CN113991086B - Zinc ion battery negative electrode composite material and preparation method and application thereof - Google Patents

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

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CN113991086B
CN113991086B CN202111261459.3A CN202111261459A CN113991086B CN 113991086 B CN113991086 B CN 113991086B CN 202111261459 A CN202111261459 A CN 202111261459A CN 113991086 B CN113991086 B CN 113991086B
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zinc
chitosan
ion battery
composite material
carbon black
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CN113991086A (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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method of a zinc ion battery negative electrode composite material, which comprises the following steps: mixing chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent to obtain slurry; and (3) scraping the slurry on the surface of zinc foil, and drying to obtain the zinc ion battery negative electrode composite material. According to the invention, chitosan is adopted in the preparation of the zinc ion battery cathode composite material, and is rich in amino and hydroxyl, and insoluble in water, so that the chitosan has a certain adsorption effect on hydrogen ions in electrolyte, and can weaken the transmission of the hydrogen ions to the surface of zinc foil when the battery is charged, inhibit side reaction, effectively prolong the cycle life of the battery and enhance the cycle stability of the battery; and carbon black is used as a conductive agent in a matching way, when the battery is charged and discharged, an electric double layer can be formed, the transmission rate of zinc ions is accelerated, the overpotential during zinc ion deposition is reduced, the surface current density and the overpotential of the zinc foil are further reduced, and the growth of dendrites is effectively inhibited.

Description

Zinc ion battery negative electrode 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 negative electrode composite material, a preparation method and application thereof.
Background
The secondary battery is an important research direction in the current energy field, and the water-based zinc ion battery is considered as an energy storage device with great prospect due to the advantages of low cost, ecological friendliness, high safety and the like. The metal zinc has sufficient resources and higher specific energy and energy density, is very suitable for the cathode of the battery, but in the water-based zinc ion battery, the zinc cathode still faces the problems of dendrite growth, hydrogen evolution, passivation and the like. The competing reaction of hydrogen evolution reaction can reduce coulomb efficiency during charging and discharging, can form bubbles on the surface of an electrode, can improve overpotential, can increase the concentration of hydroxyl on the surface of the electrode, and can generate a byproduct of basic zincate. In addition, the alkaline environment on the surface of the electrode also brings about passivation problem, so that the electric field on the surface of the electrode is unevenly distributed, thereby leading to uneven transmission rate of zinc ions, and further accelerating the growth of dendrites. It is important to fundamentally inhibit the hydrogen evolution reaction. At present, the current research on the negative electrode of the zinc ion battery mainly reduces the current density of the surface of the negative electrode through surface modification so as to inhibit the growth of dendrites, and the negative electrode is rarely designed and prepared from the aspect of inhibiting hydrogen evolution reaction. Therefore, how to prepare a zinc ion battery negative electrode composite material capable of effectively inhibiting hydrogen evolution reaction is a problem to be solved urgently.
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 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.
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 negative electrode composite material, which comprises the following steps:
(1) Mixing chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent to obtain slurry;
(2) And (3) scraping the slurry obtained in the step (1) on the surface of zinc foil, 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 carbon black in the step (1) has a particle diameter of 50 to 200nm.
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 to 100 μm.
Preferably, the thickness of the zinc foil in the step (2) is 0.1-0.3 mm, and the thickness of the doctor-blading slurry is 200-500 μm.
The invention also provides the zinc ion battery negative electrode composite material prepared by the preparation method.
The invention also provides application of the zinc ion battery negative electrode composite material in a zinc ion battery.
The invention provides a preparation method of a zinc ion battery negative electrode composite material, which comprises the following steps: mixing chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent to obtain slurry; and (3) scraping the slurry on the surface of zinc foil, and drying to obtain the zinc ion battery negative electrode composite material. According to the invention, chitosan is adopted in the preparation of the zinc ion battery cathode composite material, and is rich in amino and hydroxyl, and insoluble in water, so that the chitosan has a certain adsorption effect on hydrogen ions in electrolyte, and can weaken the transmission of the hydrogen ions to the surface of zinc foil when the battery is charged, inhibit side reaction, effectively prolong the cycle life of the battery and enhance the cycle stability of the battery; and carbon black is used as a conductive agent in a matching way, when the battery is charged and discharged, an electric double layer can be formed, 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 current density of the zinc ion battery cathode composite material prepared by the preparation method provided by the invention in the symmetrical battery is 0.25mA/cm -2 、0.05mAh/cm -2 The cycle time is greater than 480 hours under the test conditions of (c).
Drawings
FIG. 1 is an SEM image of the Bare-Zn of comparative example 1;
FIG. 2 is an SEM image of the CTC/Zn prepared in example 1;
FIG. 3 is an SEM image of zinc foil after removal of the coating after CTC/Zn has been subjected to magnification test in application example 1;
FIG. 4 is an SEM image of the Bare-Zn composition of comparative example 1 after magnification test;
FIG. 5 shows that the symmetrical cells prepared in application example 1 and comparative example 1 were at 0.25mA/cm -2 、0.05mAh/cm -2 Performance comparison graph under test conditions;
FIG. 6 is a graph showing the ratio performance of the symmetrical batteries prepared in application example 1 and comparative example 1;
FIG. 7 is an XRD pattern of CTC/Zn in application example 1 and Bare-Zn in comparative example 1 after magnification test;
FIG. 8 is Tafel curves of CTC/Zn in application example 1 and Bare-Zn in comparative example 1;
FIG. 9 is a LSV curve measured for CTC/Zn in application example 1 and for Bare-Zn in comparative example 1.
Detailed Description
The invention provides a preparation method of a zinc ion battery negative electrode composite material, which comprises the following steps:
(1) Mixing chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent to obtain slurry;
(2) And (3) scraping the slurry obtained in the step (1) on the surface of zinc foil, and drying to obtain the zinc ion battery negative electrode composite material.
According to the invention, chitosan, carbon black, polyvinylidene fluoride powder and an organic solvent are mixed to obtain slurry.
In the present invention, the operation of mixing the chitosan, carbon black, polyvinylidene fluoride powder and organic solvent preferably comprises the steps of:
1) Mixing chitosan, carbon black and polyvinylidene fluoride powder to obtain mixed powder;
2) And (3) mixing the mixed powder obtained in the step (1) with an organic solvent to obtain slurry.
In the invention, chitosan, carbon black and polyvinylidene fluoride powder are preferably mixed to obtain mixed powder.
In the present invention, the particle size of the chitosan is preferably 30 to 150 μm; the mass of the chitosan is preferably 50 to 80% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder, and more preferably 60 to 70%. 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 dendrites 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 due to excessive chitosan is avoided, and the weak adsorption effect on hydrogen ions due to insufficient chitosan is avoided, so that the effect of inhibiting side reactions is difficult to achieve.
In the present invention, the particle diameter of the carbon black is preferably 50 to 200nm; the mass of the carbon black is preferably 10 to 45% of the total mass of the chitosan, carbon black and polyvinylidene fluoride powder, more preferably 20 to 30%. The invention can further reduce the current density and overpotential of the surface of the zinc foil by controlling the dosage of the carbon black, effectively inhibit the growth of dendrites, prevent the generation of large-size bubbles on the surface of the zinc foil, and avoid the slow transmission rate of zinc ions in the coating caused by too little carbon black, and the weak adsorption effect of the carbon black on hydrogen ions caused by too much carbon black, thereby hardly achieving the effect of inhibiting side reactions.
In the present invention, the particle size of the polyvinylidene fluoride powder is preferably 20 to 100 μm; the mass of the polyvinylidene fluoride powder is preferably 5 to 10% of the total mass of chitosan, carbon black and polyvinylidene fluoride powder, more preferably 8 to 10%. In the present 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 milling time is preferably 30 to 120 minutes, more preferably 30 to 50 minutes. The source of the mortar is not particularly limited, and an instrument 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 the chitosan and the carbon black are unevenly mixed to cause different zinc ion transmission rates is avoided, and dendrite is easily generated.
After the mixed powder is obtained, the present invention preferably mixes the mixed powder with an organic solvent to obtain a 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 (0.5-1.5) mL:100mg, more preferably (0.8 to 1.2) mL:100mg. In the present invention, the organic solvent is used to dissolve the powder to prepare a slurry.
In the present invention, the mode of mixing the mixed powder and the organic solvent is preferably grinding; the time for the grinding is preferably 20 to 40 minutes, more preferably 30 to 35 minutes. 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 sizing agent is obtained, the sizing agent is coated on the surface of zinc foil in a scraping way and then dried, and the zinc ion battery cathode composite material is obtained.
In the present invention, the zinc foil is preferably subjected to a pretreatment prior to use; the pretreatment is preferably carried out by sequentially carrying out deionized water washing, ethanol washing, ultrasonic treatment and natural drying.
The pretreatment operation is not particularly limited, and may be performed by any operation known to those skilled in the art.
In the present invention, the thickness of the zinc foil is preferably 0.1 to 0.3mm, more preferably 0.2mm; the thickness of the blade-coated slurry is preferably 200 to 500. Mu.m. The specific process of the blade coating is not particularly limited, and a blade coating process well known to those skilled in the art may be adopted.
In the present invention, the drying is preferably drying. In the present invention, the temperature of the drying is preferably 60 to 80 ℃, more preferably 70 to 80 ℃; the drying time is preferably 5 to 10 hours, more preferably 8 to 10 hours.
The sources of the above raw materials are not particularly limited, and commercially available products known to those skilled in the art may be used.
According to the invention, chitosan is adopted in the preparation of the zinc ion battery cathode composite material, and is rich in amino and hydroxyl, and insoluble in water, so that the chitosan has a certain adsorption effect on hydrogen ions in electrolyte, and can weaken the transmission of the hydrogen ions to the surface of zinc foil when the battery is charged, inhibit side reaction, effectively prolong the cycle life of the battery and enhance the cycle stability of the battery; and carbon black is used as a conductive agent in a matching way, when the battery is charged and discharged, an electric double layer can be formed, 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, easy industrialization and effective inhibition of growth of zinc negative pole dendrite and side reaction.
The invention also provides the zinc ion battery negative electrode composite material prepared by the preparation method.
The zinc ion battery negative electrode composite material provided by the invention can effectively inhibit hydrogen evolution reaction and reduce the generation of byproducts.
The invention also provides application of the zinc ion battery negative electrode composite material in a zinc ion battery.
The operation of the application of the zinc ion battery negative electrode composite material in the zinc ion battery is not particularly limited, and the operation well known to the person skilled in the art can be adopted.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the zinc ion battery cathode composite material comprises the following steps:
(1) Adding 60mg of chitosan (particle size of 30-150 mu m) and 30mg of carbon black (particle size of 50-200 nm) into a mortar, and dry-grinding 10mg of polyvinylidene fluoride powder (particle size of 20-100 mu m) for 30min to obtain mixed powder;
(2) Adding 0.8mLNMP 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 0.8mL:100mg;
(3) Uniformly scraping the slurry obtained in the step (2) on zinc foil which is washed by deionized water and ethanol, ultrasonically cleaned, naturally dried and has the thickness of 0.3mm, then placing the zinc foil into an oven at 80 ℃ for 8 hours, drying the zinc foil, taking out the zinc foil to obtain a zinc ion battery negative electrode composite material, and marking the zinc ion battery negative electrode composite material as CTC/Zn; wherein the blade coating thickness is 300 μm.
Example 2
The preparation method of the zinc ion battery cathode composite material comprises the following steps:
(1) Adding 70mg of chitosan (particle size of 30-150 mu m) and 20mg of carbon black (particle size of 50-200 nm) into a mortar, and dry-grinding 10mg of polyvinylidene fluoride powder (particle size of 20-100 mu m) for 30min to obtain mixed powder;
(2) Adding 0.8mLNMP 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 0.8mL:100mg;
(3) Uniformly scraping the slurry obtained in the step (2) on zinc foil which is washed by deionized water and ethanol, ultrasonically cleaned, naturally dried and has the thickness of 0.3mm, then placing the zinc foil into an oven at 80 ℃ for 8 hours, drying the zinc foil, taking out the zinc foil to obtain a zinc ion battery negative electrode composite material, and marking the zinc ion battery negative electrode composite material as CTC/Zn; wherein the blade coating thickness is 300 μm.
Example 3
The preparation method of the zinc ion battery cathode composite material comprises the following steps:
(1) Adding 80mg of chitosan (particle size of 30-150 mu m) and 10mg of carbon black (particle size of 50-200 nm) into a mortar, and dry-grinding 10mg of polyvinylidene fluoride powder (particle size of 20-100 mu m) for 30min to obtain mixed powder;
(2) Adding 0.8mLNMP 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 0.8mL:100mg;
(3) Uniformly scraping the slurry obtained in the step (2) on zinc foil which is washed by deionized water and ethanol, ultrasonically cleaned, naturally dried and has the thickness of 0.3mm, then placing the zinc foil into an oven at 80 ℃ for 8 hours, drying the zinc foil, taking out the zinc foil to obtain a zinc ion battery negative electrode composite material, and marking the zinc ion battery negative electrode composite material as CTC/Zn; wherein the blade coating thickness is 300 μm.
Application example 1
The CTC/Zn prepared in example 1 was used as both positive and negative electrodes, glass fiber as separator, 3M ZnSO 4 And (3) packaging a battery shell with the model CR2032 serving as electrolyte to prepare the symmetrical battery.
Application example 2
The CTC/Zn prepared in example 2 was used as both positive and negative electrodes, glass fiber as separator, 3M ZnSO 4 And (3) packaging a battery shell with the model CR2032 serving as electrolyte to prepare the symmetrical battery.
Application example 3
The CTC/Zn prepared in example 3 was used as both positive and negative electrodes, glass fiber as separator, 3M ZnSO 4 And (3) packaging a battery shell with the model CR2032 serving as electrolyte to prepare the symmetrical battery.
Comparative example 1
Zinc foil (marked as Bare-Zn) is used as positive and negative electrodes, glass fiber is used as diaphragm, 3M ZnSO is used 4 And (3) packaging a battery shell with the model CR2032 serving as electrolyte to prepare the symmetrical battery.
SEM of CTC/Zn prepared in example 1 is shown in FIG. 1; an SEM image of the Bare-Zn powder in comparative example 1 is shown in FIG. 2.
As can be seen from fig. 1 and 2, the chitosan carbon black composite material in CTC/Zn prepared in example 1 has been successfully coated on the surface of zinc foil.
SEM image of CTC/Zn of application example 1 after magnification test is shown in FIG. 3; SEM images of the Bare-Zn of comparative example 1 after magnification test are shown in fig. 4.
It can be seen from FIGS. 3 and 4 that dendrite generation is evident on the surface of the bar-Zn after cycling, and that no dendrite generation is evident on the surface of the zinc foil after charge and discharge cycling with CTC/Zn as positive and negative electrodes.
Symmetrical cells prepared in application example 1 and comparative example 1 were measured at 0.25mA/cm -2 、0.05mAh/cm -2 A comparison of the performance under the test conditions of (c) 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 200 hours of cycle; the positive and negative electrodes in application example 1 were allowed to circulate steadily for 475 hours with an overpotential of 80mV, which is lower than the circulating overpotential (132 mV) of the zinc foil in comparative example 1.
The ratio performance comparison chart 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 of the symmetrical cell prepared in comparative example 1 had a current value of 5mA/cm after being cycled -2 Short-circuiting already occurs at that time; 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 electrodes have better ploidy.
XRD patterns of CTC/Zn in application example 1 and Bare-Zn in comparative example 1 after magnification test are shown in FIG. 7.
As can be seen from fig. 7, the XRD pattern of Bare-Zn after the magnification test has a new characteristic peak of basic sulfuric acid, and the XRD pattern of CTC/Zn has no obvious characteristic peak, which verifies that chitosan can inhibit the formation 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 lower corrosion current.
The 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, hydrogen evolution reaction is less likely to occur, confirming the interaction between chitosan and hydrogen ions.
The symmetric electrodes prepared in application examples 2 and 3 were measured at 0.25mA/cm -2 、0.05mAh/cm -2 The cycle time did not occur at 480h under the test conditions of (c).
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 by-product generation.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The preparation method of the 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) The sizing agent obtained in the step (1) is coated on the surface of zinc foil in a scraping way and then dried, so that the zinc ion battery cathode composite material is obtained; the zinc foil is pretreated before use;
the mass of the chitosan in the step (1) is 60-70% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder;
the mass of the carbon black in the step (1) is 20-30% of the total mass of the chitosan, the carbon black and the polyvinylidene fluoride powder;
the mass of the polyvinylidene fluoride powder in the step (1) is 8-10% of the total mass of chitosan, carbon black and polyvinylidene fluoride powder;
the operation of mixing the chitosan, the carbon black, the polyvinylidene fluoride powder and the organic solvent comprises the following steps:
1) Mixing chitosan, carbon black and polyvinylidene fluoride powder under a dry grinding condition to obtain mixed powder;
2) And (3) mixing the mixed powder obtained in the step (1) with an organic solvent to obtain slurry.
2. The preparation method of claim 1, wherein the particle size of the chitosan in the step (1) is 30-150 μm.
3. The preparation method of claim 1, wherein the particle size of the carbon black in the step (1) is 50-200 nm.
4. The method according to claim 1, wherein the particle size of the polyvinylidene fluoride powder in the step (1) is 20 to 100 μm.
5. The method according to claim 1, wherein the thickness of the zinc foil in the step (2) is 0.1-0.3 mm, and the thickness of the doctor-blading slurry is 200-500 μm.
6. A zinc ion battery negative electrode composite material prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the zinc-ion battery negative electrode composite material according to claim 6 in a zinc-ion battery.
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