CN114156539B - Sodium secondary battery electrolyte and sodium secondary battery - Google Patents
Sodium secondary battery electrolyte and sodium secondary battery Download PDFInfo
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- CN114156539B CN114156539B CN202111575711.8A CN202111575711A CN114156539B CN 114156539 B CN114156539 B CN 114156539B CN 202111575711 A CN202111575711 A CN 202111575711A CN 114156539 B CN114156539 B CN 114156539B
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- sodium
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- secondary battery
- sodium secondary
- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 226
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 171
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 171
- 239000011734 sodium Substances 0.000 title claims abstract description 171
- 239000000654 additive Substances 0.000 claims abstract description 84
- 230000000996 additive effect Effects 0.000 claims abstract description 78
- 239000003960 organic solvent Substances 0.000 claims abstract description 45
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 44
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 43
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011737 fluorine Substances 0.000 claims abstract description 35
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 57
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 48
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 40
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 37
- 239000012046 mixed solvent Substances 0.000 claims description 37
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 15
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 15
- 150000005676 cyclic carbonates Chemical group 0.000 claims description 14
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 3
- IHQMTBUROQWHDL-UHFFFAOYSA-N 5-hydroxyoxan-2-one Chemical compound OC1CCC(=O)OC1 IHQMTBUROQWHDL-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 125000003118 aryl group Chemical group 0.000 abstract description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 9
- 230000002427 irreversible effect Effects 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 238000002161 passivation Methods 0.000 abstract description 3
- 238000007747 plating Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910021385 hard carbon Inorganic materials 0.000 description 63
- 238000012360 testing method Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 23
- 238000003756 stirring Methods 0.000 description 23
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 2
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 2
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 2
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 2
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 2
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 2
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910021201 NaFSI Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008194 pharmaceutical composition Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
-
- 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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- 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
本发明涉及钠二次电池电解液及钠二次电池。该钠二次电池电解液包括有机溶剂、电解质钠盐和具有式(I)所示结构的含氟类添加剂，R1、R2、R3、R4和R5分别独立选自‑H、卤素、C1～C20烷基、卤代的C1～C20烷基、C6～C26芳基或卤代的C6～C26芳基。该钠二次电解液能减低电解液的不可逆分解反应，显著提高电解液的循环稳定性、容量保持率和库伦效率，且还能显著抑制电解液酸度和色度的升高。将其应用于钠二次电池中，其能诱导电极表面形成稳定的、低阻抗的钝化膜，进一步改善电池的循环性能，并且能够促成钠金属表面更均匀的钠电镀与脱出，还能够使电解液与电极的接触角变小，提高浸润性，有利于钠离子传输。
The present invention relates to a sodium secondary battery electrolyte and a sodium secondary battery. The sodium secondary battery electrolyte comprises an organic solvent, an electrolyte sodium salt and a fluorine-containing additive having a structure shown in formula (I), wherein R1 , R2 , R3 , R4 and R5 are independently selected from -H, halogen, C1 - C20 alkyl, halogenated C1 - C20 alkyl, C6 - C26 aryl or halogenated C6 - C26 aryl. The sodium secondary electrolyte can reduce the irreversible decomposition reaction of the electrolyte, significantly improve the cycle stability, capacity retention rate and coulomb efficiency of the electrolyte, and can also significantly inhibit the increase of the acidity and chromaticity of the electrolyte. When applied to a sodium secondary battery, it can induce the formation of a stable, low-impedance passivation film on the electrode surface, further improve the cycle performance of the battery, and can promote more uniform sodium plating and stripping on the sodium metal surface, and can also reduce the contact angle between the electrolyte and the electrode, improve the wettability, and facilitate the transmission of sodium ions.
Description
Technical Field
The invention relates to the technical field of sodium batteries, in particular to a sodium secondary battery electrolyte and a sodium secondary battery.
Background
The lithium ion battery has the advantages of high capacity, good cycle stability, low pollution and the like, becomes the first choice in the fields of digital products, hybrid electric vehicles, pure electric vehicles, power grid energy storage and the like, and realizes industrialization in the 90 th century of 20 th year. However, after 30 years of development, lithium resources which are limited and extremely unevenly distributed in space are consumed in a large amount, and at present, the market demand of lithium ion batteries is still growing year by year, and the recovery technology of lithium-containing compounds is far from keeping pace with the consumption of lithium resources, and finally, the price of raw materials such as lithium carbonate is increased.
Although the energy density of the sodium ion battery is slightly inferior to that of the lithium ion battery, the sodium ion battery has the advantages of similar working mechanism and abundant and uniformly distributed raw materials and the like as the lithium ion battery, and has been rapidly developed in recent years, and the initial industrialization is realized in 2021. Sodium ion batteries are expected to gradually replace traditional lead-acid batteries, and are also expected to be fully applied to large-scale energy storage devices in the field of electric vehicles by attempting lithium-sodium sharing.
Since the electrolyte of the sodium ion battery does not directly determine the energy density of the battery, the research progress of the electrolyte is far from that of positive and negative electrode materials at present, and along with the commercialization of the sodium ion battery, the electrolyte serving as an ion conduction carrier becomes a new research hot spot. Similar to a lithium ion battery, the sodium system electrolyte is reduced and decomposed, and the reduction and decomposition phenomenon of the sodium system electrolyte is more severe, and the main manifestation is that a carbonate solvent is reduced and decomposed under low potential to generate obvious dendritic decomposition products, the products cover the surfaces of hard carbon particles, the effective surface area of the hard carbon particles is reduced, the transmission of sodium ions on the surface of the hard carbon is seriously influenced, the battery impedance is obviously increased after multiple cycles, and the battery cycle stability and the coulombic efficiency are reduced.
In the whole battery, it is important to inhibit the reduction and decomposition of the electrolyte, and the electrolyte decomposition causes the irreversible active sodium loss of the system, so that the cycle life of the whole battery is reduced, and meanwhile, the safety problems such as thermal runaway and the like are possibly caused by the larger impedance. Therefore, the design and optimization of the electrolyte is one of the key factors for ensuring the performance of the battery.
Theoretical basis of lithium ion battery shows that electrolyte is key to constructing good solid-liquid interface, and one of measures to achieve both performance and economic benefit is to use electrolyte additive. Although electrolyte additives have found widespread use in industrial lithium ion batteries, similar research in sodium systems has been very limited. The current research also shows that the same additive does not necessarily show ideal lifting effect when applied to sodium ion batteries, even certain commercial lithium ion battery additives generate obvious harmful side reactions in sodium systems or cause degradation of battery performance, for example Komab team reports in 2011 that adding trace VC into carbonate-based electrolyte can cause obvious discoloration of electrolyte, the cycle stability and capacity of sodium ion batteries using the electrolyte are obviously reduced compared with those of basic electrolyte, which indicates that the introduction of VC can be accompanied by the harmful side reactions, and DFEC and ES cause degradation of battery cycle performance. In addition, the Ponrouch team found that in EC/PC systems, the introduction of additive FEC resulted in a decrease in hard carbon sodium storage performance, manifested by a decrease in capacity and coulombic efficiency.
The experimental results reported above show that sodium ion batteries may have different film forming rules than lithium ion batteries, and the same additives may also exert different action mechanisms in the lithium system, which fully suggests that the development of sodium ion battery additives is not a simple replication of the lithium system, but rather that the exploration of sodium ion battery additives is more challenging than the matured lithium system, and thus, the research of additives in the field of sodium ion batteries requires more attempts and deeper profiling.
Disclosure of Invention
Based on the above, the invention provides a sodium secondary battery electrolyte with less irreversible decomposition reaction, good cycle stability, high capacity retention rate and high coulombic efficiency, which can be used for preparing a sodium secondary battery with good cycle performance and low impedance.
The technical proposal is as follows:
A sodium secondary battery electrolyte comprises an organic solvent, electrolyte sodium salt and fluorine-containing additive with a structure shown in a formula (I);
Wherein:
R 1、R2、R3、R4 and R 5 are each independently selected from-H, halogen, C 1～C20 alkyl, halogenated C 1～C20 alkyl, C 6～C26 aryl or halogenated C 6～C26 aryl.
In one embodiment, R 1、R2、R3、R4 and R 5 are each independently selected from the group consisting of-H, F, C 1～C10 alkyl, C 1～C10 alkyl of the F-generation, C 6～C12 aryl, and C 6～C12 aryl of the F-generation.
In one embodiment, R 1、R2、R3、R4 and R 5 are each independently selected from the group consisting of-H, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, octyl, phenyl, naphthyl, and biphenyl.
In one embodiment, the fluorine-containing additive has a structure as shown in any one of the following (F1) to (F8):
In one embodiment, the fluorine-containing additive is
In one embodiment, the sodium secondary battery electrolyte comprises 72-92% of an organic solvent, 7-23% of electrolyte sodium salt and 1-5% of fluorine-containing additive with a structure shown in formula (I) by mass percentage.
In one embodiment, the sodium secondary battery electrolyte comprises 79-90% of an organic solvent, 9-20% of electrolyte sodium salt and 1-3% of a fluorine-containing additive with a structure shown in formula (I) by mass percentage.
In one embodiment, the organic solvent is a cyclic carbonate or a linear carbonate, or a mixed solvent composed of a cyclic carbonate and a linear carbonate.
In one embodiment, the cyclic carbonate is selected from at least one of a cyclic carbonate (EC), a Propylene Carbonate (PC), a gamma-hydroxybutyrolactone (GBL), a 4-hydroxy-n-valerolactone (GVL), and a delta-valerolactone (DVL);
the linear carbonate is at least one selected from diethyl carbonate (DEC), ethylmethyl carbonate (EMC) and dimethyl carbonate (DMC).
In one embodiment, the volume ratio of the cyclic carbonate to the linear carbonate in the mixed solvent is (0.8 to 1.2): 1.
In one embodiment, the organic solvent is a mixed solvent consisting of ethylene carbonate and diethyl carbonate according to the volume ratio of 1:1, or
The organic solvent is a mixed solvent consisting of ethylene carbonate and ethylmethyl carbonate according to the volume ratio of 1:1, or
The organic solvent is a mixed solvent consisting of gamma-hydroxybutyric acid lactone and diethyl carbonate according to the volume ratio of 1:1.
In one embodiment, the electrolyte sodium salt is selected from at least one of sodium hexafluorophosphate (NaPF 6), sodium perchlorate (NaClO 4), sodium bis (fluorosulfonyl) imide (NaFSA/NaFSI), (trifluoromethylsulfonyl) imide (NaTFSI), and sodium trifluoromethylsulfonate (NaOTF).
In one embodiment, the concentration of the electrolyte sodium salt in the organic solvent is 0.8mol/L to 1.5mol/L.
The invention also provides a sodium secondary battery comprising the electrolyte of the sodium secondary battery.
In one embodiment, the sodium secondary battery is a sodium ion battery or a sodium air battery.
In one embodiment, the sodium ion battery is a hard carbon/sodium half-cell, a sodium/sodium symmetric cell, or a sodium vanadium phosphate/hard carbon full cell.
The invention has the following beneficial effects:
The electrolyte provided by the invention comprises an organic solvent, electrolyte sodium salt and a specific fluorine-containing compound with a structure shown in a formula (I), through the synergistic effect of the organic solvent, the electrolyte sodium salt and the specific fluorine-containing compound, the irreversible decomposition reaction of the electrolyte can be reduced, the cycle stability, the capacity retention rate and the coulombic efficiency of the electrolyte are obviously improved, and the acidity and the chromaticity of the electrolyte can be obviously inhibited.
The electrolyte is applied to a sodium secondary battery, (1) the electrolyte can induce the electrode surface to form a stable passivation film with low impedance, modify an electrode interface, further promote the improvement of the cycle performance of the battery, greatly reduce the impedance of the battery after different cycle times, and improve the rate stability and the capacity performance normalization of the battery, in particular to a hard carbon/sodium half-battery. (2) The side reactions such as irreversible decomposition of electrolyte are reduced, interface impedance is reduced, interface stability is remarkably improved, capacity attenuation of the battery at normal temperature is effectively controlled, and cycle stability is remarkably improved, particularly for a hard carbon/sodium half-battery. (3) The method can promote more uniform sodium electroplating and removal of the sodium metal surface, realize more ideal modification effect of the sodium metal surface, finally lead the overpotential of the sodium metal to change stably, improve the cycling stability of the battery, and the experimental result has a certain reference value for the design and optimization of the electrolyte of the sodium metal battery. (4) The contact angle between the sodium secondary electrolyte and the electrode (particularly the hard carbon electrode) is smaller, so that the electrolyte can be better infiltrated on the surface of the hard carbon electrode, and the good wettability ensures the full contact between the electrolyte of the sodium secondary battery and the electrode, thereby ensuring effective sodium ion transmission and better film forming effect on the surface of the electrode, and finally ensuring the reversible sodium ion intercalation and deintercalation process and obviously improved electrochemical performance.
Drawings
FIG. 1 (a) is a graph comparing the cycling stability of the hard carbon/sodium half-cell prepared in example 2 with comparative example 1 according to example 1, and FIG. 1 (b) is a graph comparing the corresponding coulombic efficiencies;
FIG. 2 is a graph showing the impedance comparison of the hard carbon/sodium half cell prepared in example 1 of the present invention and comparative example 1 after various cycles;
FIG. 3 is a graph showing the comparison of the contact angle test results of the electrolytes prepared in example 1, example 2 and comparative example 1 according to the present invention;
FIG. 4 is a graph showing the comparison of the cycling stability of the sodium vanadium phosphate/hard carbon full cell prepared in example 3 of the present invention and comparative example 2 at different rates;
Fig. 5 is a graph comparing the cycling stability of sodium/sodium symmetric cells prepared in example 4 of the present invention with comparative example 3.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention, and preferred embodiments of the present invention are set forth. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
The term "alkyl" refers to a saturated hydrocarbon containing primary (positive) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. The phrase containing the term, for example, "C 1-16 alkyl" refers to an alkyl group containing 1 to 16 carbon atoms. Suitable examples include, but are not limited to, methyl (Me, -CH 3), ethyl (Et, -CH 2CH3), 1-propyl (n-Pr, n-propyl, -CH 2CH2CH3), 2-propyl (i-Pr, i-propyl), -CH (CH 3)2), 1-butyl (n-Bu, n-butyl, -CH 2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH 2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH (CH 3)CH2CH3), a catalyst for the preparation of a pharmaceutical composition, 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH 3)3), 1-pentyl (n-pentyl, -CH 2CH2CH2CH2CH3), 2-pentyl (-CH (CH 3) CH2CH2CH 3), 3-pentyl (-CH (CH 2CH3)2), a process for preparing the same, 2-methyl-2-butyl (-C (CH 3)2CH2CH3), 3-methyl-2-butyl (-CH (CH 3)CH(CH3)2), 3-methyl-1-butyl (-CH 2CH2CH(CH3)2), 2-methyl-1-butyl (-CH 2CH(CH3)CH2CH3), 1-hexyl (-CH 2CH2CH2CH2CH2CH3), 2-hexyl (-CH (CH 3)CH2CH2CH2CH3), 3-hexyl (-CH (CH 2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C (CH 3)2CH2CH2CH3)), a catalyst, 3-methyl-2-pentyl (-CH (CH 3)CH(CH3)CH2CH3), 4-methyl-2-pentyl (-CH (CH 3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C (CH 3)(CH2CH3)2), 2-methyl-3-pentyl (-CH (CH 2CH3)CH(CH3)2)), a catalyst for the preparation of a pharmaceutical composition, 2, 3-dimethyl-2-butyl (-C (CH 3)2CH(CH3)2), 3-dimethyl-2-butyl (-CH (CH 3)C(CH3)3 and octyl (- (CH 2)7CH3)).
"Aryl" refers to an aromatic hydrocarbon radical derived from the removal of one hydrogen atom on the basis of an aromatic ring compound, which may be a monocyclic aryl radical, or a fused ring aryl radical, or a polycyclic aryl radical, at least one of which is an aromatic ring system for a polycyclic species. For example, "C 6～C26 aryl" refers to aryl groups containing 6 to 26 carbon atoms, suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene.
"Halogen" or "halo" refers to F, cl, br or I.
Based on the above, the invention provides a sodium secondary battery electrolyte with less irreversible decomposition reaction, good cycle stability, high capacity retention rate and high coulombic efficiency.
The technical proposal is as follows:
A sodium secondary battery electrolyte comprises an organic solvent, electrolyte sodium salt and fluorine-containing additive with a structure shown in a formula (I);
Wherein:
R 1、R2、R3、R4 and R 5 are each independently selected from-H, halogen, C 1～C20 alkyl, halogenated C 1～C20 alkyl, C 6～C26 aryl or halogenated C 6～C26 aryl.
The electrolyte provided by the invention comprises an organic solvent, electrolyte sodium salt and a specific fluorine-containing compound with a structure shown in a formula (I), through the synergistic effect of the organic solvent, the electrolyte sodium salt and the specific fluorine-containing compound, the irreversible decomposition reaction of the electrolyte can be reduced, the cycle stability, the capacity retention rate and the coulombic efficiency of the electrolyte are obviously improved, and the acidity and the chromaticity of the electrolyte can be obviously inhibited.
In one embodiment, R 1、R2、R3、R4 and R 5 are each independently selected from the group consisting of-H, F, C 1～C10 alkyl, C 1～C10 alkyl of the F-generation, C 6～C12 aryl, and C 6～C12 aryl of the F-generation.
In one embodiment, R 1、R2、R3、R4 and R 5 are each independently selected from the group consisting of-H, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, octyl, phenyl, naphthyl, and biphenyl.
In one embodiment, the fluorine-containing additive has a structure as shown in any one of the following (F1) to (F8):
In one embodiment, the fluorine-containing additive is
In one embodiment, the sodium secondary battery electrolyte comprises 72-92% of an organic solvent, 7-23% of electrolyte sodium salt and 1-5% of fluorine-containing additive with a structure shown in formula (I) by mass percentage.
In one embodiment, the sodium secondary battery electrolyte comprises 79-90% of an organic solvent, 9-20% of electrolyte sodium salt and 1-3% of a fluorine-containing additive with a structure shown in formula (I) by mass percentage.
In one embodiment, the organic solvent is a cyclic carbonate or a linear carbonate, or a mixed solvent composed of a cyclic carbonate and a linear carbonate.
In one embodiment, the cyclic carbonate is selected from at least one of a cyclic carbonate (EC), a Propylene Carbonate (PC), a gamma-hydroxybutyrolactone (GBL), a 4-hydroxy-n-valerolactone (GVL), and a delta-valerolactone (DVL);
the linear carbonate is at least one selected from diethyl carbonate (DEC), ethylmethyl carbonate (EMC) and dimethyl carbonate (DMC).
In one embodiment, the volume ratio of the cyclic carbonate to the linear carbonate in the mixed solvent is (0.8 to 1.2): 1.
In one embodiment, the organic solvent is a mixed solvent consisting of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1.
In one embodiment, the organic solvent is a mixed solvent consisting of ethylene carbonate and ethylmethyl carbonate in a volume ratio of 1:1.
In one embodiment, the organic solvent is a mixed solvent consisting of gamma-hydroxybutyric acid lactone and diethyl carbonate in a volume ratio of 1:1.
In one embodiment, the electrolyte sodium salt is selected from at least one of sodium hexafluorophosphate (NaPF 6), sodium perchlorate (NaClO 4), sodium bis (fluorosulfonyl) imide (NaFSA/NaFSI), (trifluoromethylsulfonyl) imide (NaTFSI), and sodium trifluoromethylsulfonate (NaOTF).
In one embodiment, the concentration of the electrolyte sodium salt in the organic solvent is 0.8mol/L to 1.5mol/L.
Preferably, the purity of the sodium hexafluorophosphate is more than or equal to 99 percent so as to ensure that the sodium hexafluorophosphate can be completely dissolved in the organic solvent, and further, the concentration of the sodium hexafluorophosphate in the organic solvent is 1mol L -1.
The invention also provides a sodium secondary battery comprising the electrolyte of the sodium secondary battery.
In one embodiment, the sodium secondary battery is a sodium ion battery or a sodium air battery.
In one embodiment, the sodium ion battery is a hard carbon/sodium half-cell, a sodium/sodium symmetric cell, or a sodium vanadium phosphate/hard carbon full cell.
The electrolyte is applied to a sodium secondary battery, (1) the electrolyte can induce the electrode surface to form a stable passivation film with low impedance, modify an electrode interface, further promote the improvement of the cycle performance of the battery, greatly reduce the impedance of the battery after different cycle times, and improve the rate stability and the capacity performance normalization of the battery, in particular to a hard carbon/sodium half-battery. (2) The method reduces side reactions such as irreversible decomposition of electrolyte, reduces interface impedance, remarkably improves interface stability, effectively controls capacity attenuation of the hard battery at normal temperature, and remarkably improves cycle stability, in particular to a hard carbon/sodium half battery. (3) The method can promote more uniform sodium electroplating and removal of the sodium metal surface, realize more ideal modification effect of the sodium metal surface, finally lead the overpotential of the sodium metal to change stably, improve the cycling stability of the battery, and the experimental result has a certain reference value for the design and optimization of the electrolyte of the sodium metal battery. (4) The contact angle between the sodium secondary electrolyte and the electrode (particularly the hard carbon electrode) is smaller, so that the electrolyte can be better infiltrated on the surface of the hard carbon electrode, and the good wettability ensures the full contact between the electrolyte of the sodium secondary battery and the electrode, thereby ensuring effective sodium ion transmission and better film forming effect on the surface of the electrode, and finally ensuring the reversible sodium ion intercalation and deintercalation process and obviously improved electrochemical performance.
The present invention will be described in further detail with reference to the following examples.
(1) The base electrolyte and the electrolyte containing 1wt% and 3wt% of additive in the following examples and comparative examples are sealed by using a polytetrafluoroethylene container;
(2) The method comprises the steps of using a 1mL range injector to drop liquid in the test process, using a POWEREACH contact angle measuring instrument to test, and analyzing the contact angle value by the instrument;
(3) The preparation method of the hard carbon electrode comprises the steps of pulping by a ball mill, namely, using polyvinylidene fluoride (PVDF) as an adhesive, using Super P as a conductive agent, using N-methyl pyrrolidone as a solvent, and performing ball milling for 5-10 hours, coating the slurry on copper foil with the coating thickness of 50 mu m, firstly removing the solvent by a 80 ℃ air blast drying oven for 2 hours, and then transferring to a 120 ℃ vacuum drying oven for deep drying for 12-20 hours;
(4) The preparation method of the vanadium sodium phosphate electrode comprises the following steps of pulping by using a ball mill, wherein the used adhesive is polyvinylidene fluoride (PVDF), the used conductive agent is Super P, the used solvent is N-methyl pyrrolidone, and the ball milling time is 5-10 hours;
(5) The method comprises the steps of sequentially placing a negative electrode shell, a spring piece, a steel gasket and a metal sodium sheet, then dripping 100 mu L of electrolyte, placing a glass fiber diaphragm, dripping 100 mu L of electrolyte, sequentially placing a hard carbon electrode and a positive electrode shell, ensuring the circle centers of all parts to be aligned, and compacting by a battery packaging machine, wherein the hard carbon/sodium half battery uses a 2032 type battery shell, the diameter of the hard carbon electrode is 12mm, the diameter of the sodium sheet is kept consistent with that of the steel gasket (15.6 mm), and the diameter of the used diaphragm is 18mm;
(6) The method comprises the steps of sequentially placing a negative electrode shell, a spring piece, a steel gasket and a hard carbon electrode, then dropwise adding 40 mu L of electrolyte, placing a polymer diaphragm, dropwise adding 40 mu L of electrolyte, sequentially placing a vanadium sodium phosphate electrode and a positive electrode shell, ensuring the circle centers of all components to be aligned, and compacting by a battery packaging machine, wherein the vanadium sodium phosphate/hard carbon full battery is a 2025 type battery shell, the diameter of the hard carbon electrode is 12mm, and the diameter of the used diaphragm is 18mm;
(7) The method comprises the steps of sequentially placing a negative electrode shell, a spring piece, a steel gasket and a metal sodium sheet, then dripping 100 mu L of electrolyte, placing a glass fiber diaphragm, dripping 100 mu L of electrolyte, sequentially placing the metal sodium sheet, the steel gasket and a positive electrode shell, ensuring the circle centers of all the components to be aligned, and compacting by a battery packaging machine, wherein the sodium/sodium symmetric battery uses a 2032 type battery shell, the diameter of the sodium sheet is kept consistent with that of the steel gasket (15.6 mm), and the diameter of the diaphragm is 18mm;
(8) The constant current charge and discharge test method for the battery comprises the steps of executing constant current charge and discharge test by using a blue electric tester, activating a hard carbon/sodium half battery by 0.1C for 3 circles, circulating the battery by 0.5C for 500 circles, wherein a charge and discharge potential window is 0.01-2.5V, circulating the battery by 1C for 500 circles for the vanadium sodium phosphate/hard carbon full battery, and circulating the battery by about 150 circles (about 300 hours) by adopting a constant current charge and discharge step of 0.5mA cm -2 current density (which is equivalent to the actual current of 0.943 mA) for the sodium/sodium symmetrical battery.
(9) The impedance test method for the hard carbon/sodium battery with a certain circle of cycles is that the object for testing the impedance is 150 and 500 circles of hard carbon/sodium half batteries which are in a sodium removal state after the cycle is finished, and the frequency range adopted in the test is 100000 Hz-0.005 Hz.
(10) The characterization method of the hard carbon electrode comprises the steps of disassembling a hard carbon/sodium battery after circulation is finished, using diethyl carbonate (DEC) to rinse the hard carbon electrode taken out from the disassembled battery, scraping residual glass fibers on the surface of the electrode by using a thin blade, airing for 2-3 hours to volatilize the DEC solvent on the surface of the electrode completely, and using a 10mL centrifuge tube to store in a sealing mode for characterization.
Example 1
In this embodiment, a sodium secondary battery electrolyte and a sodium ion battery are provided.
(1) The electrolyte of the sodium secondary battery of the embodiment comprises the following components in percentage by mass:
86% of organic solvent, 13% of electrolyte sodium salt and 1% of fluorine-containing additive;
Wherein the organic solvent is a mixed solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1:1, the electrolyte sodium salt is sodium hexafluorophosphate, and the fluorine-containing additive is
(2) The sodium secondary battery electrolyte and the sodium ion battery of this example were prepared as follows:
1) Mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to a volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved to prepare a mixed solvent;
2) Adding sodium hexafluorophosphate with a given mass into the mixed solvent obtained in the step 1), enabling the concentration of the sodium hexafluorophosphate to be 1mol L -1, and fully stirring until sodium salt is completely dissolved, thus obtaining a basic electrolyte;
3) Adding an additive F1 into the basic electrolyte obtained in the step 2), wherein the mass fraction of the additive F1 is 1wt% of the total mass of the electrolyte, uniformly shaking or stirring until the additive is completely dissolved, and standing for 12 hours to obtain the sodium secondary battery electrolyte containing 1wt% of F1.
4) The hard carbon/sodium button cell was assembled with the sodium secondary battery electrolyte containing 1wt% f1 obtained in step 3), and after standing for 12 hours, a constant current charge and discharge test was performed at a rate of 0.5C to evaluate the cycle stability of the cell under the influence of the electrolyte.
5) The battery circularly tested in the step 4) was subjected to an alternating current impedance test to evaluate the effect of a sodium secondary battery electrolyte containing 1wt% f1 on the battery impedance.
6) And 3) carrying out a contact angle test on the sodium secondary battery electrolyte containing 1wt% F1 obtained in the step 3), and testing the contact angle between the sodium secondary battery electrolyte and the hard carbon electrode, wherein the contact angle can reflect the wettability of the electrolyte on the surface of the hard carbon electrode.
Example 2
In this embodiment, a sodium secondary battery electrolyte and a sodium ion battery are provided.
(1) The electrolyte of the sodium secondary battery of the embodiment comprises the following components in percentage by mass:
80% of organic solvent, 17% of electrolyte sodium salt and 3% of fluorine-containing additive;
Wherein the organic solvent is a mixed solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1:1, the electrolyte sodium salt is sodium hexafluorophosphate, and the fluorine-containing additive is
(2) The sodium secondary battery electrolyte and the sodium ion battery of this example were prepared as follows:
1) Mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to a volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved, so as to prepare a mixed solvent;
2) Adding sodium hexafluorophosphate with a given mass into the mixed solvent obtained in the step 1), enabling the concentration of the sodium hexafluorophosphate to be 1mol L -1, and fully stirring until sodium salt is completely dissolved, thus obtaining a basic electrolyte;
3) Adding an additive to the base electrolyte obtained in step 2) The mass fraction of the electrolyte is 3wt% of the total mass of the electrolyte, and the electrolyte is uniformly shaken or stirred until the additive is completely dissolved and then is stood for 12 hours, so that the sodium secondary battery electrolyte containing 3wt% of F1 is obtained.
4) The sodium secondary battery electrolyte containing 3wt% f1 obtained in step 3) was assembled with a hard carbon/sodium button cell, and after standing for 12 hours, a constant current charge and discharge test was performed at a rate of 0.5C to evaluate the cycle stability of the battery under the influence of the electrolyte.
5) And 3) carrying out a contact angle test on the sodium secondary battery electrolyte containing 3wt% of F1 obtained in the step 3), and testing the contact angle between the sodium secondary battery electrolyte and the hard carbon electrode, wherein the contact angle can reflect the wettability of the electrolyte on the surface of the hard carbon electrode.
Example 3
In this embodiment, a sodium secondary battery electrolyte and a sodium ion battery are provided.
(1) The electrolyte of the sodium secondary battery of the embodiment comprises the following components in percentage by mass:
86% of organic solvent, 13% of electrolyte sodium salt and 1% of fluorine-containing additive;
Wherein the organic solvent is a mixed solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1:1, the electrolyte sodium salt is sodium hexafluorophosphate, and the fluorine-containing additive is
(2) The sodium secondary battery electrolyte and the sodium ion battery of this example were prepared as follows:
1) Mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to a volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved to prepare a mixed solvent;
2) Adding sodium hexafluorophosphate with a given mass into the mixed solvent obtained in the step 1), enabling the concentration of the sodium hexafluorophosphate to be 1mol L -1, and fully stirring until sodium salt is completely dissolved, thus obtaining a basic electrolyte;
3) Adding an additive F1 into the basic electrolyte obtained in the step 2), wherein the mass fraction of the additive F1 is 1wt% of the total mass of the electrolyte, uniformly shaking or stirring until the additive is completely dissolved, and standing for 12 hours to obtain the sodium secondary battery electrolyte containing 1wt% of F1.
4) Assembling a sodium vanadium phosphate/hard carbon button cell with the sodium secondary battery electrolyte containing 1wt% F1 obtained in the step 3), and performing constant current charge and discharge test at 0.1C multiplying power after standing for 12 hours to evaluate the cycle stability of the cell under the influence of the electrolyte.
Example 4
In this embodiment, a sodium secondary battery electrolyte and a sodium ion battery are provided.
(1) The electrolyte of the sodium secondary battery of the embodiment comprises the following components in percentage by mass:
86% of organic solvent, 13% of electrolyte sodium salt and 1% of fluorine-containing additive;
Wherein the organic solvent is a mixed solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1:1, the electrolyte sodium salt is sodium hexafluorophosphate, and the fluorine-containing additive is
(2) The sodium secondary battery electrolyte and the sodium ion battery of this example were prepared as follows:
1) Mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to a volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved to prepare a mixed solvent;
2) Adding sodium hexafluorophosphate with a given mass into the mixed solvent obtained in the step 1), enabling the concentration of the sodium hexafluorophosphate to be 1mol L -1, and fully stirring until sodium salt is completely dissolved, thus obtaining a basic electrolyte;
3) Adding an additive F1 into the basic electrolyte obtained in the step 2), wherein the mass fraction of the additive F1 is 1wt% of the total mass of the electrolyte, uniformly shaking or stirring until the additive is completely dissolved, and standing for 12 hours to obtain the sodium secondary battery electrolyte containing 1wt% of F1.
4) The sodium/sodium button cell was assembled with the sodium secondary battery electrolyte containing 1wt% f1 obtained in step 3), and after standing for 12 hours, a constant current charge and discharge test was performed at a current density of 0.5mA cm -2 (0.943 mA) to evaluate the cycle stability of sodium ions in bipolar plating/stripping.
Example 5
In this embodiment, a sodium secondary battery electrolyte and a sodium ion battery are provided.
(1) The electrolyte of the sodium secondary battery of the embodiment comprises the following components in percentage by mass:
86% of organic solvent, 13% of electrolyte sodium salt and 1% of fluorine-containing additive;
Wherein the organic solvent is a mixed solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1:1, the electrolyte sodium salt is sodium hexafluorophosphate, and the fluorine-containing additive is
(2) The sodium secondary battery electrolyte and the sodium ion battery of this example were prepared as follows:
1) Mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to a volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved to prepare a mixed solvent;
2) Adding sodium hexafluorophosphate with a given mass into the mixed solvent obtained in the step 1), enabling the concentration of the sodium hexafluorophosphate to be 1mol L -1, and fully stirring until sodium salt is completely dissolved, thus obtaining a basic electrolyte;
3) And 2) adding an additive F5 into the basic electrolyte obtained in the step 2), wherein the mass fraction of the additive F5 is 1wt% of the total mass of the electrolyte, uniformly shaking or stirring until the additive is completely dissolved, and standing for 12 hours to obtain the sodium secondary battery electrolyte containing 1wt% of F5.
4) The hard carbon/sodium button cell was assembled with the sodium secondary battery electrolyte containing 1wt% f5 obtained in step 3), and after standing for 12 hours, a constant current charge and discharge test was performed at a rate of 0.5C to evaluate the cycle stability of the cell under the influence of the electrolyte.
5) The battery circularly tested in the step 4) was subjected to an alternating current impedance test to evaluate the effect of a sodium secondary battery electrolyte containing 1wt% f5 on the battery impedance.
6) And 3) carrying out a contact angle test on the sodium secondary battery electrolyte containing 1wt% F5 obtained in the step 3), and testing the contact angle between the sodium secondary battery electrolyte and the hard carbon electrode, wherein the contact angle can reflect the wettability of the electrolyte on the surface of the hard carbon electrode.
Example 6
In this embodiment, a sodium secondary battery electrolyte and a sodium ion battery are provided.
(1) The electrolyte of the sodium secondary battery of the embodiment comprises the following components in percentage by mass:
80% of organic solvent, 17% of electrolyte sodium salt and 3% of fluorine-containing additive;
wherein the organic solvent is a mixed solvent of Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) according to the volume ratio of 1:1, the electrolyte sodium salt is bis (fluorosulfonyl) sodium imide, and the fluorine-containing additive is
(2) The sodium secondary battery electrolyte and the sodium ion battery of this example were prepared as follows:
1) Mixing Ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) according to a volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved to prepare a mixed solvent;
2) Adding bis (fluorosulfonyl) sodium imide with a given mass into the mixed solvent obtained in the step 1), enabling the concentration of the bis (fluorosulfonyl) sodium imide to be 1mol L -1, and fully stirring until sodium salt is completely dissolved, thus obtaining a basic electrolyte;
3) And 3) adding an additive F5 into the basic electrolyte obtained in the step 2), wherein the mass fraction of the additive F5 is 3wt% of the total mass of the electrolyte, uniformly shaking or stirring until the additive is completely dissolved, and standing for 12 hours to obtain the sodium secondary battery electrolyte containing 3wt% of F5.
4) The hard carbon/sodium button cell was assembled with the electrolyte for sodium secondary battery containing 3wt% f5 obtained in step 3), and after standing for 12 hours, a constant current charge and discharge test was performed at a rate of 0.5C to evaluate the cycle stability of the battery under the influence of the electrolyte.
5) The battery circularly tested in the step 4) was subjected to an alternating current impedance test to evaluate the effect of the electrolyte of the sodium secondary battery containing 3wt% of F5 on the battery impedance.
6) And 3) carrying out a contact angle test on the sodium secondary battery electrolyte containing 3wt% of F5 obtained in the step 3), and testing the contact angle between the sodium secondary battery electrolyte and the hard carbon electrode, wherein the contact angle can reflect the wettability of the electrolyte on the surface of the hard carbon electrode.
Example 7
In this embodiment, a sodium secondary battery electrolyte and a sodium ion battery are provided.
(1) The electrolyte of the sodium secondary battery of the embodiment comprises the following components in percentage by mass:
86% of organic solvent, 13% of electrolyte sodium salt and 1% of fluorine-containing additive;
Wherein the organic solvent is a mixed solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1:1, the electrolyte sodium salt is sodium hexafluorophosphate, and the fluorine-containing additive is
(2) The sodium secondary battery electrolyte and the sodium ion battery of this example were prepared as follows:
1) Mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to a volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved to prepare a mixed solvent;
2) Adding sodium hexafluorophosphate with a given mass into the mixed solvent obtained in the step 1), enabling the concentration of the sodium hexafluorophosphate to be 1mol L -1, and fully stirring until sodium salt is completely dissolved, thus obtaining a basic electrolyte;
3) And 2) adding an additive F5 into the basic electrolyte obtained in the step 2), wherein the mass fraction of the additive F5 is 1wt% of the total mass of the electrolyte, uniformly shaking or stirring until the additive is completely dissolved, and standing for 12 hours to obtain the sodium secondary battery electrolyte containing 1wt% of F5.
4) Assembling a sodium vanadium phosphate/hard carbon button cell with the sodium secondary battery electrolyte containing 1wt% F5 obtained in the step 3), and performing constant current charge and discharge test at 0.1C multiplying power after standing for 12 hours to evaluate the cycling stability of the cell under the influence of the electrolyte.
Example 8
In this embodiment, a sodium secondary battery electrolyte and a sodium ion battery are provided.
(1) The electrolyte of the sodium secondary battery of the embodiment comprises the following components in percentage by mass:
80% of organic solvent, 17% of electrolyte sodium salt and 3% of fluorine-containing additive;
wherein the organic solvent is a mixed solvent of Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) according to the volume ratio of 1:1, the electrolyte sodium salt is bis (fluorosulfonyl) sodium imide, and the fluorine-containing additive is
(2) The sodium secondary battery electrolyte and the sodium ion battery of this example were prepared as follows:
1) Mixing Ethylene Carbonate (EC) and methyl ethyl carbonate (EMC) according to a volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved to prepare a mixed solvent;
2) Adding bis (fluorosulfonyl) sodium imide with a given mass into the mixed solvent obtained in the step 1), enabling the concentration of the bis (fluorosulfonyl) sodium imide to be 1mol L -1, and fully stirring until sodium salt is completely dissolved, thus obtaining a basic electrolyte;
3) And 3) adding an additive F5 into the basic electrolyte obtained in the step 2), wherein the mass fraction of the additive F5 is 3wt% of the total mass of the electrolyte, uniformly shaking or stirring until the additive is completely dissolved, and standing for 12 hours to obtain the sodium secondary battery electrolyte containing 3wt% of F5.
4) Assembling a sodium vanadium phosphate/hard carbon button cell with the electrolyte of the sodium secondary battery containing 3wt% F5 obtained in the step 3), and performing constant current charge and discharge test at a rate of 0.1C after standing for 12 hours to evaluate the cycle stability of the battery under the influence of the electrolyte.
Comparative example 1
In comparison with example 1, the sodium secondary battery electrolyte of comparative example 1 was not added with additives, and the rest of the operations were the same as in example 1.
Comparative example 2
In comparison with example 3, the sodium secondary battery electrolyte of comparative example 2 was not added with an additive, and the rest was the same as in example 3.
Comparative example 3
In comparison with example 4, the sodium secondary battery electrolyte of comparative example 3 was not added with an additive, and the rest was the same as in example 4.
And (3) testing:
(1) The sodium secondary battery electrolytes obtained in examples 1 to 2, examples 5 to 6 and comparative example 1 were assembled into hard carbon/sodium button cells, and after standing for 12 hours, constant current charge and discharge tests were performed at 0.5C rate to evaluate the cycle stability of the cells under the influence of the electrolyte, and the results are shown in table 1:
TABLE 1
As can be seen from table 1, examples 1 to 2 added the additive F1 shown in the present invention to the electrolyte of the sodium secondary battery, and examples 5 to 6 added the additive F5 shown in the present invention to the electrolyte of the sodium secondary battery, and the finally produced hard carbon/sodium button cell had better cycle stability, compared to comparative example 1 in which no additive was added.
(2) Contact angle tests were performed on the sodium secondary battery electrolytes obtained in examples 1 to 2, examples 5 to 6 and comparative example 1, and the contact angles of the sodium secondary battery electrolytes with hard carbon electrodes were tested, and the results are shown in table 2:
TABLE 2
| Test object | Additive agent | Contact angle/° |
| Comparative example 1 | -- | 26.8 |
| Example 1 | 1wt%F1 | 26.4 |
| Example 2 | 3wt%F1 | 23.0 |
| Example 5 | 1wt%F5 | 25.5 |
| Example 6 | 3wt%F5 | 22.7 |
As can be seen from table 2, examples 1 to 2 added the additive F1 shown in the present invention to the sodium secondary battery electrolyte, and examples 5 to 6 added the additive F5 shown in the present invention to the sodium secondary battery electrolyte, and the finally produced sodium secondary battery electrolyte had a smaller contact angle with the hard carbon electrode, as compared with comparative example 1 in which no additive was added. As can be seen from table 1, the contact angle between the sodium secondary electrolyte and the electrode is smaller, the electrolyte can be better infiltrated on the surface of the hard carbon electrode, and the good wettability ensures the full contact between the sodium secondary electrolyte and the electrode, so that the effective sodium ion transmission and the better film forming effect on the surface of the electrode are ensured, and finally the reversible sodium ion intercalation and deintercalation process and the obviously improved electrochemical performance are ensured.
(3) The sodium secondary battery electrolytes obtained in example 3, examples 7 to 8 and comparative example 2 were assembled with a sodium vanadium phosphate/hard carbon button cell, and after standing for 12 hours, a constant current charge and discharge test was performed at a rate of 0.1C to evaluate the cycle stability of the battery under the influence of the electrolyte, and the results are shown in table 3:
TABLE 3 Table 3
As can be seen from table 3, example 3 added the additive F1 shown in the present invention to the sodium secondary battery electrolyte, and examples 7 to 8 added the additive F5 shown in the present invention to the sodium secondary battery electrolyte, compared with comparative example 2 without the additive, and the finally produced sodium vanadium phosphate/hard carbon button cell had better cycle stability.
Fig. 1 (a) is a graph comparing the cycle stability of the hard carbon/sodium half cell prepared in example 2 with that of comparative example 1, fig. 1 (b) is a graph comparing the corresponding coulombic efficiencies, and experimental results show that the addition of 1wt% and 3wt% of the additive F1 achieves an improvement in the cycle stability of the hard carbon/sodium half cell in the carbonate system, and according to fig. 1 (b), it is known that 1wt% and 3wt% of the additive F1 can make the coulombic efficiency of the cell more stable in the latter cycle, and the above three cycle performance data are comprehensively compared and analyzed, and the experiment results in a preferred concentration of the additive F1 of 1wt%.
Fig. 2 is a graph showing the impedance comparison of the hard carbon/sodium half cell prepared in example 1 of the present invention and comparative example 1 after various cycles (150 cycles, 500 cycles), and the experimental results show that the addition of 1wt% of additive F1 delays the impedance increase during the whole cycle of the cell, which means that additive F1 assists in constructing a low impedance electrode/electrolyte interface.
Fig. 3 is a graph showing the comparison of the contact angle test results of the electrolyte of the sodium secondary battery prepared in the embodiment 1 and the embodiment 2 and the comparison of the embodiment 1, and the experimental result shows that the addition of the additive F1 obviously reduces the contact angle between the electrolyte and the surface of the hard carbon electrode, the wettability of the electrolyte is obviously improved, the good wettability of the electrolyte promotes the rapid sodium ion transmission and the better film forming effect on the surface of the hard carbon electrode, and the improvement of the properties is directly related to the better cycling stability of the sodium ion battery.
Fig. 4 is a graph comparing the cycling stability of the sodium vanadium phosphate/hard carbon full battery prepared in example 3 and comparative example 2 at different rates, and the experimental result shows that the stability of example 3 is better, the result has correlation with the result presented by the hard carbon/sodium half battery, and the performance of the full battery at different rates is improved, especially the main factor of improvement of rate performance is optimization of the hard carbon negative electrode interface.
Fig. 5 is a graph comparing the cycling stability of the sodium/sodium symmetric cell prepared in example 4 of the present invention with that of comparative example 3, and the experimental results show that the overpotential of the symmetric cell is significantly reduced after the addition of 1wt% of additive F1, compared to the overpotential of the cell without the addition of additive, indicating that the additive optimizes the electrode/electrolyte interface.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
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