CN108172848A - The catalyst layer and preparation method of a kind of fuel cell N doping copper/nickel alloy - Google Patents

The catalyst layer and preparation method of a kind of fuel cell N doping copper/nickel alloy Download PDF

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CN108172848A
CN108172848A CN201810093309.8A CN201810093309A CN108172848A CN 108172848 A CN108172848 A CN 108172848A CN 201810093309 A CN201810093309 A CN 201810093309A CN 108172848 A CN108172848 A CN 108172848A
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fuel cell
copper
catalyst layer
nickel
preparation
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陈庆
廖健淞
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Chengdu New Keli Chemical Science Co Ltd
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Chengdu New Keli Chemical Science Co Ltd
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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
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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 present invention provides a kind of fuel cell catalyst layers and preparation method of N doping copper/nickel alloy.After the carboxylate of copper and mickel is added in organic solvent mixing, add in rich hydroxyl organic carbon source and inorganic salts, heating esterification obtains being attached to the organic phase material of alloy on inorganic salts, dry rear high temperature sintering is blown with hot ammonia, corronil/unformed carbon phase of N doping, the catalyst layer of as described fuel cell are made after deionized water washing, drying.This method forms C N Cu/Ni class formations by preparing, alloy atom with nitrogen-atoms combination uniform close by being embedded in two-dimensional/three-dimensional carbon-coating inner space, alloy and the binding ability on carbon carrier are fabulous, catalyst layer catalytic activity obtained is strong, service life is long, and preparation process is relatively simple, and cost is relatively low, is suitble to industrialized production.

Description

The catalyst layer and preparation method of a kind of fuel cell N doping copper/nickel alloy
Technical field
The present invention relates to fuel cell fields, and in particular to the preparation of catalyst layer, more particularly to a kind of fuel cell With the catalyst layer and preparation method of N doping copper/nickel alloy.
Background technology
Fuel cell is the energy conversion device that the chemical energy of fuel is converted to electric energy directly in a manner of chemical reaction, is A kind of energy technology of green is of great significance to solving we are faced at present energy crisis and problem of environmental pollution, In the science and technology development planning in China, fuel cell technology is also listed in one of important developing direction.Fuel cell generally by Fuel electrodes（Or hydrogen pole）, air pole（Or oxygen pole）And the electrolyte being clipped between this two poles of the earth is formed.During work, by outside Supply the hydrogen of battery becomes hydrogen ion in fuel electrodes ejected electron, and hydrogen ion is by shifting to air pole after electrolyte, and electronics is then Air pole is also reached by external circuit.In air pole, by being externally supplied the oxygen of battery, carry out reacting generation with hydrogen ion and electronics Water.
Catalyst is one of critical material in fuel cell, and the cost of catalyst accounts for the 1/3 of fuel cell cost.Platinum Be proved to be the optimum catalyst active component for low-temperature fuel cell, but use platinum as fuel-cell catalyst there is also Following serious problems：Platinum scarcity of resources, expensive, poison resistance is poor.Have at present by alloy to improve the research of catalyst The platinum-ruthenium alloys catalyst that carbon loads and Pt/C and PtRu/C catalyst added with other promotion ingredients etc..But make Alloy type catalyst catalytic performance for its substitute is slightly poor, is primarily due to the binding ability of alloy-layer and carbon carrier Difference, being easily detached from carbon carrier in use causes catalytic performance to reduce.Therefore for the combination energy of raising alloy and carbon carrier Power has highly important practical significance.
Chinese invention patent application number 201510002591.0 discloses a kind of carbon-supported nano corronil core-noble metal shell Nucleocapsid catalyst and preparation method thereof, belong to fuel cell and energy saving electrolysis field, the invention using conductive carbon material as carrier, Using the high base metal CuNi alloys of anti-corrosion, alloying level as kernel, noble metal prepares carbon for shell and carries nucleocapsid metal catalytic Agent.Its preparation process is：The carbon for being impregnated with cupro-nickel salt is carried out under reducing atmosphere to be thermally treated resulting in CuNi/C, by this CuNi/C Flow back reduction in having the ethylene glycol of precious metal salt and PVP, obtains CuNi@M/C nucleocapsid catalysts.The invention improves kernel The alloying level and corrosion resistance of CuNi, while CuNi alloy surfaces are conducive to noble metal selective deposition, ensure limited amount Noble metal is deposited on the less number of plies on CuNi cores.It is urged using the catalyst prepared by the invention in noble metal carrying capacity from tradition The 20% of agent drops to 5 ~ 10%, and electro catalytic activity has good stability without decline.
Chinese invention patent application number 201310586826.6 discloses a kind of nitrogen-doped graphene fuel-cell catalyst Preparation and application.Include the following steps：Graphite oxide is scattered in solvent, is ultrasonically treated, obtains graphene oxide solution； At least one of base metal salt and its hydrate and nitrogenous organic molecule are scattered in solvent, obtain mixed solution； Graphene oxide solution is added drop-wise in above-mentioned mixed solution, solvent evaporated, nitrogen-doped graphene presoma is obtained, in indifferent gas 600~1000 DEG C are warming up under body protection, keeps the temperature 1~4h, natural cooling obtains nitrogen-doped graphene catalyst.The invention Nitrogen-doped graphene preparation process is simple, and required cost of material is low, and yield is high, it is easy to accomplish industrialized production has very high Oxygen reduction catalytic activity can be applied to the fields such as fuel cell, metal-air battery and microbiological fuel cell.
Chinese invention patent application number 201110315012.X discloses a kind of fuel cell and is urged with nitrogen-doped nanometer carbon electricity Agent and preparation method thereof, elctro-catalyst make precursors with aniline, by aniline, surfactant and soluble transition metal Polymerize under acid and high oxidizing conditions after salt blend, it is dry after by it under inert gas and/or ammonia atmosphere protection high temperature Charing finally carries out acid processing and is prepared.The elctro-catalyst preparation method of the invention is simple and easy to control, is easy to large-scale production. The catalyst has oxygen reduction catalytic activity, stability and the selectivity compared with Pt/C in acid medium fuel cell； There is catalytic activity more higher than commercialization Pt/C and stability in alkaline medium fuel cell.In addition, the catalyst also has Inexpensive and high mithridatism energy can substitute platinum as fuel cell oxygen reduction electrocatalyst.
Chinese invention patent application number 201410734991.6 discloses a kind of N doping Fe/Fe3C/C Microbial fuels electricity The preparation method of pool cathode catalyst material is related to a kind of preparation method of microorganism fuel cell cathode catalyst material.This The purpose of invention is to solve that existing there are costs as microorganism fuel cell cathode catalyst material using platinum carbon catalyst The problem of high.Method：First, it dissolves；2nd, heating water bath；3rd, it is dry；4th, high temperature cabonization reduction is to get to N doping Fe/ Fe3C/C microorganism fuel cell cathode catalyst materials.
According to above-mentioned, platinum based catalyst reserves in existing scheme are in short supply, expensive and poison resistance is poor, and traditional The alloy-layer of alloy type catalyst and carbon carrier binding ability are poor, cause catalytic activity low, and catalytic performance is poor, and service life is short. In consideration of it, the present invention proposes a kind of catalyst layer and preparation method of fuel cell N doping copper/nickel alloy, can effectively solve Certainly above-mentioned technical problem.
Invention content
For the wider fuel cell platinum based catalyst of current application, there are reserves are in short supply, expensive and poison resistance is poor The defects of, and the alloy-layer of existing alloy type catalyst and carbon carrier binding ability are poor, catalytic low there are catalytic activity The problems such as energy is poor, and service life is short, the present invention propose catalyst layer and preparation of a kind of fuel cell with N doping copper/nickel alloy Method so as to effectively realize the binding ability for improving alloy-layer and carbon carrier, improves catalytic activity and service life.
Specific technical solution of the present invention is as follows：
A kind of fuel cell preparation method of the catalyst layer of N doping copper/nickel alloy, includes the following steps：
（1）The carboxylate of the carboxylate of 10 ~ 15 parts by weight copper and 10 ~ 15 parts by weight nickel is added in into 42 ~ 58 weight parts organic solvents In be thoroughly mixed, add in 18 ~ 20 parts by weight richness hydroxyl organic carbon sources and 4 ~ 8 parts by weight of inorganic salt, be heated to 100 ~ 120 DEG C, carboxylate carries out esterification with rich hydroxyl organic carbon source by template of inorganic salts, and after reacting 70 ~ 120min, product carries out Filtering, dry, the obtained alloy-organic phase material being uniformly attached in template；
（2）Using hot ammonia to step（1）Alloy obtained-organic phase material blow dry, high temperature sintering at 450 ~ 550 DEG C, Organic phase is made thoroughly to decompose, nitrogen-atoms with metallic atom after being combined inside embedded carbon structure；
（3）Using deionized water washing step（2）Resulting materials, remove inorganic salts template, drying, and the cupro-nickel that N doping is made is closed Gold/unformed carbon phase, the catalyst layer of as described fuel cell.
Preferably, step（1）The carboxylate of the copper is at least one in copper formate, copper acetate, cupric oxalate or propionic acid copper Kind.
Preferably, step（1）The carboxylate of the nickel is at least one of nickel formate, nickel acetate or propionic acid nickel.
Preferably, step（1）The organic solvent is styrene, perchloroethylene, trichloro ethylene, ethylene glycol ether or three At least one of ethanol amine.
Preferably, step（1）The richness hydroxyl organic carbon source is cyclodextrin, cellulose, glucose, sucrose, fructose, the third three At least one of alcohol or starch.
Preferably, step（1）The inorganic salts are dystectic water soluble salt, but the neutral salt insoluble in organic solvent, Such as KCl, NaNO3At least one of.
Preferably, step（2）The temperature of the hot ammonia is 120 ~ 140 DEG C, and flow control is 5 ~ 20m/s.
Preferably, step（3）The drying temperature is 70 ~ 90 DEG C, and the time is 7 ~ 10h, and vacuum degree is 0.1 ~ 0.3Pa.
A kind of fuel cell N doping copper/nickel alloy being prepared the present invention also provides a kind of above-mentioned preparation method Catalyst layer.After the carboxylate of copper and mickel is added in organic solvent mixing, rich hydroxyl organic carbon source and inorganic salts are added in, heat ester Change the alloy-organic phase material for being obtained by the reaction and being attached on inorganic salts, blow dry rear high temperature sintering, deionization washing with hot ammonia Wash, dry after be made N doping corronil/unformed carbon phase, the catalyst layer of as described fuel cell.
Mantoquita and nickel salt are grafted on form cage surface by the present invention by organic media, washed away by hot ammonia make it is organic Object decomposes, and nitrogen-atoms inside embedded carbon structure, forms C-N-Cu/Ni class formations, improve alloy and exist after being combined with metallic atom Adhesive ability on carbon carrier.
It is and existing the present invention provides a kind of fuel cell catalyst layer and preparation method of N doping copper/nickel alloy The characteristics of technology is compared, protrusion and excellent effect are：
1st, the method by alloy-organic phase material preparation fuel cell catalyst layer of N doping copper/nickel alloy is proposed.
2nd, C-N-Cu/Ni class formations are formed by preparing, alloy atom by is combined with nitrogen-atoms be uniformly embedded in it is two-dimentional/ Inside three-dimensional carbon lamellar spacing, the binding ability of carbon atom and metallic atom is significantly improved, improve alloy on the carbon carrier attached Ability, obtained catalyst layer catalytic activity is strong, and service life is long.
3rd, preparation process of the invention is relatively simple, and manufacturing cost is relatively low, can promote production application.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Preparation process is：
（1）The carboxylate of the carboxylate of 13 parts by weight copper and 13 parts by weight nickel is added in 49 weight parts organic solvents and is sufficiently stirred Mixing adds in 19 parts by weight richness hydroxyl organic carbon sources and 6 parts by weight of inorganic salt, is heated to 110 DEG C, carboxylate and rich hydroxyl are organic Carbon source carries out esterification by template of inorganic salts, and after reacting 95min, product is filtered, dries, and is made and is uniformly attached to mould Alloy-organic phase material on plate；The carboxylate of copper is copper formate；The carboxylate of nickel is propionic acid nickel；Organic solvent is styrene； Rich hydroxyl organic carbon source is cyclodextrin；Inorganic salts are KCl；
（2）Using hot ammonia to step（1）Alloy obtained-organic phase material blow dry, and high temperature sintering at 500 DEG C makes to have Machine mutually thoroughly decomposes, and nitrogen-atoms with metallic atom after being combined inside embedded carbon structure；The temperature of hot ammonia is 130 DEG C, flow velocity control It is made as 12m/s；
（3）Using deionized water washing step（2）Resulting materials, remove inorganic salts template, drying, and the cupro-nickel that N doping is made is closed Gold/unformed carbon phase, the catalyst layer of as described fuel cell；Drying temperature is 80 DEG C, time 8h, and vacuum degree is 0.2Pa。
Test method is：
Adsorption stripping is carried out to the corronil catalyst on carbon carrier, tests the catalytic amount adsorbed, is catalyzed using remnants The mass fraction characterization corronil of agent and the binding ability of carbon carrier, absorption pressure are 5MPa, adsorption time 10min, residual The mass fraction of remaining catalyst=（The catalytic amount for catalyst gross mass-adsorbed）/ catalyst gross mass × 100%.
Under conditions of 120 DEG C of temperature, relative humidity 70%, using hydrogen as fuel, using oxygen as oxidant, test gained The catalytic activity half-life period of catalyst, to characterize the service life of catalyst.
The absorption residual qualities score of the photochemical catalyst of embodiment 1, the active half-life such as table 1 measured by the above method It is shown.
Embodiment 2
Preparation process is：
（1）The carboxylate of the carboxylate of 10 parts by weight copper and 10 parts by weight nickel is added in 58 weight parts organic solvents and is sufficiently stirred Mixing adds in 18 parts by weight richness hydroxyl organic carbon sources and 4 parts by weight of inorganic salt, is heated to 100 DEG C, carboxylate and rich hydroxyl are organic Carbon source carries out esterification by template of inorganic salts, and after reacting 120min, product is filtered, dries, and is made and is uniformly attached to Alloy-organic phase material in template；The carboxylate of copper is copper acetate；The carboxylate of nickel is nickel formate；Organic solvent is perchloro- Ethylene；Rich hydroxyl organic carbon source is cellulose；Inorganic salts are NaNO3；
（2）Using hot ammonia to step（1）Alloy obtained-organic phase material blow dry, and high temperature sintering at 450 DEG C makes to have Machine mutually thoroughly decomposes, and nitrogen-atoms with metallic atom after being combined inside embedded carbon structure；The temperature of hot ammonia is 120 DEG C, flow velocity control It is made as 20m/s；
（3）Using deionized water washing step（2）Resulting materials, remove inorganic salts template, drying, and the cupro-nickel that N doping is made is closed Gold/unformed carbon phase, the catalyst layer of as described fuel cell；Drying temperature is 70 DEG C, time 10h, and vacuum degree is 0.1Pa。
Test method is：
Adsorption stripping is carried out to the corronil catalyst on carbon carrier, tests the catalytic amount adsorbed, is catalyzed using remnants The mass fraction characterization corronil of agent and the binding ability of carbon carrier, absorption pressure are 5MPa, adsorption time 10min, residual The mass fraction of remaining catalyst=（The catalytic amount for catalyst gross mass-adsorbed）/ catalyst gross mass × 100%.
Under conditions of 120 DEG C of temperature, relative humidity 70%, using hydrogen as fuel, using oxygen as oxidant, test gained The catalytic activity half-life period of catalyst, to characterize the service life of catalyst.
The absorption residual qualities score of the photochemical catalyst of embodiment 2, the active half-life such as table 1 measured by the above method It is shown.
Embodiment 3
Preparation process is：
（1）The carboxylate of the carboxylate of 15 parts by weight copper and 15 parts by weight nickel is added in 42 weight parts organic solvents and is sufficiently stirred Mixing adds in 20 parts by weight richness hydroxyl organic carbon sources and 8 parts by weight of inorganic salt, is heated to 120 DEG C, carboxylate and rich hydroxyl are organic Carbon source carries out esterification by template of inorganic salts, and after reacting 70min, product is filtered, dries, and is made and is uniformly attached to mould Alloy-organic phase material on plate；The carboxylate of copper is cupric oxalate；The carboxylate of nickel is nickel acetate；Organic solvent is three chloroethenes Alkene；Rich hydroxyl organic carbon source is glucose；Inorganic salts are KCl；
（2）Using hot ammonia to step（1）Alloy obtained-organic phase material blow dry, and high temperature sintering at 550 DEG C makes to have Machine mutually thoroughly decomposes, and nitrogen-atoms with metallic atom after being combined inside embedded carbon structure；The temperature of hot ammonia is 140 DEG C, flow velocity control It is made as 5m/s；
（3）Using deionized water washing step（2）Resulting materials, remove inorganic salts template, drying, and the cupro-nickel that N doping is made is closed Gold/unformed carbon phase, the catalyst layer of as described fuel cell；Drying temperature is 90 DEG C, time 7h, and vacuum degree is 0.3Pa。
Test method is：
Adsorption stripping is carried out to the corronil catalyst on carbon carrier, tests the catalytic amount adsorbed, is catalyzed using remnants The mass fraction characterization corronil of agent and the binding ability of carbon carrier, absorption pressure are 5MPa, adsorption time 10min, residual The mass fraction of remaining catalyst=（The catalytic amount for catalyst gross mass-adsorbed）/ catalyst gross mass × 100%.
Under conditions of 120 DEG C of temperature, relative humidity 70%, using hydrogen as fuel, using oxygen as oxidant, test gained The catalytic activity half-life period of catalyst, to characterize the service life of catalyst.
The absorption residual qualities score of the photochemical catalyst of embodiment 3, the active half-life such as table 1 measured by the above method It is shown.
Embodiment 4
Preparation process is：
（1）The carboxylate of the carboxylate of 11 parts by weight copper and 11 parts by weight nickel is added in 55 weight parts organic solvents and is sufficiently stirred Mixing adds in 18 parts by weight richness hydroxyl organic carbon sources and 5 parts by weight of inorganic salt, is heated to 105 DEG C, carboxylate and rich hydroxyl are organic Carbon source carries out esterification by template of inorganic salts, and after reacting 80min, product is filtered, dries, and is made and is uniformly attached to mould Alloy-organic phase material on plate；The carboxylate of copper is propionic acid copper；The carboxylate of nickel is nickel formate；Organic solvent is ethylene second Glycol ethers；Rich hydroxyl organic carbon source is sucrose；Inorganic salts are NaNO3；
（2）Using hot ammonia to step（1）Alloy obtained-organic phase material blow dry, and high temperature sintering at 480 DEG C makes to have Machine mutually thoroughly decomposes, and nitrogen-atoms with metallic atom after being combined inside embedded carbon structure；The temperature of hot ammonia is 125 DEG C, flow velocity control It is made as 15m/s；
（3）Using deionized water washing step（2）Resulting materials, remove inorganic salts template, drying, and the cupro-nickel that N doping is made is closed Gold/unformed carbon phase, the catalyst layer of as described fuel cell；Drying temperature is 75 DEG C, time 9h, and vacuum degree is 0.2Pa。
Test method is：
Adsorption stripping is carried out to the corronil catalyst on carbon carrier, tests the catalytic amount adsorbed, is catalyzed using remnants The mass fraction characterization corronil of agent and the binding ability of carbon carrier, absorption pressure are 5MPa, adsorption time 10min, residual The mass fraction of remaining catalyst=（The catalytic amount for catalyst gross mass-adsorbed）/ catalyst gross mass × 100%.
Under conditions of 120 DEG C of temperature, relative humidity 70%, using hydrogen as fuel, using oxygen as oxidant, test gained The catalytic activity half-life period of catalyst, to characterize the service life of catalyst.
The absorption residual qualities score of the photochemical catalyst of embodiment 4, the active half-life such as table 1 measured by the above method It is shown.
Embodiment 5
Preparation process is：
（1）The carboxylate of the carboxylate of 14 parts by weight copper and 14 parts by weight nickel is added in 46 weight parts organic solvents and is sufficiently stirred Mixing adds in 19 parts by weight richness hydroxyl organic carbon sources and 7 parts by weight of inorganic salt, is heated to 115 DEG C, carboxylate and rich hydroxyl are organic Carbon source carries out esterification by template of inorganic salts, and after reacting 100min, product is filtered, dries, and is made and is uniformly attached to Alloy-organic phase material in template；The carboxylate of copper is copper formate；The carboxylate of nickel is nickel formate；Organic solvent is three second Hydramine；Rich hydroxyl organic carbon source is fructose；Inorganic salts are KCl；
（2）Using hot ammonia to step（1）Alloy obtained-organic phase material blow dry, and high temperature sintering at 520 DEG C makes to have Machine mutually thoroughly decomposes, and nitrogen-atoms with metallic atom after being combined inside embedded carbon structure；The temperature of hot ammonia is 135 DEG C, flow velocity control It is made as 10m/s；
（3）Using deionized water washing step（2）Resulting materials, remove inorganic salts template, drying, and the cupro-nickel that N doping is made is closed Gold/unformed carbon phase, the catalyst layer of as described fuel cell；Drying temperature is 85 DEG C, time 8h, and vacuum degree is 0.3Pa。
Test method is：
Adsorption stripping is carried out to the corronil catalyst on carbon carrier, tests the catalytic amount adsorbed, is catalyzed using remnants The mass fraction characterization corronil of agent and the binding ability of carbon carrier, absorption pressure are 5MPa, adsorption time 10min, residual The mass fraction of remaining catalyst=（The catalytic amount for catalyst gross mass-adsorbed）/ catalyst gross mass × 100%.
Under conditions of 120 DEG C of temperature, relative humidity 70%, using hydrogen as fuel, using oxygen as oxidant, test gained The catalytic activity half-life period of catalyst, to characterize the service life of catalyst.
The absorption residual qualities score of the photochemical catalyst of embodiment 5, the active half-life such as table 1 measured by the above method It is shown.
Embodiment 6
Preparation process is：
（1）The carboxylate of the carboxylate of 13 parts by weight copper and 13 parts by weight nickel is added in 47 weight parts organic solvents and is sufficiently stirred Mixing adds in 20 parts by weight richness hydroxyl organic carbon sources and 7 parts by weight of inorganic salt, is heated to 115 DEG C, carboxylate and rich hydroxyl are organic Carbon source carries out esterification by template of inorganic salts, and after reacting 90min, product is filtered, dries, and is made and is uniformly attached to mould Alloy-organic phase material on plate；The carboxylate of copper is cupric oxalate；The carboxylate of nickel is nickel acetate；Organic solvent is styrene； Rich hydroxyl organic carbon source is starch；Inorganic salts are NaNO3；
（2）Using hot ammonia to step（1）Alloy obtained-organic phase material blow dry, and high temperature sintering at 520 DEG C makes to have Machine mutually thoroughly decomposes, and nitrogen-atoms with metallic atom after being combined inside embedded carbon structure；The temperature of hot ammonia is 135 DEG C, flow velocity control It is made as 16m/s；
（3）Using deionized water washing step（2）Resulting materials, remove inorganic salts template, drying, and the cupro-nickel that N doping is made is closed Gold/unformed carbon phase, the catalyst layer of as described fuel cell；Drying temperature is 85 DEG C, time 8h, and vacuum degree is 0.2Pa。
Test method is：
Adsorption stripping is carried out to the corronil catalyst on carbon carrier, tests the catalytic amount adsorbed, is catalyzed using remnants The mass fraction characterization corronil of agent and the binding ability of carbon carrier, absorption pressure are 5MPa, adsorption time 10min, residual The mass fraction of remaining catalyst=（The catalytic amount for catalyst gross mass-adsorbed）/ catalyst gross mass × 100%.
Under conditions of 120 DEG C of temperature, relative humidity 70%, using hydrogen as fuel, using oxygen as oxidant, test gained The catalytic activity half-life period of catalyst, to characterize the service life of catalyst.
The absorption residual qualities score of the photochemical catalyst of embodiment 6, the active half-life such as table 1 measured by the above method It is shown.
Comparative example 1
Preparation process is：
（1）The carboxylate of the carboxylate of 13 parts by weight copper and 13 parts by weight nickel is added in 47 weight parts organic solvents and is sufficiently stirred Mixing adds in 20 parts by weight richness hydroxyl organic carbon sources, is heated to 115 DEG C, carboxylate with rich hydroxyl organic carbon source be esterified anti- Should, after reacting 90min, product is filtered, dries, and the alloy-organic phase material being uniformly attached in template is made；The carboxylic of copper Hydrochlorate is cupric oxalate；The carboxylate of nickel is nickel acetate；Organic solvent is styrene；Rich hydroxyl organic carbon source is starch；（2）To step Suddenly（1）Alloy obtained-organic phase material high temperature sintering at 520 DEG C, makes organic phase thoroughly decompose；
（3）Using deionized water washing step（2）Resulting materials, remove inorganic salts template, and it is fixed that corronil/nothing is made in drying Type carbon phase, the catalyst layer of as described fuel cell；Drying temperature is 85 DEG C, time 8h, vacuum degree 0.2Pa.
Test method is：
Adsorption stripping is carried out to the corronil catalyst on carbon carrier, tests the catalytic amount adsorbed, is catalyzed using remnants The mass fraction characterization corronil of agent and the binding ability of carbon carrier, absorption pressure are 5MPa, adsorption time 10min, residual The mass fraction of remaining catalyst=（The catalytic amount for catalyst gross mass-adsorbed）/ catalyst gross mass × 100%.
Under conditions of 120 DEG C of temperature, relative humidity 70%, using hydrogen as fuel, using oxygen as oxidant, test gained The catalytic activity half-life period of catalyst, to characterize the service life of catalyst.
The absorption residual qualities score of the photochemical catalyst of comparative example 1, the active half-life such as table 1 measured by the above method It is shown.
Table 1：
Performance indicator Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Comparative example 1
Adsorb residual qualities score（%） 73.5 76.4 77.3 74.8 75.6 78.3 42
Active half-life（h） 130 140 135 138 139 128 65

Claims (9)

1. a kind of fuel cell preparation method of the catalyst layer of N doping copper/nickel alloy, which is characterized in that including following step Suddenly：
（1）The carboxylate of the carboxylate of 10 ~ 15 parts by weight copper and 10 ~ 15 parts by weight nickel is added in into 42 ~ 58 weight parts organic solvents In be thoroughly mixed, add in 18 ~ 20 parts by weight richness hydroxyl organic carbon sources and 4 ~ 8 parts by weight of inorganic salt, be heated to 100 ~ 120 DEG C, carboxylate carries out esterification with rich hydroxyl organic carbon source by template of inorganic salts, and after reacting 70 ~ 120min, product carries out Filtering, dry, the obtained alloy-organic phase material being uniformly attached in template；
（2）Using hot ammonia to step（1）Alloy obtained-organic phase material blow dry, high temperature sintering at 450 ~ 550 DEG C, Organic phase is made thoroughly to decompose, nitrogen-atoms with metallic atom after being combined inside embedded carbon structure；
（3）Using deionized water washing step（2）Resulting materials, remove inorganic salts template, drying, and the cupro-nickel that N doping is made is closed Gold/unformed carbon phase, the catalyst layer of as described fuel cell.
2. the preparation method of a kind of fuel cell catalyst layer of N doping copper/nickel alloy according to claim 1, It is characterized in that：Step（1）The carboxylate of the copper is at least one of copper formate, copper acetate, cupric oxalate or propionic acid copper.
3. the preparation method of a kind of fuel cell catalyst layer of N doping copper/nickel alloy according to claim 1, special Sign is：Step（1）The carboxylate of the nickel is at least one of nickel formate, nickel acetate or propionic acid nickel.
4. the preparation method of a kind of fuel cell catalyst layer of N doping copper/nickel alloy according to claim 1, special Sign is：Step（1）The organic solvent is in styrene, perchloroethylene, trichloro ethylene, ethylene glycol ether or triethanolamine At least one.
5. the preparation method of a kind of fuel cell catalyst layer of N doping copper/nickel alloy according to claim 1, special Sign is：Step（1）The richness hydroxyl organic carbon source is cyclodextrin, cellulose, glucose, sucrose, fructose, glycerine or starch At least one of.
6. the preparation method of a kind of fuel cell catalyst layer of N doping copper/nickel alloy according to claim 1, special Sign is：Step（1）The inorganic salts are dystectic water soluble salt, but the neutral salt insoluble in organic solvent, for KCl, NaNO3At least one of.
7. the preparation method of a kind of fuel cell catalyst layer of N doping copper/nickel alloy according to claim 1, special Sign is：Step（2）The temperature of the hot ammonia is 120 ~ 140 DEG C, and flow control is 5 ~ 20m/s.
8. the preparation method of a kind of fuel cell catalyst layer of N doping copper/nickel alloy according to claim 1, special Sign is：Step（3）The drying temperature is 70 ~ 90 DEG C, and the time is 7 ~ 10h, and vacuum degree is 0.1 ~ 0.3Pa.
9. a kind of fuel cell N doping copper/nickel alloy that any one of claim 1 ~ 8 preparation method is prepared Catalyst layer.
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