CN114597329B - Preparation method and application of zinc sheet with surface coating - Google Patents
Preparation method and application of zinc sheet with surface coating Download PDFInfo
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- CN114597329B CN114597329B CN202210298641.4A CN202210298641A CN114597329B CN 114597329 B CN114597329 B CN 114597329B CN 202210298641 A CN202210298641 A CN 202210298641A CN 114597329 B CN114597329 B CN 114597329B
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- 239000011701 zinc Substances 0.000 title claims abstract description 100
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 96
- 238000000576 coating method Methods 0.000 title claims abstract description 78
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 239000002689 soil Substances 0.000 claims abstract description 21
- 241000195493 Cryptophyta Species 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000011534 incubation Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002345 surface coating layer Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 description 9
- 230000006911 nucleation Effects 0.000 description 9
- 238000010899 nucleation Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 description 4
- 238000004807 desolvation Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Abstract
The preparation method and application of the zinc sheet with the surface coating layer, wherein the preparation method comprises the following steps: 1) Slowly adding the lithium algae soil powder into the solvent under the stirring condition, and continuously stirring to obtain uniform dispersion; 2) Uniformly coating the dispersion liquid prepared in the step 1) on the surface of a zinc sheet according to a preset thickness; 3) Rapidly transferring the zinc sheet treated in the step 2) to a vacuum drying condition, heating to 60 ℃, preserving heat, taking out and cooling to obtain the zinc sheet with the surface coating. The preparation conditions of the invention are simple, and the uniform surface coating for protecting the negative electrode of the zinc ion battery can be obtained only through the steps of mixing, stirring, smearing, drying and the like, and the invention has the advantages of no need of harsh reaction conditions, low cost and high efficiency; in addition, the lithium algae soil adopted by the invention has the advantages of abundant reserve, low price, no toxic or harmful solvent in the preparation, environmental protection, uniform surface coating, stable electrochemical property and better cycle stability.
Description
Technical Field
The invention relates to the technical field of surface coating preparation, in particular to a preparation method and application of a zinc sheet with a surface coating.
Background
The rechargeable water system zinc ion battery has the advantages of high safety, low cost, environmental friendliness and the like, and has wide application prospect in the field of large-scale energy storage. However, during charge and discharge, a tip effect is generated during charge deposition due to the uneven surface of the metallic zinc anode, and zinc ions are more prone to grow at the tip to cause dendrite generation, which seriously impairs the cycle performance of the zinc ion battery and even causes short circuit of the battery. In addition, because zinc ions associate with solvent water molecules to form water and zinc ions, a large nucleation energy barrier needs to be overcome during zinc ion deposition, which is extremely detrimental to the long cycle performance and coulombic efficiency of zinc ion batteries.
The surface coating is considered to be an effective way to improve the zinc cathode problem, but most of the surface coatings used at the present stage are single in function and cannot effectively resist corrosion of zinc sheets by water and oxygen. In order to enhance the adhesion of the coating material to the zinc metal surface, most of the work uses binders which require organic solvents to dissolve, and the use of organic solvents sacrifices the advantage of low cost of the zinc ion battery to some extent, and reduces the safety. In addition, many of the works employ complex preparation processes to obtain surface coating materials with specific structures and morphologies, which can cause great difficulty in mass production and are not suitable for large-scale popularization. Therefore, the problems of high cost, low safety and the like of the surface coating in the aspect of the preparation process are required to be further optimized, and the multifunctional surface coating is required to be developed to improve the electrochemical performance of the zinc ion battery, enhance the corrosion resistance of the zinc sheet and fundamentally solve the problems of low coulomb efficiency, large nucleation energy barrier and poor cycle performance of the zinc cathode.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of a zinc sheet with a surface coating, and the zinc sheet with the surface coating prepared by the method has multifunctional application, so that the electrochemical performance of a zinc ion battery can be improved, and the corrosion resistance of the zinc sheet can be enhanced.
In order to achieve the above object, the present invention provides a method for preparing a zinc sheet having a surface coating layer, comprising the steps of:
1) Slowly adding the lithium algae soil powder into the solvent under the stirring condition, and continuously stirring to obtain uniform dispersion;
2) Uniformly coating the dispersion liquid prepared in the step 1) on the surface of a zinc sheet according to a preset thickness;
3) Rapidly transferring the zinc sheet treated in the step 2) to a vacuum drying condition, heating to 30-120 ℃, preserving heat, taking out and cooling to obtain the zinc sheet with the surface coating.
As a further preferable technical scheme of the invention, the mass fraction of the lithium algae soil powder in the dispersion liquid obtained in the step 1) is 2-7%.
As a further preferred embodiment of the present invention, the solvent in step 1) is deionized water.
As a further preferable technical scheme of the invention, the continuous stirring time in the step 1) is 30-90min, and the stirring speed is 300-500r/min.
As a further preferable technical scheme of the invention, the dispersion liquid in the step 2) is coated on the surface of the zinc sheet in a doctor blade coating or spin coating mode, and the preset thickness is 5-20 mu m.
As a further preferable technical scheme of the invention, the equipment for heating and heat preservation in the step 3) is a vacuum drying oven.
As a further preferred embodiment of the invention, the incubation time in step 3) is at least 20min.
According to another aspect of the invention, the invention further provides an application of the zinc sheet with the surface coating prepared by the preparation method of the zinc sheet with the surface coating, wherein the zinc sheet with the surface coating is applied to a zinc ion battery as a negative electrode plate.
The preparation method and the application of the zinc sheet with the surface coating have the following technical effects by adopting the technical scheme:
(1) The preparation conditions of the invention are simple, and the uniform surface coating for protecting the negative electrode of the zinc ion battery can be obtained only through the steps of mixing, stirring, smearing, drying and the like, and the invention has the advantages of no need of harsh reaction conditions, low cost and high efficiency;
(2) The lithium algae soil adopted by the invention has the advantages of abundant reserves, low price, no toxic or harmful solvent in the preparation, environmental protection, uniform surface coating, stable electrochemical property and better circulation stability;
(3) The lithium algae soil adopted by the invention has extremely strong dispersibility in water, a protective layer formed by drying the dispersion liquid on the surface of a zinc sheet can be self-assembled in situ to form a three-dimensional layered structure, zinc ions are induced to be uniformly deposited, and better desolvation effect can be realized due to stronger binding force with water, so that the nucleation energy barrier of the zinc ions is reduced;
(4) The prepared zinc sheet with the surface coating is used as a negative electrode plate, the surface coating of the lithium alginate soil can improve the coulomb efficiency of a zinc ion battery and reduce the overpotential of a symmetrical battery, and particularly the assembled zinc-manganese dioxide full battery is 1A g -1 Has good cycle performance at current density;
(5) The zinc sheet with the surface coating prepared by the method has multifunctional application, and can not only improve the electrochemical performance of the zinc ion battery, but also enhance the corrosion resistance of the zinc sheet.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is an optical photograph of a lithium algae soil dispersion in example 1 of the present invention;
FIG. 2 is a graph showing the corrosion resistance of a zinc sheet with a surface coating layer prepared in example 2 of the present invention;
FIG. 3 is a cross-sectional scanning electron micrograph of a zinc sheet with a surface coating prepared in example 3 of the present invention;
FIG. 4 is a surface scanning electron micrograph of a zinc sheet with a surface coating prepared in example 3 of the present invention;
FIG. 5 is the rate performance of a zinc-zinc symmetrical cell assembled from zinc sheets with surface coating prepared in example 3 of the present invention;
FIG. 6 shows the coulombic efficiency of a zinc-titanium battery assembled from zinc sheets with surface coating prepared in example 3 of the present invention;
FIG. 7 shows a zinc-manganese dioxide cell assembled from a surface-coated zinc sheet prepared in example 3 of the present invention at 1A g -1 Specific discharge capacity curve and coulombic efficiency at current density.
Fig. 8 is a graph showing the nucleation energy barrier of a symmetrical cell assembled from zinc sheets with a surface coating prepared according to example four of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The invention will be further described with reference to the drawings and detailed description. The terms such as "upper", "lower", "left", "right", "middle" and "a" in the preferred embodiments are merely descriptive, but are not intended to limit the scope of the invention, as the relative relationship changes or modifications may be otherwise deemed to be within the scope of the invention without substantial modification to the technical context.
Example 1
The preparation of the zinc sheet with the surface coating in this example comprises the following steps:
(1) Measuring 3mL of deionized water into a 5mL glass vial by using a measuring cylinder, slowly adding 225mg of lithium algae soil powder under the stirring condition, and continuously stirring at the speed of 500 r/mm for 1h to obtain a uniform dispersion;
(2) Uniformly coating the dispersion liquid prepared in the step 1) on the surface of a zinc sheet, and controlling the thickness to be 5 mu m;
(3) And (3) rapidly transferring the zinc sheet in the step (2) into a vacuum drying oven at 30 ℃ for heat preservation for 30min, taking out and cooling to obtain the zinc sheet with the surface coating, and marking the zinc sheet as LAP@Zn.
The dispersion obtained in step 1) of this example is shown in fig. 1, and a transparent, uniform optical photograph shows that the bentonite has been completely dispersed in deionized water.
Example 2
The preparation of the zinc sheet with the surface coating in this example comprises the following steps:
(1) Measuring 2mL of deionized water into a 3mL glass vial (2 mg of methylene blue powder is added simultaneously), slowly adding 80mg of lithium algae soil powder under stirring, and continuously stirring at a speed of 300 r/mm for 0.5h to obtain a uniform dispersion;
(2) Uniformly coating the dispersion liquid prepared in the step 1) on the surface of a zinc sheet, and controlling the thickness to be 8 mu m;
(3) And (3) rapidly transferring the zinc sheet coated with the dispersion liquid in the step (2) into a vacuum drying oven at 60 ℃ for heat preservation for 30min, taking out and cooling to obtain a zinc sheet with a surface coating, and marking the zinc sheet as LAP@Zn.
To test the corrosion protection of the surface coating, a small amount of methylene blue dye added in step 1) was used only as a color mark, and a comparative example was that an aqueous methylene blue solution was directly applied to the surface of an untreated zinc sheet and then dried. The zinc sheet with protective layer (denoted as lap@zn) prepared in this example and the pure zinc sheet (denoted as Zn) were respectively immersed in two different experimental bottles, 5mL of 2m ZnSO4 electrolyte solution was filled in the experimental bottles, the color changes of the two experimental bottles were compared, the test results were as shown in fig. 2, the test was performed for seven days, the comparison results were recorded every other day, four times in total, and as seen from the figure, the aqueous solution of the right side immersed pure zinc sheet (Zn) had been dyed with methylene blue dye, while the zinc sheet (lap@zn) with surface coating on the left side had no color change. The experiment shows that the lithium algae soil coating can effectively inhibit the diffusion of water molecules to the surface of the zinc sheet, thereby improving the corrosion resistance of zinc metal.
Example 3
The preparation of the zinc sheet with the surface coating in this example comprises the following steps:
(1) Measuring 2mL of deionized water into a 3mL glass vial by using a measuring cylinder, slowly adding 100mg of lithium algae soil powder under stirring, and continuously stirring at a speed of 400 r/mm for 1.5h to obtain a dispersion;
(2) Uniformly coating the dispersion liquid prepared in the step 1) on the surface of a zinc sheet, and controlling the thickness to be 10 mu m;
(3) And (3) rapidly transferring the zinc sheet coated with the dispersion liquid in the step (2) into a vacuum drying oven at 120 ℃ for heat preservation for 30min, taking out and cooling to obtain a zinc sheet with a surface coating, and marking the zinc sheet as LAP@Zn.
The zinc sheet with the surface coating prepared in this example is characterized by using a scanning electron microscope, the cross section and the scanning electron microscope image of the surface are shown in fig. 3, it can be seen that the obtained surface coating has a three-dimensional layered structure, the scanning electron microscope image of the surface is shown in fig. 4, it can be seen that the obtained surface coating has a smooth surface morphology, the smooth surface morphology provides uniform reaction sites for zinc ion deposition, the three-dimensional layered structure can induce zinc ions to grow in a certain direction so as to ensure uniform deposition thereof, and in the long-term circulation process, the uniform zinc ion deposition can prevent zinc dendrite growth from penetrating through a diaphragm so as to damage battery performance.
The zinc sheet with the surface coating of the embodiment is applied to a zinc ion battery, and the multiplying power performance of the assembled zinc-zinc symmetrical battery is shown in fig. 5; the zinc sheet with surface coating of this example was applied to a zinc ion battery, and the coulombic efficiency of the assembled zinc-titanium battery is shown in fig. 6. The test results of fig. 5 show lower zinc ion nucleation overpotential, the test results of fig. 6 show higher coulombic efficiency, which benefits from the flat surface morphology of the surface coating and better desolvation performance, so that the energy barrier required to be overcome by zinc ions in continuous deposition and stripping is lower and has uniform nucleation sites to induce the zinc ions to deposit, thereby showing good electrochemical performance, and the lower overpotential and higher coulombic efficiency, so that the surface-coated zinc sheet provided by the invention is applied to zinc ion batteries and has good electrochemical performance.
The zinc sheet with the surface coating prepared in the example is applied to a zinc ion battery, and a zinc-manganese dioxide battery is prepared and subjected to charge and discharge tests, and the specific steps are as follows:
(1) Preparing a positive electrode plate: 70mg of manganese dioxide powder, 10mg of carbon black and 10mg of polyvinylidene fluoride were weighed into a mortar, 600. Mu.L of N-methyl-2-pyrrolidone was added thereto, the slurry was uniformly ground in the mortar, coated on a titanium foil with a thickness of 100. Mu.m, and the coated electrode sheet was placed in a vacuum drying oven and vacuum-dried at 80℃for 24 hours.
(2) Assembling the button cell, namely assembling the positive electrode shell, the positive electrode plate, the electrolyte, the diaphragm, the zinc sheet with the surface coating, the gasket, the spring piece and the negative electrode shell in the order of the positive electrode shell, the positive electrode plate, the electrolyte, the diaphragm and the negative electrode shell at room temperature, wherein the electrolyte is 2M ZnSO 4 The amount of the solution added was 50. Mu.L, the membrane was GF/A, and the battery case was CR 2032.
(3) The assembled battery was subjected to charge and discharge tests in the range of 0.8-1.8V.
The zinc-manganese dioxide battery assembled by the steps is subjected to charge and discharge test at 1A g -1 The specific discharge capacity curve and coulombic efficiency under the current density are shown in fig. 7, and the graph shows that the zinc sheet with the surface coating is applied to a zinc ion battery, and has good electrochemical cycling stability and higher coulombic efficiency.
Example 4
The preparation of the zinc sheet with the surface coating in this example comprises the following steps:
(1) Measuring 2mL of deionized water into a 3mL glass vial by using a measuring cylinder, slowly adding 40mg of lithium algae soil powder under the stirring condition, and continuously stirring at the speed of 300 r/mm for 1h to obtain a dispersion liquid;
(2) Uniformly coating the dispersion liquid prepared in the step 1) on the surface of a zinc sheet, and controlling the thickness to be 20 mu m;
(3) And (3) rapidly transferring the zinc sheet coated with the dispersion liquid in the step (2) into a vacuum drying oven at 80 ℃ for heat preservation for 30min, taking out and cooling to obtain a zinc sheet with a surface coating, and marking the zinc sheet as LAP@Zn.
The zinc sheet with the surface coating prepared in the embodiment is applied to a zinc ion battery assembly pair cell, a test of a zinc ion nucleation energy barrier is carried out, an untreated pure zinc sheet (42.5 mV) is taken as a comparison sample for comparison test, a test result is shown in fig. 8, LAP@Zn corresponds to the zinc sheet with the surface coating, zn corresponds to the pure zinc sheet of the comparison sample, the zinc sheet with the surface coating obviously reduces the nucleation energy barrier (14.9 mV) of the zinc ion, and the result shows that the lithium algae soil surface coating has strong binding force with water, a better desolvation effect can be realized, the energy required for overcoming the energy barrier in continuous deposition and stripping of the zinc ion is lower, the deposition rate of the zinc ion is faster, and the nucleation energy barrier is lower in the symmetrical battery.
Example 5
The preparation of the zinc sheet with the surface coating in this example comprises the following steps:
(1) Measuring 2mL of deionized water into a 3mL glass vial by using a measuring cylinder, slowly adding 180mg of lithium algae soil powder under the stirring condition, and continuously stirring at the speed of 500 r/mm for 3 hours to obtain a dispersion;
(2) Coating the dispersion liquid prepared in the step 1) on the surface of a zinc sheet, and controlling the thickness to be 20 mu m;
(3) And (3) rapidly transferring the zinc sheet coated with the dispersion liquid in the step (2) into a vacuum drying oven at 60 ℃ for heat preservation for 30min, taking out and cooling to obtain the zinc sheet with the surface coating.
The dispersion prepared in the embodiment can be dispersed after being stirred for a long time, the formed dispersion has higher viscosity and poorer dispersibility, is difficult to uniformly coat on the surface of a Zn sheet, and has obvious granular substances after being dried, so that the mass fraction of the lithium algae soil is not larger and better, and needs to be controlled within a reasonable range.
Example 6
The preparation of the zinc sheet with the surface coating in this example comprises the following steps:
(1) Measuring 2mL of deionized water into a 3mL glass vial by using a measuring cylinder, slowly adding 30mg of lithium algae soil powder under stirring, and continuously stirring at a speed of 300 r/mm for 10 hours to obtain a dispersion;
(2) Uniformly coating the dispersion liquid prepared in the step 1) on the surface of a zinc sheet, and controlling the thickness to be 10 mu m;
(3) And (3) rapidly transferring the zinc sheet coated with the dispersion liquid in the step (2) into a vacuum drying oven at 100 ℃ for heat preservation for 30min, taking out and cooling to obtain the zinc sheet with the surface coating.
The dispersion prepared in this example requires a longer stirring time to form a gel-like dispersion, and according to the analysis, it has been partly evaporated under long stirring time, so that the mass fraction of the loam forming a homogeneous dispersion at this ratio is actually greater than the theoretical mass fraction.
As can be seen from the combination of examples 5 and 6, the mass fraction of the lithium algae soil used for forming the uniform dispersion and applied to the surface coating of the zinc sheet needs to be controlled within a certain reasonable range, the mass fraction is too small to form the uniform dispersion, the mass fraction is too large to form the viscosity of the dispersion, and the prepared surface coating is uneven, so that the mass fraction of the lithium algae soil needs to be controlled to be 2-7% as optimal.
It should be noted that the above comparative sample for comparison test with the examples was a treated pure Zn chip.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (5)
1. The application of the zinc sheet with the surface coating is characterized in that the zinc sheet with the surface coating is applied to a zinc ion battery as a negative electrode plate;
the preparation method of the zinc sheet with the surface coating comprises the following steps:
1) Slowly adding the lithium algae soil powder into a solvent under the stirring condition, and continuously stirring to obtain a uniform dispersion liquid, wherein the solvent is deionized water, and the mass fraction of the lithium algae soil powder in the dispersion liquid is 2-7%;
2) Uniformly coating the dispersion liquid prepared in the step 1) on the surface of a zinc sheet according to the preset thickness of 5-20 mu m;
3) Rapidly transferring the zinc sheet treated in the step 2) to a vacuum drying condition, heating to 30-120 ℃, preserving heat, taking out and cooling to obtain the zinc sheet with the surface coating.
2. The use of a zinc sheet with a surface coating according to claim 1, characterized in that the continuous stirring time in step 1) is 30-90min and the stirring speed is 300-500r/min.
3. The use of a zinc sheet with a surface coating according to claim 1, characterized in that the dispersion in step 2) is applied to the surface of the zinc sheet by means of blade coating or spin coating.
4. The use of a zinc sheet with a surface coating according to claim 1, characterized in that the equipment for heating and maintaining the temperature in step 3) is a vacuum oven.
5. Use of a zinc sheet with a surface coating according to claim 1, characterized in that the incubation time in step 3) is at least 20min.
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