFSI、NaTFSI、NaBF 4 、NaClO 4 、NaAsF 6 And NaSbF 6 Any one or more of the following.
7. A sodium ion battery, wherein the sodium ion battery comprises: a positive electrode sheet, a negative electrode sheet, a separator and the electrolyte as claimed in any one of claims 1 to 6.
8.The sodium ion battery of claim 7, wherein the positive electrode of the sodium ion battery is a layered oxide having the structural formula NaM x O y M is one or more of iron, copper, nickel, cobalt and manganese, and the value range of x and y is as follows: x is more than or equal to 0.8 and less than or equal to 1.5, and y is more than or equal to 1.5 and less than or equal to 2.5.
9. The sodium ion battery of claim 7, wherein the negative electrode material in the negative electrode sheet of the sodium ion battery is one or a combination of at least two of hard carbon, soft carbon, expanded graphite, titanium-based material, alloy material, or organic material.
10. The sodium ion battery of claim 9, wherein the negative electrode material in the negative electrode sheet of the sodium ion battery is at least one of hard carbon and soft carbon.
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|---|---|---|---|---|
| JP2006107815A (en) * | 2004-10-01 | 2006-04-20 | Sony Corp | Electrolyte and battery |
| CN101243576A (en) * | 2005-08-22 | 2008-08-13 | 宇部兴产株式会社 | Nonaqueous electrolyte solution and lithium secondary battery using same |
| JP2017117684A (en) * | 2015-12-25 | 2017-06-29 | セントラル硝子株式会社 | Electrolytic solution for nonaqueous electrolyte battery, and nonaqueous electrolyte battery using the same |
| CN116742133A (en) * | 2022-03-02 | 2023-09-12 | 珠海冠宇电池股份有限公司 | Electrolyte and mixed lithium-sodium ion battery comprising same |
-
2023
- 2023-11-07 CN CN202311473062.XA patent/CN117199532B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006107815A (en) * | 2004-10-01 | 2006-04-20 | Sony Corp | Electrolyte and battery |
| CN101243576A (en) * | 2005-08-22 | 2008-08-13 | 宇部兴产株式会社 | Nonaqueous electrolyte solution and lithium secondary battery using same |
| JP2017117684A (en) * | 2015-12-25 | 2017-06-29 | セントラル硝子株式会社 | Electrolytic solution for nonaqueous electrolyte battery, and nonaqueous electrolyte battery using the same |
| CN116742133A (en) * | 2022-03-02 | 2023-09-12 | 珠海冠宇电池股份有限公司 | Electrolyte and mixed lithium-sodium ion battery comprising same |
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