CN108365230B - Universal preparation method for active site and air electrode structure combination and application - Google Patents
Universal preparation method for active site and air electrode structure combination and application Download PDFInfo
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Abstract
The invention relates to a universal preparation method of an air electrode combining an active site with an electrode structure, which is characterized in that various polymer microspheres with an internally communicated open hierarchical pore structure are subjected to different treatment methods to combine noble metal bases, transition metal bases, heteroatom-doped carbon bases and other active sites. The different methods are one or more of a carbon tetrachloride crosslinking method, a concentrated sulfuric acid sulfonation method, a carbon dioxide gas activation method, a dopamine coating method, an ammonia gas activation method, a polyaniline coating method, an in-situ noble metal loading method, an in-situ transition metalate growth method and an in-situ heteroatom doping method. The universal method introduced by the invention can flexibly combine a plurality of different high-activity catalytic sites with an open multi-level pore electrode structure which simultaneously has super-large pores, mesopores and micropores, thereby improving the catalytic performance of the air electrode and the comprehensive performance of the fuel cell and the metal air cell.
Description
Technical Field
The invention belongs to preparation and application of an air electrode catalyst, and particularly relates to a preparation method and application of an air electrode catalyst which comprises an open multi-level pore electrode structure and a high-efficiency catalytic active site, wherein the open multi-level pore electrode structure is communicated with the interior of a super-large pore, a mesopore and a micropore.
Background
With the gradual exhaustion of global fossil fuels and the increasing severity of environmental problems, the reasonable and full utilization of renewable clean energy sources becomes the pursuit target of people. However, the intermittent problem of these renewable clean energy sources limits their wide application in the global scope, and therefore, the development and design of new efficient energy storage devices is the key to solve this problem. Although the lithium ion battery is widely applied at present, the lithium ion battery is limited by an inserted energy storage mechanism, has low energy density, cannot meet the requirements of future novel technological progress, has high cost and great potential safety hazard, and thus, the development of more advanced energy storage equipment is urgently needed to meet the requirements of future technological progress. Energy storage devices based on the reaction of continuously drawing oxygen are capable of greatly improving energy density due to the abundant oxygen in the atmosphere, such as dye batteries, metal air batteries, etc., have recently attracted much attention and become a research hotspot. A common problem with these battery storage technologies is the slow electrochemical reaction of oxygen involved in the battery cathode, including the Oxygen Reduction Reaction (ORR) and the Oxygen Evolution Reaction (OER). The oxygen electrochemical reaction is a gas-liquid-solid three-phase reaction containing reactant oxygen, reactant electrolyte and a solid catalyst, two key factors are provided for improving the reaction, and firstly, an efficient catalytic active site is developed to reduce the self energy barrier of the reaction and increase the intrinsic rate of the catalytic reaction; secondly, a reasonable catalyst structure is designed to increase more three-phase catalytic reaction interfaces. The slow cathode oxygen electrocatalytic reaction of the battery can cause the energy density of the battery to be lower and the output power density to be seriously reduced, which greatly limits the wide application of the fuel battery and the metal air battery in the novel fields of electric automobiles, static energy storage of power grids and the like. For catalyst development, the currently most effective commercial oxygen reduction catalysts are platinum carbon catalysts, while oxygen producing catalysts are iridium-based and ruthenium-based catalysts. However, the storage amount of the earth crust of the noble metal catalyst is low, the cost is high, and the utilization rate of the active sites is easy to be reduced sharply due to the accumulation among self particles caused by loading the noble metal catalyst on the active carbon, so that in order to ensure the advantage of high activity, a more reasonable porous carbon carrier is required to be developed to reduce the accumulation among the catalytic active sites and increase a contactable three-phase catalytic reaction interface to improve the utilization rate of the noble metal catalyst and the comprehensive performances such as the energy density, the power density and the like of a fuel cell and a metal-air battery. In order to further promote the large-scale application of novel fuel cells and metal air cells, the development of high-efficiency and low-price non-noble metal catalysts is trending. At present, researchers find that non-noble metal-based oxides, nitrides, phosphides, sulfides and the like all have certain activities of catalyzing ORR and OER, wherein more researches are carried out and the performances are better that the catalysts comprise oxides, nitrides, phosphides, sulfides and the like of one or more transition metals of Fe, Co, Ni, Cu and the like, such as copper oxide cobalt, iron cobalt nitrogen and the like; in addition to these transition metal-based catalysts, since nitrogen-doped carbon nanotube catalysts having excellent oxygen reduction catalytic performance were developed by the zurich group in 2009, heteroatom-doped carbon-based catalysts have also become favorable candidates for replacing noble metal-based catalysts. Carbon-based oxygen reduction or oxygen generation catalysts that are singly or multiply doped with non-metallic heteroatoms, including nitrogen, sulfur, phosphorus, boron, etc., have been developed. In addition, in 2014, an N, P double-doped carbon-based double-effect catalyst with ORR and OER catalytic performances is developed, so that a new idea is provided for developing an air electrode catalyst required by a cheap and efficient chargeable and dischargeable metal-air battery.
In terms of the construction of the metal electrode structure, research shows that the proper pore structure can greatly improve the catalytic rate of the oxygen electrocatalytic reaction, especially in the oxygen reduction reaction, because the reasonable pore structure not only can provide more catalytic active sites, but also can increase the transmission rate of liquid phase reactants and gas, so as to expose more three-phase catalytic reaction sites, and finally comprehensively improve the catalytic rate of the oxygen electrocatalytic reaction, so that the method becomes a favorable guarantee for improving the energy density and the output power of a fuel cell and a metal air cell. Because the air electrode catalytic reaction relates to gas, liquid and solid three-phase reactions, a microporous structure which can provide a large number of active sites and is required by an efficient catalyst structure are more important, namely, a mesoporous structure which can ensure the rapid gas transmission and a macroporous structure which is beneficial to the liquid transmission, even a super macroporous structure. In recent years, the combination of several pore structures in the construction of catalyst structures has been developed to achieve significant improvements in oxygen electrocatalytic performance and cell performance. The catalyst with the macroporous-microporous, macroporous-mesoporous and macroporous-mesoporous-microporous coexisting hierarchical pore structure can obviously improve the limiting current of ORR reaction, reduce the polarization loss caused by the sharp voltage drop along with the increase of current in the discharging process of the battery, further ensure larger output power density, and is beneficial to the improvement of the acceleration performance and the like of the electric automobile in practical application. This improvement can be attributed to the rapid transport and diffusion of liquid phase reactants by the macropores and the increase of accessible three-phase reaction sites by the mesopores and micropores. In addition to having a suitable pore size, an excellent electrode structure must also have a highly open pore configuration, which ensures rapid transport of reactants and products only with an internally interconnected and highly open multi-stage pore structure. In summary, the construction of an open multi-level pore electrode structure having both ultra-large pores, mesopores, and micropores and communicating with the interior is also one of the keys to large-scale application of fuel cells and metal-air cells, so that various polymer microspheres with similar morphology, which are extended and expanded on the basis of the preparation method mentioned in the prior patent CN106040121A, can be used as carriers or templates for providing excellent catalyst structures.
The combination of a high-activity catalytic site and an excellent electrode structure is an effective research idea that people follow to search a novel high-efficiency air electrode. However, most catalyst structures cannot be simply and effectively controlled, and are generally prepared by a multi-template method, most of the preparation methods are complicated, and the prepared pores have to be improved in regularity and connectivity. Moreover, most of the constructed catalyst structures are generally combined with a single catalytic active site, have no universality and cannot give full play to the structural advantages. The invention discloses a universal method, which can construct an open multi-level pore electrode structure with super-large pores, mesopores and micropores, and can exert the structural advantages of the electrode structure to the utmost extent, namely, the structure can be flexibly combined with a plurality of different high-activity catalytic sites by a proper method, so that the catalytic performance of an air electrode and the comprehensive performance of a fuel cell and a metal air cell, including the performances of energy density, power density, high rate performance, stability and the like, are improved. No studies have been reported on this universal approach to combine highly active catalytic sites with an excellent electrode structure.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a universal preparation method and application of an air electrode combining an active site and an electrode structure.
In order to solve the technical problems, the invention provides a universal preparation method of an air electrode combining an active site with an electrode structure, which is characterized in that a high-communicated multistage-skeleton polymer microsphere can combine noble metal base, transition metal base, heteroatom-doped carbon base and other active sites through different treatment methods.
Preferably, the highly-communicated multi-stage framework polymer microspheres are various types of polymer microspheres with open multi-stage pores communicated with the inside of the super-macroporous, mesoporous and microporous structures.
Preferably, the different methods are one or more of a carbon tetrachloride crosslinking method, a concentrated sulfuric acid sulfonation method, a carbon dioxide gas activation method, a dopamine coating method, an ammonia gas activation method, a polyaniline coating method, an in-situ noble metal loading method, an in-situ transition metal compound growth method and an in-situ heteroatom doping method.
Preferably, the active site noble metal is a metal selected from platinum, iridium, ruthenium, palladium, metal oxides, and alloys thereof with one or more of iron, cobalt, nickel, and copper; the transition metal-based active site comprises one or more oxides, nitrides, phosphides and sulfides of Fe, Co, Ni, Cu and the like; heteroatom-doped carbon-based active sites include one or more doped carbon-based materials of nitrogen, oxygen, phosphorus, sulfur, boron, and the like.
The present invention provides the various methods of preparing the above-described highly interconnected multi-stage backbone polymer microspheres to bind various active sites.
The first method comprises the following steps: the carbon tetrachloride crosslinking method is characterized by comprising the following specific steps: 0.5-2.0g of polymer microsphere and 30ml of carbon tetrachloride are placed in a 50ml glass bottle and uniformly shaken at 60-90 ℃ for 5-15h, 1.0-2.5g of anhydrous aluminum trichloride is added, the temperature is continuously kept at 60-90 ℃ and uniformly shaken for 5-15h, the mixed suspension is poured into a solution of acetone and 6-15% hydrochloric acid with the volume ratio of 1:1 while the mixture is hot, suction filtration is carried out after the residual aluminum chloride is completely reacted, water and ethanol are alternately filtered and washed for three times, and drying treatment is carried out at 60-80 ℃, so that the polymer microsphere after comprehensive yellow crosslinking can be obtained, and the crosslinking degree and the stability of the microsphere are improved.
And the second method comprises the following steps: the concentrated sulfuric acid sulfonation method is characterized by comprising the following specific steps: pouring 50ml of concentrated sulfuric acid into a 100ml round-bottom flask containing 1.0-3.0g of polymer microspheres or crosslinked polymer microspheres, treating at the temperature of 120-140 ℃ for 5-10h, pouring the hot solution into 600-1000ml of deionized water under stirring of a glass rod, cooling, filtering, washing with a large amount of water to be neutral, and drying at the temperature of 60-80 ℃.
And the third is that: the carbon dioxide gas activation method is characterized by comprising the following specific steps: carbonizing the polymer microspheres subjected to sulfuric acid and crosslinking treatment at the temperature of 500 ℃ and 700 ℃ for 2-4h at the temperature of 2-5 ℃/min in the inert atmosphere of nitrogen or argon, heating to the temperature of 800 ℃ and 900 ℃ at the temperature of 2-5 ℃/min in the inert atmosphere of nitrogen or argon, and calcining for 2-6h by changing the calcining gas into the inert gas of nitrogen or the volume flow ratio of argon to carbon dioxide of 1: 1.
And fourthly: the dopamine coating method is characterized by comprising the following specific steps: stirring 0.1-1.0g of polymer microspheres, 0.2-2.0g of dopamine hydrochloride and 5-30ml of methanol or ethanol for 3-5h, mixing uniformly, adding 100ml and 150ml of 0.01-0.2M Tris buffer solution, continuously stirring for 12-36h, filtering, washing, and drying at 60-80 ℃.
And a fifth mode: the polyaniline coating method is characterized by comprising the following specific steps: adding 0.05-0.2g of polymer microspheres treated by sulfuric acid into 15ml of 0.75-1.25M perchloric acid solution, stirring and mixing uniformly, adding 0.02-0.05M aniline solution, adding pre-cooled 0.015-0.045M ammonium persulfate solution into a reaction system, controlling the temperature in an ice bath in the whole process, reacting for 12-36h to obtain the product polyaniline-coated multistage skeleton microspheres, performing suction filtration and washing, and drying at 60-80 ℃.
And a sixth mode: the ammonia activation method is characterized by comprising the following specific steps: carbonizing the carbon-containing precursor or the doped precursor at 400-500 ℃ for 2-4h at 2-5 ℃/min in the nitrogen or argon atmosphere of the inert atmosphere, then continuously heating to 700-1100 ℃ at 2-5 ℃/min in the nitrogen or argon atmosphere of the inert atmosphere, and changing the calcining gas into 50% ammonia nitrogen mixed gas for calcining for 2-6 h.
Seventh, the method comprises: the in-situ noble metal loading method is characterized by comprising the following specific steps: dispersing 20-80mg of carbon dioxide activated sulfuric acid and a cross-linked polymer microsphere carrier into a water/ethanol solution, adding different noble metals or noble metal and transition metal mixed precursors according to different loading amounts, stirring and soaking for 8h, adjusting the pH value to 7-9, then quickly adding a corresponding molar equivalent of a reducing agent (M metal precursor: M reducing agent ═ 1:3-15), continuously stirring for 1-2h, carrying out suction filtration and drying.
Preferably, the noble metal salt is chloroplatinic acid, chloroauric acid, palladium chloride, iridium chloride, ruthenium chloride, and the transition metal salt is one or more of ferric nitrate, ferrous sulfate, ferric chloride, cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride, nickel acetate, copper chloride, copper nitrate, and copper acetate; the reducing agent is sodium borohydride, formic acid and glycol.
An eighth method: the in-situ growth transition metal compound method is characterized by comprising the following specific steps: 0.1-1.0g of polymer microspheres, 0.2-2.0g of dopamine hydrochloride, transition metal salt, a sulfur or phosphorus containing reagent and 5-30ml of methanol or ethanol are stirred for 3-5h and mixed evenly, 150ml of 0.01-0.2M Tris buffer solution is added and stirred for 12-36h, and then the mixture is filtered, washed and dried at the temperature of 60-80 ℃.
Preferably, the transition metal salt is one or more of ferric nitrate, ferrous sulfate, ferric chloride, cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride, nickel acetate, copper chloride, copper nitrate and copper acetate; the sulfur or phosphorus containing reagent is trithiocyanuric acid or phytic acid.
Ninth, the method comprises the following steps: the in-situ heteroatom doping method is characterized by comprising the following specific steps: stirring 0.1-1.0g of polymer microspheres, 0.2-2.0g of dopamine hydrochloride and 5-30ml of methanol or ethanol for 3-5h, uniformly mixing, adding 100 ml-150 ml of 0.01-0.2M Tris buffer solution, continuously stirring for 12-24h, adding different heteroatom-containing reagents and 50ml of 0.01-0.2M Tris buffer solution, continuously stirring for 12-24h, carrying out suction filtration washing, and drying at 60-80 ℃.
Preferably, the heteroatom reagent is mercaptoethylamine, trithiocyanuric acid, phytic acid.
The tenth way: the MOF method for loading metal framework organic matters is characterized by comprising the following specific steps: 0.05-0.2g of polymer microsphere treated by sulfuric acid and 50ml of organic solvent containing metal salt are stirred uniformly, 50ml of organic solvent containing organic ligand is added and stirred uniformly, and then the mixture is kept stand for 12-24h, filtered, washed by the organic solvent, and dried at 60-80 ℃.
Preferably, the metal salt is one or more of zinc nitrate, zinc sulfate chloride, ferric nitrate, ferrous sulfate, ferric chloride, cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride, nickel carbonate, nickel acetate, copper chloride, copper nitrate, and copper acetate; the organic ligand is common ligand such as 2-methylimidazole, terephthalic acid, aspartic acid, bipyridyl and the like.
An eleventh aspect: the hydrothermal transition metal oxide hydroxide growth method is characterized by comprising the following specific steps: 0.05-0.2g of polymer microspheres treated by sulfuric acid, 4-10mM of transition metal salt, 20-60mM of urea, 10mM of ammonium fluoride and 45ml of water are uniformly mixed, transferred into a 50ml of hydrothermal kettle and reacted at 120 ℃ for 6-18h, and then subjected to suction filtration, water washing and ethanol washing, and dried at 60-80 ℃.
The invention also provides a preparation and test method for applying the air electrode catalysts prepared by the method to a rotary disk electrode for performance test of a fuel cell and a metal-air cell, which is characterized by comprising the following specific steps: 1mg of the air electrode catalyst prepared by the above method was dispersed in 45ul of isopropyl alcohol, 45ul of water and 10ul of a Nafion mixed solution having a mass percent concentration of 5 wt%; dripping 8ul of the uniformly dispersed catalyst suspension on a rotating disk electrode with the area of 0.196cm2, and naturally airing to obtain a disk electrode for testing air electrodes of fuel cells and metal-air cells; the catalyst-loaded rotating disk electrode prepared above was subjected to an Oxygen Reduction Reaction (ORR) test, an oxygen generation reaction test (OER) and a hydrogen generation test (HER) in a KOH solution of 0.1M.
The invention also provides a preparation and test method of the membrane electrode assembly for preparing the fuel cell and the metal-air cell by using the air electrodes prepared by the method, which is characterized by comprising the following specific steps: 1mg of the air electrode catalyst prepared by the above method was dispersed in 45ul of isopropyl alcohol, 45ul of water and 10ul of a Nafion mixed solution having a mass percent concentration of 5 wt%; and dripping 40ul of the uniformly dispersed catalyst suspension on a gas diffusion electrode which is self-made in a laboratory and has the area of 1cm2, naturally airing to obtain the gas diffusion electrode for testing a fuel cell and a metal air cell, and assembling the gas diffusion electrode into a cell for testing the cell performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) the highly communicated multi-level skeleton polymer microspheres prepared by the invention can be used as a carrier to carry out polymer coating and then carbonized to generate heteroatom-doped carbon-based catalysts by forming a multi-level pore skeleton carbon carrier through carbonization and activation treatment to load noble metal-based catalysts, and can also be combined with transition metal salts to generate transition metal-based catalysts, the polymer microspheres can exert the advantages of an open multi-level pore electrode structure with super-large pores, mesopores and micropores simultaneously to the maximum extent, greatly improve the mass transfer rate of oxygen and electrolyte, carry out rapid electronic transmission through conductive frameworks with mutually communicated interiors, and can be properly treated and combined with different catalytic active sites through different methods, thereby providing a simple and effective universal method for developing an air electrode with high-activity catalytic sites and excellent electrode structure combination.
(2) The catalyst prepared by the in-situ reduction method and internally highly communicated with the hierarchical pore framework carbon microsphere loaded with trace noble metal platinum greatly improves the reaction rate of the oxygen reduction reaction and is particularly expressed on the increased limiting current, the catalyst applied to a zinc-air battery also expresses higher energy density, power density and stability than 20 percent of commercial platinum carbon, in addition, the platinum loading amount of the catalyst is only 5 percent, and the utilization rate of the noble metal platinum of the catalyst can reach 99 percent and is far higher than 50 percent of the commercial platinum carbon.
(3) The hierarchical porous carbon microsphere air cathode coated by the polyaniline array prepared by the in-situ heteroatom doping method has good oxygen reduction performance, and the limiting current is greatly increased due to the improvement of mass transfer rates of gas-liquid reactants and products caused by macropores and mesopores in the hierarchical pores, so that favorable performance support is provided for the application of the catalyst in subsequent fuel cells and metal air cells.
(4) The nitrogen-sulfur double-doped carbon-based hierarchical porous carbon microsphere air cathode catalyst prepared by the in-situ doped heteroatom method has high-efficiency oxygen reduction and oxygen production catalytic performances, has better oxygen reduction performance than a 20% commercial platinum carbon catalyst and better oxygen production performance than iridium dioxide, shows higher power density and stability than 20% commercial platinum carbon when being applied to a zinc-air battery, and more importantly, has higher charge-discharge rate and can stably circulate for 48 hours under larger 100mA charge-discharge current.
(5) The nitrogen-phosphorus double-doped hierarchical porous carbon microsphere three-way catalyst loaded with the cobalt-iron phosphide and prepared by the in-situ growth transition metal compound method has better oxygen reduction performance than a 20% commercial platinum-carbon catalyst, better oxygen production performance than iridium dioxide and basically hydrogen production performance compared with 20% commercial platinum-carbon, so that the catalyst not only provides excellent catalyst for fuel cells and metal air cells, but also provides excellent catalyst for electrocatalytic hydrolysis hydrogen production and oxygen production reaction, and opens up a new way for providing and storing renewable clean energy.
(6) The cobaltous oxide supported nitrogen-sulfur double-doped hierarchical pore carbon microsphere double-effect catalyst prepared by the in-situ growth transition metal compound method has oxygen reduction performance and high-efficiency oxygen production performance, and can be attributed to the functional combination of excellent oxygen production catalytic active site cobaltous oxide and internal highly communicated hierarchical pore framework microspheres.
Drawings
FIG. 1 is a scanning electron microscope image and a transmission electron microscope image of a hierarchical pore framework carbon microsphere loaded with trace noble metal platinum catalyst, which are highly communicated inside, under different magnifications.
FIG. 2 is a scanning electron microscope image of a polyaniline array coated hierarchical porous carbon microsphere air cathode catalyst under different magnifications.
FIG. 3 is a scanning electron microscope image of nitrogen-sulfur double-doped carbon-based hierarchical porous carbon microsphere air cathode catalyst under different magnifications.
FIG. 4 is a scanning electron microscope image of nitrogen and phosphorus double-doped hierarchical porous carbon microsphere three-way catalyst loaded with cobalt iron phosphide under different magnifications.
FIG. 5 is an X-ray diffraction pattern of a NPC double-doped hierarchical porous carbon microsphere three-way catalyst loaded with CoFeP.
FIG. 6 is a scanning electron microscope image of cobaltous oxide supported nitrogen-sulfur double-doped hierarchical porous carbon microsphere double-effect catalyst under different magnifications.
FIG. 7 is an X-ray diffraction pattern of a cobaltous oxide supported nitrogen and sulfur double doped hierarchical pore carbon microsphere double effect catalyst.
FIG. 8 is a comparison graph of oxygen reduction polarization curves of a hierarchical pore framework carbon microsphere supported trace noble metal platinum catalyst and commercial platinum carbon in an alkaline medium, wherein the internal parts of the catalyst are highly communicated, and the electrode supported platinum equivalent is 18ug/cm2。
FIG. 9 is a comparison graph of oxygen reduction polarization curves of polyaniline array coated hierarchical porous carbon microsphere air cathode catalyst and commercial platinum carbon in alkaline medium, wherein the electrode loading is 0.408mg/cm2。
FIG. 10 is a graph comparing oxygen reduction and oxygen generation polarization curves of nitrogen-sulfur double-doped carbon-based hierarchical porous carbon microsphere air cathode catalyst and commercial platinum-carbon and iridium dioxide mixed catalyst in an alkaline medium, wherein the electrode loading is 0.408mg/cm2。
FIG. 11 is a graph comparing oxygen reduction and oxygen evolution polarization curves of a cobalt iron phosphide-loaded nitrogen-phosphorus double-doped hierarchical porous carbon microsphere three-way catalyst and a commercial platinum-carbon and iridium dioxide mixed catalyst in an alkaline medium, wherein the electrode loading amounts are 0.408mg/cm2。
FIG. 12 is a graph comparing oxygen reduction and oxygen evolution polarization curves of a cobaltous oxide supported nitrogen sulfur double-doped multi-stage porous carbon microsphere double-effect catalyst and a commercial platinum carbon and iridium dioxide mixed catalyst in an alkaline medium, wherein the electrode loading is 0.408mg/cm2. FIG. 13 is a comparison graph of hydrogen production polarization curves of cobaltous oxide supported nitrogen and sulfur double-doped multi-stage porous carbon microsphere double-effect catalyst and commercial platinum-carbon and iridium dioxide mixed catalyst in alkaline medium, wherein the electrode loading is 0.408mg/cm2。
FIG. 14 is a graph showing the energy density of a hierarchical pore framework carbon microsphere loaded trace noble metal platinum catalyst and commercial platinum carbon in an alkaline metal zinc-air battery, wherein the internal height of the hierarchical pore framework carbon microsphere is communicated with the internal height of the hierarchical pore framework carbon microsphere, and the platinum equivalent loaded on a gas diffusion layer is 50ug/cm2。
FIG. 15 is a graph showing the power density of a hierarchical pore framework carbon microsphere loaded trace noble metal platinum catalyst and commercial platinum carbon in an alkaline metal zinc-air battery, wherein the internal height of the hierarchical pore framework carbon microsphere is communicated with the internal height of the hierarchical pore framework carbon microsphere, and the platinum equivalent loaded on a gas diffusion layer is 50ug/cm2。
FIG. 16 is a graph of power density of a nitrogen-sulfur double-doped carbon-based multi-stage porous carbon microsphere air cathode catalyst and commercial platinum carbon in an alkaline metal zinc air cell, wherein the loading of a gas diffusion layer is 0.4mg/cm2。
FIG. 17 is a high rate charge-discharge cycle plot of a nitrogen-sulfur double-doped carbon-based multi-stage porous carbon microsphere air cathode catalyst and commercial platinum carbon in an alkaline metal zinc-air cell, wherein the loading of a gas diffusion layer is 0.4mg/cm2。
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Example 1
A highly-communicated hierarchical pore framework carbon microsphere supported trace precious metal platinum catalyst is characterized in that a precursor of the highly-communicated hierarchical pore framework carbon microsphere supported trace precious metal platinum catalyst comprises a hierarchical pore framework carbon microsphere which is prepared by a carbon tetrachloride crosslinking method, a concentrated sulfuric acid sulfonation method and a carbon dioxide activation method and contains macropores, mesopores and micropores and is highly communicated with the inside; and chloroplatinic acid and reducing agent sodium borohydride which are required for reducing the loaded platinum nanoparticles to the multi-level pore skeleton carbon microspheres with highly communicated interiors in situ by utilizing a noble metal loading method in situ.
The preparation method of the highly communicated hierarchical pore framework carbon microsphere supported trace noble metal platinum catalyst comprises the following steps: firstly, the carbon tetrachloride crosslinking method is used for crosslinking the polymer microspheres, and the specific steps are as follows: placing 0.1g of polymer microsphere and 30ml of carbon tetrachloride in a 50ml glass bottle, uniformly shaking at 70 ℃ for 5h, adding 1.5g of anhydrous aluminum trichloride, continuously keeping the temperature at 70 ℃ and uniformly shaking for 5h, pouring the mixed suspension into a solution of acetone and 6% hydrochloric acid in a volume ratio of 1:1 while the mixed suspension is hot, performing suction filtration after the residual aluminum chloride completely reacts, alternately filtering and washing with water and ethanol for three times, and drying at 60 ℃ to obtain the comprehensive yellow crosslinked polymer microsphere; and secondly, sulfonating the crosslinked polymer microspheres by using a concentrated sulfuric acid sulfonation method, wherein the method comprises the following specific steps: pouring 50ml of concentrated sulfuric acid into a 100ml round-bottom flask containing 2.0g of crosslinked polymer microspheres, treating at 135 ℃ for 5 hours, pouring the hot concentrated sulfuric acid into 800ml of deionized water under stirring of a glass rod, cooling, performing suction filtration, washing with a large amount of water until the solution is neutral, and drying at 60 ℃; thirdly, the polymer microspheres after sulfonation treatment in the second step are treated by a carbon dioxide gas activation method to increase the specific surface area and the noble metal loading sites, and the method specifically comprises the following steps: carbonizing the polymer microsphere subjected to sulfuric acid and crosslinking treatment at the temperature of 600 ℃ for 2h in the nitrogen atmosphere at the speed of 5 ℃/min, cooling, heating to 850 ℃ in the nitrogen atmosphere at the speed of 5 ℃/min, and calcining for 4h by changing the volume flow ratio of nitrogen to carbon dioxide into the calcining gas of 1:1, so that the hierarchical pore framework carbon microsphere which simultaneously contains macropores, mesopores and micropores and is highly communicated with the interior can be prepared. And fourthly, uniformly loading noble metal platinum particles with the size of 2-5nm on the hierarchical pore framework carbon microsphere by using an in-situ noble metal method, specifically dispersing 20mg of sulfuric acid activated by carbon dioxide and a cross-linked polymer microsphere carrier into a water/ethanol solution, adding 0.28ml of 10mg/ml chloroplatinic acid precursor, stirring and soaking for 8h, adjusting the pH to 7-9, then quickly adding 3mg of sodium borohydride (M chloroplatinic acid: M sodium borohydride: 1:12) with corresponding molar equivalent, continuously stirring for 2h, performing suction filtration and drying to obtain the uniformly loaded metal platinum nanoparticles with the size of 2-5nm, wherein the specific morphology is shown in a scanning electron microscope and a transmission electron microscope of fig. 1.
Example 2
A polyaniline array-coated hierarchical porous carbon microsphere air cathode catalyst comprises a precursor of a polyaniline array-coated hierarchical porous carbon microsphere, a hierarchical porous polymer microsphere subjected to sulfonation treatment by concentrated sulfuric acid, a polyaniline array-coated sulfonated polymer microsphere prepared by a polyaniline coating method, and a nitrogen-containing polyaniline array hierarchical porous microsphere subjected to ammonia activation.
The specific method of the polyaniline array-coated hierarchical porous carbon microsphere air cathode catalyst comprises the following steps: in the first step, a concentrated sulfuric acid sulfonation method is used for sulfonating the polymer microspheres, and the specific steps are as follows: pouring 50ml of concentrated sulfuric acid into a 100ml round-bottom flask containing 2.0g of polymer microspheres, treating at 135 ℃ for 5 hours, pouring the hot concentrated sulfuric acid into 800ml of deionized water under stirring of a glass rod, cooling, performing suction filtration, washing with a large amount of water until the solution is neutral, and drying at 60 ℃; and secondly, coating the sulfonated polymer microspheres with a polyaniline array by using a polyaniline coating method, which comprises the following specific steps: adding 0.1g of sulfonated polymer microspheres into 15ml of 1mol/L perchloric acid solution, stirring and mixing uniformly, adding aniline solution with the concentration of 0.02-0.05M, adding precooled 0.03mol/L ammonium persulfate solution into a reaction system, controlling the temperature in an ice bath in the whole process, reacting for 24 hours to obtain the product polyaniline-coated multi-stage skeleton microspheres, filtering, washing and drying at 60 ℃; the third step of carbonizing the nitrogen-containing polyaniline array hierarchical porous microsphere precursor by using an ammonia activation method, which comprises the following specific steps: carbonizing a carbon-containing precursor or a doped precursor and the like at the temperature of 450 ℃ for 2h at the speed of 5 ℃/min in a nitrogen atmosphere, then continuously heating to the temperature of 900-fold at the speed of 2 ℃/min in the nitrogen atmosphere, changing the calcining gas into 50% ammonia nitrogen mixed gas for calcining for 2h, wherein the appearance of the polyaniline array is shown as a scanning electron microscope picture in figure 2.
Example 3
A nitrogen-sulfur double-doped carbon-based hierarchical porous carbon microsphere air cathode catalyst comprises precursors of dopamine hydrochloride and mercaptoethylamine, and the used methods are an in-situ heteroatom doping method and an ammonia gas activation method.
The preparation method of the nitrogen-sulfur double-doped carbon-based hierarchical porous carbon microsphere air cathode catalyst comprises the following steps: firstly, stirring 0.4g of polymer microspheres, 0.8g of dopamine hydrochloride and 30ml of methanol for 5 hours, uniformly mixing, adding 150ml of 0.02M Tris buffer solution, continuously stirring for 12 hours, adding 0.32g of mercaptoethylamine, 0.8g of dopamine hydrochloride and 50ml of 0.02M Tris buffer solution, continuously stirring for 24 hours, carrying out suction filtration and washing, and drying at 60 ℃; secondly, performing ammonia activation treatment on the dopamine and mercaptoethylamine coated polymer microspheres, which comprises the following specific steps: carbonizing a carbon-containing precursor or a doped precursor and the like at the temperature of 450 ℃ for 2h at the speed of 5 ℃/min in a nitrogen atmosphere, then continuously heating to 1000 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, and changing the calcining gas into 50% ammonia and nitrogen mixed gas for calcining for 2h, wherein the morphology of the carbon-containing precursor or the doped precursor is shown in a scanning electron microscope picture of figure 3.
Example 4
A nitrogen-phosphorus double-doped hierarchical porous carbon microsphere three-way catalyst loaded with cobalt-iron phosphide is prepared from dopamine hydrochloride, ferric nitrate, cobalt acetate and phytic acid as precursors through in-situ growth of transition metalate and ammonia activation.
The preparation method of the nitrogen-phosphorus double-doped hierarchical porous carbon microsphere three-way catalyst loaded with the cobalt-iron phosphide comprises the following steps: the first step is to load a transition metal precursor on the hierarchical porous polymer microsphere by using an in-situ growth transition metal compound method, and the method comprises the following specific steps: stirring 0.3g of polymer microspheres, 1.2g of dopamine hydrochloride, 0.2g of ferric nitrate, 0.2g of cobalt acetate, 1ml of phytic acid (50% aqueous solution) and 30ml of methanol for 5 hours, uniformly mixing, adding 100ml of 0.2M Tris buffer solution, continuously stirring for 24 hours, carrying out suction filtration and washing, and drying at 60 ℃; secondly, the transition metal precursor loaded on the hierarchical porous polymer microsphere is activated by ammonia gas, and the method comprises the following specific steps: carbonizing a carbon-containing precursor or a doped precursor and the like at the temperature of 450 ℃ for 2h at the speed of 5 ℃/min in a nitrogen atmosphere, then continuously heating to 800 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, changing the calcining gas into 50% ammonia and nitrogen mixed gas for calcining for 4h, wherein the morphology is shown as a scanning electron microscope photo in figure 4, and the phase structure is shown as an XRD diffraction pattern in figure 5.
Example 5
A cobaltous oxide supported nitrogen-sulfur double-doped hierarchical porous carbon microsphere double-effect catalyst comprises precursors of dopamine hydrochloride, ferric nitrate, cobalt acetate and phytic acid, and the used methods are an in-situ growth transition metalate method and a high-temperature carbonization method.
The preparation method of the cobaltous oxide supported nitrogen-sulfur double-doped hierarchical porous carbon microsphere double-effect catalyst comprises the following steps: the first step is to load a transition metal precursor on the hierarchical porous polymer microsphere by using an in-situ growth transition metal compound method, and the method comprises the following specific steps: stirring 0.3g of polymer microspheres, 1.2g of dopamine hydrochloride, 1.5g of cobalt acetate, 1g of trithiocyanuric acid and 30ml of methanol for 5h, uniformly mixing, adding 100ml of 0.2M Tris buffer solution, continuously stirring for 24h, performing suction filtration and washing, and drying at 60 ℃; secondly, carrying out nitrogen carbonization treatment on the transition metal precursor loaded on the hierarchical porous polymer microsphere, and specifically comprising the following steps: carbonizing a carbon-containing precursor or a doped precursor and the like at the temperature of 450 ℃ for 2h at the speed of 5 ℃/min in a nitrogen atmosphere, then continuously heating to the temperature of 700-1100 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, and calcining for 4h, wherein the morphology is shown as a scanning electron micrograph in figure 6, and the phase structure is shown as an XRD diffraction pattern in figure 7.
Example 6
A preparation method for applying the air electrode catalysts prepared by the method to a rotating disk electrode for performance test of a fuel cell and a metal-air cell comprises the following specific steps: 1mg of the air electrode catalyst prepared by the above method was dispersed in 45ul of isopropyl alcohol, 45ul of water and 10ul of a Nafion mixed solution having a mass percent concentration of 5 wt%; dripping 8ul of the uniformly dispersed catalyst suspension into the solution with the area of 0.196cm2The rotary disk electrode is naturally dried to obtain the disk electrode for testing the air electrode of the fuel cell and the metal air cell; the catalyst-loaded rotating disk electrode prepared above was used as a working electrode, a platinum sheet as a counter electrode, and silver-silver chloride as a reference electrode, and an Oxygen Reduction Reaction (ORR) test, an oxygen evolution reaction test (OER), and a Hydrogen Evolution (HER) test were performed in a solution using 0.1M KOH as an electrolyte, as shown in fig. 8 to 13.
Example 7
A method for preparing a membrane electrode assembly for a fuel cell and a metal-air cell by using a plurality of air electrodes prepared by the method comprises the following specific steps: 1mg of the air electrode catalyst prepared by the above method was dispersed in 45ul of isopropyl alcohol, 45ul of water and 10ul of a Nafion mixed solution having a mass percent concentration of 5 wt%; dripping 40ul of the uniformly dispersed catalyst suspension into a container with an area of 1cm2The gas diffusion electrode prepared by the laboratory is naturally dried to obtain the gas diffusion electrode for testing the fuel cell and the metal air cell, and the gas diffusion electrode is assembled into the metal zinc cell, 0.2M zinc chloride and 6M potassium hydroxide are used as electrolyte, a 1.5cm2 metal zinc sheet is used as an anode, the prepared gas diffusion electrode loaded with the catalyst is used as a cathode, and the gas diffusion electrode is used for electrochemical workBattery performance tests, including battery capacity tests, power density tests, charge-discharge cycling tests at high current densities, etc., were performed on the station, as shown in fig. 14-17.
In the drawings of the specification of the present invention, all potential values have been converted into potentials with respect to a standard hydrogen electrode. Fig. 1-7 show that a part of air cathode catalysts are selected preferentially, and from the structure of these catalysts, they all inherit the excellent pore structure of the multi-level pore skeleton polymer microsphere which is mentioned in the prior patent CN106040121A and contains super-large pores, mesopores and micropores and is communicated with the inside, so that the perfect combination of the catalytic active sites and the excellent electrode structure is realized, and the universality of the method of the invention is also proved, and after the activation treatment of carbon dioxide and ammonia gas, a large number of micropores are added, so that the load sites of the catalytic active sites are further improved, and the unique internally communicated large pore nucleus mesopores of the structure are combined, so that more three-phase catalytic reaction sites are exposed, which is also beneficial to the improvement of oxygen electrocatalytic performance and battery performance of these catalysts; fig. 8-13 further demonstrate that the oxygen reduction performance of the catalysts prepared by combining the catalytic active sites with the hierarchical pore framework structure is comparable to that of commercial platinum carbon, and especially, the catalyst with the hierarchical pore framework carbon microspheres loaded with trace noble metal platinum, which is highly communicated inside, not only has the initial potential superior to that of commercial platinum carbon, but also has the obviously excellent limiting current; the nitrogen-sulfur double-doped carbon-based hierarchical porous carbon microsphere air cathode catalyst has high-efficiency oxygen reduction and oxygen production catalytic performance, and has better oxygen reduction performance than a 20% commercial platinum-carbon catalyst and better oxygen production performance than iridium dioxide; the nitrogen-phosphorus double-doped hierarchical porous carbon microsphere three-way catalyst loaded with the cobalt-iron phosphide not only has better oxygen reduction performance than a 20% commercial platinum-carbon catalyst, but also has better oxygen production performance than iridium dioxide and hydrogen production performance basically compared with 20% commercial platinum-carbon. Further, the catalysts are preferentially applied to the metal zinc-air battery to be tested and found to have quite excellent performance, as shown in fig. 14-17, and fig. 14-15 show that the application of the hierarchical pore framework carbon microsphere supported trace noble metal platinum catalyst to the zinc-air battery not only has higher performance than that of commercial platinumBetter energy density of carbon, and also better power density; FIGS. 16-17 show that the nitrogen-sulfur double-doped carbon-based hierarchical porous carbon microsphere air cathode catalyst also shows better power density than commercial platinum carbon when applied to a metal zinc air battery, and more importantly, the catalyst can reach 100mA/cm2Is subjected to long-term charge-discharge cycles at high current densities, which was reported for the first time in the field as a non-metal-based dual-effect catalyst.
Claims (22)
1. The universal preparation method of the air electrode combining the active sites with the electrode structure is characterized in that the active sites such as a noble metal base, a transition metal base and heteroatom-doped carbon base are combined by communicating multistage-skeleton polymer microspheres through different treatment methods, and the communicating multistage-skeleton polymer microspheres are subjected to one or more of a carbon tetrachloride crosslinking method, a concentrated sulfuric acid sulfonation method, a carbon dioxide gas activation method, a dopamine coating method, an ammonia gas activation method, a polyaniline coating method, an in-situ noble metal loading method, an in-situ transition metal compound growing method and an in-situ heteroatom doping method through different treatment methods.
2. The universal preparation method of an air electrode combining an active site with an electrode structure according to claim 1, wherein the interconnected multi-stage framework polymer microspheres are various types of polymer microspheres comprising open multi-stage pores with interconnected inner parts of super-large pores, meso pores and micro pores.
3. The universal method of claim 1, wherein the noble metal-based active site is selected from the group consisting of platinum, iridium, ruthenium, palladium, metal oxides, and alloys thereof with one or more of iron, cobalt, nickel, and copper.
4. The universal manufacturing method of air electrode combining active site with electrode structure as claimed in claim 1, wherein said transition metal based active site is oxide, nitride, phosphide, sulfide of one or more of Fe, Co, Ni, Cu, etc.
5. The universal method of claim 1, wherein the heteroatom-doped carbon-based active site is one or more of nitrogen, oxygen, phosphorus, sulfur, boron, and the like doped carbon-based materials.
6. The universal preparation method of an air electrode for combining an active site with an electrode structure according to claim 1, wherein the carbon tetrachloride crosslinking method among the different treatment methods comprises the following specific steps: 0.5-2.0g of polymer microsphere and 30ml of carbon tetrachloride are placed in a 50ml glass bottle and uniformly shaken at 60-90 ℃ for 5-15h, 1.0-2.5g of anhydrous aluminum trichloride is added, the temperature is continuously kept at 60-90 ℃ and uniformly shaken for 5-15h, the mixed suspension is poured into a solution of acetone and 6-15% hydrochloric acid with the volume ratio of 1:1 while the mixture is hot, suction filtration is carried out after the residual aluminum chloride is completely reacted, water and ethanol are alternately filtered and washed for three times, and drying treatment is carried out at 60-80 ℃, so that the polymer microsphere after comprehensive yellow crosslinking can be obtained, and the crosslinking degree and the stability of the microsphere are improved.
7. The universal preparation method of the air electrode combining the active site and the electrode structure according to claim 1, wherein the concentrated sulfuric acid sulfonation method among the different treatment methods comprises the following specific steps: pouring 50ml of concentrated sulfuric acid into a 100ml round-bottom flask containing 1.0-3.0g of polymer microspheres or crosslinked polymer microspheres, treating at the temperature of 120-140 ℃ for 5-10h, pouring the hot solution into 600-1000ml of deionized water under stirring of a glass rod, cooling, filtering, washing with a large amount of water to be neutral, and drying at the temperature of 60-80 ℃.
8. The universal manufacturing method of air electrode for combining active site with electrode structure as claimed in claim 1, wherein the carbon dioxide gas activation method among different treatment methods comprises the following specific steps: carbonizing the polymer microspheres subjected to sulfuric acid and crosslinking treatment at the temperature of 500 ℃ and 700 ℃ for 2-4h at the temperature of 2-5 ℃/min in the inert atmosphere of nitrogen or argon, heating to the temperature of 800 ℃ and 900 ℃ at the temperature of 2-5 ℃/min in the inert atmosphere of nitrogen or argon, and calcining for 2-6h by changing the calcining gas into the inert gas of nitrogen or the volume flow ratio of argon to carbon dioxide of 1: 1.
9. The universal preparation method of an air electrode for binding an active site with an electrode structure according to claim 1, wherein the dopamine coating method among the different treatment methods comprises the following specific steps: stirring 0.1-1.0g of polymer microspheres, 0.2-2.0g of dopamine hydrochloride and 5-30ml of methanol or ethanol for 3-5h, mixing uniformly, adding 100ml and 150ml of 0.01-0.2M Tris buffer solution, continuously stirring for 12-36h, filtering, washing, and drying at 60-80 ℃.
10. The universal preparation method of the air electrode for combining the active site with the electrode structure as claimed in claim 1, wherein the polyaniline coating method among the different treatment methods comprises the following specific steps: adding 0.05-0.2g of polymer microspheres treated by sulfuric acid into 15ml of 0.75-1.25M perchloric acid solution, stirring and mixing uniformly, adding 0.02-0.05M aniline solution, adding pre-cooled 0.015-0.045M ammonium persulfate solution into a reaction system, controlling the temperature in an ice bath in the whole process, reacting for 12-36h to obtain the product polyaniline-coated multistage skeleton microspheres, performing suction filtration and washing, and drying at 60-80 ℃.
11. The universal preparation method of the air electrode for combining the active site with the electrode structure as claimed in claim 1, wherein the ammonia gas activation method among the different treatment methods comprises the following specific steps: carbonizing the carbon-containing precursor or the doped precursor at 400-500 ℃ for 2-4h at 2-5 ℃/min in the nitrogen or argon atmosphere of the inert atmosphere, then continuously heating to 700-1100 ℃ at 2-5 ℃/min in the nitrogen or argon atmosphere of the inert atmosphere, and changing the calcining gas into 50% ammonia nitrogen mixed gas for calcining for 2-6 h.
12. The universal preparation method of the air electrode combining the active site and the electrode structure as claimed in claim 1, wherein the different treatment methods are a noble metal in-situ loading method, and the method comprises the following specific steps: dispersing 20-80mg of carbon dioxide activated sulfuric acid and a cross-linked polymer microsphere carrier into a water/ethanol solution, adding different noble metals or noble metal and transition metal mixed precursors according to different loading amounts, stirring and soaking for 8 hours, adjusting the pH value to 7-9, then quickly adding a corresponding molar equivalent of a reducing agent, continuously stirring for 1-2 hours, carrying out suction filtration, and drying.
13. The universal method of claim 12, wherein the noble metal is in the form of a noble metal salt selected from the group consisting of chloroplatinic acid, chloroauric acid, palladium chloride, iridium chloride, ruthenium chloride, transition metal salts selected from the group consisting of ferric nitrate, ferrous sulfate, ferric chloride, cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride, nickel acetate, copper chloride, copper nitrate, and copper acetate; the reducing agent is sodium borohydride, formic acid and glycol.
14. The universal manufacturing method of air electrode for combining active site with electrode structure as claimed in claim 1, wherein the in-situ transition metal compound growing method among different processing methods comprises the following specific steps: 0.1-1.0g of polymer microspheres, 0.2-2.0g of dopamine hydrochloride, transition metal salt, a sulfur or phosphorus containing reagent and 5-30ml of methanol or ethanol are stirred for 3-5h and mixed evenly, 150ml of 0.01-0.2M Tris buffer solution is added and stirred for 12-36h, and then the mixture is filtered, washed and dried at the temperature of 60-80 ℃.
15. The universal method of claim 14, wherein the transition metal salt is one or more of ferric nitrate, ferrous sulfate, ferric chloride, cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride, nickel acetate, copper chloride, copper nitrate, and copper acetate; the sulfur or phosphorus containing reagent is trithiocyanuric acid or phytic acid.
16. The universal preparation method of an air electrode for combining an active site with an electrode structure according to claim 1, wherein the different treatment methods are in-situ heteroatom doping methods, and the method comprises the following specific steps: stirring 0.1-1.0g of polymer microspheres, 0.2-2.0g of dopamine hydrochloride and 5-30ml of methanol or ethanol for 3-5h, uniformly mixing, adding 100 ml-150 ml of 0.01-0.2M Tris buffer solution, continuously stirring for 12-24h, adding different heteroatom-containing reagents and 50ml of 0.01-0.2M Tris buffer solution, continuously stirring for 12-24h, carrying out suction filtration washing, and drying at 60-80 ℃.
17. The universal method of claim 16, wherein the heteroatom reagent is mercaptoethylamine, trithiocyanuric acid, or phytic acid.
18. The universal preparation method of the air electrode for combining the active site with the electrode structure, according to claim 1, wherein the MOF method of the metal framework loaded organic compound in the different treatment methods comprises the following specific steps: 0.05-0.2g of polymer microsphere treated by sulfuric acid and 50ml of organic solvent containing metal salt are stirred uniformly, 50ml of organic solvent containing organic ligand is added and stirred uniformly, and then the mixture is kept stand for 12-24h, filtered, washed by the organic solvent, and dried at 60-80 ℃.
19. The universal method of claim 18, wherein the metal salt is one or more of zinc nitrate, zinc chloride sulfate, ferric nitrate, ferrous sulfate, ferric chloride, cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride, nickel carbonate, nickel acetate, copper chloride, copper nitrate, and copper acetate; the organic ligand is common ligand such as 2-methylimidazole, terephthalic acid, aspartic acid, bipyridyl and the like.
20. The universal preparation method of the air electrode for combining the active site with the electrode structure as claimed in claim 1, wherein the hydrothermal transition metal oxide hydroxide method among the different treatment methods comprises the following specific steps: 0.05-0.2g of polymer microspheres treated by sulfuric acid, 4-10mM of transition metal salt, 20-60mM of urea, 10mM of ammonium fluoride and 45ml of water are uniformly mixed, transferred into a 50ml of hydrothermal kettle and reacted at 120 ℃ for 6-18h, and then subjected to suction filtration, water washing and ethanol washing, and dried at 60-80 ℃.
21. The use of the universal method of making an air electrode that incorporates active sites with an electrode structure according to claims 1-20, comprising the steps of: dispersing 1mg of the air electrode catalyst prepared by the method in isopropanol, water and a Nafion mixed solution with the mass percent concentration of 5 wt%; dropwise adding the uniformly dispersed catalyst suspension on a rotating disk electrode, and naturally airing to obtain a disk electrode for testing air electrodes of fuel cells and metal-air cells; and carrying out an oxygen reduction reaction test, an oxygen production reaction test and a hydrogen production test on the prepared rotating disc electrode loaded with the catalyst in an electrolyte.
22. The use of the universal method of making an air electrode that incorporates active sites with an electrode structure according to claims 1-20, comprising the steps of: dispersing 1mg of the air electrode catalyst prepared by the method in isopropanol, water and a Nafion mixed solution with the mass percent concentration of 5 wt%; and dropwise adding the uniformly dispersed catalyst suspension on a laboratory-made gas diffusion electrode with the area of the catalyst suspension, naturally airing to obtain the gas diffusion electrode for testing the fuel cell and the metal air cell, and assembling the gas diffusion electrode into a cell for testing the cell performance.
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