CN113991086A - Zinc ion battery cathode composite material and preparation method and application thereof - Google Patents

Zinc ion battery cathode composite material and preparation method and application thereof Download PDF

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CN113991086A
CN113991086A CN202111261459.3A CN202111261459A CN113991086A CN 113991086 A CN113991086 A CN 113991086A CN 202111261459 A CN202111261459 A CN 202111261459A CN 113991086 A CN113991086 A CN 113991086A
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zinc
ion battery
chitosan
zinc ion
composite material
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CN113991086B (en
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李兴华
马晓格
刘明庄
邵长路
刘益春
李晓伟
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Northeast Normal University
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/604—Polymers containing aliphatic main chain polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a preparation method of a zinc ion battery cathode composite material, which comprises the following steps: mixing chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent to obtain slurry; and scraping and coating the slurry on the surface of a zinc foil, and drying to obtain the zinc ion battery negative electrode composite material. According to the invention, chitosan is adopted when the zinc ion battery cathode composite material is prepared, and the chitosan has abundant amino and hydroxyl groups, is insoluble in water, and has a certain adsorption effect on hydrogen ions in the electrolyte, so that the transmission of the hydrogen ions to the surface of a zinc foil can be weakened, the occurrence of side reactions can be inhibited, the cycle life of the battery can be effectively prolonged, and the cycle stability of the battery can be enhanced; and carbon black is used in a matching way and is used as a conductive agent, so that a double electric layer can be formed during charging and discharging of the battery, the transmission rate of zinc ions is accelerated, and the overpotential during zinc ion deposition is reduced, so that the current density and the overpotential on the surface of the zinc foil are further reduced, and the growth of dendritic crystals is effectively inhibited.

Description

Zinc ion battery cathode composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of zinc ion batteries, in particular to a zinc ion battery cathode composite material and a preparation method and application thereof.
Background
The secondary battery is an important research direction in the current energy field, and the water system zinc ion battery is considered to be an energy storage device with great prospect due to the advantages of low cost, eco-friendliness, high safety and the like. The zinc metal has sufficient resources and higher specific energy and energy density, and is very suitable for the cathode of the battery, but in the water system zinc ion battery, the zinc cathode still faces the problems of dendritic crystal growth, hydrogen evolution, passivation and the like. Among them, the competing reaction of hydrogen evolution reduces the coulombic efficiency during charging and discharging, forms bubbles on the surface of the electrode, increases the overpotential, increases the concentration of hydroxyl on the surface of the electrode, and generates the basic zincate as a byproduct. In addition, the alkaline environment on the surface of the electrode can bring passivation problems, so that the electric field distribution on the surface of the electrode is uneven, the transmission rate of zinc ions is uneven, and the growth of dendritic crystals is further accelerated. It is important to fundamentally suppress the hydrogen evolution reaction. At present, the current research related to the zinc ion battery cathode is mainly to reduce the current density on the surface of the cathode through surface modification, so that the growth of dendrites is inhibited, and the cathode is rarely designed and prepared from the aspect of inhibiting the hydrogen evolution reaction. Therefore, how to prepare a zinc ion battery cathode composite material capable of effectively inhibiting hydrogen evolution reaction becomes an urgent problem to be solved.
Disclosure of Invention
The invention aims to provide a zinc ion battery negative electrode composite material, and a preparation method and application thereof. The zinc ion battery cathode composite material prepared by the preparation method provided by the invention can effectively inhibit hydrogen evolution reaction and reduce the generation of byproducts.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a zinc ion battery cathode composite material, which comprises the following steps:
(1) mixing chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent to obtain slurry;
(2) and (2) coating the slurry obtained in the step (1) on the surface of a zinc foil by scraping, and drying to obtain the zinc ion battery negative electrode composite material.
Preferably, the mass of the chitosan in the step (1) is 50-80% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder.
Preferably, the particle size of the chitosan in the step (1) is 30-150 μm.
Preferably, the mass of the carbon black in the step (1) is 10-45% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder.
Preferably, the particle size of the carbon black in the step (1) is 50-200 nm.
Preferably, the mass of the polyvinylidene fluoride powder in the step (1) is 5-10% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder.
Preferably, the particle size of the polyvinylidene fluoride powder in the step (1) is 20-100 μm.
Preferably, the thickness of the zinc foil in the step (2) is 0.1-0.3 mm, and the thickness of the blade-coated slurry is 200-500 μm.
The invention also provides the zinc ion battery cathode composite material prepared by the preparation method of the technical scheme.
The invention also provides the application of the zinc ion battery cathode composite material in the technical scheme in a zinc ion battery.
The invention provides a preparation method of a zinc ion battery cathode composite material, which comprises the following steps: mixing chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent to obtain slurry; and scraping and coating the slurry on the surface of a zinc foil, and drying to obtain the zinc ion battery negative electrode composite material. The invention prepares zinc ionsThe chitosan is adopted when the cathode composite material of the sub-battery is used, and has abundant amino and hydroxyl groups, is insoluble in water, and has a certain adsorption effect on hydrogen ions in the electrolyte, so that the transmission of the hydrogen ions to the surface of a zinc foil can be weakened, the occurrence of side reactions can be inhibited, the cycle life of the battery can be effectively prolonged, and the cycle stability of the battery can be enhanced when the battery is charged; and carbon black is used in cooperation as a conductive agent, so that a double electric layer can be formed during charging and discharging of the battery, the transmission rate of zinc ions is accelerated, and the overpotential during zinc ion deposition is reduced, so that the current density and the overpotential on the surface of the zinc foil are further reduced, the growth of dendrites is effectively inhibited, and the generation of large-size bubbles on the surface of the zinc foil is prevented. Experimental results show that the zinc ion battery cathode composite material prepared by the preparation method provided by the invention has a symmetrical battery current density of 0.25mA/cm-2、0.05mAh/cm-2The cycle time under the test conditions of (3) is greater than 480 hours.
Drawings
FIG. 1 is an SEM photograph of Bare-Zn in comparative example 1;
FIG. 2 is an SEM image of CTC/Zn prepared in example 1;
FIG. 3 is an SEM image of a zinc foil after removal of a coating after a multiplying power test of CTC/Zn in application example 1;
FIG. 4 is an SEM image of Bare-Zn in comparative example 1 after a magnification test;
FIG. 5 shows the results of the comparative example 1 and the application example 1, wherein the cell density of the symmetrical cell was 0.25mA/cm-2、0.05mAh/cm-2A performance comparison chart under the test conditions of (1);
FIG. 6 is a graph comparing rate performance of symmetrical batteries prepared in application example 1 and comparative example 1;
FIG. 7 is XRD patterns of CTC/Zn in application example 1 and Bare-Zn in comparative example 1 after a rate test;
FIG. 8 is a Tafel plot for CTC/Zn in application example 1 and Bare-Zn in comparative example 1;
FIG. 9 shows LSV curves measured for CTC/Zn in application example 1 and Bare-Zn in comparative example 1.
Detailed Description
The invention provides a preparation method of a zinc ion battery cathode composite material, which comprises the following steps:
(1) mixing chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent to obtain slurry;
(2) and (2) coating the slurry obtained in the step (1) on the surface of a zinc foil by scraping, and drying to obtain the zinc ion battery negative electrode composite material.
The invention mixes chitosan, carbon black, polyvinylidene fluoride powder and organic solvent to obtain slurry.
In the present invention, the mixing of the chitosan, the carbon black, the polyvinylidene fluoride powder and the organic solvent preferably comprises the steps of:
1) mixing chitosan, carbon black and polyvinylidene fluoride powder to obtain mixed powder;
2) mixing the mixed powder obtained in the step 1) with an organic solvent to obtain slurry.
According to the invention, chitosan, carbon black and polyvinylidene fluoride powder are preferably mixed to obtain mixed powder.
In the invention, the particle size of the chitosan is preferably 30-150 μm; the mass of the chitosan is preferably 50-80%, and more preferably 60-70% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder. According to the invention, the current density and overpotential on the surface of the zinc foil can be further reduced by controlling the dosage of chitosan, the growth of dendritic crystals is effectively inhibited, the generation of large-size bubbles on the surface of the zinc foil is prevented, the slow transmission rate of zinc ions in a coating layer caused by excessive chitosan is avoided, and the weak adsorption effect on hydrogen ions caused by too little chitosan is avoided, so that the effect of inhibiting side reactions is hardly achieved.
In the invention, the particle size of the carbon black is preferably 50-200 nm; the mass of the carbon black is preferably 10-45% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder, and more preferably 20-30%. According to the invention, the current density and overpotential on the surface of the zinc foil can be further reduced by controlling the using amount of the carbon black, the growth of dendritic crystals is effectively inhibited, the generation of large-size bubbles on the surface of the zinc foil is prevented, the slow transmission rate of zinc ions in a coating layer caused by too little carbon black and the weak adsorption effect on hydrogen ions caused by too much carbon black are avoided, and thus the effect of inhibiting side reactions is hardly achieved.
In the invention, the particle size of the polyvinylidene fluoride powder is preferably 20-100 μm; the mass of the polyvinylidene fluoride powder is preferably 5-10% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder, and more preferably 8-10%. In the invention, the polyvinylidene fluoride powder is a binder.
In the present invention, the mixing of the chitosan, carbon black and polyvinylidene fluoride powder is preferably performed under dry milling conditions; the dry-milling is preferably carried out in a mortar; the dry grinding time is preferably 30-120 min, and more preferably 30-50 min. The source of the mortar is not particularly limited in the present invention, and an apparatus well known to those skilled in the art may be used. According to the invention, the dry grinding can fully contact and uniformly mix the chitosan and the carbon black, so that the phenomenon that zinc ions are transmitted at different rates due to nonuniform mixing of the chitosan and the carbon black, and dendritic crystals are easily generated is avoided.
After the mixed powder is obtained, the mixed powder is preferably mixed with an organic solvent to obtain slurry.
In the present invention, the organic solvent is preferably N-methylpyrrolidone (NMP); the ratio of the volume of the organic solvent to the mass of the mixed powder is preferably (0.5 to 1.5) mL: 100mg, more preferably (0.8 to 1.2) mL: 100 mg. In the invention, the organic solvent is used for dissolving the powder to prepare the slurry.
In the present invention, the mixed powder and the organic solvent are preferably mixed by grinding; the grinding time is preferably 20-40 min, and more preferably 30-35 min. The invention can realize the uniform mixing of all raw materials in the slurry by controlling the grinding time, thereby being beneficial to the subsequent blade coating.
After the slurry is obtained, the slurry is coated on the surface of a zinc foil by scraping and then dried, and the zinc ion battery negative electrode composite material is obtained.
In the present invention, the zinc foil is preferably subjected to a pretreatment before use; the pretreatment is preferably carried out by deionized water washing, ethanol washing, ultrasonic treatment and natural airing in sequence.
In the present invention, the pretreatment operation is not particularly limited, and an operation known to those skilled in the art may be used.
In the invention, the thickness of the zinc foil is preferably 0.1-0.3 mm, and more preferably 0.2 mm; the thickness of the blade-coated slurry is preferably 200-500 mu m. The invention is not limited to any particular coating process, and any coating process known to those skilled in the art may be used.
In the present invention, the drying is preferably oven drying. In the invention, the drying temperature is preferably 60-80 ℃, and more preferably 70-80 ℃; the drying time is preferably 5-10 h, and more preferably 8-10 h.
The sources of the above raw materials are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
According to the invention, chitosan is adopted when the zinc ion battery cathode composite material is prepared, and the chitosan has abundant amino and hydroxyl groups, is insoluble in water, and has a certain adsorption effect on hydrogen ions in the electrolyte, so that the transmission of the hydrogen ions to the surface of a zinc foil can be weakened, the occurrence of side reactions can be inhibited, the cycle life of the battery can be effectively prolonged, and the cycle stability of the battery can be enhanced; and carbon black is used in cooperation as a conductive agent, so that a double electric layer can be formed during charging and discharging of the battery, the transmission rate of zinc ions is accelerated, and the overpotential during zinc ion deposition is reduced, so that the current density and the overpotential on the surface of the zinc foil are further reduced, the growth of dendrites is effectively inhibited, and the generation of large-size bubbles on the surface of the zinc foil is prevented.
The preparation method provided by the invention has the advantages of simple process operation, universal method, easy control of conditions and easy industrialization, and can effectively inhibit the growth of zinc cathode dendrites and the occurrence of side reactions.
The invention also provides the zinc ion battery cathode composite material prepared by the preparation method of the technical scheme.
The zinc ion battery cathode composite material provided by the invention can effectively inhibit hydrogen evolution reaction and reduce the generation of byproducts.
The invention also provides the application of the zinc ion battery cathode composite material in the technical scheme in a zinc ion battery.
The operation of the zinc ion battery negative electrode composite material in the zinc ion battery is not particularly limited, and the operation known by the person skilled in the art can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the zinc ion battery cathode composite material comprises the following steps:
(1) adding 60mg of chitosan (with the particle size of 30-150 mu m), 30mg of carbon black (with the particle size of 50-200 nm) and 10mg of polyvinylidene fluoride powder (with the particle size of 20-100 mu m) into a mortar, and dry-grinding for 30min for mixing to obtain mixed powder;
(2) adding 0.8ml of NMP into the mixed powder obtained in the step (1), and continuously grinding for 30min to obtain slurry; the ratio of the volume of the organic solvent to the mass of the mixed powder is 0.8 mL: 100 mg;
(3) uniformly blade-coating the slurry obtained in the step (2) on a zinc foil which is washed by deionized water and ethanol and is ultrasonically cleaned, then naturally airing the zinc foil with the thickness of 0.3mm, then putting the zinc foil into an oven at 80 ℃ for drying for 8h, and taking out the zinc ion battery negative electrode composite material which is marked as CTC/Zn; wherein the blade coating thickness was 300. mu.m.
Example 2
The preparation method of the zinc ion battery cathode composite material comprises the following steps:
(1) adding 70mg of chitosan (with the particle size of 30-150 mu m), 20mg of carbon black (with the particle size of 50-200 nm) and 10mg of polyvinylidene fluoride powder (with the particle size of 20-100 mu m) into a mortar, and dry-grinding for 30min for mixing to obtain mixed powder;
(2) adding 0.8ml of NMP into the mixed powder obtained in the step (1), and continuously grinding for 30min to obtain slurry; the ratio of the volume of the organic solvent to the mass of the mixed powder is 0.8 mL: 100 mg;
(3) uniformly blade-coating the slurry obtained in the step (2) on a zinc foil which is washed by deionized water and ethanol and is ultrasonically cleaned, then naturally airing the zinc foil with the thickness of 0.3mm, then putting the zinc foil into an oven at 80 ℃ for drying for 8h, and taking out the zinc ion battery negative electrode composite material which is marked as CTC/Zn; wherein the blade coating thickness was 300. mu.m.
Example 3
The preparation method of the zinc ion battery cathode composite material comprises the following steps:
(1) adding 80mg of chitosan (with the particle size of 30-150 mu m), 10mg of carbon black (with the particle size of 50-200 nm) and 10mg of polyvinylidene fluoride powder (with the particle size of 20-100 mu m) into a mortar, and dry-grinding for 30min for mixing to obtain mixed powder;
(2) adding 0.8ml of NMP into the mixed powder obtained in the step (1), and continuously grinding for 30min to obtain slurry; the ratio of the volume of the organic solvent to the mass of the mixed powder is 0.8 mL: 100 mg;
(3) uniformly blade-coating the slurry obtained in the step (2) on a zinc foil which is washed by deionized water and ethanol and is ultrasonically cleaned, then naturally airing the zinc foil with the thickness of 0.3mm, then putting the zinc foil into an oven at 80 ℃ for drying for 8h, and taking out the zinc ion battery negative electrode composite material which is marked as CTC/Zn; wherein the blade coating thickness was 300. mu.m.
Application example 1
The CTC/Zn prepared in example 1 was used as the positive and negative electrodes, the glass fiber was used as the separator, and 3M ZnSO was used4As an electrolyte, a symmetrical battery is packaged by a battery case with the model number of CR 2032.
Application example 2
The CTC/Zn prepared in example 2 was used as the positive and negative electrodes, the glass fiber was used as the separator, and 3M ZnSO was used4As an electrolyte, a symmetrical battery is packaged by a battery case with the model number of CR 2032.
Application example 3
The CTC/Zn prepared in example 3 was simultaneously used as the positive and negative electrodes,using glass fiber as a diaphragm and 3M ZnSO4As an electrolyte, a symmetrical battery is packaged by a battery case with the model number of CR 2032.
Comparative example 1
Zinc foil (note as Bare-Zn) as positive and negative electrodes, glass fiber as separator, and 3M ZnSO4As an electrolyte, a symmetrical battery is packaged by a battery case with the model number of CR 2032.
The SEM image of the CTC/Zn prepared in example 1 is shown in figure 1; SEM image of Bare-Zn in comparative example 1 is shown in FIG. 2.
As can be seen from FIGS. 1 and 2, the CTC/Zn chitosan carbon black composite prepared in example 1 has been successfully coated onto the surface of zinc foil.
An SEM image of the CTC/Zn in the application example 1 after a multiplying power test is shown in FIG. 3; the SEM image of Bare-Zn in comparative example 1 after the magnification test is shown in FIG. 4.
As can be seen from figures 3 and 4, dendritic crystal generation can be obviously seen on the surface of the Bare-Zn after cycling, and no obvious dendritic crystal generation is generated on the surface of the zinc foil after the CTC/Zn serving as a positive electrode and a negative electrode are subjected to charge-discharge cycling.
Application examples 1 and comparative example 1 symmetrical cells were prepared at 0.25mA/cm-2、0.05mAh/cm-2The comparative performance under the test conditions of (2) is shown in fig. 5.
As can be seen from fig. 5, the zinc foil in the symmetrical cell prepared in comparative example 1 was short-circuited after 200h cycling; the positive and negative electrodes in application example 1 were stable for 475 hours and had an overpotential of 80mV, which was lower than the cycling overpotential (132mV) of the zinc foil in comparative example 1.
A graph comparing the rate performance of the symmetrical batteries prepared in application example 1 and comparative example 1 is shown in fig. 6.
As can be seen from FIG. 6, the zinc foil in the symmetrical cell prepared in comparative example 1 was cycled to a current value of 5mA/cm-2Is short-circuited already; the positive and negative electrodes in application example 1 can still keep stable circulation at each current value when circulating from large current to small current, which shows that the electrode has better rate capability.
XRD patterns of CTC/Zn in application example 1 and Bare-Zn in comparative example 1 after magnification test are shown in figure 7.
As can be seen from FIG. 7, the XRD pattern of Bare-Zn after the multiplying power test has a new characteristic peak of basic sulfuric acid, and the XRD pattern of CTC/Zn has no obvious characteristic peak, which proves that the chitosan can inhibit the generation of byproducts by inhibiting the hydrogen evolution reaction.
Tafel curves for CTC/Zn in application example 1 and Bare-Zn in comparative example 1 are shown in FIG. 8.
As can be seen from fig. 8, CTC/Zn has a more positive corrosion potential and a lower corrosion current.
LSV curves measured for CTC/Zn in application example 1 and Bare-Zn in comparative example 1 are shown in FIG. 9.
As can be seen from FIG. 9, the hydrogen evolution potential of CTC/Zn is more negative and less prone to hydrogen evolution reaction, confirming the interaction between chitosan and hydrogen ions.
Symmetrical electrodes prepared in application examples 2 and 3 were placed at 0.25mA/cm-2、0.05mAh/cm-2Under the test conditions of (3), no short circuit occurred at 480 h.
As can be seen from the above examples, application examples and comparative examples, the zinc ion battery negative electrode composite material prepared by the preparation method provided by the invention can effectively inhibit hydrogen evolution reaction and reduce the generation of byproducts.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a zinc ion battery negative electrode composite material comprises the following steps:
(1) mixing chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent to obtain slurry;
(2) and (2) coating the slurry obtained in the step (1) on the surface of a zinc foil by scraping, and drying to obtain the zinc ion battery negative electrode composite material.
2. The method according to claim 1, wherein the mass of the chitosan in the step (1) is 50 to 80% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder.
3. The method according to claim 1 or 2, wherein the chitosan in the step (1) has a particle size of 30 to 150 μm.
4. The method according to claim 1, wherein the mass of the carbon black in the step (1) is 10 to 45% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder.
5. The method according to claim 1 or 4, wherein the carbon black in the step (1) has a particle size of 50 to 200 nm.
6. The method according to claim 1, wherein the mass of the polyvinylidene fluoride powder in the step (1) is 5 to 10% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder.
7. The method according to claim 1 or 6, wherein the particle size of the polyvinylidene fluoride powder in the step (1) is 20 to 100 μm.
8. The method according to claim 1, wherein the thickness of the zinc foil in the step (2) is 0.1 to 0.3mm, and the thickness of the spread slurry is 200 to 500 μm.
9. The zinc ion battery negative electrode composite material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the zinc ion battery negative electrode composite of claim 9 in a zinc ion battery.
CN202111261459.3A 2021-10-28 2021-10-28 Zinc ion battery negative electrode composite material and preparation method and application thereof Expired - Fee Related CN113991086B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114613980A (en) * 2022-03-30 2022-06-10 中南大学 Zinc ion battery composite negative electrode and preparation method and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5824434A (en) * 1992-11-30 1998-10-20 Canon Kabushiki Kaisha Secondary battery
US20040175624A1 (en) * 2001-08-20 2004-09-09 Power Paper Ltd. Thin layer electrochemical cell with self-formed separator
JP2014149993A (en) * 2013-02-01 2014-08-21 Nippon Shokubai Co Ltd Zinc negative electrode, battery and electrode base layer
JP2014154260A (en) * 2013-02-05 2014-08-25 Nippon Shokubai Co Ltd Zinc negative electrode mixture, zinc negative electrode and battery
CN106337194A (en) * 2016-09-26 2017-01-18 山东金宝电子股份有限公司 Surface treatment composite additive capable of improving corrosion resistance of copper foil
US20180114987A1 (en) * 2015-03-31 2018-04-26 Shenzhen Cubic-Science Co., Ltd. Rechargeable zinc ion battery with graphene oxide as positive electrode
US20190044145A1 (en) * 2017-08-04 2019-02-07 National Technology & Engineering Solutions Of Sandia, Llc Rechargeable copper and sulfur based electrodes for electrochemical applications
CN113054165A (en) * 2021-03-12 2021-06-29 国家纳米科学中心 Negative pole piece of zinc secondary battery and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5824434A (en) * 1992-11-30 1998-10-20 Canon Kabushiki Kaisha Secondary battery
US20040175624A1 (en) * 2001-08-20 2004-09-09 Power Paper Ltd. Thin layer electrochemical cell with self-formed separator
JP2014149993A (en) * 2013-02-01 2014-08-21 Nippon Shokubai Co Ltd Zinc negative electrode, battery and electrode base layer
JP2014154260A (en) * 2013-02-05 2014-08-25 Nippon Shokubai Co Ltd Zinc negative electrode mixture, zinc negative electrode and battery
US20180114987A1 (en) * 2015-03-31 2018-04-26 Shenzhen Cubic-Science Co., Ltd. Rechargeable zinc ion battery with graphene oxide as positive electrode
CN106337194A (en) * 2016-09-26 2017-01-18 山东金宝电子股份有限公司 Surface treatment composite additive capable of improving corrosion resistance of copper foil
US20190044145A1 (en) * 2017-08-04 2019-02-07 National Technology & Engineering Solutions Of Sandia, Llc Rechargeable copper and sulfur based electrodes for electrochemical applications
CN113054165A (en) * 2021-03-12 2021-06-29 国家纳米科学中心 Negative pole piece of zinc secondary battery and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114613980A (en) * 2022-03-30 2022-06-10 中南大学 Zinc ion battery composite negative electrode and preparation method and application thereof
CN114613980B (en) * 2022-03-30 2024-05-03 中南大学 Zinc ion battery composite negative electrode and preparation method and application thereof

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