CN116387444A - Zinc cathode with natural polymer protective layer and preparation method and application thereof - Google Patents
Zinc cathode with natural polymer protective layer and preparation method and application thereof Download PDFInfo
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- CN116387444A CN116387444A CN202310502373.8A CN202310502373A CN116387444A CN 116387444 A CN116387444 A CN 116387444A CN 202310502373 A CN202310502373 A CN 202310502373A CN 116387444 A CN116387444 A CN 116387444A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 102
- 239000011701 zinc Substances 0.000 title claims abstract description 102
- 239000011241 protective layer Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920005615 natural polymer Polymers 0.000 title abstract description 6
- 229920001661 Chitosan Polymers 0.000 claims abstract description 49
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- 239000003792 electrolyte Substances 0.000 claims abstract description 16
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- 238000000034 method Methods 0.000 claims abstract description 14
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- 229910052799 carbon Inorganic materials 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
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- 239000007774 positive electrode material Substances 0.000 claims description 3
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
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- LNNWVNGFPYWNQE-GMIGKAJZSA-N desomorphine Chemical compound C1C2=CC=C(O)C3=C2[C@]24CCN(C)[C@H]1[C@@H]2CCC[C@@H]4O3 LNNWVNGFPYWNQE-GMIGKAJZSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
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- HWQQCFPHXPNXHC-UHFFFAOYSA-N 6-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-3',6'-dihydroxyspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(O)=CC=C2C=1OC1=CC(O)=CC=C1C2(C1=CC=2)OC(=O)C1=CC=2NC1=NC(Cl)=NC(Cl)=N1 HWQQCFPHXPNXHC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- 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
-
- 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 invention discloses a zinc anode with a natural polymer protective layer, and a preparation method and application thereof. A method for preparing a zinc anode, comprising the steps of: taking chitosan solution as electrolyte, connecting zinc foil with a positive electrode of a power supply, connecting a counter electrode with a negative electrode of the power supply, and electrifying the zinc foil after electrolysis to obtain the zinc negative electrode; the solute in the chitosan solution comprises at least one of carboxymethyl chitosan, aminated chitosan and sulfonated chitosan. The invention constructs the organic matter protective layer on the surface of the zinc negative electrode by simple externally-applied direct current, plays an effective protective role on the zinc metal negative electrode, and is different from the conventional protective layer preparation process, the process can construct the protective layer with ideal thickness on the surface of the zinc metal negative electrode without using materials such as adhesive and the like, and the production cost is greatly reduced when the process is applied to actual production.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a zinc anode with a natural polymer protective layer, and a preparation method and application thereof.
Background
Lithium ion batteries are currently widely used energy storage devices, however, there is significant further applicationA bottleneck. Firstly, lithium resources are scarce and a large amount of lithium elements are consumed, so that the total production capacity of the lithium battery is limited, and the high cost of raw materials of the battery makes the price of the battery high; secondly, the electrolyte and the battery material have great toxicity, and once leakage causes pollution to the environment, the electrolyte and the battery material can also cause harm to human bodies, and meanwhile, the battery production condition is extremely severe. In addition, the news of the short circuit spontaneous combustion of the electric automobile battery which is gradually highlighted also shadows the development of the lithium ion battery. The water-based zinc ion battery has the advantages of low cost, abundant raw materials, high safety, high ion conductivity, environmental friendliness and the like, is easier to design and manufacture than a lithium ion battery, does not need to be manufactured under the strict conditions of no water and no oxygen, and is a very ideal supplementary choice of the lithium ion battery in the future. The zinc metal has large theoretical capacity (820 mAh g -1 、5855mAh cm -3 ) The advantages of low oxidation-reduction potential (-0.76 Vvs SHE), rich resources and the like are achieved, so that the water-based zinc ion battery can achieve higher energy density. However, in the charge and discharge process, the zinc cathode has a series of problems such as dendrite growth and hydrogen evolution side reaction, and the cycle life of the water-based zinc ion battery is severely limited.
In response to the complex and diverse problems faced by zinc metal anodes in electrodeposition processes, researchers have developed a series of strategies to address these problems. Some strategies have been widely applied to improve the cycle life of zinc, such as designing new electrodes, electrolyte optimization, membrane modification, electrodeposition regulation, and the like. The zinc anode protective coating is in direct contact with the areas of zinc deposition and side reactions, and the zinc anode coating not only regulates the diffusion of zinc ions in the electrolyte, but also acts as a selector for ions entering the coating. The adaptive coating on the zinc cathode can inhibit a series of side reactions such as zinc dendrite formation, passivation, hydrogen evolution, corrosion, morphology change and the like, and can optimize zinc deposition and improve the service life of the water-based zinc ion battery. Zhi Chunyi group [ ACS Applied Energy Materials2019,2 (9): 6490-6496 ] uses composite gold nanoparticles as zinc anode protective coating that can regulate uniform deposition of zinc and extend the life of zinc electrodes. Nucleation of zinc ions on the surface of carbon increases the stability of zinc deposition, but because carbon has excellent conductivity, it also suffers from uncontrolled zinc deposition on the surface of the carbon layer, which makes it difficult to suppress side reactions. From the research results and the processes of the prior art, the preparation of the zinc anode protective layer by using inorganic materials still has certain disadvantages that the preparation process is relatively complex, and the preparation process still has certain disadvantages in inhibiting zinc dendrite growth and hydrogen evolution side reaction.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a zinc anode with a natural polymer protective layer, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a preparation method of a zinc anode, comprising the following steps:
taking chitosan solution as electrolyte, connecting zinc foil with a positive electrode of a power supply, connecting a counter electrode with a negative electrode of the power supply, and electrifying the zinc foil after electrolysis to obtain the zinc negative electrode;
the solute in the chitosan solution comprises at least one of carboxymethyl chitosan, aminated chitosan and sulfonated chitosan.
Preferably, the amino group substitution degree of the aminated chitosan is 20-30%.
Preferably, the sulfochitosan has a degree of substitution of 35-45%.
Preferably, the solute in the chitosan solution is carboxymethyl chitosan; the chitosan has a double-helix structure, and the intramolecular hydrogen bond has extremely strong acting force, so that the chitosan is difficult to dissolve in water and transfer ions, and the requirements of the electrochemical energy storage material are difficult to meet. The carboxymethyl chitosan has wide sources and rich reserves, is modified to a certain extent on chitosan with poor water solubility, and introduces functional groups to change the secondary structure of the chitosan, destroy the hydrogen bond network inside molecules and increase the water solubility of the chitosan. The invention creatively adopts a simple and convenient process of externally adding a direct current power supply, and constructs the carboxymethyl chitosan zinc protective coating on the surface of the zinc negative electrode, amino groups and hydroxyl groups on the protective coating are coordinated with zinc ions, the specific surface area of the internal hole structure of the coating is increased, the contact of electrolyte and an electrode is promoted to reduce polarization voltage, the effects of inhibiting dendrite growth and hydrogen evolution side reaction are achieved, and the cycle life and the safety of the zinc ion battery are greatly improved. The carboxymethyl chitosan introduces a large number of carboxyl groups with different functional sites, the carboxyl groups and zinc ions carry out complexation reaction, and the zinc ions are transmitted on the zinc metal anode interface through different complexation sites, so that the desolvation activation energy of the hydrated zinc ions is reduced, and the ion conductivity is improved.
Preferably, the concentration of the chitosan solution is 10-30g/L; further preferably, the concentration of the chitosan solution is 10-25g/L; in some preferred embodiments of the invention, the chitosan solution has a concentration of 14.3g/L.
Preferably, the current of the electrified electrolysis is 0.01-0.06A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Further preferably, the current of the electrified electrolysis is 0.02-0.05A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the In some preferred embodiments of the invention, the current of the energized electrolysis is 0.02A/cm 2 。
Preferably, the time of the electrified electrolysis is 30-180s; further preferably, the time of the electrified electrolysis is 60-100s; in some preferred embodiments of the invention, the time of the energized electrolysis is 60 seconds.
Preferably, after the electrified electrolysis, the zinc foil is taken out, washed by water and dried for 8-16 hours at 20-40 ℃; in some preferred embodiments of the invention, after the galvanic electrolysis, the zinc foil is removed, rinsed with water and dried at 30 ℃ for 12 hours.
Preferably, the counter electrode comprises one of titanium foil, carbon cloth and carbon paper; further preferably, the counter electrode is a titanium foil; the material of the counter electrode of the present invention is not limited to the above-listed electrode materials.
The second aspect of the invention provides a zinc anode, which is prepared by the preparation method.
Preferably, the zinc cathode comprises zinc foil and a protective layer attached to the surface of the zinc foil, wherein the protective layer comprises chitosan zinc formed by reacting zinc with chitosan, and the thickness of the protective layer is 15-60 mu m.
The surface of the zinc anode provided by the invention is provided with a hole structure, and the diameter of the hole is 30-80 mu m.
When the electrolyte is carboxymethyl chitosan solution, the main component of the formed protective coating is carboxymethyl chitosan zinc formed by the reaction of zinc ions generated by the dissolution of zinc metal and carboxymethyl chitosan in the solution.
In a third aspect, the invention provides a zinc cell comprising the zinc anode.
Preferably, the positive electrode material of the zinc cell comprises one of manganese dioxide and ammonium vanadate. The anode suitable for water system zinc ions can be assembled with the invention. The common positive electrode materials of manganese dioxide and ammonium vanadate are matched with the invention to assemble the full battery, and have excellent battery performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention constructs an organic protective layer on the surface of the zinc negative electrode by simply externally adding direct current, has an effective protective effect on the zinc metal negative electrode, does not appear in the report of the front edge, is different from the conventional protective layer preparation process, can construct a protective layer with ideal thickness on the surface of the zinc metal negative electrode without using materials such as adhesive and the like, and greatly reduces the production cost in practical production. The process is not limited to preparing the carboxymethyl chitosan zinc protective layer, can also prepare the amino chitosan zinc protective layer, the sulfonated chitosan zinc protective layer and the like, has a wide application range, and can also be applied to other fields.
(2) The invention controls the thickness of the generated coating by adjusting the concentration of electrolyte, the magnitude of constant current value and the electrifying time, the coating is provided with a large number of amino groups and hydroxyl groups, a hydrophilic gel network is constructed on the surface of the zinc cathode, the coordination effect of the amino groups and the hydroxyl groups and zinc ions in the electrolyte regulates and controls the uniform deposition of the zinc ions in the charging process of the zinc ion battery, and the growth of zinc dendrites is inhibited.
(3) According to the invention, the transmission of the carboxymethyl chitosan and zinc ions on the zinc metal anode interface is realized through different complexing sites, so that the desolvation activation energy of the hydrated zinc ions is reduced, and the ion conductivity is improved. And the porous structure inside the coating and the large specific surface area morphology of the surface reduce polarization voltage and promote the charge and discharge efficiency of the battery. On one hand, the carboxyl of the carboxymethyl chitosan can react with a zinc sheet, and the firm chemical bond enables the protective layer to have strong adhesion with the zinc negative electrode, so that the stability of an interface is ensured in long circulation, and the prepared zinc metal negative electrode can realize uniform deposition and stripping processes; on the other hand, the carboxymethyl chitosan can carry out complexation reaction with zinc ions under the action of an electric field, so that the film is directly formed on a zinc cathode, and the zinc ions can migrate through different complexation sites with carboxyl functional groups, so that extremely high ionic conductivity is displayed, the generation of zinc dendrites and the generation of hydrogen are effectively inhibited, and the cycle stability and the safety performance of the battery are obviously improved.
Drawings
FIG. 1 is a schematic illustration of the preparation of example 1;
FIG. 2 is a scanning electron micrograph of a zinc metal anode prepared in example 1;
FIG. 3 is a graph of the different elemental profiles (zinc, carbon, oxygen, nitrogen) of the zinc metal anode prepared in example 1;
FIG. 4 is a zinc metal symmetric cell prepared in example 1 at a current density of 0.5mA cm -2 The deposition density is 0.5mAh cm -2 Is a cyclic curve of (2);
FIG. 5 is a scanning electron micrograph of the zinc metal negative electrode prepared in example 1 after 50 cycles;
FIG. 6 is a high resolution confocal laser microscopy photograph of a zinc metal negative electrode prepared in example 1;
FIG. 7 is a graph showing that the zinc metal symmetric cell prepared in comparative example 1 has a current density of 0.5mA cm -2 The deposition density is 0.5mAh cm -2 Is a cyclic curve of (2);
FIG. 8 is a scanning electron micrograph of the zinc metal anode prepared in comparative example 1 after 50 cycles;
FIG. 9 is a graph of the electrochemical performance of a full cell paired with manganese dioxide of example 1;
FIG. 10 is a graph of the electrochemical performance of a full cell paired with ammonium vanadate for example 1;
FIG. 11 is the results of electrochemical impedance spectroscopy at various temperature test conditions for the zinc metal anode prepared in example 1;
FIG. 12 is the results of electrochemical impedance spectroscopy at various temperature test conditions for the zinc metal anode prepared in comparative example 1;
FIG. 13 is a zinc ion desolvation activation energy calculated according to the Arrhenius equation;
fig. 14 is the electrochemical impedance spectroscopy test results of the zinc anode protective coating prepared in example 1.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Example 1
1g of carboxymethyl chitosan powder is weighed and dissolved in 70mL of water, stirred until the mixture is uniformly clarified, and placed for standby. Wiping the surface of the metal zinc foil with alcohol, drying the surface, clamping the zinc foil by using a crocodile clip, and connecting to the positive electrode of a direct current power supply; a titanium foil is selected as a counter electrode, and is clamped by using an alligator clip and connected to the negative electrode of a direct current power supply. Immersing both electrodes in electrolyte, and introducing 0.02A/cm 2 After 60 seconds, the power was stopped, the zinc foil was removed, the surface was rinsed three times with deionized water, and dried at 30 c for 12 hours to give example 1.
The electrode of the embodiment is composed of a zinc metal negative electrode and a composite coating, the preparation schematic diagram is shown in fig. 1, fig. 2 shows that a compact network structure is formed on the surface of the zinc foil and a certain hole exists, the specific surface area of the electrode is increased by the regular and porous morphology, fig. 3 proves that the carboxymethyl chitosan zinc protective layer is prepared in the electric spinning process and uniformly distributed, and fig. 6 shows that the hole size in the protective layer is 50um. Fig. 9 is a cycle time-voltage diagram of the present example assembled symmetric battery, which is seen to have excellent cycle stability and long cycle life. Fig. 5 is a scanning electron microscope image of the present example after 50 cycles, showing that zinc metal deposition on the surface of the zinc anode was dense and uniform and no sign of zinc dendrites.
After immersing the zinc anode prepared in example 1 in 0.1mol/L sodium bicarbonate at 10 ℃ for 24 hours, the zinc anode prepared in example 1 was dyed with 5- (4, 6-dichlorotriazinyl) amino fluorescein solution for 24 hours, the pole piece was repeatedly cleaned, and the surface holes of the zinc anode coating were observed by using a high-resolution laser confocal microscope, as shown in fig. 6.
The electrochemical performance test of the full cell was performed by using ammonium vanadate as the positive electrode, zinc metal prepared in example 1 as the negative electrode, 2mol/L zinc sulfate aqueous solution as the electrolyte, and a glass fiber membrane of Whatman as the separator, as shown in FIG. 10.
The coating of the zinc metal anode of example 1 was used as a test object, and the resistance (as shown in fig. 14) was measured using an electrochemical impedance spectrum tester, and the thickness and area of the anode were measured. The ionic conductivity of the coating was calculated according to the formula σ=l/(r×s) to give a protective layer of example 1 having a conductivity of 0.11mS/cm -2 。
Example 2
1.2g of the aminated chitosan powder is weighed and dissolved in 100mL of water, stirred until the mixture is uniformly clarified, and placed for standby. Wiping the surface of the metal zinc foil with alcohol, drying the surface, clamping the zinc foil by using a crocodile clip, and connecting to the positive electrode of a direct current power supply; a titanium foil is selected as a counter electrode, and is clamped by using an alligator clip and connected to the negative electrode of a direct current power supply. Immersing both electrodes in electrolyte, and introducing 0.02A/cm 2 After 60 seconds, the power was stopped, the zinc foil was removed, the surface was rinsed three times with deionized water, and dried at 30 c for 12 hours to give example 2.
Example 3
2g of sulfochitosan powder is weighed and dissolved in 80mL of water, stirred until the mixture is uniformly clarified, and placed for standby. Wiping with alcoholDrying the surface of the metal zinc foil after the surface is dried, clamping the zinc foil by using a crocodile clip, and connecting the metal zinc foil to the positive electrode of a direct current power supply; a titanium foil is selected as a counter electrode, and is clamped by using an alligator clip and connected to the negative electrode of a direct current power supply. Immersing both electrodes in electrolyte, and introducing 0.05A/cm 2 After 100 seconds, the power was stopped, the zinc foil was removed, the surface was rinsed three times with deionized water, and dried at 30 c for 24 hours to give example 3.
Comparative example 1
The zinc foil was cleaned with alcohol and dried to give a zinc metal negative electrode of comparative example 1. The zinc metal assembly is used for forming a battery, and the test condition is that the current density is 0.5mA/cm 2 And a deposition/dissolution capacity of 0.5mA/cm 2 When the test results are shown in fig. 7, it can be seen that the common zinc metal negative electrode has poor cycle stability and short service life. The scanning electron microscope photograph of the electrode surface after 50 cycles is shown in fig. 8, and the result shows that zinc metal deposition on the zinc metal surface is uneven, the roughness is high, and a large amount of zinc dendrites are generated in the cycle process.
Comparative example 2
1.4g of chitosan powder was weighed and dissolved in 100mL of dilute hydrochloric acid (0.1 mol/L), and 57.5g of ZnSO was added 4 ·7H 2 And (3) stirring until the mixture is uniformly clarified, and standing for later use. Wiping the surface of the metal zinc foil with alcohol, drying the surface, clamping the zinc foil by using a crocodile clip, and connecting to the positive electrode of a direct current power supply; a titanium foil is selected as a counter electrode, and is clamped by using an alligator clip and connected to the negative electrode of a direct current power supply. Immersing both electrodes in electrolyte, and introducing 0.01A/cm 2 After 90 seconds, the power supply was stopped, the zinc foil was taken out, the surface was rinsed three times with deionized water, and dried at 60 ℃ for 12 hours, to obtain comparative example 2.
The zinc metal anodes prepared in example 1 and comparative example 1, respectively, were assembled into a pair of batteries, the battery impedance was tested under different temperature test conditions (30, 40, 50, 60, 70 degrees celsius), and the data were fit (as shown in fig. 11, 12) and desolvation activation energy of zinc ions was calculated using the arrhenius equation, as shown in fig. 13. It can be seen that the addition of the natural polymer protective layer greatly reduces the desolvation activation energy of zinc ions.
The above electrode was used as a negative electrode, and a battery was assembled with a manganese dioxide positive electrode, and the charge/discharge performance was measured, and the results were shown in table 1 below.
TABLE 1
As can be seen from the above table, the transverse comparison data of examples 1, 2 and 3 with comparative examples 1 and 2, respectively, demonstrate that the electrochemical performance of zinc metal anodes prepared by functionalized chitosan monomers is superior to electrodes prepared by water-soluble chitosan alone without a protective layer.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (10)
1. The preparation method of the zinc anode is characterized by comprising the following steps of:
taking chitosan solution as electrolyte, connecting zinc foil with a positive electrode of a power supply, connecting a counter electrode with a negative electrode of the power supply, and electrifying the zinc foil after electrolysis to obtain the zinc negative electrode;
the solute in the chitosan solution comprises at least one of carboxymethyl chitosan, aminated chitosan and sulfonated chitosan.
2. The method for preparing a zinc anode according to claim 1, wherein the concentration of the chitosan solution is 10-30g/L.
3. The method for producing a zinc anode according to claim 1, wherein the current for electrolysis by energization is 0.01 to 0.06A/cm 2 。
4. The method for producing a zinc anode according to claim 1, wherein the time of the electrolysis under energization is 30 to 180 seconds.
5. The method for producing a zinc anode according to claim 1, wherein after the electrolysis by energization, the zinc foil is taken out, rinsed with water, and dried at 20 to 40 ℃ for 8 to 16 hours.
6. The method for producing a zinc anode according to claim 1, wherein the counter electrode comprises one of titanium foil, carbon cloth, and carbon paper.
7. A zinc anode, characterized in that the zinc anode is prepared by the preparation method according to any one of claims 1 to 6.
8. The zinc anode according to claim 7, wherein the zinc anode comprises a zinc foil and a protective layer attached to the surface of the zinc foil, the protective layer comprises chitosan zinc formed by reacting zinc with chitosan, and the thickness of the protective layer is 15-60 μm.
9. A zinc cell, characterized in that it comprises a zinc anode according to claim 7 or 8.
10. The zinc cell of claim 9, wherein the positive electrode material of the zinc cell comprises one of manganese dioxide and ammonium vanadate.
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