CN115911596B - Zinc metal battery electrolyte and preparation method and application thereof - Google Patents
Zinc metal battery electrolyte and preparation method and application thereof Download PDFInfo
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- CN115911596B CN115911596B CN202310108692.0A CN202310108692A CN115911596B CN 115911596 B CN115911596 B CN 115911596B CN 202310108692 A CN202310108692 A CN 202310108692A CN 115911596 B CN115911596 B CN 115911596B
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003792 electrolyte Substances 0.000 title claims abstract description 65
- 239000011701 zinc Substances 0.000 title claims abstract description 60
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000002904 solvent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 26
- 229960001763 zinc sulfate Drugs 0.000 claims description 26
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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 2
- NGTSQWJVGHUNSS-UHFFFAOYSA-N bis(sulfanylidene)vanadium Chemical compound S=[V]=S NGTSQWJVGHUNSS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [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 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 18
- 230000000052 comparative effect Effects 0.000 description 23
- 210000004027 cell Anatomy 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- 239000003365 glass fiber Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- -1 hydroxide ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses zinc metal battery electrolyte and a preparation method and application thereof. Relates to the technical field of zinc metal batteries. An electrolyte comprising the following components: a zinc source; a solvent, and the solvent does not include ethylene glycol; ethylene glycol; the volume ratio of the solvent to the glycol is 52-99.75:0.25-48. Compared with the electrolyte without adding glycol, the electrolyte provided by the invention can effectively improve the cycle stability of the zinc metal battery under the conditions of high concentration and low concentration of glycol content.
Description
Technical Field
The invention relates to the technical field of zinc metal batteries, in particular to zinc metal battery electrolyte and a preparation method and application thereof.
Background
With the increasing demand for energy and awareness of climate change, there is an urgent need to drive and accelerate the transition from fossil fuels to clean renewable energy sources. Among the numerous electrochemical energy storage devices. Batteries are widely concerned as basic units for stable power of electronic equipment and as energy storage devices for energy storage of power grids.
Among the numerous battery systems, lithium ion batteries have been widely used in various fields due to high energy density and long cycle life. However, the scarcity of lithium resources and the use of combustible organic electrolyte severely hamper the further development of lithium ion batteries in the field of mass storage. In order to reduce the cost of energy storage batteries, other energy storage batteries have been explored and developed.
Among them, aqueous zinc metal batteries have been receiving attention because of their high volume specific capacity, high zinc resource storage, and flame retardancy of the electrolyte. However, dendrites, corrosion, hydrogen production and other problems existing in the circulation process of the zinc sheet cathode greatly obstruct the actual production and application of the zinc sheet cathode.
Therefore, further research is required to improve the overall performance of zinc batteries.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows:
an electrolyte is provided.
The second technical problem to be solved by the invention is as follows:
a method for preparing the electrolyte is provided.
The third technical problem to be solved by the invention is:
the application of the electrolyte.
In order to solve the first technical problem, the invention adopts the following technical scheme:
an electrolyte comprising the following components:
a zinc source;
a solvent;
ethylene glycol;
the volume ratio of the solvent to the glycol is 52-99.75:0.25-48.
According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
compared with the electrolyte without adding glycol, the electrolyte provided by the invention can effectively improve the cycle stability of the zinc metal battery under the conditions of high concentration and low concentration of glycol content. When the volume of the ethylene glycol is smaller, the effect of inhibiting dendrites can be achieved through specific tip adsorption, and the aggregation of electrons at the tip is avoided, so that the problems of hydrogen production caused by the aggregation of electrons and the problem of passivation of the surface of a zinc sheet negative electrode caused by the precipitation of hydroxide ions and zinc ions left after hydrogen production are avoided. When the volume of the glycol is large, a series of side reactions participated by the solvent can be inhibited under high concentration, so that the effect of prolonging the service life of the battery is achieved.
According to one embodiment of the invention, the zinc source comprises at least one of zinc sulfate, zinc acetate, zinc triflate, zinc chloride and zinc perchlorate.
According to one embodiment of the invention, the zinc source is present in the electrolyte in a molar concentration of 1-2mol/L.
According to one embodiment of the invention, the zinc source is present in the electrolyte in a molar concentration of 1 to 1.5mol/L.
According to one embodiment of the invention, the zinc source is present in the electrolyte in a molar concentration of 0.5-1.5mol/L.
According to one embodiment of the invention, the volume ratio of the solvent to the glycol is 52-60:0.25-1.
According to one embodiment of the invention, the volume ratio of the solvent to the glycol is 52-60:1-48.
The electrolyte provided by the invention comprises a zinc source, a solvent and ethylene glycol, and after the dosage of the zinc source is determined, the concentration of the zinc source and the concentration of the ethylene glycol in the electrolyte can be adjusted by adjusting the volume ratio of the solvent to the ethylene glycol. The electrolyte can effectively inhibit the growth of negative dendrites at low concentration and can effectively inhibit active water from participating in a series of side reactions at high concentration, thereby obviously improving the cycle performance of the zinc metal battery and prolonging the service life.
In order to solve the second technical problem, the invention adopts the following technical scheme:
a method of preparing the electrolyte comprising the steps of:
mixing a zinc source and ethylene glycol in a solvent to obtain the electrolyte.
The method for preparing the electrolyte is simple in process, easy to operate and suitable for industrial mass production and application.
According to an embodiment of the present invention, there is also provided a zinc metal battery including a positive electrode, a negative electrode, an electrode liquid, and a separator, wherein the electrode liquid includes the one electrolyte.
According to one embodiment of the invention, the electrolyte is used in an amount of 150 to 220. Mu.L.
According to one embodiment of the invention, the electrolyte is used in an amount of 180 to 200. Mu.L.
According to one embodiment of the invention, the positive electrode comprises a vanadium disulfide pole piece.
According to one embodiment of the invention, the negative electrode comprises zinc foil.
According to one embodiment of the invention, the membrane comprises a glass fiber membrane.
According to one embodiment of the invention, zinc foil is used as a working electrode and zinc foil is used as a counter/reference electrode in the battery.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a graph showing the cycle performance of the half-cells prepared in examples 1-2 and comparative example 1;
FIG. 2 is a graph showing the cycle performance of the full cells prepared in examples 1-2 and comparative example 1;
fig. 3 is a statistical graph of electric double layer capacitance of electrodes of half cells prepared in example 1 and comparative example 1;
FIG. 4 is an X-ray diffraction chart of the zinc electrode surface product after 50 cycles of example 2 and comparative example 1.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. 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 fall within the scope of the invention.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
An electrolyte comprising the following components:
zinc sulfate;
water;
ethylene glycol;
the volume ratio of the water to the glycol was 99.75:0.25;
zinc sulfate concentration of 2mol/L ZnSO 4 。
The preparation method of the electrolyte comprises the following steps:
the volume ratio is 99.75:0.25, mixing deionized water and ethylene glycol, then adding zinc sulfate until the concentration of zinc sulfate in the electrolyte reaches 2mol/L, and stirring the solution by using a magnetic stirrer until the solution becomes transparent, thereby obtaining the electrolyte.
A zinc foil with a diameter of 12mm is used as a working electrode, a zinc foil with a diameter of 12mm is used as a counter/reference electrode, a glass fiber diaphragm and a standard CR2032 type battery case are assembled into batteries, and 180 mu L of the electrolyte is used for each battery, so that a zinc battery is obtained.
In the electrolyte of example 1, when the volume of ethylene glycol is small, the effect of inhibiting dendrite can be achieved through specific tip adsorption, and the aggregation of electrons at the tip is avoided, so that the problem of hydrogen production caused by the aggregation of electrons and the problem of passivation of the surface of a zinc sheet negative electrode caused by the precipitation of hydroxide ions and zinc ions remained in a large amount after hydrogen production are avoided.
Example 2
Example 2 differs from example 1 in that: the volume ratio of water to glycol is different. Wherein the volume ratio of the water to the ethylene glycol of example 2 is 60:40. wherein the volume ratio of the water to the ethylene glycol of example 1 was 99.75:0.25.
an electrolyte comprising the following components:
zinc sulfate;
water;
ethylene glycol;
the volume ratio of the water to the glycol is 60:40, a step of performing a;
zinc sulfate concentration of 2mol/L ZnSO 4 。
The preparation method of the electrolyte comprises the following steps:
the volume ratio is 60:40.
the preparation method of the electrolyte comprises the following steps:
the volume ratio is 60:40, mixing deionized water and ethylene glycol, then adding zinc sulfate until the concentration of zinc sulfate in the electrolyte reaches 2mol/L, and stirring the solution by using a magnetic stirrer until the solution becomes transparent, thereby obtaining the electrolyte.
A zinc foil with a diameter of 12mm is used as a working electrode, a zinc foil with a diameter of 12mm is used as a counter/reference electrode, a glass fiber diaphragm and a standard CR2032 type battery case are assembled into batteries, and 180 mu L of the electrolyte is used for each battery, so that a zinc battery is obtained.
In example 2, the ethylene glycol has a large volume, and the high concentration of ethylene glycol suppresses a series of side reactions involved in the solvent, avoiding the generation of by-products such as Zn 4 (OH) 6 SO 4 ·5H 2 O, thereby achieving the effect of improving the service life of the battery.
Example 3
Example 3 differs from example 1 in that: the battery structure is different. Wherein the battery of example 3 comprises a copper foil with a diameter of 12mm and a certain amount of zinc deposited as negative electrode (positive-negative electrode capacity ratio of 1:5), 12mm VS was used 2 The pole piece is an anode. The battery of example 1 included a 12mm diameter zinc foil as the working electrode, a 12mm zinc foil as the counter/reference electrode, and a glass fiber separator and a standard CR2032 type battery can were assembled. Wherein the loading of deposited zinc on the copper foil is about 2.85mg/cm 2 。
An electrolyte comprising the following components:
zinc sulfate;
water;
ethylene glycol;
the volume ratio of the water to the glycol was 99.75:0.25;
zinc sulfate concentration of 2mol/L ZnSO 4 。
The preparation method of the electrolyte comprises the following steps:
the volume ratio is 99.75:0.25, mixing deionized water and ethylene glycol, then adding zinc sulfate until the concentration of zinc sulfate in the electrolyte reaches 2mol/L, and stirring the solution by using a magnetic stirrer until the solution becomes transparent, thereby obtaining the electrolyte.
Diameter of12mm copper foil deposited with a certain amount of zinc is used as a negative electrode (positive-negative electrode capacity ratio is 1:5), and 12mm VS is adopted 2 The pole piece is the positive pole, and a glass fiber diaphragm and a standard CR2032 type battery shell are assembled into batteries, and each battery uses 180 mu L of the electrolyte to obtain a zinc battery.
Example 4
Example 4 differs from example 2 in that: the battery structure is different. Wherein the battery of example 4 comprises a copper foil with a diameter of 12mm and a certain amount of zinc deposited as negative electrode (positive-negative electrode capacity ratio of 1:5), 12mm VS was used 2 The pole piece is an anode. Wherein the battery of example 4 comprises a copper foil with a diameter of 12mm and a certain amount of zinc deposited as negative electrode (positive-negative electrode capacity ratio of 1:5), 12mm VS was used 2 The pole piece is an anode. The battery of example 1 included a 12mm diameter zinc foil as the working electrode, a 12mm zinc foil as the counter/reference electrode, and a glass fiber separator and a standard CR2032 type battery can were assembled. Wherein the loading of deposited zinc on the copper foil is about 2.85mg/cm 2 。
An electrolyte comprising the following components:
zinc sulfate;
water;
ethylene glycol;
the volume ratio of the water to the glycol is 60:40, a step of performing a;
zinc sulfate concentration of 2mol/L ZnSO 4 。
The preparation method of the electrolyte comprises the following steps:
the volume ratio is 60:40.
the preparation method of the electrolyte comprises the following steps:
the volume ratio is 60:40, mixing deionized water and ethylene glycol, then adding zinc sulfate until the concentration of zinc sulfate in the electrolyte reaches 2mol/L, and stirring the solution by using a magnetic stirrer until the solution becomes transparent, thereby obtaining the electrolyte.
The copper foil with a diameter of 12mm and a certain amount of zinc deposited is taken as a negative electrode (the capacity ratio of the positive electrode to the negative electrode is 1:5), and 12mm VS is adopted 2 The pole piece is the positive pole, and adopts a glass fiber diaphragm and a markThe quasi-CR 2032 type battery cases were assembled into batteries, each using 180 μl of the above electrolyte, to obtain zinc batteries. Wherein the loading of deposited zinc on the copper foil is about 2.85mg/cm 2 。
Comparative example 1
Comparative example 1 differs from example 1 in that: the volume ratio of water to glycol is different. Wherein, the volume ratio of the water to the glycol of the comparative example 1 is 100:0. wherein the volume ratio of the water to the ethylene glycol of example 1 was 99.75:0.25.
an electrolyte comprising the following components:
zinc sulfate;
water;
ethylene glycol;
the volume ratio of the water to the glycol was 99.75:0.25;
zinc sulfate concentration of 2mol/L ZnSO 4 。
The preparation method of the electrolyte comprises the following steps:
the volume ratio is 99.75:0.25, mixing deionized water and ethylene glycol, then adding zinc sulfate until the concentration of zinc sulfate in the electrolyte reaches 2mol/L, and stirring the solution by using a magnetic stirrer until the solution becomes transparent, thereby obtaining the electrolyte.
A zinc foil with a diameter of 12mm is used as a working electrode, a zinc foil with a diameter of 12mm is used as a counter/reference electrode, a glass fiber diaphragm and a standard CR2032 type battery case are assembled into batteries, and 180 mu L of the electrolyte is used for each battery, so that a zinc battery is obtained.
Comparative example 2
Comparative example 2 differs from comparative example 1 in that: the battery structure is different. Wherein the battery of comparative example 2 comprises a copper foil with a diameter of 12mm and a certain amount of zinc deposited thereon as the negative electrode (positive-negative electrode capacity ratio of 1:5), 12mm VS was used 2 The pole piece is an anode. The cell of comparative example 1 included a zinc foil of 12mm diameter as the working electrode and a zinc foil of 12mm as the counter/reference electrode. Wherein the loading of deposited zinc on the copper foil is about 2.85mg/cm 2 。
An electrolyte comprising the following components:
zinc sulfate;
water;
ethylene glycol;
the volume ratio of the water to the glycol was 99.75:0.25;
zinc sulfate concentration of 2mol/L ZnSO 4 。
The preparation method of the electrolyte comprises the following steps:
the volume ratio is 99.75:0.25, mixing deionized water and ethylene glycol, then adding zinc sulfate until the concentration of zinc sulfate in the electrolyte reaches 2mol/L, and stirring the solution by using a magnetic stirrer until the solution becomes transparent, thereby obtaining the electrolyte.
The copper foil with a diameter of 12mm and a certain amount of zinc deposited is taken as a negative electrode (the capacity ratio of the positive electrode to the negative electrode is 1:5), and 12mm VS is adopted 2 The pole piece is the positive pole, and a glass fiber diaphragm and a standard CR2032 type battery shell are assembled into batteries, and each battery uses 180 mu L of the electrolyte to obtain a zinc battery.
Test example 1
Half-cell samples were prepared for testing the cycling stability of half-cells (test system using a new-wire battery charge-discharge tester) using inventive examples 1-2 and comparative example 1. FIG. 1 is a graph showing the cycle performance test of half cell samples of examples 1-2 and comparative example 1 under a current density of 2mA/cm 2 Constant current deposition-electrolytic capacity 2mAh/cm 2 And (5) performing a cycle performance test.
As shown in fig. 1, half cells made from examples 1-2 were stable in operation cycles 2400h and 1730h, respectively. Whereas the half cell made from comparative example 1 had a short circuit after 90 hours, and the cell failed. This demonstrates that ethylene glycol can effectively improve battery life at both high and low concentrations, exhibiting excellent results.
Test example 2
Full cell samples were prepared for testing the cycle life of full cells (test system using a new battery charge and discharge tester) using inventive examples 3-4 and comparative example 2. FIG. 2 is a graph showing the cycle performance test of the full cell samples of examples 3 to 4 and comparative example 2 under the current density of 1A/g.
As shown in fig. 2, the full cells made in examples 3 and 4 were able to maintain capacity retention of 82.7% and 98.4%, respectively, after 650 cycles of steady operation. While the full cell made from comparative example 2 showed a significant drop in capacity after 165 cycles, indicating a short circuit in the cell, this also showed an effective improvement in the performance of the zinc metal cells of examples 3-4.
Test example 3
The half cell samples of inventive example 1 and comparative example 1 were prepared and the electric double layer capacitance of the electrode surface was tested (test system is a cinnabar electrochemical workstation). FIG. 3 is a graph showing the statistics of the electric double layer capacitance of the electrode surfaces of half cell samples of example 1 and comparative example 1, using cyclic voltammetry, ranging from-0.015 to 0.015V, and scanning rates ranging from 12 to 20mV.
As shown in fig. 3, the electric double layer capacitor on the electrode surface of example 1 was significantly reduced compared with comparative example 1, indicating that the adsorption behavior of ethylene glycol on the electrode surface occurred, thereby guiding the uniform deposition of zinc ions.
Test example 4
The half cell samples of inventive example 2 and comparative example 1 were prepared at a current density of 5mA/cm 2 Constant current deposition-electrolytic capacity 2mAh/cm 2 After 50 cycles of cycling under the condition, the zinc foil surface product was qualitatively analyzed by X-ray diffraction.
As shown in FIG. 4, example 2 surface by-product Zn was measured by XRD 4 (OH) 6 SO 4 ·5H 2 The signal of O (corresponding to 8 degree peak) is significantly lower than that of comparative example 1, which indicates that example 2 has a significant inhibitory effect on the generation of by-products, and thus can improve the battery performance.
The foregoing is merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention or direct or indirect application in the relevant art are intended to be included in the scope of the present invention.
Claims (7)
1. A zinc metal battery electrolyte, characterized in that: the composition comprises the following components:
a zinc source;
a solvent, and the solvent does not include ethylene glycol;
ethylene glycol;
the solvent is water, and the volume ratio of water to the ethylene glycol is 99.75:0.25;
the zinc source comprises at least one of zinc sulfate, zinc acetate, zinc triflate, zinc chloride and zinc perchlorate.
2. A zinc metal battery electrolyte according to claim 1, characterized in that: the molar concentration of the zinc source in the electrolyte is 1-2mol/L.
3. A method of preparing a zinc metal battery electrolyte as claimed in any one of claims 1 to 2, characterized in that: the method comprises the following steps:
mixing a zinc source and ethylene glycol in a solvent to obtain the electrolyte.
4. A zinc metal battery characterized in that: a zinc metal battery electrolyte comprising a positive electrode, a negative electrode, a separator and any one of claims 1 to 2.
5. The zinc metal battery according to claim 4, wherein: the positive electrode comprises a vanadium disulfide pole piece.
6. The zinc metal battery according to claim 4, wherein: the negative electrode comprises zinc foil.
7. The zinc metal battery according to claim 4, wherein: the separator includes a fiberglass separator.
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| JP2021180116A (en) * | 2020-05-14 | 2021-11-18 | 昭和電工マテリアルズ株式会社 | Electrolytic solution for zinc battery and zinc battery |
| CN113097576A (en) * | 2021-03-30 | 2021-07-09 | 广东工业大学 | Water-based zinc ion battery electrolysis for protecting vanadium-containing compound positive electrode and application thereof |
| CN115312879A (en) * | 2021-05-06 | 2022-11-08 | 陈璞 | Aqueous electrolyte and battery |
| CN114447446A (en) * | 2022-01-07 | 2022-05-06 | 齐鲁工业大学 | Aqueous zinc ion battery additive, electrolyte prepared from same and application of electrolyte |
| CN114447445A (en) * | 2022-01-07 | 2022-05-06 | 齐鲁工业大学 | Preparation and application of aqueous zinc ion battery electrolyte |
| CN114243127A (en) * | 2022-02-21 | 2022-03-25 | 浙江金羽新能源科技有限公司 | Aqueous electrolyte with low dissolved oxygen, preparation method thereof and aqueous ion battery |
| CN114628801A (en) * | 2022-03-21 | 2022-06-14 | 中国科学院化学研究所 | Aqueous electrolyte based on deuterated water, preparation method thereof and application of aqueous electrolyte in metal ion secondary battery |
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