CN109473682B - Supported binuclear perovskite type oxide carbon nano microsphere catalyst, and preparation method and application thereof - Google Patents
Supported binuclear perovskite type oxide carbon nano microsphere catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of metal-air battery catalysts, in particular to a supported binuclear perovskite type oxide carbon nano microsphere catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: a, B, D, dissolving water-soluble salts of three metals in deionized water according to a molar ratio, adding a carbon sphere raw material, and mixing and stirring to prepare a mixed solution; mixing and reacting supercritical water with the mixed solution, cooling, washing and drying a cooled sample to obtain catalyst powder; carrying out heat treatment on the catalyst powder, and cooling to obtain the supported binuclear perovskite type oxide carbon nano microsphere catalyst; the general formula of the supported binuclear perovskite type oxide carbon nano microsphere catalyst is ABxD1‑xO3@ C nanospheres. The prepared supported binuclear perovskite type oxide carbon nanosphere catalyst is uniform and fine in size and high in catalytic activity, and can improve the catalytic performance of ORR and OER reactions, so that the electrochemical performance of the metal-air battery is greatly improved.
Description
Technical Field
The invention relates to the field of metal-air battery catalysts, in particular to a supported binuclear perovskite type oxide carbon nano microsphere catalyst, and a preparation method and application thereof.
Background
The metal-air cell is a semi-fuel cell integrating the characteristics of primary cell and fuel cell, and is formed from positive electrode, negative electrode and electrolyte. Oxygen in the air is used as a positive active material, aluminum, magnesium and zinc are used as negative active materials, and the electrolyte is KOH solution, NaOH solution, NaCl aqueous solution or seawater and the like. The metal-air battery has the advantages of high energy density, large capacity, low price, environmental friendliness and the like, and is widely concerned by researchers at home and abroad in recent years. Only the zinc-air battery is chargeable and dischargeable, the other two air batteries are not chargeable and dischargeable, and the anode plate must be replaced to realize mechanical chargeable and dischargeable, so that the metal-air battery is inconvenient in practical application. In order to realize charge and discharge, development of a bifunctional catalyst for simultaneously performing an Oxygen Reduction Reaction (ORR) and an Oxygen Evolution Reaction (OER) is the basis of research. The performance of the air cathode directly affects the electrochemical performance of the metal-air battery, and thus the catalyst catalyzing the oxidation and reduction reactions of the air cathode is a key factor for the commercialization of the metal-air battery. Among them, the performance of the air cathode is limited by the poor kinetics of the oxygen reduction reaction and the high overpotential, which directly results in the power reduction of the battery. In the specific reaction process, oxygen in the air passes through the gas diffusion layer through the nickel mesh and enters the catalytic layer of the air cathode, and the oxygen reduction reaction is carried out under the dual functions of the catalytic layer and the current. Therefore, the role played by the activity of the catalyst in the air cathode is of critical importance.
Among numerous catalysts, perovskite oxides have great development potential due to their characteristics of high electrical conductivity, abundant reserves and the like. The general structure of the perovskite type oxide is ABO3The cation at A site is alkali metal, alkaline earth metal or rare earth metal with larger ionic radius, such as La, Ca, Sr, Ba, etc., and the cation at B site is high valence transition metal ion with smaller ionic radius, such as Ni, Co, Fe, Mn, Cr, etc. In the perovskite oxide, B is a key element to play a catalytic role, and A-site element mainly plays a role in stabilizing the crystal structure of the whole material. And the A, B site cation can be replaced by other metals, the element selectivity is more, and the catalytic performance can be improved more.
There are many methods for producing perovskite oxides, and the solid-phase synthesis method has a large particle size although the yield is high. The coprecipitation method is suitable for preparing fine and uniform catalyst powder, but the process is complex and difficult to control. Meanwhile, the pure perovskite type oxide has the defects of large powder particles, poor uniformity, poor oxygen adsorption capacity, low specific surface area and the like, and is used as a metal-air battery catalyst, so that the catalytic activity is low, the power density of the metal-air battery is improved slightly, and the stability of constant-current discharge is reduced.
In addition, the composite of the metal oxide and the carbon material such as carbon nanotube, graphene, carbon nanoball, or the like is generally performed by a method of impregnation reduction or mechanical mixing. The uniformity and the particle size of the composite catalyst obtained by the preparation methods cannot be controlled. For the metal load of the carbon nanospheres with the core-shell structure, a template method and multiple hydrothermal reactions are mostly adopted to obtain the metal load, the preparation method is more complex in preparation process and not beneficial to large-scale production, the composite metal oxide is coated or loaded on the surfaces of the carbon nanospheres by the multiple hydrothermal methods, the load is uncontrollable, the coating effect is poor, the particle size of the obtained catalyst is not uniform, and the carbon nanospheres are easy to agglomerate. These problems present serious obstacles to the commercial use of metal-air batteries.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a supported binuclear perovskite type oxide carbon nanosphere catalyst, and a preparation method and application thereof. The method uses a continuous supercritical hydrothermal synthesis method and a heat treatment technology to carry out continuous supercritical hydrothermal synthesis on a plurality of metal salt solutions and carbon sphere raw materials to obtain the carbon sphere with a general structure ABxD1-xO3Perovskite type oxide in situ embedded into carbon nanospheres (with ABxD1-xO3@ C nanosphere form), to obtain the supported binuclear perovskite-type oxide carbon nanosphere catalyst. The prepared supported binuclear perovskite type oxide carbon nano microsphere catalyst is uniform and fine in size (300-500nm), and the purity of the perovskite type metal oxide is high. The bifunctional perovskite type metal oxide embedded into the carbon nanosphere can show high-efficiency and stable catalytic activity, can improve the catalytic performance of ORR and OER reactions, and further greatly improves the electrochemical performance of the metal-air battery.
In order to achieve the purpose of the present invention, an embodiment of the present invention provides a preparation method of a supported binuclear perovskite-type oxide carbon nanosphere catalyst, which includes the following steps:
a, B, D, dissolving water-soluble salts of three metals in deionized water according to a molar ratio, adding a carbon sphere raw material, and mixing and stirring to prepare a mixed solution;
mixing and reacting supercritical water with the mixed solution, cooling, washing and drying a cooled sample to obtain catalyst powder; wherein the reaction temperature is 400-550 ℃, optionally 430-510 ℃; the reaction pressure is 20-50MPa, optionally 28-38 MPa; the reaction time is 30-200s, optionally 45-120 s;
carrying out heat treatment on the catalyst powder, and cooling to obtain the supported binuclear perovskite type oxide carbon nano microsphere catalyst; wherein the heat treatment temperature is 300-500 ℃, optionally 300-400 ℃;
the general formula of the supported binuclear perovskite type oxide carbon nano microsphere catalyst is ABxD1-xO3@ C nanospheres; a comprises at least one of La, Sr, Ca and Ba; b or D respectively and independently comprises at least one of Fe, Cr, Co, Mn and Ni; x is more than 0 and less than 1.
According to the common knowledge in the field, in practical operation, the addition amount of the water-soluble salts of the three metal salts can be adjusted up and down according to the molar ratio.
In one possible implementation manner of the preparation method of the supported binuclear perovskite type oxide carbon nanosphere catalyst, the mass ratio of water-soluble salts of A, B, D three metals to the carbon nanosphere raw material is 0.9-1.5, optionally 1.1-1.35;
the addition amount of the deionized water is as follows: 80-110ml of deionized water is added into each 1g of carbon sphere raw material.
In a possible implementation manner, the preparation method of the supported binuclear perovskite-type oxide carbon nanosphere catalyst comprises the following steps: the deionized water is heated to a supercritical state, wherein the heating temperature is 350-.
In one possible implementation mode, the preparation method of the supported binuclear perovskite type oxide carbon nano microsphere catalyst comprises the steps of adding carbon sphere raw materials, mixing and stirring to prepare a mixed solution, and adding 30% of H2O2The adding amount of the solution is 1 to 4 percent of the total volume of the mixed solution. H2O2The solution is added to improve the oxidizing property of the supercritical water.
In a possible implementation manner of the preparation method of the supported binuclear perovskite-type oxide carbon nanosphere catalyst, the carbon nanosphere raw material comprises at least one of starch, glucose, maltose or cellulose.
In one possible implementation manner of the preparation method of the supported binuclear perovskite-type oxide carbon nanosphere catalyst, the step of mixing and reacting supercritical water and the mixed solution comprises the following steps: pumping the mixed solution into a reactor by using a pump, wherein the flow range of the pump is 5-16 ml/min; pumping the deionized water into the reactor by another pump, heating the deionized water to a supercritical state by a heater in the middle, wherein the flow range of the pump is 20-30 ml/min; the reactor is a jet reactor; the reacted fluid passes through a cooling system and a filtering system;
optionally, the pump is a high performance liquid chromatography pump; the flow range of a pump for pumping the mixed solution into the reactor is 8-12 ml/min; the flow rate of the other pump is in the range of 22-27 ml/min.
Mix supercritical water and mixed solution at the injection formula reactor, can reach required temperature and pressure of reaction in the twinkling of an eye, react rapidly, reaction time is short, because perovskite type metal oxide is very low in the supercritical water solubility, can make the product separate out rapidly, gets into cooling device, has prevented the growth grow and the reunion of granule.
In one possible implementation manner of the preparation method of the supported binuclear perovskite type oxide carbon nanosphere catalyst, the step of carrying out heat treatment on the catalyst powder comprises the steps of placing the catalyst powder in a crucible, and putting N in a tube furnace2Or heat treatment in an Ar atmosphere.
In a possible implementation manner of the preparation method of the supported binuclear perovskite type oxide carbon nano microsphere catalyst, the catalyst powder is subjected to heat treatment, and then the cooling manner is natural cooling.
The embodiment of the invention also provides a supported binuclear perovskite type oxide carbon nano microsphere catalyst, and the general formula of the supported binuclear perovskite type oxide carbon nano microsphere catalyst is ABxD1-xO3@ C nanospheres; wherein A comprises at least one of La, Sr, Ca and Ba; b or D respectively and independently comprises at least one of Fe, Cr, Co, Mn and Ni; x is more than 0 and less than 1.
In one possible implementation mode, the supported binuclear perovskite type oxide carbon nano microsphere catalyst is perovskite type oxide ABxD1-xO3Embedded in both sides of the carbon nanoball; the size of the supported binuclear perovskite type oxide nano microsphere catalyst is 300-500 nm.
In one possible implementation mode, the supported binuclear perovskite type oxide carbon nanosphere catalyst has a general formula of LaFe0.5Cr0.5O3@ C nanospheres, or of the general formula LaFe0.5Mn0.5O3@ C nanospheres, or of the general formula BaNi0.5Cr0.5O3@ C nanospheres, or of the general formula BaNi0.5Co0.5O3@ C nanospheres.
The embodiment of the invention also provides a preparation method of the cathode catalyst slurry of the metal-air battery, which comprises the following steps:
mixing the supported binuclear perovskite type oxide carbon nano microsphere catalyst, conductive carbon black, Polytetrafluoroethylene (PTFE) and absolute ethyl alcohol to obtain the catalyst.
The embodiment of the invention also provides cathode catalyst slurry of a metal-air battery, which comprises the supported binuclear perovskite type oxide carbon nano microsphere catalyst, conductive carbon black, PTFE and absolute ethyl alcohol.
The embodiment of the invention also provides application of the supported binuclear perovskite oxide carbon nano microsphere catalyst or the cathode catalyst slurry in a cathode plate of a metal-air battery.
Has the advantages that:
(1) according to the preparation method of the supported binuclear perovskite oxide carbon nanosphere catalyst provided by the embodiment of the invention, the catalyst with the perovskite oxide embedded in the carbon nanospheres with the binuclear structure is obtained through a continuous supercritical hydrothermal method and heat treatment. The special physical and chemical properties (low dielectric constant, high saturation and the like) of supercritical water are ideal reaction media for preparing nano metal oxides, and the surface of the carbon sphere can have more defects and active sites through heat treatment. The method mixes the supercritical water and the metal salt solution and reacts quickly, the reaction time is short, and the perovskite type metal oxide has low solubility in the supercritical water, so that the product can be separated out quickly, and the growth, enlargement and agglomeration of particles are prevented by cooling. The prepared supported binuclear perovskite type oxide carbon nano microsphere catalyst is uniform and fine in size (300-500nm), and does not have an agglomeration phenomenon.
(2) According to the preparation method of the supported binuclear perovskite oxide carbon nanoparticle catalyst provided by the embodiment of the invention, the loading capacity of the titanium ore type oxide in the carbon nanoparticles can be controlled by controlling the adding amount ratio of the metal salt and the carbon sphere raw material, so that the perovskite oxide carbon nanoparticle catalyst with a binuclear structure is prepared.
(3) The embodiment of the invention provides a preparation method of a supported binuclear perovskite type oxide carbon nano microsphere catalyst, and H2O2The solution is added to improve the oxidizing property of the supercritical water.
(4) According to the preparation method of the supported binuclear perovskite type oxide carbon nanoparticle catalyst provided by the embodiment of the invention, supercritical water and a metal salt solution are mixed in a reactor, so that the temperature and the pressure required by the reaction can be instantly reached, and the reaction time is short.
And the high-purity perovskite oxide can be embedded into the carbon nanospheres in situ by one-step operation through further controlling parameters such as reaction flow rate, heating temperature, pressure and the like. The whole reaction process can effectively prevent the cross contamination of various metal salts, generate other impurities (such as oxide containing only one metal or oxide containing only two metals), and obtain the bifunctional perovskite type metal oxide with high purity.
(5) The preparation method of the supported binuclear perovskite type oxide carbon nano microsphere catalyst provided by the embodiment of the invention adopts a continuous production process, and is beneficial to promoting industrialization.
(6) The supported binuclear perovskite type oxide carbon nanosphere catalyst provided by the embodiment of the invention has high conductivity. In the later-stage cathode piece preparation process, the perovskite oxide not only plays the effect of the bifunctional catalyst of oxygen reduction and oxygen catalytic reaction, but also is more firmly combined between the carrier carbon nanospheres and the conductive carbon black, so that the adhesion capability of the catalyst is improved, and the problems of falling phenomenon, poor conductivity and the like of the metal oxide catalyst are solved. And the catalyst and the conductive carbon black are mixed more uniformly, and the cathode sheet catalyst obtained by coating the catalyst on a nickel net and sintering is dispersed more uniformly. Therefore, the bifunctional perovskite metal oxide embedded into the carbon nanosphere can show high-efficiency and stable catalytic activity, and the catalytic performance of ORR and OER reactions is improved, so that the electrochemical performance of the metal-air battery is greatly improved. The improvement of the catalytic performance of the catalyst for catalyzing the OER reaction accelerates the step of realizing charge and discharge of the metal air battery.
Drawings
One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
FIG. 1 shows La of a binuclear structure prepared in example 1 of the present invention0.5Fe0.5Cr0.5O3TEM image of @ C nanospheres.
FIG. 2 is a binuclear La cell prepared in example 1 of the present invention0.5Fe0.5Cr0.5O3The @ C nanosphere catalyst is applied to the constant current discharge curve of the aluminum-air battery.
FIG. 3 is a binuclear La cell prepared in example 1 of the present invention0.5Fe0.5Cr0.5O3The @ C nanosphere catalyst is applied to the charge-discharge curve of a zinc-air battery.
FIG. 4 shows a binuclear LaFe structure prepared in example 2 of the present invention0.5Mn0.5O3The @ C nanosphere catalyst is applied to the charge-discharge curve of a zinc-air battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
Example 1
Loaded binuclear perovskite type oxide carbon nano microsphere catalyst LaFe0.5Cr0.5O3@ C nanospheres, with a size of 500 nm.
The supported binuclear perovskite type oxide carbon nano microsphere catalyst LaFe0.5Cr0.5O3The preparation method of the @ C nanosphere comprises the following steps of:
adding La (NO)3)3·6H2O、Fe(NO3)3·9H2O、Cr(NO3)3·9H2Weighing O according to a molar ratio (3.3643 g, 1.5694g and 1.5543g are taken as three metal salts respectively), adding 600ml of deionized water, magnetically stirring to obtain a plurality of metal salt solutions, weighing 6g of starch, adding a small amount of starch into the plurality of metal salt solutions for multiple times, heating in a water bath at 50 ℃, stirring for 1H, adding H2O2Stirring the solution (30%, 12ml) for 30min to improve the oxidability of supercritical water, and obtaining the final productTo a mixed solution of various metal salts and starch;
in-situ preparation of dual-core-structure LaFe by adopting continuous supercritical hydrothermal synthesis method0.5Cr0.5O3@ C nanosphere: firstly, pumping a mixed solution of various metal salts and starch into a reactor through a high performance liquid chromatography pump, wherein the flow rate is 8 ml/min; meanwhile, the deionized water is heated to a supercritical state by another high performance liquid chromatography pump through a heater at the heating temperature of 400 ℃, and then pumped into the reactor at the flow rate of 22 ml/min; the reactor adopts a jet design, so that supercritical water and mixed solution of various metal salts and starch are uniformly mixed in the reactor and quickly react for 45s (the temperature of the reactor is 400 ℃, and the reaction pressure is 30 MPa); the fluid after reaction sequentially passes through a cooling system, a filtering system and a back pressure valve, then is repeatedly washed to be neutral by deionized water and absolute ethyl alcohol, is centrifuged for 2 hours by a centrifuge (rotating speed: 600r/min), is put into a refrigerator for freezing for 24 hours, and is frozen and dried for 10 hours at 80 ℃ to obtain catalyst powder;
placing the freeze-dried catalyst powder in a crucible, and placing the crucible in a tube furnace N2Heating to 300 ℃ for annealing for 1.5h at room temperature for 40min under the atmosphere, and cooling to room temperature to obtain LaFe0.5Cr0.5O3@ C catalyst.
A preparation method of cathode catalyst slurry of a metal-air battery comprises the following steps:
taking the prepared LaFe0.5Cr0.5O32.4g of @ C nanosphere catalyst, 4.7g of conductive carbon black VXC-72R powder, 7.320g of 60% (the mass of the PTFE powder accounts for 60% of the total mass) PTFE solution and 100ml of absolute ethyl alcohol are mixed and stirred for 2.6h to obtain cathode catalyst slurry for the metal-air battery.
And (3) coating the cathode slurry on the nickel screen of the current collector by using the nickel screen as the current collector conductive network, and sintering at 300 ℃ for 60min to obtain the air cathode of the metal-air battery.
The air cathode and the anode aluminum plate are assembled into a battery in a self-made testing device, the electrolyte is 4M potassium hydroxide aqueous solution, and the discharge performance test is carried out, and the result shows that the air cathode and the anode aluminum plate adopt the aluminum plateThe catalyst of the invention is used for assembling an aluminum-air battery, and the highest power density is 293.64mW/cm after testing2At this time, the corresponding discharge voltage was 1.0213V, and the current density was 287.50mA/cm2. Then the prepared aluminum-air battery is subjected to constant current discharge test, and the current density is 250mA/cm2Under the condition that the environmental temperature is about 25 ℃, the voltage can still be kept at 1.32V after discharging for 2000min, and the test result is shown in figure 2.
The prepared air cathode sheet and an anode (zinc plate) are assembled into a zinc-air battery, the charge and discharge performance is tested in KOH (added with zinc acetate) of electrolyte 6M, the test result shows that the battery does not attenuate after 100 cycles of charge and discharge, the charge voltage is stabilized at about 2.03V, the discharge voltage is stabilized at about 1.21V, and the test result is shown in figure 3.
Example 2
Loaded binuclear perovskite type oxide carbon nano microsphere catalyst LaFe0.5Mn0.5O3@ C nanospheres, with a size of 470 nm.
The supported binuclear perovskite type oxide carbon nano microsphere catalyst LaFe0.5Mn0.5O3The preparation method of the @ C nanosphere comprises the following steps of:
adding La (NO)3)3·6H2O、Fe(NO3)3·9H2O、Mn(NO3)2·4H2Weighing O according to a molar ratio (3.1314 g, 1.4608g and 0.9076g are taken as three metal salts respectively), adding 450ml of deionized water, magnetically stirring to obtain a plurality of metal salt solutions, weighing 5g of glucose, adding a small amount of glucose into the plurality of metal salt solutions for multiple times, heating in a water bath at 50 ℃, stirring for 1H, adding H2O2Continuously stirring the solution (30 percent and 9ml) for 30min to improve the oxidability of the supercritical water, and finally obtaining a mixed solution of various metal salts and starch;
the remaining steps and process parameters were the same as in example 1.
A preparation method of cathode catalyst slurry of a metal-air battery comprises the following steps:
taking the prepared LaFe0.5Mn0.5O32.3g of @ C nanosphere catalyst, 5.32g of conductive carbon black VXC-72R powder, 6.820g of 60% (the mass of the PTFE powder accounts for 60% of the total mass) PTFE solution and 100ml of absolute ethyl alcohol, and mixing and stirring for 2.4h to obtain cathode catalyst slurry for the metal-air battery; and coating the cathode slurry on the nickel screen of the current collector by using the nickel screen as a current collector conductive network, and sintering at 320 ℃ for 45min to obtain the air cathode of the metal-air battery.
The air cathode and the anode aluminum plate are assembled into a battery in a self-made testing device, the electrolyte is 4M potassium hydroxide aqueous solution, and a discharge performance test is carried out, so that the result shows that the highest power density of 296.87mW/cm is obtained by testing the aluminum-air battery assembled by using the catalyst provided by the invention2At this time, the corresponding discharge voltage was 0.9896V, and the current density was 300.00mA/cm2. Then the prepared aluminum-air battery is subjected to constant current discharge test, and the current density is 245mA/cm2And under the condition that the environmental temperature is about 24 ℃, discharging is carried out for 2000min, and the voltage can still be kept at 1.30V. The prepared air cathode sheet and an anode (zinc plate) are assembled into a zinc-air battery, the charge and discharge performance is tested in KOH (added with zinc acetate) of electrolyte 6M, the test result shows that the battery does not attenuate after 100 cycles of charge and discharge, the charge voltage is stabilized at about 2.02V, the discharge voltage is stabilized at about 1.19V, and the test result is shown in figure 4.
Example 3
Supported binuclear perovskite type oxide carbon nano microsphere catalyst BaNi0.5Cr0.5O3@ C nanospheres, with a size of 360 nm.
The supported binuclear perovskite type oxide carbon nano microsphere catalyst BaNi0.5Cr0.5O3The preparation method of the @ C nanosphere comprises the following steps of:
mixing Ba (NO)3)2、Ni(NO3)2·6H2O、Cr(NO3)3·9H2Weighing O according to a molar ratio (3.6177 g, 2.0127g and 2.7696g are taken as three metal salts respectively), adding 665ml of deionized water, magnetically stirring to obtain a plurality of metal salt solutions, weighing 7g of maltose, and adding a small amount of maltose for multiple timesAdding into multi-metal salt solution, heating in water bath at 50 deg.C, stirring for 1H, adding H2O2Continuously stirring the solution (30 percent, 16.63ml) for 30min to improve the oxidizability of the supercritical water, and finally obtaining a mixed solution of various metal salts and starch;
the remaining steps and process parameters were the same as in example 1.
A preparation method of cathode catalyst slurry of a metal-air battery comprises the following steps:
taking the BaNi prepared above0.5Cr0.5O3Mixing and stirring 1.9g of @ C catalyst, 3.2g of conductive carbon black VXC-72R powder, 4.520g of 60% (the mass of the PTFE powder accounts for 60% of the total mass) PTFE solution and 100ml of absolute ethyl alcohol for 2.3h to obtain cathode catalyst slurry for the metal-air battery; and (3) coating the cathode slurry on the nickel screen of the current collector by using the nickel screen as the current collector conductive network, and sintering at 350 ℃ for 40min to obtain the air cathode of the metal-air battery.
The air cathode and the anode aluminum plate are assembled into a battery in a self-made testing device, the electrolyte is 4M potassium hydroxide aqueous solution, and a discharge performance test is carried out, so that the result shows that the highest power density of 316.05mW/cm is obtained by testing the aluminum-air battery assembled by using the catalyst provided by the invention2At this time, the corresponding discharge voltage was 1.0535V, and the current density was 300.00mA/cm2。
Constant current discharge test of the aluminum-air battery shows that the current density is 262.5mA/cm2And under the condition that the ambient temperature is about 26 ℃, discharging is carried out for 2000min, and the voltage can still be kept at 1.33V.
Example 4
Supported binuclear perovskite type oxide carbon nano microsphere catalyst BaNi0.5Co0.5O3@ C nanospheres, having a size of 420 nm.
The supported binuclear perovskite type oxide carbon nano microsphere catalyst BaNi0.5Co0.5O3The preparation method of the @ C nanosphere comprises the following steps of:
mixing Ba (NO)3)2、Ni(NO3)2·6H2O、Co(NO3)2·6H2Weighing O according to a molar ratio (5.1110 g, 2.8431g and 2.8459g are taken as three metal salts respectively), adding 900ml of deionized water, magnetically stirring to obtain a plurality of metal salt solutions, weighing 9g of cellulose, adding a small amount of cellulose into the plurality of metal salt solutions for multiple times, heating and stirring in a water bath at 50 ℃ for 1H, adding H2O2Continuously stirring the solution (30 percent and 26.5ml) for 30min to improve the oxidability of the supercritical water, and finally obtaining a mixed solution of various metal salts and starch;
the remaining steps and process parameters were the same as in example 1.
A preparation method of cathode catalyst slurry of a metal-air battery comprises the following steps:
taking the BaNi prepared above0.5Co0.5O32.9g of @ C catalyst, 4.29g of conductive carbon black VXC-72R powder, 7.370g of 60% (the mass of the PTFE powder accounts for 60% of the total mass) PTFE solution and 100ml of absolute ethyl alcohol, and mixing and stirring the materials for 2.7h to obtain cathode catalyst slurry for the metal-air battery; and (3) coating the cathode slurry on the nickel screen of the current collector by using the nickel screen as the current collector conductive network, and sintering at 380 ℃ for 25min to obtain the air cathode of the metal-air battery.
The air cathode and the anode aluminum plate are assembled into a battery in a self-made testing device, the electrolyte is 4M potassium hydroxide aqueous solution, and a discharge performance test is carried out, so that the result of the test shows that the highest power density of the aluminum-air battery assembled by the catalyst is 304.10mW/cm2At this time, the corresponding discharge voltage was 1.0137V, and the current density was 300.00mA/cm2。
Constant current discharge test of the aluminum-air battery shows that the current density is 275mA/cm2And under the condition that the environmental temperature is about 24.5 ℃, discharging is carried out for 2000min, and the voltage can still be kept at 1.35V.
Comparative example
LaFe is prepared by adopting a traditional hydrothermal method0.5Cr0.5O3Perovskite type oxide, no carbon source is added in the whole preparation process, and the prepared LaFe0.5Cr0.5O3The catalyst has a size of800nm-1 μm, and non-uniform particle size.
Taking the prepared LaFe0.5Cr0.5O32.4g of catalyst, 4.7g of conductive carbon black VXC-72R powder, 7.320g of 60% (the mass of the PTFE powder accounts for 60% of the total mass) PTFE solution and 100ml of absolute ethyl alcohol are mixed and stirred for 2.6h to obtain cathode catalyst slurry for the metal air battery; and (3) coating the cathode slurry on the nickel screen of the current collector by using the nickel screen as the current collector conductive network, and sintering at 300 ℃ for 60min to obtain the air cathode of the metal-air battery.
The air cathode and the anode aluminum plate are assembled into a battery in a self-made testing device, the electrolyte is 4M potassium hydroxide aqueous solution, and a discharge performance test is carried out, so that the result shows that the aluminum air battery is assembled by adopting the catalyst synthesized by the comparative example, and the highest power density is 202.75mW/cm through the test2At this time, the corresponding discharge voltage was 0.6758V, and the current density was 300.00mA/cm2。
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (17)
1. A preparation method of a loaded binuclear perovskite type oxide carbon nano microsphere catalyst comprises the following steps:
a, B, D, dissolving water-soluble salts of three metals in deionized water according to a molar ratio, adding a carbon sphere raw material, and mixing and stirring to prepare a mixed solution;
mixing and reacting supercritical water with the mixed solution, cooling, washing and drying a cooled sample to obtain catalyst powder; wherein the reaction temperature is 400-550 ℃; the reaction pressure is 20-50 MPa; the reaction time is 30-200 s; carrying out heat treatment on the catalyst powder, and cooling to obtain the supported binuclear perovskite type oxide carbon nano microsphere catalyst; wherein the heat treatment temperature is 300-500 ℃;
the general formula of the supported binuclear perovskite type oxide carbon nano microsphere catalyst is ABxD1-xO3@ C nanospheres; a comprises at least one of La, Sr, Ca and Ba; b or D respectively and independently comprises at least one of Fe, Cr, Co, Mn and Ni; x is more than 0 and less than 1.
2. The method of claim 1, wherein: the reaction temperature is 430-510 ℃; the reaction pressure is 28-38 MPa; the reaction time is 45-120 s; the heat treatment temperature is 300-400 ℃.
3. The method of claim 1, wherein: A. b, D the mass ratio of the water-soluble salt of the three metals to the carbon ball raw material is 0.9-1.5.
4. The production method according to claim 3, characterized in that: A. b, D the mass ratio of the water-soluble salt of the three metals to the carbon ball raw material is 1.1-1.35.
5. The method of claim 1, wherein: adding carbon ball raw material, mixing and stirring to prepare mixed solution, then adding 30% of H2O2The adding amount of the solution is 1 to 4 percent of the total volume of the mixed solution.
6. The method of claim 1, wherein: the step of mixing and reacting supercritical water with the mixed solution includes: pumping the mixed solution into a reactor by using a pump, wherein the flow range of the pump is 5-16 ml/min; pumping the deionized water into the reactor by another pump, heating the deionized water to a supercritical state by a heater in the middle, wherein the flow range of the pump is 20-30 ml/min; the reactor is a jet reactor; the reacted fluid passes through a cooling system and a filtering system.
7. The method of claim 6, wherein: the pump is a high performance liquid chromatography pump; the flow range of a pump for pumping the mixed solution into the reactor is 8-12 ml/min; the flow rate of the other pump is in the range of 22-27 ml/min.
8. The method of claim 1, wherein: the carbon ball raw material comprises at least one of starch, glucose, maltose or cellulose.
9. The method of claim 1, wherein: the addition amount of the deionized water is as follows: 80-110ml of deionized water is added into each 1g of carbon sphere raw material.
10. The method of claim 1, wherein: the preparation method of supercritical water comprises the following steps: heating deionized water to a supercritical state; wherein the heating temperature is 350-550 ℃.
11. The method of manufacturing according to claim 10, wherein: the heating temperature is 400-480 ℃.
12. The method of claim 1, wherein: the step of heat-treating the catalyst powder comprises placing the catalyst powder in a crucible and N in a tube furnace2Or heat treatment in an Ar atmosphere.
13. A supported binuclear perovskite type oxide carbon nano microsphere catalyst with a general formula of ABxD1-xO3@ C nanospheres; wherein A comprises at least one of La, Sr, Ca and Ba; b or D respectively and independently comprises at least one of Fe, Cr, Co, Mn and Ni; x is more than 0 and less than 1.
14. The supported binuclear perovskite-type oxide carbon nanosphere catalyst of claim 13, wherein: perovskite type oxide ABxD1-xO3Embedded in carbon nanoTwo sides of the rice ball; the size of the supported binuclear perovskite type oxide carbon nano microsphere catalyst is 300-500 nm.
15. A preparation method of cathode catalyst slurry of a metal-air battery comprises the following steps: the supported binuclear perovskite-type oxide carbon nanosphere catalyst of claim 13, conductive carbon black, polytetrafluoroethylene and absolute ethyl alcohol.
16. A cathode catalyst slurry for a metal-air battery comprising the supported binuclear perovskite-type oxide carbon nanosphere catalyst of claim 13, conductive carbon black, polytetrafluoroethylene and absolute ethanol.
17. Use of the supported binuclear perovskite-type oxide carbon nanosphere catalyst of claim 13 or the cathode catalyst slurry of claim 16 in a cathode sheet of a metal-air battery.
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