CN114520331A - Negative electrode material and application thereof - Google Patents
Negative electrode material and application thereof Download PDFInfo
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- CN114520331A CN114520331A CN202111625313.2A CN202111625313A CN114520331A CN 114520331 A CN114520331 A CN 114520331A CN 202111625313 A CN202111625313 A CN 202111625313A CN 114520331 A CN114520331 A CN 114520331A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention discloses a negative electrode material and application thereof, wherein the negative electrode material comprises: the negative electrode comprises metal zinc, a binder, a conductive agent and a negative electrode additive, wherein the negative electrode additive comprises at least one of montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate. Therefore, the negative electrode material can improve the hydrogen evolution overpotential of the negative electrode, inhibit the generation of hydrogen in the charging and discharging process, improve the stability of the negative electrode, simultaneously improve the migration of ions in the negative electrode and the uniformity of the dissolution/deposition of metal zinc, inhibit the formation of dendrites, and improve the stability and the cycle life of the water-based zinc ion battery when being applied to the water-based zinc ion battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a negative electrode material and application thereof.
Background
The water system zinc ion battery uses zinc with rich reserves as a cathode material, uses a safe and environment-friendly aqueous solution as an electrolyte, has the advantages of low cost, safety, friendliness and the like, and has the potential of large-scale application in the fields of energy storage, low-speed electric vehicles and the like. However, zinc metal often has challenges such as dendritic growth, hydrogen evolution side reaction, self-corrosion and the like in weak acid electrolyte, and the performance of the zinc ion battery is seriously influenced. In order to solve the above problems, researchers have invested a lot of efforts in electrolyte additives, surface modification of negative electrodes, and the like. However, the influence of the composition of the zinc negative electrode conductive agent, additives, etc. on dendrite growth and hydrogen evolution side reactions has been relatively rarely studied.
The surface modification of the cathode mainly takes an artificial organic coating and an inorganic coating as main materials, on one hand, the structural stability of the coatings is insufficient,on the other hand, control is difficult due to the uniformity of the coating. Insufficient coating uniformity tends to cause local ion flux and electric field concentration, which tends to cause rapid growth of local dendrites. In addition, the effectiveness of these strategies is often limited to lower current densities (< 1 mA/cm)2) And low surface capacity condition (< 1 mA.h/cm)2) The applicability is insufficient.
Therefore, the existing anode material is in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a negative electrode material and an application thereof, wherein the negative electrode material can improve hydrogen evolution overpotential of a negative electrode, suppress hydrogen generation during charge and discharge, improve stability of the negative electrode, improve migration of ions and uniformity of dissolution/deposition of metallic zinc in the negative electrode, suppress formation of dendrite, and improve stability and cycle life of an aqueous zinc ion battery when applied to the aqueous zinc ion battery.
In one aspect of the invention, an anode material is provided. According to an embodiment of the present invention, the anode material includes: metal zinc, a binder, a conductive agent and a negative electrode additive,
wherein the negative electrode additive comprises at least one of montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate.
According to the negative electrode material provided by the embodiment of the invention, the metal zinc, the binder, the conductive agent and the negative electrode additive are mixed, wherein the negative electrode additive comprises at least one of montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate. Montmorillonite is a natural mineral of silicate, has typical layered structure, and has good cation (Zn) between layers2+、Ca2+、Li+、Na+、K+Etc.) transport properties, thereby improving migration of ions inside the negative electrode, uniformity of an ion flow field, and uniformity of dissolution/deposition of metallic zinc. Kaolin, bismuth oxide, tin oxide, zinc oxide or zinc carbonate can improve hydrogen evolution overpotential of the negative electrodeThe generation of hydrogen in the charging and discharging process is inhibited, and the stability of the cathode is improved. Therefore, the negative electrode material can improve the hydrogen evolution overpotential of the negative electrode, inhibit the generation of hydrogen in the charging and discharging process, improve the stability of the negative electrode, simultaneously improve the migration of ions in the negative electrode and the uniformity of the dissolution/deposition of metal zinc, inhibit the formation of dendrites, and improve the stability and the cycle life of the water-based zinc ion battery when being applied to the water-based zinc ion battery.
In addition, the anode material according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the present invention, the mass ratio of the metallic zinc, the binder, the conductive agent, and the negative electrode additive is (78-85): (0.1-10): (0-10): (0-10). Thus, the generation of hydrogen gas during charge and discharge and the formation of dendrites can be suppressed.
In some embodiments of the invention, the negative electrode additive comprises montmorillonite and at least one selected from the group consisting of kaolin, bismuth oxide, tin oxide, zinc oxide, and zinc carbonate. Thereby, the generation of hydrogen gas during charge and discharge and the formation of dendrites can be suppressed.
In a second aspect of the present invention, a negative electrode sheet is provided. According to an embodiment of the present invention, the negative electrode tab includes: a negative current collector; and the negative pole piece is formed on the negative current collector and is formed by pressing the negative pole material. Therefore, the negative electrode has a good conductive network, can improve the migration of internal ions and the uniformity of dissolution/deposition of metal zinc, inhibit the formation of dendrites, and simultaneously inhibit the generation of hydrogen in the charging and discharging process, and can improve the stability and the cycle life of the aqueous zinc ion battery when being applied to the aqueous zinc ion battery.
In addition, the negative electrode sheet according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the negative current collector includes at least one of a yellow copper foil, a red copper foil, a stainless steel foil, a copper mesh, a stainless steel mesh, and a nickel foam.
In a third aspect of the invention, an aqueous zinc-ion battery is presented. According to the embodiment of the invention, the water-based zinc ion battery comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein the negative electrode sheet is formed by pressing the negative electrode material. This improves the stability and cycle life of the aqueous zinc-ion battery.
In some embodiments of the present invention, the electrolyte comprises a mixed aqueous solution of a zinc salt and a manganese salt.
In some embodiments of the invention, the zinc salt comprises at least one of zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctoate;
in some embodiments of the invention, the manganese salt comprises at least one of manganese chloride, manganese sulfate, and manganese nitrate.
In some embodiments of the invention, the cation concentration in the mixed aqueous solution is 1.0-2.0 mol.L-1。
In some embodiments of the invention, the separator comprises at least one of a glass fiber separator, a non-woven separator, and a PP separator.
Additional aspects and advantages of the invention 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 invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a time-voltage graph of the battery obtained in comparative example 1.
Detailed Description
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
In one aspect of the invention, an anode material is provided. According to an embodiment of the present invention, the anode material includes: the negative electrode comprises metal zinc, a binder, a conductive agent and a negative electrode additive, wherein the negative electrode additive comprises at least one of montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate.
The inventors have found that by mixing metallic 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. Montmorillonite is a natural mineral of silicate, has typical layered structure, and has good cation (Zn) between layers2+、Ca2+、Li+、Na+、K+Etc.) so as to improve the migration of ions inside the negative electrode, the uniformity of an ion flow field and the uniformity of the dissolution/deposition of metal zinc, thereby inhibiting the formation of dendrites. The kaolin, the bismuth oxide, the tin oxide, the zinc oxide or the zinc carbonate can improve the hydrogen evolution overpotential of the cathode, inhibit the generation of hydrogen in the charging and discharging process, improve the stability of the cathode, and the cathode can still be suitable under higher current density and low surface capacity.
Further, 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). Preferably, the mass ratio of the metal zinc, the binder, the conductive agent and the negative electrode additive is (78-85): (0.1-10): (1-10): (1-10). The inventor finds that if the adding amount of the negative electrode additive is too much, the internal resistance of the negative electrode plate is increased; if the addition amount of the conductive agent is too much, the gas evolution rate is increased; if the addition amount of the binder is too large, the internal resistance of the negative pole piece is increased and the affinity with the electrolyte is reduced. If the addition amount of the binder is too small, the negative electrode plate can be subjected to powder removal. Preferably, the 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 conductive agent and the binder are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the 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 invention, a negative electrode sheet is provided. According to an embodiment of the present invention, the negative electrode tab includes: the negative pole current collector and negative pole piece, negative pole piece form on the negative pole current collector, wherein, negative pole piece adopts above-mentioned negative pole material suppression to form. The manner in which the negative electrode tab is formed on the negative electrode current collector is not particularly limited, and for example, a pressing manner may be employed. Therefore, the negative plate has a good conductive network, can improve the migration of internal ions and the uniformity of dissolution/deposition of metal zinc, inhibit the formation of dendrites, and simultaneously inhibit the generation of hydrogen in the charging and discharging process. The application of the zinc oxide can improve the stability and the cycle life of the water-based zinc ion battery. It should be noted that, the specific type of the negative electrode current collector is not particularly limited, and may be selected by one skilled in the art according to actual needs, for example, including at least one of a yellow copper foil, a purple copper foil, a stainless steel foil, a copper mesh, a stainless steel mesh, and nickel foam.
It should be noted that the features and advantages described above for the negative electrode material also apply to the negative electrode sheet, and are not described herein again.
In a third aspect of the invention, an aqueous zinc-ion battery is presented. According to an embodiment of the present invention, the aqueous zinc-ion battery includes a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the negative electrode employs the above negative electrode sheet. This improves the stability and cycle life of the aqueous zinc-ion battery.
The positive electrode is a positive electrode commonly used in the field of aqueous zinc ion batteries, and will not be described herein. Meanwhile, the specific type of the above-described separator is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the separator includes at least one of a glass fiber separator, a non-woven fabric separator, and a PP separator.
Further, the electrolyte comprises a mixed aqueous solution of a zinc salt and a manganese salt. It should be noted that the specific types of the above-mentioned zinc salt and manganese salt are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the zinc salt includes at least one of zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctanoate; the manganese salt includes at least one of manganese chloride, manganese sulfate and manganese nitrate.
Further, the cation concentration in the mixed aqueous solution is 1.0 to 2.0 mol.L-1. The inventors have found that when the cation concentration in the mixed aqueous solution is too high, the electrolyte is likely to be deposited; if the cation concentration in the mixed aqueous solution is too low, the battery ion conductivity becomes insufficient, and the battery capacity is suppressed from being exhibited.
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 are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
Adding 78 wt% of zinc powder, 5 wt% of KS-15 and 10 wt% of bismuth oxide into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, adding 7 wt% of PTFE emulsion, fully and uniformly mixing, then rolling, placing the mixture into a blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: MnO2As the anode material, the anode current collector is a yellow copper foil, the cathode piece formed by pressing the cathode piece and the yellow copper foil is a cathode, and the diaphragm is a glass fiber diaphragm. Electrolyte solution: water as solvent, zinc sulfate as zinc salt, Zn2+Concentration ofIs 1.8 mol/L; manganese sulfate as manganese salt, Mn2+The concentration is 0.2 mol/L;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Example 2
Adding 80 wt% of zinc powder, 5 wt% of KS-15 and 8 wt% of bismuth oxide into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, adding 7 wt% of PTFE emulsion, fully and uniformly mixing, then rolling, placing the mixture into a blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Example 3
Adding 83 wt% of zinc powder, 5 wt% of KS-15 and 5 wt% of bismuth oxide into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, adding 7 wt% of PTFE emulsion, fully and uniformly mixing, then rolling, placing the mixture into a blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Example 4
Adding 85 wt% of zinc powder, 5 wt% of KS-15 and 3 wt% of bismuth oxide into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, adding 7 wt% of PTFE emulsion, fully and uniformly mixing, then rolling, placing the mixture into a blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Example 5
Adding 85 wt% of zinc powder, 5 wt% of KS-15 and 3 wt% of montmorillonite into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, adding 7 wt% of PTFE emulsion, fully and uniformly mixing, then rolling, placing the mixture into a blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Example 6
Adding 83 wt% of zinc powder, 5 wt% of KS-15 and 5 wt% of montmorillonite into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, adding 7 wt% of PTFE emulsion, fully and uniformly mixing, then rolling, placing the mixture into a blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Example 7
Adding 80 wt% of zinc powder, 5 wt% of KS-15, 5 wt% of montmorillonite and 3 wt% of bismuth oxide into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, then adding 7 wt% of PTFE emulsion, fully and uniformly mixing, then rolling, placing the rolled product into an air-blast drying oven for fully drying after the rolling thickness reaches 200 mu m, obtaining a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Example 8
Adding 84 wt% of zinc powder, 3 wt% of KS-15, 3 wt% of montmorillonite and 3 wt% of bismuth oxide into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, then adding 7 wt% of PTFE emulsion, fully and uniformly mixing, then rolling, placing the rolled product into an air-blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Comparative example 1
Adding 83 wt% of zinc powder into a mortar, adding isopropanol, fully and uniformly mixing, then adding 7 wt% of PTFE emulsion, fully and uniformly mixing, rolling until the rolling thickness reaches 200 mu m, placing the mixture into a blast drying oven for fully drying to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in table 1;
as shown in fig. 1, the time-voltage curve of the battery obtained in comparative example 1, which indicates that a significant short-circuit phenomenon occurred when the battery was operated for about 50 hours.
Comparative example 2
Adding 80 wt% of zinc powder and 3 wt% of KS-15 into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, then adding 7 wt% of PTFE emulsion, fully and uniformly mixing, rolling, placing into an air-blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Comparative example 3
Adding 78 wt% of zinc powder and 5 wt% of KS-15 into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, then adding 7 wt% of PTFE emulsion, fully and uniformly mixing, rolling, placing into an air-blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Comparative example 4
Adding 73 wt% of zinc powder and 10 wt% of KS-15 into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, then adding 7 wt% of PTFE emulsion, fully and uniformly mixing, rolling, placing the mixture into an air-blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Comparative example 5
Adding 80 wt% of zinc powder and 3 wt% of KS-6 into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, then adding 7 wt% of PTFE emulsion, fully and uniformly mixing, rolling, placing into an air-blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Comparative example 6
Adding 80 wt% of zinc powder and 3 wt% of AB into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, then adding 7 wt% of PTFE emulsion, fully and uniformly mixing, rolling, placing in an air-blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
Comparative example 7
Adding 77 wt% of zinc powder, 3 wt% of KS-15 and 3 wt% of AB into a mortar, uniformly mixing, then adding isopropanol, fully and uniformly mixing, then adding 7 wt% of PTFE emulsion, fully and uniformly mixing, then rolling, placing the mixture into a blast drying oven for fully drying after the rolling thickness reaches 200 mu m to obtain a negative pole piece, and finally cutting the negative pole piece for later use;
assembling the battery: the same as example 1;
and (3) testing the battery: in the environment of 25 ℃, the battery discharges firstly, and the current density is 50 mA/g. The test results are shown in Table 1.
TABLE 1 results of testing of examples 1-8 and comparative examples 1-7 batteries
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. An anode material, comprising: metal zinc, a binder, a conductive agent and a negative electrode additive,
wherein the negative electrode additive comprises at least one of montmorillonite, kaolin, bismuth oxide, tin oxide, zinc oxide and zinc carbonate.
2. The negative electrode material as claimed in claim 1, wherein the mass ratio of the metallic 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 of 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, comprising:
a negative current collector;
the negative pole piece is formed on the negative pole current collector, wherein the negative pole piece is formed by pressing the negative pole material in any one of claims 1 to 3.
5. The negative electrode sheet according to claim 4, wherein the negative electrode current collector comprises at least one of a brass foil, a red copper foil, a stainless steel foil, a copper mesh, a stainless steel mesh, and a nickel foam.
6. An aqueous zinc ion battery comprising a positive electrode, a negative electrode, an electrolyte and a separator, wherein the negative electrode uses the negative electrode sheet according to any one of claims 4 or 5.
7. The aqueous zinc-ion battery of claim 6, wherein the electrolyte comprises a mixed aqueous solution of a zinc salt and a manganese salt.
8. The aqueous zinc-ion battery of claim 7, wherein the zinc salt comprises at least one of zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctanoate;
optionally, the manganese salt comprises at least one of manganese chloride, manganese sulfate and manganese nitrate.
9. The aqueous zinc-ion battery according to claim 7, wherein the cation concentration in the mixed aqueous solution is 1.0 to 2.0 moL-L-1。
10. The aqueous zinc-ion battery of claim 6, 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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| CN202111625313.2A CN114520331A (en) | 2021-12-28 | 2021-12-28 | Negative electrode material and application thereof |
| PCT/CN2022/142294 WO2023125523A1 (en) | 2021-12-28 | 2022-12-27 | Negative electrode material and application thereof |
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| CN (1) | CN114520331A (en) |
| WO (1) | WO2023125523A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023125523A1 (en) * | 2021-12-28 | 2023-07-06 | 瑞海泊(常州)能源科技有限公司 | Negative electrode material and application thereof |
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| CN117293304A (en) * | 2023-09-19 | 2023-12-26 | 兰州城市学院 | Method for improving electrochemical capacity by using lattice oxygen in bimetallic oxide to participate in water-based ion battery reaction through electrochemical method |
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| EP2953190B1 (en) * | 2013-02-01 | 2019-05-22 | Nippon Shokubai Co., Ltd. | Electrode precursor, electrode, and battery |
| JP6148873B2 (en) * | 2013-02-05 | 2017-06-14 | 株式会社日本触媒 | Zinc negative electrode mixture, zinc negative electrode and battery |
| CN106549189A (en) * | 2015-09-22 | 2017-03-29 | 苏州宝时得电动工具有限公司 | Battery, set of cells and uninterrupted power source |
| CN114520331A (en) * | 2021-12-28 | 2022-05-20 | 瑞海泊有限公司 | Negative electrode material and application thereof |
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| US20020177043A1 (en) * | 2001-05-24 | 2002-11-28 | Ernest Ndzebet | Ionically conductive additive for zinc-based anode in alkaline electrochemical cells |
| CN1971978A (en) * | 2005-11-23 | 2007-05-30 | 比亚迪股份有限公司 | Zinc cathode secondary battery, zinc cathode of the battery and preparation method thereof |
| US20070122709A1 (en) * | 2005-11-30 | 2007-05-31 | Rovcal, Inc. | Ionically conductive clay additive for use in electrochemical cells |
| CN101465439A (en) * | 2007-12-19 | 2009-06-24 | 日立麦克赛尔株式会社 | Alkaline battery |
| CN108807910A (en) * | 2018-06-13 | 2018-11-13 | 深圳市寒暑科技新能源有限公司 | A kind of water system Zinc ion battery |
| CN110416549A (en) * | 2019-08-19 | 2019-11-05 | 中南大学 | A kind of metal zinc load and its preparation method and application with uniform meso-hole structure coating |
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| WO2023125523A1 (en) * | 2021-12-28 | 2023-07-06 | 瑞海泊(常州)能源科技有限公司 | Negative electrode material and application thereof |
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| WO2023125523A1 (en) | 2023-07-06 |
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