CN113078328A - Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof - Google Patents

Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof Download PDF

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CN113078328A
CN113078328A CN202110284212.7A CN202110284212A CN113078328A CN 113078328 A CN113078328 A CN 113078328A CN 202110284212 A CN202110284212 A CN 202110284212A CN 113078328 A CN113078328 A CN 113078328A
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fpoh
water
zinc
air battery
microsphere material
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CN113078328B (en
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宋璐涛
吕建国
吕斌
和庆钢
侯阳
张庆华
高翔
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Zhejiang University ZJU
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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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
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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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking

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Abstract

The invention discloses Co-Fe for a water system zinc-air battery5(PO4)4(OH)3•H2An O (Co-FPOH) microsphere positive electrode material and a preparation method thereof. The preparation method comprises the following steps: firstly, dissolving phytic acid in water to form a water phase and dissolving ferric stearate and cobalt stearate in toluene to form an oil phase; and then sequentially transferring the water phase and the oil phase to a polytetrafluoroethylene inner container for hydrothermal reaction to obtain the Co-FPOH microsphere positive electrode material. The preparation method is simple to operate, does not need complex equipment and has low cost; the prepared Co-FPOH microspheres have uniform size, and a rough porous structure is formed on the surfaces of the microspheres. 817 mAh g is shown during the test of the zinc-air batteryzn ‑1Discharge capacity and 167.8 Wh cm‑2Peak power density of (d); at 2 mA cm‑2Can be cycled for 2500 h at the current density of (2).

Description

Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof
Technical Field
The invention relates to the field of electrode materials of water-system zinc-air batteries, in particular to a transition metal phosphate electrode material for a water-system zinc-air battery and a preparation method thereof.
Background
With the development of economy, the living standard of common people is continuously improved, and how to improve the living environment and enhance the living happiness of common people becomes the biggest civil problem at present. However, the acquisition of the necessary energy for survival, often accompanied by a large amount of pollution, greatly affects the vision of people for high-quality life. The electric power is mainly derived from the conversion of fossil energy, and the residual heat generated by the thermal power station is discharged into lakes, the atmosphere or the ocean, which is likely to cause thermal pollution and destroy the ecological environment of the area. In addition, fossil fuels, due to their high carbon content, emit large amounts of the greenhouse gas carbon dioxide during combustion, which is an important factor in global warming; the sulfur dioxide, nitrogen oxide and a large amount of dust particles generated along with combustion are the primitive fierce of haze, and serious influence is brought to the life and health of people. Solar energy, wind energy and the like are used as novel environment-friendly sustainable development energy sources, and the possibility is provided for the greening process. The high cost and inefficiency of photovoltaic power generation, the intermittency of wind power generation, and noise problems have led to a long-felt need for the advancement of such green energy sources. In addition, in recent years, with the popularization of renewable energy and the increase of policy strength, a series of highly integrated smart grids and electric vehicle industries are rapidly developed, and therefore, electrochemical energy storage and conversion are an important link for the development of new green energy. Research hotspots for electrochemical energy storage and conversion include: primary batteries, secondary batteries, supercapacitors, fuel cells and photoelectrochemical cells. Among them, the fuel cell of interest has its unique advantages as an energy conversion device: the chemical energy is directly converted into the electric energy without the limitation of Carnot cycle, the energy conversion rate is high (46-75%), the environment is friendly, and the safety is high. The super capacitor of the special energy storage device between the traditional capacitor and the battery also has great development potential, according to incomplete statistics, the domestic keeping quantity of the super capacitor exceeds 40 ten thousand of all-electric driven automobiles and oil-electric hybrid automobiles, and the super capacitor and the secondary battery are accepted by mainstream markets, so that the electric automobiles tend to be scaled. However, with the progress of practical application, the requirements for electrochemical energy conversion devices are higher and higher, and only energy storage devices with high power density, low self-discharge, fast charge and discharge performance, etc. can really meet the challenges in practical application, especially how to maintain the conversion efficiency and safety of the system in a harsh environment is a great challenge, and it is necessary to understand the operation mechanism thereof in an all-round manner and to adopt corresponding improvement means.
Zinc-air batteries (ZABs) are a special class of alkaline fuel cells whose specific energy is determined primarily by the negative metallic zinc. It has a higher specific energy (about 5-7 times that of a conventional dry battery) than a conventional battery. The battery system allows deep discharge, has wide working current range (depending on the reactivity of the oxygen evolution reaction OER and the oxygen reduction reaction ORR of the air electrode), and can normally work in the temperature range of-10-70 ℃. The production cost of the battery is low, the reaction substance of the positive electrode is oxygen in the air, and the source of the negative electrode active substance zinc is rich. Most importantly, the zinc-air battery has no pollution problem no matter the battery is made of the material or in the working process, toxic elements such as lead, mercury, cadmium and the like in the traditional battery are fundamentally abandoned, the pollution problem of the traditional battery is solved, and the zinc-air battery meets the basic requirements of developing a new energy plan. As one of the important development directions in the field of typical clean energy conversion, the battery system is widely applied to small-sized mobile electronic equipment and has practicability in small and medium-sized fields such as electric vehicles and smart grids, and the battery system mainly comprises three parts: anode metal Zn, alkaline or neutral salt electrolyte, cathode air electrode. The air electrode is generally composed of a catalytic layer, a current collecting layer and a hydrophobic layer.
At present, the anode of the water system zinc-air battery has low dual-functional oxygen catalytic activity, which is a key and bottleneck link for restricting the wide application of the battery. The key for improving the dual-functional oxygen catalytic activity of the anode of the water system zinc-air battery is to improve the surface catalytic active site of the electrocatalyst. Compared with a lithium-air battery, the zinc-air battery has lower cost and higher safety coefficient, so that the zinc-air battery is the focus of research and development. Currently, the research and development of electrode materials for zinc-air batteries mainly include: transition metal selenides, transition metal oxides and double hydroxides, transition metal sulfides, and the like. However, these materials have disadvantages such as high toxicity of the transition metal selenides, low conductivity of the oxides and double hydroxides, and low conductivity of the sulfides, and more importantly, the catalytic activity of the above materials is not satisfactory for the positive electrode of the zinc-air battery. Therefore, the search for an environmentally-friendly, low-cost and high-oxygen catalytic activity zinc-air battery electrode material becomes a research and industrialization target.
The transition metal phosphate has high chemical stability, low cost and environment friendliness, and the characteristics are very favorable for the application of the transition metal phosphate in an electrode material of a water system zinc-air battery. Transition phosphates have been widely used in the fields of photocatalysis, lithium ion batteries, sodium ion batteries, supercapacitors and the like, but have been studied and applied very little in aqueous zinc-air batteries. The transition metal phosphate material and the application thereof in the water-based zinc-air battery are a very potential research and development field and are also the direction of the industrialization development of the high-performance water-based zinc-air battery in the future.
Disclosure of Invention
The invention aims to design the doped Co-Fe according to the practical application requirements5(PO4)4(OH)3•H2The O (Co-FPOH) microsphere material is synthesized by a water-oil two-phase hydrothermal method, the process parameters are controlled, the surface of the O (Co-FPOH) microsphere material becomes rough and porous, the specific surface area and the space utilization rate of an electrode are effectively improved, the electrocatalytic performance of the material and the performance of a zinc-air battery are improved, the O (Co-FPOH) microsphere material has good electrochemical performance, and the O (Co-FPOH) microsphere material becomes excellent waterIs an electrode material for zinc-air batteries.
Based on the above purpose, the technical problem to be solved by the invention is to provide a Co-FPOH microsphere material for a water system zinc-air battery and a preparation method thereof, and the water system zinc-air battery electrode material prepared by the invention has high discharge capacity, good rate capability and excellent electrochemical stability; the preparation method is simple in operation, free of complex equipment and low in cost.
The invention provides a Co-FPOH microsphere material for a water system zinc-air battery, which is characterized by comprising the following components in parts by weight: the Co-FPOH microsphere material is a micro-nano material formed by doping Co in FPOH, is in a microspherical structure, is 3-4.5 microns in size, is formed by staggered stacking of secondary nano particles, is 40-150 nm in size, has a three-dimensional pore structure among the nano particles, and has rough porous nano structures with uneven surface.
Furthermore, the Co-FPOH microsphere material for the water-based zinc-air battery prepared by the invention shows 817 mAh g in the test process of the zinc-air batteryzn -1Discharge capacity and 167.8 Wh cm-2Peak power density of (d); at 2 mA cm-2Can be cycled for 2500 h at the current density of (2).
The invention discloses a Co-FPOH microsphere material for a water system zinc-air battery, which takes a water-oil two-phase hydrothermal method as a synthesis method. The invention also provides a preparation method of the Co-FPOH microsphere aqueous zinc-air battery anode material, which comprises the following steps:
1) mixing phytic acid and deionized water, and stirring to obtain a water phase, wherein the ratio of the phytic acid to the deionized water is 0.60 ml to 40 ml;
2) mixing cobalt stearate, ferric stearate and toluene, and performing ultrasound for several hours at room temperature to prepare a uniformly dispersed toluene solution serving as an oil phase, wherein the ratio of the cobalt stearate to the ferric stearate to the toluene is 0.8 mmol: 1.6 mmol: 40 mL;
3) firstly transferring the water phase obtained in the step 1) into a reaction kettle, then transferring the oil phase obtained in the step 2) into the reaction kettle, carrying out water-oil two-phase hydrothermal reaction at the reaction temperature of 120-180 ℃ for 12-24 h, cooling to room temperature, collecting a final product deposited at the bottom of water, washing, drying and grinding to obtain the Co-FPOH microsphere aqueous zinc-air battery material.
4) Mixing the Co-FPOH microsphere powder obtained in the step 3) with Ketjen black, placing the mixture into a 5ml reagent bottle, and adding Nafion solution and isopropanol into the reagent bottle. And finally, carrying out ultrasonic treatment, stirring and shaking on the mixed solution to form uniformly dispersed zinc-air battery anode slurry. Wherein the proportion ratio of Co-FPOH, Ketjen black, Nafion solution and isopropanol is 10 mg: 10 mg: 80 μ L:4mL;
5) uniformly coating the positive electrode slurry obtained in the step 4) on a carbon paper current collector supported by foamed nickel by using a writing brush, and drying the coated carbon paper current collector supported by foamed nickel in an oven for later use. Wherein the loading amount of the positive electrode active material is 1mg cm-2。
In the above process steps, the ratio of the raw materials, and the temperature and time control of the hydrothermal reaction are the key to the formation of the final specific microscopic morphology and chemical composition of the material of the present invention.
In the step (1), the mass fraction of the phytic acid is 50 wt.%, and the stirring time is 20 min.
The ultrasonic time in the step (2) is 240 min.
And in the step (3), washing is carried out for 3-5 times by respectively washing with ethanol and deionized water.
And (4) performing ultrasonic treatment for 30min and stirring for 20 min.
In the step (5), the drying temperature is 60 ℃, and the drying time is 6 h.
The invention has the beneficial effects that:
(1) the Co-FPOH microsphere electrode material prepared by the method is a doped transition metal phosphate material, and the local structure of local electrons can be changed, the number of active sites of electrocatalysis is increased, and the electrocatalysis activity of the material and the performance of a zinc-air battery are improved.
(2) The Co-FPOH material prepared by the method contains two metal elements of Fe and Co and a non-metal P element, and the three elements have respective advantages in catalytic performance and can effectively play a role in coordination, so that the comprehensive catalytic property of the material is improved, and the application field is expanded.
(3) The Co-FPOH electrode material prepared by the method has a microspherical form with a rough and porous surface, the rough and porous structure of the surface is favorable for the electrolyte to permeate into the electrode, the microspherical structure with the rough surface is favorable for increasing the specific surface area of the electrode, increasing the full contact between the electrolyte and the electrode material and obtaining more active points, and the morphology, the pore diameter and the size distribution of the microspherical form are favorable for promoting the high-speed diffusion of ions and obtaining high electrochemical performance.
(4) The Co-FPOH electrode material prepared by the method has excellent OER and/ORR reaction activity, is a dual-function electrode material, can normally work at the temperature of-10-70 ℃, and has wide application fields.
(5) The Co-FPOH electrode material prepared by the method has higher discharge capacity, good rate performance, excellent cycle stability and good electrochemical stability, is an excellent water system zinc-air battery electrode material, and can be applied to water system zinc-air battery products with high energy density and cycle performance.
(6) The invention adopts a water-oil two-phase hydrothermal synthesis method, does not need complex equipment, has simple operation and is very suitable for industrialized mass production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the Co-FPOH microsphere material prepared in example 1.
FIG. 2 is an X-ray diffraction (XRD) pattern of the FPOH and Co-FPOH microsphere materials prepared in example 1.
FIG. 3 shows the Co-FPOH microsphere material and Pt/C @ RuO prepared in example 12Constant current discharge diagram.
FIG. 4 shows the Co-FPOH microsphere material and Pt/C @ RuO prepared in example 12The rate performance graph of (1).
FIG. 5 shows the Co-FPOH microsphere material and Pt/C @ RuO prepared in example 12Discharge performance and power density map.
FIG. 6 shows the Co-FPOH microsphere material prepared in example 1 at 2 mA cm-2Cycling performance plot at current density.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Mixing 50 wt.% of phytic acid and deionized water, and stirring for 20min to obtain a water phase, wherein the ratio of the phytic acid to the deionized water is 0.60 ml: 40 ml;
(2) mixing cobalt stearate, ferric stearate and toluene, and preparing a uniformly dispersed toluene solution at room temperature for over 240min to obtain an oil phase, wherein the ratio of cobalt stearate to ferric stearate to toluene is 0.8 mmol: 1.6 mmol: 40 mL;
(3) firstly transferring the water phase obtained in the step (1) into a reaction kettle, then transferring the oil phase obtained in the step (2) into the reaction kettle, carrying out water-oil two-phase hydrothermal reaction at the reaction temperature of 120 ℃ for 24 hours, cooling to room temperature, collecting a final product deposited at the bottom of the water, washing with deionized water and ethanol for 3-5 times, drying, and grinding to obtain a Co-FPOH microsphere aqueous zinc-air battery material, namely Co-doped Fe5(PO4)4(OH)3•H2O。
(4) The Co-FPOH microsphere powder obtained in the above was mixed with Ketjen black and put into a 5ml reagent bottle, and then Nafion solution and isopropyl alcohol were added into the reagent bottle. And finally, carrying out ultrasonic treatment on the mixed solution for 30min, stirring for 20min, and oscillating to form uniformly dispersed zinc-air battery anode slurry. Wherein the proportion ratio of Co-FPOH, Ketjen black, Nafion solution and isopropanol is 10 mg: 10 mg: 80 μ L:4mL;
(5) and uniformly coating the positive electrode slurry obtained in the above step on a carbon paper current collector supported by foamed nickel by using a writing brush, and drying the coated carbon paper current collector supported by foamed nickel in an oven at 60 ℃ for 6 hours for later use. Wherein the positive electrode active material is loadedIs 1mg cm-2。
Example 2
(1) Mixing 50 wt.% of phytic acid and deionized water, and stirring for 20min to obtain a water phase, wherein the ratio of the phytic acid to the deionized water is 0.60 ml: 40 ml;
(2) mixing cobalt stearate, ferric stearate and toluene, and preparing a uniformly dispersed toluene solution at room temperature for over 240min to obtain an oil phase, wherein the ratio of cobalt stearate to ferric stearate to toluene is 0.8 mmol: 1.6 mmol: 40 mL;
(3) firstly transferring the water phase obtained in the step (1) into a reaction kettle, then transferring the oil phase obtained in the step (2) into the reaction kettle, carrying out water-oil two-phase hydrothermal reaction at 160 ℃ for 24h, cooling to room temperature, collecting a final product deposited at the bottom of the water, washing with deionized water and ethanol for 3-5 times, drying, and grinding to obtain a Co-FPOH microsphere aqueous zinc-air battery material, namely Co-doped Fe5(PO4)4(OH)3•H2O。
(4) The Co-FPOH microsphere powder obtained in the above was mixed with Ketjen black and put into a 5ml reagent bottle, and then Nafion solution and isopropyl alcohol were added into the reagent bottle. And finally, carrying out ultrasonic treatment on the mixed solution for 30min, stirring for 20min, and oscillating to form uniformly dispersed zinc-air battery anode slurry. Wherein the proportion ratio of Co-FPOH, Ketjen black, Nafion solution and isopropanol is 10 mg: 10 mg: 80 μ L:4mL;
(5) and uniformly coating the positive electrode slurry obtained in the above step on a carbon paper current collector supported by foamed nickel by using a writing brush, and drying the coated carbon paper current collector supported by foamed nickel in an oven at 60 ℃ for 6 hours for later use. Wherein the loading amount of the positive electrode active material is 1mg cm-2。
Example 3
Mixing 50 wt.% phytic acid and deionized water, and stirring for 20min to obtain a water phase, wherein the ratio of the phytic acid to the deionized water is 0.60 ml: 40 ml;
(2) mixing cobalt stearate, ferric stearate and toluene, and preparing a uniformly dispersed toluene solution at room temperature for over 240min to obtain an oil phase, wherein the ratio of cobalt stearate to ferric stearate to toluene is 0.8 mmol: 1.6 mmol: 40 mL;
(3) firstly transferring the water phase obtained in the step (1) into a reaction kettle, then transferring the oil phase obtained in the step (2) into the reaction kettle, carrying out water-oil two-phase hydrothermal reaction at the reaction temperature of 180 ℃ for 24 hours, cooling to room temperature, collecting a final product deposited at the bottom of the water, washing with deionized water and ethanol for 3-5 times, drying, and grinding to obtain a Co-FPOH microsphere aqueous zinc-air battery material, namely Co-doped Fe5(PO4)4(OH)3•H2O。
(4) The Co-FPOH microsphere powder obtained in the above was mixed with Ketjen black and put into a 5ml reagent bottle, and then Nafion solution and isopropyl alcohol were added into the reagent bottle. And finally, carrying out ultrasonic treatment on the mixed solution for 30min, stirring for 20min, and oscillating to form uniformly dispersed zinc-air battery anode slurry. Wherein the proportion ratio of Co-FPOH, Ketjen black, Nafion solution and isopropanol is 10 mg: 10 mg: 80 μ L:4mL;
(5) and uniformly coating the positive electrode slurry obtained in the above step on a carbon paper current collector supported by foamed nickel by using a writing brush, and drying the coated carbon paper current collector supported by foamed nickel in an oven at 60 ℃ for 6 hours for later use. Wherein the loading amount of the positive electrode active material is 1mg cm-2。
Example 4
(1) Mixing 50 wt.% of phytic acid and deionized water, and stirring for 20min to obtain a water phase, wherein the ratio of the phytic acid to the deionized water is 0.60 ml: 40 ml;
(2) mixing cobalt stearate, ferric stearate and toluene, and preparing a uniformly dispersed toluene solution at room temperature for over 240min to obtain an oil phase, wherein the ratio of cobalt stearate to ferric stearate to toluene is 0.8 mmol: 1.6 mmol: 40 mL;
(3) firstly, transferring the water phase obtained in the step (1) into a reaction kettle, then transferring the oil phase obtained in the step (2) into the reaction kettle, and carrying out water-oil two-phase hydrothermal reaction at the reaction temperature of 180 ℃ for a period of timeCooling to room temperature for 12 h, collecting the final product deposited at the bottom of the water, washing with deionized water and ethanol for 3-5 times, drying, and grinding to obtain the Co-FPOH microsphere water system zinc-air battery material, namely Co-doped Fe5(PO4)4(OH)3•H2O。
(4) The Co-FPOH microsphere powder obtained in the above was mixed with Ketjen black and put into a 5ml reagent bottle, and then Nafion solution and isopropyl alcohol were added into the reagent bottle. And finally, carrying out ultrasonic treatment on the mixed solution for 30min, stirring for 20min, and oscillating to form uniformly dispersed zinc-air battery anode slurry. Wherein the proportion ratio of Co-FPOH, Ketjen black, Nafion solution and isopropanol is 10 mg: 10 mg: 80 μ L:4mL;
(5) and uniformly coating the positive electrode slurry obtained in the above step on a carbon paper current collector supported by foamed nickel by using a writing brush, and drying the coated carbon paper current collector supported by foamed nickel in an oven at 60 ℃ for 6 hours for later use. Wherein the loading amount of the positive electrode active material is 1mg cm-2。
And (3) performance testing:
1) and (4) SEM test: the Co-FPOH material prepared by the embodiments has a microsphere shape, and the surface of the microsphere is a rough porous structure. For example, fig. 1 is an SEM image of a sample obtained in example 1 under a scanning electron microscope, and it can be seen that the sample has a microspherical microscopic morphology with a size of 3 to 4.5 micrometers, the rough and porous surface of the microsphere facilitates the electrolyte to permeate into the electrode, increases the specific surface area of the electrode, increases the contact between the electrolyte and the electrode material, and obtains more active sites, and the morphology, the pore size, and the size distribution thereof are very advantageous for promoting the high-speed diffusion of ions and obtaining high electrochemical performance. Elements such as Co, Fe, P, O and the like are uniformly distributed in the material through EDS test equipped by SEM.
2) XRD test: XRD tests of the finally obtained samples prepared in the above examples can confirm that the Co-FPOH sample prepared in each example is Co-doped Fe5(PO4)4(OH)3•H2And O. For example, FIG. 2 shows the results obtained for the sample prepared in example 1To XRD pattern, X-ray diffraction peak and Fe5(PO4)4(OH)3•H2The characteristic peaks of O (FPOH) are corresponding to each other, so that the FPOH of the sample is Fe5(PO4)4(OH)3•H2And (C) O.
3) And (3) electrochemical performance testing: the materials prepared in the above examples are respectively assembled into a zinc-air battery mould for an electrode to carry out electrochemical performance test, and fig. 3 is a constant current discharge curve of the sample prepared in example 1, so that the obtained material has 817 mA gzn -1The discharge capacity of the catalyst is superior to that of Pt @ C// RuO used in the commercial industry at present2A material. FIG. 4 is a graph showing the charge and discharge curves at different current densities for the samples prepared in example 1, showing a rate capability significantly better than the Pt @ C// RuO currently in commercial use2A material. FIG. 5 is a graph showing the discharge performance and power density curves measured for the samples prepared in example 1, and also showing significantly better characteristics than the Pt @ C// RuO currently used in the commercial industry2A material. FIG. 6 is a graph of the cycle performance of the sample prepared in example 1, and the obtained material can stably cycle for 2500 h, which shows that the Co-FPOH microsphere material has good electrochemical performance.

Claims (10)

1. A Co-FPOH microsphere material for a water system zinc-air battery is characterized in that: the Co-FPOH microsphere material is a micro-nano material formed by doping Co in FPOH, is in a microspherical structure, is formed by staggered accumulation of secondary nano particles, has a three-dimensional pore structure among the nano particles, and has rough porous nano structures with uneven surfaces; wherein FPOH has the chemical formula of Fe5(PO4)4(OH)3•H2O。
2. The Co-FPOH microsphere material for water-based zinc-air batteries according to claim 1, characterized in that: the size of the microspheres is 3-4.5 microns.
3. The Co-FPOH microsphere material for water-based zinc-air batteries according to claim 1, characterized in that: the size of the nano particles is 40-150 nm.
4. The Co-FPOH microsphere material for water-based zinc-air batteries according to claim 1, characterized in that: the discharge capacity value of the Co-FPOH microsphere material reaches 817 mAh g-1At 2 mA cm-2The current density of the material is up to 2500 h in circulation, and the peak power density of the material reaches 167.8 Wh cm-2。
5. A method of preparing a Co-FPOH microsphere material for water-based zinc-air batteries according to any one of claims 1 to 4, characterized in that it comprises the steps of:
1) mixing phytic acid and deionized water, and stirring to obtain a water phase;
2) mixing cobalt stearate, ferric stearate and toluene, and performing ultrasound for several hours at room temperature to prepare a uniformly dispersed toluene solution which is an oil phase;
3) firstly transferring the water phase obtained in the step 1) into a reaction kettle, then transferring the oil phase obtained in the step 2) into the reaction kettle, carrying out water-oil two-phase hydrothermal reaction, cooling to room temperature after the reaction is finished, collecting a final product deposited at the bottom of the water, washing, drying and grinding to obtain the Co-FPOH microsphere material.
6. The method for preparing Co-FPOH microsphere material for water-based zinc-air battery according to claim 5, wherein the method comprises the following steps: the volume ratio of the phytic acid to the deionized water in the step 1) is 0.30: 20.
7. The method for preparing Co-FPOH microsphere material for water-based zinc-air battery according to claim 5, wherein the method comprises the following steps: the proportion ratio of the cobalt stearate, the ferric stearate and the methylbenzene in the step 2) is 0.1mmol to 0.2 mmol to 5 mL.
8. The method for preparing Co-FPOH microsphere material for water-based zinc-air battery according to claim 5, wherein the method comprises the following steps: the reaction temperature of the water-oil two-phase hydrothermal reaction in the step 3) is 120-180 ℃, and the reaction time is 12-24 hours.
9. Use of a Co-FPOH microsphere material according to any of claims 1 to 4, to prepare an electrode for an aqueous zinc-air battery, comprising the steps of:
I) mixing the Co-FPOH microsphere material with Ketjen black; then adding Nafion solution and isopropanol to form mixed solution; carrying out ultrasonic, stirring and shaking on the mixed solution to form uniformly dispersed anode slurry of the zinc-air battery;
II) coating the positive electrode slurry on a foam nickel-supported carbon paper current collector, and drying the coated foam nickel-supported carbon paper current collector in an oven.
10. Use of a Co-FPOH microsphere material according to claim 9, characterized in that: wherein the proportion ratio of the Co-FPOH, the Ketjen black, the Nafion solution and the isopropanol is 1mg to 8 muL to 0.4 mL.
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