CN108365230A - A kind of universality preparation method and application for the air electrode that active site is combined with electrode structure - Google Patents
A kind of universality preparation method and application for the air electrode that active site is combined with electrode structure Download PDFInfo
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
The present invention relates to a kind of universality preparation methods for the air electrode being combined active site with electrode structure, it is characterized in that, all kinds of polymer microballoons of the hierarchical porous structure of the opening with inside connection can be combined the carbon-based isoreactivity site of noble metal base, transition metal base and Heteroatom doping by different disposal method.The distinct methods are carbon tetrachloride cross-linking method, concentrated acid sulfonation method, carbon dioxide gas activation method, dopamine cladding process, ammonia activation method, polyaniline-coated method, carried noble metal method in situ, growth in situ transiting metal compound method are in situ to adulterate one or more of hetero atom method.This universality method that the present invention introduces can by and meanwhile have super big hole, macropore, mesoporous, micropore inside connection opening multi-stage porous electrode structure by proper method flexibly combine a variety of different high activities catalytic site, to improve air-electrode catalyst performance and fuel cell and metal-air battery comprehensive performance.
Description
Technical field
The invention belongs to the preparation of air electrode catalyst and its applications, more particularly to a kind of to include super big hole, macropore, Jie
Hole, micropore inside connection opening the air electrode catalyst that is combined with high-efficiency catalytic activity site of multi-stage porous electrode structure
Preparation method and application.
Background technology
With the getting worse of global fossil fuel petered out with environmental problem, renewable cleaning is rationally made full use of
The energy becomes the target that people pursue.However the intermittent problems present in these renewable and clean energy resources limit it in the whole world
Extensive use in range, therefore it is the key that solve the problems, such as this to develop the new and effective energy storage equipment of design.Although
Widely used at present is lithium ion battery, but since it is limited by intercalation energy storage mechanism, energy density is relatively low, cannot meet not
Carry out the demand of new technology progress, and itself cost is higher, and there are larger security risks, just there is an urgent need to us for this
More advanced energy storage equipment is developed to meet the needs of future technology progress.Due in air there are abundant oxygen, because
This can greatly improve energy density, such as dye cell based on the energy storage device for continually drawing oxygen reaction,
Metal-air battery etc. is obtaining the extensive concern of people and is being increasingly becoming research hotspot recently.In these battery storage technologies
Common problem is that the oxygen electrochemical reaction involved by cell cathode is slower, including redox reactions (ORR) and oxygen
Gas reaction of formation (OER).This is because the oxygen electrochemical reaction, which is one, includes reactant oxygen, reactant electrolyte, solid
The gas-liquid-solid phase reaction of body catalyst, there are two the key factors for improving the reaction, first, the efficient catalytic active site of exploitation
Point reacts the intrinsic rate of itself energy barrier increase catalysis reaction to reduce；Second is that the catalyst structure of reasonable design is more to increase
Three phase catalytic reaction interface.Slow cell cathode oxygen electrocatalytic reaction can lead to that the energy density of battery is relatively low, output work
Rate density degradation, this is by great fuel cell and metal-air battery in electric vehicle and power grid static state energy storage
Etc. the extensive use in novel field.
For the exploitation of catalyst, commercial oxygen reduction catalyst most effective at present is platinum carbon catalyst, and produces oxygen
Catalyst is iridium base and ruthenium-based catalyst.But the earth's crust amount of storage of these noble metal catalysts itself is relatively low, and cost is higher, and by
Itself intergranular accumulation easily causes the drastically decline of active site utilization rate caused by it is loaded on activated carbon, therefore is
Ensure that the advantage of its high activity must develop more reasonably porous carbon support and reduce the accumulation between active site and increase
The utilization rate and fuel cell and metal-air battery of noble metal catalyst are improved in accessible three phase catalytic reaction interface
The comprehensive performances such as energy density and power density.For the extensive of further genralrlization new fuel cell and metal-air battery
Using the non-precious metal catalyst for developing high efficiency low cost is trend of the times.At present researcher find base metal base oxide,
Nitride, phosphide, sulfide etc. all have the activity of certain catalysis ORR and OER, wherein studying more and better performances
It is the catalyst such as the oxide for forgiving one or more transition-metal Fes, Co, Ni, Cu etc., nitride, phosphide, sulfide, example
Such as copper oxide cobalt, iron cobalt nitrogen；Other than these transition metal based catalysts, tool is developed from 2009 Nian Dai dawn seminars
Since the nitrogen-doped carbon nanometer pipe catalyst for having excellent hydrogen reduction catalytic performance, the carbon-supported catalysts of Heteroatom doping, which also become, to be taken
For the advantageous candidate catalyst of noble metal-based catalysts.Include that the nonmetallic heteroatoms lists such as nitrogen, sulphur, phosphorus, boron are mixed or mixed more since then
Carbon-based hydrogen reduction or production VPO catalysts gradually developed by people.It is even more to be had developed in 2014 together to wear dawn seminar
When the N with ORR and OER catalytic performances, carbon-based dual purpose catalyst double-doped P, this be develop Cheap highly effective can charge and discharge gold
Belong to the air electrode catalyst needed for air cell and provides new approaches.
And for the structure of metal electrode structure, research shows that suitable pore structure can greatly improve oxygen electricity and urge
The catalytic rate for changing reaction, especially in redox reactions, this is because rational pore structure can not only provide it is more
Active site, and the transmission rate of liquid phase reactor object and gas can be increased, and then the more three-phase catalytics of exposure
Reaction site, the final comprehensive catalytic rate for improving oxygen electrocatalytic reaction, which becomes, improves fuel cell and metal-air battery
The advantageous guarantee of energy density and output power.Since air-electrode catalyst reaction is related to gas, liquid, solid phase reaction,
Needed for one efficient catalyst structure other than it can provide the microcellular structure of a large amount of active sites, it is often more important that Neng Goubao
Macropore that is mesoporous and the being conducive to liquid transmission even super big hole that card gas quickly transmits.In recent years, in catalyst structure
This several pore structure is gradually combined and is achieved the notable of oxygen electrocatalysis characteristic and battery performance by people on structure
It improves.The catalyst for the hierarchical porous structure that this macropore-micropore, foramen magnum-mesoporous, foramen magnum-mesoporous-micropore coexist can significantly improve
The carrying current of ORR reactions reduces in battery discharge procedure and increases the voltage polarization loss that drastically descent tape is come with electric current, in turn
It ensure that larger output power density, be conducive to the raising of the performances such as the electric vehicle acceleration in practical application.This performance
Raising can be attributed to the quick transmission and diffusion of liquid phase reactor object caused by macropore, what mesoporous and micropore was brought connects
The increase in tactile phase reaction site.Other than having suitable pore size, excellent electrode structure must also have height to open
The hierarchical porous structure of the hole configuration put, only internal connection and high opening could ensure the quick biography of reactants and products
It is defeated.In conclusion structure simultaneously have super big hole, macropore, mesoporous, micropore inside be connected to opening multi-stage porous electrode structure
And fuel cell and metal-air battery are pushed to one of the key of large-scale application, therefore in priority patent
Extend the similar all kinds of polymer microballoons of the pattern of expansion on the basis of the preparation method being previously mentioned in CN106040121A
As the carrier or template of offer excellent catalysts structure.
It is always that people explore new and effective air electrode that the catalytic site of high activity and excellent electrode structure, which are combined,
The effective Research Thinking followed.But most of catalyst structure structure cannot still be accomplished simply and effectively to control,
Typically assembling multiple forms method is used to prepare, but preparation method is mostly comparatively laborious in this, and the hole regularity and connection prepared
The general character is to be improved.Moreover, most of catalyst structures constructed generally only combine single active site, do not have
Universality cannot give full play to its structural advantage.What the present invention was introduced is a kind of method with universality, and this method both may be used
With construct while having super big hole, macropore, the connection of mesoporous, micropore inside opening multi-stage porous electrode structure, and can be with
The structural advantage of the electrode configuration is performed to ultimate attainment, you can a variety of different flexibly to combine the structure by proper method
The catalytic site of high activity, to improve air-electrode catalyst performance and fuel cell and metal-air battery comprehensive performance, packet
Include energy density, power density is with performances such as, high rate capability and stability.It is this by the catalytic site of high activity and excellent
The correlative study of universality method that combines of electrode structure have not been reported.
Invention content
Technical problem to be solved by the invention is to provide a kind of air electrodes being combined active site with electrode structure
Universality preparation method and application.
In order to solve the above technical problem, the present invention provides a kind of air electricity being combined active site with electrode structure
The universality preparation method of pole, which is characterized in that the multistage skeleton polymer microballoon of height connection is passed through into different disposal method
The carbon-based isoreactivity site of noble metal base, transition metal base and Heteroatom doping can be combined.
Preferably, the multistage skeleton polymer microballoon of height connection is to include super big hole, macropore, mesoporous, micropore
Inside connection opening multi-stage porous all kinds of polymer microballoons.
Preferably, the distinct methods be carbon tetrachloride cross-linking method, concentrated acid sulfonation method, carbon dioxide gas activation method,
Dopamine cladding process, ammonia activation method, polyaniline-coated method, carried noble metal method in situ, growth in situ transiting metal compound method,
One or more of doping hetero atom method in situ.
Preferably, active site noble metal be platinum, iridium, ruthenium, palladium metal with metal oxide and they with iron, cobalt,
Nickel, copper one or more of which composition alloy；Transition metal base active site include the one of which such as Fe, Co, Ni, Cu or
Oxide, nitride, phosphide, the sulfide of a variety of compositions；The carbon-based active site of Heteroatom doping include nitrogen, oxygen, phosphorus,
The carbon-based material of the one or more of which such as sulphur, boron doping.
The present invention provides the multistage skeleton polymer microballoons of above-mentioned various processing height connection to combine various differences
The preparation method of active site.
The first：Carbon tetrachloride cross-linking method, which is characterized in that the specific steps are：By 0.5-2.0g polymer microballoons and
30ml carbon tetrachloride is placed in 50ml vials 60-90 DEG C and uniformly shakes 5-15h, be added 1.0-2.5g aluminum trichloride (anhydrous)s and after
Continuation of insurance holds 60-90 DEG C and uniformly shakes 5-15h, and the mixing suspension is poured into acetone and 6-15% hydrochloric acid volume ratio 1 while hot:1 is molten
It in liquid, is filtered after remaining aluminium reaction is complete, is used in combination water and ethyl alcohol to replace diafiltration three times, at 60-80 DEG C of drying
Reason, you can the polymer microballoon after yellow crosslinking must be integrated, the degree of cross linking and stability of the microballoon increase.
Second：Concentrated acid sulfonation method, which is characterized in that the specific steps are：The 50ml concentrated sulfuric acids are poured into equipped with 1.0-
In the 100ml round-bottomed flasks of polymer microballoon after 3.0g polymer microballoons or crosslinking, 5-10h is handled at 120-140 DEG C, is taken advantage of
Heat is poured under glass bar stirring in 600-1000ml deionized waters, and cooling suction filtration is simultaneously only neutral with massive laundering, and 60-80 DEG C dry
It is dry.
The third：Carbon dioxide gas activation method, which is characterized in that the specific steps are：Sulfuric acid and crosslinking Treatment are crossed
Polymer microballoon with 2-5 DEG C/min under inert atmosphere nitrogen or argon gas atmosphere 500-700 DEG C carbonization 2-4h, after cooling again with
2-5 DEG C/min is warming up to 800-900 DEG C under inert atmosphere nitrogen or argon gas atmosphere, and calcined gas is changed to inert nitrogen gas
Or argon gas and carbon dioxide volume flow ratio 1:1 calcining 2-6h.
4th kind：Dopamine cladding process, which is characterized in that the specific steps are：By 0.1-1.0g polymer microballoons, 0.2-
2.0g Dopamine hydrochlorides and 5-30ml methanol or ethyl alcohol stir 3-5h mixings, and 0.01-0.2M Tris buffer solutions 100- is added
150ml continues to stir 12-36h, filtering and washing, 60-80 DEG C of drying.
5th kind：Polyaniline-coated method, which is characterized in that the specific steps are：The polymer microballoon that sulfuric acid treatment is crossed
0.05-0.2g is added in the perchloric acid solution of the 0.75-1.25M of 15ml, is uniformly mixed, and a concentration of 0.02- is added
The aniline solution of 0.05M the ammonium persulfate solution of the 0.015-0.045M of precooling is added in reaction system, whole ice bath control
Temperature, reaction 12-36h terminate the multistage skeleton microballoon as product polyaniline-coated, filtering and washing, 60-80 DEG C of drying.
6th kind：Ammonia activation method, which is characterized in that the specific steps are：To contain carbon matrix precursor or doping presoma etc. with
2-5 DEG C/min 400-500 DEG C of carbonization 2-4h under inert atmosphere nitrogen or argon gas atmosphere, is further continued for 2-5 DEG C/min in inertia
It is warming up to 700-1100 DEG C under atmosphere nitrogen or argon gas atmosphere, calcined gas, which is changed to 50% ammonia nitrogen mixed gas, calcines 2-
6h。
7th kind：Carried noble metal method in situ, which is characterized in that the specific steps are：By the carbon dioxide activation of 20-80mg
Sulfuric acid and the carriers of polymer microballons crossed of crosslinking Treatment be distributed in water/ethanol solution, be added according to different loads amount different
Noble metal or noble metal and transition metal mixing presoma stirring dipping 8h, adjust pH to 7-9, are then quickly added into corresponding mole
Reducing agent (the M metal precursors of equivalent：Reducing agent=1 M:3-15), continue to stir 1-2h, filter, is dry.
Preferably, the precious metal salt is chloroplatinic acid, and gold chloride, palladium bichloride, iridium chloride, ruthenic chloride, transition metal salt is
Ferric nitrate, ferrous sulfate, iron chloride, cobalt chloride, cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride, nickel acetate, copper chloride, nitric acid
Copper, copper acetate it is one or more；The reducing agent is sodium borohydride, formic acid, ethylene glycol.
8th kind：Growth in situ transiting metal compound method, which is characterized in that the specific steps are：By 0.1-1.0g polymer
Microballoon, 0.2-2.0g Dopamine hydrochlorides, transition metal salt, sulfur-bearing or phosphorus reagent and 5-30ml methanol or ethyl alcohol stirring 3-5h are mixed
It is even, 0.01-0.2M Tris buffer solutions 100-150ml is added and continues to stir 12-36h, filtering and washing, 60-80 DEG C of drying.
Preferably, the transition metal salt is ferric nitrate, ferrous sulfate, iron chloride, cobalt chloride, cobalt nitrate, cobalt acetate, nitre
Sour nickel, nickel chloride, nickel acetate, copper chloride, copper nitrate, copper acetate it is one or more；The sulfur-bearing or phosphorus reagent is trimerization
Thiocyanic acid, phytic acid.
9th kind：Doping hetero atom method in situ, which is characterized in that the specific steps are：By 0.1-1.0g polymer microballoons,
0.2-2.0g Dopamine hydrochlorides and 5-30ml methanol or ethyl alcohol stir 3-5h mixings, and 0.01-0.2M Tris buffer solutions are added
100-150ml continues to stir 12-24h, and the 0.01-0.2M Tris buffer solutions that different reagents containing hetero atom and 50ml are added continue
Stir 12-24h, filtering and washing, 60-80 DEG C of drying.
Preferably, the hetero atom reagent is mercaptoethylmaine, trithiocyanuric acid, phytic acid.
Tenth kind：Carried metal skeleton organic matter MOF methods, which is characterized in that the specific steps are：Sulfuric acid treatment is crossed poly-
Close object microballoon 0.05-0.2g, the organic solvent 50ml of metalline is stirred evenly, then by the organic solvent 50ml containing organic ligand
Addition stirs evenly and stands 12-24h, filters and with organic solvent washing, 60-80 DEG C of drying.
Preferably, the metal salt be zinc nitrate, zinc chloride zinc sulfate, ferric nitrate, ferrous sulfate, iron chloride, cobalt chloride,
Cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride, nickelous carbonate, nickel acetate, copper chloride, copper nitrate, copper acetate it is one or more；Have
Machine ligand is 2-methylimidazole, terephthalic acid (TPA), asparatate, the common ligand such as bipyridyl.
Tenth is a kind of：Hydrothermal growth transition metal oxide hydroxide process, which is characterized in that the specific steps are：By sulphur
Processed polymer microballoon 0.05-0.2g, 4-10mM transition metal salt of acid, 20-60mM urea and 10mM ammonium fluorides and
The water of 45ml is uniformly mixed, and is transferred to 120 DEG C of reaction 6-18h in 50ml water heating kettles, is filtered washing ethyl alcohol and is washed, 60-80 DEG C of drying.
The present invention also provides a kind of a variety of air electrode catalysts preparing the above method to be applied to fuel cell and metal-air
The preparation of the rotating disk electrode (r.d.e) of battery performance test and test method, which is characterized in that the specific steps are：Above-mentioned side will be used
It is 5wt% that 1mg air electrode catalysts prepared by method, which are dispersed in 45ul isopropanols, 45ul water and 10ul mass percent concentrations,
Nafion mixed solutions in；Above-mentioned finely dispersed catalyst suspension 8ul is added dropwise in the rotation that area is 0.196cm2
On disk electrode, naturally dry obtains fuel cell and metal-air battery air electrode test disk electrode；By above-mentioned system
The standby rotating disk electrode (r.d.e) for being loaded with catalyst carries out oxygen reduction reaction (ORR) test, production oxygen reaction in the KOH solution of 0.1M
Test (OER) and production hydrogen test (HER).
The present invention also provides a variety of air electrodes prepared by the application above method to prepare fuel cell and metal-air electricity
The preparation of pond membrane electrode assembly and test method, which is characterized in that the specific steps are：The 1mg that will be prepared in aforementioned manners
It is mixed that air electrode catalyst is dispersed in the Nafion that 45ul isopropanols, 45ul water and 10ul mass percent concentrations are 5wt%
It closes in solution；Above-mentioned finely dispersed catalyst suspension 40ul is added dropwise and is expanded in the homemade gas in laboratory that area is 1cm2
It dissipates on electrode, naturally dry obtains the gas-diffusion electrode of fuel cell and metal-air battery test, and is assembled into battery
Carry out battery performance test.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) the multistage skeleton polymer microballoon of the height connection prepared by the present invention can both pass through carbonization-activation processing shape
Carry out carried noble metal base catalyst at multi-stage porous skeleton carbon carrier, and carrier can be used as to carry out polymer overmold and then the life that is carbonized
At the carbon-supported catalysts of Heteroatom doping, it can also be combined with transition metal salt and generate transition metal base catalyst, the Type of Collective
Object microballoon can play oneself to greatest extent and meanwhile have super big hole, macropore, mesoporous, micropore inside connection opening multistage
The advantage of pore electrod structure, the conductive bone that greatly improves the mass transfer rate of oxygen and electrolyte and can be interconnected by inside
Frame carries out quick electron-transport, and can carry out suitable treatments by distinct methods and combine different active sites, is
The air electrode that people develop the catalytic site of high activity and excellent electrode structure combines provides a kind of simply and effectively general
Adaptive method.
(2) the multi-stage porous skeleton carbon micro-ball load for the internal height connection that the present invention is prepared by in-situ reducing method is micro
The reaction rate that precious metals platinum catalyst greatly improves oxygen reduction reaction is in particular on increased carrying current, by this
Catalyst, which is applied to, also shows the high energy density of the business platinum carbon compared with 20%, power density and stabilization on zinc and air cell
Property, the platinum load capacity of the catalyst only has 5% in addition, and the noble metal platinum utilization of the catalyst may be up to 99%, remote high
In the 50% of business platinum carbon.
(3) present invention passes through the multi-stage porous carbon microballoon air in situ that coated by polyaniline array for adulterating hetero atom method and preparing
Cathode has good hydrogen reduction performance, and carrying current is due to macropore, mesoporous caused gas liquid reaction object and production in multi-stage porous
The raising of the mass transfer rate of object and greatly increase, this also will be the catalyst in subsequent fuel cell and metal-air battery
Application advantageous performance be provided support.
(4) present invention is urged by the nitrogen sulphur double-doped carbon-based multi-stage porous carbon microballoon air cathode in situ for adulterating the preparation of hetero atom method
Agent has efficient hydrogen reduction and production oxygen catalytic performance, the hydrogen reduction for having the business platinum carbon catalyst compared with 20% good simultaneously
Energy and the production oxygen performance better than iridium dioxide, and it is applied to and shows the high work(of the platinum carbon of the business compared with 20% on zinc and air cell
Rate density and stability, it is often more important that the double-doped catalyst of the nitrogen sulphur has higher charge-discharge magnification, can be larger
100mA charging and discharging currents under stablize cycle 48h.
(5) the double-doped multistage of the nitrogen phosphorus for the phosphatization ferro-cobalt load that the present invention is prepared by growth in situ transiting metal compound method
Hole carbosphere three-way catalyst has the good hydrogen reduction performance of business platinum carbon catalyst compared with 20%, the production oxygen better than iridium dioxide
Performance and substantially can be with the H2-producing capacity compared with 20% business platinum carbon, this is not only that fuel cell and metal-air battery provide
Excellent catalyst also hydrolyzes production hydrogen for electro-catalysis and production oxygen reaction provides excellent catalyst, renewable to provide and storing
Clean energy resource opens new road.
(6) the nitrogen sulphur for the cobalt protoxide load that the present invention is prepared by growth in situ transiting metal compound method through the invention
Double-doped multi-stage porous carbon microballoon dual purpose catalyst, the catalyst is not only with hydrogen reduction performance but also with efficient production oxygen
Can, this can be attributed to the fact that the work(for the multistage hole on framework microballoon that excellent production oxygen active site cobalt protoxide is connected to internal height
It can property combination.
Description of the drawings
Fig. 1 is the multi-stage porous skeleton carbon micro-ball load minute amount of noble metal platinum catalyst of internal height connection, different times magnifications
Scanning electron microscope (SEM) photograph under several and transmission electron microscope picture.
Fig. 2 is the multi-stage porous carbon microballoon air cathode catalyst of polyaniline array cladding, the scanning under different amplification
Electron microscope.
Fig. 3 is the double-doped carbon-based multi-stage porous carbon microballoon air cathode catalyst of nitrogen sulphur, the scanning electron microscope under different amplification
Figure.
Fig. 4 is the double-doped multi-stage porous carbon microballoon three-way catalyst of nitrogen phosphorus of phosphatization ferro-cobalt load, under different amplification
Scanning electron microscope (SEM) photograph.
Fig. 5 is the double-doped multi-stage porous carbon microballoon three-way catalyst of the nitrogen phosphorus of phosphatization ferro-cobalt load, X-ray diffractogram.
Fig. 6 is the double-doped multi-stage porous carbon microballoon dual purpose catalyst of nitrogen sulphur of cobalt protoxide load, under different amplification
Scanning electron microscope (SEM) photograph.
Fig. 7 is the double-doped multi-stage porous carbon microballoon dual purpose catalyst of the nitrogen sulphur of cobalt protoxide load, X-ray diffractogram.
Fig. 8 is that the multi-stage porous skeleton carbon micro-ball load minute amount of noble metal platinum catalyst of internal height connection exists with business platinum carbon
Polarization curves of oxygen reduction comparison diagram in alkaline medium, wherein electrode load platinum equivalent are 18ug/cm2。
Fig. 9 is the multi-stage porous carbon microballoon air cathode catalyst that polyaniline array coats and business platinum carbon in alkaline medium
Polarization curves of oxygen reduction comparison diagram, wherein electrode load amount is 0.408mg/cm2。
Figure 10 is that the double-doped carbon-based multi-stage porous carbon microballoon air cathode catalyst of nitrogen sulphur is mixed with business platinum carbon and iridium dioxide
Hydrogen reduction of the catalyst in alkaline medium and production oxygen polarization curve comparison diagram, wherein electrode load amount is 0.408mg/cm2。
Figure 11 is the double-doped multi-stage porous carbon microballoon three-way catalyst of the nitrogen phosphorus of phosphatization ferro-cobalt load and business platinum carbon and dioxy
Changing hydrogen reduction and production oxygen polarization curve comparison diagram, wherein electrode load amount of the iridium mixed catalyst in alkaline medium is
0.408mg/cm2。
Figure 12 is the double-doped multi-stage porous carbon microballoon dual purpose catalyst of the nitrogen sulphur of cobalt protoxide load and business platinum carbon and dioxy
Changing hydrogen reduction and production oxygen polarization curve comparison diagram, wherein electrode load amount of the iridium mixed catalyst in alkaline medium is
0.408mg/cm2.Figure 13 be cobalt protoxide load the double-doped multi-stage porous carbon microballoon dual purpose catalyst of nitrogen sulphur and business platinum carbon and
Production hydrogen polarization curve comparison figure of the iridium dioxide mixed catalyst in alkaline medium, wherein electrode load amount is 0.408mg/
cm2。
Figure 14 is the multi-stage porous skeleton carbon micro-ball load minute amount of noble metal platinum catalyst and business platinum carbon of internal height connection
Energy density figure in alkalinous metal zinc-air battery, wherein gas diffusion layers Supported Pt Nanoparticles equivalent are 50ug/cm2。
Figure 15 is the multi-stage porous skeleton carbon micro-ball load minute amount of noble metal platinum catalyst and business platinum carbon of internal height connection
Power density diagram in alkalinous metal zinc-air battery, wherein gas diffusion layers Supported Pt Nanoparticles equivalent are 50ug/cm2。
Figure 16 is that the double-doped carbon-based multi-stage porous carbon microballoon air cathode catalyst of nitrogen sulphur and business platinum carbon are empty in alkalinous metal zinc
Power density diagram in pneumoelectric pond, wherein gas diffusion layers load capacity are 0.4mg/cm2。
Figure 17 is that the double-doped carbon-based multi-stage porous carbon microballoon air cathode catalyst of nitrogen sulphur and business platinum carbon are empty in alkalinous metal zinc
Charge and discharge cycles figure under high magnification in pneumoelectric pond, wherein gas diffusion layers load capacity are 0.4mg/cm2。
Specific implementation mode
In order to make the present invention more obvious and understandable, example is hereby applied with preferred embodiment, be described in detail below.
Embodiment 1
A kind of multi-stage porous skeleton carbon micro-ball load minute amount of noble metal platinum catalyst of height connection, presoma including the use of
Comprising in macropore, mesoporous, micropore while prepared by carbon tetrachloride cross-linking method, concentrated acid sulfonation method and carbon dioxide activation method
The multi-stage porous skeleton carbosphere of portion's height connection；And the in-situ reducing supported platinum nano prepared using carried noble metal method in situ
Chloroplatinic acid needed on the multi-stage porous skeleton carbosphere that particle is connected to above-mentioned internal height and reducing agent sodium borohydride.
The preparation method of the multi-stage porous skeleton carbon micro-ball load minute amount of noble metal platinum catalyst of above-mentioned height connection is：First
With carbon tetrachloride cross-linking method to polymer microballoon carry out crosslinking Treatment the specific steps are：By 0.1g polymer microballoons and 30ml tetrachloros
Change carbon and be placed in 70 DEG C of uniform shaking 5h in 50ml vials, 1.5g aluminum trichloride (anhydrous)s are added and simultaneously continue to keep 70 DEG C of uniformly shakings
The mixing suspension is poured into acetone and 6% hydrochloric acid volume ratio 1 by 5h while hot:In 1 solution, wait for that remaining aluminium reaction is complete
After filtered, be used in combination water and ethyl alcohol to replace diafiltration three times, 60 DEG C of drying process, you can must integrate the polymer after yellow is crosslinked
Microballoon；Second step carries out sulfonation processing with concentrated acid sulfonation method to the above-mentioned polymer microballoon being crosslinked, the specific steps are：It will
The 50ml concentrated sulfuric acids pour into the 100ml round-bottomed flasks of the polymer microballoon after being crosslinked equipped with 2.0g, handle 5h at 135 DEG C, take advantage of
Heat is poured under glass bar stirring in 800ml deionized waters, simultaneously, the 60 DEG C dryings only neutral with massive laundering of cooling suction filtration；Third
Sulfonation treated polymer microballoon is to increase specific surface area increasing in the above-mentioned second step of step carbon dioxide gas activation method processing
Add noble-metal-supported site, the specific steps are：The polymer microballoon that sulfuric acid and crosslinking Treatment are crossed is with 5 DEG C/min in nitrogen atmosphere
It is lower 600 DEG C carbonization 2h, be warming up to 850 DEG C in a nitrogen atmosphere again with 5 DEG C/min after cooling, by calcined gas be changed to nitrogen with
Carbon dioxide volume flow ratio 1:1 calcining 4h, you can prepare while being connected to comprising macropore, mesoporous, micropore internal height
Multi-stage porous skeleton carbosphere.Uniform load size on the multi-stage porous skeleton carbosphere is 2- using noble metal method in situ by the 4th step
The noble metal platinum grain of 5nm, the specific steps are the polymer for crossing the sulfuric acid of the carbon dioxide activation of 20mg and crosslinking Treatment is micro-
Balloon borne body is distributed in water/ethanol solution, and the 10mg/ml chloroplatinic acid presomas stirring dipping 8h of 0.28ml is added, adjusts pH and arrives
7-9 is then quickly added into sodium borohydride 3mg (the M chloroplatinic acids of corresponding molar equivalent：Sodium borohydride=1 M:12), continue to stir
2h, the metal platinum nano-particle that the size that suction filtration, drying can obtain Load Balanced is 2-5nm, specific pattern such as Fig. 1 scanning electron microscope
Shown in transmission electron microscope.
Embodiment 2
A kind of multi-stage porous carbon microballoon air cathode catalyst of polyaniline array cladding, presoma and used method
Polyaniline array for multistage pore polymer microsphere and the preparation of polyaniline-coated method by concentrated acid sulfonation processing coats sulfonation
Polymer microballoon afterwards, and the nitrogenous polyaniline array multi-stage porous microballoon by the processing of ammonia activation method.
The specific method of the multi-stage porous carbon microballoon air cathode catalyst of above-mentioned polyaniline array cladding is：The first step is with dense
Sulfuric acid sulfonation method carries out sulfonation processing to polymer microballoon, the specific steps are：The 50ml concentrated sulfuric acids are poured into equipped with 2.0g polymer
In the 100ml round-bottomed flasks of microballoon, 5h is handled at 135 DEG C, is poured into 800ml deionized waters under glass bar stirring while hot,
Simultaneously, the 60 DEG C dryings only neutral with massive laundering of cooling suction filtration；Second step is with polyaniline-coated method to the polymer after above-mentioned sulfonation
Microballoon carries out polyaniline array cladding, the specific steps are：By the polymer microballoon 0.1g after sulfonation, it is added the 1mol/L's of 15ml
It in perchloric acid solution, is uniformly mixed, the aniline solution of a concentration of 0.02-0.05M is added, by the 0.03mol/L's of precooling
Ammonium persulfate solution is added in reaction system, whole ice bath temperature control, and reaction terminates the multistage bone as product polyaniline-coated for 24 hours
Frame microballoon, filtering and washing, 60 DEG C of dryings；Third step utilizes the nitrogenous polyaniline array multi-stage porous microballoon forerunner of ammonia activation method carbonization
Body, the specific steps are：Carbon matrix precursor or doping presoma etc. will be contained with 5 DEG C/min, 450 DEG C of carbonization 2h in a nitrogen atmosphere, followed by
Continuous to be warming up to 900-1000 DEG C in a nitrogen atmosphere with 2 DEG C/min, calcined gas, which is changed to 50% ammonia nitrogen mixed gas, to be forged
2h is burnt, polyaniline array pattern is as shown in Fig. 2 stereoscan photographs.
Embodiment 3
A kind of double-doped carbon-based multi-stage porous carbon microballoon air cathode catalyst of nitrogen sulphur, presoma are Dopamine hydrochloride and sulfydryl
Ethamine, used method are doping hetero atom method and ammonia activation method in situ.
The preparation method of the above-mentioned double-doped carbon-based multi-stage porous carbon microballoon air cathode catalyst of nitrogen sulphur is：The first step gathers 0.4g
It closes object microballoon, 0.8g Dopamine hydrochlorides and 30ml methanol and stirs 5h mixings, 0.02M Tris buffer solutions 150ml is added and continues to stir
12h is mixed, the 0.02M Tris buffer solutions that 0.32g mercaptoethylmaines, 0.8g Dopamine hydrochlorides and 50ml is added continue stirring for 24 hours, take out
Filter washing, 60 DEG C of dryings；The polymer microballoon that above-mentioned dopamine and mercaptoethylmaine coat is carried out ammonia activation processing by second step,
The specific steps are：Carbon matrix precursor or doping presoma etc. will be contained with 5 DEG C/min, 450 DEG C of carbonization 2h in a nitrogen atmosphere, be further continued for
It is warming up to 1000 DEG C in a nitrogen atmosphere with 2 DEG C/min, calcined gas, which is changed to 50% ammonia nitrogen mixed gas, calcines 2h,
Pattern is as shown in Fig. 3 stereoscan photographs.
Embodiment 4
A kind of multi-stage porous carbon microballoon three-way catalyst that the nitrogen phosphorus of phosphatization ferro-cobalt load is double-doped, presoma is hydrochloric acid DOPA
Amine, ferric nitrate, cobalt acetate and phytic acid, used method are growth in situ transiting metal compound method and ammonia activation method.
The preparation method of the double-doped multi-stage porous carbon microballoon three-way catalyst of nitrogen phosphorus of above-mentioned phosphatization ferro-cobalt load is：The first step
Using growth in situ transiting metal compound method on multistage pore polymer microsphere carrying transition metal presoma, the specific steps are：
By 0.3g polymer microballoons, 1.2g Dopamine hydrochlorides, 0.2g ferric nitrates, 0.2g cobalt acetates, 1ml phytic acid (50% aqueous solution) and
30ml methanol stirs 5h mixings, and 0.2M Tris buffer solutions 100ml is added and continues stirring for 24 hours, filtering and washing, 60 DEG C of dryings；Second
Step handles carrying transition metal presoma on above-mentioned multistage pore polymer microsphere by ammonia activation, the specific steps are：It will contain
Carbon matrix precursor or doping presoma etc. are further continued for 2 DEG C/min with 5 DEG C/min, 450 DEG C of carbonization 2h in a nitrogen atmosphere in nitrogen
800 DEG C are warming up under atmosphere, calcined gas, which is changed to 50% ammonia nitrogen mixed gas, calcines 4h, pattern such as Fig. 4 scanning electricity
Shown in mirror photo, phase structure is shown in Fig. 5 XRD diffracting spectrums.
Embodiment 5
A kind of multi-stage porous carbon microballoon dual purpose catalyst that the nitrogen sulphur of cobalt protoxide load is double-doped, presoma is hydrochloric acid DOPA
Amine, ferric nitrate, cobalt acetate and phytic acid, used method are growth in situ transiting metal compound method and high temperature cabonization method.
The preparation method of the double-doped multi-stage porous carbon microballoon dual purpose catalyst of nitrogen sulphur of above-mentioned cobalt protoxide load is：The first step
Using growth in situ transiting metal compound method on multistage pore polymer microsphere carrying transition metal presoma, the specific steps are：
0.3g polymer microballoons, 1.2g Dopamine hydrochlorides, 1.5g cobalt acetates, 1g trithiocyanuric acids and 30ml methanol stirring 5h are mixed
It is even, 0.2M Tris buffer solutions 100ml is added and continues stirring for 24 hours, filtering and washing, 60 DEG C of dryings；Second step, by above-mentioned multi-stage porous
Carrying transition metal presoma passes through nitrogen carbonization treatment on polymer microballoon, the specific steps are：Carbon matrix precursor or doping will be contained
Presoma etc. with 5 DEG C/min in a nitrogen atmosphere 450 DEG C carbonization 2h, be further continued for being warming up to 700 in a nitrogen atmosphere with 2 DEG C/min
DEG C of -1100 DEG C calcining 4h, pattern is as shown in Fig. 6 stereoscan photographs, and phase structure is shown in Fig. 7 XRD diffracting spectrums.
Embodiment 6
A kind of a variety of air electrode catalysts by above method preparation are applied to fuel cell and metal-air battery
The preparation method of the rotating disk electrode (r.d.e) of energy test, the specific steps are：The 1mg air-electrode catalysts that will be prepared in aforementioned manners
Agent is dispersed in the Nafion mixed solutions that 45ul isopropanols, 45ul water and 10ul mass percent concentrations are 5wt%；It will be upper
It is 0.196cm to state finely dispersed catalyst suspension 8ul and be added dropwise in area2Rotating disk electrode (r.d.e) on, naturally dry obtains
Fuel cell and metal-air battery air electrode test disk electrode；With the rotating circular disk for being loaded with catalyst of above-mentioned preparation
Electrode is working electrode, and platinized platinum is to electrode, and silver-colored silver chlorate is reference electrode, using the KOH of 0.1M as in the solution of electrolyte
It carries out oxygen reduction reaction (ORR) to test, production oxygen reaction test (OER) and production hydrogen (HER) are tested, as shown in figures 8-13.
Embodiment 7
A kind of a variety of air electrodes using above method preparation prepare fuel cell and metal-air battery membrane electrode
The method of aggregate, the specific steps are：By the 1mg air electrode catalysts prepared in aforementioned manners be dispersed in 45ul isopropanols,
In 45ul water and the Nafion mixed solutions that 10ul mass percent concentrations are 5wt%；By above-mentioned finely dispersed catalyst
It is 1cm that suspension 40ul, which is added dropwise in area,2The homemade gas-diffusion electrode in laboratory on, naturally dry obtains fuel cell
With the gas-diffusion electrode of metal-air battery test, and it is assembled into metal zinc battery, with 0.2M zinc chloride and 6M hydroxides
Potassium is electrolyte, and the metal zinc metal sheet of 1.5cm2 is cooked anode, and the gas-diffusion electrode of prepared supported catalyst makees cathode, and
Charge and discharge under battery performance test, including battery capacity test, power density test, high current density is carried out on electrochemical workstation
Electric loop test etc., as shown in figures 14-17.
In the Figure of description of the present invention, all potential values have been converted into the current potential relative to standard hydrogen electrode.Fig. 1-7
The portion of air cathod catalyst that has been optimum selecting, it can be found that they inherit previously specially from these catalyst structures
It is poly- comprising super big hole, macropore, the multistage hole on framework of mesoporous, micropore inside connection while being previously mentioned in sharp CN106040121A
The excellent pore structure for closing object microballoon, realizes the perfect adaptation of active site and excellent electrode structure, also turns out simultaneously
The universality of the inventive method, and increase a large amount of micropore into one again after carbon dioxide and ammonia activation processing
Step improves the load site of active site and combines the unique internal macropore core being connected to possessed by the structure mesoporous
Expose more three phase catalytic reaction sites, this is also beneficial to the oxygen electrocatalysis characteristic and battery performance of these catalyst
It improves；Fig. 8-13 further demonstrate this viewpoint, these active sites are combined made with the multi-stage porous skeleton structure
The hydrogen reduction performance of standby catalyst can be suitable with business platinum carbon, especially the multi-stage porous skeleton carbosphere of internal height connection
Loading minute amount of noble metal platinum catalyst not only has better than the take-off potential of business platinum carbon also with obviously excellent carrying current；
And the double-doped carbon-based multi-stage porous carbon microballoon air cathode catalyst of nitrogen sulphur has efficient hydrogen reduction and production oxygen catalytic performance simultaneously, tool
The hydrogen reduction performance and the production oxygen performance better than iridium dioxide for having the business platinum carbon catalyst compared with 20% good；More there is phosphatization ferro-cobalt
The double-doped multi-stage porous carbon microballoon three-way catalyst of the nitrogen phosphorus of load, the catalyst not only have the business platinum carbon catalyst compared with 20%
Good hydrogen reduction performance, the production oxygen performance better than iridium dioxide also has substantially can be the same as the production hydrogen compared with 20% business platinum carbon
Energy.Further preferentially these catalyst are applied in metal zinc-air battery test and find that its performance is also quite excellent,
As shown in figures 14-17, Figure 14-15 shows that multi-stage porous skeleton carbon micro-ball load minute amount of noble metal platinum catalyst is applied to zinc and air cell
In not only have energy density more better than business platinum carbon, also have better power density；Same Figure 16-17 shows that nitrogen sulphur is double
Carbon dope base multi-stage porous carbosphere air cathode catalyst, which is applied in metal zinc and air cell, also to be shown better than business platinum carbon
Power density, it is often more important that the catalyst can be in up to 100mA/cm2High current density under carry out prolonged charge and discharge
Cycle, this is to report first time of the non-metal base dual purpose catalyst in the field.
Claims (23)
1. a kind of universality preparation method for the air electrode being combined active site with electrode structure, which is characterized in that will even
Logical multistage skeleton polymer microballoon can be by noble metal base, transition metal base and Heteroatom doping by different disposal method
Carbon-based isoreactivity site combine.
2. a kind of universality preparation side for the air electrode being combined active site with electrode structure as described in claim 1
Method, which is characterized in that the multistage skeleton polymer microballoon of the described height connection is comprising super big hole, macropore, mesoporous, micropore
All kinds of polymer microballoons of the multi-stage porous of the opening of inside connection.
3. a kind of universality preparation side for the air electrode being combined active site with electrode structure as described in claim 1
Method, which is characterized in that the multistage skeleton polymer ball warp of the height connection is crossed different disposal method and is crosslinked for carbon tetrachloride
Method, concentrated acid sulfonation method, carbon dioxide gas activation method, dopamine cladding process, ammonia activation method, polyaniline-coated method are in situ
Carried noble metal method, growth in situ transiting metal compound method are in situ to adulterate one or more of hetero atom method.
4. a kind of universality preparation side for the air electrode being combined active site with electrode structure as described in claim 1
Method, which is characterized in that the noble-metal based active site be platinum, iridium, ruthenium, palladium metal with metal oxide and they
The alloy formed with the one or more of which of iron, cobalt, nickel, copper.
5. a kind of universality preparation side for the air electrode being combined active site with electrode structure as described in claim 1
Method, which is characterized in that the transition metal base active site is the oxidation of the one or more of which such as Fe, Co, Ni, Cu composition
Object, nitride, phosphide, sulfide.
6. a kind of universality preparation side for the air electrode being combined active site with electrode structure as described in claim 1
Method, which is characterized in that the carbon-based active site of the Heteroatom doping is the one or more of which such as nitrogen, oxygen, phosphorus, sulphur, boron
The carbon-based material of doping.
7. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the carbon tetrachloride cross-linking method in the different disposal method, which is characterized in that the specific steps are：It will
0.5-2.0g polymer microballoons and 30ml carbon tetrachloride are placed in 50ml vials and uniformly shake 5-15h for 60-90 DEG C, and 1.0- is added
2.5g aluminum trichloride (anhydrous)s simultaneously continue to be kept for 60-90 DEG C uniformly shake 5-15h, and the mixing suspension is poured into acetone and 6- while hot
15% hydrochloric acid volume ratio 1:It in 1 solution, is filtered after remaining aluminium reaction is complete, water and ethyl alcohol is used in combination to replace diafiltration
Three times, 60-80 DEG C of drying process, you can the polymer microballoon after yellow crosslinking, the degree of cross linking and stability of the microballoon must be integrated
It increases.
8. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the concentrated acid sulfonation method in the different disposal method, which is characterized in that the specific steps are：By 50ml
The concentrated sulfuric acid pours into the 100ml round-bottomed flasks equipped with the polymer microballoon after 1.0-3.0g polymer microballoons or crosslinking, in 120-
5-10h is handled at 140 DEG C, is poured into 600-1000ml deionized waters under glass bar stirring while hot, it is cooling to filter and with largely
Washing is only neutral, 60-80 DEG C of drying.
9. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the carbon dioxide gas activation method in the different disposal method, which is characterized in that the specific steps are：
The polymer microballoon that sulfuric acid and crosslinking Treatment are crossed is with 2-5 DEG C/min 500-700 DEG C under inert atmosphere nitrogen or argon gas atmosphere
Be carbonized 2-4h, is warming up to 800-900 DEG C under inert atmosphere nitrogen or argon gas atmosphere with 2-5 DEG C/min again after cooling, will forge
It burns gas and is changed to inert nitrogen gas or argon gas and carbon dioxide volume flow ratio 1:1 calcining 2-6h.
10. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the dopamine cladding process in the different disposal method, which is characterized in that the specific steps are：By 0.1-
1.0g polymer microballoons, 0.2-2.0g Dopamine hydrochlorides and 5-30ml methanol or ethyl alcohol stir 3-5h mixings, and 0.01- is added
0.2M Tris buffer solutions 100-150ml continues to stir 12-36h, filtering and washing, 60-80 DEG C of drying.
11. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the polyaniline-coated method in the different disposal method, which is characterized in that the specific steps are：By sulfuric acid
Processed polymer microballoon 0.05-0.2g, is added in the perchloric acid solution of the 0.75-1.25M of 15ml, is uniformly mixed,
The aniline solution of a concentration of 0.02-0.05M is added, reaction system is added in the ammonium persulfate solution of the 0.015-0.045M of precooling
In, whole ice bath temperature control, reaction 12-36h terminates the multistage skeleton microballoon as product polyaniline-coated, filtering and washing, 60-80
DEG C drying.
12. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the ammonia activation method in the different disposal method, which is characterized in that the specific steps are：Before carbon containing
The 400-500 DEG C of carbonization 2-4h under inert atmosphere nitrogen or argon gas atmosphere with 2-5 DEG C/min such as drive body or doping presoma, followed by
It is continuous to be warming up to 700-1100 DEG C under inert atmosphere nitrogen or argon gas atmosphere with 2-5 DEG C/min, calcined gas is changed to 50% ammonia
Gas nitrogen mixed gas calcines 2-6h.
13. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the carried noble metal method in situ in the different disposal method, which is characterized in that the specific steps are：It will
The carriers of polymer microballons that the sulfuric acid and crosslinking Treatment of the carbon dioxide activation of 20-80mg are crossed is distributed in water/ethanol solution, root
Different noble metals or noble metal and transition metal mixing presoma stirring dipping 8h is added according to different loads amount, adjusts pH to 7-9,
It is then quickly added into reducing agent (the M metal precursors of corresponding molar equivalent：Reducing agent=1 M:3-15), continue to stir 1-2h, take out
Filter, drying.
14. original position carried noble metal method as claimed in claim 13, which is characterized in that the precious metal salt is chloroplatinic acid,
Gold chloride, palladium bichloride, iridium chloride, ruthenic chloride, transition metal salt are ferric nitrate, ferrous sulfate, iron chloride, cobalt chloride, cobalt nitrate,
Cobalt acetate, nickel nitrate, nickel chloride, nickel acetate, copper chloride, copper nitrate, copper acetate it is one or more；The reducing agent is boron
Sodium hydride, formic acid, ethylene glycol.
15. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the growth in situ transiting metal compound method in the different disposal method, which is characterized in that specific step
Suddenly it is：By 0.1-1.0g polymer microballoons, 0.2-2.0g Dopamine hydrochlorides, transition metal salt, sulfur-bearing or phosphorus reagent and 5-
30ml methanol or ethyl alcohol stir 3-5h mixings, and 0.01-0.2M Tris buffer solutions 100-150ml is added and continues to stir 12-36h, takes out
Filter washing, 60-80 DEG C of drying.
16. growth in situ transiting metal compound method as claimed in claim 15, which is characterized in that the transition metal salt is
Ferric nitrate, ferrous sulfate, iron chloride, cobalt chloride, cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride, nickel acetate, copper chloride, nitric acid
Copper, copper acetate it is one or more；The sulfur-bearing or phosphorus reagent is trithiocyanuric acid, phytic acid.
17. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the doping hetero atom method in situ in the different disposal method, which is characterized in that the specific steps are：It will
0.1-1.0g polymer microballoons, 0.2-2.0g Dopamine hydrochlorides and 5-30ml methanol or ethyl alcohol stir 3-5h mixings, are added
0.01-0.2M Tris buffer solutions 100-150ml continues to stir 12-24h, and the 0.01- of different reagents containing hetero atom and 50ml is added
0.2M Tris buffer solutions continue to stir 12-24h, filtering and washing, 60-80 DEG C of drying.
18. doping hetero atom method in situ as claimed in claim 17, which is characterized in that the hetero atom reagent is sulfydryl second
Amine, trithiocyanuric acid, phytic acid.
19. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the carried metal skeleton organic matter MOF methods in the different disposal method, which is characterized in that specific step
Suddenly it is：The organic solvent 50ml of polymer microballoon 0.05-0.2g, metalline that sulfuric acid treatment is crossed are stirred evenly, then will be contained
The organic solvent 50ml addition of organic ligand stirs evenly and stands 12-24h, filters and use organic solvent washing, and 60-80 DEG C is done
It is dry.
20. carried metal skeleton organic matter MOF methods as claimed in claim 19, which is characterized in that the metal salt is nitre
Sour zinc, zinc chloride zinc sulfate, ferric nitrate, ferrous sulfate, iron chloride, cobalt chloride, cobalt nitrate, cobalt acetate, nickel nitrate, nickel chloride,
Nickelous carbonate, nickel acetate, copper chloride, copper nitrate, copper acetate it is one or more；Organic ligand is 2-methylimidazole, terephthaldehyde
Acid, asparatate, the common ligand such as bipyridyl.
21. a kind of universality preparation side for the air electrode being combined active site with electrode structure as claimed in claim 3
Method, which is characterized in that the hydrothermal growth transition metal oxide hydroxide process in the different disposal method, feature exist
In, the specific steps are：Polymer microballoon 0.05-0.2g, 4-10mM transition metal salt, the 20-60mM urea that sulfuric acid treatment is crossed
It is uniformly mixed with the water of 10mM ammonium fluorides and 45ml, is transferred to 120 DEG C of reaction 6-18h in 50ml water heating kettles, filters washing second
Alcohol is washed, 60-80 DEG C of drying.
22. a kind of answer a variety of air electrode catalysts prepared by any one of above-mentioned 1-22 the methods using claim
The preparation and test method, feature for using the rotating disk electrode (r.d.e) of fuel cell and metal-air battery performance test exist
In, the specific steps are：The 1mg air electrode catalysts prepared in aforementioned manners are dispersed in isopropanol, water and quality percentage
Specific concentration is in the Nafion mixed solutions of 5wt%；Above-mentioned finely dispersed catalyst suspension is added dropwise in rotating circular disk electricity
On extremely, naturally dry obtains fuel cell and metal-air battery air electrode test disk electrode；By the load of above-mentioned preparation
Have the rotating disk electrode (r.d.e) of catalyst carry out in the electrolytic solution oxygen reduction reaction (ORR) test, production oxygen reaction test (OER) and
Produce hydrogen test (HER).
23. a kind of preparing combustion using claim using a variety of air electrodes prepared by any one of above-mentioned 1-22 the methods
Expect preparation and the test method of battery and metal-air battery membrane electrode assembly, which is characterized in that the specific steps are：It will use
It is 5wt%'s that 1mg air electrode catalysts prepared by the above method, which are dispersed in isopropanol, water and mass percent concentration,
In Nafion mixed solutions；Above-mentioned finely dispersed catalyst suspension is added dropwise and is expanded in the homemade gas in the laboratory that area is
It dissipates on electrode, naturally dry obtains the gas-diffusion electrode of fuel cell and metal-air battery test, and is assembled into battery
Carry out battery performance test.
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