CN115125568A - Large-area nickel-based electrocatalyst film and preparation method and application thereof - Google Patents
Large-area nickel-based electrocatalyst film and preparation method and application thereof Download PDFInfo
- Publication number
- CN115125568A CN115125568A CN202110323172.2A CN202110323172A CN115125568A CN 115125568 A CN115125568 A CN 115125568A CN 202110323172 A CN202110323172 A CN 202110323172A CN 115125568 A CN115125568 A CN 115125568A
- Authority
- CN
- China
- Prior art keywords
- substrate
- nickel
- precursor solution
- area
- based electrocatalyst
- 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.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 68
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 239000002243 precursor Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000000889 atomisation Methods 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 17
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 85
- 239000010408 film Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 16
- 239000010409 thin film Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 description 36
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 16
- 230000009471 action Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- -1 metal cations Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1258—Spray pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a large-area nickel-based electrocatalyst film and a preparation method and application thereof. The preparation method comprises the following steps: the ultrasonic atomization is carried out in a mode of 0.1-2 mL/cm 2 Min, applying a precursor solution containing a nickel salt to the surface of the substrate, and then pyrolyzing at 260-400 ℃ to form a large-area nickel-based electrocatalyst film; wherein, the process conditions adopted by the ultrasonic atomization comprise: the ultrasonic power of the ultrasonic atomization device is 80-120 kHz, and the total amount of the precursor solution containing the nickel salt applied to the surface of the substrate is 5-20 mL/cm 2 . The large-area nickel-based electrocatalyst film prepared by the method has the advantages of larger electrode current density, larger electrode area, low material cost and strong stability, only contains one precursor substance, and compared with other preparation methods, the prepared large-area nickel-based electrocatalyst film prepared by the method has the advantages of higher electrode current density, higher electrode area, low material cost and strong stabilityThe process is simpler and more convenient, is easy to be amplified to actual commercial production, and has large-scale marketization prospect.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to a large-area nickel-based electrocatalyst film as well as a preparation method and application thereof.
Background
Non-renewable fossil energy resources have entered a stage where it is difficult to meet future development expectations of humans. At present, the search for alternative energy sources with abundant reserves and clean energy is urgent. Among them, hydrogen energy is considered as one of the most advantageous energy sources. Generally, the main way to obtain hydrogen energy is to carry out the hydrogen production by decomposing water by photocatalysis or electrocatalysis or the photoelectrocatalysis of the combination of the photocatalysis and the electrocatalysis. Among them, Oxygen Evolution Reaction (OER) has been attracting much attention as a half reaction for electrocatalytic decomposition of water. The most important problem is slow reaction kinetics. Compared with the traditional noble metal water hydrolysis electrocatalysts of Pt, Rh and Ir and the noble metal oxide IrO 2 And RuO 2 Compared with the prior art, the metal nickel element has the advantages of rich reserves, low cost and various raw material sources, and is considered to be the material of the electrocatalyst with faster OER dynamics. Studies have shown that multilevel or porous nanostructures can expose more active sites and accelerate charge transfer, which can reduce charge transfer resistance. In the prior art, most of the methods through chemical change require multiple steps and long-time heat treatment to complete the process, more solutions are needed, the area cannot be large, the condition of non-uniformity appears after the solution is large, the performance cannot be met, and the thickness is difficult to increase after a certain stage. The requirement on the substrate is high, the process can be carried out under a certain substrate condition, and the universality is not strong enough.
Disclosure of Invention
The invention mainly aims to provide a large-area nickel-based electrocatalyst film and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a large-area nickel-based electrocatalyst film, which comprises the following steps:
providing a substrate;
the ultrasonic atomization is carried out in a mode of 0.1-2 mL/cm 2 Min, applying a precursor solution containing a nickel salt to the surface of the substrate, and then pyrolyzing at 260-400 ℃ to form a large-area nickel-based electrocatalyst film; wherein, the process conditions adopted by the ultrasonic atomization comprise: the ultrasonic power of the ultrasonic atomization device is 80-120 kHz, and the total amount of the precursor solution containing the nickel salt applied to the surface of the substrate is 5-20 mL/cm 2 。
Further, the preparation method specifically comprises the following steps: and (3) integrally moving the ultrasonic atomization device by using an xyz triaxial moving platform in a circulating reciprocating mode to uniformly apply the precursor solution to the surface of the substrate, wherein the amount of the precursor solution applied to the unit area of the substrate is at least the same.
The embodiment of the invention also provides the large-area nickel-based electrocatalyst film prepared by the method, and the thickness of the large-area nickel-based electrocatalyst film is 50-800 nm.
The embodiment of the invention also provides application of the large-area nickel-based electrocatalyst film in the field of hydrogen production by electrolyzing water.
Compared with the prior art, the invention has the beneficial effects that:
(1) the large-area nickel-based electrocatalyst film is formed by a spray pyrolysis method, and a good practical effect is obtained when the film is applied to the field of electrocatalysis, compared with the traditional methods such as electrodeposition, hydrothermal method, solvothermal method, spin coating method and the like, the method is simpler and more convenient, secondary calcination is not needed, the program is simplified, and the efficiency is saved;
(2) the invention keeps a balance between droplet formation and thermal decomposition by controlling the speed of the precursor solution of the nickel salt, is also important for controlling the temperature, and has different products formed by pyrolysis under the action of different temperatures; meanwhile, the solvent used in the invention is water
(3) The method has low actual production cost, is favorable for accurately controlling the dosage, has large current density, strong stability, larger area and easy operation process when the prepared large-area nickel-based electrocatalyst film is used as an electrode, and is favorable for enlarging the area of a substrate and gradually realizing commercialization and marketization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1 a-1 b are SEM images of large-area nickel-based electrocatalyst films prepared according to example 1 of the present invention;
FIG. 2 is an XRD pattern of a large area nickel-based electrocatalyst film prepared in example 1 according to the invention;
FIG. 3 is a CV diagram of a large area nickel-based electrocatalyst thin film prepared in example 1, according to the present invention;
FIG. 4 is a CA diagram of a large-area nickel-based electrocatalyst thin film prepared in example 1 of the present invention
FIGS. 5 a-5 b are sample graphs and graphs of electrocatalytic performance studies of a 50mm by 50mm large area nickel-based electrocatalyst thin film in example 7 of the present invention;
FIG. 6 is a CV diagram of a nickel-based thin film prepared under electrodeposition conditions of comparative example 1 in accordance with the present invention;
fig. 7 is a CV diagram of a nickel-based thin film prepared by using a conventional ultrasonic atomization sheet in comparative example 2 according to the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made a long-term study and a great deal of practice to provide a technical scheme of the present invention, and the present invention develops a method for preparing a large-area nickel-based electrocatalyst film in order to solve the problem of preparing a large-area nickel-based electrocatalyst film, the method has the advantages of wide raw material sources, simple process, high efficiency, no need of complex step procedures, short film preparation forming time, large prepared electrode current density and strong stability, and the large-area nickel-based electrocatalyst film prepared can be directly expanded and applied to commercialization and marketization operations in the future. The ultrasonic atomization is mainly realized by the action of the ultrasonic atomization nozzle, the mode that the ultrasonic generator of the nozzle is used for carrying out ultrasonic atomization on the precursor solution to form liquid drops is utilized, and the whole nozzle is moved regularly to a certain degree, so that the uniformity of the amount of the liquid drops sprayed on a unit area is ensured, and the formed whole thin film can be relatively uniform in a microscopic scale. In the method in the prior art, a plurality of ultrasonic generators are directly used in precursor solution to form integral spray, and then carrier gas is used to bring the integral spray into a substrate material.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of an embodiment of the present invention provides a method for preparing a large-area nickel-based electrocatalyst thin film, comprising:
providing a substrate;
the ultrasonic atomization is carried out in a mode of 0.1-2 mL/cm 2 Min, applying a precursor solution containing a nickel salt to the surface of the substrate, and then pyrolyzing at 260-400 ℃ to form a large-area nickel-based electrocatalyst film; wherein, the process conditions adopted by the ultrasonic atomization comprise: the ultrasonic power of the ultrasonic atomization device is 80-120 kHz, and the total amount of the precursor solution containing the nickel salt applied to the surface of the substrate is 5-20 mL/cm 2 。
In some more specific embodiments, the preparation method comprises:
dissolving nickel salt in a solvent to form the precursor solution containing the nickel salt, and then placing the precursor solution in an injection device, wherein the injection device is fixedly arranged on a power device;
and connecting the injection device with the ultrasonic atomization device, applying the precursor solution to the surface of the substrate in an ultrasonic atomization mode, and performing pyrolysis treatment to obtain the large-area nickel-based electrocatalyst film.
Furthermore, the pumping speed of the power device (injection pump) into the precursor solution is 40-80 mL/h.
Further, the solvent includes water, and is not limited thereto.
Further, the concentration of the nickel salt in the precursor solution is 0.25-10 mmol/L.
In some more specific embodiments, the preparation method specifically comprises: and (3) utilizing an xyz triaxial moving platform, and adopting a cyclic reciprocating mode to integrally move the ultrasonic atomization device to uniformly apply the precursor solution to the surface of the substrate, wherein the amount of the precursor solution applied to the unit area of the substrate is at least the same.
Further, the area size of the precursor solution applied to the substrate surface includes: the length is 80-100 mm, and the width is 40-80 mm.
Furthermore, the area size of the precursor solution applied to the surface of the substrate is larger than the area of the prepared large-area nickel-based electrocatalyst film, mainly in order to make the prepared large-area nickel-based electrocatalyst film more uniform.
Further, the parameters of the xyz three-axis mobile platform include: the speed of the moving speed in the x-axis direction is 30-60 mm/s, and the speed in the y-axis direction is 10-20 mm/s.
In some more specific embodiments, a heating device is disposed below the substrate, and the heating device at least pyrolyzes the precursor solution on the surface of the substrate.
In some more specific embodiments, the preparation method further comprises: firstly, cleaning and ultraviolet irradiating the substrate.
Further, the cleaning process includes: and sequentially using acetone, ethanol and a surfactant solution to ultrasonically clean the matrix for 10-30 min.
Further, the surfactant in the surfactant solution is a nonionic surfactant.
Further, the surfactant in the surfactant solution includes any one or a combination of two or more of triton, polyoxyethylene ether, and fatty acid methyl ester polyoxyethylene ether, but is not limited thereto.
Further, the preparation method comprises the following steps: and (3) placing the substrate in an ozone ultraviolet irradiation device for irradiation treatment for 15-20 min.
In some more specific embodiments, the substrate includes any one of a conductive glass substrate, a metal material substrate, a fiber cloth substrate, and a non-metal material substrate, and is not limited thereto.
Further, the substrate includes any one of FTO glass, ITO glass, copper sheet, fiber cloth, silicon wafer, carbon sheet, and nickel foam, but is not limited thereto.
Specifically, the preparation method of the large-area nickel-based electrocatalyst film specifically comprises the following steps:
weighing a certain amount of nickel nitrate, and adding the nickel nitrate into deionized water to form a precursor aqueous solution. After the precursor solution is conveyed into the novel ultrasonic sprayer, the precursor solution is directly converted into small liquid drops by utilizing the ultrasonic atomization effect of the ultrasonic sprayer, the using amount of the precursor solution can be effectively controlled, the small liquid drops are uniformly distributed in a certain range by a unique circulating reciprocating spraying mode, the small liquid drops have atomization-decomposition-synthesis effects under the high-temperature action of a bottom heating table, and finally a large-area nickel-based electrocatalyst film is formed on an FTO substrate material.
Further, the preparation method of the large-area nickel-based electrocatalyst thin film may include:
(1) dissolving nickel nitrate hexahydrate in deionized water to form a solution with the concentration of 0.25 mmol-10 mol/L, wherein the solution is used as a precursor solution for synthesizing the electrocatalyst film;
(2) the conductive glass substrate (such as FTO conductive glass and the like) can be used only by multi-step cleaning and finally under the cleaning action of a surfactant;
(3) spraying the precursor solution at normal temperature on a conductive glass substrate (such as FTO conductive glass) controlled to be 260-400 ℃ by a planar heating table by adopting an ultrasonic atomization device: an ultrasonic atomizing nozzle with ultrasonic frequency of 120kHz is adopted, precursor solution filled by a 50mL injector is placed in an injection pump with flow rate of 60mL/h, the flow rate of the solution is controlled, the nozzle is integrally moved to ensure that the amount of sprayed solution droplets on a unit area is the same under the action of an xyz triaxial moving platform in a certain range, and the solution in the sprayed area range can have enough time to perform decomposition and synthesis; the spraying speed of the precursor solution is 0.1-2 milliliters per square centimeter per minute, and the total spraying amount is 5-20 milliliters per square centimeter; the thickness of the large-area nickel-based electrocatalyst film formed under the condition is 50-800 nanometers, and the spraying total amount and the thickness are in a linear relation.
Furthermore, in the preparation process of the film formed by integral spray pyrolysis, the spray head adopts a cyclic flow reciprocating spraying mode under the action of an xyz three-axis platform, the spraying is carried out within the range of 100mm in length and 60mm in width, the flow control mode is adopted, the advancing speed is 45mm/s on the x axis and 10mm/s on the y axis, and the number of the spraying is calculated to be one circle in a reciprocating mode.
The embodiment of the invention also provides the large-area nickel-based electrocatalyst film prepared by the method, and the thickness of the large-area nickel-based electrocatalyst film is 50-800 nm.
Furthermore, the area of the large-area nickel-based electrocatalyst film is 50mm multiplied by 50 mm-500 mm multiplied by 500 mm.
Further, the area of the large-area nickel-based electrocatalyst film is 50mm × 50mm or 100mm × 100 mm.
The large-area nickel-based electrocatalyst film is an electrocatalytic film material of a nickel-based multiple mixture, and mainly comprises a multiple ion mixed substance formed by mutually composing anions such as metal cations, OH hydroxyl, nitryl, nitroso and the like.
In another aspect, the embodiment of the invention also provides the application of the large-area nickel-based electrocatalyst film in the field of hydrogen production by water electrolysis.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
0.25mmol of nickel nitrate is dissolved in 100mL of deionized water, and the precursor solution is formed after the nickel nitrate is magnetically stirred and uniformly mixed. Directly and uniformly spraying a normal-temperature precursor solution on an FTO conductive glass substrate controlled to 320 ℃ by a planar heating table in an ultrasonic atomization nozzle manner, wherein the rate of applying the precursor solution to the substrate is 1.0mL/cm 2 And min, wherein the ultrasonic power of the ultrasonic atomization device is 120kHz, spraying is carried out within the range of 100mm in length and 60mm in width by adopting a cyclic flow reciprocating spraying mode, the moving speed is 45mm/s on the x axis and 10mm/s on the y axis by adopting a flow control mode, the reciprocating calculation is one circle, and the total spraying is 20 circles. The thickness of the nickel-based electrocatalyst film formed in large area under this condition was calculated to be about 200 nm.
And (3) performance characterization:
(1) SEM images of the large-area nickel-based electrocatalyst film prepared in this example 1 are shown in FIGS. 1 a-1 b, and XRD patterns of the large-area nickel-based electrocatalyst film prepared in this example are shown in FIG. 2;
(2) the electrocatalytic properties for the large-area nickel-based electrocatalyst thin film prepared in this example 1 are shown in fig. 3, and the stability is shown in fig. 4.
Example 2
0.025mmol of nickel nitrate is dissolved in 100mL of deionized water, and the precursor solution is formed after the nickel nitrate is magnetically stirred and uniformly mixed. Uniformly spraying a normal-temperature precursor solution on an FTO conductive glass substrate controlled to 300 ℃ by a planar heating table in an ultrasonic atomizing nozzle manner, wherein the rate of applying the precursor solution to the substrate is 0.1mL/cm 2 Min, ultraThe ultrasonic power of the sound atomization device is 80kHz, the spraying is carried out within the range of 100mm in length and 60mm in width by adopting a reciprocating spraying mode of a circulating flow, the moving speed is 45mm/s on an x-axis and 10mm/s on a y-axis by adopting a flow control mode, the moving speed is calculated to be one circle by reciprocating back and forth, and the total spraying time is 10 circles. Preparing the final large-area nickel-based electrocatalyst film. The film thickness formed under this condition was calculated to be about 100 nm.
Example 3
0.05mmol of nickel nitrate is dissolved in 100mL of deionized water, and the precursor solution is formed after the nickel nitrate is magnetically stirred and uniformly mixed. Directly and uniformly spraying a normal-temperature precursor solution on an ITO (indium tin oxide) substrate controlled to 340 ℃ by a planar heating table in an ultrasonic atomization nozzle manner, wherein the rate of applying the precursor solution to the substrate is 1mL/cm 2 And min, wherein the ultrasonic power of the ultrasonic atomization device is 90kHz, spraying is carried out within the range of 100mm in length and 60mm in width by adopting a cyclic flow reciprocating spraying mode, the moving speed is 45mm/s on the x axis and 10mm/s on the y axis by adopting a flow control mode, the reciprocating calculation is one circle, and the total spraying is 20 circles. It is calculated that the formation of a large area of the nickel-based electrocatalyst film under this condition is about 300 nm.
Example 4
0.5mmol of nickel nitrate is dissolved in 100mL of deionized water, and the precursor solution is formed after the nickel nitrate is magnetically stirred and uniformly mixed. Uniformly spraying a normal-temperature precursor solution on a silicon wafer substrate controlled to 380 ℃ by a planar heating table in the form of an ultrasonic atomizing nozzle, wherein the rate of applying the precursor solution to the substrate is 2mL/cm 2 And min, wherein the ultrasonic power of the ultrasonic atomization device is 120kHz, spraying is carried out within the range of 100mm in length and 60mm in width by adopting a cyclic flow reciprocating spraying mode, the moving speed is 60mm/s on the x axis and 20mm/s on the y axis by adopting a flow control mode, the reciprocating calculation is one circle, and the total spraying is 40 circles. It is calculated that the thickness of the large-area nickel-based electrocatalyst film formed under this condition is about 500 nm.
Example 5
0.75mmol of nickel nitrate is dissolved in 100mL of deionized water, and the precursor solution is formed after the nickel nitrate is magnetically stirred and uniformly mixed.Directly and uniformly spraying a normal-temperature precursor solution on an FTO conductive glass substrate controlled to 260 ℃ by a planar heating table in an ultrasonic atomization nozzle manner, wherein the rate of applying the precursor solution to the substrate is 1.0mL/cm 2 And min, wherein the ultrasonic power of the ultrasonic atomization device is 80kHz, spraying is carried out within the range of 100mm in length and 40mm in width by adopting a cyclic flow reciprocating spraying mode, the moving speed is 45mm/s on the x axis and 15mm/s on the y axis by adopting a flow control mode, the reciprocating calculation is one circle, and the total spraying is 30 circles. It is calculated that the thickness of the large-area nickel-based electrocatalyst film formed under this condition is about 600 nm.
Example 6
1mmol of nickel nitrate is dissolved in 100mL of deionized water, and the precursor solution is formed after the nickel nitrate is magnetically stirred and uniformly mixed. Directly and uniformly spraying a normal-temperature precursor solution on an FTO conductive glass substrate controlled to 400 ℃ by a planar heating table in an ultrasonic atomizing nozzle manner, wherein the rate of applying the precursor solution to the substrate is 2mL/cm 2 And min, wherein the ultrasonic power of the ultrasonic atomization device is 120kHz, spraying is carried out within the range of 80mm in length and 80mm in width by adopting a cyclic flow reciprocating spraying mode, the traveling speed is 30mm/s on the x axis and 10mm/s on the y axis by adopting a flow control mode, the reciprocating calculation is one circle, and the total spraying is 50 circles. It is calculated that the thickness of the large-area nickel-based electrocatalyst film formed under this condition is about 800 nm.
The performance test result of the large-area nickel-based electrocatalyst film prepared by the invention shows that the large-area nickel-based electrocatalyst film prepared by the invention has excellent oxygen evolution performance, higher reaction activity and better stability. The hydrogen production by water electrolysis is divided into two half reactions, one is an oxygen evolution reaction on an anode, and the other is a hydrogen evolution reaction on a cathode, and the catalyst of the invention is mainly used for improving the performance of the oxygen evolution catalytic reaction, thereby accelerating the whole process of the hydrogen production by water electrolysis.
Example 7
The preparation method is the same as that of the embodiment 1, 2.5mmol of nickel nitrate is dissolved in 100mL of deionized water, and the precursor solution is formed after the nickel nitrate is magnetically stirred and uniformly mixed. Using ultrasonic wavesDirectly and uniformly spraying a normal-temperature precursor solution on an FTO conductive glass substrate controlled to 320 ℃ by a plane heating table in the form of an atomizing nozzle, wherein the rate of applying the precursor solution to the substrate is 1.0mL/cm 2 And min, wherein the ultrasonic power of an ultrasonic atomization device is 120kHz, a circulation flow reciprocating spraying mode is adopted, a 50mm x 50mm FTO conductive substrate is selected and placed in a central range with the length of 150mm and the width of 80mm for spraying, a flow control mode is adopted, the traveling speed is 45mm/s on the x axis and 10mm/s on the y axis, the reciprocating calculation is one circle, and the total spraying time is 20 circles. The thickness of the nickel-based electrocatalyst film formed in large area under this condition was calculated to be about 200 nm.
The prepared large-area nickel-based electrocatalyst film with the thickness of 50mm multiplied by 50mm is used as an electrocatalyst to electrolyze water to prepare hydrogen. Specifically, the performance of the electrocatalyst is tested in a three-electrode system, in order to ensure that the test is basically carried out under a stable condition, the scanning speed is set to be 5mV/s, the solution resistance iR compensation is set, an LSV curve corresponding to the oxygen evolution reaction of the catalyst can be obtained, and the measured potential passes through E Ag/AgCl By the formula: e RHE ＝E Ag/AgCl +0.197V +0.059 pH; a calibration is performed and finally the reversible hydrogen electrode ereh is calibrated. By using an electrode material loaded with a large-area nickel-based electrocatalyst film, under a three-electrode system, the scanning voltage range is 1V-1.6V, the scanning rate is 5mV/s, and the total number of scanning turns is set to be 5 turns. The method is characterized in that: the size of the large-area nickel-based electrocatalyst thin film is shown in fig. 5a, and the corresponding catalytic performance is shown in fig. 5 b.
Comparative example 1
By mixing Ni (NO) 3 ) 2 ·6H 2 O was mixed with ultrapure 18.2M Ω. cm water to prepare a 0.1M solution, which was used as a cathodic deposition solution. Introducing N into the deposition solution before film deposition 2 And 20 min. All films were deposited under a cathodic current at a density of-10 mA cm -2 . The film deposited continuously is subjected to the lowering potential for a period of 3 to 20 seconds. The pulse deposition film is continuously subjected to 2s cathode current pulse at-10 mA-cm -2 To (3). The solution was stirred for 10s after each pulse to ensure homogeneity of the solution, at the next pulseThe solution was deposited before rinsing, and circulated between 2 and 20 for obtaining a load range similar to those, and the electrodeposited thin film was obtained using continuous deposition, and its CV chart is shown in fig. 6.
Comparative example 2 nickel-based thin film prepared by means of conventional ultrasonic atomization sheet
By mixing Ni (NO) 3 ) 2 ·6H 2 Preparing O into 0.2M solution, directly delivering the solution into a glass container filled with a precursor by using an ultrasonic generator, directly ultrasonically processing the solution into superfine droplets by using the high frequency of 1.6MHz of the ultrasonic generator, blowing the superfine droplets onto a substrate material with a heating table at the bottom under the action of carrier gas, and finally forming the nickel-based thin film material, wherein the CV diagram of the nickel-based thin film material is shown in FIG. 7.
In addition, the inventors of the present invention have also made experiments with other raw materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the invention.
Throughout this specification, where compositions are described as having, containing, or comprising specific components, or where processes are described as having, containing, or comprising specific process steps, it is contemplated that compositions taught by the present invention also consist essentially of, or consist of, the recited components, and that processes taught by the present invention also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A preparation method of a large-area nickel-based electrocatalyst film is characterized by comprising the following steps:
providing a substrate;
the ultrasonic atomization is carried out in a mode of 0.1-2 mL/cm 2 Min applying a precursor solution containing a nickel salt to the substrate surface, followed by pyrolysis at 260-400 ℃ to form a large area nickel-based electrocatalyst thin film; wherein, the process conditions adopted by the ultrasonic atomization comprise: the ultrasonic power of the ultrasonic atomization device is 80-120 kHz, and the total amount of the precursor solution containing the nickel salt applied to the surface of the substrate is 5-20 mL/cm 2 。
2. The production method according to claim 1, characterized by comprising:
dissolving nickel salt in a solvent to form the precursor solution containing the nickel salt, and then placing the precursor solution in an injection device, wherein the injection device is fixedly arranged on a power device;
and connecting the injection device with the ultrasonic atomization device, applying the precursor solution on the surface of the substrate in an ultrasonic atomization mode, and performing pyrolysis treatment to obtain the large-area nickel-based electrocatalyst film.
3. The method of claim 2, wherein: the pumping speed of the power device into the precursor solution is 40-80 mL/h;
and/or, the nickel salt comprises nickel nitrate hexahydrate;
and/or, the solvent comprises water;
and/or the concentration of nickel salt in the precursor solution is 0.25-10 mmol/L.
4. The method according to claim 1, comprising: and (3) utilizing an xyz triaxial moving platform, and adopting a cyclic reciprocating mode to integrally move the ultrasonic atomization device to uniformly apply the precursor solution to the surface of the substrate, wherein the amount of the precursor solution applied to the unit area of the substrate is at least the same.
5. The method according to claim 4, wherein the size of the region of the precursor solution applied to the substrate surface includes: the length is 80-100 mm, and the width is 40-80 mm;
and/or the parameters of the xyz three-axis mobile platform include: the speed of the moving speed in the x-axis direction is 30-60 mm/s, and the speed in the y-axis direction is 10-20 mm/s.
6. The method of claim 1, wherein: and a heating device is arranged below the substrate and at least pyrolyzes the precursor solution on the surface of the substrate.
7. The method for preparing according to claim 1, characterized by further comprising: firstly, cleaning and ultraviolet irradiating a substrate;
preferably, the cleaning process includes: sequentially using acetone, ethanol and a surfactant solution to ultrasonically clean the matrix for 10-30 min; preferably, the surfactant in the surfactant solution comprises one or a combination of more than two of triton, polyoxyethylene ether and fatty acid methyl ester polyoxyethylene ether; preferably, the surfactant in the surfactant solution is a nonionic surfactant;
preferably, the preparation method comprises the following steps: and (3) placing the substrate in an ozone ultraviolet irradiation device for irradiation treatment for 15-20 min.
8. The method of claim 1, wherein: the substrate comprises any one of a conductive glass substrate, a metal material substrate, a fiber cloth substrate and a non-metal material substrate; preferably, the substrate comprises any one of FTO glass, ITO glass, copper sheet, fiber cloth, silicon wafer, carbon sheet, and foamed nickel.
9. The large area nickel-based electrocatalyst film prepared by the process of any one of claims 1 to 8, having a thickness of from 50 to 800 nm;
preferably, the area of the large-area nickel-based electrocatalyst thin film is 50mm × 50mm to 500mm × 500 mm.
10. Use of the large area nickel-based electrocatalyst film according to claim 9 in the field of hydrogen production from electrolysis of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110323172.2A CN115125568B (en) | 2021-03-25 | 2021-03-25 | Large-area nickel-based electrocatalyst film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110323172.2A CN115125568B (en) | 2021-03-25 | 2021-03-25 | Large-area nickel-based electrocatalyst film and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115125568A true CN115125568A (en) | 2022-09-30 |
| CN115125568B CN115125568B (en) | 2024-01-26 |
Family
ID=83374379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110323172.2A Active CN115125568B (en) | 2021-03-25 | 2021-03-25 | Large-area nickel-based electrocatalyst film and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115125568B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070298961A1 (en) * | 2006-06-22 | 2007-12-27 | Rice Gordon L | Method of producing electrodes |
| KR20100096389A (en) * | 2009-02-24 | 2010-09-02 | 한양대학교 산학협력단 | Preparation method of nio-ysz thin film |
| US20110177356A1 (en) * | 2010-01-21 | 2011-07-21 | Korea Institute Of Science And Technology | METHOD FOR PREPARING Pt THIN FILMS USING ELECTROSPRAY DEPOSITION AND Pt THIN FILMS FORMED BY THE METHOD |
| CN107248453A (en) * | 2017-05-11 | 2017-10-13 | 大连理工大学 | A kind of preparation method of hydroxyl nickel nitrate/carbon composite electrode material |
-
2021
- 2021-03-25 CN CN202110323172.2A patent/CN115125568B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070298961A1 (en) * | 2006-06-22 | 2007-12-27 | Rice Gordon L | Method of producing electrodes |
| KR20100096389A (en) * | 2009-02-24 | 2010-09-02 | 한양대학교 산학협력단 | Preparation method of nio-ysz thin film |
| US20110177356A1 (en) * | 2010-01-21 | 2011-07-21 | Korea Institute Of Science And Technology | METHOD FOR PREPARING Pt THIN FILMS USING ELECTROSPRAY DEPOSITION AND Pt THIN FILMS FORMED BY THE METHOD |
| CN107248453A (en) * | 2017-05-11 | 2017-10-13 | 大连理工大学 | A kind of preparation method of hydroxyl nickel nitrate/carbon composite electrode material |
Non-Patent Citations (1)
| Title |
|---|
| HENGZHENG TIAN: "Instant formation of excellent oxygen evolution catalyst film via controlled spray pyrolysis for electrocatalytic and photoelectrochemical water splitting", 《JOURNAL OF ENERGY CHEMISTRY》, pages 657 - 665 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115125568B (en) | 2024-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104846397B (en) | One kind being used for electrochemical reduction CO2The electrode and its preparation method and application of formic acid processed | |
| CN110201670A (en) | Based on ferric trichloride/urea eutectic solvent ferronickel double-metal hydroxide/foamed nickel catalyst agent, preparation method and application | |
| CN106011926A (en) | Electrocatalyst with cobalt-based multi-stage nano-composite structure for oxygen production by electrolysis of water and preparation method of electrocatalyst | |
| CN106191916A (en) | A kind of efficient porous Ni Mo hydrogen-precipitating electrode and preparation method thereof | |
| CN103422116B (en) | A kind of porous Ni-base ru oxide is combined the preparation method of hydrogen-precipitating electrode | |
| CN110711596B (en) | Efficient full-hydrolysis water catalyst IPBAP/Ni2P@MoOx/NF and preparation method thereof | |
| CN104894595B (en) | A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof | |
| CN107051568A (en) | One kind analysis oxygen Fe two cobaltous selenide@N CT composite catalysts of doping and its preparation method and application | |
| CN110512228B (en) | Preparation method of nickel phosphide/nickel foam electrochemical functional hydrogen evolution material | |
| CN108179433B (en) | Ordered mesopore carbon loads nanometer iridium base electrocatalytic hydrogen evolution electrode and its preparation and application | |
| CN104313637A (en) | Metal sulfide electrode with hydrogen reduction activity and preparation method of metal sulfide electrode | |
| CN109594098B (en) | Water electrolysis reaction device with external magnetic field and method for enhancing electrocatalysis performance of water electrolysis reaction device | |
| CN109576730A (en) | A kind of preparation method and application of the cobaltosic oxide nano chip arrays electrode of iron modification | |
| CN106876722A (en) | A kind of Carbon dioxide electrochemical reduction gas-diffusion electrode and its preparation and application | |
| CN107904570B (en) | method for preparing nickel nanoparticle-graphene-nickel foam material | |
| CN113174600A (en) | Porous nickel screen electrolytic water catalytic material and preparation method thereof | |
| CN106567102B (en) | A kind of TiO2The preparation method of/carbon nanotube/Ni photoelectric activity combination electrodes | |
| CN112981449A (en) | Ordered PEM water electrolysis membrane electrode anode catalyst layer and preparation method and application thereof | |
| CN110120524A (en) | A kind of load cobalt protoxide/nitrogen-doped carbon nickel foam composite material and preparation method and application | |
| CN115125568B (en) | Large-area nickel-based electrocatalyst film and preparation method and application thereof | |
| CN113249743B (en) | Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof | |
| CN109778296A (en) | A method of polishing and CuO surface | |
| CN108018583A (en) | A kind of electrolytic anode plate and preparation method and application | |
| CN103924262B (en) | The hydro-thermal method preparation method containing ruthenium coating catalyst | |
| CN111822024B (en) | Environment-friendly copper-iron MOF material with two-dimensional nano wall array structure and controllable iron content and preparation method 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 |