WO2023125523A1 - Negative electrode material and application thereof - Google Patents

Abstract

Disclosed are a negative electrode material and an application thereof. The negative electrode material comprises: metal zinc, a binder, a conductive agent, and a negative electrode additive. The negative electrode additive comprises at least one of montmorillonite, kaolinite, bismuth oxide, tin oxide, zinc oxide, and zinc carbonate.

Description

Anode materials and their applications

priority information

This disclosure claims the priority of the Chinese patent application with the patent application number 202111625313.2 and the application title "Negative Electrode Material and Its Application" filed with the State Intellectual Property Office of China on December 28, 2021, and the entire contents of which are incorporated by reference in In this disclosure.

technical field

The disclosure belongs to the technical field of batteries, and in particular relates to a negative electrode material and its application.

Background technique

Aqueous zinc-ion batteries use abundant zinc as the negative electrode material and safe and environmentally friendly aqueous solution as the electrolyte, which has the advantages of low cost, safety and friendliness, and has the potential for large-scale application in energy storage, low-speed electric vehicles and other fields. However, zinc metal often has challenges such as dendrite growth, hydrogen evolution side reactions, and self-corrosion in weakly acidic electrolytes, which seriously affect the performance of zinc-ion batteries. In order to solve the above problems, researchers have invested a lot of energy in electrolyte additives, negative electrode surface modification and so on. However, there are relatively few studies on the effects of the composition of zinc anode conductive agents and additives on dendrite growth and hydrogen evolution side reactions.

The surface modification of the negative electrode is mainly based on artificial organic coatings and inorganic coatings. On the one hand, the structural stability of these coatings is insufficient, and on the other hand, it is difficult to control the uniformity of the coating. Insufficient coating uniformity can easily lead to local ion flow and electric field concentration, which can easily lead to rapid growth of local dendrites. In addition, the effectiveness of these strategies is often limited to low current densities (<1mA/cm ² ) and low areal capacity conditions (<1mA·h/cm ² ), and their applicability is insufficient.

Therefore, the existing negative electrode materials need to be improved.

public content

The present disclosure aims to solve one of the technical problems in the related art at least to a certain extent. Therefore, an object of the present disclosure is to propose a negative electrode material and its application. The negative electrode material can increase the hydrogen evolution overpotential of the negative electrode, suppress the generation of hydrogen gas during charging and discharging, thereby improving the stability of the negative electrode and at the same time increasing the internal ion density of the negative electrode. The migration and the uniformity of metal zinc dissolution/deposition can inhibit the formation of dendrites. Applying it to aqueous zinc-ion batteries can improve the stability and cycle life of aqueous zinc-ion batteries.

In one aspect of the present disclosure, the present disclosure provides a negative electrode material. According to an embodiment of the present disclosure, the negative electrode material includes: metal zinc, a binder, a conductive agent and a negative electrode additive,

Wherein, the negative electrode additive includes at least one of montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate.

According to the negative electrode material of the embodiment of the present disclosure, by mixing metal zinc, binder, conductive agent and negative electrode additive, wherein, the negative electrode additive includes at least one of montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate one. Montmorillonite is a natural silicate mineral with a typical layered structure and good cation (Zn ²⁺ , Ca ²⁺ , Li ⁺ , Na ⁺ , K ^{+ ,} etc.) Improve the migration of ions inside the negative electrode, the uniformity of the ion flow field and the uniformity of the dissolution/deposition of metal zinc. Kaolin, bismuth oxide, tin oxide, zinc oxide or zinc carbonate can increase the hydrogen evolution overpotential of the negative electrode, inhibit the generation of hydrogen gas during charge and discharge, and improve the stability of the negative electrode. Therefore, the negative electrode material can increase the hydrogen evolution overpotential of the negative electrode, suppress the generation of hydrogen gas during charge and discharge, thereby improving the stability of the negative electrode, and at the same time improve the migration of ions inside the negative electrode and the uniformity of metal zinc dissolution/deposition, and suppress dendrites. The formation of , and its application in the aqueous zinc-ion battery can improve the stability and cycle life of the aqueous zinc-ion battery.

In addition, the negative electrode material according to the above-mentioned embodiments of the present disclosure may also have the following additional technical features:

In some embodiments of the present disclosure, the mass ratio of the metal zinc, the binder, the conductive agent and the negative electrode additive is (78-85):(0.1-10):(0-10) : (0~10). Thereby, the generation of hydrogen gas and the formation of dendrites during charge and discharge can be suppressed.

In some embodiments of the present disclosure, the negative electrode additive includes montmorillonite and at least one selected from kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate. Thereby, the generation of hydrogen gas and the formation of dendrites during charge and discharge can be suppressed.

In a second aspect of the present disclosure, the present disclosure provides a negative electrode sheet. According to an embodiment of the present disclosure, the negative electrode sheet includes: a negative electrode current collector; a negative electrode sheet formed on the negative electrode current collector, wherein the negative electrode sheet is formed by pressing the above negative electrode material. As a result, the negative electrode has a good conductive network, which can improve the migration of internal ions and the uniformity of metal zinc dissolution/deposition, inhibit the formation of dendrites, and at the same time inhibit the generation of hydrogen gas during charge and discharge. On the battery, the stability and cycle life of the aqueous zinc-ion battery can be improved.

In addition, the negative electrode sheet according to the above-mentioned embodiments of the present disclosure may also have the following additional technical features:

In some embodiments of the present disclosure, the negative electrode current collector includes at least one of brass foil, red copper foil, stainless steel foil, copper mesh, stainless steel mesh and nickel foam.

In a third aspect of the present disclosure, the present disclosure provides an aqueous zinc-ion battery. According to an embodiment of the present disclosure, the water-based zinc-ion battery includes a positive electrode, a negative electrode, an electrolyte and a separator, wherein the negative electrode sheet is formed by pressing the above-mentioned negative electrode material. Thus, the stability and cycle life of the aqueous zinc-ion battery are improved.

In some embodiments of the present disclosure, the electrolytic solution includes a mixed aqueous solution of zinc salt and manganese salt.

In some embodiments of the present disclosure, the zinc salts include zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p- At least one of zinc tosylate and zinc isooctanoate;

In some embodiments of the present disclosure, the manganese salt includes at least one of manganese chloride, manganese sulfate and manganese nitrate.

In some embodiments of the present disclosure, the cation concentration in the mixed aqueous solution is 1.0˜2.0 moL·L ⁻¹ .

In some embodiments of the present disclosure, the separator includes at least one of a glass fiber separator, a non-woven fabric separator and a PP separator.

Additional aspects and advantages of the disclosure will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the disclosure.

Description of drawings

The above and/or additional aspects and advantages of the present disclosure will become apparent and comprehensible from the description of the embodiments in conjunction with the following drawings, in which:

Fig. 1 is the time-voltage graph of the battery that comparative example 1 obtains;

Fig. 2 is the surface SEM picture of dismantling the negative plate of the battery of embodiment 1 after 30 cycles of charge and discharge;

3 is a SEM image of the surface of the disassembled negative electrode sheet of the battery of Comparative Example 2 after 30 cycles of charging and discharging.

Detailed ways

The present disclosure will be described below with reference to specific embodiments. It should be noted that these embodiments are only illustrative and do not limit the present disclosure in any way.

In one aspect of the present disclosure, the present disclosure provides a negative electrode material. According to an embodiment of the present disclosure, the negative electrode material includes: metal zinc, a binder, a conductive agent, and a negative electrode additive, wherein the negative electrode additive includes montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide, and zinc carbonate. at least one of the .

The inventors found that by mixing metal zinc, binder, conductive agent and negative electrode additive, wherein the negative electrode additive includes at least one of montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate. Montmorillonite is a natural silicate mineral with a typical layered structure and good cation (Zn ²⁺ , Ca ²⁺ , Li ⁺ , Na ⁺ , K ^{+ ,} etc.) Improve the migration of ions inside the negative electrode, the uniformity of the ion flow field, and the uniformity of the dissolution/deposition of metal zinc, thereby inhibiting the formation of dendrites. Kaolin, bismuth oxide, tin oxide, zinc oxide or zinc carbonate can increase the hydrogen evolution overpotential of the negative electrode, inhibit the generation of hydrogen gas during charge and discharge, improve the stability of the negative electrode, and at higher current density and low surface capacity, Negative poles can still be used.

Further, the mass ratio of the zinc metal, the binder, the conductive agent and the negative electrode additive is (78-85):(0.1-10):(0-10):(0-10). Preferably, the mass ratio of metal zinc, binder, conductive agent and negative electrode additive is (78-85):(0.1-10):(1-10):(1-10). The inventors found that if the amount of the negative electrode additive added is too much, the internal resistance of the negative electrode sheet will increase; if the amount of the conductive agent is too much, the gas evolution rate will increase; The internal resistance increases and the affinity with the electrolyte decreases. If the addition amount of the binder is too small, it will cause the negative pole piece to fall off the powder. Preferably, the above-mentioned negative electrode additive includes montmorillonite and at least one selected from kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate.

It should be noted that the specific types of the above-mentioned conductive agent and binder are not particularly limited, and those skilled in the art can select according to actual needs. For example, the above-mentioned binder is PTFE (polytetrafluoroethylene), and the conductive agent includes At least one of KS-6 (conductive graphite), KS-15 (conductive graphite), AB (acetylene black), and SP (conductive carbon black).

In a second aspect of the present disclosure, the present disclosure provides a negative electrode sheet. According to an embodiment of the present disclosure, the negative electrode sheet includes: a negative electrode collector and a negative electrode sheet, and the negative electrode sheet is formed on the negative electrode collector, wherein the negative electrode sheet is formed by pressing the above-mentioned negative electrode material. It should be noted that the manner of forming the negative electrode sheet on the negative electrode current collector is not particularly limited, for example, pressing may be used. Thus, the negative electrode sheet has a good conductive network, which can improve the migration of internal ions and the uniformity of metal zinc dissolution/deposition, suppress the formation of dendrites, and simultaneously suppress the generation of hydrogen gas during charging and discharging. Applying it to an aqueous zinc-ion battery can improve the stability and cycle life of the aqueous zinc-ion battery. It should be noted that the specific type of the above-mentioned negative electrode current collector is not particularly limited, and those skilled in the art can choose according to actual needs, for example, including brass foil, red copper foil, stainless steel foil, copper mesh, stainless steel mesh and nickel foam at least one of the .

It should be noted that the features and advantages described above for the negative electrode material are also applicable to the negative electrode sheet, and will not be repeated here.

In a third aspect of the present disclosure, the present disclosure provides an aqueous zinc-ion battery. According to an embodiment of the present disclosure, the aqueous zinc-ion battery includes a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the negative electrode uses the above-mentioned negative electrode sheet. Thus, the stability and cycle life of the aqueous zinc-ion battery are improved.

It should be noted that the above-mentioned cathode is a commonly used cathode in the field of aqueous zinc-ion batteries, and will not be repeated here. At the same time, the specific type of the above separator is not particularly limited, those skilled in the art can select according to actual needs, for example, the separator includes at least one of glass fiber separator, non-woven fabric separator and PP separator.

Further, the electrolytic solution includes a mixed aqueous solution of zinc salt and manganese salt. It should be noted that the specific types of the above-mentioned zinc salts and manganese salts are not particularly limited, and those skilled in the art can select according to actual needs. For example, zinc salts include zinc chloride, zinc tetrafluoroborate, zinc perchlorate, At least one of zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate and zinc isooctanoate; manganese salts include manganese chloride, manganese sulfate and manganese nitrate at least one.

Further, the cation concentration in the above mixed aqueous solution is 1.0 mol·L ^-1 to 2.0 mol·L ^-1 . The inventors found that if the concentration of cations in the mixed aqueous solution is too high, it is easy to cause electrolyte precipitation; if the concentration of cations in the mixed aqueous solution is too low, the ionic conductivity of the battery will be insufficient, and the capacity of the battery will be inhibited.

It should be noted that the features and advantages described above for the negative electrode material and the negative electrode sheet are also applicable to the aqueous zinc-ion battery, and will not be repeated here.

The embodiments of the present disclosure are described in detail below, and it should be noted that the embodiments described below are exemplary, and are only used to explain the present disclosure, and should not be construed as limiting the present disclosure. In addition, if not clearly stated, all reagents used in the following examples are commercially available, or can be synthesized according to this article or known methods, and for the reaction conditions not listed, they are all readily available to those skilled in the art.

Example 1

Add 78wt% zinc powder, 5wt% KS-15 and 10wt% bismuth oxide into the mortar and mix well, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and then roll press, roll press thickness After reaching 200μm, put it in a blast drying oven to dry fully to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: MnO ₂ is used as the positive electrode material, the positive electrode current collector is brass foil, the negative electrode piece pressed by the brass foil is the negative electrode, and the separator is a glass fiber separator. Electrolyte: water as solvent, zinc sulfate as zinc salt, Zn ²⁺ concentration is 1.8mol/L; manganese sulfate as manganese salt, Mn ²⁺ concentration is 0.2mol/L;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Example 2

Add 80wt% zinc powder, 5wt% KS-15 and 8wt% bismuth oxide into the mortar and mix well, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and then roll press, roll press thickness After reaching 200μm, put it in a blast drying oven to dry fully to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, discharge to 1.0V at a current density of 50mA/g, and then perform a charge-discharge cycle at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Example 3

Add 83wt% zinc powder, 5wt% KS-15 and 5wt% bismuth oxide into the mortar and mix well, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and then roll press, roll press thickness After reaching 200μm, put it in a blast drying oven to dry fully to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Example 4

Add 85wt% zinc powder, 5wt% KS-15 and 3wt% bismuth oxide into the mortar and mix well, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and then carry out roll pressing, roll pressing thickness After reaching 200μm, put it in a blast drying oven to dry fully to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Example 5

Add 85wt% zinc powder, 5wt% KS-15 and 3wt% montmorillonite into the mortar and mix evenly, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and roll press, roll press After the thickness reaches 200μm, put it in a blast drying oven to dry fully to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Example 6

Add 83wt% zinc powder, 5wt% KS-15 and 5wt% montmorillonite into the mortar and mix well, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and then carry out roll pressing, roll pressing After the thickness reaches 200μm, put it in a blast drying oven to dry fully to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Example 7

Add 80wt% zinc powder, 5wt% KS-15, 5wt% montmorillonite and 3wt% bismuth oxide into the mortar and mix well, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and proceed Rolling, after the rolling thickness reaches 200μm, put it in the blast drying box and dry it fully to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Example 8

Add 84wt% zinc powder, 3wt% KS-15, 3wt% montmorillonite and 3wt% bismuth oxide into the mortar and mix well, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and proceed Rolling, after the rolling thickness reaches 200μm, put it in the blast drying box and dry it fully to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Comparative example 1

Add 83wt% zinc powder into the mortar, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and then carry out rolling, after the thickness of rolling reaches 200μm, put it in the blast drying box Dry to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1;

As shown in Figure 1, the time-voltage curve of the battery obtained in Comparative Example 1 shows that a significant short circuit phenomenon occurred when the battery was operated for about 50 hours.

Comparative example 2

Add 80wt% zinc powder and 3wt% KS-15 into the mortar and mix evenly, then add isopropanol, mix thoroughly and evenly, then add 7wt% PTFE emulsion, mix well and then carry out rolling, after the rolling thickness reaches 200μm, Put it in the blast drying box and dry it fully to get the negative pole piece, and finally cut the negative pole piece for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Comparative example 3

Add 78wt% zinc powder and 5wt% KS-15 into the mortar and mix evenly, then add isopropanol, mix thoroughly and uniformly, then add 7wt% PTFE emulsion, mix well and then carry out rolling, after the rolling thickness reaches 200μm, Put it in the blast drying box and dry it fully to get the negative pole piece, and finally cut the negative pole piece for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Comparative example 4

Add 73wt% zinc powder and 10wt% KS-15 into the mortar and mix evenly, then add isopropanol, mix thoroughly and evenly, then add 7wt% PTFE emulsion, mix well and then carry out rolling, after the rolling thickness reaches 200μm, Put it in the blast drying box and dry it fully to get the negative pole piece, and finally cut the negative pole piece for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Comparative example 5

Add 80wt% zinc powder and 3wt% KS-6 into the mortar and mix evenly, then add isopropanol, mix thoroughly and evenly, then add 7wt% PTFE emulsion, mix well and then carry out rolling, after the rolling thickness reaches 200μm, Put it in the blast drying box and dry it fully to get the negative pole piece, and finally cut the negative pole piece for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Comparative example 6

Add 80wt% zinc powder and 3wt% AB into the mortar and mix evenly, then add isopropanol, mix thoroughly and uniformly, then add 7wt% PTFE emulsion, mix well and then carry out roll pressing, after the rolling thickness reaches 200μm, put in Fully dry in the blast drying box to obtain the negative pole piece, and finally cut the negative pole piece for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

Comparative example 7

Add 77wt% zinc powder, 3wt% KS-15 and 3wt% AB into the mortar and mix evenly, then add isopropanol, mix well and then add 7wt% PTFE emulsion, mix well and then roll press, roll press thickness After reaching 200μm, put it in a blast drying oven to dry fully to obtain the negative electrode sheet, and finally cut the negative electrode sheet for use;

Battery assembly: same as embodiment 1;

Battery test: In an environment of 25°C, the battery is first discharged to 1.0V at a current density of 50mA/g, and then charged and discharged at a current density of 50mA/g. The discharge cut-off voltage is 1.0V, and the charge cut-off voltage is 1.9V. The test results are shown in Table 1.

The batteries of Examples 1-8 and Comparative Examples 1-7 were charged and discharged for 30 cycles at 50 mA/g, and then the negative electrode sheet was disassembled. The surface morphology of the negative electrode sheet is shown in Table 1. The surface morphology of the negative electrode sheet of Example 1 is shown in FIG. 2 , and the surface morphology of the negative electrode sheet of Comparative Example 2 is shown in FIG. 3 .

Table 1 embodiment 1-8 and comparative example 1-7 battery test result

the	Gas evolution rate ml/(Ah h)	Is it prone to short circuit	Dismantling the surface morphology of the negative electrode sheet
Example 1	0.30～0.40	no	dendrite free
Example 2	0.20～0.25	no	dendrite free
Example 3	0.15～0.20	no	dendrite free
Example 4	0.15～0.20	no	dendrite free
Example 5	0.60～0.65	no	dendrite free
Example 6	0.55～0.60	no	dendrite free
Example 7	0.15～0.20	no	dendrite free
Example 8	0.14～0.17	no	dendrite free
Comparative example 1	0.35～0.50	yes	/
Comparative example 2	0.85～1.15	no	There are obvious dendrites
Comparative example 3	1.50～1.70	no	There are obvious dendrites

Comparative example 4	1.63～1.90	no	There are obvious dendrites
Comparative example 5	1.10～1.25	no	There are obvious dendrites
Comparative example 6	1.30～1.55	no	There are obvious dendrites
Comparative example 7	1.45～1.90	no	There are obvious dendrites

It can be seen from the data in Table 1 that the gas evolution rate of the batteries of Examples 1-8 is significantly lower than that of Comparative Examples 1-7, and the batteries of Examples 1-8 have not formed dendrites on the surface of the disassembled negative electrode sheet after 30 cycles. However, the battery of Comparative Example 1 was short-circuited during the cycle, and the batteries of Comparative Examples 2-7 were disassembled after 30 cycles to form obvious dendrites on the surface of the negative electrode sheet, indicating that the negative electrode material used in the present application can inhibit the charging and discharging process. The generation of hydrogen gas can inhibit the formation of dendrites.

The embodiments of the present application have been described above in conjunction with the accompanying drawings, but the present application is not limited to the above-mentioned specific implementations. The above-mentioned specific implementations are only illustrative and not restrictive. Those of ordinary skill in the art will Under the inspiration of this application, without departing from the purpose of this application and the scope of protection of the claims, many forms can also be made, all of which belong to the protection of this application.

Claims (11)

1. A negative electrode material, including: metal zinc, binding agent, conductive agent and negative electrode additive,

   The negative electrode additive includes at least one of montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate.
2. The negative electrode material according to claim 1, wherein the mass ratio of the metal zinc, the binder, the conductive agent and the negative electrode additive is (78～85):(0.1～10):(0 ~10): (0~10).
3. The negative electrode material according to claim 1 or 2, wherein the negative electrode additive comprises montmorillonite and at least one selected from kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate.
4. A negative electrode sheet, including:

   Negative current collector;

   Negative electrode sheet, the negative electrode sheet is formed on the negative electrode current collector, and the negative electrode sheet is formed by pressing the negative electrode material according to any one of claims 1-3.
5. The negative electrode sheet according to claim 4, wherein the negative electrode current collector comprises at least one of brass foil, red copper foil, stainless steel foil, copper mesh, stainless steel mesh and nickel foam.
6. A water system zinc ion battery, wherein, comprises positive pole, negative pole, electrolytic solution and diaphragm, and described negative pole adopts the negative electrode sheet described in claim 4 or 5.
7. The aqueous zinc-ion battery according to claim 6, wherein the electrolytic solution comprises a mixed aqueous solution of zinc salt and manganese salt.
8. The aqueous zinc-ion battery according to claim 6 or 7, wherein the zinc salt comprises zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate , zinc benzenesulfonate, zinc p-toluenesulfonate and zinc isooctanoate at least one.
9. The aqueous zinc-ion battery according to any one of claims 6-8, wherein the manganese salt comprises at least one of manganese chloride, manganese sulfate and manganese nitrate.
10. The aqueous zinc-ion battery according to any one of claims 6-9, wherein the cation concentration in the mixed aqueous solution is 1.0moL·L ^-1 to 2.0moL·L ^-1 .
11. The aqueous zinc-ion battery according to any one of claims 6-10, wherein the separator comprises at least one of a glass fiber separator, a non-woven fabric separator and a PP separator.

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