CN111048771A - Zinc-based battery and preparation method and application thereof - Google Patents

Zinc-based battery and preparation method and application thereof Download PDF

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Publication number
CN111048771A
CN111048771A CN202010006011.6A CN202010006011A CN111048771A CN 111048771 A CN111048771 A CN 111048771A CN 202010006011 A CN202010006011 A CN 202010006011A CN 111048771 A CN111048771 A CN 111048771A
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CN
China
Prior art keywords
zinc
powder
mixture
based battery
sponge
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202010006011.6A
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Chinese (zh)
Inventor
何祚
曹令花
其他发明人请求不公开姓名
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Lingzhuo Smart Co ltd
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Shenzhen Lingzhuo Smart Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Lingzhuo Smart Co ltd filed Critical Shenzhen Lingzhuo Smart Co ltd
Priority to CN202010006011.6A priority Critical patent/CN111048771A/en
Publication of CN111048771A publication Critical patent/CN111048771A/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a zinc-based battery, which adopts sponge Zn as a negative electrode, a porous pp film and non-woven fabric as a diaphragm, NiOOH as a positive electrode, Zn (OH)2The mixed solution of KOH/LiOH is used as electrolyte, the cycle performance is good, and no dendritic crystal is generated.

Description

Zinc-based battery and preparation method and application thereof
Technical Field
The invention relates to the field of rechargeable batteries, in particular to a zinc-based battery and a preparation method and application thereof.
Background
Lithium ion batteries are currently in widespread use. However, lithium is hazardous in nature due to its low melting point. Accidents caused by lithium battery explosion are seen in the newspaper end from time to time for many years. Furthermore, the content of lithium in the earth's crust is low. And the zinc content is rich and has no danger. Therefore, the zinc-based battery is expected to overcome the weak points of the lithium battery and be applied. However, the current zinc-based battery has zinc dendrites, so that the charging capability and the cycling performance of the zinc-based battery are poor, and the application of the zinc-based battery is limited.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a nickel-zinc battery and a preparation technology thereof, aiming at overcoming dendrite existing in a zinc-based battery.
In order to achieve the purpose, the invention adopts the technical scheme that: the nickel-zinc battery is assembled by adopting the sponge zinc, and the result shows that the battery does not have zinc dendrite and has good charging and discharging performance.
The preparation method comprises the following steps:
1. zinc powder, Bi powder, carboxymethyl cellulose, magnesium lauryl sulfate, Bi powder were vigorously stirred in a water/decane mixture (4.28 mL water/9.51 mL) for about 20 minutes, and the resulting emulsion was poured into a cylindrical mold and dried for 10 hours to obtain a disk-shaped mixture.
2. Taking out the mixture from the mold, annealing the mixture in a tube furnace for 2 hours, and then reacting the mixture for 0.5 hour under the environment of argon protection at 400-450 ℃; the temperature was then increased to 640-660 ℃. The heating step oxidizes the surface of the sponge to create a zinc oxide shell, and the interior of the zinc oxide shell is continuously oxidized.
3. Electro-reducing a sponge zinc electrode: the zinc sponge was electro-reduced in a three electrode cell at 6ml/l KOH under a voltage of 50 mv.
4. Sponge Zn is used as a negative electrode, a porous pp film and non-woven fabric are used as a diaphragm, NiOOH is used as a positive electrode, Zn (OH)2The mixed solution of KOH/LiOH is used as the electrolyte. And assembling the battery.
The zinc powder and the Bi powder are particles with the particle size of less than 300 meshes, and the mass percentage of the zinc powder, the carboxymethyl cellulose and the 50 mg of lauryl magnesium sulfate is 100: 4-5: 0.1-0.5, wherein the mass fraction of Bi powder is 10-200 ppm; the ratio of the water/decane mixture is 1: 2-1: 3.
The invention adopts the sponge zinc as the anode, and as a result, the invention discovers that the cycle performance of the battery is greatly improved, and no dendrite is generated. Lithium ions are added into the electrolyte, so that the precipitation of oxygen can be inhibited, the rechargeable performance of NiOOH is enhanced, and the precipitation of hydrogen can be inhibited by adding Bi powder.
Detailed Description
The present invention will be further illustrated by the following examples.
Example 1:
1. 50 g of zinc powder, 2 g of carboxymethyl cellulose, 50 mg of magnesium lauryl sulfate, 3 mg of Bi powder were vigorously stirred in a water/decane mixture (5 mL of water/10 mL of decane) for about 20 minutes, and the resulting emulsion was poured into a cylindrical mold and dried for 10 hours to obtain a disk-shaped mixture.
2. Taking the mixture out of the mold, annealing in a tube furnace for 2 hours, and then reacting for 0.5 hour at 400 ℃ under the protection of argon; the temperature was then increased to 660 ℃.
3. In a three-electrode cell with 6ml/l KOH, the zinc sponge is reduced under the condition of 50mv voltage.
4. Sponge Zn is used as a negative electrode, a porous pp film and non-woven fabric are used as a diaphragm, NiOOH is used as a positive electrode, Zn (OH)2The mixed solution of KOH/LiOH is used as electrolyte to assemble the battery; wherein the molar ratio of Zn (OH)2:KOH:LiOH=100:6:1。
The battery was charged and discharged for 200 cycles at a current density of 10 milliampere/square centimeter, the capacity retention rate was 81%, and the battery was disassembled and no dendrite was found to be generated.
Example 2:
1. 50 g of zinc powder, 2.5 g of carboxymethylcellulose, 150 mg of magnesium lauryl sulfate, 6 mg of Bi powder in a water/decane mixture (5 mL of water/15 mL of decane) were vigorously stirred for about 20 minutes, and the resulting emulsion was poured into a cylindrical mold and dried for 10 hours to obtain a disk-shaped mixture.
2. Taking the mixture out of the mold, annealing in a tube furnace for 2 hours, and then reacting for 0.5 hour at 450 ℃ under the protection of argon; the temperature was then increased to 600 ℃.
3. In a three-electrode cell with 6ml/l KOH, the zinc sponge is reduced under the condition of 50mv voltage.
4. Sponge Zn is adopted as a negative electrode, a porous pp film and a non-woven fabric are adopted as a diaphragm, NiOOH is a positive electrode, and the proportion of electrolyte is as follows: zn (OH)2KOH LiOH =100:5:1, and the cell was assembled.
The battery was charged and discharged for 200 cycles at a current density of 10 milliampere/square centimeter, the capacity retention rate was 83%, and the battery was disassembled and no dendrite was found to be generated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1. The zinc-based battery is characterized in that the zinc-based battery adopts sponge Zn as a negative electrode, a porous pp film and non-woven fabric as a diaphragm, NiOOH as a positive electrode, Zn (OH)2The mixed solution of KOH/LiOH is used as the electrolyte.
2. A zinc-based battery according to claim 1, characterised in that the negative electrode material contains Bi.
3. A zinc-based battery according to claim 1, characterized in that the method of manufacturing the zinc-based battery comprises the steps of:
1) zinc powder, Bi powder, carboxymethyl cellulose, lauryl magnesium sulfate and Bi powder are stirred vigorously in a water/decane mixture, the obtained emulsion is poured into a cylindrical mold, and the cylindrical mold is dried to obtain a disc-shaped mixture;
2) taking out the mixture from the mold, annealing the mixture in a tube furnace, and then reacting the mixture for 0.5 hour in an environment protected by argon at 400-450 ℃; then the temperature is increased to 640-660 ℃; oxidizing the surface of the sponge formed in the heating step to create a zinc oxide shell, and continuously performing oxidation reaction in the zinc oxide shell;
3) electro-reducing a sponge zinc electrode: electro-reducing zinc sponge in a three electrode cell at 6ml/l KOH under 50mv voltage;
4) sponge Zn is used as a negative electrode, a porous pp film and non-woven fabric are used as a diaphragm, NiOOH is used as a positive electrode, Zn (OH)2And the mixed solution of KOH/LiOH is used as electrolyte to assemble the battery.
4. The method of claim 3, wherein the zinc powder and the Bi powder are particles of 300 mesh or less.
5. The method for preparing a zinc-based battery according to claim 3, wherein the zinc powder, the carboxymethyl cellulose and the 50 mg of magnesium lauryl sulfate are mixed in a mass percentage of 100: 4-5: 0.1-0.5, wherein the mass fraction of Bi powder is 10-200 ppm; the ratio of the water/decane mixture is 1: 2-1: 3.
CN202010006011.6A 2020-01-03 2020-01-03 Zinc-based battery and preparation method and application thereof Withdrawn CN111048771A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010006011.6A CN111048771A (en) 2020-01-03 2020-01-03 Zinc-based battery and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010006011.6A CN111048771A (en) 2020-01-03 2020-01-03 Zinc-based battery and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN111048771A true CN111048771A (en) 2020-04-21

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010006011.6A Withdrawn CN111048771A (en) 2020-01-03 2020-01-03 Zinc-based battery and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111048771A (en)

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