CN115084454B - Alkaline zinc-manganese battery cathode and preparation method thereof - Google Patents

Alkaline zinc-manganese battery cathode and preparation method thereof Download PDF

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CN115084454B
CN115084454B CN202110941516.6A CN202110941516A CN115084454B CN 115084454 B CN115084454 B CN 115084454B CN 202110941516 A CN202110941516 A CN 202110941516A CN 115084454 B CN115084454 B CN 115084454B
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parts
zinc
solid powder
powder
alkaline
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CN115084454A (en
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吴嘉豪
李政文
李思睿
黎少伟
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Guangzhou Zhuoyue New Material Technology Research Co ltd
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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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses an alkaline zinc-manganese battery cathode which comprises the following raw materials in parts by weight: 30-80 parts of solid powder, 1-30 parts of alkaline agent, 1-10 parts of zinc oxide, 0.01-5 parts of silicate, 0.1-5 parts of binder and 10-60 parts of deionized water. The solid powder is carboxylated graphene quantum dots and composite carbon nanotube materials. The negative electrode prepared in the application of the invention is added into the zinc-manganese battery, so that the overall capacitance, conductivity and cycle performance of the battery are effectively improved, the service life of the zinc-manganese battery is effectively prolonged, and the zinc-manganese battery is suitable for popularization in the field of batteries and has wide development prospect.

Description

Alkaline zinc-manganese battery cathode and preparation method thereof
Technical Field
The invention relates to the field of IPC classified H01M10, in particular to an alkaline zinc-manganese battery cathode and a preparation method thereof.
Background
Zinc ion batteries have been widely studied as a new type of battery since the advent of zinc ion batteries. This is mainly because it has the following advantages: 1. the safety is high, the flame and explosion are not generated, and the heat and cold can be realized; 2. the battery has excellent battery performance, can realize quick charge and quick discharge, and has large specific energy and large specific capacity; 3. the cost per watt-hour is not more than 0.6 yuan, the reserve is abundant, the cost is low, the production is simple and convenient, and the continuity is high; 4. the service life is long, the full charge and the full discharge can be realized, and the cyclic use can be effectively carried out; 5. zero pollution, no toxicity and harm, and environmental protection. In recent years, zinc-manganese batteries are widely used in civilian applications and industries, and are particularly suitable for use in flash cameras, miniature recorders, video cameras, interphones, shavers, palm-type color televisions and game consoles, toys, telemeters, alarms, calculators, hearing aids, flashlights, and clocks. Along with the increasing functions of instruments and equipment, the requirements on the high-power high-current discharge performance of the zinc-manganese battery are higher.
The zinc paste is used as an important component material for preparing the zinc-manganese battery, and the performance of the zinc paste has key effects on the discharging capability and the service life of the zinc-manganese battery. In an alkaline zinc-manganese battery, the zinc cathode is unstable in thermodynamics, so that dissolution of zinc in alkali liquor and synchronous generation of hydrogen are easy to occur, and the internal air pressure of the battery is gradually increased, so that the storage performance of the battery is reduced and the battery leaks. The traditional solution is mainly to add mercury into zinc powder to form amalgam, but the method is stopped at present due to the inherent toxicity of mercury. At present, metals or metal oxides with high hydrogen evolution overpotential such as indium, bismuth and the like are added in the zinc powder smelting and zinc paste preparation processes. However, metals such as indium and bismuth are expensive, so that a great cost burden is caused, and the prepared zinc-manganese battery has defects in capacitance and cycle effect.
Therefore, research on a novel zinc paste negative electrode with corrosion inhibition effect close to indium and bismuth and good capacitance and circulation effect is a very significant work.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides an alkaline zinc-manganese dioxide battery cathode, which comprises the following raw materials in parts by weight: 30-80 parts of solid powder, 1-30 parts of alkaline agent, 1-10 parts of zinc oxide, 0.01-5 parts of silicate, 0.1-5 parts of binder and 10-60 parts of deionized water.
As a preferred scheme, the raw materials comprise the following parts by weight: 60-65 parts of solid powder, 10-15 parts of alkaline agent, 1-3 parts of zinc oxide, 0.01-0.5 part of silicate, 0.1-0.5 part of binder and 30-35 parts of deionized water.
As a preferable scheme, the alkaline agent is at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide and magnesium hydroxide.
As a preferred embodiment, the silicate is zinc silicate or a di-zinc orthosilicate.
As a preferred embodiment, the binder is at least one of hydroxymethyl cellulose, sodium silicate, polyacrylic acid, and polymethyl methacrylate.
As a preferred scheme, the solid powder raw material comprises the following components in parts by weight: 40-50 parts of nano zinc powder, 1-10 parts of conductive additive, 15-20 parts of organic resin, 30-35 parts of ketone solvent, 1-5 parts of plasticizer and 1-3 parts of coupling agent.
As a preferable scheme, the particle size of the nano zinc powder is 300-600 nm; the organic resin is at least one of polyvinyl chloride, polyvinylidene fluoride and polyethylene peroxide resin; the ketone solvent is at least one of acetone, butanone and cyclohexanone; the plasticizer is at least one of dioctyl phthalate, n-octyl phthalate and dibutyl phthalate; the coupling agent is at least one of vinyl trichlorosilane, methyl trimethoxy silane and vinyl triethoxy silane.
As a preferable scheme, the conductive auxiliary agent is graphene quantum dots and composite carbon nanotubes.
As a preferable scheme, the graphene quantum dots are carboxylated graphene quantum dots.
As a preferred scheme, the composite carbon nanotube is a composite material of carbon nanotube and zinc oxide.
The composite carbon nano tube is self-made, and comprises the following steps (in parts by weight): (1) Adding 0.5 part of multi-wall carbon nano tube into 150 parts of deionized water to form a mixed solution, and performing ultrasonic dispersion for 1-2 hours; (2) After the dispersion is completed, 20 parts of zinc nitrate hexahydrate and 4 parts of citric acid are added into the mixed solution, and the mixture is stirred and reacted for 1 to 2 hours; (3) Heating to 80-90 ℃, continuously stirring and reacting for 15-18 hours, heating to 160-180 ℃, stopping stirring and preserving heat and reacting for 20-40 minutes; (4) Taking out the solid powder, and placing the solid powder in a tube furnace at 600 ℃ for heat preservation for 1-2 hours to obtain the composite material of the carbon nano tube and the zinc oxide.
As a preferable scheme, the weight ratio of the graphene quantum dots to the composite carbon nanotubes is 1-2: 3 to 5.
The second aspect of the invention provides a preparation method of the cathode of the alkaline zinc-manganese dioxide battery, which comprises the following steps: (1) Weighing and mixing the conductive auxiliary agent, the organic resin, the ketone solvent, the plasticizer and the coupling agent, and then putting the mixture into a high-speed stirring and dispersing reaction kettle for high-speed stirring for 30-50 minutes to obtain a mixed solution; (2) Mixing and stirring the mixed solution obtained in the step (1) and nano zinc powder for 20-30 minutes, and then centrifuging, volatilizing and drying to obtain solid powder; (3) Then putting the solid powder, the binder and the silicate into a mixer, and uniformly stirring to prepare dry powder; adding an alkaline agent and zinc oxide into deionized water to prepare a strong alkali solution; (4) And (3) adding the dry powder and the strong alkali solution into a zinc paste machine, uniformly stirring, vacuumizing, and removing bubbles to obtain the negative electrode material.
The third aspect of the invention provides an application of the cathode of the alkaline zinc-manganese battery, which comprises an application of the cathode of the zinc-manganese battery in the alkaline zinc-manganese battery.
As a preferable scheme, the positive electrode of the alkaline zinc-manganese dioxide battery is a cathode reaction, and the reaction formula of the cathode reaction is as follows:
MnO2+H2O+e→MnO(OH)+OH-；
MnO(OH)+H2O+OH-→Mn(OH)4 -；
Mn(OH)4 -+e→Mn(OH)4 2-。
as a preferable scheme, the anode of the alkaline zinc-manganese dioxide battery is an anode reaction, and the reaction formula of the anode reaction is as follows:
Zn+2OH-→Zn(OH)2+2e；
Zn(OH)2+2OH-→Zn(OH)4 2-。
as a preferred scheme, the total cell reaction formula of the alkaline zinc-manganese cell is as follows:
Zn+MnO2+2H2O+4OH-→Mn(OH)4 2-+Zn(OH)4 2-。
The beneficial effects are that:
1. The negative electrode of the zinc-manganese battery prepared by the method can effectively reduce the hydrogen precipitation amount in the working process of the battery, improve the storage performance of the zinc-manganese battery, improve the recycling performance of the battery and reduce the cost.
2. The zinc-manganese battery cathode prepared by the method effectively improves various performances of the zinc-manganese battery through the synergistic effect of the carboxylated graphene quantum dot material and the composite material of the carbon nano tube and the zinc oxide. The carboxyl graphene quantum dot material is rich in carboxyl groups, hydroxyl groups and other groups, has strong specific adsorption capacity on metal ions of the negative electrode, and can play a good role in anchoring and coating, so that active components of a motor are protected, the current density is more uniform, and dendrites and corrosion phenomena of the negative electrode are effectively reduced by synergistic action with the composite carbon nano tube; the composite material of the carbon nano tube and the zinc oxide can obviously reduce the impedance of the negative electrode of the zinc-manganese battery, plays a good supporting role on active substances of the negative electrode battery, effectively reduces the electrochemical risk of the zinc-manganese battery in the charge and discharge process, and effectively improves the service quality and service life of the zinc-manganese battery by the synergistic effect of the composite material and the carboxyl graphene quantum dot material.
Detailed Description
Example 1
Example 1 provides an alkaline zinc-manganese dioxide battery cathode, which comprises the following raw materials in parts by weight: 60 parts of solid powder, 12 parts of potassium hydroxide, 2 parts of zinc oxide, 0.2 part of zinc silicate, 0.3 part of hydroxymethyl cellulose and 35 parts of deionized water.
The solid powder comprises the following components in parts by weight: 40 parts of nano zinc powder (average particle size 350 nm), 8 parts of conductive additive, 15 parts of polyvinylidene fluoride, 30 parts of acetone, 2 parts of dioctyl phthalate and 1.5 parts of vinyl trichlorosilane.
Conductive auxiliary agent: a composite material of carboxylated graphene quantum dots, carbon nanotubes and zinc oxide; the weight ratio of the two is 1:3.
The composite material of the carbon nanotube and the zinc oxide in the embodiment is self-made, and the steps comprise the following steps (in parts by weight): (1) Adding 0.5 part of multi-wall carbon nano tube into 150 parts of deionized water to form a mixed solution, and performing ultrasonic dispersion for 2 hours; (2) After the dispersion is completed, 20 parts of zinc nitrate hexahydrate and 4 parts of citric acid are added into the mixed solution, and the mixture is stirred and reacted for 2 hours; (3) Heating to 85 ℃, continuously stirring and reacting for 16 hours, heating to 170 ℃, stopping stirring and preserving heat and reacting for 30 minutes; (4) And taking out the solid powder, and placing the solid powder in a tubular furnace at 600 ℃ for heat preservation for 2 hours to obtain the composite material of the carbon nano tube and the zinc oxide.
The embodiment also provides a preparation method of the alkaline zinc-manganese dioxide battery cathode, which comprises the following steps: (1) Mixing 8 parts of a conductive additive, 15 parts of polyvinylidene fluoride, 30 parts of acetone, 2 parts of dioctyl phthalate and 1.5 parts of vinyl trichlorosilane, and then putting the mixture into a high-speed stirring and dispersing reaction kettle to be stirred at a high speed for 30-50 minutes to obtain a mixed solution; (2) Mixing and stirring the mixed solution obtained in the step (1) with 40 parts of nano zinc powder (with the average particle size of 350 nm) for 25 minutes, and then centrifuging, volatilizing and drying to obtain solid powder; (3) Then 60 parts of solid powder, 0.3 part of hydroxymethyl cellulose and 0.2 part of zinc silicate are put into a mixer and uniformly stirred to prepare dry powder; adding 12 parts of potassium hydroxide and 2 parts of zinc oxide into 35 parts of deionized water to prepare a strong alkali solution; (4) And (3) adding the dry powder and the strong alkali solution into a zinc paste machine, uniformly stirring, vacuumizing, and removing bubbles to obtain the negative electrode material.
In the embodiment, the carboxylated graphene quantum dot is a product of XF-090-1 model sold by Nanjing Xianfeng nanomaterial technologies, inc.
The multiwall carbon nanotubes in this embodiment are multiwall carbon nanotubes manufactured and sold by Beijing, island gold technologies, inc.
The negative electrode of the alkaline zinc-manganese dioxide cell prepared in this example was designated as T1.
Example 2
The specific implementation of this example is the same as example 1, except that: the average particle size of the nano zinc powder is 600nm.
The negative electrode of the alkaline zinc-manganese dioxide cell prepared in this example was designated as T2.
Example 3
The specific implementation of this example is the same as example 1, except that: the weight ratio of the graphene quantum dot, carbon nano tube and zinc oxide composite material is 2:5.
The negative electrode of the alkaline zinc-manganese dioxide cell prepared in this example was designated as T3.
Comparative example 1
The specific embodiment of this comparative example is the same as example 1, except that: the weight ratio of the graphene quantum dot, carbon nano tube and zinc oxide composite material is 5:1.
The negative electrode of the alkaline zinc-manganese dioxide cell prepared in this comparative example was designated as D1.
Comparative example 2
The specific embodiment of this comparative example is the same as example 1, except that: the particle size of the nano zinc powder is 1000nm.
The negative electrode of the alkaline zinc-manganese dioxide cell prepared in this comparative example was designated as D2.
Comparative example 3
The specific embodiment of this comparative example is the same as example 1, except that: the conductive auxiliary agent is a common multiwall carbon nanotube.
The negative electrode of the alkaline zinc-manganese dioxide cell prepared in this comparative example was designated as D3.
Evaluation of Performance
Discharge capacity and cycle performance: preparing a 2Ah LR6 type zinc-manganese battery by using the cathodes prepared in each example and comparative example, and assembling a secondary chargeable columnar Zn/Mn battery by using a stainless steel shell, a positive electrode ring (containing electrolyte), the electrolyte and the cathodes, wherein the electrolyte in each cycle test of each battery is the same; the discharge capacity was measured by constant current charging and discharging at a current density of 0.1C of the assembled battery in a voltage interval of 0.8 to 2.2V, 5 samples were tested for each comparative example, and the measured values were averaged over 100 cycles and recorded in table 1.
TABLE 1
It can be known from examples 1-3 and comparative examples 1-3 that the negative electrode of the alkaline zinc-manganese battery and the preparation method thereof provided by the invention effectively improve the overall capacitance, conductivity and cycle performance of the battery after being added into the zinc-manganese battery, effectively prolong the service life of the zinc-manganese battery, are suitable for popularization in the battery field, and have wide development prospects. Wherein example 1 obtained the best performance index with the best weight ratio of raw materials.

Claims (2)

1. The alkaline zinc-manganese battery cathode is characterized by comprising the following raw materials in parts by weight: 60-65 parts of solid powder, 10-15 parts of alkaline agent, 1-3 parts of zinc oxide, 0.01-0.5 part of silicate, 0.1-0.5 part of binder and 30-35 parts of deionized water;
The solid powder raw materials comprise the following components in parts by weight: 40-50 parts of nano zinc powder, 1-10 parts of conductive additive, 15-20 parts of organic resin, 30-35 parts of ketone solvent, 1-5 parts of plasticizer and 1-3 parts of coupling agent;
The particle size of the nano zinc powder is 300-600 nm; the organic resin is at least one of polyvinyl chloride, polyvinylidene fluoride and polyethylene peroxide resin; the ketone solvent is at least one of acetone, butanone and cyclohexanone; the plasticizer is at least one of dioctyl phthalate, n-octyl phthalate and dibutyl phthalate; the coupling agent is at least one of vinyl trichlorosilane, methyl trimethoxy silane and vinyl triethoxy silane;
the conductive auxiliary agent is graphene quantum dots and composite carbon nanotubes;
The weight ratio of the graphene quantum dots to the composite carbon nanotubes is 1-2: 3 to 5;
The graphene quantum dots are carboxylated graphene quantum dots;
the composite carbon nano tube is a composite material of carbon nano tube and zinc oxide;
The preparation method of the composite carbon nano tube comprises the following steps of: (1) Adding 0.5 part of multi-wall carbon nano tube into 150 parts of deionized water to form a mixed solution, and performing ultrasonic dispersion for 1-2 hours; (2) After the dispersion is completed, 20 parts of zinc nitrate hexahydrate and 4 parts of citric acid are added into the mixed solution, and the mixture is stirred and reacted for 1 to 2 hours; (3) Heating to 80-90 ℃, continuously stirring and reacting for 15-18 hours, heating to 160-180 ℃, stopping stirring and preserving heat and reacting for 20-40 minutes; (4) And taking out the solid powder, and placing the solid powder in a tubular furnace at 600 ℃ for heat preservation for 1-2 hours to obtain the composite material of the carbon nano tube and the zinc oxide.
2. A method for preparing the cathode of the alkaline zinc-manganese dioxide battery according to claim 1, which is characterized in that: the method comprises the following steps: (1) Weighing and mixing the conductive auxiliary agent, the organic resin, the ketone solvent, the plasticizer and the coupling agent, and then putting the mixture into a high-speed stirring and dispersing reaction kettle for high-speed stirring for 30-50 minutes to obtain a mixed solution; (2) Mixing and stirring the mixed solution obtained in the step (1) and nano zinc powder for 20-30 minutes, and then centrifuging, volatilizing and drying to obtain solid powder; (3) Then putting the solid powder, the binder and the silicate into a mixer, and uniformly stirring to prepare dry powder; adding an alkaline agent and zinc oxide into deionized water to prepare a strong alkali solution; (4) And (3) putting the dry powder and the strong alkali solution into a zinc paste machine, uniformly stirring, vacuumizing, and removing bubbles to obtain the negative electrode material.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102938464A (en) * 2012-11-22 2013-02-20 浙江特源电池有限公司 Low-gassing-amount alkaline zinc-manganese battery cathode additive and preparation method thereof
JP2014026951A (en) * 2011-08-23 2014-02-06 Nippon Shokubai Co Ltd Zinc negative electrode mixture, and battery arranged by use thereof
CN108172854A (en) * 2016-12-07 2018-06-15 广东力王新能源股份有限公司 Alkaline zinc-manganese battery containing zinc oxide and preparation method thereof
CN110783560A (en) * 2019-09-24 2020-02-11 宁波泰意德过滤技术有限公司 Alkaline zinc-manganese battery containing modified nano zinc powder and preparation method thereof
CN111162329A (en) * 2019-12-25 2020-05-15 浙江野马电池股份有限公司 Alkaline zinc-manganese battery cathode additive and preparation method thereof
CN111788714A (en) * 2017-08-31 2020-10-16 纽约城市大学研究基金会 Ion-selective membranes for selective ion permeation in alkaline cells
CN112838213A (en) * 2021-01-25 2021-05-25 广州倬粤电能科技有限公司 Zinc-manganese battery containing modified nano zinc powder and preparation method thereof
CN112864390A (en) * 2021-01-27 2021-05-28 广州倬粤电能科技有限公司 Cathode material for zinc-manganese battery and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014026951A (en) * 2011-08-23 2014-02-06 Nippon Shokubai Co Ltd Zinc negative electrode mixture, and battery arranged by use thereof
CN102938464A (en) * 2012-11-22 2013-02-20 浙江特源电池有限公司 Low-gassing-amount alkaline zinc-manganese battery cathode additive and preparation method thereof
CN108172854A (en) * 2016-12-07 2018-06-15 广东力王新能源股份有限公司 Alkaline zinc-manganese battery containing zinc oxide and preparation method thereof
CN111788714A (en) * 2017-08-31 2020-10-16 纽约城市大学研究基金会 Ion-selective membranes for selective ion permeation in alkaline cells
CN110783560A (en) * 2019-09-24 2020-02-11 宁波泰意德过滤技术有限公司 Alkaline zinc-manganese battery containing modified nano zinc powder and preparation method thereof
CN111162329A (en) * 2019-12-25 2020-05-15 浙江野马电池股份有限公司 Alkaline zinc-manganese battery cathode additive and preparation method thereof
CN112838213A (en) * 2021-01-25 2021-05-25 广州倬粤电能科技有限公司 Zinc-manganese battery containing modified nano zinc powder and preparation method thereof
CN112864390A (en) * 2021-01-27 2021-05-28 广州倬粤电能科技有限公司 Cathode material for zinc-manganese battery and preparation method thereof

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