A negative electrode material modified with a polymer, and its preparation method and application

Abstract

The present invention discloses a negative electrode material modified with a polymer, a preparation method and an application thereof, wherein the negative electrode material comprises titanium disulfide and a polymer embedded between titanium disulfide layers; the polymer is polypyrrole, polyaniline or polythiophene. Traditional zinc ion batteries generally use metallic zinc as the negative electrode. Although metallic zinc has the characteristics of good conductivity, low toxicity and high specific energy, it is easy to form dendrites during the charge and discharge cycle of the battery, piercing the diaphragm and causing the battery to short-circuit, thereby affecting the cycle life of the battery. The negative electrode material provided by the present invention is obtained by modifying the titanium disulfide interlayer with a polymer. When used in aqueous zinc ion batteries, it not only avoids the zinc dendrite problem caused by using metallic zinc as the negative electrode material, but also can effectively improve the battery's specific capacity, cycle stability and rate capability, thereby extending the service life of the aqueous zinc ion battery and expanding the scope of application of the aqueous zinc ion battery.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical energy storage devices, and more particularly to a negative electrode material modified with a polymer, a preparation method thereof, and applications thereof. Background Art

[0002] As a highly efficient energy storage device, secondary batteries are widely used in fields such as mobile communications and electric vehicles. Currently, the most widely used secondary battery in commercial applications is lithium-ion battery. However, due to the high cost of lithium resources, low safety and supply risks, it is not suitable for application in large-scale power grid energy technology. Compared with lithium-ion batteries, zinc-based ion batteries are a good alternative because they have higher capacity (two-electron reaction), lower cost, and more moderate redox potential (-0.762V vs. H / H + ). Therefore, the development of rechargeable zinc-ion batteries has become an urgent and attractive task nowadays.

[0003] Aqueous zinc-ion batteries (AZBs), based on water-based electrolytes, are a new energy storage system with lower cost, higher safety, and greater cost-effectiveness, and are expected to replace existing energy storage technologies. Unlike organic electrolytes, aqueous electrolytes have a narrower stable potential window, necessitating careful consideration of water decomposition when selecting electrode materials for AZBs. In principle, cathode materials such as MnO2, V2O5, and organic materials, as well as anode materials such as TiS2 and metallic zinc, have reaction potentials above the water decomposition potential, making them suitable electrode materials for AZBs. Furthermore, within the voltage range of hydrogen decomposition from water, a low-potential Zn-accepting anode and a high-potential Zn-donating anode can theoretically form an AZB. However, conventional ZnBs typically use metallic zinc as the anode, which boasts excellent conductivity, low toxicity, and high specific energy. However, dendrites are prone to forming during charge-discharge cycling, piercing the separator and causing short circuits, thus impacting the battery's cycle life. Therefore, the development of new, high-performance anode materials is of great significance. Summary of the Invention

[0004] The first object of the present invention is to provide a negative electrode material modified with a polymer.

[0005] The second object of the present invention is to provide a method for preparing a negative electrode material modified with a polymer.

[0006] The third object of the present invention is to provide an application of a negative electrode material modified with a polymer in an aqueous zinc ion battery.

[0007] A fourth object of the present invention is to provide an aqueous zinc ion battery.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a negative electrode material modified with a polymer, wherein the negative electrode material comprises titanium disulfide and a polymer embedded between titanium disulfide layers; the polymer is polypyrrole, polyaniline or polythiophene.

[0010] Titanium disulfide (TiS2) has an excellent layered structure and can be used as the negative electrode material of aqueous zinc ion batteries to reversibly store zinc ions. The present invention found that the use of polymer in situ embedding strategy can not only promote the Zn 2+ The embedding kinetics of Zn can be improved and Zn can be stored for a long time. 2+ , and then using it as the negative electrode material of aqueous zinc ion batteries can effectively improve the cycle stability and rate performance of aqueous zinc ion batteries. Among them, the polymer in situ embedding strategy mainly promotes the Zn in TiS2 from the following aspects. 2+ Embedment dynamics: First, polymer embedding can construct a significantly larger interlayer distance between TiS2 layers, thus facilitating the Zn 2+ Provides a convenient diffusion channel; secondly, the polymer selected by the present invention has a unique π conjugated structure, which can effectively prevent Zn 2+ With subject S 2- The electrostatic interaction between Zn 2+ Diffusion dynamics; Thirdly, the present invention shows through simulation methods such as first principle calculation that polymer embedded in TiS2 interlayer can significantly reduce Zn 2+ With subject S 2- The binding energy between Zn 2+ Reaction kinetics of TiS2 intercalation.

[0011] Furthermore, in the negative electrode material, the mass fraction of the polymer is 1%-50%. The present invention has discovered that the cycle stability and rate performance of aqueous zinc-ion batteries are not directly proportional to the mass fraction of the polymer in the negative electrode material. Only within the range of the present invention can the mass fraction of the polymer in the negative electrode material effectively improve the cycle stability and rate performance of aqueous zinc-ion batteries. Preferably, the mass fraction of the polymer is 1%-20%; more preferably, the mass fraction of the polymer is 1%-10%. This mass fraction of polymer can further improve the cycle stability and rate performance of aqueous zinc-ion batteries.

[0012] Furthermore, the degree of polymerization of the polymer is less than 10000. If the degree of polymerization of the polymer is too high, it will affect its successful embedding between titanium disulfide layers. As a further preferred embodiment of the present invention, the degree of polymerization of the polymer is 1000-3000.

[0013] In a second aspect, the present invention provides a method for preparing a negative electrode material modified with a polymer, comprising the following steps:

[0014] The titanium disulfide is placed in an oxidant solution and subjected to an ultrasonic treatment once, and then a polymer monomer is added and subjected to a second ultrasonic treatment to obtain the product.

[0015] Furthermore, in the above method, the oxidant includes ferric chloride or ammonium persulfate.

[0016] The concentration of the oxidant solution is 0.0005-0.5 M. The present invention has found that if the concentration of the oxidant solution is too low, most of the polymer is coated on the surface of titanium disulfide and is difficult to embed between the titanium disulfide layers. Preferably, the concentration of the oxidant solution is 0.05-0.5 M. The oxidant solution within this concentration range can promote more polymer embedding between the titanium disulfide layers.

[0017] The duration of the ultrasonic treatment is 0.1-1 hour. The ultrasonic treatment can not only make the titanium disulfide layer structure clear, but also make more oxidants adhere to the titanium disulfide layer.

[0018] The second ultrasonic treatment lasts for 0.5-12 hours, wherein the second ultrasonic treatment can promote more polymers to be embedded in the titanium disulfide interlayer.

[0019] After the secondary ultrasonic treatment, washing and drying are further performed, wherein the washing is performed by sequentially washing with deionized water and ethanol for at least 3 times.

[0020] In a third aspect, the present invention provides an application of the above-mentioned negative electrode material in an aqueous zinc ion battery.

[0021] In a fourth aspect, the present invention provides an aqueous zinc ion battery.

[0022] Furthermore, the aqueous zinc ion battery includes a negative electrode material, a positive electrode material, an electrolyte and a separator; wherein the negative electrode material is the above-mentioned negative electrode material modified with a polymer.

[0023] Furthermore, the positive electrode material is pre-embedded zinc manganese dioxide or pre-embedded zinc vanadium pentoxide (pre-embedded zinc manganese dioxide or pre-embedded zinc vanadium pentoxide can be prepared according to existing methods. According to a specific embodiment of the present invention, the specific method comprises the following steps: preparing manganese dioxide or vanadium pentoxide by a liquid phase redox method, mixing manganese dioxide or vanadium pentoxide with conductive carbon black and a binder in a mass ratio of 8:1:1 to form a slurry, and then coating the slurry on a graphite paper current collector to make an electrode sheet. The electrode sheets are assembled into batteries with metal zinc negative electrodes and then subjected to a constant current discharge test, wherein the manganese dioxide electrode is discharged to 1.0V and stopped to obtain pre-embedded zinc manganese dioxide (ZnMnO2), or the vanadium pentoxide electrode is discharged to 0.3V and stopped to obtain pre-embedded zinc vanadium pentoxide (Zn2V2O5). Finally, the battery is disassembled to obtain the electrode material of pre-embedded zinc manganese dioxide or pre-embedded zinc vanadium pentoxide; the electrolyte is a soluble salt containing zinc.

[0024] Preferably, the positive electrode material is manganese dioxide pre-embedded with zinc; and the soluble zinc-containing salt is zinc sulfate or zinc trifluoromethanesulfonate.

[0025] In addition, unless otherwise specified, any range described herein includes the endpoints and any values ​​between the endpoints, as well as any subranges formed by the endpoints or any values ​​between the endpoints. The preparation methods herein are all conventional methods unless otherwise specified, and the raw materials used are all commercially available or prepared according to prior art unless otherwise specified. The percentages are all mass percentages unless otherwise specified, and the solutions are all aqueous solutions unless otherwise specified.

[0026] The beneficial effects of the present invention are as follows:

[0027] The negative electrode material provided by the present invention is obtained by modifying the titanium disulfide layer by embedding a polymer. When used in aqueous zinc-ion batteries, the negative electrode material can not only avoid the zinc dendrite problem caused by using metallic zinc as the negative electrode material, but also effectively improve the battery's specific capacity, cycle stability, and rate capability, thereby extending the service life of the aqueous zinc-ion battery, expanding the scope of application of the aqueous zinc-ion battery, and laying the foundation for the promotion and application of electrochemical energy storage devices.

[0028] The method for preparing the negative electrode material provided by the present invention has cheap and readily available raw materials, a simple process, and convenient operation, and is suitable for large-scale production applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0030] Figure 1 A graph showing the cycle performance test of the aqueous zinc ion battery 1 of Example 1 is shown.

[0031] Figure 2 A comparison chart showing the specific capacities of the aqueous zinc ion battery 1 and the aqueous zinc ion battery 2 of Example 1 at different current densities is shown. DETAILED DESCRIPTION

[0032] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the following detailed description is illustrative rather than restrictive and should not be used to limit the scope of protection of the present invention.

[0033] Example 1

[0034] (1) Preparing a negative electrode material modified with a polymer, comprising the following steps:

[0035] TiS2 was added to a 0.1M FeCl3 solution and ultrasonicated for 0.5 hours. Then 0.1mL of pyrrole monomer was added and ultrasonicated for 3 hours. The resulting product was washed with deionized water and ethanol at least 3 times and then dried to obtain a negative electrode material modified with a polymer, wherein the polymer accounted for 5wt% of the negative electrode material and the degree of polymerization of polypyrrole was 2000.

[0036] (2) Assembly of aqueous zinc ion batteries

[0037] Assembly of Aqueous Zinc Ion Battery 1: The negative electrode material was the polymer-modified negative electrode material prepared in this example, and the positive electrode material was zinc-pre-embedded manganese dioxide. The positive and negative electrode materials were mixed in a weight ratio of 8 / 1 / 1 to form positive and negative electrode slurries. The positive electrode slurry was coated on titanium foil, and the negative electrode slurry was coated on carbon-coated aluminum foil. After drying, the electrodes were formed. The aqueous zinc ion battery was then assembled. The separator used in the battery was a glass fiber (GFF) separator, and the electrolyte was 2M zinc sulfate.

[0038] Assembly of Aqueous Zinc-Ion Battery 2: The negative electrode material is TiS2, and the positive electrode material is zinc-embedded manganese dioxide. A positive and negative electrode slurry is prepared by mixing the materials in a weight ratio of 8:1:1. The positive electrode slurry is coated on titanium foil, and the negative electrode slurry is coated on carbon-coated aluminum foil. After drying, the electrodes are assembled into an aqueous zinc-ion battery. The separator used in this battery is a glass fiber (GFF) membrane, and the electrolyte is 2M zinc sulfate.

[0039] (3) Performance testing

[0040] 1) The aqueous zinc ion battery 1 was subjected to charge and discharge tests at 0.8-2 V, a current density of 1 A / g, and cycled 3000 times at room temperature, with a capacity retention rate of 94% (e.g. Figure 1 shown).

[0041] 2) The aqueous zinc ion batteries 1 and 2 were subjected to charge and discharge tests at 0.8-2 V, with current densities of 0.1 A / g, 0.3 A / g, 0.5 A / g, 1 A / g, 5 A / g, 10 A / g and 0.1 A / g, respectively (e.g. Figure 2 (As shown). At a current density of 0.1 A / g, the specific capacities of aqueous zinc-ion batteries 1 and 2 were 280 mAh / g and 260 mAh / g, respectively. At a current density of 10 A / g, the specific capacity of aqueous zinc-ion battery 1 was 36% of that at 0.1 A / g, while the specific capacity of aqueous zinc-ion battery 2 was 15% of that at 0.1 A / g. This indicates that the polymer-intercalated anode material has a higher specific capacity than the unmodified one.

[0042] Example 2

[0043] (1) Preparing a negative electrode material modified with a polymer, comprising the following steps:

[0044] TiS2 was added to a 0.1M FeCl3 solution and ultrasonicated for 0.5 hours. Then 0.1mL of aniline monomer was added and ultrasonicated for 3 hours. The resulting product was washed with deionized water and ethanol at least 3 times and then dried to obtain a negative electrode material modified with a polymer, wherein the polymer accounted for 5wt% of the negative electrode material and the degree of polymerization of polypyrrole was 1000.

[0045] (2) Assembly of aqueous zinc ion batteries

[0046] The negative electrode material was the polymer-modified negative electrode material prepared in this example, and the positive electrode material was zinc-embedded manganese dioxide. The positive and negative electrode materials were mixed in a weight ratio of 8:1:1 for carbon black and PVDF, respectively. The positive electrode slurry was coated on titanium foil, and the negative electrode slurry was coated on carbon-coated aluminum foil. After drying, the electrodes were assembled into an aqueous zinc-ion battery. The separator used in the battery was a glass fiber (GFF) separator, and the electrolyte was 2M zinc sulfate.

[0047] (3) Performance testing

[0048] 1) The aqueous zinc ion battery of this embodiment was subjected to charge and discharge tests at 0.8-2 V, a current density of 1 A / g, and 3000 cycles at room temperature, with a capacity retention rate of 95%.

[0049] 2) The aqueous zinc ion battery of this example was subjected to charge and discharge tests at 0.8-2 V, with current densities of 0.1 A / g, 0.3 A / g, 0.5 A / g, 1 A / g, 5 A / g, 10 A / g, and 0.1 A / g. At a current density of 0.1 A / g, the battery system had a specific capacity of 285 mAh / g; at a current density of 10 A / g, the specific capacity of the battery system was 35% of that at 0.1 A / g.

[0050] Example 3

[0051] (1) Preparing a negative electrode material modified with a polymer, comprising the following steps:

[0052] TiS2 was added to a 0.1M FeCl3 solution and ultrasonicated for 0.5 hours. Then 0.1mL of thiophene monomer was added and ultrasonicated for 3 hours. The resulting product was washed with deionized water and ethanol at least 3 times and then dried to obtain a negative electrode material modified with a polymer, wherein the polymer accounted for 5wt% of the negative electrode material and the degree of polymerization of polypyrrole was 1500.

[0053] (2) Assembly of aqueous zinc ion batteries

[0054] The negative electrode material was the polymer-modified negative electrode material prepared in this example, and the positive electrode material was zinc-pre-embedded manganese dioxide. The positive and negative electrode slurries were mixed in a weight ratio of 8:1:1 for positive / negative electrode material / carbon black / PVDF, respectively. The positive electrode slurry was coated on titanium foil, and the negative electrode slurry was coated on carbon-coated aluminum foil. After drying, the electrodes were assembled into an aqueous zinc-ion battery. The separator used in the battery was a glass fiber (GFF) separator, and the electrolyte was 2M zinc sulfate.

[0055] (3) Performance testing

[0056] 1) The aqueous zinc ion battery of this embodiment was subjected to charge and discharge tests at 0.8-2 V, a current density of 1 A / g, and 3000 cycles at room temperature, with a capacity retention rate of 90%.

[0057] 2) The aqueous zinc ion battery of this example was subjected to charge and discharge tests at 0.8-2 V, with current densities of 0.1 A / g, 0.3 A / g, 0.5 A / g, 1 A / g, 5 A / g, 10 A / g, and 0.1 A / g. At a current density of 0.1 A / g, the battery system had a specific capacity of 270 mAh / g; at a current density of 10 A / g, the specific capacity of the battery system was 33% of that at 0.1 A / g.

[0058] Example 4

[0059] (1) Preparing a negative electrode material modified with a polymer, comprising the following steps:

[0060] TiS2 was added to a 0.1M FeCl3 solution and ultrasonicated for 0.5 hours. Then 0.1mL of thiophene monomer was added and ultrasonicated for 3 hours. The resulting product was washed with deionized water and ethanol at least 3 times and then dried to obtain a negative electrode material modified with a polymer, wherein the polymer accounted for 5wt% of the negative electrode material and the degree of polymerization of polypyrrole was 1500.

[0061] (2) Assembly of aqueous zinc ion batteries

[0062] Assembly of Aqueous Zinc Ion Battery 1: The negative electrode material was the polymer-modified negative electrode material prepared in this example, and the positive electrode material was zinc-pre-embedded manganese dioxide. The positive and negative electrode materials were mixed in a weight ratio of 8 / 1 / 1 to form positive and negative electrode slurries. The positive electrode slurry was coated on titanium foil, and the negative electrode slurry was coated on carbon-coated aluminum foil. After drying, the electrodes were formed. The aqueous zinc ion battery was then assembled. The separator used in the battery was a glass fiber (GFF) separator, and the electrolyte was 3M zinc trifluoromethanesulfonate.

[0063] Assembly of Aqueous Zinc-Ion Battery 2: The negative electrode material is TiS2, and the positive electrode material is zinc-embedded manganese dioxide. A slurry is prepared by mixing the positive and negative electrode materials in a weight ratio of 8:1:1. The positive electrode slurry is coated on titanium foil, and the negative electrode slurry is coated on carbon-coated aluminum foil. After drying, the electrodes are assembled into an aqueous zinc-ion battery. The separator used in this battery is glass fiber (GFF) and the electrolyte is 3M zinc trifluoromethanesulfonate.

[0064] (3) Performance testing

[0065] 1) The aqueous zinc ion battery 1 of this embodiment was subjected to a charge and discharge test at 0.8-2 V, a current density of 1 A / g, and 3000 cycles at room temperature, with a capacity retention rate of 90%.

[0066] 2) The aqueous zinc ion batteries 1 and 2 of this embodiment were subjected to charge and discharge tests at 0.8-2V, with current densities of 0.1A / g, 0.3A / g, 0.5A / g, 1A / g, 5A / g, 10A / g, and 0.1A / g, respectively. At a current density of 0.1A / g, the specific capacities of aqueous zinc ion batteries 1 and 2 were 265mAh / g and 250mAh / g, respectively. At a current density of 10A / g, the specific capacity of aqueous zinc ion battery 1 was 31% of that at 0.1A / g, while the specific capacity of aqueous zinc ion battery 2 was 12% of that at 0.1A / g.

[0067] Example 5

[0068] (1) The steps for preparing the negative electrode material modified with the polymer are the same as those in Example 1 except that 0.1 M FeCl 3 is replaced by 0.1 M (NH 4 ) 2 S 2 O 8 , and the other conditions remain unchanged.

[0069] (2) Assembly of aqueous zinc ion batteries

[0070] The negative electrode material was the polymer-modified negative electrode material prepared in this example, and the positive electrode material was zinc-embedded manganese dioxide. The positive and negative electrode materials were mixed in a weight ratio of 8:1:1 for carbon black and PVDF, respectively. The positive electrode slurry was coated on titanium foil, and the negative electrode slurry was coated on carbon-coated aluminum foil. After drying, the electrodes were assembled into an aqueous zinc-ion battery. The separator used in the battery was a glass fiber (GFF) separator, and the electrolyte was 2M zinc sulfate.

[0071] (3) Performance testing

[0072] 1) The aqueous zinc ion battery of this embodiment was subjected to charge and discharge tests at 0.8-2 V, a current density of 1 A / g, and 3000 cycles at room temperature, with a capacity retention rate of 92%.

[0073] 2) The aqueous zinc ion battery of this embodiment was subjected to charge and discharge tests at 0.8-2 V, with current densities of 0.1 A / g, 0.3 A / g, 0.5 A / g, 1 A / g, 5 A / g, 10 A / g, and 0.1 A / g. At a current density of 0.1 A / g, the battery system had a specific capacity of 278 mAh / g; at a current density of 10 A / g, the specific capacity of the battery system was 35% of that at 0.1 A / g.

[0074] Comparative Example 1

[0075] (1) The steps for preparing the polymer-modified negative electrode material differed from those in Example 2 only in that the aniline monomer was replaced with a 3,4-ethylenedioxythiophene monomer. In the resulting polymer-modified negative electrode material, the polymer accounted for 5 wt % of the negative electrode material, and the degree of polymerization of poly(3,4-ethylenedioxythiophene) was 1000.

[0076] (2) Assembly of aqueous zinc ion batteries

[0077] The negative electrode material was the polymer-modified negative electrode material prepared in this example, and the positive electrode material was zinc-pre-embedded manganese dioxide. The positive and negative electrode slurries were mixed in a weight ratio of 8:1:1 for positive / negative electrode material / carbon black / PVDF, respectively. The positive electrode slurry was coated on titanium foil, and the negative electrode slurry was coated on carbon-coated aluminum foil. After drying, the electrodes were assembled into an aqueous zinc-ion battery using a glass fiber (GFF) separator and 2M zinc sulfate as the electrolyte.

[0078] (3) Performance testing

[0079] The aqueous zinc ion battery of this example was subjected to charge and discharge tests at 0.8-2V, a current density of 1A / g, and cycled 3000 times at room temperature, with a capacity retention rate of only 25%.

[0080] The above results show that only when the specific polymer of the present invention is embedded in the titanium disulfide layer can a negative electrode material with improved specific capacity, good cycle stability and good rate capability be obtained.

[0081] Comparative Example 2

[0082] The only difference from Example 1 is that the liquid phase polymerization reaction in step (1) is replaced by a gas phase polymerization reaction, which specifically includes the following steps:

[0083] TiS2 was placed in a 0.1 M FeCl3 solution and fully soaked, then filtered and dried and placed in a 2 mL sealed container containing gaseous pyrrole monomer for gas phase polymerization.

[0084] The results showed that gas phase polymerization could not embed polypyrrole between titanium disulfide layers.

[0085] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

Claims

1. A negative electrode material modified with a polymer, characterized in that: The negative electrode material is used in an aqueous zinc ion battery, and the negative electrode material comprises titanium disulfide and a polymer embedded between titanium disulfide layers; the polymer is polypyrrole, polyaniline or polythiophene; The mass fraction of the polymer is 1%-50%; the degree of polymerization of the polymer is less than 10,000; The negative electrode material is prepared by the following steps: Titanium disulfide is placed in an oxidant solution and subjected to an ultrasonic treatment, and then a polymer monomer is added and subjected to a second ultrasonic treatment to obtain the product; The oxidant includes ferric chloride or ammonium persulfate; The time of the first ultrasonic treatment is 0.1-1 hour; the time of the second ultrasonic treatment is 0.5-12 hours; The concentration of the oxidant solution is 0.0005-0.5M.

2. A method for preparing the negative electrode material according to claim 1, characterized in that: The negative electrode material is used in an aqueous zinc ion battery, comprising the following steps: Titanium disulfide is placed in an oxidant solution and subjected to an ultrasonic treatment, and then a polymer monomer is added and subjected to a second ultrasonic treatment to obtain the product; The oxidizing agent includes ferric chloride or ammonium persulfate; The time of the first ultrasonic treatment is 0.1-1 hour; the time of the second ultrasonic treatment is 0.5-12 hours; The concentration of the oxidant solution is 0.0005-0.5M.

3. The preparation method according to claim 2, characterized in that After the secondary ultrasonic treatment, washing and drying are further performed, wherein the washing is performed by sequentially washing with deionized water and ethanol for at least 3 times.

4. Use of the negative electrode material according to claim 1 in an aqueous zinc ion battery.

5. An aqueous zinc ion battery, characterized in that The aqueous zinc ion battery comprises a negative electrode material, a positive electrode material, an electrolyte and a separator; wherein the negative electrode material is the negative electrode material according to claim 1.

6. The aqueous zinc ion battery according to claim 5, wherein The positive electrode material is manganese dioxide pre-embedded with zinc or vanadium pentoxide pre-embedded with zinc; and the electrolyte is a soluble salt containing zinc.

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