CN116936957A - Low-temperature-resistant water-based metal ion electrolyte and metal ion battery - Google Patents
Low-temperature-resistant water-based metal ion electrolyte and metal ion battery Download PDFInfo
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- CN116936957A CN116936957A CN202311148224.2A CN202311148224A CN116936957A CN 116936957 A CN116936957 A CN 116936957A CN 202311148224 A CN202311148224 A CN 202311148224A CN 116936957 A CN116936957 A CN 116936957A
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- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 66
- 239000003792 electrolyte Substances 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000654 additive Substances 0.000 claims abstract description 44
- 230000000996 additive effect Effects 0.000 claims abstract description 41
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 63
- 239000011230 binding agent Substances 0.000 claims description 30
- 239000006258 conductive agent Substances 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 239000007774 positive electrode material Substances 0.000 claims description 16
- -1 1-dichloroethane Chemical compound 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 6
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 claims description 6
- 229930195725 Mannitol Natural products 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 claims description 6
- 229960000367 inositol Drugs 0.000 claims description 6
- 239000000594 mannitol Substances 0.000 claims description 6
- 235000010355 mannitol Nutrition 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229960003351 prussian blue Drugs 0.000 claims description 2
- 239000013225 prussian blue Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 230000008014 freezing Effects 0.000 abstract description 5
- 238000007710 freezing Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 208000032953 Device battery issue Diseases 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000006229 carbon black Substances 0.000 description 8
- FFDNCLQDXZUPCF-UHFFFAOYSA-N [V].[Zn] Chemical compound [V].[Zn] FFDNCLQDXZUPCF-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-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
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M2300/0002—Aqueous electrolytes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an aqueous electrolyte containing a low-temperature-resistant additive and an aqueous metal ion battery. The water-based electrolyte uses water as a solvent, metal salt as a solute and low-temperature resistant substances as additives. The additive has better coordination ability with metal ions, regulates and controls the coordination environment of the metal ions, and further inhibits dendrite development. The capacity attenuation and the battery failure of the anode and the cathode caused by short circuit are reduced, and the cycle stability and the service life of the battery are obviously improved. The low-temperature-resistant additive has higher melting point, better freezing resistance and unique interaction between metal ions and additive molecules, can effectively destroy continuous hydrogen bond network among water molecules in the electrolyte, greatly reduces the freezing point of the mixed electrolyte, and can also keep the long cycle performance of the water-based metal ion battery in a low-temperature environment.
Description
Technical Field
The invention relates to the technical field of aqueous battery electrolyte, in particular to a low-temperature-resistant additive aqueous electrolyte and an aqueous metal ion battery prepared from the low-temperature-resistant aqueous metal ion electrolyte.
Background
Since human beings enter the 21 st century, global economy has rapidly developed, and non-renewable resources are widely used by human beings for a long time, so that global climate warming and various natural disasters frequently occur, and the survival of human beings is seriously affected. The battery is a large-scale electrochemical energy storage system, has the characteristics of low carbon, environmental protection and controllability, and can well solve the environmental problem in the economic development process. The aqueous battery is a secondary battery using water as an electrolyte. Compared with an organic electrolyte battery, the water-based battery has the advantages of high safety, environmental friendliness, high ion conductivity and the like, so that the water-based battery has a wider application prospect in large-scale electric energy storage in the future. Zinc metal has a high theoretical capacity (820 mAh/g) and a suitable reduction potential (-0.76 Vvs standard hydrogen electrode). The open-circuit voltage is improved to have high hydrogen evolution potential (1.2V), so that the decomposition of water can be reduced, the hydrogen evolution reaction is reduced, and the battery can obtain higher stability and longer cycle life. The metallic zinc is relatively stable in aqueous solution and has high conductivity as compared with alkali metals and alkaline earth metals such as lithium, sodium, magnesium, aluminum, and the like, and thus is an ideal negative electrode for aqueous secondary batteries. And the metal zinc has larger reserves than lithium, is easy to prepare, has low price, low toxicity, stable property and difficult combustion, and is a hot spot for current research.
However, zinc anodes always suffer from serious problems during long-term reversible plating/stripping due to complex interfacial chemical reactions between the zinc surface and the electrolyte. Including zinc dendrites, dead zinc, side reactions (corrosion, hydrogen evolution), etc., which result in zinc cathodes with low Coulombic Efficiency (CE) and poor long cycle stability during reversible cycling. The energy and power characteristics of the battery are severely degraded in low temperature use. The low temperature performance of a battery is manifested in a great decay in its available capacity and power as the temperature decreases.
Disclosure of Invention
Based on the defects of the prior art, one of the purposes of the invention is to provide a low-temperature-resistant water-based metal ion electrolyte, and the problems of corrosion, dendrite and the like of a battery are solved by adding an additive with freezing resistance. Meanwhile, the addition of the low-temperature-resistant additive can effectively destroy a continuous hydrogen bond network among water molecules in the electrolyte, greatly reduce the solidifying point of the mixed electrolyte, and can also keep the long-cycle performance of the water-system metal ion battery in a low-temperature environment. The electrolyte is simple to manufacture, can be prepared at room temperature, has simple raw materials, low price and environment friendliness, and is suitable for commercial large-scale production and application.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the low-temperature-resistant water-based metal ion electrolyte consists of water, metal ion salt and a low-temperature-resistant additive, wherein the low-temperature-resistant additive is one or more of isopropanol, mannitol, inositol, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-butanol, 2-methyl-1-propanol, polyethylene glycol, pentaerythritol, diethylene glycol, ethylene glycol butyl ether, propylene glycol butyl ether, dichloromethane, 1-dichloroethane, 1, 2-dichloroethane, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
As a low-temperature-resistant aqueous metal ion electrolyte, further improvement:
preferably, the concentration of the metal ion salt in the low-temperature-resistant water-based metal ion electrolyte is 1-3mol/L.
Preferably, when the low temperature resistant additive is in a liquid state at normal temperature, the concentration of the low temperature resistant additive in the low temperature resistant water-based metal ion electrolyte is 1-30wt%; when the low temperature resistant additive is solid at normal temperature, the concentration of the low temperature resistant additive in the low temperature resistant water-based metal ion electrolyte is 0.1-0.5mol/L.
Preferably, the metal ion salt is one or more of lithium salt, zinc salt, magnesium salt, aluminum salt and calcium salt.
The second object of the invention is to provide a metal ion battery, comprising a negative electrode, a positive electrode, a diaphragm and the low-temperature-resistant water-based metal ion electrolyte.
As a further improvement of the metal ion battery:
preferably, the negative electrode comprises a negative electrode current collector, a negative electrode active material, a conductive agent and a binder in a mass ratio of 7:2:1, and the positive electrode comprises a positive electrode active material, a conductive agent and a binder in a mass ratio of 7:2:1.
Preferably, the negative electrode active material is one or a combination of two or more of zinc, zinc oxide, aluminum oxide, magnesium oxide, calcium, and calcium oxide.
Preferably, the positive electrode active material is one or a combination of more than two of lithium iron phosphate, lithium manganate, lithium cobaltate, lithium nickelate, prussian blue, nickel cobalt manganese and vanadium pentoxide.
Preferably, the material of the negative electrode current collector is one or a combination of more than two of copper, stainless steel, aluminum and nickel.
Preferably, the conductive agent is carbon; the binder is one or the combination of more than two of acrylonitrile multipolymer, high molecular alcohol polymer, polytetrafluoroethylene and rubber polymer.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention relates to an aqueous battery electrolyte containing a low-temperature-resistant additive, which comprises metal salt, water and the low-temperature-resistant additive, wherein the addition of the low-temperature-resistant additive can improve the cycle life of a battery in a low-temperature environment. By changing the coordination form of metal ions in the electrolyte, the corrosion of the cathode, dendrite and other side reactions are inhibited, so that the charge and discharge performance and the cycle life of the metal ion battery based on the current aqueous electrolyte are remarkably improved. Meanwhile, the low-temperature-resistant additive can reduce the number of water molecules of solvated shell layers of metal ions in the solution, and reduce side effects generated by the reaction of the water molecules and the metal negative electrode, so that the cycle stability of the battery is improved. The low-temperature-resistant additive has high melting point and good freezing resistance, and the continuous hydrogen bond network among water molecules in the electrolyte can be effectively destroyed by adding the low-temperature-resistant additive, so that the freezing point of the mixed electrolyte is greatly reduced, and the serious deterioration of the electrochemical performance of the metal ion battery at low temperature due to slow reaction dynamics is avoided.
2) The low-temperature-resistant additive is added into the water-based zinc metal electrolyte, and the introduced low-temperature-resistant additive has the advantages of environmental friendliness, low cost and the like, and is suitable for batch and large-scale battery preparation and production. The metal salt in the water-based electrolyte mainly plays a role in ion transportation, has low-temperature-resistant substances as additives, has the advantages of environmental friendliness, low cost and the like, and finally forms the inorganic/organic composite electrolyte, so that the electrolyte keeps the high safety of the original water-based electrolyte, meanwhile, the reversible reaction of zinc in the deposition/stripping of the negative electrode is improved, and the stability of the metal battery of the current water-based electrolyte is improved to the greatest extent. Also provides a preparation method of the electrolyte. The preparation method of the electrolyte is simple, safe and efficient, and is beneficial to the production of the water-based metal battery.
Drawings
FIG. 1 shows Zn-V as a low temperature resistant additive with and without isopropyl alcohol (IPA) added to the electrolyte of example 2 2 O 5 Full cell at-20deg.C, 1Ag -1 Constant current charge-discharge curve of (2);
FIG. 2 shows Zn-V of example 2 in which isopropyl alcohol (IPA) was added as a low temperature resistant additive to the electrolyte 2 O 5 Full cell at-20deg.C, 1Ag -1 Is a cyclic stability test curve of (2).
FIG. 3 is a Zn-V composition of the electrolyte of example 1 with isopropyl alcohol (IPA) as a low temperature resistant additive 2 O 5 Full cell at-20deg.C, 1Ag -1 Is a cyclic stability test curve of (2).
FIG. 4 is a Zn-V composition of example 3 in which isopropyl alcohol (IPA) was added as a low temperature resistant additive to an electrolyte 2 O 5 Full cell at-20deg.C, 1Ag -1 Is a cyclic stability test curve of (2).
FIG. 5 is a Zn-V composition of example 4 in which isopropyl alcohol (IPA) was added as a low temperature resistant additive to an electrolyte 2 O 5 Full cell at-20deg.C, 1Ag -1 Is a cyclic stability test curve of (2).
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
The experimental methods used in the examples below are conventional, unless otherwise specified.
Reagents, materials, and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The embodiment provides a metal ion battery, which is a battery assembled by a negative electrode, a positive electrode, a diaphragm and a low-temperature-resistant water-based metal ion electrolyte:
the negative electrode comprises a negative electrode current collector, a conductive agent, a binder and a negative electrode active material; the negative electrode active material is magnesium, the conductive agent is carbon black, the binder is polytetrafluoroethylene, and the negative electrode current collector is nickel; wherein the mass ratio of the anode active material to the conductive agent to the binder is 7:2:1;
the positive electrode includes a positive electrode active material, a conductive agent, and a binder; the positive electrode active material is vanadium pentoxide, the conductive agent is carbon black, and the binder is polytetrafluoroethylene; wherein the mass ratio of the positive electrode active material to the conductive agent to the binder is 7:2:1;
the membrane is filter paper with the aperture of 19 mm;
the preparation method of the low-temperature-resistant water-based metal ion electrolyte comprises the following steps: water is used as a solvent, zinc sulfonate is used as metal ion salt, and mannitol is used as a low-temperature-resistant additive; weigh 0.01mol Zn (OTf) 2 Mixing with 0.005mol mannitol, dissolving in deionized water to 10ml, stirring to clear, and preparing 1M Zn (OTf) 2 +0.5M mannitol.
Example 2
The embodiment provides a metal ion battery, which is a battery assembled by a negative electrode, a positive electrode, a diaphragm and a low-temperature-resistant water-based metal ion electrolyte:
the negative electrode comprises a negative electrode current collector, a conductive agent, a binder and a negative electrode active material; the negative electrode active material is zinc, the conductive agent is carbon black, the binder is polytetrafluoroethylene, and the negative electrode current collector is copper; wherein the mass ratio of the anode active material to the conductive agent to the binder is 7:2:1;
the positive electrode includes a positive electrode active material, a conductive agent, and a binder; the positive electrode active material is vanadium pentoxide, the conductive agent is carbon black, and the binder is polytetrafluoroethylene; wherein the mass ratio of the positive electrode active material to the conductive agent to the binder is 7:2:1;
the membrane is filter paper with the aperture of 19 mm;
the preparation method of the low-temperature-resistant water-based metal ion electrolyte comprises the following steps: water is used as a solvent, zinc sulfonate is used as metal ion salt, and isopropyl alcohol (IPA) is used as a low-temperature-resistant additive; uniformly mixing water and isopropanol according to a volume ratio of 7:3, and weighing 0.01mol of Zn (OTf) 2 Dissolving in mixed solvent to constant volume of 10ml, stirring to clear, and preparing 1M Zn (OTf) 2 +30% isopropyl alcohol.
As a control, 1M Zn (OTf) was prepared without adding isopropanol to the metal ion electrolyte 2 As an electrolyte, and assembled together with a negative electrode, a positive electrode, and a separator into a metal ion battery.
Example 3
The embodiment provides a metal ion battery, which is a battery assembled by a negative electrode, a positive electrode, a diaphragm and a low-temperature-resistant water-based metal ion electrolyte:
the negative electrode comprises a negative electrode current collector, a conductive agent, a binder and a negative electrode active material; the negative electrode active material is a combination of zinc oxide and zinc, the conductive agent is carbon black, the binder is polytetrafluoroethylene, and the negative electrode current collector is copper; wherein the mass ratio of the anode active material to the conductive agent to the binder is 7:2:1;
the positive electrode includes a positive electrode active material, a conductive agent, and a binder; the positive electrode active material is lithium nickelate, the conductive agent is carbon black, and the binder is polytetrafluoroethylene; wherein the mass ratio of the positive electrode active material to the conductive agent to the binder is 7:2:1;
the membrane is filter paper with the aperture of 19 mm;
the preparation method of the low-temperature-resistant water-based metal ion electrolyte comprises the following steps: water is used as a solvent, zinc sulfonate is used as metal ion salt, and inositol is used as a low-temperature-resistant additive; weigh 0.01mol Zn (OTf) 2 Mixing with 0.005mol of inositol, dissolving in deionized water to constant volume of 10ml, stirring to clear, and preparing 1M Zn (OTf) 2 +0.5M inositol.
Example 4
The embodiment provides a metal ion battery, which is a battery assembled by a negative electrode, a positive electrode, a diaphragm and a low-temperature-resistant water-based metal ion electrolyte:
the negative electrode comprises a negative electrode current collector, a conductive agent, a binder and a negative electrode active material; the negative electrode active material is aluminum, the conductive agent is carbon black, the binder is polytetrafluoroethylene, and the negative electrode current collector is copper; wherein the mass ratio of the anode active material to the conductive agent to the binder is 7:2:1;
the positive electrode includes a positive electrode active material, a conductive agent, and a binder; the positive electrode active material is a combination of lithium iron phosphate and lithium cobalt oxide, the conductive agent is carbon black, and the binder is polytetrafluoroethylene; wherein the mass ratio of the positive electrode active material to the conductive agent to the binder is 7:2:1;
the membrane is filter paper with the aperture of 19 mm;
the preparation method of the low-temperature-resistant water-based metal ion electrolyte comprises the following steps: water is used as a solvent, zinc sulfonate is used as metal ion salt, and butanediol is used as a low temperature resistant additive; uniformly mixing water and butanediol according to a volume ratio of 9:1, and weighing 0.01mol of Zn (OTf) 2 Dissolving in mixed solvent to constant volume of 10ml, stirring to clear, and preparing 1M Zn (OTf) 2 +10% butanediol.
The aqueous zinc-vanadium metal ion batteries of example 2 with and without isopropyl alcohol (IPA) as a low temperature resistant additive were tested separately, and the effect of the energy storage performance of the aqueous zinc-vanadium battery at-20 ℃ was tested using a constant current charge-discharge test (GCD), and the results are shown in fig. 1. The results show that at 1A g -1 The long-cycle stability of the zinc-vanadium battery with the electrolyte added with the isopropanol is obviously improved under the current density.
The results of the cycle stability test of the aqueous zinc-vanadium metal ion battery of example 2 with isopropyl alcohol (IPA) added as a low temperature resistant additive are shown in fig. 2. As can be seen from FIG. 2, the use of an electrolyte with added isopropanol, at 1Ag -1 Under the current density, the zinc-vanadium battery still has the coulombic efficiency of 99.93 percent after being continuously charged and discharged for 1000 times, and the cycle stability of the zinc-vanadium battery is greatly improved, which indicates the excellent cycle stability of the zinc-vanadium battery.
Cycling stabilization for metal particle batteries with different low temperature additives in example 1, example 3 and example 4The constant performance was tested and the results are shown in figures 3, 4 and 5, respectively. As can be seen from FIGS. 3, 4 and 5, the composition is 1Ag -1 At current density, the metal particle battery of example 1 using mannitol as the low temperature resistant additive still has 99.69% coulombic efficiency after 1000 times of continuous charge and discharge, the metal particle battery of example 3 using inositol as the low temperature resistant additive still has 99.77% coulombic efficiency after 1000 times of continuous charge and discharge, and the metal particle battery of example 4 using butanediol as the low temperature resistant additive still has 99.86% coulombic efficiency after 1000 times of continuous charge and discharge.
The test results prove that the water-based electrolyte containing the low-temperature-resistant additive can effectively improve the cycle stability of the rechargeable water-based metal ion battery under the low-temperature condition, and has great application prospect in the aspect of energy storage.
Those skilled in the art will appreciate that the foregoing is merely a few, but not all, embodiments of the invention. It should be noted that many variations and modifications can be made by those skilled in the art, and all variations and modifications which do not depart from the scope of the invention as defined in the appended claims are intended to be protected.
Claims (10)
1. The low-temperature-resistant water-based metal ion electrolyte is characterized by comprising water, metal ion salt and a low-temperature-resistant additive, wherein the low-temperature-resistant additive is one or a combination of more than two of isopropanol, mannitol, inositol, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-butanol, 2-methyl-1-propanol, polyethylene glycol, pentaerythritol, diethylene glycol, ethylene glycol butyl ether, propylene glycol butyl ether, methylene dichloride, 1-dichloroethane, 1, 2-dichloroethane, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
2. The low-temperature-resistant aqueous metal ion electrolyte according to claim 1, wherein the concentration of the metal ion salt in the low-temperature-resistant aqueous metal ion electrolyte is 1 to 3mol/L.
3. The low temperature-resistant aqueous metal ion electrolyte according to claim 1, wherein the concentration of the low temperature-resistant additive in the low temperature-resistant aqueous metal ion electrolyte is 1 to 30wt% when it is in a liquid state at normal temperature; when the low temperature resistant additive is solid at normal temperature, the concentration of the low temperature resistant additive in the low temperature resistant water-based metal ion electrolyte is 0.1-0.5mol/L.
4. The low-temperature-resistant aqueous metal ion electrolyte according to claim 1,2 or 3, wherein the metal ion salt is one or a combination of two or more of lithium salt, zinc salt, magnesium salt, aluminum salt and calcium salt.
5. A metal ion battery comprising a negative electrode, a positive electrode, a separator, and the low temperature water-resistant aqueous metal ion electrolyte of any one of claims 1 to 4.
6. The metal-ion battery of claim 5, wherein the negative electrode comprises a negative electrode current collector and a negative electrode active material, a conductive agent and a binder in a mass ratio of 7:2:1, and the positive electrode comprises a positive electrode active material, a conductive agent and a binder in a mass ratio of 7:2:1.
7. The metal-ion battery according to claim 6, wherein the negative electrode active material is one or a combination of two or more of zinc, zinc oxide, aluminum oxide, magnesium oxide, calcium, and calcium oxide.
8. The metal ion battery of claim 6, wherein the positive electrode active material is one or a combination of two or more of lithium iron phosphate, lithium manganate, lithium cobaltate, lithium nickelate, prussian blue, nickel cobalt manganese and vanadium pentoxide.
9. The metal-ion battery of claim 6, wherein the negative current collector is made of one or a combination of two or more of copper, stainless steel, aluminum and nickel.
10. The metal-ion battery of claim 6, wherein the conductive agent is carbon; the binder is one or the combination of more than two of acrylonitrile multipolymer, high molecular alcohol polymer, polytetrafluoroethylene and rubber polymer.
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