CN115832438A - Electrolyte applied to magnesium ion battery and preparation method thereof - Google Patents
Electrolyte applied to magnesium ion battery and preparation method thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 118
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title description 5
- 239000011777 magnesium Substances 0.000 claims abstract description 85
- 239000002904 solvent Substances 0.000 claims abstract description 75
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 59
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000654 additive Substances 0.000 claims abstract description 57
- 230000000996 additive effect Effects 0.000 claims abstract description 56
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001450 anions Chemical class 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 13
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 44
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- -1 hexafluorophosphate Chemical compound 0.000 claims description 14
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 12
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 12
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 10
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 5
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 14
- 238000004807 desolvation Methods 0.000 abstract description 13
- 239000007774 positive electrode material Substances 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 86
- 159000000003 magnesium salts Chemical class 0.000 description 25
- 238000012360 testing method Methods 0.000 description 17
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 16
- 238000007614 solvation Methods 0.000 description 13
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical group [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 7
- 239000010405 anode material Substances 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229940096405 magnesium cation Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- AHXNYDBSLAVPLY-UHFFFAOYSA-M 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonimidate Chemical compound [O-]S(=O)(=NS(=O)(=O)C(F)(F)F)C(F)(F)F AHXNYDBSLAVPLY-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- WYPTZCBYSQFOQS-UHFFFAOYSA-N magnesium;bis(trimethylsilyl)azanide Chemical compound [Mg+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C WYPTZCBYSQFOQS-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002734 organomagnesium group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte applied to a magnesium ion battery, which comprises a solute, a solvent and an additive; wherein the solute comprises magnesium hexafluoroisopropoxyborate, the additive comprises an ionic compound having an anion different from the anion in the solute, and the solvent comprises an organic ether solvent. The electrolyte has a wide electrochemical stability window, high ionic conductivity, excellent reversible magnesium deposition characteristic and a rapid desolvation process, has excellent intrinsic performance, can be applied to a magnesium ion battery, promotes the desolvation process, has high compatibility with a positive electrode material, and greatly improves the magnesium ion storage performance of the positive electrode material under high current.
Description
Technical Field
The invention relates to the technical field of magnesium ion batteries, in particular to electrolyte applied to a magnesium ion battery and a preparation method thereof.
Background
Due to the limited and uneven distribution of lithium resources in the crust, the cost of lithium metal is increased dramatically, and therefore, the development of energy storage systems other than lithium is urgently needed to meet the market demand. The theoretical specific capacity of the metal magnesium as a negative electrode is 2205mAh/g (3833 mAh/mL), the electrode potential is about-2.37V vs. SHE, and the mining cost of the metal magnesium is only about 1/24 of that of lithium. Rechargeable magnesium ion batteries have been regarded as one of the most promising energy storage technologies other than lithium due to the use of polyvalent magnesium metal cathodes with high capacity, high safety, high abundance, and uniform deposition. Although research on magnesium ion batteries is still in the early stages compared to lithium ion batteries, several breakthrough research advances have been made, including the construction of highly reversible electrode systems, the design of ether-based electrolytes for efficient magnesium deposition and reversible magnesium ion transport, and the development of magnesium storage positive electrode materials with high theoretical energy density. However, a key obstacle to practical application of high-performance magnesium ion batteries is slow magnesium ion storage kinetics in the positive electrode material, which leads to a large gap between the performance of the positive electrode material and the theoretical capacity in practical tests.
Copper selenide (e.g. CuSe, cu) 2 Se、Cu 3 Se 2 And Cu 2-x Se) material due to metal ions and Se 2- The weak interaction between the materials and the good conductivity are considered by researchers to be potential cathode materials with rapid magnesium storage kinetics. In the initial study, a nanosized CuSe positive electrode was 50mA g in chlorine-containing electrolyte -1 Exhibit about 200mAh g -1 (54% of theoretical capacity) reversible discharge capacity. However, the CuSe positive electrode has poor performance at high currents, which may be due to the large energy barrier for Mg — Cl bond rupture in chlorine-containing electrolytes and the corrosive effects of chlorine-containing electrolytes.
The chlorine-free electrolyte can avoid the corrosion effect of the chlorine-containing electrolyte in the magnesium ion battery, so that the high-current performance of the nano CuSe anode material is obviously improved, but the reversible discharge specific capacity is still far lower than the theoretical capacity (376 mAh/g), and the high-current magnesium storage performance of the magnesium ion battery anode cannot be met.
Disclosure of Invention
The invention aims to provide an electrolyte applied to a magnesium ion battery and a preparation method thereof, aiming at the defects of the prior art, the electrolyte is prepared from a boron-based magnesium salt solute, an organic ether solvent and an additive, the electrolyte promotes the desolvation process, has high compatibility with a positive electrode material, and greatly improves the magnesium ion storage performance of the positive electrode material under large current.
The invention provides an electrolyte applied to a magnesium ion battery in a first aspect, which comprises a solute, a solvent and an additive; wherein the solute comprises magnesium hexafluoroisopropoxyborate, the additive comprises an ionic compound having an anion different from the anion in the solute, and the solvent comprises an organic ether solvent.
In alternative embodiments, the additive comprises an ionic compound having an anion that is triflate, hexafluorophosphate, bis-triflimide, bis-fluorosulfonimide, perchlorate, or hexamethyldisilazane.
In an alternative embodiment, the organic ether solvent comprises one or more mixtures of tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
In an alternative embodiment, the concentration of the magnesium hexafluoroisopropoxyborate in the electrolyte is 0.05 to 0.5mol/L.
In an alternative embodiment, the concentration of the additive in the electrolyte is 0.05 to 0.5mol/L.
The second aspect of the present invention provides a preparation method of the foregoing electrolyte for a magnesium ion battery, including the following steps:
dispersing magnesium borohydride into a first organic ether solvent to obtain a magnesium borohydride dispersion liquid, adding hexafluoroisopropanol into the magnesium borohydride dispersion liquid under the stirring condition, reacting under the protection of inert atmosphere, and obtaining a mixed solution after the reaction is finished;
filtering the mixed solution under the protection of inert atmosphere, and removing the solvent from the filtrate in vacuum to obtain hexafluoroisopropoxy magnesium borate;
continuously dissolving magnesium hexafluoroisopropoxyborate and an additive in a second organic ether solvent under the protection of inert atmosphere to obtain a required electrolyte; wherein the additive is an ionic compound having an anion different from the anion in the solute.
In an alternative embodiment, the concentration of the magnesium borohydride dispersion is 10 to 50g/L.
In alternative embodiments, the molar ratio of the magnesium hexafluoroisopropoxyborate to the magnesium borohydride is (4-6): 1, and the molar ratio of the magnesium hexafluoroisopropoxyborate to the additive is 3: (1-5).
In an alternative embodiment, the concentration of the additive is 0.05 to 0.5mol/L, and the additive includes an ionic compound having an anion of trifluoromethanesulfonate, hexafluorophosphate, bis-trifluoromethanesulfonimide, bis-fluorosulfonimide, perchlorate or hexamethyldisilazane.
In an alternative embodiment, the concentration of the magnesium hexafluoroisopropoxyborate is 0.05 to 0.5mol/L.
In an alternative embodiment, the first organic ether solvent comprises one or more mixtures of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran;
the second organic ether solvent comprises one or more of tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
The third aspect of the invention provides a magnesium ion battery, wherein the electrolyte adopts the electrolyte applied to the magnesium ion battery.
According to the scheme, the electrolyte applied to the magnesium ion battery has the following remarkable advantages:
the electrolyte adopts organic ether solvent and hexafluoroisopropoxy magnesium borate (MgBHFIP) solute, and is added simultaneouslyWhen the concentration of solute magnesium salt is 0.3mol/L, solvent is glycol dimethyl ether, and additive is sodium trifluoromethanesulfonate of 0.1-0.5 mol/L, the conductivity is more than 10mS/cm, the ionic conductivity is high, the reversible magnesium deposition-dissolution performance is excellent, and the oxidation stable potential is high (more than 2.5V vs 2+ And the working electrode is copper foil), can be successfully applied to the magnesium ion battery.
According to the electrolyte, the solvation structure of magnesium ions in the electrolyte is changed by introducing anions in the additive, the reaction energy barrier of the desolvation is reduced, the desolvation process is promoted, the charge transfer of electrode reaction is accelerated, the electrolyte has high compatibility with a positive electrode material, and the positive electrode material has excellent reversible discharge specific capacity under high current.
Drawings
FIG. 1 is Nuclear Magnetic Resonance (NMR) data of powders obtained after volatilization of a solvent by an electrolytic solution in example 1 and example 3 of the present invention.
Fig. 2 is laser Raman spectroscopy (Raman) data of the electrolytes of examples 1 and 3 of the present invention.
FIG. 3 is a LSV curve of the electrolyte of example 1 of the present invention on copper foil, aluminum foil and stainless steel.
FIG. 4 is a LSV curve of the electrolyte of example 2 of the present invention on copper foil, aluminum foil and stainless steel.
FIG. 5 is a LSV curve of the electrolyte of example 3 of the present invention on copper foil, aluminum foil and stainless steel.
FIG. 6 is a LSV curve of the electrolyte of example 4 of the present invention on copper foil, aluminum foil and stainless steel.
Fig. 7 is a magnesium deposition-dissolution curve of a Mg | | | Mg full cell assembled using the electrolyte in example 3 of the present invention.
Fig. 8 is an ac impedance spectrum of the copper selenide positive electrode after being left standing for 10 hours in the electrolytes of example 1 and example 3 of the present invention.
Fig. 9 is a graph of the cycling stability and coulombic efficiency of copper selenide anodes at 100mA/g current density in the electrolytes of example 1 and example 3 of the present invention.
Fig. 10 is a graph of the cycling stability and coulombic efficiency of copper selenide anodes at different current densities (200, 500, 1000 mA/g) in the electrolytes of examples 1 and 3 of the present invention.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways.
In order to improve the high-current magnesium storage performance of the magnesium ion battery anode and promote the development of a high-power magnesium ion battery, the invention provides the electrolyte which has a wide electrochemical stability window, high ionic conductivity, excellent reversible magnesium deposition characteristic and a rapid desolvation process and can be applied to the high-power magnesium ion battery.
In one embodiment of the invention, an electrolyte applied to a magnesium ion battery is provided, which comprises a solute, a solvent and an additive; wherein the solute comprises magnesium hexafluoroisopropoxyborate (MgBHFIP), the additive comprises an ionic compound having an anion different from the anion in the solute, and the solvent comprises an organic ether solvent.
In an alternative embodiment, the additive comprises a triflate (OTf) anion - ) Hexafluorophosphate radical (PF) 6 - ) Bis (trifluoromethanesulfonyl) imide (TFSI) - ) Bis (fluorosulfonyl) imide (FSI) - ) Perchlorate (ClO) 4 - ) Or hexamethyldisiloxaneAmino radical (HMDS) - ) The ionic compound of (1).
The anion in the additive can interact with magnesium ion, and the anion participates in the solvation structure of the magnesium ion to change the solvation structure of the magnesium ion, wherein the solvation structure of the magnesium ion is formed by [ Mg (solvent) x ] 2+ Change to [ Mg (solvent) m (anion) n ] + . The introduction of anions lengthens the bond length between magnesium ions and the solvent, and the interaction force is weakened, so that the special magnesium ion solvation structure has a rapid desolvation process.
In an alternative embodiment, the organic ether solvent comprises one or more mixtures of tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
The solvent is used as a solvent to dissolve an organic magnesium salt, namely hexafluoroisopropoxy magnesium borate (MgBHFIP), and is also coordinated with the organic magnesium salt, so that a complex magnesium cation is obtained through a complex ether solvent, and the process is as follows: after the organomagnesium salt is dissolved in the ethereal solvent, the magnesium salt is dissociated into magnesium cations [ Mg (solvent) complexed with the solvent x ] 2+ (the amount of solvent complexed depends on the type of solvent) and the anion BHFIP - Wherein the complex magnesium cation plays a role in transmitting magnesium ions in the operation of the magnesium ion battery.
[Mg(solvent) x ] 2+ And [ Mg (solvent) m (anion) n ] + The solvent refers to a solvent used by the electrolyte, and the anion is the anion in the additive.
In an alternative embodiment, the concentration of the magnesium hexafluoroisopropoxyborate in the electrolyte solution is 0.05 to 0.5mol/L.
In an alternative embodiment, the concentration of the additive in the electrolyte is 0.05 to 0.5mol/L.
In another embodiment of the present invention, there is provided a method for preparing the electrolyte for a magnesium ion battery, including the steps of:
dispersing magnesium borohydride into a first organic ether solvent to obtain a magnesium borohydride dispersion liquid, adding hexafluoroisopropanol into the magnesium borohydride dispersion liquid under the stirring condition, reacting under the protection of inert atmosphere, and obtaining a mixed solution after the reaction is finished;
filtering the mixed solution under the protection of inert atmosphere, and removing the solvent from the filtrate in vacuum to obtain hexafluoroisopropoxy magnesium borate;
continuously dissolving magnesium hexafluoroisopropoxyborate and an additive in a second organic ether solvent under the protection of inert atmosphere to obtain a required electrolyte; wherein the additive is an ionic compound having an anion different from the anion in the solute.
In an alternative embodiment, the concentration of the magnesium borohydride dispersion is 10 to 50g/L.
In alternative embodiments, the molar ratio of the magnesium hexafluoroisopropoxyborate to the magnesium borohydride is (4-6): 1, and the molar ratio of the magnesium hexafluoroisopropoxyborate to the additive is 3: (1-5).
In an alternative embodiment, the concentration of the additive is 0.05 to 0.5mol/L, and the additive comprises an ionic compound having an anion of trifluoromethanesulfonate, hexafluorophosphate, bis-trifluoromethanesulfonylimide, bis-fluorosulfonylimide, perchlorate or hexamethyldisilazane.
In an alternative embodiment, the concentration of the magnesium hexafluoroisopropoxyborate is 0.05 to 0.5mol/L.
In an alternative embodiment, the first organic ether solvent comprises one or more mixtures of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran;
the second organic ether solvent comprises one or more of tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
In other embodiments of the present invention, there is provided a magnesium ion battery, the electrolyte of which employs the aforementioned electrolyte applied to the magnesium ion battery, the electrolyte having a wide electrochemical stability window, high ionic conductivity, excellent reversible magnesium deposition characteristics, and a rapid desolvation process, and thus, the magnesium ion battery has excellent electrochemical properties.
For better understanding, the present invention is further described below with reference to several specific examples, but the materials and processing are not limited thereto, and the present disclosure is not limited thereto.
Example 1
Comparison sample: no additive in electrolyte
0.8g of magnesium borohydride and 50mL of ethylene glycol dimethyl ether (DME) were added to a 100mL round-bottomed flask, followed by the slow dropwise addition of 13mL of hexafluoroisopropanol solution with continuous magnetic stirring, and after the addition was complete, stirring was continued for 12 hours under an argon atmosphere.
And then filtering the reaction solution under the protection of argon, and removing a glyme (DME) solvent in the filtrate by adopting vacuum treatment to obtain magnesium hexafluoroisopropoxyborate solid (MgBHFIP).
In an argon atmosphere glove box, the solid was dissolved in ethylene glycol dimethyl ether to prepare a 0.3M MgBHFIP/DME electrolyte.
Example 2
MgBHFIP prepared in example 1 is taken as an electrolyte magnesium salt, ethylene glycol dimethyl ether (DME) is taken as a solvent, and sodium trifluoromethanesulfonate (NaOTf) which is commercially purchased is taken as an additive to prepare an electrolyte, and the component is 0.3M MgBHFIP +0.1MNaOTf/DME.
Example 3
MgBHFIP prepared in example 1 is taken as an electrolyte magnesium salt, ethylene glycol dimethyl ether (DME) is taken as a solvent, and sodium trifluoromethanesulfonate (NaOTf) which is commercially purchased is taken as an additive to prepare an electrolyte, and the component is 0.3M MgBHFIP +0.3MNaOTf/DME.
Example 4
An electrolyte solution was prepared with MgBHFIP prepared in example 1 as an electrolyte magnesium salt, ethylene glycol dimethyl ether (DME) as a solvent, and sodium triflate (NaOTf) commercially available as an additive, and the component was 0.3m MgBHFIP +0.5mnaotf/DME.
Commercially available sodium hexafluorophosphate (NaPF) was prepared using MgBHFIP prepared in example 1 as the electrolyte magnesium salt and ethylene glycol dimethyl ether (DME) as the solvent 6 ) Electrolyte is prepared for additive, and the component is 0.3M MgBHFIP +0.1MNaPF 6 /DME。
Example 6
An electrolyte solution is prepared by taking MgBHFIP prepared in example 1 as an electrolyte magnesium salt, ethylene glycol dimethyl ether (DME) as a solvent and commercially available sodium bistrifluoromethanesulfonylimide (NaTFSI) as an additive, and the component is 0.3M MgBHFIP +0.1MNaTFSI/DME.
Example 7
An electrolyte solution is prepared by using MgBHFIP prepared in example 1 as an electrolyte magnesium salt, ethylene glycol dimethyl ether (DME) as a solvent and commercially available sodium bis (fluorosulfonyl) imide (NaFSI) as an additive, and the component is 0.3M MgBHFIP +0.1MNaFSI/DME.
Example 8
An electrolyte solution is prepared by using MgBHFIP prepared in example 1 as an electrolyte magnesium salt, diethylene glycol dimethyl ether (DEGDME) as a solvent and sodium trifluoromethanesulfonate (NaOTf) purchased commercially as an additive, and the component is 0.3M MgBHFIP +0.3MNaOTf/DEGDME.
Example 9
Commercially available sodium perchlorate (NaClO) was prepared using MgBHFIP prepared in example 1 as the electrolyte magnesium salt and ethylene glycol dimethyl ether (DME) as the solvent 4 ) Electrolyte is prepared for additive, and the component is 0.3M MgBHFIP +0.1MNaClO 4 /DME。
Example 10
Commercially available magnesium bis (hexamethyldisilazide) (Mg (HMDS)) using MgBHFIP prepared in example 1 as the electrolyte magnesium salt and ethylene glycol dimethyl ether (DME) as the solvent 2 ) Preparing electrolyte for additive with the component of 0.3M MgBHFIP +0.1M Mg (HMDS) 2 /DME。
Example 11
MgBHFIP prepared in example 1 is taken as an electrolyte magnesium salt, ethylene glycol dimethyl ether (DME) is taken as a solvent, and sodium trifluoromethanesulfonate (NaOTf) which is commercially purchased is taken as an additive to prepare an electrolyte, and the component is 0.1M MgBHFIP +0.1MNaOTf/DME.
Example 12
An electrolyte solution is prepared by using MgBHFIP prepared in example 1 as an electrolyte magnesium salt, tetrahydrofuran (THF) as a solvent and sodium trifluoromethanesulfonate (NaOTf) purchased commercially as an additive, and the component is 0.3M MgBHFIP +0.3M NaOTf/THF.
Example 13
An electrolyte solution is prepared by taking MgBHFIP prepared in example 1 as an electrolyte magnesium salt, tetrahydrofuran (THF) as a solvent and commercially available sodium trifluoromethanesulfonate (NaOTf) as an additive, wherein the component is 0.5M MgBHFIP +0.5M NaOTf/THF.
Example 14
MgBHFIP prepared in example 1 is taken as an electrolyte magnesium salt, and the volume ratio of ethylene glycol dimethyl ether (DME) to Tetrahydrofuran (THF) is 1:1 is solvent, commercial sodium trifluoromethanesulfonate (NaOTf) is additive to prepare electrolyte, and the component is 0.3M MgBHFIP +0.3M NaOTf/(DME + THF).
Nuclear magnetic resonance testing
The powders obtained by volatilizing the solvent in the electrolytes of examples 1 and 3 were subjected to Nuclear Magnetic Resonance (NMR), and the results are shown in fig. 1.
NMR results showed that the end group-CH on DME, which is more sensitive to shielding, was found after addition of the magnesium salt of electrolyte MgBHFIP in solvent DME (curve ii) 3 Chemical shifts to the high field direction occurred, indicating Mg dissolved in DME 2+ There is an interaction force for the DME. According to the integration result of the hydrogen spectrum area, the structure of magnesium ions in the electrolyte of example 1 is [ Mg (DME) 3 ] 2+ 。
After simultaneous addition of the magnesium salt of electrolyte MgBHFIP and the additive NaOTf in the solvent DME (curve iii), the end group-CH on DME 3 Further deflection to higher field direction indicates stronger interaction of cations to DME in the mixed electrolyte. From the results of integration of the hydrogen spectral area, examples3 cation (Mg) in electrolyte 2+ And Na + ) The 4 DME molecules are complexed together.
Laser Raman spectroscopy test
Laser Raman (Raman) spectroscopy was performed on the electrolytes of examples 1 and 3, and the results are shown in fig. 2.
Raman spectroscopy showed that, after addition of the magnesium salt of electrolyte MgBHFIP in solvent DME (curve ii), a peak representing the interaction of magnesium ions with DME appeared at 878cm -1 This result corresponds to the NMR result, and the structure of magnesium ions in the electrolyte in example 1 is [ Mg (DME) ] 3 ] 2+ 。
After the simultaneous addition of the magnesium salt of electrolyte MgBHFIP and the additive NaOTf in solvent DME (curve iii), the peak representing the interaction of magnesium ions with DME was 878cm -1 Offset to 876cm -1 Indicating that the number of molecules of DME interacting with magnesium ions is reduced. While a peak representing the interaction between sodium ions and DME appeared at 866cm -1 Magnesium ion and OTf - The peak of anionic interaction appeared at 1054cm -1 And 766cm -1 . Combined 780-900cm -1 The result of area integration after peak separation of Raman spectrum of DME and NMR data between the two results revealed that the structure of magnesium ion in the electrolyte of example 3 was [ Mg (DME) 2.5 OTf] + 。
In combination with NRM and Raman, it can be seen that the solvation structure of magnesium ions in the electrolyte of example 1 is [ Mg (DME) 3 ] 2+ Example 3 solvation structure of magnesium ions in electrolyte was [ Mg (DME) 2.5 OTf] + 。
It can be demonstrated that when the organic magnesium salt of the electrolyte is dissolved in the ether solvent, the organic magnesium salt is dissociated into magnesium cations [ Mg (solvent) complexed with the solvent x ] 2+ And the anion BHFIP - The anion in the additive participates in the solvation structure of the magnesium ion to change the solvation structure of the magnesium ion, and the solvation structure of the magnesium ion is formed by [ Mg (solvent) x ] 2+ Change to [ Mg (solvent) m (anion) n ] + 。
Conductivity test
The electrolytes obtained in examples 1 to 8 were tested using a Mettler Toledo conductivity tester.
The electrolyte conductivity was measured to be 11.2mS/cm in example 1, 12.4mS/cm in example 2, 13.3mS/cm in example 3, 10.9mS/cm in example 4, 11.5mS/cm in example 5, 11.7mS/cm in example 6, 11.5mS/cm in example 7, 12.3mS/cm in example 8, 12.6mS/cm in example 9, 10.5mS/cm in example 10, 8.6mS/cm in example 11, 13.4mS/cm in example 12, 11.7mS/cm in example 13, and 13.7mS/cm in example 14.
From the above, it can be seen that the addition of a suitable concentration of NaOTf additive can increase the conductivity of the magnesium ion electrolyte, but too high a concentration of the additive can decrease the conductivity. The conductivity of the electrolyte exceeds 8mS/cm, and when the concentration of solute magnesium salt is 0.3mol/L, the conductivity of the electrolyte exceeds 10mS/cm, thereby proving that the electrolyte has high ionic conductivity.
Electrochemical window testing
[ Battery Assembly ]
And (3) respectively adding 80 mu L of the electrolyte obtained in the examples 1-4 into a copper foil, an aluminum foil or stainless steel serving as a working electrode, metal magnesium serving as a counter electrode and a reference electrode and a glass fiber membrane serving as a diaphragm, and assembling the button cell.
[ test ]
The anodic oxidation potential of the electrolyte of example 1 was measured to be about 2.8V vs. Mg/Mg for the working electrode copper foil as shown in FIG. 3, FIG. 4, FIG. 5 and FIG. 6 using the Biologic VMP3 electrochemical workstation with a scan rate of 5mV/s for the electrochemical window test 2+ The anodic oxidation potentials of the electrolytes after the addition of additives (example 2,3,4) all exceeded 3.0Vvs. Mg/Mg 2+ Especially in embodiment 3The electrolyte can reach 3.2V vs. Mg/Mg 2+ The electrolyte of the present invention has been described above as having a wide electrochemical stability window.
Magnesium deposition-dissolution Performance test
[ Battery Assembly ]
And assembling the symmetrical battery of metal magnesium, taking a glass fiber membrane as a diaphragm, and adding 80 mu L of the electrolyte obtained in the embodiment 3.
[ test ]
At 0.1-2 mA cm -2 The current density of (A) was cycled, and a magnesium deposition-dissolution performance test was carried out, and the deposition-dissolution results are shown in FIG. 7 at 0.1,0.2,0.5,1.0,2.0mA cm -2 The polarization of the battery is relatively small under the current density, the obvious polarization increase condition does not occur, and the excellent reversible magnesium deposition characteristic is shown, so that the electrolyte can be used for stably transmitting magnesium ions.
The tests prove that the electrolyte for the magnesium ion battery successfully prepared by the method has a wide electrochemical stability window, high ionic conductivity, excellent reversible magnesium deposition characteristic and excellent intrinsic performance.
AC impedance testing
[ Battery Assembly ]
Preparing a positive electrode: fully stirring and mixing copper selenide serving as an active material of the positive plate, acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a binder in a proper amount of an N-methyl pyrrolidone solvent according to a mass ratio of 6.
Assembling a button battery: the prepared positive plate is used as a working electrode, metal magnesium is used as a counter electrode and a reference electrode, a glass fiber membrane is used as a diaphragm, 80 mu L of the electrolyte obtained in the examples 1 and 3 is added, and the button cell is assembled.
[ test ]
Charge and discharge tests were performed using a Biologic VMP3 electrochemical workstation.
As shown in fig. 8, the copper selenide positive electrode has a smaller impedance in the electrolyte of example 3 than that in example 1, and the value is only about 40%, which indicates that the copper selenide positive electrode in example 3 has a faster charge transfer, which is mainly due to the special magnesium ion solvation structure in the electrolyte of example 3, and the fast desolvation process is the main reason why the copper selenide positive electrode has a superior high-current performance in the electrolyte of example 3.
Therefore, the electrolyte provided by the invention can be directly proved to have a rapid desolvation process, so that the magnesium ion storage performance of the anode material under a large current is greatly improved.
Charge and discharge test
[ Battery Assembly ]
Preparing a positive electrode: fully stirring and mixing a positive electrode active material copper selenide, a conductive agent acetylene black and a binding agent polyvinylidene fluoride in a proper amount of an N-methyl pyrrolidone solvent according to a mass ratio of 6.
Assembling a button battery: the prepared positive plate is used as a working electrode, metal magnesium is used as a counter electrode and a reference electrode, a glass fiber membrane is used as a diaphragm, 80 mu L of the electrolyte obtained in the examples 1 and 3 is added, and the button cell is assembled.
[ test ]
The charge and discharge test was performed using the novyi electrochemical workstation.
As shown in FIG. 9, the specific discharge capacity of the copper selenide positive electrode at a current density of 100mA/g in the electrolyte of example 1 at the first turn is 58mAh/g. After 60 cycles of charge-discharge activation, the copper selenide positive electrode reaches the maximum discharge specific capacity of 228mAh/g (61 percent of the theoretical specific capacity). In the electrolyte of example 3, the first circle of the copper selenide positive electrode has a specific discharge capacity of 170mAh/g, and the maximum specific discharge capacity is 357mAh/g (95% of the theoretical specific capacity) after the activation of 40 circles. The result shows that the copper selenide positive electrode has higher first-turn specific discharge capacity, shorter activation turns and higher reversible specific discharge capacity in the electrolyte of example 3 containing the additive.
Meanwhile, as shown in fig. 10, when the current density was further increased to 200, 500, 1000mAh/g, the specific discharge capacity of the copper selenide positive electrode was 193/304, 150/277, 117/246mAh/g in examples 1 and 3. With the increase of the current density, the influence of the additive on the capacity of the copper selenide positive electrode is more obvious, and particularly under the heavy current of 1000mA/g, the reversible discharge specific capacity of the copper selenide positive electrode is improved to more than two times.
Through charge and discharge tests, the electrolyte disclosed by the invention has high reversible discharge specific capacity every time in a circulation process under a large current when applied to a magnesium ion battery, and can be further proved to have a rapid desolvation process from the side, so that the magnesium ion storage performance of the anode material under the large current is greatly improved.
The tests show that the electrolyte applied to the magnesium ion battery has a wide electrochemical stability window, high ionic conductivity, excellent reversible magnesium deposition characteristic, a rapid desolvation process and excellent intrinsic performance.
The electrolyte has a special magnesium ion solvation structure, and the anion additive enters the magnesium ion solvation structure, so that the magnesium ion desolvation process is easier, and the key problem that the discharge specific capacity of the anode material is sharply attenuated under a large current is solved.
The electrolyte disclosed by the invention is friendly to conversion reaction type anode materials, the maximum specific discharge capacity of the anode materials released in the electrolyte disclosed by the invention is greatly improved, and the specific discharge capacity of the anode materials is more remarkably improved under larger current.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (12)
1. The electrolyte applied to the magnesium ion battery is characterized by comprising a solute, a solvent and an additive; wherein the solute comprises magnesium hexafluoroisopropoxyborate, the additive comprises an ionic compound having an anion different from the anion in the solute, and the solvent comprises an organic ether solvent.
2. The electrolyte solution applied to the magnesium-ion battery according to claim 1, wherein the additive comprises an ionic compound having an anion of trifluoromethanesulfonate, hexafluorophosphate, bis-trifluoromethanesulfonylimide, bis-fluorosulfonylimide, perchlorate or hexamethyldisilazane.
3. The electrolyte applied to the magnesium ion battery as recited in claim 1, wherein the organic ether solvent comprises one or more of tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
4. The electrolyte applied to the magnesium ion battery according to any one of claims 1 to 3, wherein the concentration of the magnesium hexafluoroisopropoxyborate in the electrolyte is 0.05 to 0.5mol/L.
5. The electrolyte applied to the magnesium ion battery according to any one of claims 1 to 3, wherein the concentration of the additive in the electrolyte is 0.05 to 0.5mol/L.
6. A method for preparing the electrolyte applied to the magnesium ion battery according to any one of claims 1 to 5, which is characterized by comprising the following steps:
dispersing magnesium borohydride into a first organic ether solvent to obtain a magnesium borohydride dispersion liquid, adding hexafluoroisopropanol into the magnesium borohydride dispersion liquid under the stirring condition, reacting under the protection of inert atmosphere, and obtaining a mixed solution after the reaction is finished;
filtering the mixed solution under the protection of inert atmosphere, and removing the solvent from the filtrate in vacuum to obtain hexafluoroisopropoxy magnesium borate;
continuously dissolving magnesium hexafluoroisopropoxyborate and an additive in a second organic ether solvent under the protection of inert atmosphere to obtain a required electrolyte; wherein the additive is an ionic compound having an anion different from the anion in the solute.
7. The method according to claim 6, wherein the concentration of the magnesium borohydride dispersion is 10 to 50g/L.
8. The method according to claim 6, wherein the molar ratio of the magnesium hexafluoroisopropoxyborate to the magnesium borohydride is (4-6): 1, and the molar ratio of the magnesium hexafluoroisopropoxyborate to the additive is 3 (1-5).
9. The method according to claim 6, wherein the concentration of the additive is 0.05 to 0.5mol/L, and the additive comprises an ionic compound having an anion of trifluoromethanesulfonate, hexafluorophosphate, bistrifluoromethylsulfonyl imide, bistrifluorosulfonimide, perchlorate or hexamethyldisilazane.
10. The method according to claim 6, wherein the concentration of the magnesium hexafluoroisopropoxyborate is 0.05 to 0.5mol/L.
11. The method of claim 6, wherein the first organic ether solvent comprises one or more mixtures of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran;
the second organic ether solvent comprises one or more of tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
12. A magnesium ion battery, characterized in that the electrolyte adopts the electrolyte applied to the magnesium ion battery as claimed in any one of claims 1 to 5.
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| CN109075326A (en) * | 2016-04-26 | 2018-12-21 | 株式会社村田制作所 | Mg secondary cell cathode and its manufacturing method and Mg secondary cell |
| CN112534621A (en) * | 2018-08-01 | 2021-03-19 | 株式会社村田制作所 | Electrolyte solution and electrochemical device |
| JP2021178801A (en) * | 2020-05-15 | 2021-11-18 | 国立研究開発法人物質・材料研究機構 | Method for manufacturing boron based magnesium salt, method for manufacturing electrolyte solution, boron based magnesium salt, electrolyte solution and secondary battery |
| US20220416301A1 (en) * | 2019-12-04 | 2022-12-29 | Agency For Science, Technology And Research | An electrolyte for magnesium ion batteries |
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| CN109075326A (en) * | 2016-04-26 | 2018-12-21 | 株式会社村田制作所 | Mg secondary cell cathode and its manufacturing method and Mg secondary cell |
| CN112534621A (en) * | 2018-08-01 | 2021-03-19 | 株式会社村田制作所 | Electrolyte solution and electrochemical device |
| US20220416301A1 (en) * | 2019-12-04 | 2022-12-29 | Agency For Science, Technology And Research | An electrolyte for magnesium ion batteries |
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