CN117895101A - Water-based zinc ion battery additive and battery electrolyte - Google Patents
Water-based zinc ion battery additive and battery electrolyte Download PDFInfo
- Publication number
- CN117895101A CN117895101A CN202211218362.9A CN202211218362A CN117895101A CN 117895101 A CN117895101 A CN 117895101A CN 202211218362 A CN202211218362 A CN 202211218362A CN 117895101 A CN117895101 A CN 117895101A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- zinc
- additive
- ion battery
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 53
- 239000000654 additive Substances 0.000 title claims abstract description 32
- 230000000996 additive effect Effects 0.000 title claims abstract description 29
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 15
- 229960001763 zinc sulfate Drugs 0.000 claims description 14
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 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 3
- 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 3
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 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 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000011701 zinc Substances 0.000 abstract description 13
- 229910052725 zinc Inorganic materials 0.000 abstract description 11
- 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 14
- 210000004027 cell Anatomy 0.000 description 7
- 210000001787 dendrite Anatomy 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002699 waste material Substances 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 a water-based zinc ion battery additive and electrolyte, wherein the water-based zinc ion battery additive is silver nitrate, and the electrolyte is a water-based zinc ion electrolyte containing silver nitrate. The concentration of the additive is 0.001-0.1mol/L. Compared with other electrolyte, the electrolyte provided by the invention has the advantages that the circulation stability of the zinc anode is greatly improved when the electrolyte is used, the short circuit time can be increased from 25 hours to 460 hours at most, and the maximum increase amplitude is 1700%.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and relates to a water-based zinc ion battery additive and electrolyte.
Technical Field
Currently, lithium ion batteries have been widely used in energy storage power stations, electric vehicles, and other various electronic devices. However, the lithium ion battery has the problems of fire explosion, higher cost, resource shortage, high waste disposal cost and the like, and the application of the lithium ion battery in the field of large-scale energy storage is restricted. Aqueous zinc ion batteries are receiving wide attention due to safe and environment-friendly aqueous electrolytes and abundant and cheap electrode materials, and are considered as one of ideal schemes for large-scale electrochemical energy storage. However, the zinc cathode of the water-based zinc ion battery has the problems of hydrogen evolution, surface passivation and dendrite growth which are mutually coupled, and the problems of battery swelling, performance degradation and short circuit failure are respectively caused. Currently, the addition of additives to the electrolyte is one of the most effective methods for inhibiting zinc dendrite growth and shorting problems. However, current electrolyte additives are mainly small molecule organics and polymers, and these two types of additives have poor dendrite inhibition effect.
Disclosure of Invention
In view of the shortcomings pointed out in the background art, the invention provides an aqueous zinc ion battery additive and a battery electrolyte, which are used for solving the problem of short circuit of a battery caused by dendrite growth of a zinc cathode.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a water-based zinc ion battery additive comprises silver nitrate.
The aqueous zinc ion battery electrolyte containing the additive consists of common electrolyte and 0.001-0.1mol/L additive; the electrolyte in the electrolyte is one or two of zinc sulfate, zinc triflate, zinc perchlorate and zinc nitrate. The concentration of the ordinary electrolyte is preferably 3mol/L.
Through tests, the water system zinc ion battery electrolyte can greatly prolong the short-circuit time of a zinc cathode; according to the functions and effects, the aqueous zinc ion battery electrolyte can improve the circulation stability of the aqueous zinc ion battery.
The invention has the advantages that: the silver nitrate additive is added into the zinc ion battery water-based electrolyte, so that a silver-zinc alloy protective layer can be formed on the surface of the zinc foil. The alloy protective layer can effectively inhibit hydrogen gas precipitation and passivation of the zinc cathode by isolating the zinc cathode from electrolyte. The alloy protective layer also has high zinc affinity, is favorable for uniform migration and deposition of zinc ions on the surface of the negative electrode, thereby inhibiting formation and growth of zinc dendrites, greatly prolonging the short-circuit time of the zinc negative electrode, prolonging the service life of the device of the water-based zinc ion battery, and obviously improving the effect over the current small molecular organic matters and polymer additives. The additive has the advantages of less consumption, convenient use and less pollution.
Drawings
FIG. 1 is a scanning electron micrograph of a zinc foil after grinding in example 1 of the present invention.
Fig. 2 is a scanning electron micrograph of a zinc foil after 18 cycles in an additive-free electrolyte in example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of a zinc foil after 18 cycles in an electrolyte containing 0.005mol/L silver nitrate additive using example 1 of the present invention.
Fig. 4 is a graph comparing the cycle test performance of symmetrical cells in example 1 of the present invention with additive electrolytes having different concentrations.
Fig. 5 is a graph of the cyclic test short circuit time line for symmetrical cells in example 1 containing different concentrations of additive electrolyte according to the present invention.
Detailed Description
For the purpose of making the technical solution and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and examples. It should be understood that the detailed description is presented by way of example only and is not intended to limit the invention.
A water-based zinc ion battery additive comprises silver nitrate.
The aqueous zinc ion battery electrolyte containing the additive consists of common electrolyte and the additive with the concentration of 0.001-0.1 mol/L; through experimental screening, the electrolyte of the common electrolyte can be one or two of zinc sulfate, zinc trifluoromethane sulfonate, zinc perchlorate and zinc nitrate, and the concentration of the common electrolyte is preferably 3mol/L.
Example 1
(1) Preparation of electrolyte:
taking ultrapure water prepared by the ultrapure water machine as a solvent, adding zinc sulfate heptahydrate, and stirring and dissolving to prepare a zinc sulfate aqueous solution with the concentration of 3mol/L. Adding the required silver nitrate solid salt into the zinc sulfate solution, stirring and dissolving to obtain the aqueous zinc ion battery electrolyte containing 0.001-0.1mol/L silver nitrate additive. In addition, a 3mol/L zinc sulfate electrolyte to which no silver nitrate was added was prepared as a control experiment.
(2) Preparation of Zn// Zn symmetric cell
Clean zinc foil (thickness 100 μm) was selected, polished with sand paper, cut into a wafer with a diameter of 10mm, used as an electrode of a symmetrical battery, glass fiber was used as a separator, the electrolyte package 2025 containing the additive described in (1) was used, and the electrolyte package 2025 containing no additive was used as a control.
(3) Additive Effect test
The symmetrical cell was set at 2mA/cm 2 Current density and 2mAh/cm 2 And (5) carrying out cyclic charge and discharge test on the electric quantity density. When a sudden change in potential is observed, the sudden change time point is taken as the short-circuit time of the symmetrical cell.
The test results were as follows: fig. 1 is a scanning electron micrograph of a polished zinc foil. FIG. 2 is a graph of a battery at 2mA/cm using 3mol/L zinc sulfate electrolyte 2 Current density and 2mAh/cm 2 Scanning electron micrographs after 18 cycles at bulk density. After a plurality of charge-discharge cycles in 3mol/L zinc sulfate electrolyte, the surface of the zinc foil cathode is severely corroded, and obvious dendrites grow on the surface. FIG. 3 is a graph of a battery at 2mA/cm using a 3mol/L zinc sulfate electrolyte containing 0.005mol/L silver nitrate additive 2 Current density and 2mAh/cm 2 Scanning electron micrographs after 18 cycles of cycling at the volume density show that after cycling in the electrolyte containing the additive, the surface of the zinc electrode sheet is relatively flat and dendrite formation and growth are significantly inhibited. FIG. 4 is an illustration of an assembled symmetrical cell using 3mol/L zinc sulfate electrolyte and 3mol/L zinc sulfate electrolyte containing 8 different concentrations of silver nitrate additives at 2mA/cm 2 Current density and 2mAh/cm 2 Cycling performance plot at capacity density. It can be seen that the zinc foil cathode has the best cycle performance in 3mol/L zinc sulfate electrolyte added with 0.005mol/L silver nitrate additive, and the short circuit of the symmetrical battery can reach 460 hours. FIG. 5 is a graph of the use of 3 containing different concentrations of silver nitrate additiveThe mol/L zinc sulfate electrolyte assembled symmetrical battery is at 2mA/cm 2 Current density and 2mAh/cm 2 Line graph of short circuit time at capacity density. It can be seen that the short-circuit time of the symmetrical cell using 3mol/L zinc sulfate electrolyte was 25 hours, whereas the cycle performance using electrolyte containing 0.005mol/L silver nitrate additive was best, and the short-circuit time could reach 460 hours, and the cycle life time was 1700% increased.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (4)
1. An additive of aqueous zinc ion battery electrolyte, silver nitrate.
2. An aqueous zinc ion battery electrolyte, characterized in that the electrolyte contains the additive of claim 1.
3. The aqueous zinc-ion battery electrolyte according to claim 2, wherein the concentration of the additive in the electrolyte is 0.001-0.1mol/L.
4. A water-based zinc-ion battery electrolyte as claimed in claims 2 and 3, wherein the electrolyte in the electrolyte is one or two of zinc sulfate, zinc trifluoromethane sulfonate, zinc perchlorate and zinc nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211218362.9A CN117895101A (en) | 2022-10-05 | 2022-10-05 | Water-based zinc ion battery additive and battery electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211218362.9A CN117895101A (en) | 2022-10-05 | 2022-10-05 | Water-based zinc ion battery additive and battery electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117895101A true CN117895101A (en) | 2024-04-16 |
Family
ID=90642880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211218362.9A Pending CN117895101A (en) | 2022-10-05 | 2022-10-05 | Water-based zinc ion battery additive and battery electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117895101A (en) |
-
2022
- 2022-10-05 CN CN202211218362.9A patent/CN117895101A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111477957B (en) | Lithium metal battery electrolyte containing composite additive and preparation method thereof | |
| CN113054165B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN110071284B (en) | Method for protecting lithium metal electrode | |
| CN111653834B (en) | Aqueous electrolyte, aqueous metal ion battery, and method for producing same | |
| CN104716372A (en) | Aqueous lithium ion flow battery | |
| CN112635698B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN104347894A (en) | A sedimentary type aqueous lithium ion battery | |
| CN103280559A (en) | Sealed zinc-nickel secondary cell zinc negative electrode, and cell and preparation method thereof | |
| CN108808053B (en) | Zinc-nickel liquid flow energy storage battery | |
| CN113809408A (en) | Aqueous zinc ion battery additive, battery electrolyte and application thereof | |
| CN115863799A (en) | Electrolyte additive for zinc battery and application thereof | |
| CN114373982B (en) | Liquid ether organic electrolyte-based low-negative electrode secondary sodium battery and preparation method thereof | |
| CN113690397B (en) | Zinc cathode pole piece and preparation method and application thereof | |
| CN113314773A (en) | Aqueous zinc ion battery electrolyte and preparation method and application thereof | |
| CN115832460A (en) | Electrolyte additive, electrolyte containing additive and application of electrolyte | |
| CN117895101A (en) | Water-based zinc ion battery additive and battery electrolyte | |
| CN115051047A (en) | Electrolyte additive for water-based zinc ion battery and application thereof | |
| CN114361581B (en) | Calcium metal battery electrolyte and calcium metal battery based on same | |
| CN117060002A (en) | Modification method of zinc ion battery diaphragm and water-based zinc ion battery | |
| CN116231113A (en) | Composite electrolyte for inhibiting zinc dendrite and prolonging cycle life of battery and application thereof | |
| CN115939471A (en) | Water-based electrolyte and application thereof in alkaline zinc-based flow battery | |
| CN117790932A (en) | Aqueous zinc ion battery electrolyte capable of inhibiting zinc dendrite and corrosion, preparation method and application thereof | |
| CN2692850Y (en) | Ultra-delay charging-free communication spare power source | |
| CN118213637A (en) | Aqueous zinc ion battery electrolyte additive, electrolyte containing same and application thereof | |
| CN116598703A (en) | Black phosphorus modified composite diaphragm for water-based zinc ion battery and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |