CN107507984A - A kind of preparation method of fuel battery anode catalyst - Google Patents
A kind of preparation method of fuel battery anode catalyst Download PDFInfo
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- CN107507984A CN107507984A CN201710740443.8A CN201710740443A CN107507984A CN 107507984 A CN107507984 A CN 107507984A CN 201710740443 A CN201710740443 A CN 201710740443A CN 107507984 A CN107507984 A CN 107507984A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of preparation method of fuel battery anode catalyst, belong to the preparing technical field of fuel battery nano composite catalyst, specifically include and prepare phosphorus, nitrogen, iron codope carbon material carrier and load the steps such as palladium-copper alloy active component on this support, there is good cooperative effect between carrier and alloy active component.Phosphorus, nitrogen, the iron codope carbon material of the present invention plays an important role as a kind of new fuel cell catalyst carrier to improving catalyst activity, on the one hand copper has played promoting catalysis as transition metal, improve the activity of noble metal catalyst, on the other hand the dosage of noble metal is reduced, the cost of fuel-cell catalyst is reduced, therefore is had broad application prospects.
Description
Technical field
The invention belongs to the preparing technical field of fuel-cell catalyst, and in particular to a kind of fuel battery anode catalyst
Preparation method.
Background technology
Fuel cell has the advantages that the high and low discharge of operational efficiency, is acknowledged as the energy conversion system of cleaning.But
The high cost of fuel cell constrains its commercialization process, is one of most important key issue of this area research.Urge
Agent is the important component of fuel cell, and its cost accounts for the 50% of whole fuel cell.Your gold the most frequently used catalyst is
Metal catalyst, but the reserves of noble metal are limited, expensive, while noble metal catalyst dynamics in anodic oxidation reactionses
Process is slow, less stable.Therefore it is fuel-cell catalyst urgent problem to improve performance and reduce cost.
According to the skin effect of catalyst, it is desirable to meet the requirement of low-cost high-efficiency, first have to make active component abundant
Micronized is realized, on this basis, catalyst particle, which is fixed on suitable carrier, can make catalyst utilization reach maximization.
Therefore, it is the key factor for influenceing catalyst activity to select appropriate carrier, and carrier also just turns into the key component in catalyst
One of.Domestic and international recent study finds that the carbon material of metal and N codopes has good chemical property, enrichment and development
Such material system, it is expected to obtain preferable electrochemistry carbon material carrier.
Using carbon material as carrier, generally require to introduce dressing agent in carrier surface, play to catalyst-loaded activearm
The anchorage effect divided, so as to improve dispersiveness of the catalyst activity component in carrier surface, but this physical modification acts on
It is easy to decay in cell operations so that carrier interface absorption stability declines, and causes battery life to decline.And
This method for introducing dressing agent, will also increase process complexity and material cost.
Nano material with shell structurre shows that huge application potential, such as Shell Materials have in every field
Higher specific surface area, its abundant hole can also promote mass transfer and electronics to shift, therefore, be advantageous to raising and urge
The activity of agent.
The content of the invention
Present invention solves the technical problem that a kind of preparation method of fuel battery anode catalyst is there is provided, so as to effectively
Improve direct methanoic acid fuel cell anode catalyst performance, this method using optimize fuel battery anode catalyst for guiding, from
The angle of carrier innovation is set out, and the special appearance nano material that will be provided with unique physical and chemical characteristic is expensive as carrier, load
Metal nano alloy so that cooperative effect, pattern effect and carrier effect, Jin Erzhan are given full play between catalyst components
Reveal good chemical property.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of preparation of fuel battery anode catalyst
Method, it is characterised in that concretely comprise the following steps：
（1）Melamine and pyrophosphoric acid are well mixed wiring solution-forming through ultrasonic disperse with deionized water, add iron chloride simultaneously
It is uniformly mixed to obtain suspension, obtained suspension is transferred in autoclave and sealed, reacts 6h in 150 DEG C, instead
Naturally cool to room temperature after should terminating, by obtained product be washed with deionized until filtrate become colorless, put to vacuum and do
Dried in dry case in 80 DEG C to constant weight, then in N2Under atmosphere in 800 DEG C calcine 4h obtain double-deck ghost spherical structure phosphorus, nitrogen,
Iron codope carbon material；
（2）By step（1）Obtained phosphorus, nitrogen, iron codope carbon material is scattered in ethylene glycol, and ultrasonic agitation 2h is disperseed
Liquid, PdCl will be sequentially added in obtained dispersion liquid2The aqueous solution and CuSO4·5H2O, stir to well mixed and obtain mixed liquor,
Obtained mixed liquor is transferred in autoclave and sealed, 6h is reacted in 160 DEG C, reaction naturally cools to room temperature after terminating,
Then product is centrifuged, and be washed with deionized, put into vacuum drying chamber drying to constant weight and obtain loading ghost spherical junctions
Structure palladium-copper alloy fuel battery anode catalyst.
Further preferably, step（1）Described in melamine, the mass ratio that feeds intake of pyrophosphoric acid and iron chloride for 1:1:10.
Further preferably, step（2）Described in phosphorus, nitrogen, iron co-doped material and CuSO4·5H2The O mass ratio that feeds intake is
2:1, PdCl2With CuSO4·5H2O molar ratio is 5:8.
The present invention has the advantages that compared with prior art：
1st, the present invention innovates based on the appearance structure of fuel-cell catalyst carrier, has synthesized first spherical with double-deck ghost
Phosphorus, nitrogen, the iron codope carbon material of structure, and as fuel-cell catalyst carrier, the phosphorus of double-deck ghost spherical structure,
Nitrogen, iron codope carbon material carrier provide three-phase for electrode reaction（Solid-liquid-gas）Area, passage is provided for electrolyte transmission, and then
The specific surface area of catalyst is improved, increases the catalytic activity of elctro-catalyst；
2nd, phosphorus, nitrogen, iron codope, which act on, causes carbon material to have more active sites, together with the copper in palladium-copper alloy
The good cooperative effect to noble metal is played, the electrocatalysis characteristic of noble metal is effectively increased, reduces noble metal catalyst
Cost, the utilization rate of noble metal is improved, there is good prospect in fuel battery anode catalysis material application；
3rd, phosphorus, nitrogen, iron codope, which act on, causes carbon material carrier surface property to vary widely, to the anchor of metal catalytic component
Gu effect enhancing, in the case of no added dressing agent, it is possible to achieve to the uniform load of metal catalytic component, substantially increase
The activity and stability of catalyst.
Brief description of the drawings
Fig. 1 is the TEM figures that palladium-copper alloy in fuel battery anode catalyst is made in embodiment 1；
Fig. 2 is the XRD that palladium-copper alloy is made in embodiment 1；
Fig. 3 is that the electrochemistry of catalyst in embodiment 1 and comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5 is followed
Ring volt-ampere test curve.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
0.01g melamines and 0.01g pyrophosphoric acids are well mixed wiring solution-forming through ultrasonic disperse with 40mL deionized waters, then added
Enter 0.1g iron chloride and be uniformly mixed to obtain suspension；Obtained suspension is transferred in autoclave and sealed, in
150 DEG C of reaction 6h, reaction naturally cool to room temperature after terminating；Obtained product is washed with deionized until filtrate is changed into nothing
Color, put into vacuum drying chamber and dried in 80 DEG C to constant weight, then in N2In 800 DEG C calcining 4h under atmosphere, to obtain phosphorus, nitrogen, iron common
Adulterate carbon material；Obtained phosphorus, nitrogen, iron codope carbon material 40mg are scattered in 20mL ethylene glycol, ultrasonic agitation 2h is obtained
Dispersion liquid；2.5mL 20mM PdCl will be sequentially added in obtained dispersion liquid2The aqueous solution and 20mg CuSO4·5H2O, stirring is extremely
It is well mixed to obtain mixed liquor, obtained mixed liquor is transferred in autoclave and sealed, 6h, reaction knot are reacted in 160 DEG C
Room temperature is naturally cooled to after beam, then centrifuges product, and is washed with deionized, puts into vacuum drying chamber and dries to constant weight
Obtain fuel battery anode catalyst.
Fuel battery anode catalyst hollow shell spherical structure PdCu alloy hollow nano particles are uniform as seen from Figure 1
Ground is dispersed in double-deck ghost spherical structure phosphorus, nitrogen, on iron codope carbon material carrier, and this is due to that Fe-P-N-C avtive spots change
The electronic structure of carrier surface is become, further have adjusted the surface nature of carrier, so as to optimize carrier to noble metal nano
The anchorage effect of particle, in the case of without modification, be still advantageous to the nucleation of noble metal nano particles and disperse, be advantageous to be catalyzed
The raising of agent performance.
Fig. 2 XRD spectrum illustrates the formation of PdCu alloys.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M formic acid+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 3.
Comparative example 1
0.01g melamines and 0.05g mass concentrations are mixed for 37% formalin with 40mL deionized waters through ultrasonic disperse
Uniform wiring solution-forming, add 0.1g iron chloride and be uniformly mixed to obtain suspension；Obtained suspension is shifted paramount
Sealed in pressure reactor, 6h is reacted in 180 DEG C, reaction naturally cools to room temperature after terminating；The product deionized water that will be obtained
Washing becomes colorless up to filtrate, puts into vacuum drying chamber and is dried in 80 DEG C to constant weight, then in N2Forged under atmosphere in 800 DEG C
Burn 2h and obtain nitrogen, iron codope carbon material；Obtained nitrogen, iron codope carbon material 40mg are scattered in 20mL ethylene glycol, added
Enter 50mg sodium glutamates and obtain dispersion liquid as dressing agent, ultrasonic agitation 2h；2.5mL will be sequentially added in obtained dispersion liquid
20mM PdCl2The aqueous solution and 20mg CuSO4·5H2O, stir to well mixed and obtain mixed liquor, obtained mixed liquor is shifted
Being sealed into autoclave, 6 h are reacted in 160 DEG C, reaction naturally cools to room temperature after terminating, then centrifuges product, and
It is washed with deionized, puts into vacuum drying chamber drying to constant weight and obtain the carbon material supported palladium-copper alloy combustion of nitrogen, iron codope
Expect cell catalyst.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M formic acid+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 3.
Comparative example 2
Main preparation flow is identical with comparative example 1, is not add sodium glutamate as modification with the difference of comparative example 1
Agent.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M formic acid+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 3.
Comparative example 3
Take Xc-72 carbon materials to be scattered in for carrier 40mg in 20mL ethylene glycol, add 50mg sodium glutamates as dressing agent, ultrasound
Stirring 2h obtains dispersion liquid；2.5mL 20mM PdCl will be sequentially added in obtained dispersion liquid2The aqueous solution and 20mg CuSO4·
5H2O, stir to well mixed and obtain mixed liquor, obtained mixed liquor is transferred in autoclave and sealed, add in 160 DEG C
Hot 6h, reaction naturally cools to room temperature after terminating, then centrifuges product, and is washed with deionized, and puts to vacuum drying chamber
Middle drying to constant weight obtains the carbon material supported palladium-copper alloy fuel-cell catalysts of Xc-72.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M formic acid+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 3.
Comparative example 4
0.01g melamines and 0.01g pyrophosphoric acids are well mixed wiring solution-forming through ultrasonic disperse with 40mL deionized waters, then added
Enter 0.1g iron chloride and be uniformly mixing to obtain suspension；Obtained suspension is transferred in autoclave and sealed, in 150 DEG C
6h is reacted, reaction naturally cools to room temperature after terminating；By obtained product be washed with deionized until filtrate become colorless, put
Dried into vacuum drying chamber in 80 DEG C to constant weight, then in N24h is calcined in 800 DEG C obtain phosphorus, nitrogen, iron codope under atmosphere
Carbon material；Obtained phosphorus, nitrogen, iron codope carbon material 40mg are scattered in 20mL ethylene glycol, ultrasonic agitation 2h is disperseed
Liquid；2.5mL 20mM PdCl will be added in obtained dispersion liquid2The aqueous solution, stir to well mixed and obtain mixed liquor, will obtain
Mixed liquor be transferred in autoclave and seal, 6h are reacted in 160 DEG C, reaction naturally cools to room temperature after terminating, and then will
Product centrifuges, and is washed with deionized, and puts into vacuum drying chamber drying to constant weight and obtains phosphorus, nitrogen, iron codope carbon material
Supported palladium fuel-cell catalyst.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M formic acid+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 3.
Comparative example 5
Take 20% Pt/Xc-72 of JM companies of the business platinum catalyst U.S..
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M formic acid+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 3.
Fuel-cell catalyst obtained by the present invention is applied to the catalysis oxidation of formic acid, and is lived with good electro-catalysis
Property.Integrated embodiment 1 and comparative example 1-5, it can be seen that in fuel-cell catalyst produced by the present invention PdCu ghosts ball be by
The accumulation of PdCu little particles forms, and wherein the particle diameter of PdCu ghosts ball is about in 50nm or so, and the short grained particle diameters of PdCu are in 5nm
Left and right, and PdCu ghost balls are uniformly dispersed on carrier；Electric performance test result（Fig. 3）In, curve a is to be made in embodiment 1
The electrical property of standby catalyst, b, c, d, e, f correspond to comparative example 4, comparative example 5, comparative example 1, comparative example 2 and comparative example 3 respectively
Catalyst electrical property, compared with comparative example 1-5, fuel-cell catalyst is in formic acid electrolyte solution made from embodiment 1
Current density can reach 500mAcm-2More than, peak area corresponding to curve is also maximum, shows the fuel cell catalyst
Agent is to Oxidation of Formic Acid electro-chemical activity highest, and we think, as catalyst carrier, the PdCu supported receives Fe-P-N-C
Meter Jing dispersiveness is enhanced, and improves the utilization ratio of metal, and enhances the cooperative effect between carrier and metal,
Therefore the electro catalytic activity excellent performance of fuel-cell catalyst, is expected to turn into a kind of fuel cell with broad prospect of application
Catalyst.
Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (3)
1. a kind of preparation method of fuel battery anode catalyst, it is characterised in that concretely comprise the following steps：
（1）Melamine and pyrophosphoric acid are well mixed wiring solution-forming through ultrasonic disperse with deionized water, add iron chloride simultaneously
It is uniformly mixed to obtain suspension, obtained suspension is transferred in autoclave and sealed, reacts 6h in 150 DEG C, instead
Naturally cool to room temperature after should terminating, by obtained product be washed with deionized until filtrate become colorless, put to vacuum and do
Dried in dry case in 80 DEG C to constant weight, then in N2Under atmosphere in 800 DEG C calcine 4h obtain double-deck ghost spherical structure phosphorus, nitrogen,
Iron codope carbon material；
（2）By step（1）Obtained phosphorus, nitrogen, iron codope carbon material is scattered in ethylene glycol, and ultrasonic agitation 2h is disperseed
Liquid, PdCl will be sequentially added in obtained dispersion liquid2The aqueous solution and CuSO4·5H2O, stir to well mixed and obtain mixed liquor,
Obtained mixed liquor is transferred in autoclave and sealed, 6h is reacted in 160 DEG C, reaction naturally cools to room temperature after terminating,
Then product is centrifuged, and be washed with deionized, put into vacuum drying chamber drying to constant weight and obtain loading ghost spherical junctions
Structure palladium-copper alloy fuel battery anode catalyst.
2. the preparation method of fuel battery anode catalyst according to claim 1, it is characterised in that：Step（1）Middle institute
The mass ratio that feeds intake for stating melamine, pyrophosphoric acid and iron chloride is 1:1:10.
3. the preparation method of fuel battery anode catalyst according to claim 1, it is characterised in that：Step（2）Middle institute
State phosphorus, nitrogen, iron co-doped material and CuSO4·5H2The O mass ratio that feeds intake is 2:1, PdCl2With CuSO4·5H2O's feeds intake mole
Than for 5:8.
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| CN109037606A (en) * | 2018-06-22 | 2018-12-18 | 合肥国轩高科动力能源有限公司 | A kind of carbon coating porous silicon Antaciron composite negative pole material and its preparation, application |
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| CN110571440B (en) * | 2019-08-14 | 2022-01-25 | 电子科技大学 | FeN4-CNT oxygen reduction catalyst preparation method |
| CN111250008A (en) * | 2020-02-08 | 2020-06-09 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111250008B (en) * | 2020-02-08 | 2021-09-21 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN112397731A (en) * | 2020-11-13 | 2021-02-23 | 安徽大学 | Preparation of hollow PdCoP/C alloy electrocatalyst and application thereof in ethanol electrocatalytic oxidation |
| CN113270600A (en) * | 2021-04-21 | 2021-08-17 | 上海电力大学 | Pd/P-NCNS catalyst for high-activity direct formic acid fuel cell and preparation and application thereof |
| CN113594478A (en) * | 2021-08-12 | 2021-11-02 | 河南师范大学 | Preparation method and application of one-dimensional carrier composite fuel cell catalyst |
| CN113594478B (en) * | 2021-08-12 | 2024-03-08 | 河南师范大学 | Preparation method and application of one-dimensional carrier composite fuel cell catalyst |
| CN114361486A (en) * | 2022-01-11 | 2022-04-15 | 贵州梅岭电源有限公司 | High-performance low-cost fuel cell anti-reversal anode catalyst and preparation method thereof |
| CN115020719A (en) * | 2022-06-21 | 2022-09-06 | 北京化工大学 | Preparation method of dual-site catalyst for direct formate fuel cell anode |
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Application publication date: 20171222 |