Preparation method of Ni-Co-P alkaline water electrolysis hydrogen production catalyst

Abstract

The invention discloses a preparation method of a Ni-Co-P alkaline water electrolysis hydrogen production catalyst. The preparation method comprises the steps of nickel net pretreatment, catalyst formation through electro-deposition, calcination and the like. Through the mode, according to the preparation method of the Ni-Co-P alkaline electrolytic water hydrogen production catalyst, a nickel pre-plating method is adopted, the complexing agent and the surfactant are added into the plating solution, meanwhile, the components such as the complexing agent and the use amount are optimized, the phenomena of cracks and pinholes on the surface of the catalyst are avoided, and subsequent calcination phosphating treatment is matched, so that the surface of the catalyst is more stable. The hydrogen production performance of the Ni-Co-P alkaline electrolysis water hydrogen production catalyst is improved, the mechanical performance is excellent, and the preparation process is simple.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogen production by water electrolysis, and in particular to a method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst. Background Art

[0002] Hydrogen energy is considered as a strong candidate to replace traditional fossil fuels in the future due to its clean, renewable and high energy density. Water electrolysis is an important method for hydrogen production, and its efficiency depends on efficient catalysts.

[0003] At present, precious metals such as platinum (Pt) and ruthenium dioxide (RuO2) perform well in hydrogen and oxygen evolution, but their scarce reserves and high prices greatly limit their large-scale use in industry. Therefore, it is particularly important to develop efficient non-precious metal hydrogen evolution catalysts. Transition metal phosphides have attracted widespread attention due to their abundant raw material reserves, low cost and good catalytic hydrogen evolution performance. However, these materials generally have poor stability, complex preparation processes for some materials and high synthesis costs. Therefore, the development of efficient, cheap and stable nickel-cobalt-phosphorus hydrogen evolution electrocatalysts is of great practical significance for the industrial development in this field. Summary of the invention

[0004] In order to solve the above technical problems, a technical solution adopted by the present invention is: Provided is a method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst, the steps comprising: Step S1, performing sandblasting, polishing and cleaning pretreatment on the nickel mesh; Step S2, adding nickel salt, cobalt salt, hypophosphite ion, complexing agent and surfactant into deionized water and ultrasonicating until they are completely dissolved to obtain a plating solution, so that the concentration of each ion in the plating solution is respectively 0.036-0.048 mol / L for nickel ion, 0.024-0.03 mol / L for cobalt ion, 0.03-0.042 mol / L for hypophosphite ion, 100-140 g / L for complexing agent and 0.1-0.5 g / L for surfactant; Step S3, using the nickel mesh pretreated in step S1 as a cathode and placing it in a plating solution for electrodeposition to generate a Ni-Co-P catalyst crude product on the surface of the nickel mesh; Step S4: The Ni—Co—P catalyst crude product obtained in step S3 is washed, dried, and then placed in a muffle furnace for calcination to form a Ni—Co—P alkaline water electrolysis hydrogen evolution catalyst on the surface of the nickel mesh.

[0005] In a preferred embodiment of the present invention, in step S1, a sandblasting machine is used to grind the surface of the woven nickel mesh.

[0006] In a preferred embodiment of the present invention, in the cleaning pretreatment step S1, deionized water, anhydrous ethanol and deionized water are used to clean the oil and impurities on the surface of the nickel mesh respectively.

[0007] In a preferred embodiment of the present invention, in step S2, the nickel salt is preferably nickel sulfate, and the cobalt salt is preferably cobalt sulfate.

[0008] In a preferred embodiment of the present invention, in step S2, the source of hypophosphite ions is sodium hypophosphite.

[0009] In a preferred embodiment of the present invention, in step S2, the complexing agent is preferably 100-140 g / L of sodium citrate.

[0010] In a preferred embodiment of the present invention, in step S2, the surfactant is preferably 0.1-0.5 g / L sodium dodecyl sulfate, and in step S2, the deposition current density is 0.1-0.5 Acm -2 , the electrodeposition time is 1000~3600s.

[0011] In a preferred embodiment of the present invention, in step S2, a dual-electrode system is used for electrodeposition, the cathode is a pure nickel mesh that has been polished and cleaned, and the anode is a pure nickel mesh that has not been polished but has been cleaned.

[0012] In a preferred embodiment of the present invention, in step S3, the calcination temperature is 200-400°C, and the treatment is carried out at this temperature for 3-4 hours, and then the temperature is naturally cooled to room temperature.

[0013] A Ni-Co-P alkaline water electrolysis hydrogen production catalyst is prepared by any of the above methods.

[0014] The beneficial effects of the present invention are: a pre-nickel plating method is adopted, and a complexing agent and a surfactant are added to the plating solution, and at the same time, the components and dosage of the complexing agent are optimized, so as to solve the crack and pinhole phenomena on the catalyst surface, and then cooperate with subsequent calcination and phosphating treatment to improve the hydrogen production performance of the Ni-Co-P alkaline water electrolysis hydrogen production catalyst, and the mechanical properties are excellent and the preparation process is simple. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work, among which: Figure 1 It is a schematic diagram of the structure of a pretreated nickel mesh according to a preferred embodiment of a method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst of the present invention; Figure 2 It is a schematic diagram of the structure of the nickel mesh with Ni-Co-P catalyst in the present invention; Figure 3 is a comparison diagram of the HER performance curves of Example 1 of the present invention and the nickel mesh; Figure 4 is a comparison diagram of the HER performance curves of Example 2 of the present invention and the nickel mesh; Figure 5 is a comparison diagram of the HER performance curves of Example 3 of the present invention and the nickel mesh; Figure 6 It is a comparison diagram of the HER performance curves of Example 4 of the present invention and the nickel mesh. DETAILED DESCRIPTION

[0016] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] See also Figure 1-6 , the embodiment of the present invention includes: A method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst, the steps comprising: Step S1, performing sandblasting, polishing and cleaning pretreatment on the nickel mesh.

[0018] Further preferably, a sandblaster is used to grind the surface of the woven nickel mesh, and the grinding dust is cleaned and removed.

[0019] Further preferably, the cleaning pretreatment process is to use deionized water, anhydrous ethanol and deionized water to clean the oil and impurities on the surface of the nickel mesh respectively.

[0020] Step S2, adding nickel salt, cobalt salt, hypophosphite ion, complexing agent and surfactant into deionized water and ultrasonicating until they are completely dissolved to obtain a plating solution, so that the concentration of each ion in the plating solution is respectively 0.036-0.048 mol / L for nickel ion, 0.024-0.03 mol / L for cobalt ion, 0.03-0.042 mol / L for hypophosphite ion, 100-140 g / L for complexing agent and 0.1-0.5 g / L for surfactant.

[0021] Step S3, using the nickel mesh pretreated in step S1 as a cathode and placing it in a plating solution for electrodeposition to generate a Ni-Co-P catalyst crude product on the surface of the nickel mesh.

[0022] More preferably, the nickel salt is nickel sulfate, the cobalt salt is cobalt sulfate, the source of hypophosphite ions is sodium hypophosphite, and the molar ratio of nickel, cobalt and phosphorus is preferably 6-8:4-5:5-7.

[0023] More preferably, the complexing agent is preferably 100 to 140 g / L of sodium citrate, and the surfactant is preferably 0.1 to 0.5 g / L of sodium dodecyl sulfate.

[0024] Preferably, the electrodeposition is carried out by constant current method in an electrochemical workstation, and the deposition current density is preferably set to 0.1-0.5 Acm -2 , the electrodeposition time is 1000~3600s.

[0025] More preferably, a dual-electrode system is used for electrodeposition, the cathode is a pure nickel mesh that has been polished and pre-treated by cleaning, and the anode is a pure nickel mesh that has not been polished but pre-treated by cleaning.

[0026] Step S4, washing the crude Ni-Co-P catalyst product obtained in step S3, drying it, and then placing it in a muffle furnace for calcination to form a Ni-Co-P alkaline water electrolysis hydrogen evolution catalyst on the surface of the cathode nickel mesh.

[0027] More preferably, the crude product can be washed with deionized water and ethanol.

[0028] More preferably, the calcination temperature is 200-400° C., and the treatment is carried out at this temperature for 3-4 hours, and then the temperature is naturally cooled to room temperature.

[0029] The Ni-Co-P alkaline water electrolysis hydrogen evolution catalyst prepared by the above method has no cracks or pinholes, so that the nickel mesh with the Ni-Co-P catalyst can be used in the field of alkaline water electrolysis hydrogen production as an electrode for water electrolysis hydrogen production. Example

[0030] First, the surface of the woven nickel mesh was polished with 80 mesh white corundum, and then the oil and impurities on the surface of the nickel mesh were cleaned with deionized water, anhydrous ethanol, and deionized water to complete the pretreatment. NiSO4·7H2O, CoSO4·7H2O, NaH2PO2, C6H5Na3O7·2H2O and C 12 H 25 SO4Na and ultrasonically dissolve it completely to obtain a plating solution, so that the concentrations of the components in the plating solution are as follows: NiSO4·7H2O is 127g / L, CoSO4·7H2O is 127g / L, NaH2PO2 is 56g / L, C6H5Na3O7·2H2O is 140g / L, and C 12 H 25SO4Na is 0.1g / L. A dual-electrode system was used for electrodeposition, with the cathode being a polished and pretreated pure nickel mesh and the anode being an unpolished pure nickel mesh pretreated with deionized water, anhydrous ethanol, and deionized water. The constant current method in the electrochemical workstation was used for electrodeposition, and the current density was set to 0.1Acm -2 , the electrodeposition time is 3600s. After the electrodeposition is completed, the catalyst is left to stand in the plating solution for about 5 minutes, and then taken out, rinsed with deionized water and anhydrous ethanol respectively, and dried with a hair dryer. Example

[0031] First, the surface of the woven nickel mesh was polished with 80 mesh white corundum, and then the oil and impurities on the surface of the nickel mesh were cleaned with deionized water, anhydrous ethanol, and deionized water to complete the pretreatment. NiSO4•7H2O, CoSO4•7H2O, NaH2PO2, C6H5Na3O7•2H2O and C 12 H 25 SO4Na and ultrasonically dissolve it completely to obtain a plating solution. The concentrations of the components in the plating solution are as follows: NiSO4•7H2O is 127g / L, CoSO4•7H2O is 127g / L, NaH2PO2 is 56g / L, C6H5Na3O7•2H2O is 140g / L, and C 12 H 25 SO4Na is 0.1g / L. A dual-electrode system was used for electrodeposition, with the cathode being a polished and pretreated pure nickel mesh and the anode being an unpolished pure nickel mesh pretreated with deionized water, anhydrous ethanol, and deionized water. The constant current method in the electrochemical workstation was used for electrodeposition, and the current density was set to 0.5Acm -2 , the electrodeposition time is 1200s. After the electrodeposition is completed, the catalyst is left to stand in the plating solution for about 5 minutes, and then taken out, rinsed with deionized water and anhydrous ethanol respectively, and dried with a hair dryer. Example

[0032] First, the surface of the woven nickel mesh was polished with 80 mesh white corundum, and then the oil and impurities on the surface of the nickel mesh were cleaned with deionized water, anhydrous ethanol, and deionized water to complete the pretreatment. NiSO4•7H2O, CoSO4•7H2O, NaH2PO2, C6H5Na3O7•2H2O and C 12 H 25 SO4Na and ultrasonically dissolve it completely to obtain a plating solution. The concentrations of the components in the plating solution are as follows: NiSO4•7H2O is 127g / L, CoSO4•7H2O is 127g / L, NaH2PO2 is 56g / L, C6H5Na3O7•2H2O is 140g / L, and C 12 H 25SO4Na is 0.1g / L. A dual-electrode system was used for electrodeposition, with the cathode being a polished and pretreated pure nickel mesh and the anode being an unpolished pure nickel mesh pretreated with deionized water, anhydrous ethanol, and deionized water. The constant current method in the electrochemical workstation was used for electrodeposition, and the current density was set to 0.1Acm -2 , the electrodeposition time is 3600s. After the electrodeposition is completed, the catalyst is left to stand in the plating solution for about 5 minutes, and then taken out, rinsed with deionized water and anhydrous ethanol respectively, and blown dry with a hair dryer. Then the dried catalyst is placed in a muffle furnace for calcination, the heating temperature is set to 300℃, and the calcination time is 3 hours. Example

[0033] First, the surface of the woven nickel mesh was polished with 80 mesh white corundum, and then the oil and impurities on the surface of the nickel mesh were cleaned with deionized water, anhydrous ethanol, and deionized water to complete the pretreatment. NiSO4•7H2O, CoSO4•7H2O, NaH2PO2, C6H5Na3O7•2H2O and C 12 H 25 SO4Na and ultrasonically dissolve it completely to obtain a plating solution. The concentrations of the components in the plating solution are as follows: NiSO4•7H2O is 127g / L, CoSO4•7H2O is 127g / L, NaH2PO2 is 56g / L, C6H5Na3O7•2H2O is 140g / L, and C 12 H 25 SO4Na is 0.1g / L. A dual-electrode system was used for electrodeposition, with the cathode being a polished and pretreated pure nickel mesh and the anode being an unpolished pure nickel mesh pretreated with deionized water, anhydrous ethanol, and deionized water. The constant current method in the electrochemical workstation was used for electrodeposition, and the current density was set to 0.1Acm -2 , the electrodeposition time is 3600s. After the electrodeposition is completed, the catalyst is left to stand in the plating solution for about 5 minutes, and then taken out, rinsed with deionized water and anhydrous ethanol respectively, and blown dry with a hair dryer. Then the dried catalyst is placed in a muffle furnace for calcination, the heating temperature is set to 400℃, and the calcination time is 2 hours.

[0034] See also Figure 3-6 The performance of the Ni-Co-P catalyst prepared in the present application has been effectively improved. When conducting alkaline water electrolysis tests, it has good alkaline water electrolysis hydrogen production performance and excellent stability at high current density.

[0035] The beneficial effects of the preparation method of a Ni-Co-P alkaline water electrolysis hydrogen production catalyst of the present invention are: 1. The nickel pre-plating method is adopted, and a complexing agent and a surfactant are added to the plating solution. At the same time, the components and dosage of the complexing agent are optimized to solve the cracks and pinholes on the catalyst surface. Combined with the subsequent calcination and phosphating treatment, the hydrogen production performance of the Ni-Co-P alkaline water electrolysis hydrogen production catalyst is improved, and the mechanical properties are excellent; 2. The preparation process is simple, the preparation conditions are controllable, it has good application prospects, and is easy to promote and apply in the market.

[0036] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst, characterized in that the steps include: Step S1, performing sandblasting, polishing and cleaning pretreatment on the nickel mesh; Step S2, adding nickel salt, cobalt salt, hypophosphite ion, complexing agent and surfactant into deionized water and ultrasonicating until they are completely dissolved to obtain a plating solution, so that the concentration of each ion in the plating solution is respectively 0.036-0.048 mol / L for nickel ion, 0.024-0.03 mol / L for cobalt ion, 0.03-0.042 mol / L for hypophosphite ion, 100-140 g / L for complexing agent and 0.1-0.5 g / L for surfactant; Step S3, using the nickel mesh pretreated in step S1 as a cathode and placing it in a plating solution for electrodeposition to generate a Ni-Co-P catalyst crude product on the surface of the nickel mesh; Step S4: The Ni—Co—P catalyst crude product obtained in step S3 is washed, dried, and then placed in a muffle furnace for calcination to form a Ni—Co—P alkaline water electrolysis hydrogen evolution catalyst on the surface of the nickel mesh.

2. The method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst according to claim 1, characterized in that: In step S1, a sandblasting machine is used to grind the surface of the woven nickel mesh.

3. The method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst according to claim 1, characterized in that: In the cleaning pretreatment step S1, deionized water, anhydrous ethanol and deionized water are used to clean the oil and impurities on the surface of the nickel mesh respectively.

4. The method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst according to claim 1, characterized in that: In step S2, the nickel salt is preferably nickel sulfate, and the cobalt salt is preferably cobalt sulfate.

5. The method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst according to claim 1, characterized in that: In step S2, the source of hypophosphite ions is sodium hypophosphite.

6. The method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst according to claim 1, characterized in that: In step S2, the complexing agent is preferably 100-140 g / L of sodium citrate, and in step S2, the surfactant is preferably 0.1-0.5 g / L of sodium dodecyl sulfate.

7. The method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst according to claim 1, characterized in that: In step S2, the deposition current density is 0.1-0.5Acm -2 , the electrodeposition time is 1000~3600s.

8. The method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst according to claim 1, characterized in that: In step S2, a dual-electrode system is used for electrodeposition, wherein the cathode is a pure nickel mesh that has been polished and cleaned, and the anode is a pure nickel mesh that has not been polished but has been cleaned.

9. The method for preparing a Ni-Co-P alkaline water electrolysis hydrogen production catalyst according to claim 1, characterized in that: In step S3, the calcination temperature is 200-400°C, and the treatment is carried out at this temperature for 3-4 hours, and then the temperature is naturally lowered to room temperature.

10. A Ni-Co-P alkaline water electrolysis hydrogen production catalyst, characterized in that: Prepared by any of the methods of claims 1 to 9.

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