CN117613432B - Aqueous zinc ion battery composite electrolyte and preparation method and application thereof - Google Patents
Aqueous zinc ion battery composite electrolyte and preparation method and application thereof Download PDFInfo
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- CN117613432B CN117613432B CN202410095047.4A CN202410095047A CN117613432B CN 117613432 B CN117613432 B CN 117613432B CN 202410095047 A CN202410095047 A CN 202410095047A CN 117613432 B CN117613432 B CN 117613432B
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- zinc
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 127
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 110
- 125000004185 ester group Chemical group 0.000 claims abstract description 30
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 125000000468 ketone group Chemical group 0.000 claims abstract description 28
- 239000006259 organic additive Substances 0.000 claims abstract description 23
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- BDCLDNALSPBWPQ-UHFFFAOYSA-M 3-oxohexanoate Chemical compound CCCC(=O)CC([O-])=O BDCLDNALSPBWPQ-UHFFFAOYSA-M 0.000 claims abstract description 5
- CZTKGERSDUGZPQ-UHFFFAOYSA-N methyl 3-oxoheptanoate Chemical compound CCCCC(=O)CC(=O)OC CZTKGERSDUGZPQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- SJPCQNABHNCLPB-UHFFFAOYSA-N methyl 3-oxohexanoate Chemical compound CCCC(=O)CC(=O)OC SJPCQNABHNCLPB-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229960001763 zinc sulfate Drugs 0.000 claims description 25
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 25
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 10
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 113
- 229910052725 zinc Inorganic materials 0.000 abstract description 84
- 239000013078 crystal Substances 0.000 abstract description 36
- 210000001787 dendrite Anatomy 0.000 abstract description 14
- 230000001351 cycling effect Effects 0.000 abstract description 12
- 238000007614 solvation Methods 0.000 abstract description 12
- 239000002000 Electrolyte additive Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 125000002252 acyl group Chemical group 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract 1
- 150000001335 aliphatic alkanes Chemical group 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 55
- 210000004027 cell Anatomy 0.000 description 39
- 239000000654 additive Substances 0.000 description 24
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 24
- 230000008021 deposition Effects 0.000 description 21
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 230000000996 additive effect Effects 0.000 description 16
- 238000012512 characterization method Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 7
- 230000005684 electric field Effects 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 238000013112 stability test Methods 0.000 description 6
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- -1 acyl ester Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005520 electrodynamics Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WEFZXWJJPHGTTN-UHFFFAOYSA-N methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate Chemical group COC(=O)C(C)CCC(=O)N(C)C WEFZXWJJPHGTTN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001075 voltammogram 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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 present invention provides a process for producing an acid ester C comprising an acyl group having both a ketone group and an ester group 5~8 An aqueous zinc ion battery composite electrolyte of alkane chain organic additive, a preparation method and application thereof. The electrolyte additive is at least one of methyl acetoacetate, methyl levulinate, methyl acetoacetate, methyl propionylacetate, methyl acetoacetate, methyl butyrylacetate and methyl valerylacetate, and has the advantages of low cost and environmental protection, and the reversible cycling stability of the zinc cathode can be obviously improved by adding a small amount of electrolyte additive; the invention utilizes the high polarity of acyl acid ester organic molecules to change the solvation structure of zinc ions, and simultaneously the molecules are adsorbed on the surface of a zinc cathode to induce the zinc ions to deposit in a (002) crystal face which is parallel to a basal plane and has more stable thermodynamics, thereby effectively solving the problems of zinc dendrite, hydrogen evolution reaction and the like, greatly improving the cycle performance of the zinc cathode, being matched with a proper positive electrode and applied to a battery, and effectively delaying capacity attenuation.
Description
Technical Field
The invention relates to the technical field of aqueous zinc ion batteries, in particular to an aqueous zinc ion battery composite electrolyte containing acyl acid ester alkane chain organic additives with ketone groups and ester groups, a preparation method and application thereof.
Background
The water-based zinc ion battery (AZIB) has initiated research hot-water in the technical field of efficient electrochemical energy storage due to the outstanding advantages of green and safe, low cost, excellent electrochemical performance and the like. The performance of aqueous zinc ion batteries depends largely on the reversibility and cycling stability of the zinc anode. However, the zinc anode inevitably faces three problems, and the three are not separable from each other. The solvation structure of zinc ions in the electrolyte is that the zinc ions carry 4-6 water molecules, the migration of the zinc ions brings water to the interface under the action of an electric field, during the zinc deposition process, partial pH value is raised due to hydrogen evolution reaction generated by hydrolysis of the solvation sheath layer at the interface, thereby generating byproducts and further forming a loose Solid Electrolyte Interface (SEI), so that the partial electric field is uneven to cause dendrite growth, and notably, the metal Zn has much higher Mohs hardness than the metal Li (Zn is 2.5 and Li is 0.5), so that dendrite problems of the zinc cathode are more serious than those of the lithium metal cathode, rigid Zn dendrites can puncture a diaphragm to cause short circuit of a battery or fracture from the root part to generate dead zinc, so that Coulombic Efficiency (CE) is reduced and capacity is attenuated. Accordingly, a great deal of work is devoted to zinc anode protection to solve the above-mentioned problems.
In order to improve the stability of zinc cathode, there are zinc structure optimization, surface modification, electrolyte optimization and separator design which are conventionally adopted at present, wherein the electrolyte optimization is the easiest way to operate with the lowest cost, and additives can be added into the electrolyte to control solvation structure and electrode interface simultaneously. The additive is adsorbed on the zinc cathode under the action of an electric field or interacts with the zinc cathode to construct a dynamic soft protective layer, and the interface is continuously repaired and reconstructed, so that the problem that the artificial coating is damaged and falls off in long-term circulation is effectively solved. Introducing a substance which is rich in polar groups and has stronger polarity than water, wherein some substances can enter a first solvation sheath layer of zinc ions to replace water so as to reduce hydrogen evolution reaction when the zinc ions are desolvated; some of which can adsorb on the zinc cathode to form hydrogen bond with water molecules upon desolvation of zinc ions to inhibit water decomposition or to regulate growth of diffusion-induced (002) crystal planes upon deposition of zinc ions to inhibit dendrites. Esters are generally incompatible with water and therefore have received little attention as additives to aqueous electrolytes. Although small molecule lactone structures such as gamma-butyrolactone or gamma-valerolactone can be dispersed in water to function in aqueous electrolytes, most of the additives reported so far have the above single effect, and there is a need for an additive which is green, safe and has a multifunctional optimizing effect to stabilize zinc negative electrode and thereby improve the performance of aqueous zinc ion battery.
Disclosure of Invention
The invention provides a water-based zinc ion battery composite electrolyte containing acyl acid ester alkane chain organic additives with ketone groups and ester groups, and a preparation method and application thereof, and aims to solve the problems in the prior art.
In order to achieve the above purpose, the embodiment of the invention provides a water-based zinc ion battery composite electrolyte containing acyl acid ester alkane chain organic additives with ketone groups and ester groups, and a preparation method and application thereof, wherein the electrolyte additive has low cost and is environment-friendly, the reversible cycling stability of a zinc cathode can be obviously improved by only adding a small amount of the electrolyte additive, the concentration of the additive is too high or too low, and the battery stability time is shorter in a cycling test of Zn// Zn of a symmetrical battery; the high polarity of acyl acid ester organic molecules is utilized to change the solvation structure of zinc ions, and molecules are adsorbed on the surface of a zinc negative electrode, so that the transport and deposition kinetics of the zinc ions is enhanced at a negative electrode-electrolyte interface, the zinc ions are induced to be deposited in a (002) crystal face which is parallel to a basal plane and is more thermodynamically stable, the adsorption induces the uniform and compact deposition of the zinc ions and the growth of the Zn (002) crystal face which is parallel to a substrate, the problems of zinc dendrite, hydrogen evolution reaction and the like are effectively solved, the cycle performance of the zinc negative electrode is greatly improved, and the zinc negative electrode is matched with a proper positive electrode and applied to a full battery, and the capacity attenuation is effectively delayed.
In one aspect, the embodiment of the invention provides an aqueous zinc ion battery composite electrolyte containing acyl ester alkane chain organic additive with ketone groups and ester groups, wherein the acyl ester alkane chain organic additive with ketone groups and ester groups is any one of methyl acetoacetate, methyl levulinate, methyl acetoacetate, methyl propionylacetate, methyl acetoacetate, methyl butyrylacetate and methyl valerylacetate, and the concentration is 0.1-3 vol%.
Based on one general inventive concept, an aspect of the present invention provides a method for preparing an aqueous zinc ion battery composite electrolyte containing an acyl ester alkane chain organic additive having both ketone groups and ester groups, comprising the following steps:
s1: adding soluble zinc salt into deionized water to be fully dissolved, so as to obtain basic aqueous zinc salt electrolyte;
s2: adding acyl ester alkane chain organic additive with ketone group and ester group into the basic aqueous zinc salt electrolyte, continuously stirring under a magnetic stirrer until the acyl ester alkane chain organic additive is completely dissolved, and standing to obtain the aqueous zinc ion battery composite electrolyte containing the acyl ester alkane chain organic additive with ketone group and ester group.
Preferably, the soluble zinc salt is at least one of zinc sulfate, zinc chloride, zinc acetate, zinc trifluoromethane sulfonate and hydrate thereof, and the concentration is 1-4 mol/L.
In another aspect, the embodiment of the invention provides a water-based zinc ion battery, which comprises an electrolyte, wherein the electrolyte is the water-based zinc ion battery composite electrolyte containing the acyl ester alkane chain organic additive with ketone groups and ester groups or the water-based zinc ion battery composite electrolyte containing the acyl ester alkane chain organic additive with ketone groups and ester groups, which is prepared by the preparation method.
Preferably, the aqueous zinc ion battery is a symmetrical battery, a half battery or a full battery.
Preferably, the symmetrical cell consists of a commercial 100 micron thick zinc foil, a fiberglass separator, and an electrolyte; the half cell consists of a commercial zinc foil with the thickness of 100 microns, a commercial current collector and an electrolyte; the full battery is composed of a commercial zinc foil with the thickness of 100 microns as a negative electrode, a manganese material or a vanadium material as a positive electrode and an electrolyte.
Preferably, the current collector is selected from any one of copper foil, copper mesh, copper foam, stainless steel mesh, titanium foil, and nickel foam.
Preferably, the manganese-based material is MnO 2 The vanadium material is V 2 O 5 Or MNVO.
Preferably, the working current density of the water-based zinc ion battery is 0.5-10 mA cm -2 。
The scheme of the invention has the following beneficial effects:
in the aqueous zinc ion battery composite electrolyte containing the acyl ester alkane chain organic additive with ketone groups and ester groups, the high polarity of acyl ester organic molecules is utilized to change the solvation structure of zinc ions, and simultaneously the molecules are adsorbed on the surface of a zinc negative electrode to induce the zinc ions to deposit in a (002) crystal face which is parallel to a basal plane and is more thermodynamically stable, so that the growth of dendrites is inhibited, and the reversible cycling stability of the zinc negative electrode is effectively improved.
The acyl acid ester alkane chain organic molecular additive has low price, mature synthesis process and environment protection, and can improve the electrochemical performance of the zinc cathode only by adding a trace amount. Symmetrical cell at 1mA cm -2 The continuous charge and discharge for 1h respectively under the current density, the stable circulation time is prolonged by more than 28 times than that of the basic electrolyte, and the stable circulation time is matched with the high-efficiency positive electrode, so that the capacity attenuation of the water-based zinc ion battery is greatly delayed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a surface SEM image of a commercial zinc foil of the present invention immersed in a 2mol/L base zinc sulfate electrolyte and an electrolyte containing Methyl Levulinate (ML), respectively; wherein, FIG. 1a is an SEM image of the surface of a zinc foil immersed in a 2mol/L base zinc sulfate electrolyte; FIG. 1b is an SEM image of the surface of a zinc foil immersed in an electrolyte with Methyl Levulinate (ML) added;
FIG. 2 is a Taphillips corrosion current curve of a commercial zinc foil of the present invention in a 2mol/L base zinc sulfate electrolyte and a Methyl Levulinate (ML) -containing electrolyte, respectively;
FIG. 3 is a linear sweep voltammogram of an aqueous solution of 1M sodium sulfate with and without Methyl Levulinate (ML) of example 1 of the present invention;
FIG. 4 is a comparative graph of the coulombic efficiency test of the button cell of example 2 of the present invention versus comparative example 2;
FIG. 5 is an SEM image of the surface of a zinc anode after 50 cycles of constant current charge and discharge of a symmetric battery assembled with the electrolyte of the present invention; wherein, FIG. 5a is an SEM image of the surface of a zinc cathode after a symmetric battery assembled by zinc sulfate electrolyte with a 2mol/L basis is subjected to constant current charge-discharge cycle for 50 circles; FIG. 5b is an SEM image of the surface of a zinc anode after 50 cycles of constant current charge and discharge for the electrolyte assembled symmetric cell of example 3;
FIG. 6 is an X-ray diffraction characterization of a zinc anode after 25 cycles of constant current charge and discharge cycles for the electrolyte assembled symmetric cell of example 3 of the present invention;
FIG. 7 is an X-ray diffraction characterization of a zinc anode after 25 cycles of constant current charge and discharge cycles for a symmetric cell assembled from the electrolyte of comparative example 3 of the present invention;
FIG. 8 is a graph showing that the symmetrical battery assembled in example 3 of the present invention and comparative example 3 was fabricated at 1mA cm -2 A time-voltage comparison graph for carrying out cycle stability test under the current density of (1) h of continuous charge and discharge;
FIG. 9 is a graph showing that the symmetrical cells assembled in comparative example 3 and comparative example 4 of the present invention were fabricated at 1mA cm -2 A time-voltage comparison graph for carrying out cycle stability test under the current density of (1) h of continuous charge and discharge;
FIG. 10 is an X-ray diffraction characterization of a zinc anode after 25 cycles of constant current charge and discharge cycles for the electrolyte assembled symmetric cell of comparative example 5 of the present invention;
FIG. 11 is an X-ray diffraction characterization of a zinc anode after 25 cycles of constant current charge and discharge cycles for a comparative example 6 electrolyte assembled symmetric cell of the present invention;
FIG. 12 shows a symmetric cell assembled from the electrolytes of example 4 and comparative example 7 of the present invention at 5mA cm -2 A time-voltage comparison graph for carrying out cycle stability test under the current density of (1) h of continuous charge and discharge;
FIG. 13 is an SEM image of the surface of a zinc anode after 50 cycles of constant current charge and discharge for a symmetric cell assembled with the electrolyte of comparative example 8 of the present invention; wherein, fig. 13a is an SEM image of the surface of a zinc anode after 50 cycles of constant current charge and discharge of a symmetric battery assembled with a zinc sulfate electrolyte based on 2mol/L, and fig. 13b is an SEM image of the surface of a zinc anode after 50 cycles of constant current charge and discharge of a symmetric battery assembled with an electrolyte of comparative example 8;
FIG. 14 is an X-ray diffraction characterization of a zinc anode after 50 cycles of constant current charge and discharge for a symmetric cell assembled from the electrolyte of comparative example 8 of the present invention;
FIG. 15 shows the electrolyte solution assembled symmetrical cell of example 4 and comparative example 8 of the present invention at 5mA cm -2 A time-voltage comparison graph for carrying out cycle stability test under the current density of (1) h of continuous charge and discharge;
FIG. 16 is an SEM image of the surface of a zinc anode after 50 cycles of constant current charge and discharge for a symmetric cell assembled from the electrolyte of example 9;
FIG. 17 is an X-ray diffraction characterization of a zinc anode after 50 cycles of constant current charge and discharge for a comparative example 9 electrolyte assembled symmetric cell of the present invention;
FIG. 18 shows the electrolyte solution of example 4 and comparative example 9 of the present invention assembled symmetrical cell at 5mA cm -2 A time-voltage comparison graph for carrying out cycle stability test under the current density of (1) h of continuous charge and discharge;
FIG. 19 is a graph showing that the electrolyte solution of example 5 and comparative example 10 of the present invention was assembled at 5 mA.cm -2 A time-voltage comparison graph for carrying out cycle stability test under the current density of (1) h of continuous charge and discharge;
FIG. 20 shows the assembled full cell of example 6 and comparative example 11 of the present invention at 3 A.g -1 A cyclic specific capacity diagram of constant current charge and discharge test is carried out under the current density;
FIG. 21 is a graph showing the assembly of the symmetrical cells of example 4 and comparative example 12 of the present invention at 2mA cm -2 Continuous charge and discharge for 1h respectively under the current density, and X-ray diffraction characterization graph of the zinc cathode after 25 circles of constant-current charge and discharge cycles;
FIG. 22 is an electrodynamic polarization curve of a symmetric cell Zn// Zn in ML and polar clear composite electrolyte, assembled in accordance with example 4 and comparative example 12 of the present invention;
FIG. 23 shows the Zn// Zn concentration at 5mA cm for the symmetrical cells assembled in example 4 and comparative example 12 of the present invention -2 Initial nucleation overpotential in ML and polar clean composite electrolyte at current density;
FIG. 24 is a self-discharge curve of assembled full cell Zn// MNVO of example 4 and comparative example 12 of the present invention in a base zinc trifluoromethane sulfonate electrolyte, ML and polar clear composite electrolyte.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more easily understood, the following detailed description will be made with reference to the accompanying drawings and specific embodiments. It should be understood that these examples are presented by way of illustration only and not by way of limitation, and it is apparent that the described examples are merely some, but not all of the examples of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise specified, the materials, reagents, equipment referred to herein may be purchased commercially or prepared by well known methods.
The performance of aqueous zinc ion batteries depends largely on the reversibility and cycling stability of the zinc anode. However, the zinc anode inevitably faces three problems, and the three are not separable from each other. The solvation structure of zinc ions in the electrolyte is that the zinc ions carry 4-6 water molecules, the migration of the zinc ions brings water to the interface under the action of an electric field, during the zinc deposition process, partial pH value is raised due to hydrogen evolution reaction generated by hydrolysis of the solvation sheath layer at the interface, thereby generating byproducts and further forming a loose Solid Electrolyte Interface (SEI), so that the partial electric field is uneven to cause dendrite growth, and notably, the metal Zn has much higher Mohs hardness than the metal Li (Zn is 2.5 and Li is 0.5), so that dendrite problems of the zinc cathode are more serious than those of the lithium metal cathode, rigid Zn dendrites can puncture a diaphragm to cause short circuit of a battery or fracture from the root part to generate dead zinc, so that Coulombic Efficiency (CE) is reduced and capacity is attenuated. Accordingly, a great deal of work is devoted to zinc anode protection to solve the above-mentioned problems.
In order to improve the stability of zinc cathode, there are zinc structure optimization, surface modification, electrolyte optimization and separator design which are conventionally adopted at present, wherein the electrolyte optimization is the easiest way to operate with the lowest cost, and additives can be added into the electrolyte to control solvation structure and electrode interface simultaneously. The additive is adsorbed on the zinc cathode under the action of an electric field or interacts with the zinc cathode to construct a dynamic soft protective layer, and the interface is continuously repaired and reconstructed, so that the problem that the artificial coating is damaged and falls off in long-term circulation is effectively solved. Introducing a substance which is rich in polar groups and has stronger polarity than water, wherein some substances can enter a first solvation sheath layer of zinc ions to replace water so as to reduce hydrogen evolution reaction when the zinc ions are desolvated; some of which can adsorb on the zinc cathode to form hydrogen bond with water molecules upon desolvation of zinc ions to inhibit water decomposition or to regulate growth of diffusion-induced (002) crystal planes upon deposition of zinc ions to inhibit dendrites. Esters are generally incompatible with water and therefore have received little attention as additives to aqueous electrolytes. Although small molecule lactone structures such as gamma-butyrolactone or gamma-valerolactone can be dispersed in water to function in aqueous electrolytes, most of the additives reported so far have the above single effect, and there is a need for an additive which is green, safe and has a multifunctional optimizing effect to stabilize zinc negative electrode and thereby improve the performance of aqueous zinc ion battery.
Aiming at the problems of zinc dendrite, hydrogen evolution reaction and the like in charge-discharge circulation of a zinc cathode in the prior art, the primary aim of the invention is to provide a water-based zinc ion battery composite electrolyte containing acyl ester alkane chain organic additives with ketone groups and ester groups, and a preparation method and application thereof, wherein the electrolyte additive has low cost and is green and environment-friendly, the reversible circulation stability of the zinc cathode can be obviously improved by only adding a small amount of additive, the concentration of the additive is too high or too low, and the battery stability time is shorter in the circulation test of Zn// Zn of a symmetrical battery; the high polarity of acyl acid ester organic molecules is utilized to change the solvation structure of zinc ions, and simultaneously, the molecules are adsorbed on the surface of a zinc cathode to induce zinc ions to deposit on a (002) crystal face which is parallel to a basal plane and has more stable thermodynamics, so that the problems of zinc dendrite, hydrogen evolution reaction and the like are effectively solved.
Wherein in the drawings of the present application, "ZnSO 4 Or ZSO "is a zinc sulfate aqueous solution (also called as water-based zinc salt electrolyte)" Zn (otf) 2 Or ZOTF' is zinc trifluoromethane sulfonate aqueous solution; "1-200ML-2M ZnSO in the drawings of the present application 4 /2ZSO”“1-200MAA-2M ZnSO 4 /2ZSO”“1-200M3OVA-2M ZnSO 4 /2ZSO”“1-2002-HA-2M ZnSO 4 /2ZSO”“1-200MVA-2MZnSO 4 /2ZSO”“1-200M4OHA-2M ZnSO 4 2 ZSO' are respectively aqueous composite electrolytes containing methyl levulinate, methyl acetoacetate, methyl propionylacetate, 2-hexanone, methyl valerate and 4-cyclohexanone carboxylic acid methyl ester additives, and the volume ratio of the additives to the zinc sulfate aqueous solution is 1:200. "N e" and ML e "in the drawings of the present application are 2M zinc sulfate electrolyte and 1-200ML-2M ZnSO 4 A composite electrolyte; in the drawings of the application, "without additive" is based on zinc trifluoromethane sulfonate electrolyte, "Coulombic efficiency" is coulombic efficiency, "Rest 48h" is 48 hours of storage, "Charing" is charging and "discharging" is discharging.
The following will describe by way of specific examples.
Example 1
At room temperature, 11.5g of zinc sulfate heptahydrate powder is added into 15mL of deionized water, and stirring is continued until the solution is clear, so as to obtain zinc sulfate electrolyte with a 2mol/L basis. 14.2g of sodium sulfate powder was added to 100mL of deionized water, and stirring was continued until the solution was clear, to give 1mol/L sodium sulfate electrolyte. And adding 20mL of deionized water into 21.81g of zinc trifluoromethane sulfonate powder, and continuously stirring until the solution is clear to obtain 3 mol/L-based zinc trifluoromethane sulfonate electrolyte.
100 mu L of Methyl Levulinate (ML) is added into the basic zinc sulfate electrolyte to be completely dispersed for 20min, so as to obtain the composite electrolyte.
The surface with the diameter of 16mm and the thickness of 0.1mm is pressed to be flat commercial zinc sheets by a heavy object, the commercial zinc sheets are respectively ultrasonically cleaned by ultrapure water and ethanol for 5min, then are put into a 60 ℃ oven for drying, and are soaked in 10mL of composite electrolyte for 8-28 days.
Comparative example 1
This comparative example was conducted in parallel with example 1, using only the zinc sulfate electrolyte of the 2mol/L basis of example 1, and the remaining operation steps were the same as in example 1.
The commercial zinc foil obtained in example 1 was immersed in a 10mL composite electrolyte for 8-28 days. The microstructure of the immersed zinc foil is characterized by adopting a Scanning Electron Microscope (SEM), and compared with fig. 1a, the surface of the immersed zinc foil in fig. 1b, which has almost no byproducts, is flat, so that the composite electrolyte in the embodiment 1 of the invention can inhibit self corrosion of zinc metal in a weak acid environment. The commercial zinc foil was subjected to electrodynamic polarization curve measurement (fig. 2) and linear sweep voltammetry curve measurement (fig. 3) in a 2mol/L base zinc sulfate electrolyte and an aqueous composite electrolyte containing an acyl ester additive in example 1, and the composite electrolyte obtained in example 1 significantly reduced corrosion current and hydrogen evolution reaction rate, and reduced damage to zinc anode by the aqueous electrolyte.
Example 2
Taking copper foil as an anode, zinc foil as a cathode and glass fiber as a diaphragm, taking 100 mu L of the composite electrolyte in the embodiment 1 to assemble a CR2025 Zn|Cu button cell, and performing a circulating constant current charge-discharge test on a New Wei cell test system, wherein the working current density is 1mA cm -2 The surface capacity is 1mAh cm -2 。
Comparative example 2
This comparative example was conducted in parallel with example 2, using only the zinc sulfate electrolyte of the 2mol/L basis of example 1, and the remaining operation steps were the same as in example 2.
As a result, as shown in FIG. 4, the temperature was set at 1mA cm -2 After discharging for 1h at a current density of 0.5V, the cycle stability was tested. The commercial zinc sheet exhibited superior cycle stability in the cell of example 2 of the present invention, was able to stabilize cycles more than 2.5 times that of the cell of comparative example 2, and had a coulombic efficiency as high as 99.55%.
Example 3
The 100. Mu.L composite electrolyte in example 1 was used to assemble CR2025 Zn|Zn button type symmetrical cells using zinc foil as positive and negative electrodes and glass fiber as separator, and a cycle constant current charge and discharge test was performed on a New Wei cell test system. For the battery in this example, the operating current density was 2mA cm -2 The surface capacity is 2mAh cm -2 The zinc cathode after 50 circles and 25 circles is respectively subjected to SEM characterization and X-ray diffraction characterization under the condition of (2) and (ML) to verify the effect of the ML on inducing zinc ions to deposit in a (002) crystal face. The deposition morphology is shown in figure 5; FIG. 6 is a zinc negative after cyclingAs can be seen from the characteristics of the polar X-ray diffraction, all characteristic peaks are well matched with the standard phase (PDF#04-0381) of metallic zinc, and the peak intensity ratio of (002) crystal face to (101) crystal face is compared with that of the original zinc foil I (002)/(101) (0.67) is significantly raised to 2.18, indicating that the main crystal plane of zinc ion deposition is the Zn (002) plane parallel to the basal plane.
Comparative example 3
This comparative example was conducted in parallel with example 3, using only the zinc sulfate electrolyte of the 2mol/L basis of example 1, and the remaining operation steps were the same as in example 3.
Fig. 7 is an X-ray diffraction characterization of the zinc cathode after cycling, and it can be seen that all characteristic peaks are well matched with the standard phase (pdf#04-0381) of metallic zinc, and the peak intensity ratio of the (002) crystal face to the (101) crystal face is not obviously improved compared with the original zinc foil I (002)/(101) (0.67), and the peak intensity of the (101) crystal face is highest, which indicates that the main crystal face of zinc ion deposition is a Zn (101) crystal face vertical to a basal plane. As can be seen from FIG. 8, the commercial zinc sheet exhibited superior cycle stability and life in the cell of example 3 of the present invention, at 1mA cm -2 The current density of the battery is more than or equal to 2600h, and the battery is improved by more than 28 times compared with the battery in comparative example 3. Example 3 greatly increases the working time by more than 28 times, and benefits from the high-efficiency induction of ML to zinc ions deposited in a (002) crystal face, regulates and controls the reversible dissolution deposition behavior of the zinc ions on a zinc cathode, and inhibits dendrite growth.
Comparative example 4
This comparative example was conducted in parallel with example 3, and the electrolyte was prepared by reducing the amount of the basic zinc sulfate electrolyte additive in example 1 to 40. Mu.L, and the remaining operation steps were the same as in example 3. As shown in FIG. 9, it was found that even when the amount of the catalyst was very small, the commercial zinc sheet exhibited excellent cycle stability and life at 1mA cm -2 The current density of the battery is more than or equal to 1500 hours, and the battery is improved by 16 times compared with the battery in comparative example 3.
Comparative example 5
A parallel test similar to that of example 3 was performed in this comparative example, with the additive being changed to methyl acetoacetate (MAA), the remainder of the procedureThe procedure was the same as in example 3. FIG. 10 is an X-ray diffraction characterization of a zinc anode after cycling, showing that all characteristic peaks match well with the standard phase of metallic zinc (PDF#04-0381), the peak intensity ratio of (002) crystal face to (101) crystal face is compared with the original zinc foil I (002)/(101) (0.67) is significantly raised to 1.28, indicating that the principal crystal plane of the zinc ion deposition is the Zn (002) crystal plane parallel to the basal plane.
Comparative example 6
This comparative example was run in parallel similar to example 3, except that the additive was changed to methyl propionylacetate (M3 OVA) and the remaining procedure was the same as in example 3. FIG. 11 is a graph showing X-ray diffraction of a zinc anode after cycling, showing that all characteristic peaks are well matched with the standard phase of metallic zinc (PDF#04-0381), and the peak intensity ratio of (002) crystal face to (101) crystal face is compared with that of the original zinc foil I (002)/(101) (0.67) is significantly raised to 2.89, indicating that the predominant crystal plane of zinc ion deposition is the Zn (002) plane parallel to the basal plane.
Example 4
Taking zinc foil as positive and negative electrodes and glass fiber as a diaphragm, taking 100 mu L of composite electrolyte in example 1 to assemble a CR2025 Zn|Zn button cell, and performing a circulating constant current charge and discharge test on a New Wei cell test system, wherein the working current density is 5mA cm -2 The surface capacity is 5mAh cm -2 。
Comparative example 7
This comparative example was conducted in parallel with example 4 in a similar manner, and the electrolyte was prepared as a composite electrolyte by reducing the amount of the basic zinc sulfate electrolyte additive in example 1 to 40 or increasing it to 160. Mu.L, and the remaining operation steps were the same as in example 4. As a result, as shown in fig. 12, it was found that the commercial zinc sheet exhibited superior cycle stability and life in the battery of example 4 of the present invention, indicating that too little or too much addition reduced the cycle stability of the battery.
Comparative example 8
This comparative example was conducted in a parallel test similar to example 4, and the electrolyte was prepared by changing the basic zinc sulfate electrolyte additive of example 1 to 2-hexanone (2-HA) having the same carbon chain length and only ketone groups, and the other steps were the same as in example 4. Pair of causesSymmetrical cells assembled with the electrolyte of this comparative example were at 2mA cm -2 The negative electrode after 50 cycles of current density was subjected to SEM and X-ray diffraction characterization, and the effect of 2-HA on induction of zinc ion deposition in the (002) crystal face was investigated. The deposition morphology is shown in fig. 13b, and compared with the zinc cathode 13a using the basic zinc sulfate electrolyte circulation, the deposition morphology has no obvious effect of inducing uniform deposition of zinc ions; FIG. 14 is a graph showing X-ray diffraction of a zinc anode after cycling, showing that all characteristic peaks match well with the standard phase of metallic zinc (PDF#04-0381), the peak intensity ratio of (002) crystal face to (101) crystal face is 0.7 compared with the original zinc foil I (002)/(101) (0.67) did not significantly increase, indicating that 2-HA did not induce zinc ion deposition in the (002) crystal plane. As shown in FIG. 15, the commercial zinc sheet exhibited superior cycle stability and life in the inventive example 4 cell at 5mA cm -2 The current density of the battery is stable and can be circulated for more than or equal to 980h, and compared with the battery of comparative example 8, the battery is improved by more than 6 times. It is shown that the modification effect of the ketone group and the ester group is stronger than that of the ketone group alone.
Comparative example 9
This comparative example was conducted in a parallel test similar to example 4, and the electrolyte was prepared as a composite electrolyte by changing the additive of the base electrolyte in example 1 to Methyl Valerate (MVA) having the same carbon chain length and containing only ester groups, and the remaining operation steps were the same as in example 4. For a symmetrical cell assembled using the electrolyte of this comparative example, the electrolyte was used at 2 mA.cm -2 The negative electrode after 50 cycles of current density was subjected to SEM and X-ray diffraction characterization, and the effect of MVA on induction of zinc ion deposition in the (002) crystal face was investigated. The deposition morphology is as shown in fig. 16, and compared with the zinc cathode 13a using the basic zinc sulfate electrolyte circulation, the deposition morphology has no obvious effect of inducing uniform deposition of zinc ions; FIG. 17 is a graph showing X-ray diffraction of a zinc anode after cycling, showing that all characteristic peaks are well matched with the standard phase of metallic zinc (PDF#04-0381), and the peak intensity ratio of (002) crystal face to (101) crystal face is 0.63 compared with the original zinc foil I (002)/(101) (0.67) did not significantly increase, indicating that MVA did not induce zinc ion deposition in the (002) crystal plane. As shown in FIG. 18, the commercial zinc sheet exhibited superior cycle stability and life in the inventive example 4 cell at 5mA cm -2 Is stable at current density of (2)The constant cycle is more than or equal to 980h, which is improved by nearly 9 times compared with the battery of the comparative example 9. It is shown that the modification effect of the ketone group and the ester group is stronger than that of the single ester group.
Example 5
Electrolyte the basic zinc sulfate electrolyte additive of example 1 was changed to a chain-like Propyl Levulinate (PL) molecule containing 8 carbon atoms and both ketone and ester groups to prepare a composite electrolyte, and the rest of the operation steps were the same as in example 4.
Comparative example 10
This comparative example was conducted in a parallel test similar to example 5, and the electrolyte was prepared by changing the basic zinc sulfate electrolyte additive of example 1 to methyl 4-cyclohexanone carboxylate (M4 OHA) having the same carbon chain length and containing both ketone groups and ester groups, and the remaining operation steps were the same as in example 5. As a result, as shown in fig. 19, the commercial zinc sheet exhibited superior cycle stability and life in the battery of example 5 of the present invention, indicating that the chain-like organic molecular additive containing both ketone groups and ester groups was more effective than the cyclic modification.
Example 6
Commercial zinc sheet is used as negative electrode, and the loading capacity is 1.3-2.5 mg cm -2 The electrolyte is prepared by adding 100 mu L ML into the basic zinc trifluoromethane sulfonate electrolyte in the example 1, and the glass fiber is a diaphragm, and the full cell is assembled at 3A g -1 Constant current charge and discharge test was performed at the current density of (c).
Comparative example 11
This comparative example was run in parallel similar to example 6. The electrolyte was changed to the basic zinc trifluoromethane sulfonate electrolyte of example 1 from the composite electrolyte of example 6, and the remaining operation steps were the same as those of example 6. As a result, as shown in fig. 20, the assembled full cell of example 6 had a better capacity retention rate.
Comparative example 12
This comparative example was conducted in parallel with example 4, and the electrolyte was changed to the basic electrolyte additive of example 1 to an additive having the same carbon chain length and containing both amide groups and ester groupsThe additive (composition of 5- (dimethylamino) -2-methyl-5-oxopentanoic acid methyl ester and N, N, N ', N' -2-pentamethylglutaramide) (polar clear) with a mass ratio of 20:1 was prepared into a composite electrolyte, and the rest of the operation steps were the same as in example 4. For a symmetrical cell assembled using the electrolyte of this comparative example, the electrolyte was used at 2 mA.cm -2 The effect of polar clean on induction of zinc ion deposition in the (002) crystal face was investigated by negative X-ray diffraction characterization after 25 cycles of current density. Fig. 21 is an X-ray diffraction characterization of the zinc negative electrode after cycling, and it can be seen that all characteristic peaks are well matched with the standard phase of metallic zinc (pdf#04-0381), the peak intensity ratio of (002) crystal face to (101) crystal face is 0.78, which is much smaller than I (002)/(101) (2.18) of ML, indicating that polar clear is much less likely to induce zinc ions to deposit in (002) crystal face than ML. The electrokinetic polarization curve was determined for commercial zinc foil in the ML composite electrolyte of example 1 and the polar clean composite electrolyte of this comparative example (fig. 22), and the ML composite electrolyte obtained in example 1 significantly reduced the corrosion current and reduced the damage to the zinc anode by the aqueous electrolyte compared to this comparative example. At 5 mA.cm -2 The initial nucleation overpotential of Zn// Zn in the ML composite electrolyte is smaller than in the polar clear (FIG. 23). As can be seen from fig. 24, the storage capacity retention rate of the ML-containing Zn// MNVO full cell after 48 hours of storage after charging was significantly improved over that of the base zinc sulfate electrolyte and the polar clean composite electrolyte. It is shown that the modification effect is stronger when both ketone group and ester group are contained than when both amide group and ester group are contained.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The aqueous zinc ion battery composite electrolyte containing acyl ester alkane chain organic additive with ketone group and ester group is characterized in that the acyl ester alkane chain organic additive with ketone group and ester group is any one of methyl acetoacetate, methyl levulinate, methyl acetoacetate, methyl propionylacetate, methyl acetoacetate, methyl butyrylacetate and methyl valerylacetate, and the concentration is 0.1-3 vol%; the solvent of the water-based zinc ion battery composite electrolyte is deionized water;
the solute of the aqueous zinc ion battery composite electrolyte is at least one of zinc sulfate, zinc chloride, zinc acetate, zinc trifluoromethane sulfonate and hydrate thereof.
2. A method for preparing the aqueous zinc ion battery composite electrolyte containing the acyl ester alkane chain organic additive with ketone groups and ester groups according to claim 1, which is characterized by comprising the following steps:
s1: adding soluble zinc salt into deionized water to be fully dissolved, so as to obtain basic aqueous zinc salt electrolyte;
s2: adding acyl ester alkane chain organic additive with ketone group and ester group into the basic aqueous zinc salt electrolyte, continuously stirring under a magnetic stirrer until the acyl ester alkane chain organic additive is completely dissolved, and standing to obtain the aqueous zinc ion battery composite electrolyte containing the acyl ester alkane chain organic additive with ketone group and ester group.
3. The method for producing a composite electrolyte for an aqueous zinc ion battery comprising an acyl ester alkane chain organic additive having both ketone groups and ester groups according to claim 2, wherein the soluble zinc salt is at least one of zinc sulfate, zinc chloride, zinc acetate, zinc trifluoromethane sulfonate and a hydrate thereof, and the concentration is 1 to 4mol/L.
4. An aqueous zinc ion battery comprising an electrolyte, wherein the electrolyte is the aqueous zinc ion battery composite electrolyte comprising the acyl ester alkane chain organic additive with ketone groups and ester groups according to claim 1 or the aqueous zinc ion battery composite electrolyte comprising the acyl ester alkane chain organic additive with ketone groups and ester groups according to claim 2 or 3.
5. The aqueous zinc-ion battery of claim 4, wherein the aqueous zinc-ion battery is a symmetrical battery, a half-battery, or a full-battery.
6. The aqueous zinc-ion battery of claim 5, wherein the symmetrical battery is comprised of a commercial 100 micron thick zinc foil, a fiberglass separator, and an electrolyte; the half cell consists of a commercial zinc foil with the thickness of 100 microns, a commercial current collector and an electrolyte; the full battery is composed of a commercial zinc foil with the thickness of 100 microns as a negative electrode, a manganese material or a vanadium material as a positive electrode and an electrolyte.
7. The aqueous zinc-ion battery according to claim 6, wherein the current collector is selected from any one of copper foil, copper mesh, foam copper, stainless steel mesh, titanium foil, and foam nickel.
8. The aqueous zinc-ion battery according to claim 6, wherein the manganese-based material is MnO 2 The vanadium material is V 2 O 5 Or MNVO.
9. The aqueous zinc-ion battery according to claim 4, wherein the working current density of the aqueous zinc-ion battery is 0.5 to 10mA cm -2 。
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