CN108832141B - Honeycomb structure nickel-cobalt-boron alloy catalyst for fuel cell and preparation method thereof - Google Patents

Honeycomb structure nickel-cobalt-boron alloy catalyst for fuel cell and preparation method thereof Download PDF

Info

Publication number
CN108832141B
CN108832141B CN201810643543.3A CN201810643543A CN108832141B CN 108832141 B CN108832141 B CN 108832141B CN 201810643543 A CN201810643543 A CN 201810643543A CN 108832141 B CN108832141 B CN 108832141B
Authority
CN
China
Prior art keywords
borohydride
solution
preparing
fuel cell
cobalt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810643543.3A
Other languages
Chinese (zh)
Other versions
CN108832141A (en
Inventor
李赛
王丽娜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian University of Science and Technology
Original Assignee
Xian University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian University of Science and Technology filed Critical Xian University of Science and Technology
Priority to CN201810643543.3A priority Critical patent/CN108832141B/en
Publication of CN108832141A publication Critical patent/CN108832141A/en
Application granted granted Critical
Publication of CN108832141B publication Critical patent/CN108832141B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a honeycomb structure nickel-cobalt-boron alloy catalyst for a fuel cell and a preparation method thereof, wherein the preparation method of the catalyst comprises the following steps: step one, preparing a borohydride-hydroxide mixed solution; step two, preparing a cobalt salt solution; step three, preparing a Co-B solution; step four, preparing a nickel salt solution; step five, preparing borohydride-hydroxide again; step six, preparing a mixed solution; and seventhly, performing suction filtration on the mixed solution prepared in the sixth step, 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-shaped Ni-Co-B catalyst. The invention solves the technical problems of low catalytic performance and high cost of most of the existing fuel cell catalysts in a core-shell structure, and the preparation method is simple and easy to operate, and the prepared catalyst is prepared by adopting a step-by-step reduction method and has uniform appearance.

Description

Honeycomb structure nickel-cobalt-boron alloy catalyst for fuel cell and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts for fuel cells, and particularly relates to a nickel-cobalt-boron alloy catalyst with a lamellar and three-dimensional honeycomb structure for the fuel cells.
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, where reducing the precious metal content in the electrode assembly can directly improve the cost-effectiveness of the cell, but also affects the performance and long-term stability of the cell, currently, the cost of electrode catalysts is mainly reduced by (1) preparing platinum alloy to reduce the platinum content, chinese patent CN 102820475 a describes a platinum alloy catalyst PtXNb, where X is nickel, cobalt, chromium, copper, titanium or manganese, characterized by an atomic percentage of platinum of 46 to 75 at%, which has excellent oxygen reduction catalytic activity for use as fuel cells, particularly for phosphoric acid fuel cell cathodes, the process is harsh, such as: annealing treatment at high temperature 1000-1200 ℃ and in an inert atmosphere is required. CN 101083325A introduces a method for preparing 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 101667644 a describes a preparation method of a high-performance low-platinum catalyst, which covers a small amount of Pt or Pt, Ru on the surface of Pd alloy through 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 has good catalytic performance, but still uses precious metal Pt, 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 Chinese patent CN105702971B greatly reduces the consumption of noble metal, the cost of the fuel cell is obviously reduced; but due to the core-shell structure, the contact area of reactants is small, and the catalytic performance is not high.
Disclosure of Invention
The invention provides a nickel-cobalt-boron alloy catalyst with a honeycomb structure for a fuel cell and a preparation method thereof, aiming at solving the technical problems of low catalytic performance and high cost of most of the existing fuel cell catalysts with a core-shell structure. The catalyst structure is a honeycomb structure, has a large contact area with reactants, and can greatly improve the catalytic performance. Meanwhile, the catalyst has low preparation cost and simple preparation process.
The technical scheme adopted by the invention is as follows:
a preparation method of a Ni-Co-B alloy catalyst with a honeycomb structure for a fuel cell is characterized by comprising the following steps:
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.
further, 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 honeycomb structure Ni-Co-B alloy catalyst for fuel cells is characterized by comprising metallic Ni elements, Co elements and B elements, wherein 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).
Furthermore, 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 honeycomb-shaped.
Compared with the prior art, the invention has the following effects:
1. the catalyst structure 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. Ni-Co-B as direct borohydrideFuel cell DBFC anode catalyst, 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 of the invention has non-noble metal components, avoids the use of noble metals such as platinum and the like, and greatly reduces the cost of the fuel cell.
3. The preparation method is simple and easy to operate, the catalyst is prepared by adopting a step-by-step reduction method, and the prepared catalyst has uniform appearance.
Drawings
FIG. 1 is a scanning electron microscope image of a Ni-Co-B catalyst prepared in example 1 of the present invention at 25000 times magnification;
FIG. 2 is a scanning electron microscope image of Ni-Co-B catalyst prepared in example 1 of the present invention at 240000 times magnification;
FIG. 3 is a graph comparing the power performance of the Ni-Co-B catalyst prepared in example 1 of the present invention as an anode of a direct borohydride fuel cell with the cell performance of the Au @ Co-B catalyst prepared in Chinese patent CN105702971B as an anode of a direct borohydride fuel cell.
Detailed Description
The technical solution of the present invention is further described in detail by the following examples.
Example 1
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. 1 is an SEM scan of Ni-Co-B at low magnification. FIG. 2 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. 3 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 Compared with the battery performance of the core-shell catalyst (Au @ Co-B) in the Chinese patent CN105702971B as the anode catalyst under the same condition, the Ni-Co-B catalyst prepared by the embodiment has obviously improved battery discharge performance.
Example 2
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 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 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 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:
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 (7)

1. A preparation method of a Ni-Co-B alloy catalyst with a honeycomb structure for a fuel cell is characterized by comprising the following steps:
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 method for preparing a Ni-Co-B alloy catalyst with a honeycomb structure for a fuel cell according to claim 1, wherein the borohydride in the step one is potassium borohydride, and the concentration of the prepared potassium borohydride solution is 0.2 mol/L.
3. The method for preparing a Ni-Co-B alloy catalyst having a honeycomb structure for a fuel cell according to claim 1, wherein the cobalt salt in the second step is cobalt chloride, and a molar ratio of cobalt element to potassium borohydride is 1: 3; the cobalt salt solution was 0.1 mol/L.
4. The method of producing a Ni-Co-B alloy catalyst having a honeycomb structure for a fuel cell according to claim 1, 2 or 3, wherein the nickel salt in the fourth step is nickel chloride; the concentration of the prepared nickel salt solution is 0.01-0.1 mol/L.
5. The method for preparing a Ni-Co-B alloy catalyst having a honeycomb structure for a fuel cell according to claim 4, wherein the boron hydride 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.
6. the method for preparing a Ni-Co-B alloy catalyst having a honeycomb structure for a fuel cell according to claim 5, wherein the molar ratio of metal Ni to Co in the sixth step is (0.01 to 1): 1.
7. the method for preparing a Ni-Co-B alloy catalyst with a honeycomb structure for a fuel cell according to claim 6, 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.
CN201810643543.3A 2018-06-21 2018-06-21 Honeycomb structure nickel-cobalt-boron alloy catalyst for fuel cell and preparation method thereof Active CN108832141B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810643543.3A CN108832141B (en) 2018-06-21 2018-06-21 Honeycomb structure nickel-cobalt-boron alloy catalyst for fuel cell and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810643543.3A CN108832141B (en) 2018-06-21 2018-06-21 Honeycomb structure nickel-cobalt-boron alloy catalyst for fuel cell and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108832141A CN108832141A (en) 2018-11-16
CN108832141B true CN108832141B (en) 2020-09-22

Family

ID=64141898

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810643543.3A Active CN108832141B (en) 2018-06-21 2018-06-21 Honeycomb structure nickel-cobalt-boron alloy catalyst for fuel cell and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108832141B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109994744B (en) * 2019-01-31 2021-09-07 重庆大学 Nickel-cobalt binary catalyst for promoting direct oxidation of sodium borohydride
CN112499641B (en) * 2020-12-09 2022-03-11 浙江帕瓦新能源股份有限公司 Boron-doped precursor material with core-shell structure, positive electrode material and preparation method
CN113774217A (en) * 2021-08-19 2021-12-10 南方科技大学 Method for synchronously recovering multiple metal ions in electronic product leaching solution

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103877979B (en) * 2014-03-05 2016-05-18 上海师范大学 A kind of nickel cobalt boron amorphous alloy nano-sphere catalyst with hollow structure and its preparation method and application
CN105521804B (en) * 2015-12-08 2018-07-31 广东石油化工学院 A kind of preparation method of cellular graphene/carbon tungsten/platinum composite electrocatalyst and application

Also Published As

Publication number Publication date
CN108832141A (en) 2018-11-16

Similar Documents

Publication Publication Date Title
CN109378482B (en) Non-noble metal catalytic material loaded core-shell catalyst, preparation method and application thereof
CN101455970B (en) Preparation method of carbon supported core-shell Ni-Pt particles for direct methanol fuel cells
EP1799342B1 (en) Platinum/ruthenium catalyst for direct methanol fuel cells
CN108832141B (en) Honeycomb structure nickel-cobalt-boron alloy catalyst for fuel cell and preparation method thereof
CN111672514A (en) Bifunctional electrocatalytic material and preparation method and application thereof
JP4994605B2 (en) Membrane-electrode assembly for fuel cell and fuel cell system including the same
CN109759066B (en) Preparation method of boron-doped graphene-loaded cobalt-nickel bimetallic oxide oxygen evolution catalyst
CN111224113A (en) Ni-N4 monoatomic catalyst anchored by multistage carbon nanostructure and preparation method and application thereof
CN113224334A (en) Preparation method of platinum-containing high-entropy alloy/MXene composite catalyst
WO2024093285A1 (en) Electrocatalytic water oxidation homogeneous diatomic catalyst, and preparation method therefor and use thereof
CN111883785B (en) Co-N Co-doped drum-shaped porous carbon catalyst and preparation method and application thereof
CN109755600A (en) The application of carbon cloth nickel-loaded cobalt oxide nano-sheet composite material and preparation method and electrode
CN114744224B (en) Preparation and application of nitrogen-doped carbon nanotube-loaded nickel-cobalt composite nanowire
CN112626550B (en) Method for directly preparing porous nickel sulfide nanosheet electrocatalyst by one-step hydrothermal method
CN117107286A (en) Batch preparation method of NiFe-based composite oxygen evolution anode
CN108598494B (en) Fuel cell anode and fuel cell using same
CN115161691A (en) Oxygen evolution catalyst of FeCoNiMg high-entropy amorphous alloy powder and preparation method thereof
CN113774425B (en) Preparation method and application of Ru-modified FeCo @ NF electrocatalyst
CN110783580B (en) Preparation method of alkaline system fuel cell anode catalyst
US9147886B2 (en) Electrode catalyst for fuel cell, method of preparing the same, membrane electrode assembly, and fuel cell including the same
CN117174920A (en) Preparation method and application of heterostructure ruthenium cobalt boron-based oxide catalyst
CN117374304A (en) Preparation method of platinum-based ordered alloy catalyst
Pérez García et al. Rhodium-based cathodes with ultra-low metal loading to increase the sustainability in the hydrogen evolution reaction
CN114628700A (en) Preparation method of platinum-nickel-gold alloy nano catalyst
CN115404515A (en) Carbon-loaded ruthenium-manganese compound, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant