CN114447445A - Preparation and application of aqueous zinc ion battery electrolyte - Google Patents
Preparation and application of aqueous zinc ion battery electrolyte Download PDFInfo
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- CN114447445A CN114447445A CN202210013507.5A CN202210013507A CN114447445A CN 114447445 A CN114447445 A CN 114447445A CN 202210013507 A CN202210013507 A CN 202210013507A CN 114447445 A CN114447445 A CN 114447445A
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- zinc
- electrolyte
- ion battery
- water
- methanol
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 68
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 102
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims abstract description 37
- 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 abstract description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 4
- 239000011592 zinc chloride Substances 0.000 claims abstract description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 206010067484 Adverse reaction Diseases 0.000 abstract 1
- 230000006838 adverse reaction Effects 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Images
Classifications
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- 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
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- 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 a water-based zinc ion battery electrolyte and application thereof. Wherein, the solvent is one or more of water and methanol, ethanol and glycol, the solute is one or more of zinc trifluoromethanesulfonate, zinc sulfate and zinc chloride, and the volume ratio of one or more of the solvent methanol, ethanol and glycol to the water is 1: 1 to 10. One or more of methanol, ethanol, ethylene glycol may be mixed with water in any proportion, and may form hydrogen bonds with water. The interaction between one or more of zinc ions, methanol, ethanol and glycol and water can effectively inhibit the adverse reaction in the water system zinc ion battery, thereby improving the electrochemical performance of the water system zinc ion battery.
Description
Technical Field
The invention belongs to the field of water-system zinc ion batteries, and particularly relates to a water-system zinc ion battery electrolyte and a preparation method and application thereof.
Background
Due to safety issues and resource shortages of lithium ion batteries, developing a new generation of energy storage devices as a substitute has attracted increasing research interest. As one of the most promising alternatives, aqueous rechargeable zinc ion batteries have entered the field of view of researchers, and have advantages of safety, environmental protection, high theoretical capacity, and the like. While zinc ion batteries are considered an important alternative to lithium ion batteries, dendrite problems and side reactions remain major obstacles limiting their development. To overcome these obstacles, many strategies have been explored to modify zinc anodes or to perform electrolyte design, such as surface coating modification, anode structure optimization, and electrolyte modification. Compared with coating modification and structure optimization, electrolyte modification is an economic way for improving the performance of the water system zinc ion battery. Compared with the prior art, the water system electrolyte has the advantages of low impedance, high power, environmental protection, safety and the like.
The invention takes one or more of methanol, ethanol and glycol and water as electrolyte solvent, and one or more of zinc trifluoromethanesulfonate, zinc sulfate and zinc chloride as electrolyte. Methanol, ethanol and glycol are proved to be effective solvents of zinc ion electrolyte in the water-based zinc ion battery, and the solvents can improve the cycle stability and inhibit side reaction on a negative electrode, thereby improving the electrochemical performance of the water-based zinc ion battery.
Disclosure of Invention
The invention aims to overcome the technical problems in the application of the water system zinc ion battery. Therefore, one of the purposes of the invention is to provide an aqueous zinc ion battery electrolyte and a preparation method thereof, which are used for improving the rate capability and the cycle performance of an aqueous zinc ion battery.
The invention also aims to provide an aqueous 2032 type coin zinc ion battery based on the electrolyte.
In order to achieve the purpose, the invention provides the following technical scheme:
an aqueous electrolyte, characterized in that;
preferably, the electrolyte consists of one or more of methanol, ethanol and glycol, electrolyte and water.
Further preferably, the concentration of the electrolyte is 1-3 mol/L.
Further preferably, the solvent of the electrolyte is one or more of methanol, ethanol and ethylene glycol and water.
Further preferably, the volume ratio of one or more of methanol, ethanol and ethylene glycol as electrolyte solvents to water is 1: 1 to 10.
Further preferably, the electrolyte is one or more of zinc trifluoromethanesulfonate, zinc sulfate and zinc chloride.
The invention also provides a water system 2032 type button zinc ion battery containing the water system zinc ion battery electrolyte.
More preferably, the water system 2032 type coin zinc ion battery comprises a battery case, a pole core and electrolyte, wherein the pole core and the electrolyte are sealed in the battery case, the pole core comprises a positive pole piece, a zinc negative pole piece and a diaphragm positioned between the positive pole piece and the negative pole piece, and the electrolyte is the water system zinc ion battery electrolyte.
The advantages of the invention are mainly embodied in the following aspects:
methanol, ethanol and glycol have the inherent advantages of low price, wide application range, hydrophilicity and the like.
The electrolyte provided by the invention has the advantages of low cost of raw materials, simple preparation method and great application prospect and research value in the safety field of zinc ion batteries.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 is an SEM image of a cross section of a zinc negative electrode after the zinc ion battery of example 1 of the present invention was cycled, and an electrolyte thereof was a 1mol/L zinc trifluoromethanesulfonate mixed solution to which methanol was added.
Fig. 2 is an SEM image of a cross section of a zinc negative electrode after cycling of the zinc ion battery of example 1 of the present invention, in which the electrolyte is a 1mol/L zinc trifluoromethanesulfonate aqueous solution.
FIG. 3 is a graph showing the electrochemical performance test of the zinc ion battery of example 1 of the present invention, wherein ZHM is a battery assembled by adding 1mol/L zinc trifluoromethanesulfonate mixed solution of methanol, ZH is a battery assembled by 1mol/L zinc trifluoromethanesulfonate aqueous solution, and FIGS. 4 and 5 are the same.
Fig. 4 is a graph showing the electrochemical performance test of the zinc-ion battery of example 2 of the present invention.
FIG. 5 is a graph showing the electrochemical performance of the zinc-ion battery according to example 3 of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
The embodiment provides a preparation method of an aqueous zinc-ion battery electrolyte, the aqueous zinc-ion battery electrolyte prepared by the method and a corresponding battery, wherein the method comprises the following steps: adding methanol into a zinc trifluoromethanesulfonate solution, wherein the volume ratio of the methanol to water is 1:3, and then obtaining 1mol/L zinc trifluoromethanesulfonate mixed solution electrolyte; 1mol/L zinc trifluoromethanesulfonate aqueous solution is taken as electrolyte; and (3) assembling the 2032 type button battery by using the stainless steel foil coated with manganese dioxide as an anode, a zinc sheet as a cathode, glass fiber as a diaphragm and electrolyte as a 1mol/L zinc trifluoromethanesulfonate mixed solution added with methanol. Assembling a 2032 type button cell under the same conditions by taking 1mol/L zinc trifluoromethanesulfonate aqueous solution as a comparison group as electrolyte; and (3) carrying out electrochemical performance test on the manufactured battery by using an electrochemical workstation, wherein the cycle conditions are as follows: the current density was 0.1A g-1The number of cycles was 100 cycles.
Example 2
The embodiment provides a preparation method of an aqueous zinc-ion battery electrolyte, the aqueous zinc-ion battery electrolyte prepared by the method and a corresponding battery, wherein the method comprises the following steps: adding methanol into a zinc trifluoromethanesulfonate solution, wherein the volume ratio of the methanol to water is 1:3, and then obtaining 1mol/L zinc trifluoromethanesulfonate mixed solution electrolyte; 1mol/L zinc trifluoromethanesulfonate aqueous solution is taken as electrolyte; and (3) assembling the 2032 type button battery by taking the stainless steel foil coated with manganese dioxide as a positive electrode, a zinc sheet as a negative electrode, glass fiber as a diaphragm and electrolyte as a 1mol/L zinc trifluoromethanesulfonate mixed solution added with methanol. Assembling a 2032 type button cell under the same conditions by taking 1mol/L zinc trifluoromethanesulfonate aqueous solution as a comparison group as electrolyte; and (3) carrying out electrochemical performance test on the manufactured battery by using an electrochemical workstation, wherein the cycle conditions are as follows: the current density was 0.1A g-1，0.2 A g-1，0.4 A g-1，0.8 A g-1，0.1 A g-1And the cycle number is as follows: each current density cycle was 10 cycles.
Example 3
The embodiment provides a preparation method of an aqueous zinc-ion battery electrolyte, the aqueous zinc-ion battery electrolyte prepared by the method and a corresponding battery, wherein the method comprises the following steps: then obtaining 1mol/L zinc trifluoromethanesulfonate mixed solution electrolyte; 1mol/L zinc trifluoromethanesulfonate aqueous solution is taken as electrolyte; and (3) assembling the 2032 type button battery by using the stainless steel foil coated with manganese dioxide as an anode, a zinc sheet as a cathode, glass fiber as a diaphragm and electrolyte as a 1mol/L zinc trifluoromethanesulfonate mixed solution added with methanol. Assembling a 2032 type button cell under the same conditions by taking 1mol/L zinc trifluoromethanesulfonate aqueous solution as a comparison group as electrolyte; and (3) carrying out electrochemical performance test on the manufactured battery by using an electrochemical workstation, wherein the cycle conditions are as follows: the temperature was 25 ℃, 10(± 1) ° c, 0(± 1) ° c, 25 ℃, cycle number: each temperature cycle was 10 cycles.
Analysis of results
FIG. 1 is an SEM image of a zinc negative electrode section after circulation of a zinc ion battery with an electrolyte of a 1mol/L zinc trifluoromethanesulfonate mixed solution added with methanol, and FIG. 2 is an SEM image of a zinc negative electrode section after circulation of a zinc ion battery with an electrolyte of a 1mol/L zinc trifluoromethanesulfonate aqueous solution. It can be seen that: the zinc ion battery zinc cathode with the electrolyte being 1mol/L of zinc trifluoromethanesulfonate mixed solution added with methanol has a neat surface, and a more uniform zinc coating is generated; the zinc ion battery zinc cathode with 1mol/L zinc trifluoromethanesulfonate electrolyte has a severely corroded surface, and the surface is covered with white by-products, which can cause uneven surface, promote dendritic growth and possibly cause short circuit of the battery. This shows that methanol can significantly suppress its side reactions, thereby improving electrochemical performance.
FIG. 3 shows the current density at 0.1A g-1The following cycle chart shows that the zinc ion battery with the electrolyte of 1mol/L zinc trifluoromethanesulfonate mixed solution added with methanol has high capacity retention rate, and the remarkable improvement of the capacity retention rate can be attributed toExcellent corrosion resistance after introduction of methanol.
FIG. 4 is a graph of current density at 0.1A g at various temperatures-1The cycle chart below shows that the capacity of both cells shows a tendency to fade as the temperature is reduced from 25 c to 0 c. It is noted that the capacities of the zinc ion battery with the electrolyte of 1mol/L zinc trifluoromethanesulfonate mixed solution added with methanol and the zinc ion battery with the electrolyte of 1mol/L zinc trifluoromethanesulfonate aqueous solution are approximately consistent at 25 ℃. When the temperature is reduced to 10 ℃ and 0 ℃, the capacity of the zinc ion battery with the electrolyte of 1mol/L zinc trifluoromethanesulfonate mixed solution added with methanol is higher than that of the zinc ion battery with the electrolyte of 1mol/L zinc trifluoromethanesulfonate aqueous solution, and the capacity retention rate of the zinc ion battery with the electrolyte of 1mol/L zinc trifluoromethanesulfonate mixed solution added with methanol is higher than that of the zinc ion battery with the electrolyte of 1mol/L zinc trifluoromethanesulfonate aqueous solution, which means that the electrochemical performance of the battery in a low-temperature environment can be effectively improved by adding methanol into the electrolyte.
FIG. 5 is a graph showing the rate at different current densities, and it can be seen that the capacity of both the zinc ion battery in which the electrolyte is a 1mol/L zinc trifluoromethanesulfonate mixed solution to which methanol is added and the zinc ion battery in which the electrolyte is a 1mol/L zinc trifluoromethanesulfonate aqueous solution are reduced as the current density is increased. However, in general, the capacity retention rate of the zinc ion battery with the electrolyte of 1mol/L zinc trifluoromethanesulfonate mixed solution added with methanol is higher than that of the zinc ion battery with the electrolyte of 1mol/L zinc trifluoromethanesulfonate aqueous solution. This indicates that the addition of methanol improves the electrochemical performance.
Claims (7)
1. The water-based electrolyte is characterized by consisting of one or more of methanol, ethanol and glycol, electrolyte and water.
2. The aqueous electrolyte of claim 1, wherein the solvent is water and one or more of methanol, ethanol, and ethylene glycol.
3. The aqueous electrolyte of claim 1, wherein one or more of zinc trifluoromethanesulfonate, zinc sulfate, and zinc chloride are used.
4. The aqueous electrolyte of claim 1, wherein the volume ratio of one or more of methanol, ethanol, and ethylene glycol to water is 1: 1 to 10.
5. The aqueous electrolyte solution according to claim 1, wherein the concentration is 1 to 3 mol/L.
6. A 2032 coin zinc ion battery comprising the aqueous electrolyte according to any of claims 1 to 5.
7. The 2032 type coin zinc-ion battery of claim 6, further comprising a positive electrode, a separator, a negative electrode, wherein the positive electrode is stainless steel foil coated with manganese dioxide, the negative electrode is zinc sheet, the separator is glass fiber;
the separator is located between the positive electrode and the negative electrode.
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|---|---|---|---|
| CN202210013507.5A CN114447445A (en) | 2022-01-07 | 2022-01-07 | Preparation and application of aqueous zinc ion battery electrolyte |
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|---|---|---|---|
| CN202210013507.5A CN114447445A (en) | 2022-01-07 | 2022-01-07 | Preparation and application of aqueous zinc ion battery electrolyte |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115911596A (en) * | 2023-01-17 | 2023-04-04 | 南方科技大学 | Zinc metal battery electrolyte and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112038593A (en) * | 2020-08-06 | 2020-12-04 | 北京航空航天大学 | Positive electrode material of zinc-polymer water system rechargeable battery and preparation method of low-temperature-resistant electrolyte thereof |
| 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 |
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- 2022-01-07 CN CN202210013507.5A patent/CN114447445A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112038593A (en) * | 2020-08-06 | 2020-12-04 | 北京航空航天大学 | Positive electrode material of zinc-polymer water system rechargeable battery and preparation method of low-temperature-resistant electrolyte thereof |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115911596A (en) * | 2023-01-17 | 2023-04-04 | 南方科技大学 | Zinc metal battery electrolyte and preparation method and application thereof |
| CN115911596B (en) * | 2023-01-17 | 2023-09-01 | 南方科技大学 | Zinc metal battery electrolyte and preparation method and application thereof |
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Application publication date: 20220506 |