CN118117172A - Sodium ion battery - Google Patents
Sodium ion battery Download PDFInfo
- Publication number
- CN118117172A CN118117172A CN202211507055.2A CN202211507055A CN118117172A CN 118117172 A CN118117172 A CN 118117172A CN 202211507055 A CN202211507055 A CN 202211507055A CN 118117172 A CN118117172 A CN 118117172A
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- China
- Prior art keywords
- equal
- ether
- fluoroether
- less
- ion battery
- Prior art date
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 38
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- 238000007599 discharging Methods 0.000 claims abstract description 21
- 238000007600 charging Methods 0.000 claims abstract description 19
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- -1 2,2,3,3,4,4,5-heptafluoropentylethyl ether Chemical compound 0.000 claims description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- 239000011734 sodium Substances 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 150000004292 cyclic ethers Chemical class 0.000 claims description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical group 0.000 claims description 4
- 150000005678 chain carbonates Chemical class 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- OSSBKXMASZTOSG-UHFFFAOYSA-N 2-(trifluoromethyl)oxolane Chemical compound FC(F)(F)C1CCCO1 OSSBKXMASZTOSG-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims description 2
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 claims description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002000 Electrolyte additive Substances 0.000 claims description 2
- 229910014235 MyOz Inorganic materials 0.000 claims description 2
- QXZNUMVOKMLCEX-UHFFFAOYSA-N [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F Chemical compound [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F QXZNUMVOKMLCEX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- SVTMLGIQJHGGFK-UHFFFAOYSA-N carbonic acid;propa-1,2-diene Chemical compound C=C=C.OC(O)=O SVTMLGIQJHGGFK-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-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
- 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 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 229940090181 propyl acetate Drugs 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
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 claims description 2
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 3
- 125000004122 cyclic group Chemical group 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 13
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000000284 resting effect Effects 0.000 description 8
- 238000010277 constant-current charging Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 102100028667 C-type lectin domain family 4 member A Human genes 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 101000766908 Homo sapiens C-type lectin domain family 4 member A Proteins 0.000 description 2
- 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 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 101100039010 Caenorhabditis elegans dis-3 gene Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015193 FePO4F Inorganic materials 0.000 description 1
- 229910015818 MPO4 Inorganic materials 0.000 description 1
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 description 1
- 101100030351 Schizosaccharomyces pombe (strain 972 / ATCC 24843) dis2 gene Proteins 0.000 description 1
- 229910000540 VOPO4 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of electrochemistry, in particular to a sodium ion battery. The sodium ion battery comprises a positive electrode, a negative electrode and a nonaqueous electrolyte, wherein the nonaqueous electrolyte comprises electrolyte salt, a solvent and an additive, and the solvent comprises fluoroether with a molecular formula of F xCnH2n+1-xOCmH2m+1, wherein X/(2n+1) < 80%, n/m is more than 1.5,4 and less than or equal to n and less than or equal to 10, and m is more than or equal to 1 and less than or equal to 5; the mass percent of the fluoroether C is more than or equal to 5% and less than or equal to 50%, and the charging direct current internal resistance A and the discharging direct current internal resistance B of the sodium ion battery at 25 ℃ are more than or equal to 85 and less than or equal to 115, and the mass percent of the fluoroether C is more than or equal to 80 and less than or equal to 110,1 and less than or equal to 4; 5< C× (A-B) < 200. According to the sodium ion battery, fluoroether with a specific structure and content is selected as the solvent, and the relationship between the fluoroether solvent content and the battery charge-discharge direct-current internal resistance is controlled, so that the low charge-discharge tributary internal resistance is kept to be increased in the circulation process, and meanwhile, the high and stable circulation coulomb efficiency is kept, and the circulation performance of the battery is further improved.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a sodium ion battery.
Background
Due to the rapid increase in clean energy demand, secondary battery technology has been rapidly developed, and sodium ion batteries, in which raw material resources are abundant, are attracting attention. The sodium ion battery has similar working principle with the lithium ion battery widely applied at present, and the energy density and the cycle life of the sodium ion battery are similar to those of the lithium ion battery. In addition, the sodium source is widely distributed, the cost is low, the safety of the sodium ion battery is good, and the sodium ion battery is easy to maintain. In the application fields of energy storage and the like with high cost sensitivity and safety requirements, the sodium ion battery has a great technical advantage. However, the current sodium ion battery generally has the problems of insufficient battery cycle performance and the like, and further development of the sodium ion battery is affected.
Disclosure of Invention
Aiming at the technical problems, the invention provides a sodium ion battery for improving the cycling stability of the sodium ion battery.
The invention adopts the following technical scheme:
A sodium ion battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolyte comprising an electrolyte salt, a solvent comprising a fluoroether of formula F xCnH2n+1-xOCmH2m+1, and an additive, wherein: x/(2n+1) < 80%, n/m > 1.5,4 < n < 10, m < 1 < 5;
The sodium ion battery has a charging direct current internal resistance A at 25 ℃ and a discharging direct current internal resistance B at 25 ℃, and meets the following conditions: a is more than or equal to 85 and less than or equal to 115, B is more than or equal to 80 and less than or equal to 110,1 and A-B is more than or equal to 4;
the mass percentages of the charging direct current internal resistance A, the discharging direct current internal resistance B and the fluoroether C are as follows: 5 < C× (A-B) < 200;
the unit of the charging direct current internal resistance A is mΩ, the unit of the discharging direct current internal resistance B is mΩ, and the unit of the fluoroether mass percentage content C is%.
The sodium ion battery limits the structure and the use amount of the fluoroether solvent, can partially replace the conventional solvent to form a cosolvent, and can improve the electric conduction of the electrolyte and reduce the viscosity; the charge-discharge direct current internal resistance at normal temperature meets the requirements, and the high and stable cycle coulomb efficiency can be maintained while the low charge-discharge direct current internal resistance is increased in the cycle process, so that the cycle performance of the battery is improved.
Specifically, in some embodiments of the present invention, the fluoroether is contained in an amount of 100% by mass of the nonaqueous electrolytic solution, based on the total mass of the nonaqueous electrolytic solution, such that the percentage by mass C of the fluoroether relative to the nonaqueous electrolytic solution satisfies: c is more than or equal to 5% and less than or equal to 50%.
The inventor finds through a large number of experiments that when fluoroether in electrolyte used by a battery meets the requirements, the solvent has good stability to the positive and negative electrodes and has certain solubility to salt; fluoroether as cosolvent participates in solvation structure of ion to affect SEI and CEI constitution, and improve high temperature storage stability and cycle performance. The mass percentage of the fluoroether is more than or equal to 5 percent and less than or equal to 50 percent of C; when the mass percentage of the fluoroether is lower than the range, the conductivity of the electrolyte is too low; above this range, the sodium salt is difficult to dissolve and the mass ratio of the sodium salt is lowered. Preferably, the mass percentage content C of the fluoroether is as follows: 7% < C% < 30%. Specifically, in some embodiments of the present invention, the mass percent c% of the fluoroether is 5%, 7%, 9%, 11%, 14%, 16%, 18%, 20%, 24%, 27%, 29%, 32%, 35%, 38%, 42%, 45%, 48%, 50%.
For the molecular formula F xCnH2n+1-xOCmH2m+1 of fluoroether, the X/(2n+1) < 80%, n/m > 1.5; the inventor finds through a large number of experiments that when n/m is less than or equal to 1.5, the dipole moment is reduced, the solubility of lithium salt is reduced, and the rate performance of the battery is seriously reduced; when X/(2n+1) is more than or equal to 80%, the solubility of fluoroether to salt is reduced, so that the conductivity of the electrolyte is reduced, and the low-temperature discharge performance is seriously reduced.
Preferably, the mass percentages of the charging direct current internal resistance A, the discharging direct current internal resistance B and the fluoroether C are as follows: 7 < C× (A-B) < 120.
In particular, in some embodiments of the invention, the fluoroether comprises 2,3, 4, 5-octafluoropentyl methyl ether, 2,3, 4, 5-octafluoropentyl ethyl ether, 2,3, 4, 5-heptafluoropentyl methyl ether 2,3, 4, 5-heptafluoropentylethyl ether, 2,2,3,3,4,4,5-heptafluoropentylethyl ether, 2,2,3,3,4,4,5-heptafluoropentylethyl ether 2,3, 4, 5-heptafluoropentylethyl ether 2,2,3,3,4,4,5-heptafluoropentylmethyl ether, 2,2,3,3,4,4,5-heptafluoropentylethyl ether.
Preferably, the method comprises the steps of, the fluoroether is selected from the group consisting of 2,3, 4, 5-octafluoropentylethyl ether 2,3, 4, 5-octafluoropentylmethyl ether 2,3, 4, 5-heptafluoropentylmethyl ether.
Further, the specific structure of the fluoroether compound may be as shown in the following table:
specifically, in some embodiments of the present invention, the solvent further comprises one or more of a C3-C5 carbonate solvent, a C2-C6 carboxylate solvent, and a C4-C10 ether solvent;
the solvent is 70-92% by mass relative to the nonaqueous electrolyte based on 100% by mass of the total nonaqueous electrolyte.
Specifically, in some embodiments of the present invention, the carbonate-based solvent includes a C3 to C5 cyclic carbonate or chain carbonate selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), gamma-butyrolactone (GBL), butylene Carbonate (BC); the chain carbonate is selected from one or more of dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) and dipropyl carbonate (DPC); the carboxylic ester solvent of C2-C6 is selected from one or more of Ethyl Propionate (EP), methyl Acetate (MA), ethyl Acetate (EA), propyl acetate (EP), butyl acetate and Propyl Propionate (PP); the ether solvent comprises C4-C10 cyclic ether or chain ether, and the cyclic ether is selected from one or more of 1, 3-Dioxolane (DOL), 1, 4-Dioxane (DX), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH 3 -THF) and 2-trifluoromethyl tetrahydrofuran (2-CF 3 -THF); the chain ether is selected from one or more of dimethoxy methane (DMM), 1, 2-dimethoxy ethane (DME), diethylene glycol dimethyl ether (TEGDME), ethylene glycol diethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
Specifically, in some embodiments of the invention, the electrolyte salt comprises one or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium trifluoroacetate, sodium tetraphenylborate, sodium trifluoromethylsulfonate, sodium bis (fluorosulfonyl) imide, or sodium bis (trifluoromethylsulfonyl) imide;
the electrolyte salt is contained in an amount of 2.5 to 16.5% by mass relative to the nonaqueous electrolytic solution based on 100% by mass of the total nonaqueous electrolytic solution.
Specifically, in some embodiments of the present invention, the additive is selected from one or more of cyclic carbonate compounds, fluorinated cyclic carbonate compounds, cyclic sulfonate compounds, cyclic sulfate compounds, phosphate compounds, borate compounds, and nitrile compounds;
Preferably, the cyclic carbonate compound is selected from one or more of ethylene carbonate, ethylene carbonate and methylene ethylene carbonate;
The fluoro-cyclic carbonate compound is selected from one or more of fluoro-ethylene carbonate and difluoro-ethylene carbonate;
The cyclic sulfonate compound is selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone and propenyl-1, 3-sultone;
The cyclic sulfate compound is selected from one or more of vinyl sulfate, 4-methyl vinyl sulfate and propylene sulfate;
The phosphate compound is one or more of tripolyl phosphate, trimethyl phosphate, triethyl phosphate and tri (trimethyl silane) phosphate;
the borate compound is selected from one or more of tri (trimethylsilane) borate and tri (triethylsilane) borate;
The nitrile compound is selected from one or more of succinonitrile, glutaronitrile, ethylene glycol bis (propionitrile) ether, hexanedinitrile, adiponitrile, pimelic nitrile, suberonitrile, nonyldinitrile and decyldinitrile.
Specifically, the electrolyte additive is 1-5% by mass relative to the nonaqueous electrolyte based on 100% by mass of the total nonaqueous electrolyte.
Specifically, in some embodiments of the present invention, the negative electrode includes a negative electrode active material including a carbon material selected from one or more of hard carbon, soft carbon.
Specifically, in some embodiments of the present invention, the positive electrode includes a positive electrode active material selected from one or more of layered transition metal oxides, prussian compounds, phosphate compounds, sulfate compounds;
The chemical formula of the layered transition metal oxide is Na xMyOz, x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, z is more than 1 and less than or equal to 2, and M is one or more than one of Cr, fe, co, ni, cu, mn, sn, mo, sb, V; the transition metal oxide is NaNimFenMnpO2(m+n+p＝1,0≤m≤1,0≤n≤1,0≤p≤1)、NaNimConMnpO2(m+n+p＝1,0≤m≤1,0≤n≤1,0≤p≤1);
Preferably, the layered transition metal oxide is selected from one or more of Na[Cu1/9Ni2/9Fe1/3Mn1/3]O2、Na0.44MnO2、Na2/3[Fe1/2Mn1/2]O2、Na[Ni1/3Fe1/3Mn1/3]O2、Na7/9[Cu2/9Fe1/9Mn2/3]O2、NaNi0.7Co0.15Mn0.15O2;
The molecular formula of the Prussian compound is Na xM[M′(CN)6]y·zH2 O, M is transition metal, M' is transition metal, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 20;
Preferably, the Prussian compound is Na xMn[Fe(CN)6]y·nH2 O (x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 20) or Na xFe[Fe(CN)6]y·nH2 O (x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 20);
the chemical formula of the phosphate compound is Na 3(MO1-xPO4)2F1+2x, x is more than or equal to 0 and less than or equal to 1, and M is one or more than one kind of Al, V, ge, fe, ga;
preferably, the chemical formula of the phosphate compound is Na 3(VPO4)2F3、Na3(VOPO4)2 F;
the chemical formula of the phosphate compound is Na 2MPO4 F, and M is one or more of Fe and Mn;
Preferably, the chemical formula of the phosphate compound is Na 2FePO4F、Na2MnPO4 F;
The chemical formula of the sulfate compound is Na 2M(SO4)2·2H2 O, and M is one or more than one of Cr, fe, co, ni, cu, mn, sn, mo, sb, V.
Compared with the prior art, the invention has the following beneficial effects:
the fluoroether solvent used in the invention can participate in the solvation structure of ions, form SEI film and CEI film with stable structure on the surface of the electrode material, and improve the interface stability of the electrode material and electrolyte, thereby improving the cycle performance of the sodium ion secondary battery
However, the use of the fluoroether can increase the viscosity of the electrolyte, especially the viscosity is seriously increased at low temperature, and the adverse effect of degrading the low-temperature performance of the battery can be generated, and the adverse effect can be eliminated/lightened by regulating the charge-discharge direct current internal resistance defined by the invention, so as to achieve the effect of improving the low-temperature performance of the sodium battery.
According to the sodium ion battery, fluoroether with a specific structure and content is selected as the solvent, and the relationship between the fluoroether solvent content and the battery charge-discharge direct current internal resistance is controlled, so that the electrolyte conductivity can be improved, the viscosity can be reduced, the low charge-discharge direct current internal resistance which is slowly increased in the circulating process can be maintained, the excellent and stable coulomb efficiency of the battery in the circulating process can be maintained, the low charge-discharge tributary internal resistance can be increased, and the circulating performance of the battery can be further improved.
Detailed Description
The following description of the embodiments of the present invention will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is apparent 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, are intended to fall within the scope of the invention.
1) The method for adjusting and processing the charging direct current internal resistance A and the discharging direct current internal resistance B comprises the following steps:
the direct current internal resistance of the battery can be regulated and controlled by regulating and controlling the use amount of fluoroether and negative electrode conductive agent to meet a specific range.
Wherein, when the fluoroether content is more than or equal to 5% and less than or equal to 50% of C and the content of the negative electrode conductive agent is 2-6%, the charging direct current internal resistance can reach more than or equal to 85 and less than or equal to 115A, and the discharging direct current internal resistance can reach more than or equal to 80 and less than or equal to 110B.
2) The testing method comprises the following steps:
The full-charged battery is charged and discharged for a short time with the following different multiplying powers:
Constant current charging at 0.05C for 10s, resting for 40s, constant current discharging at 0.05C for 10s, resting for 40s;
Constant current charging at 0.25C for 10s, resting for 40s, constant current discharging at 0.25C for 10s, resting for 40s;
Constant current charging for 10s at 0.45C, resting for 40s, constant current discharging for 10s at 0.45C, resting for 40s;
Constant current charging for 10s at 0.65C, resting for 40s, constant current discharging for 10s at 0.65C, resting for 40s;
Recording the charge cut-off voltage and the discharge cut-off voltage of different charge and discharge multiplying power, and calculating the formula of the charge and discharge direct current internal resistance as follows:
Charging DC internal resistance= (V 0.65C Charging method -V0.25C Charging method )/(0.65C-0.25C)
Discharge DC internal resistance= (V 0.65C Discharge of electric power -V0.25C Discharge of electric power )/(0.65C-0.25C)
Examples 1 to 10
The invention provides a sodium ion battery, which comprises a positive electrode, a negative electrode and electrolyte.
(1) Preparation of fluoroether: the fluoroether synthesis method of the present invention can be carried out by reacting corresponding alcohol with alcohol reagent or other alkylating reagent in NMP solvent under catalysis of NaOH to produce corresponding ether.
Taking example 1 as an example, 2,3, 4, 5-octafluoro-1-pentanol was used, in NMP solvent, reacting with ethanol under the catalysis of NaOH to obtain 2,3, 4, 5-octafluoropentyl ethyl ether.
(2) Preparation of electrolyte
Fluoroether solvent and Ethyl Methyl Carbonate (EMC) as well as 13% sodium hexafluorophosphate (NaPF 6) and 2% fluorinated ethylene carbonate were added in the mass percentages shown in table 1 based on 100% of the total weight of the electrolyte.
(3) Preparation of positive plate
Taking and mixing an anode active material NaNi 1/3Fe1/3Mn1/3O2, conductive carbon black Super-P and a binder polyvinylidene fluoride (PVDF) according to the mass ratio of 93:4:3, and dispersing the materials in a proper amount of N-methyl-2-pyrrolidone (NMP) to obtain anode slurry; the obtained sizing agent is evenly coated on two sides of an aluminum foil, and the positive plate is obtained after drying, calendaring and vacuum drying, and an aluminum outgoing line is welded by an ultrasonic welder, and the thickness of the positive plate is 120-150 mu m.
(4) Preparation of negative plate
Taking hard carbon, conductive carbon black Super-P, binder Styrene Butadiene Rubber (SBR) and carboxymethyl cellulose (CMC) according to the mass ratio of 94:1:2.5:2.5, mixing, and dispersing the mixture in a proper amount of deionized water to obtain negative electrode slurry; coating the slurry on two sides of a copper foil, drying, calendaring and vacuum drying, and welding a nickel lead-out wire by an ultrasonic welder to obtain a negative plate, wherein the thickness of the negative plate is 120-150 mu m.
(5) Preparation of the cell
And placing a three-layer diaphragm with the thickness of 20 mu m between the prepared positive plate and the negative plate, winding a sandwich structure formed by the positive plate, the negative plate and the diaphragm, flattening the winding body, putting into an aluminum foil packaging bag, and baking for 48 hours at the temperature of 75 ℃ in vacuum to obtain the battery cell to be injected with the liquid.
(6) Injection and formation of battery cell
In a glove box with the dew point controlled below-40 ℃, the prepared electrolyte is injected into a battery cell, and the battery cell is subjected to vacuum packaging and is kept for 24 hours.
Then the first charge is conventionally formed by the following steps: and (3) carrying out constant current charging at 0.05C for 180min, carrying out constant current charging at 0.2C to 3.95V, carrying out secondary vacuum sealing, then further carrying out constant current charging at 0.2C to 4.2V, and carrying out constant current discharging at 0.2C to 3.0V after standing at normal temperature for 24h to obtain the sodium ion battery, wherein the values of the charging direct current internal resistance A and the discharging direct current internal resistance B of the sodium ion battery are shown in the table 1.
Comparative examples 1 to 5
Comparative examples 1-5 include most of the operating steps in the examples described above, except that: in the preparation process of the electrolyte, the fluoroether solvent with the mass percentage shown in the comparative examples 1-5 in the table 1 and the charging direct current internal resistance A and the discharging direct current internal resistance B shown in the comparative examples 1-5 in the table 1 are added by taking 100% of the total mass of the electrolyte as a reference, so that test results are obtained and filled in the table 1.
Performance testing
The sodium ion batteries prepared in examples 1 to 10 and comparative examples 1 to 5 were respectively subjected to the following performance tests:
1. DC impedance test (DCIR test)
DCR ch = (charge off-voltage-start voltage)/current
DCR dis = (discharge cut-off voltage-start voltage)/current
DCIR test at 25 ℃):
The first step: the cell was charged for 10s at a constant current of 0.05C, DCR ch1 was measured, set aside for 40s, discharged for 10s at a constant current of 0.05C, set aside for 40s, and DCR dis1 was measured.
And a second step of: the cell was charged for 10s at a constant current of 0.25C, DCR ch2 was measured, left at rest for 40s, discharged for 10s at a constant current of 0.25C, left at rest for 40s, and DCR dis2 was measured.
And a third step of: the cell was charged for 10s at a constant current of 0.45C, DCR ch3 was measured, set aside for 40s, discharged for 10s at a constant current of 0.45C, set aside for 40s, and DCR dis3 was measured.
Fourth step: the cell was charged for 10s at a constant current of 0.65C, DCR ch4 was measured, set aside for 40s, discharged for 10s at a constant current of 0.65C, set aside for 40s, and DCR dis4 was measured.
DCRch taking the average of the measured DCR ch1、DCRch2、DCRch3、DCRch4;
DCRdis the average of the measured DCR dis1、DCRdis2、DCRdis3、DCRdis4 was taken.
2. And (3) testing the viscosity of an electrolyte: each of the prepared electrolyte sets was tested with a viscometer at 25℃and-20℃respectively.
3. Battery performance test
1) Coulomb efficiency test
Coulombic efficiency test at 25 ℃): the resulting battery was charged to 3.9V and 0.05C at 1/3C at 25 ℃, left to stand for 5min, and discharged to 1.5V at 1/3C to obtain its charge capacity and discharge capacity, and the coulombic efficiency was calculated.
Coulombic efficiency test at 45 ℃): the obtained battery was charged to 3.9V and 0.05C at 1/3C at 45℃and was left to stand for 5 minutes, then discharged to 1.5V at 1/3C to obtain the charge capacity and discharge capacity, and the coulombic efficiency was calculated.
2) Cycle performance test
And (3) high-temperature cycle test at 45 ℃): charging the battery to 3.9V at a constant current of 0.7C under a high temperature condition of 45 ℃, then reducing the constant voltage charging current to 0.05C, then discharging to 1.5V at a constant current of 1C, and circulating for 500 weeks;
The 500-week capacity retention rate=500-week discharge capacity/1-week discharge capacity×100% was calculated.
And (3) performing normal-temperature cycle test at 25 ℃: the battery is charged to 3.9V at constant current of 0.7C under normal temperature of 25 ℃, then charged at constant voltage of 3.9V, cut-off current of 0.05C, then discharged to 1.5V at constant current of 1C, and the cycle is 500 weeks;
The 500-week capacity retention = 500-week discharge capacity/1-3-week cycle discharge capacity average x 100% was calculated.
TABLE 1
As can be seen from the test results of examples 1 to 10 in Table 1, when the fluoroether solvent content satisfies the range of 5 to 50%, the battery has a higher cycle capacity retention rate and cycle coulombic efficiency, and the battery performance is superior; as is apparent from the test results of examples 1 to 10 and comparative examples 1 to 5, when the fluoroether solvent is not contained in the electrolyte, the stability of the CEI and SEI films formed on the positive and negative electrode sides is poor, and side reactions continue to occur in the electrolyte during high-temperature storage and circulation, so that the electrolyte and active materials are continuously consumed, thereby deteriorating the battery performance; when the fluoroether solvent content is too low, the fluoroether solvent cannot effectively participate in the formation process of CEI and SEI films, so that the stability of an electrode-electrolyte interface is poor in the circulation process, side reactions are aggravated, and the circulation performance is seriously deteriorated; when the fluoroether solvent content is too high, the viscosity of the electrolyte is increased, and the cycle performance of the battery is poor.
As is apparent from the test results of examples 1-2, 8, 10 and examples 3-5 in Table 1, when the relationship of 5 < C× (A-B) < 200 is satisfied between the charge-discharge DC internal resistance value and the fluoroether solvent content value on the basis that the fluoroether solvent content satisfies the range of 5-50%, it is possible to maintain a high and stable cycle coulombic efficiency while maintaining a low charge-discharge DC internal resistance increase during the cycle.
Examples 11 to 13
Examples 11-13 include most of the operation steps of the above examples, and their charging dc internal resistance and discharging dc internal resistance are the same as those of example 4. The difference is that: in the preparation process of the electrolyte, fluoroether solvents with structural formulas and contents shown in examples 11-13 in table 2 are added based on 100% of the total mass of the electrolyte, so that test results are obtained and filled in table 2.
Comparative examples 6 to 8
Comparative examples 6 to 8 include most of the operation steps in the above examples, and their charging dc internal resistance and discharging dc internal resistance are the same as those in example 4. The difference is that: in the preparation process of the electrolyte, the fluoroether solvent with the structural formula and the content shown in comparative examples 6-8 in Table 2 is added based on 100% of the total mass of the electrolyte, so that a test result is obtained and filled in Table 2.
TABLE 2
As can be seen from the test results in examples 4, 11 to 13 and comparative examples 6 to 8 in Table 2, when fluoroether solvents of appropriate structures are selected, the battery has a higher cycle capacity retention rate and cycle coulombic efficiency, and the battery performance is superior; when n/m is less than or equal to 1.5, the dipole moment is reduced, the solubility of lithium salt is reduced, and the rate performance of the battery is seriously reduced; when X/(2n+1) is more than or equal to 80%, the solubility of fluoroether to salt is reduced, so that the conductivity of the electrolyte is reduced, and the cycle reversibility of the battery is reduced.
In summary, the invention provides a nonaqueous electrolyte, which can improve the electric conduction of the electrolyte and reduce the viscosity by selecting fluoroether with specific structure and content as a solvent, and keep the low charge-discharge direct current internal resistance which is slowly increased in the circulation process, so that the battery can keep excellent and stable coulombic efficiency in the circulation process. Meanwhile, by adopting the sodium ion battery of the nonaqueous electrolyte, the relationship between the fluoroether solvent content and the direct current internal resistance of the battery charge and discharge can be controlled, so that the low internal resistance of the charge and discharge branches is kept to be increased in the circulation process, and meanwhile, the high and stable circulation coulomb efficiency is kept, and the circulation performance of the battery is further improved.
The invention has been further described with reference to specific embodiments, but it should be understood that the detailed description is not to be construed as limiting the spirit and scope of the invention, but rather as providing those skilled in the art with the benefit of this disclosure with the benefit of their various modifications to the described embodiments.
Claims (10)
1. A sodium ion battery comprises a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the non-aqueous electrolyte comprises electrolyte salt, a solvent and an additive,
The solvent comprises a fluoroether of the formula F xCnH2n+1-xOCmH2m+1, wherein: x/(2n+1) < 80%, n/m > 1.5,4 < n < 10, m < 1 < 5;
The sodium ion battery has a charging direct current internal resistance A at 25 ℃ and a discharging direct current internal resistance B at 25 ℃, and meets the following conditions: a is more than or equal to 85 and less than or equal to 115, B is more than or equal to 80 and less than or equal to 110,1 and A-B is more than or equal to 4;
the mass percentages of the charging direct current internal resistance A, the discharging direct current internal resistance B and the fluoroether C are as follows: 5 < C× (A-B) < 200;
the unit of the charging direct current internal resistance A is mΩ, the unit of the discharging direct current internal resistance B is mΩ, and the unit of the fluoroether mass percentage content C is%.
2. The sodium ion battery of claim 1 wherein the electrolyte comprises,
The fluoroether content C relative to the total mass of the nonaqueous electrolyte is 100 percent, and the fluoroether content C relative to the nonaqueous electrolyte satisfies the following conditions: c is more than or equal to 5% and less than or equal to 50%;
Preferably, the fluoroether is contained in an amount of 100% by mass based on the total mass of the nonaqueous electrolytic solution, wherein the amount of the fluoroether is: 7% < C% < 30%;
The mass percentages of the charging direct current internal resistance A, the discharging direct current internal resistance B and the fluoroether C are as follows: 7 < C× (A-B) < 120.
3. The sodium ion battery of claim 1 wherein the electrolyte comprises, the fluoroether comprises 2,3, 4, 5-octafluoropentyl methyl ether, 2,3, 4, 5-octafluoropentyl ethyl ether, 2,3, 4, 5-heptafluoropentyl methyl ether 2,3, 4, 5-heptafluoropentylethyl ether, 2,2,3,3,4,4,5-heptafluoropentylethyl ether, 2,2,3,3,4,4,5-heptafluoropentylethyl ether 2,3, 4, 5-heptafluoropentylethyl ether 2,2,3,3,4,4,5-heptafluoropentylmethyl ether, 2,2,3,3,4,4,5-heptafluoropentylethyl ether.
4. The sodium ion battery of claim 1, wherein the solvent further comprises one or more of a C3-C5 carbonate solvent, a C2-C6 carboxylate solvent, a C4-C10 ether solvent;
the solvent is 70-92% by mass relative to the nonaqueous electrolyte based on 100% by mass of the total nonaqueous electrolyte.
5. The sodium ion battery of claim 4 wherein the electrolyte comprises,
The carbonic ester solvent comprises C3-C5 cyclic carbonic ester or chain carbonic ester, wherein the cyclic carbonic ester is selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), gamma-butyrolactone (GBL) and Butylene Carbonate (BC); the chain carbonate is selected from one or more of dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) and dipropyl carbonate (DPC);
The carboxylic ester solvent of C2-C6 is selected from one or more of Ethyl Propionate (EP), methyl Acetate (MA), ethyl Acetate (EA), propyl acetate (EP), butyl acetate and Propyl Propionate (PP);
The ether solvent comprises C4-C10 cyclic ether or chain ether, and the cyclic ether is selected from one or more of 1, 3-Dioxolane (DOL), 1, 4-Dioxane (DX), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH 3 -THF) and 2-trifluoromethyl tetrahydrofuran (2-CF 3 -THF); the chain ether is selected from one or more of dimethoxy methane (DMM), 1, 2-dimethoxy ethane (DME), diethylene glycol dimethyl ether (TEGDME), ethylene glycol diethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
6. The sodium ion battery of claim 1, wherein the electrolyte salt comprises one or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium trifluoroacetate, sodium tetraphenylborate, sodium trifluoromethylsulfonate, sodium bis (fluorosulfonyl) imide, or sodium bis (trifluoromethylsulfonyl) imide;
the electrolyte salt is contained in an amount of 2.5 to 16.5% by mass relative to the nonaqueous electrolytic solution based on 100% by mass of the total nonaqueous electrolytic solution.
7. The sodium ion battery of claim 1, wherein the additive is selected from one or more of cyclic carbonate compounds, fluorinated cyclic carbonate compounds, cyclic sulfonate compounds, cyclic sulfate compounds, phosphate compounds, borate compounds, and nitrile compounds;
Preferably, the cyclic carbonate compound is selected from one or more of ethylene carbonate, ethylene carbonate and methylene ethylene carbonate;
The fluoro-cyclic carbonate compound is selected from one or more of fluoro-ethylene carbonate and difluoro-ethylene carbonate;
The cyclic sulfonate compound is selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone and propenyl-1, 3-sultone;
The cyclic sulfate compound is selected from one or more of vinyl sulfate, 4-methyl vinyl sulfate and propylene sulfate;
The phosphate compound is one or more of tripolyl phosphate, trimethyl phosphate, triethyl phosphate and tri (trimethyl silane) phosphate;
the borate compound is selected from one or more of tri (trimethylsilane) borate and tri (triethylsilane) borate;
The nitrile compound is selected from one or more of succinonitrile, glutaronitrile, ethylene glycol bis (propionitrile) ether, hexanedinitrile, adiponitrile, pimelic nitrile, suberonitrile, nonyldinitrile and decyldinitrile.
8. The sodium ion battery according to claim 7, wherein the electrolyte additive is contained in an amount of 1 to 5% by mass relative to the nonaqueous electrolyte based on 100% by mass of the nonaqueous electrolyte.
9. The sodium ion battery of claim 1, wherein the negative electrode comprises a negative electrode active material comprising a carbon material selected from one or more of hard carbon, soft carbon.
10. The sodium ion battery of claim 1, wherein the positive electrode comprises a positive electrode active material selected from one or more of layered transition metal oxides, prussian compounds, phosphate compounds, sulfate compounds;
Preferably, the chemical formula of the layered transition metal oxide is Na xMyOz, x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, z is more than 1 and less than or equal to 2, and M is one or more than one of Cr, fe, co, ni, cu, mn, sn, mo, sb, V; the transition metal oxide is NaNimFenMnpO2(m+n+p＝1,0≤m≤1,0≤n≤1,0≤p≤1)、NaNimConMnpO2(m+n+p＝1,0≤m≤1,0≤n≤1,0≤p≤1);
The molecular formula of the Prussian compound is Na xM[M′(CN)6]y·zH2 O, M is transition metal, M' is transition metal, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 20;
the chemical formula of the phosphate compound is Na 3(MO1-xPO4)2F1+2x, x is more than or equal to 0 and less than or equal to 1, and M is one or more than one kind of Al, V, ge, fe, ga;
The chemical formula of the sulfate compound is Na 2M(SO4)2·2H2 O, and M is one or more than one of Cr, fe, co, ni, cu, mn, sn, mo, sb, V.
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