CN105047876B - Preparation method of composite cathode material of ferroelectric battery - Google Patents

Preparation method of composite cathode material of ferroelectric battery Download PDF

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CN105047876B
CN105047876B CN201510389307.XA CN201510389307A CN105047876B CN 105047876 B CN105047876 B CN 105047876B CN 201510389307 A CN201510389307 A CN 201510389307A CN 105047876 B CN105047876 B CN 105047876B
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potassium ferrate
battery
coated
conductive polymer
ferrate
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CN105047876A (en
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王素琴
黎泓波
侯豪情
王瑶瑶
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Jiangxi Normal University
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Jiangxi Normal University
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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

Abstract

The invention discloses a preparation method of a composite cathode material of a ferrate battery, which is characterized in that a layer of conductive polymer is coated on the surface of potassium ferrate, the conductive polymer can block the contact of the potassium ferrate and an electrolyte, the conductivity of an electrode material is enhanced, the charge transfer resistance in an electrode is reduced, the utilization rate of the ferrate cathode material is improved, and the ferrate cathode material is used as a cathode material of an alkaline ferrate battery, so that the development and the application of the ferrate battery have wide prospects.

Description

Preparation method of composite cathode material of ferroelectric battery
Technical Field
The invention relates to a preparation method of a battery anode material, in particular to a preparation method of a composite anode material of a ferroelectric battery.
Background
The high potassium carbonate battery is a battery taking a hexavalent iron compound as a positive electrode material, the theoretical specific capacitance of the potassium ferrate battery is 406 mAh/g, and the specific alkaline Zn-MnO is2The battery capacity is 32 percent, the potassium ferrate has strong oxidizability and can be generally used for sewage treatment, and the discharge product of the potassium ferrate is Fe2O3·nH2O, has flocculation function and can be used for sewage treatment, so the potassium ferrate battery does not pollute the environment and is a green battery. The material can be used as the anode of an alkaline potassium ferrate battery and can also be used as the anode material of a lithium ion battery.
Ferrate is unstable in moist environments and is susceptible to decomposition. When the potassium ferrate is used as a positive electrode material of a battery in an alkaline electrolyte, the potassium ferrate is partially decomposed, the conductivity of a decomposition product is poor, the utilization rate and the discharge efficiency of the potassium ferrate are reduced, and the development of the potassium ferrate alkaline battery is hindered by the instability of the potassium ferrate.
In the currently published patents and literature reports, the methods for improving the stability of the potassium ferrate battery mainly include: by means of an inorganic compound SiO2、ZrO2Or Y2O3Doped ZrO2Is coated at equal heightThe surface of the potassium ferrite improves the stability of the potassium ferrate; the stability of the potassium ferrate can also be improved by coating the surface of the potassium ferrate with a micromolecule organic compound 2, 3-naphthalocyanine or porphyrin; or coating a small amount of sodium bismuthate on the surface of the porphyrin-coated potassium ferrate. Coating sodium bismuthate, 2, 3-naphthalocyanine, Y2O3Doped ZrO2The stability of the potassium ferrate is improved, and the conductivity of the potassium ferrate is improved at the same time.
Disclosure of Invention
The invention aims to provide a preparation method of a composite cathode material of a high-iron battery, which coats a layer of conductive polymer on the surface of potassium ferrate, wherein the conductive polymer can block the contact of the potassium ferrate and electrolyte, enhance the conductivity of an electrode material and reduce the charge transfer resistance in an electrode, thereby achieving the purpose of improving the stability and the discharge efficiency of the cathode of the potassium ferrate.
The invention is realized by the following steps:
dissolving a certain amount of conductive polymer in a low-boiling-point solvent, adding a certain proportion of potassium ferrate crystals into the solvent, drying the mixture under reduced pressure, removing the solvent to obtain the conductive polymer-coated potassium ferrate crystals, and taking the conductive polymer-coated potassium ferrate electrode as the anode of the alkaline potassium ferrate battery.
The low boiling point solvent can be one or more of diethyl ether, chloroform, dichloromethane, acetonitrile, acetone, toluene and benzene.
The conductive polymer can be one or more of polythiophene and derivatives thereof, polyaniline and derivatives thereof, polypyrrole and derivatives thereof, and polyphenylacetylene and derivatives thereof.
The mass proportion of the conductive polymer in the coated potassium ferrate is 0-10%.
The mass ratio of the potassium ferrate in the coated potassium ferrate is between 90 and 100 percent.
The battery anode is a battery containing hexavalent iron oxysalt.
The invention has the technical effects that: the surface of the potassium ferrate crystal is uniformly coated with the conductive polymer, and the conductive polymer is difficult to dissolve in alkaline electrolyte and has high conductivity, so that the stability and the conductivity of the ferrate are greatly improved, the utilization rate of a ferrate anode material is improved, and the ferrate anode material is used as an anode material of an alkaline ferrate battery, so that the development and the application of the potassium ferrate battery have wide prospects.
Drawings
FIG. 1 is an XPS spectrum of poly-3-hexylthiophene coated potassium ferrate obtained in example.
FIG. 2 is an SEM of poly-3-hexylthiophene coated potassium ferrate obtained in the example.
Detailed Description
The following detailed description will be provided with the advantages of the present invention in conjunction with the embodiments of the drawings, which are intended to help the reader to better understand the spirit of the present invention, but not to limit the scope of the present invention.
Example 1:
dissolving a certain amount of poly-3-hexylthiophene in chloroform, adding a certain amount of potassium ferrate crystals into the chloroform to ensure that the proportion of the poly-3-hexylthiophene in the coated material is 1%, drying the mixture under reduced pressure, removing the chloroform to obtain the poly-3-hexylthiophene coated potassium ferrate crystals, and taking the poly-3-hexylthiophene coated potassium ferrate electrode as the anode of the alkaline potassium ferrate battery.
Example 2:
dissolving a certain amount of polythiophene in chloroform, adding a certain amount of potassium ferrate crystals to ensure that the ratio of polythiophene in the coated material is 1%, drying under reduced pressure, removing the chloroform to obtain the polythiophene-coated potassium ferrate crystals, and taking the polythiophene-coated potassium ferrate electrode as the anode of the alkaline potassium ferrate battery.
Example 3:
dissolving a certain amount of poly (ethylenedioxythiophene) in chloroform, adding a certain amount of potassium ferrate crystals into the chloroform to ensure that the proportion of the poly (ethylenedioxythiophene) in the coated material is 1%, drying the coated material under reduced pressure, removing the chloroform to obtain the poly (ethylenedioxythiophene) -coated potassium ferrate crystals, and taking the poly (ethylenedioxythiophene) -coated potassium ferrate electrode as the anode of the alkaline potassium ferrate battery.
Example 4:
dissolving a certain amount of polyaniline in acetonitrile, adding a certain amount of potassium ferrate crystals to ensure that the proportion of the polyaniline in the coated material is 1%, drying under reduced pressure, removing the acetonitrile to obtain the polyaniline-coated potassium ferrate crystals, and taking the polyaniline-coated potassium ferrate electrode as the anode of the alkaline potassium ferrate battery.
Example 5:
dissolving a certain amount of polypyrrole in chloroform, adding a certain amount of potassium ferrate crystals into the chloroform to enable the proportion of the polypyrrole in the coated material to be 1%, drying the material under reduced pressure, removing the chloroform to obtain the polypyrrole-coated potassium ferrate crystals, and taking the polypyrrole-coated potassium ferrate electrode as the anode of the alkaline potassium ferrate battery.
Example 6:
dissolving a certain amount of poly-3-methylpyrrole in chloroform, adding a certain amount of potassium ferrate crystals into the chloroform to ensure that the proportion of the poly-3-methylpyrrole in the coated material is 1 percent, drying the coated material under reduced pressure, removing the chloroform to obtain the poly-3-methylpyrrole coated potassium ferrate crystals, and taking the poly-3-methylpyrrole coated potassium ferrate electrode as the anode of the alkaline potassium ferrate battery.
Example 7:
dissolving a certain amount of polyphenylacetylene in a mixed solvent of chloroform and acetonitrile, adding a certain amount of potassium ferrate crystals into the mixed solvent to ensure that the proportion of the polyphenylacetylene in the coated material is 1%, drying the material under reduced pressure, removing the chloroform and the acetonitrile to obtain the polyphenylacetylene-coated potassium ferrate crystals, and taking the polyphenylacetylene-coated potassium ferrate electrode as the anode of the alkaline potassium ferrate battery.
The low boiling point solvent can be one or more of diethyl ether, chloroform, dichloromethane, acetonitrile, acetone, toluene and benzene.
The conductive polymer can be one or more of polythiophene and derivatives thereof, polyaniline and derivatives thereof, polypyrrole and derivatives thereof, and polyphenylacetylene and derivatives thereof.
The mass proportion of the conductive polymer in the coated potassium ferrate is 0-10%.
The mass ratio of the potassium ferrate in the coated potassium ferrate is between 90 and 100 percent.
The battery anode is a battery containing hexavalent iron oxysalt.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.

Claims (3)

1. The preparation method of the alkaline super-iron battery composite positive electrode material is characterized by comprising the following steps: dissolving a certain amount of conductive polymer in a low-boiling-point solvent, adding a certain proportion of potassium ferrate crystals into the solvent, drying the mixture under reduced pressure, and removing the solvent to obtain the conductive polymer-coated potassium ferrate crystals, wherein a conductive polymer-coated potassium ferrate electrode is used as the anode of an alkaline potassium ferrate battery;
the conductive polymer is one or more of polythiophene and derivatives thereof, polyaniline and derivatives thereof, polypyrrole and derivatives thereof, and polyphenylacetylene and derivatives thereof;
the composite positive electrode material of the alkaline ferroelectric battery contains an oxysalt of hexavalent iron, and particularly relates to a potassium ferrate electrode coated by a conductive polymer, wherein the conductive polymer accounts for 1% of the coated potassium ferrate by mass.
2. The preparation method of the alkaline ferroelectric battery composite positive electrode material according to claim 1, characterized in that: the low boiling point solvent is one or more of diethyl ether, chloroform, dichloromethane, acetonitrile, acetone, toluene and benzene.
3. A battery comprising the alkaline ferroelectric battery composite positive electrode material prepared according to claim 1.
CN201510389307.XA 2015-07-06 2015-07-06 Preparation method of composite cathode material of ferroelectric battery Active CN105047876B (en)

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CN112117136B (en) * 2020-09-14 2021-09-14 东北石油大学 GO-CS coated potassium ferrate material and preparation method and application thereof
CN112820873B (en) * 2020-12-31 2022-07-05 深圳市德方创域新能源科技有限公司 Polymer-coated lithium battery positive electrode material and preparation method thereof
CN115050947B (en) * 2022-07-29 2023-07-28 湖北亿纬动力有限公司 Modified ferrate positive electrode material, preparation method thereof and lithium ion battery

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CN102522563A (en) * 2011-12-30 2012-06-27 中国科学院广州能源研究所 Conducting-polymer dipped and coated lithium-ion battery composite-electrode material and preparation method thereof
CN103985853A (en) * 2013-12-16 2014-08-13 青岛乾运高科新材料股份有限公司 Modification method of lithium-enriched manganese-based solid solution lithium battery cathode material
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CN103259012B (en) * 2013-05-15 2015-07-22 江西师范大学 Preparation method of three-dimensional conductive super-iron battery K2FeO4/C composite negative pole material
CN104466135B (en) * 2014-12-15 2017-01-25 中信大锰矿业有限责任公司大新锰矿分公司 Method for coating conductive polymer on Ni-Co-Mn acid lithium positive electrode material

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CN102185140A (en) * 2011-03-31 2011-09-14 中国科学院过程工程研究所 Preparation method of nano-network conductive polymer coated lithium iron phosphate anode material
CN102522563A (en) * 2011-12-30 2012-06-27 中国科学院广州能源研究所 Conducting-polymer dipped and coated lithium-ion battery composite-electrode material and preparation method thereof
CN103985853A (en) * 2013-12-16 2014-08-13 青岛乾运高科新材料股份有限公司 Modification method of lithium-enriched manganese-based solid solution lithium battery cathode material
CN104466139A (en) * 2014-12-28 2015-03-25 刘娜 Preparation method of polyaniline-clad germanium-doped lithium manganate composite cathode material

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