CN116960475A - Rare earth additive for water-based zinc ion battery and application thereof - Google Patents
Rare earth additive for water-based zinc ion battery and application thereof Download PDFInfo
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- CN116960475A CN116960475A CN202210386274.3A CN202210386274A CN116960475A CN 116960475 A CN116960475 A CN 116960475A CN 202210386274 A CN202210386274 A CN 202210386274A CN 116960475 A CN116960475 A CN 116960475A
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- additive
- zinc
- rare earth
- ion battery
- zinc ion
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000000654 additive Substances 0.000 title claims abstract description 76
- 230000000996 additive effect Effects 0.000 title claims abstract description 69
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 46
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 48
- 239000003792 electrolyte Substances 0.000 claims abstract description 85
- -1 rare earth salt Chemical class 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 150000001768 cations Chemical class 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 17
- 229960001763 zinc sulfate Drugs 0.000 claims description 17
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 17
- 239000002000 Electrolyte additive Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000012983 electrochemical energy storage Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 42
- 239000011701 zinc Substances 0.000 abstract description 41
- 229910052725 zinc Inorganic materials 0.000 abstract description 41
- 210000001787 dendrite Anatomy 0.000 abstract description 23
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000022131 cell cycle Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The application discloses a rare earth additive for a water-based zinc ion battery, and belongs to the technical field of zinc battery electrolyte. The rare earth additive is rare earth salt, and the general formula of the rare earth additive can be expressed as M x N y . Wherein M is a rare earth metal (Cr, sm, er, yb) cation, and N is an anion comprising Cl ‑ ，NO 3 ‑ And SO 4 2‑ X and y are coordination numbers of anions and cations, respectively. The additive is one or more of the rare earth metal salts. The dosage of the additive is 0.1-3g/L. Rare earth metal ions can be spontaneously adsorbed on dendrite active sites, so that dendrite growth is inhibited, and the cycle life of the water-based zinc ion battery is remarkably prolonged. The rare earth additive has the advantages of low cost, environmental protection and the like, and the electrolyte formula and the preparation process are simple, so that the rare earth additive has very wide application prospect in the field of water-based zinc ion batteries.
Description
Technical Field
The application relates to the technical field of water-based zinc ion batteries, in particular to a water-based zinc ion battery electrolyte modifier, a preparation method and application thereof.
Background
With the rapid development of electronic science and technology, the demand for renewable energy is increasing, which has greatly driven the development of safe, stable, low-cost and environmentally friendly electrochemical energy storage systems. The water-based zinc ion battery has the advantages of high safety performance, low cost, high water-splitting overpotential, high theoretical specific capacity and the like. In addition, aqueous systems have significant advantages such as high safety, low cost, high ionic conductivity, and the like, as compared to organic systems. And thus has received extensive attention from researchers in recent years.
The zinc metal has rich reserves and wide sources, and can be directly used as the negative electrode of the water-based zinc ion battery. The conversion of zinc ions into zinc ions involves two electron transfer, which can lead to a higher capacity of the battery. However, zinc dendrite, dead zinc, side reactions (hydrogen evolution, corrosion) and other problems can be generated in the zinc cathode due to uneven distribution of electrons and ions in the charge-discharge cycle process, so that coulomb efficiency is reduced, and finally the service life of the battery is poor, which hinders practical application of the water-based zinc ion battery. Therefore, inhibition of zinc dendrite growth and improvement of cycle life are one of the prerequisites for practical application of aqueous zinc ion batteries.
Disclosure of Invention
The application aims to provide a rare earth electrolyte additive of a water-based zinc ion battery and application thereof, aiming at the problems of uncontrollable growth of zinc dendrites, irreversible side reaction between a zinc cathode and the water-based electrolyte and the like commonly existing in the water-based zinc ion battery.
Specifically, the inventive arrangements of the present disclosure are as follows:
in a first aspect of the present disclosure, an embodiment of the present application provides a rare earth additive for an aqueous zinc-ion battery, wherein the additive is a rare earth element-containing metal salt, and the general formula of the additive may be represented as M x N y 。
Wherein M is a cation of a rare earth metal element (Cr, sm, er, yb), and N is an anion comprising Cl - ，NO 3 - And SO 4 2- X and y are coordination numbers of anions and cations, respectively.
The aqueous zinc ion battery electrolyte containing the additive consists of a common aqueous zinc ion battery electrolyte and the additive; the additive may be one or more of the above rare earth salts; the electrolyte of the common zinc ion battery electrolyte can be one or more of zinc sulfate, zinc acetate or zinc triflate.
The key of the application is to add a small amount of rare earth metal salt based on the existing aqueous zinc ion battery electrolyte. Regarding zinc salts in aqueous zinc ion battery electrolytes, reference may be made to existing conventional aqueous zinc ion battery electrolytes, and high-concentration "water-in-salt" electrolytes are not contemplated. The aqueous zinc ion battery electrolyte can achieve the purposes of inhibiting zinc dendrite growth and improving the circulation stability of a zinc cathode by adding a small amount of rare earth salt.
In a preferred scheme, the volume molar concentration of the zinc salt in the electrolyte is 1 mol/L-3 mol/L.
Preferably, the concentration of the rare earth additive is 0.1 g-3 g/L.
The application also provides an application example of the rare earth additive in a zinc-based battery. The negative electrode of the zinc-based battery is metallic zinc, and the positive electrode is one of lithium iron phosphate, manganese dioxide, lithium manganate and Prussian blue.
Through tests, the aqueous zinc ion battery electrolyte can effectively improve the circulation stability of a zinc cathode; based on the test data, the electrolyte can be used in a zinc ion battery energy storage device.
The application has the advantages and beneficial effects that:
1. the additive provided by the application has low price, little rare earth consumption in the additive, environmental friendliness and contribution to amplification application.
2. The radius of rare earth ions in the rare earth additive introduced into the electrolyte is 90-103ppm, which is far more than the radius of zinc ions by 74ppm, so that the surface defects of growing zinc grains are easily filled, thereby refining the grains, and simultaneously, rare earth metal ions can be spontaneously adsorbed on dendrite active sites, thereby inhibiting dendrite growth.
3. According to the rare earth additive introduced into the electrolyte, the characteristic adsorption of rare earth ions improves the precipitation potential of hydrogen ions on the zinc negative electrode, so that the hydrogen evolution reaction is inhibited, and the problems of gas expansion, liquid leakage and the like of the battery in the use process can be prevented to a certain extent.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a scanning electron microscope image of a zinc anode after the electrolyte containing additives provided in example 1 of the present application is circulated;
FIG. 2 is a photograph of a negative electrode scanning electron microscope of zinc after the electrolyte without additives provided in example 1 of the present application is circulated;
FIG. 3 is a linear sweep voltammogram of a zinc-titanium cell using the two electrolytes provided in example 1 of the present application;
fig. 4 is a graph of the cycle life of a zinc ion full cell employing two electrolytes provided in example 1 of the present application.
Detailed Description
In order to make the technical solution of the present application better understood by those skilled in the art, the technical solution of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
Example 1
The water-based zinc ion battery electrolyte of the example comprises solvent water, zinc sulfate and CeCl 3 . The preparation method comprises the following steps: zinc sulfate was weighed at a molar concentration of 2mol/L and CeCl was weighed at a molar concentration of 2g/L 3 The two are dissolved in a certain amount of distilled water, and the aqueous zinc ion battery electrolyte containing the additive is obtained.
In addition, as a comparison, a water-based zinc ion battery electrolyte without additives was prepared, specifically, zinc sulfate was weighed according to a volume molar concentration of 2mol/L and dissolved in water to obtain a water-based zinc ion battery electrolyte for comparison test.
The electrolyte containing the additive and the electrolyte not containing the additive obtained in the example are applied to a zinc-zinc symmetrical cell with a current of 10mA/cm -2 And (3) carrying out charge and discharge at current density, wherein the charge and discharge cycle time is 1 hour, and observing dendrite growth conditions on the surface of the zinc electrode by using a scanning electron microscope after 10 cycles.
The electron microscope observation results are shown in fig. 1 and 2, wherein fig. 1 is a zinc negative electrode scanning electron microscope image of the electrolyte of the zinc ion battery containing the additive, and fig. 2 is a zinc negative electrode scanning electron microscope image of the electrolyte of the zinc ion battery not containing the additive. The results show that the surface of the zinc sheet containing the additive zinc ion battery electrolyte is even and uniform, and no obvious dendrite exists; the surface of the zinc sheet without the additive zinc ion battery electrolyte in the comparative experiment has a plurality of columnar dendrites.
The electrolyte containing the additive and the electrolyte not containing the additive obtained in the example are applied to a zinc-titanium battery, a linear sweep voltammetry test is carried out, a voltage window is 0.01-2.9V, the sweep speed is 0.1mV/s, and the condition of hydrogen evolution potential is observed.
The results are shown in fig. 3, where the zinc-titanium cell containing the additive zinc ion cell electrolyte has a higher hydrogen evolution potential. The rare earth additive can effectively inhibit hydrogen evolution reaction of the water-based zinc ion battery.
The two electrolytes in this example were used in zinc ion batteries respectively, the positive electrode was lithium iron phosphate, the negative electrode was zinc foil, the positive electrode was uniformly mixed according to the weight of active material/conductive carbon black/pvdf=8/1/1, coated on a titanium foil of 0.1mm thickness, and dried, and then assembled with a negative electrode zinc sheet to form a button cell. The electrolyte adopts zinc ion electrolyte containing rare earth additive and zinc ion electrolyte not containing additive respectively. The aqueous zinc ion battery was charged and discharged at a voltage range of 0.9 to 1.35V, and the current density was 0.5A/g, and the capacity retention rate was measured for 100 cycles.
The test results show that after 100 cycles, the capacity retention rate of the zinc ion battery adopting the electrolyte containing the rare earth additive is 91%, and the capacity retention rate of the zinc ion battery adopting the electrolyte without the rare earth additive is only 20%, which shows that the zinc ion battery adopting the electrolyte containing the rare earth additive has very excellent cycle stability.
Example 2
The water-based zinc ion battery electrolyte of the example comprises solvent water, zinc sulfate and Ce 2 (SO 4 ) 3 . The preparation method comprises the following steps: zinc sulfate was weighed at a molar concentration of 2mol/L and Ce was weighed at a molar concentration of 2g/L 2 (SO 4 ) 3 The two are dissolved in a certain amount of distilled water, and the aqueous zinc ion battery electrolyte containing the additive is obtained.
In addition, as a comparison, a water-based zinc ion battery electrolyte without additives was prepared, specifically, zinc sulfate was weighed according to a volume molar concentration of 2mol/L and dissolved in water to obtain a water-based zinc ion battery electrolyte for comparison test.
Dendrite growth on the surface of the zinc sheet of this example was observed by the same method as in example 1. The results show that the surface of the zinc sheet containing the additive zinc ion battery electrolyte is even and uniform, and no obvious dendrite exists; the surface of the zinc sheet without the additive zinc ion battery electrolyte in the comparative experiment has a plurality of columnar dendrites.
The hydrogen evolution potential of this example was measured by the same method as in example 1. The results show that the zinc-titanium cell containing the additive zinc ion cell electrolyte has a higher hydrogen evolution potential. The rare earth additive can effectively inhibit hydrogen evolution reaction of the water-based zinc ion battery.
The zinc ion full cell cycle stability of this example was tested using the same method as in example 1. The results show that after 500 cycles, the capacity retention rate of the zinc ion battery adopting the electrolyte containing the rare earth additive is 78%, and the capacity retention rate of the zinc ion battery adopting the electrolyte without the rare earth additive is only 20%.
Example 3
The water-based zinc ion battery electrolyte of the example comprises solvent water, zinc sulfate and Ce (NO) 3 ) 3 . The preparation method comprises the following steps: zinc sulfate was weighed at a molar concentration of 2mol/L and Ce (NO) was weighed at a molar concentration of 2g/L 3 ) 3 The two are dissolved in a certain amount of distilled water, and the aqueous zinc ion battery electrolyte containing the additive is obtained.
In addition, as a comparison, a water-based zinc ion battery electrolyte without additives was prepared, specifically, zinc sulfate was weighed according to a volume molar concentration of 2mol/L and dissolved in water to obtain a water-based zinc ion battery electrolyte for comparison test.
Dendrite growth on the surface of the zinc sheet of this example was observed by the same method as in example 1. The results show that the surface of the zinc sheet containing the additive zinc ion battery electrolyte is even and uniform, and no obvious dendrite growth exists; the surface of the zinc sheet without the additive zinc ion battery electrolyte in the comparative experiment has a plurality of columnar dendrites.
The hydrogen evolution potential of this example was measured by the same method as in example 1. The results show that the zinc-titanium cell containing the additive zinc ion cell electrolyte has a higher hydrogen evolution potential. The rare earth additive can effectively inhibit hydrogen evolution reaction of the water-based zinc ion battery.
The zinc ion full cell cycle stability of this example was tested using the same method as in example 1. The results show that after 1000 cycles, the capacity retention rate of the zinc ion battery adopting the electrolyte containing the rare earth additive is 90%, and the capacity retention rate of the zinc ion battery adopting the electrolyte without the rare earth additive is only 20%.
Example 3
The water-based zinc ion battery electrolyte of the example comprises solvent water, zinc sulfate and Ce (NO) 3 ) 3 . The preparation method comprises the following steps: zinc sulfate was weighed at a molar concentration of 2mol/L and Ce (NO) was weighed at a molar concentration of 2g/L 3 ) 3 The two are dissolved in a certain amount of distilled water, and the aqueous zinc ion battery electrolyte containing the additive is obtained.
In addition, as a comparison, a water-based zinc ion battery electrolyte without additives was prepared, specifically, zinc sulfate was weighed according to a volume molar concentration of 2mol/L and dissolved in water to obtain a water-based zinc ion battery electrolyte for comparison test.
Dendrite growth on the surface of the zinc sheet of this example was observed by the same method as in example 1. The results show that the surface of the zinc sheet containing the additive zinc ion battery electrolyte is even and uniform, and no obvious dendrite growth exists; the surface of the zinc sheet without the additive zinc ion battery electrolyte in the comparative experiment has a plurality of columnar dendrites.
The hydrogen evolution potential of this example was measured by the same method as in example 1. The results show that the zinc-titanium cell containing the additive zinc ion cell electrolyte has a higher hydrogen evolution potential. The rare earth additive can effectively inhibit hydrogen evolution reaction of the water-based zinc ion battery.
The zinc ion full cell cycle stability of this example was tested using the same method as in example 1. The results show that after 1000 cycles, the capacity retention rate of the zinc ion battery adopting the electrolyte containing the rare earth additive is 90%, and the capacity retention rate of the zinc ion battery adopting the electrolyte without the rare earth additive is only 20%.
Example 4
The water-based zinc ion battery electrolyte of the example comprises solvent water, zinc sulfate and SmCl 3 . The preparation method comprises the following steps: zinc sulfate was weighed at a molar concentration of 2mol/L and SmCl was weighed at a molar concentration of 2g/L 3 The two are dissolved in a certain amount of distilled water, and the aqueous zinc ion battery electrolyte containing the additive is obtained.
In addition, as a comparison, a water-based zinc ion battery electrolyte without additives was prepared, specifically, zinc sulfate was weighed according to a volume molar concentration of 2mol/L and dissolved in water to obtain a water-based zinc ion battery electrolyte for comparison test.
Dendrite growth on the surface of the zinc sheet of this example was observed by the same method as in example 1. The results show that the surface of the zinc sheet containing the additive zinc ion battery electrolyte is even and uniform, and no obvious dendrite growth exists; the surface of the zinc sheet without the additive zinc ion battery electrolyte in the comparative experiment has a plurality of columnar dendrites.
The hydrogen evolution potential of this example was measured by the same method as in example 1. The results show that the zinc-titanium cell containing the additive zinc ion cell electrolyte has a higher hydrogen evolution potential. The rare earth additive can effectively inhibit hydrogen evolution reaction of the water-based zinc ion battery.
The zinc ion full cell cycle stability of this example was tested using the same method as in example 1. The results show that after 1000 cycles, the capacity retention rate of the zinc ion battery adopting the electrolyte containing the rare earth additive is 78%, and the capacity retention rate of the zinc ion battery adopting the electrolyte without the rare earth additive is only 20%.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The same or similar parts between the various embodiments in this specification are referred to each other. In particular, for the terminal embodiment, since it is substantially similar to the method embodiment, the description is relatively simple, and reference should be made to the description in the method embodiment for relevant points.
The embodiments of the present application described above do not limit the scope of the present application.
Claims (6)
1. An aqueous zinc ion battery electrolyte additive is characterized in that rare earth salt is adopted, and the general formula of the additive can be expressed as M x N y 。
Wherein M is a cation of a rare earth metal element (Cr, sm, er, yb), and N is an anion comprising Cl - ，NO 3 - And SO 4 2- X and y are coordination numbers of anions and cations, respectively.
2. The aqueous zinc-ion battery electrolyte additive according to claim 1, wherein the additive is one or more of the above rare earth metal salts.
3. An aqueous zinc-ion battery electrolyte comprising the additive of claim 1.
4. The aqueous zinc-ion battery electrolyte according to claim 3, wherein the concentration of the additive in the electrolyte is 0.1-3g/L.
5. The aqueous zinc-ion battery electrolyte of claim 3 or 4, wherein the electrolyte in the electrolyte is one or more of zinc sulfate, zinc acetate, or zinc triflate.
6. Use of the aqueous zinc-ion battery electrolyte according to any one of claims 3 to 5 in an aqueous zinc-ion battery or a zinc-ion electrochemical energy storage device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210386274.3A CN116960475A (en) | 2022-04-13 | 2022-04-13 | Rare earth additive for water-based zinc ion battery and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210386274.3A CN116960475A (en) | 2022-04-13 | 2022-04-13 | Rare earth additive for water-based zinc ion battery and application thereof |
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| CN116960475A true CN116960475A (en) | 2023-10-27 |
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| CN202210386274.3A Pending CN116960475A (en) | 2022-04-13 | 2022-04-13 | Rare earth additive for water-based zinc ion battery and application thereof |
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