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CN115101744B - An iron-doped cobalt tetroxide cathode material, its preparation method, and its application in zinc-based alkaline batteries. - Google Patents

An iron-doped cobalt tetroxide cathode material, its preparation method, and its application in zinc-based alkaline batteries.

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Publication number
CN115101744B
CN115101744B CN202210632243.1A CN202210632243A CN115101744B CN 115101744 B CN115101744 B CN 115101744B CN 202210632243 A CN202210632243 A CN 202210632243A CN 115101744 B CN115101744 B CN 115101744B
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iron
zinc
doped
cathode material
alkaline battery
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CN115101744A (en
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马天翼
李嘉斫
张思文
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Liaoning University
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Liaoning 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/521—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of iron for aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the technical field of battery anode materials, and particularly relates to an application of an iron-doped tricobalt tetraoxide anode material in a zinc-based alkaline battery. Adding cobalt nitrate, ferric nitrate and hexamethylenetetramine into deionized water, stirring, transferring the obtained mixed solution into a reaction kettle, vertically immersing the pretreated conductive substrate into the solution, carrying out hydrothermal reaction, taking out the solution, drying in vacuum, and placing the obtained sample loaded with the precursor into a muffle furnace for calcination to obtain the iron-doped cobaltosic oxide anode material. The iron-doped cobaltosic oxide positive electrode material is applied to a zinc-based alkaline battery, and the electrochemical test shows that the iron-doped cobaltosic oxide material has higher specific capacity than the original cobaltosic oxide. The invention has simple synthesis process, is economical and environment-friendly, has low price and is hopeful to become a novel energy storage device.

Description

Iron-doped tricobalt tetraoxide positive electrode material, preparation method thereof and application thereof in zinc-based alkaline battery
Technical Field
The invention belongs to the technical field of battery anode materials, and particularly relates to an iron-doped tricobalt tetraoxide anode material, a preparation method thereof and application thereof in zinc-based alkaline batteries.
Background
Due to the rapid consumption of fossil fuels, it is very necessary to find sustainable energy sources. Successful use of fluctuating and intermittent renewable energy sources requires reliable and efficient energy storage. Batteries have achieved great success as an energy storage strategy. For example, lithium ion batteries have been successfully commercialized because of their high energy density and stability. However, many problems, such as high cost (about 9 tens of thousands of dollars per ton), potential hazards, and health hazards, have not been adequately addressed. In addition to lithium ion batteries, zinc-based batteries have attracted considerable attention in recent years because of the abundance of zinc resources, low cost, inherent safety and high theoretical capacity. To date, zn-Mn, zn-NiO and Zn-Ag batteries have been widely explored. The charge and discharge process involves oxidation and reduction reactions of metallic zinc and active materials. However, limited by the shortage of theoretical capacity and low utilization of the cathode material, the actual capacity is not attractive. For example, the operating capacity of a Zn-Ni battery is 165mAh/g. Only 46% of theory (360 mAh/g) resulted in a lower energy density (228 Wh/kg). Among zinc-based batteries, zn-Co batteries have recently made great progress. Cobalt-based materials are considered to be a great electrode material due to their high theoretical capacity, high potential, high redox activity and good reversibility. However, due to the low conductivity and small specific surface area, the practical capacity is far lower than the theoretical capacity. Cobalt oxide (Co 3O4) as a transition metal oxide can be used as a positive electrode material, and has a higher theoretical capacity of 446mAh/g in alkaline batteries, and operating voltages as high as 1.8V. Even with good success, the utilization of active materials is still under (less than 50%) considering the theoretical capacity of Co 3O4, resulting in wasted capacity. In addition to using alkaline electrolyte, zinc cells assembled from Co (III) rich Co 3O4 can operate at 2V voltage with a capacity of 205mAh/g using mild electrolyte. In contrast, the potential of zinc potential (-1.22 VvsSHE) in alkaline electrolyte is lower than in mild electrolyte (-0.76V vs SHE), which provides the possibility of higher cell voltages. In addition, in a mild electrolyte, the hydrogen evolution reaction and the formation of inactive zinc hydrate are serious, resulting in poor reversibility of the Zn electrode, so that the theoretical capacity of Co 3O4 in an alkaline electrolyte is almost twice that of a mild solution. For this purpose, we selected an alkaline solution as the electrolyte to prepare a zinc-based alkaline cell.
Disclosure of Invention
The invention aims to provide an application of an iron-doped cobaltosic oxide positive electrode material in a zinc-based alkaline battery, and the specific capacity of the zinc-based alkaline battery is obviously improved.
The technical scheme includes that the preparation method of the iron-doped cobaltosic oxide positive electrode material comprises the following steps of adding cobalt nitrate, ferric nitrate and hexamethylenetetramine into deionized water, stirring and dissolving, continuously stirring for 1h, transferring the obtained mixed solution into a reaction kettle, vertically immersing foam nickel which is treated in advance into the solution, performing hydrothermal reaction, taking out, and vacuum drying to obtain a sample loaded with a precursor. And finally, placing the obtained product in a muffle furnace for calcination to obtain the iron-doped tricobalt tetraoxide anode material.
Preferably, according to the iron-doped cobaltosic oxide positive electrode material, the molar ratio of cobalt nitrate to hexamethylenetetramine to ferric nitrate=1:1:0.1-1 is calculated.
Preferably, an iron-doped tricobalt tetraoxide positive electrode material as described above, the hydrothermal reaction is carried out at 120 ℃ for 16 hours.
Preferably, the above-mentioned iron-doped cobaltosic oxide cathode material is dried in a vacuum drying oven at 60 ℃ for 12 hours.
Preferably, the above-mentioned iron-doped cobaltosic oxide cathode material is calcined in a muffle furnace at 450 ℃ for 2 hours.
The invention provides an application of an iron-doped cobaltosic oxide positive electrode material in a zinc-based alkaline battery.
A zinc-based alkaline battery based on an iron-doped cobaltosic oxide positive electrode material is prepared by respectively cutting an iron-doped cobaltosic oxide positive electrode and a negative electrode zinc sheet, clamping the positive electrode sheet and the negative electrode sheet in an electrode clamp, and placing the electrode clamp in an electrolytic cell with electrolyte, wherein the uppermost part of the electrode material is flush with the electrolyte to form the iron-doped cobaltosic oxide zinc-based alkaline battery.
Preferably, the conductive substrate is one of foam nickel, foam copper and carbon cloth.
Preferably, the electrolyte is one of potassium hydroxide, sodium hydroxide and calcium hydroxide.
The beneficial effects of the invention are as follows:
1. The invention designs a zinc-based alkaline battery based on an iron-doped cobaltosic oxide positive electrode material. The cobalt and iron atoms are adjacent in the periodic table of elements and have similar ionic radii and oxidation states and physicochemical properties. Meanwhile, the doping of iron atoms does not cause large distortion of Co 3O4 crystal lattice. The synthesis method has the advantages of low cost, environmental friendliness, controllable morphology and the like.
2. According to the zinc-based alkaline battery assembled by the iron-doped cobaltosic oxide positive electrode material, after iron doping, the specific capacity is increased by 149.53mAh/g, the specific capacity is up to 171.97mAh/g, and the specific capacity is increased by about 7.7 times compared with the original cobaltosic oxide positive electrode material.
3. The selected material has good pseudocapacitance performance, and has the advantages of low cost, environmental protection and recoverability. And simultaneously has high theoretical specific capacity value and good stability.
Drawings
Fig. 1 is an XRD spectrum of the prepared tricobalt tetraoxide and iron-doped tricobalt tetraoxide electrode sheet of the present invention.
Fig. 2 is an SEM spectrum of an iron-doped tricobalt tetraoxide electrode sheet prepared according to the present invention.
Fig. 3 is a comparison plot of cyclic voltammograms of an iron-doped tricobalt zinc oxide-based alkaline cell prepared in accordance with the present invention.
Fig. 4 is a comparative plot of specific capacity of an iron-doped tricobalt zinc oxide-based alkaline cell prepared according to the present invention.
Detailed Description
Example 1
The preparation method of the iron-doped cobaltosic oxide positive electrode material comprises the following steps:
1.5g of cobalt nitrate and 1.5g of hexamethylenetetramine are weighed and dissolved in 30mL of distilled water respectively, and after mixing, ferric nitrate with the molar ratio of cobalt to iron of 1:0.4 is added, and magnetic stirring is carried out for 1h at room temperature, so that the cobalt and the ferric nitrate are fully mixed. Transferring the well mixed solution into a stainless steel water heating reaction kettle with polytetrafluoroethylene lining, soaking foam nickel (3 cm multiplied by 4 cm) with hydrochloric acid to remove an oxide layer, and sequentially cleaning with acetone and deionized water to remove impurities. And vertically immersing the treated foam nickel into the solution of the reaction kettle, and sealing. And (3) carrying out constant temperature treatment for 16h at 120 ℃, taking out the foam nickel when the reaction kettle is completely cooled to room temperature, repeatedly leaching with deionized water and absolute ethyl alcohol so as to remove residual reactants and unsupported nanoparticle fragments, and drying in a vacuum drying oven at 60 ℃ for 12h. Obtaining a sample loaded with the precursor. And finally, placing the obtained product in a muffle furnace and calcining for 2 hours at 450 ℃ to obtain the Fe-Co 3O4 electrode slice growing on the foam nickel.
(II) detection
Fig. 1 is an XRD spectrum of an iron-doped tricobalt tetraoxide positive electrode material and tricobalt tetraoxide positive electrode material prepared according to the present invention. As can be seen from fig. 1, the XRD patterns of the samples did not show significant changes after Fe doping, and the shift of individual peaks indicated that Fe ions were successfully doped into Co 3O4.
Fig. 2 is an SEM spectrum of the iron-doped tricobalt tetraoxide cathode material prepared according to the present invention. As can be seen from fig. 2, the iron-doped tricobalt tetraoxide uniformly grows on the foam nickel conductive substrate, and the morphology of the sample is not changed obviously.
Example 2
The preparation method of the iron-doped cobaltosic oxide positive electrode material comprises the following steps:
3g of cobalt nitrate and 3g of hexamethylenetetramine are weighed and respectively dissolved in 30mL of distilled water, and after mixing, ferric sulfate with the molar ratio of cobalt to iron being 1:0.1 is added, and magnetic stirring is carried out for 2 hours at room temperature, so that the cobalt and the ferric sulfate are fully mixed. Transferring the well mixed solution into a stainless steel water heating reaction kettle with polytetrafluoroethylene lining, soaking foam nickel (3 cm multiplied by 4 cm) with hydrochloric acid to remove an oxide layer, and sequentially cleaning with acetone and deionized water to remove impurities. And vertically immersing the treated foam nickel into the solution of the reaction kettle, and sealing. And (3) carrying out constant-temperature treatment for 12 hours at 150 ℃, taking out the foam nickel when the reaction kettle is completely cooled to room temperature, repeatedly leaching with deionized water and absolute ethyl alcohol so as to remove residual reactants and unsupported nanoparticle fragments, and drying for 12 hours at 60 ℃ in a vacuum drying oven. Obtaining a sample loaded with the precursor. And finally, placing the obtained product in a muffle furnace and calcining for 2 hours at 450 ℃ to obtain the Fe-Co 3O4 electrode slice growing on the foam nickel.
Example 3
The preparation method of the iron-doped cobaltosic oxide positive electrode material comprises the following steps:
1.5g of cobalt chloride and 1.5g of hexamethylenetetramine are weighed and dissolved in 30mL of distilled water respectively, and after mixing, ferric chloride with the molar ratio of cobalt to iron of 1:0.2 is added, and magnetic stirring is carried out for 1h at room temperature, so that the cobalt and the ferric chloride are fully mixed. Transferring the well mixed solution into a stainless steel water heating reaction kettle with polytetrafluoroethylene lining, soaking foam nickel (3 cm multiplied by 4 cm) with hydrochloric acid to remove an oxide layer, and sequentially cleaning with acetone and deionized water to remove impurities. And vertically immersing the treated foam nickel into the solution of the reaction kettle, and sealing. And (3) carrying out constant temperature treatment for 20h at 150 ℃, taking out the foam nickel when the reaction kettle is completely cooled to room temperature, repeatedly leaching with deionized water and absolute ethyl alcohol so as to remove residual reactants and unsupported nanoparticle fragments, and drying in a vacuum drying oven at 60 ℃ for 12h. Obtaining a sample loaded with the precursor. And finally, placing the obtained product in a muffle furnace and calcining for 2 hours at 450 ℃ to obtain the Fe-Co 3O4 electrode slice growing on the foam nickel.
Example 4
The preparation method of the iron-doped cobaltosic oxide positive electrode material comprises the following steps:
3g of cobalt nitrate and 3g of hexamethylenetetramine are weighed and respectively dissolved in 30mL of distilled water, and after mixing, ferric nitrate with the molar ratio of cobalt to iron of 1:0.5 is added, and magnetic stirring is carried out for 2 hours at room temperature, so that the cobalt and the ferric nitrate are fully mixed. Transferring the well mixed solution into a stainless steel water heating reaction kettle with polytetrafluoroethylene lining, soaking foam nickel (3 cm multiplied by 4 cm) with hydrochloric acid to remove an oxide layer, and sequentially cleaning with acetone and deionized water to remove impurities. And vertically immersing the treated foam nickel into the solution of the reaction kettle, and sealing. And (3) carrying out constant temperature treatment for 16h at 120 ℃, taking out the foam nickel when the reaction kettle is completely cooled to room temperature, repeatedly leaching with deionized water and absolute ethyl alcohol so as to remove residual reactants and unsupported nanoparticle fragments, and drying in a vacuum drying oven at 60 ℃ for 12h. Obtaining a sample loaded with the precursor. And finally, placing the obtained product in a muffle furnace and calcining for 2 hours at 450 ℃ to obtain the Fe-Co 3O4 electrode slice growing on the foam nickel.
Example 5
The preparation method of the iron-doped cobaltosic oxide positive electrode material comprises the following steps:
1.5g of cobalt chloride and 1.5g of hexamethylenetetramine are weighed and dissolved in 30mL of distilled water respectively, and after mixing, ferric chloride with the molar mass ratio of cobalt to iron of 1:0.6 is added, and magnetic stirring is carried out for 1.5h at room temperature, so that the cobalt and the ferric chloride are fully mixed. Transferring the well mixed solution into a stainless steel water heating reaction kettle with polytetrafluoroethylene lining, soaking foam nickel (3 cm multiplied by 4 cm) with hydrochloric acid to remove an oxide layer, and sequentially cleaning with acetone and deionized water to remove impurities. And vertically immersing the treated foam nickel into the solution of the reaction kettle, and sealing. And (3) carrying out constant temperature treatment for 16h at 120 ℃, taking out the foam nickel when the reaction kettle is completely cooled to room temperature, repeatedly leaching with deionized water and absolute ethyl alcohol so as to remove residual reactants and unsupported nanoparticle fragments, and drying in a vacuum drying oven at 60 ℃ for 12h. Obtaining a sample loaded with the precursor. And finally, placing the obtained product in a muffle furnace and calcining for 2 hours at 450 ℃ to obtain the Fe-Co 3O4 electrode slice growing on the foam nickel.
Example 6
The preparation method of the iron-doped cobaltosic oxide positive electrode material comprises the following steps:
3g of cobalt nitrate and 3g of hexamethylenetetramine are weighed and respectively dissolved in 30mL of distilled water, and after mixing, ferric sulfate with the molar mass ratio of cobalt to iron of 1:0.8 is added, and magnetic stirring is carried out for 2 hours at room temperature, so that the cobalt and the ferric sulfate are fully mixed. Transferring the well mixed solution into a stainless steel water heating reaction kettle with polytetrafluoroethylene lining, soaking foam nickel (3 cm multiplied by 4 cm) with hydrochloric acid to remove an oxide layer, and sequentially cleaning with acetone and deionized water to remove impurities. And vertically immersing the treated foam nickel into the solution of the reaction kettle, and sealing. And (3) carrying out constant-temperature treatment for 12 hours at 150 ℃, taking out the foam nickel when the reaction kettle is completely cooled to room temperature, repeatedly leaching with deionized water and absolute ethyl alcohol so as to remove residual reactants and unsupported nanoparticle fragments, and drying for 12 hours at 60 ℃ in a vacuum drying oven. Obtaining a sample loaded with the precursor. And finally, placing the obtained product in a muffle furnace and calcining for 2 hours at 450 ℃ to obtain the Fe-Co 3O4 electrode slice growing on the foam nickel.
Example 7
The preparation method of the iron-doped cobaltosic oxide positive electrode material comprises the following steps:
1.5g of cobalt chloride and 1.5g of hexamethylenetetramine are weighed and dissolved in 30mL of distilled water respectively, and after mixing, ferric nitrate with the molar mass ratio of cobalt to iron of 1:1 is added, and magnetic stirring is carried out for 1h at room temperature, so that the cobalt and the ferric nitrate are fully mixed. Transferring the well mixed solution into a stainless steel water heating reaction kettle with polytetrafluoroethylene lining, soaking foam nickel (3 cm multiplied by 4 cm) with hydrochloric acid to remove an oxide layer, and sequentially cleaning with acetone and deionized water to remove impurities. And vertically immersing the treated foam nickel into the solution of the reaction kettle, and sealing. And (3) carrying out constant temperature treatment for 16h at 120 ℃, taking out the foam nickel when the reaction kettle is completely cooled to room temperature, repeatedly leaching with deionized water and absolute ethyl alcohol so as to remove residual reactants and unsupported nanoparticle fragments, and drying in a vacuum drying oven at 60 ℃ for 12h. Obtaining a sample loaded with the precursor. And finally, placing the obtained product in a muffle furnace and calcining for 2 hours at 450 ℃ to obtain the Fe-Co 3O4 electrode slice growing on the foam nickel.
Example 8
An alkaline battery based on iron doped cobaltosic oxide anode material as anode material and a preparation method thereof comprises the following steps:
The Fe-Co 3O4 anode and the cathode zinc sheet of the iron-doped cobaltosic oxide anode material obtained in the example 1 are respectively cut, then the anode electrode sheet and the cathode are clamped in an electrode clamp and placed in an electrolytic cell with electrolyte, the uppermost part of the electrode material is flush with the electrolyte, and the iron-doped cobaltosic oxide zinc-based alkaline battery is prepared.
The preparation method comprises the following steps:
The preparation of the zinc-based alkaline battery taking the iron-doped cobaltosic oxide positive electrode material as the positive electrode comprises the steps of respectively cutting an Fe-Co 3O4 positive electrode and a negative electrode zinc sheet into the size of 1X 1cm, clamping the positive electrode sheet and the negative electrode sheet on an electrode clamp, placing the electrode clamp in an electrolytic cell with 3M potassium hydroxide electrolyte, and flushing the uppermost part of the electrode material with the electrolyte to obtain the iron-doped cobaltosic oxide zinc-based alkaline battery.
(II) Performance test
Comparative example a zinc-based alkaline battery containing a tricobalt tetraoxide positive electrode material was prepared as above using a tricobalt tetraoxide electrode material as the positive electrode material.
Fig. 3 is a cyclic voltammogram of a zinc-based alkaline cell assembled from an iron-doped tricobalt tetraoxide positive electrode material and a tricobalt tetraoxide positive electrode material prepared according to the present invention, respectively. As can be seen from fig. 3, after the iron-doped cobaltosic oxide positive electrode material obtained in example 2 is doped with iron, the cyclic voltammetry curve does not show an obvious hydrogen evolution trend at about 1.9V, has an obvious voltage plateau, and can be seen that the capacity of the cyclic voltammetry curve is greater than that of the original cobaltosic oxide positive electrode material.
Fig. 4 is a specific capacity diagram of a zinc-based alkaline battery assembled from an iron-doped tricobalt tetraoxide positive electrode material and a tricobalt tetraoxide positive electrode material prepared according to the present invention, respectively. As can be seen from fig. 4, the specific capacity of the iron-doped cobaltosic oxide cathode material obtained in example 2 is increased by 149.53mAh/g after iron doping, the specific capacity is up to 171.97mAh/g, and the specific capacity is increased by about 7.7 times compared with the original cobaltosic oxide cathode material.

Claims (3)

1.一种基于铁掺杂四氧化三钴正极材料的锌基碱性电池，其特征在于，包括铁掺杂四氧化三钴正极材料，所述的铁掺杂四氧化三钴正极材料，制备方法包括如下步骤：称取3 g硝酸钴和3 g六次甲基四胺分别溶解在30mL蒸馏水中，将其混合后加入钴与铁摩尔比为1：0.1的硫酸铁，在室温下进行磁力搅拌2 h，使之充分混合，将充分混合好的溶液转移到聚四氟乙烯内衬的不锈钢水热反应釜中，将3 cm×4 cm的泡沫镍用盐酸浸泡去除氧化层，再用丙酮和去离子水依次清洗去除杂质，再将处理好的泡沫镍垂直浸末于反应釜的溶液中，密封，在150℃下恒温处理12h，待反应釜完全冷却至室温时，将泡沫镍取出，用去离子水、无水乙醇反复淋洗，以便去除残余的反应物和未负载的纳米颗粒碎片，于真空干燥箱中在60℃下干燥12 h，得到负载有前躯体的样品，最后将所得的产物置于马弗炉中于450℃下煅烧2h，即可制备得到在泡沫镍上生长的Fe-Co3O4正极材料。1. A zinc-based alkaline battery based on iron-doped cobalt tetroxide cathode material, characterized in that it comprises iron-doped cobalt tetroxide cathode material, wherein the preparation method of the iron-doped cobalt tetroxide cathode material includes the following steps: 3 g of cobalt nitrate and 3 g of hexamethylenetetramine are weighed and dissolved in 30 mL of distilled water, mixed, and then ferric sulfate with a cobalt to iron molar ratio of 1:0.1 is added. The mixture is magnetically stirred at room temperature for 2 h to ensure thorough mixing. The thoroughly mixed solution is transferred to a stainless steel hydrothermal reactor lined with polytetrafluoroethylene. 3 cm × 4 cm nickel foam is soaked in hydrochloric acid to remove the oxide layer, then washed with acetone and deionized water sequentially to remove impurities. The treated nickel foam is then vertically immersed in the solution in the reactor, sealed, and treated at 150°C for 12 h. When the reactor has completely cooled to room temperature, the nickel foam is removed and repeatedly rinsed with deionized water and anhydrous ethanol to remove residual reactants and unloaded nanoparticle fragments. It is then dried in a vacuum drying oven at 60°C for 12 h. h, a sample loaded with the precursor is obtained, and finally the obtained product is placed in a muffle furnace and calcined at 450℃ for 2h to prepare Fe- Co3O4 cathode material grown on nickel foam. 2.根据权利要求1所述的基于铁掺杂四氧化三钴正极材料的锌基碱性电池，其特征在于，所述的基于铁掺杂四氧化三钴正极材料的锌基碱性电池制备方法包括如下步骤，铁掺杂四氧化三钴泡沫镍正极材料和负极锌片分别裁剪，然后将正极电极片和负极锌片夹在电极夹，放在带有电解液的电解池里，电极材料最上方与电解液齐平，得铁掺杂四氧化三钴锌基碱性电池。2. The zinc-based alkaline battery based on iron-doped cobalt tetroxide cathode material according to claim 1, characterized in that the preparation method of the zinc-based alkaline battery based on iron-doped cobalt tetroxide cathode material includes the following steps: cutting iron-doped cobalt tetroxide foamed nickel cathode material and negative zinc sheet respectively, then clamping the positive electrode sheet and negative zinc sheet in an electrode clamp, placing them in an electrolytic cell with electrolyte, with the top of the electrode material flush with the electrolyte, to obtain the iron-doped cobalt tetroxide zinc-based alkaline battery. 3.根据权利要求2所述的基于铁掺杂四氧化三钴正极材料的锌基碱性电池，其特征在于，所述电解液是氢氧化钾，氢氧化钠，氢氧化钙的一种。3. The zinc-based alkaline battery based on iron-doped cobalt tetroxide cathode material according to claim 2, wherein the electrolyte is one of potassium hydroxide, sodium hydroxide, and calcium hydroxide.
CN202210632243.1A 2022-06-07 2022-06-07 An iron-doped cobalt tetroxide cathode material, its preparation method, and its application in zinc-based alkaline batteries. Active CN115101744B (en)

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