CN114335447B - Surface treatment method for improving zinc cathode performance and application - Google Patents
Surface treatment method for improving zinc cathode performance and application Download PDFInfo
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- CN114335447B CN114335447B CN202111625976.4A CN202111625976A CN114335447B CN 114335447 B CN114335447 B CN 114335447B CN 202111625976 A CN202111625976 A CN 202111625976A CN 114335447 B CN114335447 B CN 114335447B
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- 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 invention relates to the technical field of zinc batteries, in particular to a method for carrying out surface modification on a zinc cathode and application of the method in the aspect of electrochemical energy storage devices. The method comprises the following steps: (1) soaking the cleaned zinc sheet in a selenium-containing solution; (2) And (3) sequentially cleaning the soaked zinc sheets with deionized water and absolute ethyl alcohol, and vacuum drying to obtain the modified zinc anode with zinc selenide deposited on the surface. The invention utilizes the chemical activity of the metal zinc sheet in the selenium-containing solution by a simple water bath soaking method to generate the zinc selenide nanometer coating layer on the surface of the metal zinc sheet, and can further inhibit the corrosion of a zinc cathode and the generation of zinc dendrites in a water-based zinc ion battery. The production and preparation process of the invention is simple, and only the commercial common metal zinc sheet is soaked in the solution containing selenium and alkali metal salt for a certain time. The invention has the advantages of wide sources of raw materials, low price and low cost of zinc surface treatment, and is suitable for large-scale production. After the modified zinc cathode is prepared into a full battery, the cycle stability is greatly improved compared with the commercial common zinc sheet cathode, and the parasitic reaction and hydrogen evolution phenomenon of the cathode are also inhibited.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage devices, and mainly aims at water-based zinc batteries, including zinc ion batteries, zinc ion hybrid supercapacitors, zinc-air batteries and other technical fields related to metal zinc sheets. In particular to a preparation method and application of a surface modified zinc anode. The technical method for treating the surface of the zinc cathode can inhibit corrosion of the zinc electrode, avoid dendrites and prolong the service life of the battery. Has the advantages of low material cost, simple operation, good repeatability, good cycle performance and the like, and is suitable for mass production.
Background
Metallic zinc (Zn) as an electrode material has a low oxidation-reduction potential (-0.76V, relative to a standard hydrogen electrode), a high specific capacity (820 mAh g) -1 ) High conductivity, superior chemical stability and low cost have received extensive attention from researchers. At present, a rechargeable secondary water-based zinc ion battery mainly uses metallic zinc as a negative electrode material, but conventional zinc sheets are easy to corrode and hydrogen evolution in a water-based electrolyte, and in repeated charge and discharge processesZinc dendrite formation can result, creating a risk of shorting the cell. These problems seriously hamper the progress of practical use of aqueous zinc batteries. The result is a reduced service life of the zinc cell, as zinc dendrite formation pierces the diaphragm between the anode and cathode and renders the device ineffective; secondly, parasitic chemical reaction on the surface of the zinc sheet generates a large amount of byproducts such as zinc oxide, basic zinc sulfate and the like, so that the coulomb efficiency of the device is reduced; thirdly, hydrogen is evolved from the surface of the zinc sheet, resulting in the sealed cell expanding gas. If the zinc cell is large in capacity and large in size, internal hydrogen production may bring about the risk of combustion explosion.
The existing method for improving the performance of the zinc anode comprises the following steps: surface deposition of copper film (CN 202011546177.3), coating of metal oxide (CN 202111035061.8) or the like to inhibit zinc corrosion or zinc dendrite growth; electrolyte additive (cn202110628613. X). In addition, researchers have also coated MXene (angel. Chem. Int. Ed.2021,60,2861) and ionic liquid impregnated Metal Organic Framework (MOF) coatings (angel. Chem. Int. Ed.2020,59,9377) on the surface of zinc sheets to improve the negative electrode performance. However, the preparation steps of the material coatings are complicated and the cost is high. In addition, some other substances, such as vanillin (cn202110628613. X), are added to the aqueous electrolyte to inhibit dendrite growth on the surface of the zinc anode. Although some organic additives can inhibit dendrite growth of zinc sheets, the ionic conductivity of the electrolyte can also decrease. Therefore, the technology of the invention researches a method for growing ZnSe film on the surface of a zinc sheet based on the principle of low-cost simple preparation, thereby achieving the purpose of improving the performance of the zinc cathode.
Disclosure of Invention
In order to achieve the above object, the present invention proposes a method of surface-treating a negative electrode to improve electrochemical properties. The zinc sheet surface modification method is simple, is suitable for large-scale zinc sheet surface treatment, has no obvious increase in quality after treatment, and has the effects of no dendrite generation, inhibition of hydrogen evolution, ultra-long cycle stability and the like when used for a water-based zinc battery.
In order to achieve the above purpose, the preparation method of the modified zinc anode comprises the following steps:
1. the cleaned zinc sheet is soaked in the aqueous solution of selenium-containing compound and chloride salt and kept for a period of time.
2. The soaked zinc sheet is washed by deionized water, absolute ethyl alcohol and the like in sequence, and is dried in vacuum to obtain the surface modified zinc cathode, namely the zinc sheet with zinc selenide grown on the surface, which is marked as ZnSe/Zn.
In a preferred embodiment, the selenium source used in step (1) with the selenium-containing solution is one or more of selenium dioxide, selenic acid, sodium selenite, and sodium hydrosulfite.
In a preferred embodiment, the chloride salt used in step (1) is one or more of lithium chloride, sodium chloride and potassium chloride.
In a preferred embodiment, the soaking in step (1) is carried out at room temperature and pressure for a period of 1 to 12 hours.
In a preferred embodiment, the concentration of selenium element in the selenium-containing solution used in step (1) is 0.01-0.1M.
In a preferred embodiment, the concentration of chloride salt in the selenium-containing solution used in step (1) is 0.01-0.1M.
The invention has the advantages and beneficial effects that:
(1) The invention adopts a simple soaking reaction method to deposit ZnSe on the surface of the zinc sheet.
(2) The Zn cathode with ZnSe deposited on the surface has excellent effects in corrosion resistance, dendrite growth inhibition and charge-discharge cycle life prolongation.
(3) The method is suitable for normal temperature and normal pressure conditions, does not need expensive equipment, is easy to expand preparation, and can simultaneously treat a plurality of large-size zinc sheets.
(4) The zinc sheet after surface modification by the method of the invention can be applied to various water-based zinc batteries, such as MnO 2 、V 2 O 5 Prussian blue analogues, and aromatic polymer based positive electrode materials in combination to construct rechargeable batteries, can also be used in zinc-air batteries.
Drawings
FIG. 1 is a scanning electron microscope image of a zinc sheet after a ZnSe nano layer has been grown on the surface. (a) a low-magnification plot; (b) high magnification graph.
FIG. 2 shows XPS spectra of (a) XPS full spectrum and (b) Se 3d peak of zinc cathode modified with ZnSe.
FIG. 3 shows a comparison of polarization curves of a surface ZnSe-modified zinc sheet and a common Zn foil.
FIG. 4 cycle performance of ZnSe-modified zinc sheet in half cell compared to common Zn foil.
FIG. 5A voltammogram of a full cell was constructed with ZnSe-modified zinc sheet and plain Zn foil, respectively, together with Poly (p-aminophenol), poly (4-AP), supported on activated carbon. The voltage sweep rate for the test was 5mV/s.
Detailed Description
The invention is further illustrated by the following examples, but is not limited to the specific embodiments.
Example 1
(1) A surface treatment method for zinc cathode and its application, the said method mainly uses commercial zinc sheet/foil as raw material, after cutting out small sheet whose width is 2cm and length is 5cm, it is respectively cleaned in acetone and absolute ethyl alcohol for 10-30 min, and the impurities of surface organic matter, etc. are removed.
(2) Preparing a solution: weighing 0.2g of selenium dioxide (SeO) 2 ) And 0.5g lithium chloride (LiCl) dissolved in 100mL deionized water.
(3) The cleaned zinc sheet is soaked in the water solution containing selenium and lithium chloride and kept at room temperature for 3 hours, so that the zinc sheet with the surface covered with ZnSe is obtained, and the microscopic morphology of the zinc sheet is shown in figure 1. X-ray photoelectron spectroscopy (XPS) analysis determined the presence of Se elements and the formation of ZnSe, as shown in fig. 2.
(4) And (3) using the zinc sheet with the surface modified in the step (3) as a working electrode, a saturated calomel electrode as a reference electrode, and a graphite rod as a counter electrode, and running linear sweep voltammetry in a 2M zinc sulfate aqueous solution at a sweep speed of 1mV/s, as shown in figure 3. As can be seen from FIG. 3, the nucleation potential of the zinc sheet surface-modified with ZnSe is improved compared to the ordinary Zn foil.
(5) Punching the zinc sheet with the surface modified in the step (3) to obtain two identical wafers, and adopting glassThe fiber membrane and 2M zinc sulfate aqueous solution were assembled into CR2032 coin cells for cyclic charge and discharge test analysis, the results of which are shown in fig. 4. The cyclic test was performed on a blue-electric test system under test conditions of 1.0mA/cm 2 Constant current discharge for 1h at a current density of 1.0mA/cm 2 Constant current charged to 0.8V at current density, and alternately cycled. FIG. 4 shows that the cycle life of the surface-modified zinc sheet is greatly prolonged compared with that of the ordinary Zn sheet.
(6) The surface modified zinc sheet in step (3) was used as the negative electrode and a zinc ion battery was constructed based on a positive electrode combination of poly (p-aminophenol) for test analysis. A glass fiber diaphragm is arranged between the positive electrode and the negative electrode, and the electrolyte is a 2M zinc sulfate aqueous solution. The voltammetric Cycle (CV) curves tested are shown in fig. 5.
(7) The organic positive electrode in step (6) is prepared as follows: dissolving p-Aminophenol (4-amino alcohol, 4-AP) in 1M sulfuric acid water solution, wherein the concentration range is 0.1-0.8M; the solution is placed in a three-electrolysis electrolytic cell, a platinum mesh counter electrode, an Ag/AgCl reference electrode and conductive carbon cloth with the surface coated with active carbon, conductive carbon black and polyvinylidene fluoride adhesive (the mass ratio is 8:1:1) are used as working electrodes, a voltammetric cycle is operated, the sweeping speed is 20mV/s, the voltage range is-0.2 to 0.8V, and after 20-100 circles of cycles, 4-AP can be polymerized and deposited on the active carbon coating. Poly (p-aminophenol) is used for the positive electrode of a zinc ion battery, and is charged and discharged by means of reversible oxidation-reduction reaction.
A comparison of examples 1-4 is shown in Table 1. Examples 2-4 show that the solution for preparing ZnSe is different in composition and the rest is the same as in example 1.
Table 1, solution ratios of ZnSe films grown on zinc sheet surfaces in different examples.
| Example of the other | Se source additive and concentration | Chloride salt and concentration | Zinc sheet soaking time (h) | Reaction temperature (. Degree. C.) |
| 1 | SeO 2 ,0.02mol/L | LiCl,0.05mol/L | 2 | 25 |
| 2 | SeO 2 ,0.05mol/L | NaCl,0.02mol/L | 1 | 25 |
| 3 | Na 2 SeO 3 ,0.02mol/L | LiCl,0.1mol/L | 3 | 15 |
| 4 | Na 2 SeO 3 ,0.05mol/L | NaCl,0.1mol/L | 2 | 20 |
| 5 | H 2 SeO 3 ,0.05mol/L | KCl,0.08mol/L | 3 | 15 |
| 6 | H 2 SeO 3 ,0.05mol/L | LiCl,0.05mol/L | 1 | 25 |
| 7 | NaHSeO 3 ,0.05mol/L | NaCl,0.02mol/L | 1 | 25 |
| 8 | NaHSeO 3 ,0.05mol/L | KCl,0.08mol/L | 1 | 20 |
Conclusion: the implementation of the invention can generate ZnSe nano coating on the surface of the zinc sheet, thereby inhibiting corrosion of the zinc cathode and zinc dendrite generation and hydrogen evolution in the circulating process.
In summary, the above embodiments are merely illustrative of the principles and embodiments, and are not intended to limit the invention, but any modifications, equivalents, improvements or the like can be made without departing from the principles of the invention.
Claims (7)
1. A surface treatment method for improving zinc cathode performance is characterized by comprising the following steps:
(1) Soaking the cleaned zinc sheet in an aqueous solution of a selenium-containing compound and a chloride salt, wherein the selenium-containing compound is one of selenium dioxide, selenic acid, sodium selenite and sodium hydrogen selenite;
(2) And washing the soaked zinc sheet with deionized water and absolute ethyl alcohol, and carrying out vacuum drying to obtain the modified zinc cathode.
2. The surface treatment method according to claim 1, wherein the chloride salt used in step (1) is one of lithium chloride, sodium chloride and potassium chloride.
3. The surface treatment method according to claim 1, wherein the immersing in step (1) is performed at room temperature and normal pressure.
4. The surface treatment method according to claim 1, wherein the concentration of selenium in the selenium-containing aqueous solution used in step (1) is 0.01 to 0.1mol/L.
5. The surface treatment method according to claim 1, wherein the concentration of the alkali metal chloride salt in the aqueous selenium-containing compound solution used in step (1) is 0.01 to 0.1mol/L.
6. The surface treatment method according to claim 1, wherein the soaking time in step (1) is 1 to 12 hours.
7. The modified zinc negative electrode obtained by the surface treatment method according to claim 1, which is applicable to a water-based zinc ion battery, a zinc-air battery, a zinc-vanadium battery, a zinc-manganese battery.
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