CN114156539A - Sodium secondary battery electrolyte and sodium secondary battery - Google Patents
Sodium secondary battery electrolyte and sodium secondary battery Download PDFInfo
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- CN114156539A CN114156539A CN202111575711.8A CN202111575711A CN114156539A CN 114156539 A CN114156539 A CN 114156539A CN 202111575711 A CN202111575711 A CN 202111575711A CN 114156539 A CN114156539 A CN 114156539A
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- secondary battery
- sodium secondary
- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 225
- 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 177
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 177
- 239000011734 sodium Substances 0.000 title claims abstract description 177
- 239000000654 additive Substances 0.000 claims abstract description 83
- 230000000996 additive effect Effects 0.000 claims abstract description 79
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 45
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003960 organic solvent Substances 0.000 claims abstract description 43
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 43
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011737 fluorine Substances 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 58
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 36
- 239000012046 mixed solvent Substances 0.000 claims description 36
- -1 2-pentyl Chemical group 0.000 claims description 35
- 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 12
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 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 claims description 4
- 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 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 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
- 150000002596 lactones Chemical class 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 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
- 238000009713 electroplating Methods 0.000 abstract description 3
- 238000002161 passivation Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 229910021385 hard carbon Inorganic materials 0.000 description 67
- 238000012360 testing method Methods 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 24
- 238000003756 stirring Methods 0.000 description 23
- 230000001351 cycling effect Effects 0.000 description 19
- 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 15
- 230000002829 reductive effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 230000000694 effects Effects 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
- 238000001035 drying Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 239000002904 solvent Substances 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
- 238000011160 research Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007086 side reaction Methods 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
- 230000007423 decrease Effects 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
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000002000 Electrolyte additive Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical group FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 2
- 238000010606 normalization Methods 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
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 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
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000007747 plating Methods 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
- 230000010076 replication Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
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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
The present invention relates to a sodium secondary battery electrolyte and a sodium secondary battery. The electrolyte of the sodium secondary battery comprises an organic solvent, an electrolyte sodium salt and a fluorine-containing additive with a structure shown in a formula (I), R1、R2、R3、R4And R5Each independently selected from-H, halogen, C1～C20Alkyl, halogenated C1～C20Alkyl radical, C6～C26Aryl or halogenated C6～C26And (4) an aryl group. The sodium secondary electrolyte can reduce the irreversible decomposition reaction of the electrolyte, remarkably improve the circulation stability, the capacity retention rate and the coulombic efficiency of the electrolyte, and also remarkably inhibit the increase of the acidity and the chromaticity of the electrolyte. It is prepared byThe sodium ion conductive film can induce the surface of an electrode to form a stable and low-impedance passivation film, further improves the cycle performance of the battery, can promote more uniform sodium electroplating and separation of the surface of sodium metal, can reduce the contact angle between electrolyte and the electrode, improves the wettability and is beneficial to sodium ion transmission.
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, so that the lithium ion battery becomes the first choice in the fields of digital products, hybrid electric vehicles, pure electric vehicles, power grid energy storage and the like, and the industrialization is realized in 90 years in the 20 th century. However, after 30 years of development, lithium resources with limited and extremely uneven spatial distribution are consumed in large quantities, and currently, the market demand of lithium ion batteries is still increasing year by year, and the technology for recovering lithium-containing compounds is far from reaching the pace of lithium resource consumption, 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, so the sodium ion battery is rapidly developed in recent years, and the preliminary industrialization is realized in 2021. The sodium ion battery is expected to gradually replace the traditional lead-acid storage battery, and is also expected to be used in the field of electric vehicles for lithium-sodium sharing and in large-scale energy storage devices.
Because the energy density of the battery is not directly determined by the electrolyte of the sodium-ion battery, the research progress is far beyond the positive and negative electrode materials, and the electrolyte serving as an ion conduction carrier becomes a new research hotspot along with the commercialization of the sodium-ion battery. Similar to lithium ion batteries, sodium electrolyte is also decomposed by reduction, and the phenomenon of decomposition by reduction of sodium electrolyte is more severe, which is mainly expressed as: the carbonate solvent is reduced and decomposed at a low potential to generate obvious dendritic decomposition products, and the products cover the surfaces of the hard carbon particles, so that the effective surface area of the hard carbon particles is reduced, and the transmission of sodium ions on the surfaces of the hard carbon particles is seriously influenced; the battery impedance is obviously increased after multiple cycles, and the battery cycling stability and the coulombic efficiency are reduced.
In the full-cell, it is important to inhibit the reductive decomposition of the electrolyte, and the decomposition of the electrolyte causes the loss of irreversible active sodium in the system, which leads to the reduction of the cycle life of the full-cell, and the resulting large impedance may cause safety problems such as thermal runaway and the like. Therefore, the design and optimization of the electrolyte is one of the key factors for ensuring the performance of the battery.
The theoretical basis of lithium ion batteries indicates that the electrolyte is the key to constructing a good solid-liquid interface, and one of the measures for taking into account performance and economic benefits is to use an electrolyte additive. Although electrolyte additives have been widely used in the industrial lithium ion batteries, similar research progress in the sodium system has been very limited. The current research also shows that the same additive is not necessarily applied to the sodium ion battery to show an ideal promotion effect, even some commercial lithium ion battery additives generate obvious harmful side reactions or cause battery performance decline in a sodium system, for example, Komab group reports in 2011 work that the addition of a trace amount of VC in a carbonate-based electrolyte can cause the electrolyte to obviously discolor, the circulation stability and the capacity of the sodium ion battery using the electrolyte are obviously reduced compared with those of the basic electrolyte, which indicates that the introduction of VC is possibly accompanied with harmful side reactions; DFEC and ES lead to degradation of the battery cycling performance. In addition, the Ponrouch team found that in EC/PC systems, the introduction of the additive FEC resulted in a decrease in the hard sodium storage performance, manifested as a decrease in capacity and coulombic efficiency.
The above reported experimental results show that sodium-ion batteries may have different film-forming rules from lithium-ion batteries, and the same additive may also play different action mechanisms in a sodium system in a lithium system, which fully indicates that the development of the sodium-ion battery additive is not a simple replication of the lithium system, and on the contrary, the exploration of the sodium-ion battery additive is more challenging than that of a mature lithium system, so that additive research in the field of sodium-ion batteries requires more attempts and deeper analysis.
Disclosure of Invention
Based on the electrolyte, the sodium secondary battery electrolyte provided by the invention has the advantages of less irreversible decomposition reaction, good cycle stability, high capacity retention rate and high coulombic efficiency, and can be used for preparing a sodium secondary battery with good cycle performance and low impedance.
The technical scheme is as follows:
a sodium secondary battery electrolyte comprises an organic solvent, an electrolyte sodium salt and a fluorine-containing additive with a structure shown in a formula (I);
wherein:
R1、R2、R3、R4and R5Each independently selected from-H, halogen, C1～C20Alkyl, halogenated C1～C20Alkyl radical, C6～C26Aryl or halogenated C6～C26And (4) an aryl group.
In one embodiment, R1、R2、R3、R4And R5Each independently selected from-H, F, C1～C10Alkyl, C of F generation1～C10Alkyl radical, C6～C12Aryl or C of F6～C12And (4) an aryl group.
In one embodiment, R1、R2、R3、R4And R5Each independently selected from-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 or biphenyl.
In one embodiment, the fluorine-containing additive has a structure as shown in any one of (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 an electrolyte sodium salt and 1-5% of a fluorine-containing additive with a structure shown in a formula (I) in percentage by mass.
In one embodiment, the sodium secondary battery electrolyte comprises 79-90% of an organic solvent, 9-20% of an electrolyte sodium salt and 1-3% of a fluorine-containing additive with a structure shown in a formula (I) in percentage by mass.
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 includes at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), gamma-hydroxybutyric acid lactone (GBL), 4-hydroxy-n-valerolactone (GVL) and delta-valerolactone (DVL);
the linear carbonate is selected from at least one of diethyl carbonate (DEC), Ethyl Methyl 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 composed of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1; or
The organic solvent is a mixed solvent consisting of ethylene carbonate and methyl ethyl carbonate according to the volume ratio of 1: 1; or
The organic solvent is a mixed solvent consisting of gamma-hydroxy butyrate lactone and diethyl carbonate according to the volume ratio of 1: 1.
In one embodiment, the sodium salt of the electrolyte is selected from sodium hexafluorophosphate (NaPF)6) Sodium perchlorate (NaClO)4) At least one of sodium bis (fluorosulfonyl) imide (NaFSA/NaFSI), (trifluoromethylsulfonyl) imide (NaTFSI), and sodium trifluoromethylsulfonate (NaOTF).
In one embodiment, the concentration of the sodium salt of the electrolyte in the organic solvent is 0.8mol/L to 1.5 mol/L.
The invention also provides a sodium secondary battery, which comprises the sodium secondary battery electrolyte.
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, an electrolyte sodium salt and a specific fluorine-containing compound with a structure shown in a formula (I), and 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 circulation stability, the capacity retention rate and the coulombic efficiency of the electrolyte are obviously improved, and the increase of the acidity and the chromaticity of the electrolyte can be obviously inhibited.
The electrolyte disclosed by the invention is applied to a sodium secondary battery, (1) the electrolyte can induce the surface of an electrode to form a stable and low-impedance passivation film, the electrode interface is modified, the optimization of the electrode interface further promotes the improvement of the cycle performance of the battery, the impedance of the battery after different cycle times is greatly reduced, the rate stability and the capacity exertion normalization of the battery are improved, and particularly the hard carbon/sodium half battery is obtained. (2) The side reactions such as irreversible decomposition of the electrolyte and the like are reduced, the interface impedance is reduced, the interface stability is obviously improved, the capacity attenuation of the battery at normal temperature is effectively controlled, and the cycle stability is obviously improved, particularly for hard carbon/sodium half batteries. (3) The method can promote more uniform sodium electroplating and stripping of the sodium metal surface, realize more ideal modification effect of the sodium metal surface, finally enable the overpotential of the sodium metal to change stably, improve the cycle stability of the battery, and the experimental result has 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 (especially the hard carbon electrode) is smaller, the electrolyte can be better infiltrated on the surface of the hard carbon electrode, and the good infiltration ensures the full contact between the electrolyte of the sodium secondary battery and the electrode, thereby ensuring the effective sodium ion transmission and the better film forming effect on the surface of the electrode, and finally ensuring the reversible sodium ion intercalation and deintercalation process and the obviously improved electrochemical performance.
Drawings
Fig. 1(a) is a graph comparing the cycling stability of hard carbon/sodium half-cells prepared according to example 1, example 2 and comparative example 1 of the present invention, and fig. 1(b) is a graph comparing the corresponding coulombic efficiencies;
FIG. 2 is a graph comparing the impedance of hard carbon/sodium half cells prepared in example 1 of the present invention and comparative example 1 after cycling for different times;
FIG. 3 is a graph comparing contact angle test results of electrolytes prepared in example 1 and example 2 of the present invention with that of comparative example 1;
fig. 4 is a graph comparing the cycling stability at different rates of sodium vanadium phosphate/hard carbon full cells prepared in example 3 of the present invention and comparative example 2;
fig. 5 is a graph comparing the cycle stability of sodium/sodium symmetric cells prepared in example 4 of the present invention and comparative example 3.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Term(s) for
Unless otherwise stated or contradicted, terms or phrases used herein have the following meanings:
the term "alkyl" refers to a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Phrases containing the term, e.g., "C1-16The alkyl group means an alkyl group having 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) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH)3)3) 1-pentyl (n-pentyl, -CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH3) CH2CH2CH3), 3-pentyl (-CH (CH)2CH3)2) 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(CH3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 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) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3And octyl (- (CH)2)7CH3)。
"aryl" refers to an aromatic hydrocarbon group derived by removing one hydrogen atom from the aromatic ring compound and may be a monocyclic aryl group, or a fused ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system for polycyclic ring species. For example, "C6～C26Aryl "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 electrolyte, the invention provides the sodium secondary battery electrolyte with less irreversible decomposition reaction, good cycle stability, high capacity retention rate and high coulombic efficiency.
The technical scheme is as follows:
a sodium secondary battery electrolyte comprises an organic solvent, an electrolyte sodium salt and a fluorine-containing additive with a structure shown in a formula (I);
wherein:
R1、R2、R3、R4and R5Each independently selected from-H, halogen, C1～C20Alkyl, halogenated C1～C20Alkyl radical, C6～C26Aryl or halogenated C6～C26And (4) an aryl group.
The electrolyte provided by the invention comprises an organic solvent, an electrolyte sodium salt and a specific fluorine-containing compound with a structure shown in a formula (I), and 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 circulation stability, the capacity retention rate and the coulombic efficiency of the electrolyte are obviously improved, and the increase of the acidity and the chromaticity of the electrolyte can be obviously inhibited.
In one embodiment, R1、R2、R3、R4And R5Each independently selected from-H, F, C1～C10Alkyl, C of F generation1～C10Alkyl radical, C6～C12Aryl or C of F6～C12And (4) an aryl group.
In one embodiment, R1、R2、R3、R4And R5Each independently selected from-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 or biphenyl.
In one embodiment, the fluorine-containing additive has a structure as shown in any one of (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 an electrolyte sodium salt and 1-5% of a fluorine-containing additive with a structure shown in a formula (I) in percentage by mass.
In one embodiment, the sodium secondary battery electrolyte comprises 79-90% of an organic solvent, 9-20% of an electrolyte sodium salt and 1-3% of a fluorine-containing additive with a structure shown in a formula (I) in percentage by mass.
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 includes at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), gamma-hydroxybutyric acid lactone (GBL), 4-hydroxy-n-valerolactone (GVL) and delta-valerolactone (DVL);
the linear carbonate is selected from at least one of diethyl carbonate (DEC), Ethyl Methyl 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 composed of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1.
In one embodiment, the organic solvent is a mixed solvent composed of ethylene carbonate and ethyl methyl carbonate in a volume ratio of 1: 1.
In one embodiment, the organic solvent is a mixed solvent composed of gamma-hydroxy butyrate lactone and diethyl carbonate according to a volume ratio of 1: 1.
In one embodiment, the sodium salt of the electrolyte is selected from sodium hexafluorophosphate (NaPF)6) Sodium perchlorate (NaClO)4) At least one of sodium bis (fluorosulfonyl) imide (NaFSA/NaFSI), (trifluoromethylsulfonyl) imide (NaTFSI), and sodium trifluoromethylsulfonate (NaOTF).
In one embodiment, the concentration of the sodium salt of the electrolyte in the organic solvent is 0.8mol/L to 1.5 mol/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; further, the concentration of sodium hexafluorophosphate in the organic solvent was 1mol L-1。
The invention also provides a sodium secondary battery, which comprises the sodium secondary battery electrolyte.
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 disclosed by the invention is applied to a sodium secondary battery, (1) the electrolyte can induce the surface of an electrode to form a stable and low-impedance passivation film, the electrode interface is modified, the optimization of the electrode interface further promotes the improvement of the cycle performance of the battery, the impedance of the battery after different cycle times is greatly reduced, the rate stability and the capacity exertion normalization of the battery are improved, and particularly the hard carbon/sodium half battery is obtained. (2) The side reactions such as irreversible decomposition of the electrolyte and the like are reduced, the interface impedance is reduced, the interface stability is obviously improved, the capacity attenuation of the hard battery at normal temperature is effectively controlled, and the circulation stability is obviously improved, particularly the hard carbon/sodium half battery. (3) The method can promote more uniform sodium electroplating and stripping of the sodium metal surface, realize more ideal modification effect of the sodium metal surface, finally enable the overpotential of the sodium metal to change stably, improve the cycle stability of the battery, and the experimental result has 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 (especially the hard carbon electrode) is smaller, the electrolyte can be better infiltrated on the surface of the hard carbon electrode, and the good infiltration ensures the full contact between the electrolyte of the sodium secondary battery and the electrode, thereby ensuring the effective sodium ion transmission and the better film forming effect on the surface of the electrode, and finally ensuring the reversible sodium ion intercalation and deintercalation process and the obviously improved electrochemical performance.
The present invention will be described in further detail with reference to the following examples.
(1) In the following examples and comparative examples, the base electrolyte and the electrolyte containing 1 wt% and 3 wt% of additives were sealed in a container made of polytetrafluoroethylene;
(2) the amount of the sodium secondary battery electrolyte used for the contact angle test is 0.2 mL-0.5 mL, an inert container is used for sealing before the test and the sealing is ensured, and the test objects are a hard carbon electrode and the sodium secondary electrolyte; in the test process, a syringe with the range of 1mL is used for dripping liquid drops, a POWEREACH contact angle measuring instrument is used for testing, and the contact angle value is analyzed by the instrument;
(3) the steps for preparing the hard carbon electrode are as follows: 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; coating the slurry on a copper foil, wherein the coating thickness is 50 μm; drying for 2 hours by using an air-blast drying oven at the temperature of 80 ℃ to remove the solvent, and then transferring to a vacuum drying oven at the temperature of 120 ℃ for deep drying, wherein the duration is 12-20 hours;
(4) the preparation method of the sodium vanadium phosphate electrode comprises the following steps: 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; coating the slurry on an aluminum foil with a coating thickness of 100 μm; drying for 2 hours by using an air-blast drying oven at the temperature of 80 ℃ to remove the solvent, and then transferring to a vacuum drying oven at the temperature of 120 ℃ for deep drying, wherein the duration is 12-20 hours;
(5) the steps for preparing the hard carbon/sodium half cell are as follows: placing a negative electrode shell, a spring piece, a steel gasket and a metal sodium sheet in sequence, then dropwise adding 100 mu L of electrolyte, placing a glass fiber diaphragm, dropwise adding 100 mu L of electrolyte, and sequentially placing a hard carbon electrode and a positive electrode shell to ensure that the centers of circles of all the parts are aligned, and tightly pressing the parts by using a battery packaging machine; wherein, the hard carbon/sodium half cell uses a 2032 type battery case, the diameter of the hard carbon electrode is 12mm, the diameter of the sodium sheet is kept consistent with that of the steel gasket (15.6mm), and the diameter of the used diaphragm is 18 mm;
(6) the preparation method of the vanadium sodium phosphate/hard carbon full cell comprises the following steps: placing a negative electrode shell, a spring piece, a steel gasket and a hard carbon electrode in sequence, then dropwise adding 40 mu L of electrolyte, placing a polymer diaphragm, dropwise adding 40 mu L of electrolyte, sequentially placing a sodium vanadium phosphate electrode and a positive electrode shell, ensuring that the centers of circles of all the parts are aligned, and pressing by using a battery packaging machine; the vanadium sodium phosphate/hard carbon full battery adopts a 2025 type battery case, the diameter of a hard carbon electrode is 12mm, and the diameter of a diaphragm is 18 mm;
(7) the steps for preparing a sodium/sodium symmetric cell are as follows: placing a negative electrode shell, a spring piece, a steel gasket and a metal sodium sheet in sequence, then dropwise adding 100 mu L of electrolyte, placing a glass fiber diaphragm, dropwise adding 100 mu L of electrolyte, and sequentially placing the metal sodium sheet, the steel gasket and a positive electrode shell to ensure that the centers of circles of all the components are aligned, and tightly pressing the components by using a battery packaging machine; the sodium/sodium symmetrical battery adopts a 2032 type battery case, the diameter of a sodium sheet is kept consistent with that of a steel gasket (15.6mm), and the diameter of a used diaphragm is 18 mm;
(8) the method for testing constant current charging and discharging of the battery comprises the following steps: the method uses a blue tester to execute constant current charge and discharge test, and adopts the working steps of 0.1C activation for 3 circles and 0.5C circulation for 500 circles for the hard carbon/sodium half cell, wherein the charge and discharge potential window is 0.01-2.5V; for the vanadium sodium phosphate/hard carbon full battery, the working step of circulating 500 circles at the multiplying power of 1C is adopted, and the charge and discharge potential window is 1.5-3.70V; for sodium/sodium symmetrical battery, 0.5mA cm is adopted-2Current density (0.943mA reduced by actual current), constant current charging and discharging steps of one hour respectively, and circulating for about 150 circles (about 300 hours).
(9) The invention executes impedance test for hard carbon/sodium battery circulating to certain circle number in the following mode: the impedance was tested on a hard carbon/sodium half cell at the end of 150 and 500 cycles and in a sodium depleted state, using a frequency range of 100000Hz to 0.005Hz in the test.
(10) The characterization method of the hard carbon electrode comprises the following steps: the method comprises the steps of disassembling a hard carbon/sodium battery after circulation is finished, rinsing a hard carbon electrode taken out of the disassembled battery by using diethyl carbonate (DEC), scraping residual glass fibers on the surface of the electrode by using a thin blade, airing for 2-3 hours to enable DEC solvent on the surface of the electrode to be completely volatilized, and sealing and storing by using a 10mL centrifuge tube for characterization.
Example 1
The present embodiment provides a sodium secondary battery electrolyte and a sodium ion battery.
(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 composed 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 preparation methods of the electrolyte for the sodium secondary battery and the sodium ion battery of the embodiment are 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) to ensure that the concentration is 1mol L-1Fully stirring until the sodium salt is completely dissolved to obtain a basic electrolyte;
3) adding an additive F1 into the base electrolyte obtained in the step 2), wherein the mass fraction of the additive F1 is 1 wt% of the total mass of the electrolyte, uniformly shaking or stirring the mixture until the additive is completely dissolved, and then standing the mixture for 12 hours to obtain the electrolyte of the sodium secondary battery containing 1 wt% of F1.
4) Assembling a hard carbon/sodium button cell by using the sodium secondary battery electrolyte containing 1 wt% of F1 obtained in the step 3), standing for 12 hours, and then performing constant current charge and discharge test at 0.5C rate to evaluate the cycling stability of the battery under the influence of the electrolyte.
5) And (3) carrying out an alternating current impedance test on the battery which is circularly tested for a certain number of times in the step 4), and evaluating the influence of the electrolyte of the sodium secondary battery containing 1 wt% of F1 on the impedance of the battery.
6) And 3) carrying out a contact angle test on the sodium secondary battery electrolyte containing 1 wt% 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 size of the contact angle can reflect the wettability of the electrolyte on the surface of the hard carbon electrode.
Example 2
The present embodiment provides a sodium secondary battery electrolyte and a sodium ion battery.
(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 composed 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 preparation methods of the electrolyte for the sodium secondary battery and the sodium ion battery of the embodiment are 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) to ensure that the concentration is 1mol L-1Fully stirring until the sodium salt is completely dissolved to obtain a basic electrolyte;
3) adding an additive into the basic electrolyte obtained in the step 2)
The mass fraction of which is electricity3 wt% of the total mass of the electrolyte, uniformly shaking or stirring the electrolyte until the additive is completely dissolved, and then standing the electrolyte for 12 hours to obtain the sodium secondary battery electrolyte containing 3 wt% of F1.
4) Assembling a hard carbon/sodium button cell with the sodium secondary battery electrolyte containing 3 wt% of F1 obtained in the step 3), standing for 12 hours, and performing constant current charge and discharge test at 0.5C rate to evaluate the cycling 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 3 wt% 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 size of the contact angle can reflect the wettability of the electrolyte on the surface of the hard carbon electrode.
Example 3
The present embodiment provides a sodium secondary battery electrolyte and a sodium ion battery.
(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 composed 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 preparation methods of the electrolyte for the sodium secondary battery and the sodium ion battery of the embodiment are 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) to ensure that the concentration is 1mol L-1Fully stirring until the sodium salt is completely dissolved to obtain a basic electrolyte;
3) adding an additive F1 into the base electrolyte obtained in the step 2), wherein the mass fraction of the additive F1 is 1 wt% of the total mass of the electrolyte, uniformly shaking or stirring the mixture until the additive is completely dissolved, and then standing the mixture for 12 hours to obtain the electrolyte of the sodium secondary battery containing 1 wt% of F1.
4) Assembling the sodium vanadium phosphate/hard carbon button cell with the sodium secondary battery electrolyte containing 1 wt% of F1 obtained in the step 3), standing for 12 hours, and then performing constant current charge-discharge test at 0.1C rate to evaluate the cycling stability of the battery under the influence of the electrolyte.
Example 4
The present embodiment provides a sodium secondary battery electrolyte and a sodium ion battery.
(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 composed 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 preparation methods of the electrolyte for the sodium secondary battery and the sodium ion battery of the embodiment are 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) to ensure that the concentration is 1mol L-1Fully stirring until the sodium salt is completely dissolved to obtain a basic electrolyte;
3) adding an additive F1 into the base electrolyte obtained in the step 2), wherein the mass fraction of the additive F1 is 1 wt% of the total mass of the electrolyte, uniformly shaking or stirring the mixture until the additive is completely dissolved, and then standing the mixture for 12 hours to obtain the electrolyte of the sodium secondary battery containing 1 wt% of F1.
4) Assembling sodium/sodium button cell with the sodium secondary battery electrolyte containing 1 wt% of F1 obtained in the step 3), standing for 12 hours, and then standing at 0.5mA cm-2Constant current charge and discharge tests were performed at a current density (0.943mA) to assess the cycling stability of sodium ions at bipolar plating/stripping.
Example 5
The present embodiment provides a sodium secondary battery electrolyte and a sodium ion battery.
(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 composed 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 preparation methods of the electrolyte for the sodium secondary battery and the sodium ion battery of the embodiment are 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) to ensure that the concentration is 1mol L-1Fully stirring until the sodium salt is completely dissolved to obtain a basic electrolyte;
3) adding an additive F5 into the base electrolyte obtained in the step 2), wherein the mass fraction of the additive F5 is 1 wt% of the total mass of the electrolyte, uniformly shaking or stirring the mixture until the additive is completely dissolved, and then standing the mixture for 12 hours to obtain the electrolyte of the sodium secondary battery containing 1 wt% of F5.
4) Assembling a hard carbon/sodium button cell by using the sodium secondary battery electrolyte containing 1 wt% of F5 obtained in the step 3), standing for 12 hours, and then performing constant current charge and discharge test at 0.5C rate to evaluate the cycling stability of the battery under the influence of the electrolyte.
5) And (3) carrying out an alternating current impedance test on the battery which is circularly tested for a certain number of times in the step 4), and evaluating the influence of the electrolyte of the sodium secondary battery containing 1 wt% of F5 on the impedance of the battery.
6) And 3) carrying out a contact angle test on the sodium secondary battery electrolyte containing 1 wt% 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 size of the contact angle can reflect the wettability of the electrolyte on the surface of the hard carbon electrode.
Example 6
The present embodiment provides a sodium secondary battery electrolyte and a sodium ion battery.
(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 composed of Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) according to the volume ratio of 1:1, the electrolyte sodium salt is bis (fluorosulfonyl) imide sodium, and the fluorine-containing additive is
(2) The preparation methods of the electrolyte for the sodium secondary battery and the sodium ion battery of the embodiment are as follows:
1) mixing Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) according to the volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved to prepare a mixed solvent;
2) adding a given mass of sodium bis (fluorosulfonyl) imide into the mixed solvent obtained in the step 1) to make the concentration of the sodium bis (fluorosulfonyl) imide be 1mol L-1Fully stirring until the sodium salt is completely dissolved to obtain a basic electrolyte;
3) adding an additive F5 into the base electrolyte obtained in the step 2), wherein the mass fraction of the additive F5 is 3 wt% of the total mass of the electrolyte, uniformly shaking or stirring the mixture until the additive is completely dissolved, and then standing the mixture for 12 hours to obtain the electrolyte of the sodium secondary battery containing 3 wt% of F5.
4) Assembling a hard carbon/sodium button cell by using the sodium secondary battery electrolyte containing 3 wt% of F5 obtained in the step 3), standing for 12 hours, and then performing constant current charge-discharge test at 0.5C rate to evaluate the cycling stability of the battery under the influence of the electrolyte.
5) And (3) carrying out an alternating current impedance test on the battery which is circularly tested for a certain number of times in the step 4), and evaluating the influence of the electrolyte of the sodium secondary battery containing 3 wt% of F5 on the impedance of the battery.
6) And 3) carrying out a contact angle test on the sodium secondary battery electrolyte containing 3 wt% 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 size of the contact angle can reflect the wettability of the electrolyte on the surface of the hard carbon electrode.
Example 7
The present embodiment provides a sodium secondary battery electrolyte and a sodium ion battery.
(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 composed 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 preparation methods of the electrolyte for the sodium secondary battery and the sodium ion battery of the embodiment are 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) to ensure that the concentration is 1mol L-1Air chargerStirring until the sodium salt is completely dissolved to obtain a basic electrolyte;
3) adding an additive F5 into the base electrolyte obtained in the step 2), wherein the mass fraction of the additive F5 is 1 wt% of the total mass of the electrolyte, uniformly shaking or stirring the mixture until the additive is completely dissolved, and then standing the mixture for 12 hours to obtain the electrolyte of the sodium secondary battery containing 1 wt% of F5.
4) Assembling the sodium vanadium phosphate/hard carbon button cell with the sodium secondary battery electrolyte containing 1 wt% of F5 obtained in the step 3), standing for 12 hours, and then performing constant current charge-discharge test at 0.1C rate to evaluate the cycling stability of the battery under the influence of the electrolyte.
Example 8
The present embodiment provides a sodium secondary battery electrolyte and a sodium ion battery.
(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 composed of Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) according to the volume ratio of 1:1, the electrolyte sodium salt is bis (fluorosulfonyl) imide sodium, and the fluorine-containing additive is
(2) The preparation methods of the electrolyte for the sodium secondary battery and the sodium ion battery of the embodiment are as follows:
1) mixing Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) according to the volume ratio of 1:1, and stirring until the Ethylene Carbonate (EC) is completely dissolved to prepare a mixed solvent;
2) adding a given mass of sodium bis (fluorosulfonyl) imide into the mixed solvent obtained in the step 1) to make the concentration of the sodium bis (fluorosulfonyl) imide be 1mol L-1Fully stirring until the sodium salt is completely dissolved to obtain a basic electrolyte;
3) adding an additive F5 into the base electrolyte obtained in the step 2), wherein the mass fraction of the additive F5 is 3 wt% of the total mass of the electrolyte, uniformly shaking or stirring the mixture until the additive is completely dissolved, and then standing the mixture for 12 hours to obtain the electrolyte of the sodium secondary battery containing 3 wt% of F5.
4) Assembling the sodium vanadium phosphate/hard carbon button cell with the sodium secondary battery electrolyte containing 3 wt% of F5 obtained in the step 3), standing for 12 hours, and then performing constant current charge-discharge test at 0.1C rate to evaluate the cycling 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 prepared without adding additives, and the rest of the procedure was the same as in example 1.
Comparative example 2
In comparison with example 3, the sodium secondary battery electrolyte of comparative example 2 was prepared in the same manner as example 3 except that no additive was added.
Comparative example 3
In comparison with example 4, the sodium secondary battery electrolyte of comparative example 3 was prepared in the same manner as example 4 except that no additive was added.
And (3) testing:
(1) the sodium secondary battery electrolytes obtained in examples 1 to 2, 5 to 6 and comparative example 1 were assembled into a hard carbon/sodium button cell, and a constant current charge and discharge test was performed at a 0.5C rate after standing for 12 hours to evaluate the cycle stability of the battery under the influence of the electrolyte, and the results are shown in table 1:
TABLE 1
As can be seen from table 1, compared to comparative example 1 without additives, examples 1 to 2 added the additive F1 shown in the present invention to the electrolyte of the sodium secondary battery, examples 5 to 6 added the additive F5 shown in the present invention to the electrolyte of the sodium secondary battery, and the hard carbon/sodium button cell finally obtained had better cycle stability.
(2) The sodium secondary battery electrolytes obtained in examples 1 to 2, 5 to 6, and comparative example 1 were subjected to a contact angle test, and the contact angle of the sodium secondary battery electrolyte to a hard carbon electrode was measured, with the results 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, compared to comparative example 1 in which no additive is added, examples 1 to 2 in which the additive F1 according to the present invention is added to the sodium secondary battery electrolyte, and examples 5 to 6 in which the additive F5 according to the present invention is added to the sodium secondary battery electrolyte, the contact angle of the finally prepared sodium secondary battery electrolyte with the hard carbon electrode is smaller. The combination of table 1 shows that 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 infiltration ensures the sufficient 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 the reversible sodium ion intercalation and deintercalation process and the remarkably improved electrochemical performance are finally ensured.
(3) The sodium secondary battery electrolytes obtained in example 3, examples 7 to 8, and comparative example 2 were assembled into a sodium vanadium phosphate/hard carbon button cell, and a constant current charge and discharge test was performed at a 0.1C rate after standing for 12 hours to evaluate the cycle stability of the battery under the influence of the electrolyte, and the results are shown in table 3:
TABLE 3
As can be seen from table 3, the vanadium sodium phosphate/hard carbon button cell finally obtained by adding the additive F1 shown in the present invention to the sodium secondary battery electrolyte in example 3 and the additive F5 shown in the present invention to the sodium secondary battery electrolyte in examples 7 to 8 has better cycle stability than the case of adding no additive in comparative example 2.
Fig. 1(a) is a graph comparing the cycling stability of the hard carbon/sodium half-cells prepared in example 1, example 2 and comparative example 1 of the present invention, fig. 1(b) is a graph comparing the corresponding coulombic efficiency, the experimental results show that the addition of 1 wt% and 3 wt% of the additive F1 achieves the improvement of the cycling stability of the hard carbon/sodium half-cell in the carbonate system, and according to fig. 1(b), at the later stage of the cycling, 1 wt% and 3 wt% of the additive F1 can make the coulombic efficiency of the cell more stable, and the experimental results show that the superior concentration of the additive F1 is 1 wt% by combining the comparison and analyzing the above three cycling performance data.
Fig. 2 is a graph comparing the impedance of the hard carbon/sodium half-cell prepared in example 1 of the present invention and that of the hard carbon/sodium half-cell prepared in comparative example 1 after different cycles (150 cycles and 500 cycles), and the experimental results show that the addition of 1 wt% of the additive F1 retards the impedance increase during the whole battery cycle, which indicates that the additive F1 assists in constructing a low impedance electrode/electrolyte interface.
Fig. 3 is a comparison graph of contact angle test results of the sodium secondary battery electrolytes prepared in example 1 and example 2 of the present invention and comparative example 1, and the experimental results show that the addition of the additive F1 significantly reduces the contact angle between the electrolyte and the surface of the hard carbon electrode, significantly improves the wettability of the electrolyte, promotes rapid sodium ion transmission and better film forming effect on the surface of the hard carbon electrode due to good wettability of the electrolyte, and the improvement of the properties is directly related to better cycle stability of the sodium ion battery.
Fig. 4 is a graph comparing the cycling stability of the sodium vanadium phosphate/hard carbon full cell prepared in example 3 of the present invention and that of the sodium vanadium phosphate/hard carbon full cell prepared in comparative example 2 at different rates, and the experimental results show that the stability of example 3 is better, and the results are correlated with the results presented by the hard carbon/sodium half cell, and the performance of the full cell at different rates is improved, especially the main factor of the improvement of the rate performance is the optimization of the hard carbon negative electrode interface.
Fig. 5 is a graph comparing the cycling stability of the sodium/sodium symmetrical cells prepared in example 4 of the present invention and comparative example 3, and the experimental results show that the overpotential of the symmetrical cell is significantly reduced after the addition of 1 wt% of the additive F1, compared to the overpotential of the cell without the additive, indicating that the additive optimizes the electrode/electrolyte interface.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The electrolyte of the sodium secondary battery is characterized by comprising an organic solvent, an electrolyte sodium salt and a fluorine-containing additive with a structure shown in a formula (I);
wherein:
R1、R2、R3、R4and R5Each independently selected from-H, halogen, C1～C20Alkyl, halogenated C1～C20Alkyl radical, C6～C26Aryl or halogenated C6～C26And (4) an aryl group.
2. The sodium secondary battery electrolyte of claim 1 wherein R is1、R2、R3、R4And R5Each independently selected from-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 or biphenyl.
3. The sodium secondary battery electrolyte according to claim 2, wherein the fluorine-containing additive has a structure represented by any one of the following (F1) to (F8):
4. the sodium secondary battery electrolyte according to any one of claims 1 to 3, characterized by comprising 72 to 92% of an organic solvent, 7 to 23% of an electrolyte sodium salt, and 1 to 5% of a fluorine-containing additive having a structure represented by formula (I), in mass percentage based on the sodium secondary battery electrolyte.
5. The sodium secondary battery electrolyte according to claim 4, wherein the organic solvent is a cyclic carbonate or a linear carbonate, or a mixed solvent of a cyclic carbonate and a linear carbonate.
6. The sodium secondary battery electrolyte of claim 5, wherein the cyclic carbonate is selected from at least one of ethylene carbonate, propylene carbonate, γ -hydroxybutyric lactone, 4-hydroxy-n-valerolactone, and δ -valerolactone;
the linear carbonate is at least one selected from the group consisting of diethyl carbonate, ethyl methyl carbonate and dimethyl carbonate.
7. The sodium secondary battery electrolyte according to claim 6, wherein a volume ratio of the cyclic carbonate to the linear carbonate in the mixed solvent is (0.8 to 1.2): 1.
8. the sodium secondary battery electrolyte of any one of claims 1 to 3, wherein the electrolyte sodium salt is selected from at least one of sodium hexafluorophosphate, sodium perchlorate, sodium bis (fluorosulfonyl) imide, sodium bis (trifluoromethylsulfonyl) imide and sodium trifluoromethanesulfonate; and/or
The concentration of the electrolyte sodium salt in the organic solvent is 0.8-1.5 mol/L.
9. A sodium secondary battery comprising the sodium secondary battery electrolyte according to any one of claims 1 to 8.
10. The sodium secondary battery according to claim 9, characterized in that the sodium secondary battery is a sodium ion battery or a sodium air battery.
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