CN108598494B - Fuel cell anode and fuel cell using same - Google Patents

Fuel cell anode and fuel cell using same Download PDF

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CN108598494B
CN108598494B CN201810645243.9A CN201810645243A CN108598494B CN 108598494 B CN108598494 B CN 108598494B CN 201810645243 A CN201810645243 A CN 201810645243A CN 108598494 B CN108598494 B CN 108598494B
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borohydride
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nickel
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CN108598494A (en
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李赛
王丽娜
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Xian University of Science and Technology
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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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • 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

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Abstract

The invention relates to a fuel cell anode and a fuel cell using the anode, which comprises a lead, a foam nickel polar plate and a catalyst layer, wherein the catalyst layer is coated on one side of the foam nickel polar plate, the lead is connected with the foam nickel polar plate, and the catalyst used by the catalyst layer has a honeycomb structure. The invention solves the technical problems of high cost and low catalytic performance of the existing electrode for the fuel cell. The catalyst structure used by the electrode is a three-dimensional sheet honeycomb structure and a graphene-like structure, and compared with a spherical structure, a core-shell structure or a hollow structure reported in documents, the catalyst structure can provide a larger contact area of reactants, promote the diffusion of the reactants, improve the mass transfer rate and improve the catalytic performance of the catalyst.

Description

Fuel cell anode and fuel cell using same
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a fuel cell anode and a fuel cell using the same.
Background
In recent years, fuel cells have become high-tech items competitively developed in countries around the world. The electrochemical generating device is an efficient and clean electrochemical generating device for directly converting chemical energy of reactants into electric energy. The fuel can be hydrogen, alcohol, hydrocarbon, borohydride, etc., and the oxidant is oxygen or air. In the path of commercialization of low temperature fuel cells such as Proton Exchange Membrane Fuel Cells (PEMFC), methanol fuel cells (DMFC), borohydride fuel cells (DBFC), durability and cost of fuel cells are two major challenges, wherein reducing the noble metal content in the electrode assembly can directly improve the cost efficiency of the cell, but also affects the performance and long-term stability of the cell, currently, reducing the cost of the electrode assembly is mainly achieved by reducing the cost of the electrode catalyst by (1) preparing a platinum alloy to reduce the platinum content, chinese patent CN 102820475 a describes a platinum alloy catalyst PtXNb, wherein X is nickel, cobalt, chromium, copper, titanium or manganese, characterized in that the atomic percent of platinum is 46 to 75 at%, which has excellent oxygen reduction catalytic activity for use as the cathode of a fuel cell, particularly a phosphoric acid fuel cell, but the preparation route is complicated, the process is harsh, such as: annealing treatment at high temperature 1000-1200 ℃ and in an inert atmosphere is required. CN 101083325A introduces a preparation method of palladium-platinum alloy electrocatalyst, the method prepares nano palladium or palladium-platinum catalyst by water phase solution reduction and heat treatment method, the preparation method is simple, but the active component of the synthesized catalyst is still noble metal platinum or palladium, and the cost problem is not solved fundamentally. Chinese patent CN 101667644A describes a preparation method of a high performance low platinum catalyst, which covers a small amount of Pt or Pt, Ru on the Pd alloy surface by simple replacement reaction, and then loads on carbon powder together, so that the consumption of precious metal Pt is greatly reduced, and the catalyst can be used for the cathode and anode of methanol fuel cell, and the catalytic performance is excellent, but precious metal Pt is still used, which can not solve the cost problem fundamentally. (2) The core-shell structure platinum catalyst is prepared to reduce the content of platinum and increase the utilization rate and the dispersibility of the platinum. Such as: chinese patent CN 10526853 a introduces a core-shell platinum catalyst, which has the advantage of improving the preparation efficiency of the core-shell structure, but has the disadvantage of complicated preparation method, requiring hydrazine hydrate reduction and high-temperature treatment. Chinese patent CN105702971B discloses a core-shell gold @ cobalt-boron catalyst for fuel cells, which is a gold-cobalt-boron alloy with a core-shell structure, wherein amorphous cobalt-boron is the shell and crystalline gold is the core. The structure has the common characteristics of the amorphous material and the crystalline material, has excellent catalytic performance, can effectively improve the discharge performance of the fuel cell, greatly reduces the consumption of noble metal, obviously reduces the cost of the fuel cell, and is favorable for promoting the development of the fuel cell. Although the catalyst prepared by the Chinese patent CN105702971B greatly reduces the dosage of noble metal, the cost of the fuel cell is obviously reduced; however, due to the core-shell structure, the contact area of reactants is small, so that the catalytic performance of the electrode is not high.
Disclosure of Invention
The invention provides a fuel cell and an electrode for the fuel cell, aiming at solving the technical problems of high cost and low catalytic performance of the conventional electrode for the fuel cell.
The technical scheme adopted by the invention is as follows:
the utility model provides a fuel cell positive pole, includes wire, foam nickel polar plate and catalyst layer, the coating of catalyst layer is in one side of foam nickel polar plate, the wire is connected its characterized in that with the foam nickel polar plate: the structure of the catalyst used in the catalyst layer is a honeycomb structure.
Furthermore, the catalyst comprises metallic Ni element, Co element and B element, and the molar ratio of Ni to Co is (0.01-1): 1, the molar ratio of Ni to B is 1: (2-5), the molar ratio of Co to B is 1: (2-5).
Further, the catalyst comprises metallic Ni element, Co element and B element, wherein the molar ratio of Ni to Co is 0.01: 1, the molar ratio of Ni to B is 1: 3, the molar ratio of Co to B is 1: 3.
further, the catalyst is prepared by the following method:
step one, preparing a borohydride-hydroxide mixed solution:
weighing borohydride, dissolving the borohydride in deionized water to prepare a borohydride solution, and then adding hydroxide into the borohydride solution until the pH value of the solution is 12-13 to obtain a borohydride-hydroxide mixed solution;
the borohydride is potassium borohydride, and the hydroxide is potassium hydroxide;
step two, preparing a cobalt salt solution: according to the molar ratio of cobalt element to boron element of 1: weighing cobalt salt according to the standard of (2-5), and dissolving the cobalt salt in deionized water to prepare a cobalt salt solution;
step three, preparing a Co-B solution:
adding the borohydride-hydroxide mixed solution in the step one into the metal cobalt salt solution in the step two at a slow speed under the stirring condition at the temperature of 0 ℃, and continuing stirring until the reaction is complete after no gas is generated in the reaction, so as to obtain a Co-B solution;
step four, preparing a nickel salt solution:
weighing nickel salt, and dissolving the nickel salt in deionized water to prepare a nickel salt solution;
step five, preparing borohydride-hydroxide again:
according to the molar ratio of nickel element to boron element of 1: (2-5) weighing borohydride according to the standard, dissolving the borohydride in deionized water to prepare borohydride solution, and then adding hydroxide into the borohydride solution until the pH value of the solution is 12-13 to obtain borohydride-hydroxide mixed solution;
step six, preparing a mixed solution:
simultaneously dropwise adding the nickel salt solution prepared in the fourth step and the borohydride-hydroxide solution prepared in the fifth step into the Co-B solution prepared in the third step, keeping the reaction temperature at 0 ℃, and continuously stirring until no gas is generated until the reaction is complete to obtain a Ni-Co-B mixed solution;
step seven, preparing the Ni-Co-B catalyst:
and (4) carrying out suction filtration on the mixed solution prepared in the step six, then washing to be neutral, and drying the obtained product in a vacuum drying oven at the temperature of 60-120 ℃ to obtain the honeycomb Ni-Co-B catalyst.
Further, the borohydride in the step one is potassium borohydride, and the concentration of the prepared potassium borohydride solution is 0.2 mol/L; step three: and (3) adding the borohydride-hydroxide mixed solution in the step one into the metal cobalt salt solution in the step two at the speed of 1-2 mL/min.
Further, the cobalt salt in the second step is cobalt chloride, and the molar ratio of the cobalt element to the potassium borohydride is 1: 3; the cobalt salt solution was 0.1 mol/L.
Further, in the fourth step, the nickel salt is nickel chloride; the concentration of the prepared nickel salt solution is 0.01-0.1 mol/L.
Further, the borohydride in the fifth step is potassium borohydride, and the molar ratio of the nickel element in the fourth step to the boron element in the fifth step is 1: 3; the molar ratio of the metal Ni to the metal Co in the sixth step is (0.01-1): 1.
further, the vacuum degree of the vacuum drying in the seventh step is 80 Pa-100 Pa, the temperature is 60 ℃ -120 ℃, and the drying time is 1 h-8 h.
A fuel cell uses the anode.
Compared with the prior art, the invention has the following effects:
1. the catalyst used in the electrode of the present invention has a structure of a three-dimensional sheet honeycomb structure, a graphene-like structure, and a grapheneCompared with a spherical structure, a core-shell structure or a hollow structure, the structure can provide a larger contact area of reactants, promote the diffusion of the reactants, improve the mass transfer rate and improve the catalytic performance of the catalyst. Ni-Co-B is DBFC anode catalyst of direct borohydride fuel cell, LaNi0.9Ru0.1O3The maximum power density of the fuel cell assembled by the cathode catalyst is measured to be 90.58mW cm-2。
2. The catalyst used by the electrode of the invention is composed of non-noble metals, thus avoiding the use of noble metals such as platinum and the like, and greatly reducing the cost of the fuel cell.
3. The catalyst used by the electrode is simple in preparation method and easy to operate, and is prepared by adopting a step-by-step reduction method, so that the prepared catalyst is uniform in appearance.
Drawings
FIG. 1 is a schematic view of the anode structure of a fuel cell according to the present invention;
FIG. 2 is a scanning electron microscope image of a Ni-Co-B catalyst prepared in example 2 of the present invention at 25000 times magnification;
FIG. 3 is a scanning electron microscope image of Ni-Co-B catalyst prepared in example 2 of the present invention at 240000 times magnification;
FIG. 4 is a graph comparing the performance of Ni-Co-B prepared in example 2 of the present invention and Au @ Co-B prepared in CN105702971B as anode of direct borohydride fuel cell.
Detailed Description
The technical solution of the present invention is further described in detail by the following examples.
Example 1
As shown in fig. 1, an electrode for a fuel cell includes a conductive wire 1, a nickel foam plate 1, and a catalyst layer 3, wherein the catalyst layer is coated on one side of the nickel foam plate, the conductive wire is located on the other side of the nickel foam plate, and the catalyst used in the catalyst layer has a honeycomb structure. The catalyst comprises metal Ni element, Co element and B element, wherein the molar ratio of Ni to Co is 0.01: 1, the molar ratio of Ni to B is 1: 3, the molar ratio of Co to B is 1: 3.
fuelThe battery comprises a cathode, a fiber membrane and the anode electrode of example 1, wherein the cathode comprises a cathode lead, a cathode plate and a cathode catalyst LaNi coated on the cathode plate0.9Ru0.1O3. The anode electrode comprises an anode lead, a foam nickel polar plate and a catalyst layer, the catalyst layer is coated on one side of the foam nickel polar plate, the lead is positioned on the other side of the foam nickel polar plate, and the catalyst used by the catalyst layer is of a honeycomb structure.
Several examples of the preparation of the catalyst of the present invention, and the fuel cell performance after the use of the catalyst, are listed below.
Example 2
The catalyst of the embodiment is nickel-cobalt-boron alloy with a honeycomb structure, and the preparation method adopts a step-by-step reduction method:
step one, dissolving 1.19g of cobalt chloride hexahydrate in 50ml of deionized water to prepare 0.1mol/L cobalt salt solution;
dissolving 0.81g of potassium borohydride in deionized water to prepare a potassium borohydride solution with the concentration of 0.2mol/L, and then adding a proper amount of potassium hydroxide solution into the potassium borohydride solution until the pH value is 12 to obtain a potassium borohydride-potassium hydroxide mixed solution;
step three, adding 75mL of 0.2mol/L potassium borohydride-potassium hydroxide solution into the cobalt chloride solution in the step one at the speed of 1mL/min under the vigorous stirring at 0 ℃, and continuing stirring for 1h after no gas is generated in the reaction until the reaction is complete;
step four, dissolving 0.71g of nickel chloride hexahydrate in 150ml of deionized water to prepare 0.02mol/L nickel salt solution;
dissolving 0.054g of potassium borohydride in deionized water to prepare 0.2mol/L potassium borohydride solution, adding a proper amount of potassium hydroxide, and adjusting the pH value to 12;
step six, dropwise adding the potassium borohydride-potassium hydroxide mixed solution prepared in the step five and the nickel chloride solution prepared in the step four into the precipitation solution completely reacted in the step three under the ice bath condition, and continuing stirring for 2 hours after no gas is generated until the reaction is complete;
and seventhly, repeatedly washing the precipitate obtained in the sixth step with deionized water, then washing with absolute ethyl alcohol for 2-3 times, and drying in vacuum at 80 ℃ and 80pa for 4 hours to obtain the Ni-Co-B catalyst with the honeycomb structure.
The product prepared in this example was physically characterized and FIG. 2 is an SEM scan of Ni-Co-B at low magnification. FIG. 3 is an SEM scan of Ni-Co-B at high magnification, from which it can be seen that Ni-Co-B synthesized according to example 1 is a honeycomb three-dimensional lamellar structure. FIG. 4 shows the Ni-Co-B prepared in this example as DBFC anode catalyst of direct borohydride fuel cell, LaNi0.9Ru0.1O3A fuel cell assembled for the cathode catalyst, the maximum power density of the fuel cell is measured to be 90.58mW cm-2(ii) a Under the same condition, compared with the cell performance of the direct borohydride fuel cell DBFC anode of the Chinese patent CN105702971B core-shell type catalyst (Au @ Co-B), the discharge performance of the cell is obviously improved by adopting the Ni-Co-B catalyst prepared by the embodiment.
Example 3
The catalyst of the embodiment is a nickel-cobalt-boron alloy with a honeycomb structure, and the preparation method adopts a step-by-step reduction method:
step one, dissolving 2.38g of cobalt chloride hexahydrate in 50ml of deionized water to prepare 0.2mol/L cobalt salt solution;
step two, dissolving 1.62g of potassium borohydride in deionized water to prepare a potassium borohydride solution with the concentration of 0.3mol/L, and then adding a proper amount of potassium hydroxide solution into the potassium borohydride solution until the pH value is 13 to obtain a potassium borohydride-potassium hydroxide mixed solution;
step three, adding 100mL of 0.3mol/L potassium borohydride-potassium hydroxide solution into the cobalt chloride solution in the step one at the speed of 2mL/min under the vigorous stirring at 0 ℃, and continuing stirring for 1h after no gas is generated in the reaction until the reaction is complete;
step four, dissolving 0.36g of nickel chloride hexahydrate in 150ml of deionized water to prepare 0.01mol/L nickel salt solution;
dissolving 0.243g of potassium borohydride in deionized water to prepare 0.3mol/L potassium borohydride solution, adding a proper amount of potassium hydroxide, and adjusting the pH value to 13;
step six, dropwise adding the potassium borohydride-potassium hydroxide mixed solution prepared in the step five and the nickel chloride solution prepared in the step four into the precipitation solution completely reacted in the step three under the ice bath condition, and continuing stirring for 2 hours after no gas is generated until the reaction is complete;
and seventhly, repeatedly washing the precipitate obtained in the sixth step with deionized water, then washing with absolute ethyl alcohol for 2-3 times, and drying in vacuum at 80 ℃ and 80pa for 4 hours to obtain the Ni-Co-B catalyst with the honeycomb structure.
The product prepared in this example was physically characterized, and the result was the same as example 1, and was a honeycomb three-dimensional lamellar structure. The Ni-Co-B prepared in this example is used as DBFC anode catalyst of direct borohydride fuel cell, LaNi0.9Ru0.1O3Assembling a fuel cell for the cathode catalyst, the maximum power density of the fuel cell being 88.45mW cm-2。
Example 4
The catalyst of the embodiment is a nickel-cobalt-boron alloy with a honeycomb structure, and the preparation method adopts a step-by-step reduction method:
step one, dissolving 3.81g of cobalt chloride hexahydrate in 100ml of deionized water to prepare 0.16mol/L cobalt salt solution;
dissolving 1.29g of potassium borohydride in deionized water to prepare a potassium borohydride solution with the concentration of 0.4mol/L, and then adding a proper amount of potassium hydroxide solution into the potassium borohydride solution until the pH value is 12 to obtain a potassium borohydride-potassium hydroxide mixed solution;
step three, adding 60mL of 0.4mol/L potassium borohydride-potassium hydroxide solution into the cobalt chloride solution in the step one at the speed of 1mL/min under the vigorous stirring at 0 ℃, and continuing stirring for 1h after no gas is generated in the reaction until the reaction is complete;
step four, dissolving 1.19g of nickel chloride hexahydrate in 100ml of deionized water to prepare 0.05mol/L nickel salt solution;
dissolving 0.81g of potassium borohydride in deionized water to prepare 0.3mol/L potassium borohydride solution, adding a proper amount of potassium hydroxide, and adjusting the pH value to 13;
step six, dropwise adding the potassium borohydride-potassium hydroxide mixed solution prepared in the step five and the nickel chloride solution prepared in the step four into the completely reacted precipitation solution in the step three under the ice bath condition, stirring vigorously, and continuing stirring for 2 hours after no gas is generated until the reaction is complete;
and seventhly, repeatedly washing the precipitate obtained in the sixth step with deionized water, then washing with absolute ethyl alcohol for 2-3 times, and drying in vacuum at 80 ℃ and 80pa for 5 hours to obtain the Ni-Co-B catalyst with the honeycomb structure.
The product prepared in this example was physically characterized, and the result was the same as example 1, and was a honeycomb three-dimensional lamellar structure. The Ni-Co-B prepared in this example is used as DBFC anode catalyst of direct borohydride fuel cell, LaNi0.9Ru0.1O3Assembling a fuel cell for the cathode catalyst, the fuel cell having a maximum power density of 91.08mW cm-2。
Example 5
The catalyst of the embodiment is a nickel-cobalt-boron alloy with a honeycomb structure, and the preparation method adopts a step-by-step reduction method:
firstly, 23.793g of cobalt chloride hexahydrate is dissolved in 100ml of deionized water to prepare 1mol/L cobalt salt solution;
step two, 10.788g of potassium borohydride is dissolved in deionized water to prepare a potassium borohydride solution with the concentration of 1mol/L, and then a proper amount of potassium hydroxide solution is added into the potassium borohydride solution until the pH value is 13, so that a potassium borohydride-potassium hydroxide mixed solution is obtained;
step three, adding 200mL of 1mol/L potassium borohydride-potassium hydroxide solution into the cobalt chloride solution in the step one at the speed of 2mL/min under the condition of vigorous stirring at 0 ℃, and continuing stirring for 1h after no gas is generated in the reaction until the reaction is complete;
step four, 23.769g of nickel chloride hexahydrate is dissolved in 100ml of deionized water to prepare 1mol/L of nickel salt solution;
dissolving 5.394g of potassium borohydride in deionized water to prepare 1mol/L potassium borohydride solution, adding a proper amount of potassium hydroxide, and adjusting the pH value to 13;
step six, dropwise adding the potassium borohydride-potassium hydroxide mixed solution prepared in the step five and the nickel chloride solution prepared in the step four into the completely reacted precipitation solution in the step three under the ice bath condition, stirring vigorously, and continuing stirring for 2 hours after no gas is generated until the reaction is complete;
and seventhly, repeatedly washing the precipitate obtained in the sixth step with deionized water, then washing with absolute ethyl alcohol for 2-3 times, and drying in vacuum at 60 ℃ and 80pa for 6 hours to obtain the Ni-Co-B catalyst with the honeycomb structure.
The product prepared in this example was physically characterized, and the result was the same as example 1, and was a honeycomb three-dimensional lamellar structure. The Ni-Co-B prepared in this example is used as DBFC anode catalyst of direct borohydride fuel cell, LaNi0.9Ru0.1O3Assembling a fuel cell for the cathode catalyst, the maximum power density of the fuel cell being 82.37mW cm-2。
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalent changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (6)

1. A fuel cell anode comprises a lead, a foamed nickel polar plate and a catalyst layer, wherein the catalyst layer is coated on one side of the foamed nickel polar plate, the lead is connected with the foamed nickel polar plate, and the catalyst used by the catalyst layer is of a honeycomb structure;
the method is characterized in that the catalyst is prepared by the following method:
step one, preparing a borohydride-hydroxide mixed solution:
weighing borohydride, dissolving the borohydride in deionized water to prepare a borohydride solution, and then adding hydroxide into the borohydride solution until the pH value of the solution is 12-13 to obtain a borohydride-hydroxide mixed solution;
the borohydride is potassium borohydride, and the hydroxide is potassium hydroxide;
step two, preparing a cobalt salt solution: according to the molar ratio of cobalt element to boron element of 1: weighing cobalt salt according to the standard of (2-5), and dissolving the cobalt salt in deionized water to prepare a cobalt salt solution;
step three, preparing a Co-B solution:
under the stirring condition at the temperature of 0 ℃, adding the borohydride-hydroxide mixed solution in the step one into the cobalt salt solution in the step two at the speed of 1-2 mL/min, and continuing stirring until the reaction is complete after no gas is generated, so as to obtain a Co-B solution;
step four, preparing a nickel salt solution:
weighing nickel salt, and dissolving the nickel salt in deionized water to prepare a nickel salt solution;
step five, preparing borohydride-hydroxide again:
according to the molar ratio of nickel element to boron element of 1: (2-5) weighing borohydride according to the standard, dissolving the borohydride in deionized water to prepare borohydride solution, and then adding hydroxide into the borohydride solution until the pH value of the solution is 12-13 to obtain borohydride-hydroxide mixed solution;
step six, preparing a mixed solution:
simultaneously dropwise adding the nickel salt solution prepared in the fourth step and the borohydride-hydroxide solution prepared in the fifth step into the Co-B solution prepared in the third step, keeping the reaction temperature at 0 ℃, and continuously stirring until no gas is generated until the reaction is complete to obtain a Ni-Co-B mixed solution;
step seven, preparing the Ni-Co-B catalyst:
and (4) carrying out suction filtration on the mixed solution prepared in the step six, then washing to be neutral, and drying the obtained product in a vacuum drying oven at the temperature of 60-120 ℃ to obtain the honeycomb Ni-Co-B catalyst.
2. The fuel cell anode of claim 1, wherein the borohydride compound in the first step is potassium borohydride, and the concentration of the prepared potassium borohydride solution is 0.2 mol/L.
3. The fuel cell anode of claim 2, wherein the cobalt salt in step two is cobalt chloride, and the molar ratio of cobalt element to potassium borohydride is 1: 3; the cobalt salt solution was 0.1 mol/L.
4. The fuel cell anode according to claim 1, 2 or 3, wherein the nickel salt in step four is nickel chloride; the concentration of the prepared nickel salt solution is 0.01-0.1 mol/L.
5. The anode according to claim 4, wherein the borohydride in the fifth step is potassium borohydride, and the molar ratio of the nickel element in the fourth step to the boron element in the fifth step is 1: 3; the molar ratio of the metal Ni to the metal Co in the sixth step is (0.01-1): 1.
6. the fuel cell anode according to claim 5, wherein the vacuum degree of the vacuum drying in the seventh step is 80Pa to 100Pa, the temperature is 60 ℃ to 120 ℃, and the drying time is 1h to 8 h.
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