CN117144388A - PEM electrolytic hydrogen production composite diffusion layer and preparation method thereof - Google Patents
PEM electrolytic hydrogen production composite diffusion layer and preparation method thereof Download PDFInfo
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- CN117144388A CN117144388A CN202311008440.7A CN202311008440A CN117144388A CN 117144388 A CN117144388 A CN 117144388A CN 202311008440 A CN202311008440 A CN 202311008440A CN 117144388 A CN117144388 A CN 117144388A
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 119
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- 239000011148 porous material Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 230000005540 biological transmission Effects 0.000 claims abstract description 3
- 230000003247 decreasing effect Effects 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 81
- 239000010936 titanium Substances 0.000 claims description 61
- 229910052719 titanium Inorganic materials 0.000 claims description 61
- 239000011159 matrix material Substances 0.000 claims description 39
- 210000001595 mastoid Anatomy 0.000 claims description 32
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- 229920001169 thermoplastic Polymers 0.000 claims description 20
- 239000004416 thermosoftening plastic Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- -1 polyethylene Polymers 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910003460 diamond Inorganic materials 0.000 claims description 14
- 239000010432 diamond Substances 0.000 claims description 14
- 229910000510 noble metal Inorganic materials 0.000 claims description 14
- 229920000573 polyethylene Polymers 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 8
- 238000004080 punching Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 3
- 230000002687 intercalation Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000006056 electrooxidation reaction Methods 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 230000003116 impacting effect Effects 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000001603 reducing effect Effects 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- SMVPNBSENDTIEH-UHFFFAOYSA-M [Ir]Br Chemical compound [Ir]Br SMVPNBSENDTIEH-UHFFFAOYSA-M 0.000 claims 1
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000000879 optical micrograph Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
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- 238000012546 transfer Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- 238000007711 solidification Methods 0.000 description 1
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Classifications
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
Abstract
The invention discloses a PEM electrolytic hydrogen production composite diffusion layer and a preparation method thereof, wherein metal reticular porous materials with different specifications and models are sequentially placed according to the sequence from a membrane electrode to a bipolar plate when the diffusion layer is used and the principles of gradually decreasing mesh number or specific surface area, gradually increasing thickness and gradually improving mechanical strength are adopted; the metal mesh porous material near the membrane electrode side serves as a diffusion base layer, the high-density small mesh of the metal mesh porous material serves as a protection membrane electrode surface catalytic layer and improves the gas transmission rate, the metal mesh porous material near the bipolar plate side serves as a support base layer, the high mechanical strength and the large mesh of the metal mesh porous material serve as an equilibrium reaction pressure to reduce the deformation of the diffusion layer, and meanwhile, the surface tension of water seepage on the cathode side of the bipolar plate is reduced, so that the water seepage along the bipolar plate flow channel is accelerated to flow out of the electrolytic stack. The composite diffusion layer prepared by the invention can be effectively used for PEM electrolytic hydrogen production under high-pressure reaction conditions, and has the characteristics of low cost, high stability, high activity and the like.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis of renewable energy sources, in particular to a PEM electrolytic hydrogen production composite diffusion layer and a preparation method thereof.
Background
Current water electrolysis technologies can be broadly divided into three types, alkaline water electrolysis, proton Exchange Membrane (PEM) electrolysis and solid oxide electrolysis technologies. The PEM electrolyzed water is a market force for producing hydrogen by water electrolysis in the future due to high current density, compact structure and high dynamic response speed, and a plurality of enterprises in China and the world carry out related industrial layout.
The PEM electrolytic stack mainly comprises core parts such as a membrane electrode, a diffusion layer, a bipolar plate and the like, wherein the diffusion layer is a bridge for connecting the bipolar plate and the membrane electrode, is a guarantee for high-efficiency continuous execution of an electrolytic water reaction, and is an important research direction for cost reduction and synergy of the PEM electrolytic stack due to reasonable design and development.
The diffusion layer mainly applied to the PEM water electrolysis hydrogen production at present is a titanium fiber felt, micron-sized titanium metal fibers are formed by adopting a cutting or drawing process, and the diffusion layer is formed by non-woven paving and high-temperature vacuum sintering, has a good three-dimensional net structure, can provide higher porosity and specific surface area, and promotes mass and heat transfer of electrolytic reaction, wherein the common diffusion layer on the cathode side is provided with carbon paper and titanium felt or adopts a combined mode of the carbon paper and the titanium felt. However, the fiber structure on the surface of the titanium felt is extremely easy to damage the surface catalytic layer of the membrane electrode under the high-pressure reaction condition to reduce the reaction activity, and meanwhile, the penetration of the membrane electrode can cause oxyhydrogen mutual penetration so as to cause safety risk. Secondly, burrs generated by cutting the titanium felt edge also easily aggravate shearing force at the frame of the membrane electrode, so that the structure is damaged. Furthermore, the three-dimensional network structure of the fiber mat makes it difficult to completely coat the noble metal coating on the surface of the fiber mat, and thus the corrosion-preventing effect of the fiber mat cannot be fully exerted. On the other hand, although the carbon paper has excellent air permeability and compression characteristics, the carbon material is extremely easy to corrode and has poor toughness, and long-time coupling fluctuation wind-solar power supply application of the electrolytic stack cannot be ensured. In addition, new low cost high performance corrosion resistant coatings are also under further design development.
At present, a series of researches on improvement and optimization of a diffusion layer for hydrogen production by PEM water electrolysis have been carried out, and patent CN115852408A proposes that stainless steel fibers are used for replacing titanium fibers, coating treatment is carried out on the surfaces in advance, and then the fibers are woven and pressed into a fiber felt, so that the consumption of noble metals is reduced, and meanwhile, the economical efficiency is improved. However, the impurity components in the stainless steel are extremely easy to generate electrochemical reaction in the electrolytic stack, so that the service life of the diffusion layer is easily reduced, and the generated cations can pollute the membrane electrode. Patent CN115852410a proposes the use of titanium nanotubes of different pore sizes, large pore size titanium nanotubes for transporting liquids, small pore size titanium nanotubes for transporting gases, so that gas and liquid transport is highly ordered in the PEM water electrolysis process, achieving good liquid and gas management functions. However, bubbles are easy to form and stay in the process of water electrolysis reaction, and water and gas are difficult to be transported respectively according to the original design concept. Patent CN115090879a adopts metal titanium powder to sinter and form a metal titanium layer, and simultaneously, a pore-forming agent is added into titanium powder slurry, and porous diffusion layers with different pore diameters are obtained through tape casting treatment and phase inversion solidification treatment. However, the titanium powder sintering can increase the strength and flatness of the diffusion layer, but has lower porosity and specific surface area, which is unfavorable for mass transfer under the condition of large flow.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art, and provides a PEM electrolytic hydrogen production composite diffusion layer and a preparation method thereof.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows: according to the sequence from a membrane electrode to a bipolar plate when the diffusion layer is used, metal reticular porous materials with different specifications and types are sequentially placed according to the principles of gradually decreasing mesh number or specific surface area, gradually increasing thickness and gradually improving mechanical strength; the metal mesh porous material near the membrane electrode side serves as a diffusion base layer, the high-density small mesh of the metal mesh porous material serves as a protection membrane electrode surface catalytic layer and improves the gas transmission rate, the metal mesh porous material near the bipolar plate side serves as a support base layer, the high mechanical strength and the large mesh of the metal mesh porous material serve as an equilibrium reaction pressure to reduce the deformation of the diffusion layer, and meanwhile, the surface tension of water seepage on the cathode side of the bipolar plate is reduced, so that the water seepage along the bipolar plate flow channel is accelerated to flow out of the electrolytic stack.
Preferably, the metal mesh porous material between the diffusion substrate and the support substrate acts as a reinforcing and/or finishing layer to further enhance the performance of the composite diffusion layer.
Preferably, the surface of each metal mesh porous material forms a micro-mastoid structure, and adjacent metal mesh porous materials are fixed together to form a whole by embedding mastoid protrusions into concave parts and static friction force between the mastoid protrusions and the metal mesh porous materials to serve as a composite diffusion layer matrix.
Preferably, the surface of the composite diffusion layer matrix forms g-C 3 N 4 And a thin layer of an intercalation structure of the noble metal and the nitrogen doped titanium oxide, and embedding the noble metal into the thin layer in a punctiform form through high-temperature reduction to form the corrosion-resistant coating with stronger binding force.
Preferably, the metal mesh porous material is made of metal titanium so as to relieve electrochemical corrosion of the metal mesh porous material under high potential; the metal mesh porous material has a structure of one or a combination of a plurality of fiber felts, fiber meshes, foam metals and porous metals.
Preferably, the brand of the metallic titanium is TA1, so as to reduce the cation content generated in the reaction process of impurities; the fiber mat is a drawn or cut fiber mat and must be long fiber; the fiber net is a woven net or a punching stretching net, and the placing direction keeps the holes to be in the same direction or in different directions, and is overlapped or penetrated.
Preferably, the wire diameter of the woven mesh is 0.05-0.1mm, the mesh number is 80-200 mesh, and the woven mesh is formed by plain weave or twill weave; the hole patterns of the punching and stretching net are diamond or hexagon, and the aperture is 1-2 x 2-4mm; the maximum diameter of the mastoid is required to be adjusted according to the size of the diffusion layer, and the maximum diameter of the mastoid corresponding to the 50mm diffusion layer is not more than 5mm.
The invention also provides a preparation method of the PEM electrolytic hydrogen production composite diffusion layer, which comprises the following steps:
1) According to the order from the membrane electrode to the bipolar plate when the diffusion layer is used, the metal mesh porous materials with different specifications and models are sequentially placed according to the principles that the mesh number or the specific surface area is gradually reduced, the thickness is gradually increased and the mechanical strength is gradually improved; the metal reticular porous material close to the membrane electrode side serves as a diffusion base layer, the metal reticular porous material close to the bipolar plate side serves as a support base layer, and meanwhile, the metal reticular porous material can be added between the diffusion base layer and the support base layer as a reinforcing layer and/or a modifying layer according to requirements, so that the performance of the composite diffusion layer is further enhanced;
2) Before the metal mesh porous materials are overlapped, a micro mastoid structure is formed on the surface of each metal mesh porous material by adopting a die, when the metal mesh porous materials are overlapped, every two metal mesh porous materials are fixed together to form a whole by embedding the mastoid bulges into the concave mode and static friction force between the metal mesh porous materials, the metal mesh porous materials are used as a composite diffusion layer matrix, the mastoid positions are coated with liquid thermoplastic conductive materials, and then the thermoplastic conductive materials are cooled, so that the binding force between different layers is further improved; then, ultrasonic washing is carried out through dilute acid solution and deionized water to remove greasy dirt on the surface of the composite diffusion layer matrix, after full drying, the composite diffusion layer matrix is put into a vacuum sintering furnace or protective atmosphere with reducing property, after vacuum sintering, the surface flatness of the composite diffusion layer matrix is improved through a leveling and annealing stress-removing process, and the final composite diffusion layer matrix is obtained, wherein a thermoplastic conductive material breaks away from the composite diffusion layer matrix under the high-temperature condition, and a support base layer is arranged at the lowest part during sintering;
3) And (2) the final composite diffusion layer obtained in the step (2) is basedAnd (3) carrying out surface treatment on the body: putting the composite diffusion layer matrix into a mixed solution containing a noble metal precursor and a carbon nitride precursor, fully stirring, putting the mixed solution into a muffle furnace for calcining, decomposing the carbon nitride precursor at high temperature to form gas molecules, inserting and impacting the surface of the composite diffusion layer matrix, and oxidizing the titanium material of the composite diffusion layer matrix at high temperature to form g-C 3 N 4 And the noble metal is embedded into the thin layer in a punctiform form through high-temperature reduction to form a corrosion-resistant coating with stronger binding force, so that the preparation is completed.
Preferably, in the step 2), the thermoplastic conductive material is one or a combination of several of polyethylene emulsion, polypropylene emulsion, polyvinyl chloride emulsion, polystyrene emulsion, polyester emulsion and polyamide emulsion; the dilute acid solution is hydrochloric acid or sulfuric acid with the mass fraction of 10-20%; the temperature and pressure of the vacuum sintering are required to be customized for different wire diameters and structures, and the vacuum degree is less than 3 x 10 -2 Pa, sintering temperature is 1000-1500 ℃; and flattening the sintered composite diffusion layer matrix by adopting a flattening machine through multiple pressing rollers.
Preferably, in step 3), the noble metal precursor is any one of chloroplatinic acid, platinum tetrachloride, platinum nitrate, chloroiridic acid, iridium trichloride and bromoiridic acid; the mass feed ratio of the noble metal precursor is 5-10%; the carbon nitride precursor is any one of urea, thiourea, melamine and dicyandiamide; in the mixed solution, the mass ratio of the carbon nitride precursor to deionized water is 1:1-2; the high-temperature calcination temperature is 450-550 ℃, and the heat preservation time is 2-5h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the surface of the composite diffusion layer is smoother, and the composite diffusion layer has certain porosity and specific surface area, so that on one hand, the phenomenon that a simple titanium fiber felt damages a surface catalytic layer of a membrane electrode under a high-pressure reaction condition to cause activity reduction and safety risk can be avoided, and on the other hand, the problems of easy corrosion and poor toughness of carbon paper are avoided, and a guarantee is provided for the application of the long-time coupling fluctuation wind-solar power supply of an electrolytic stack; in addition, the composite diffusion layer structure can also be better and evenly coated with an anti-corrosion coating, so that the service life of the diffusion layer is prolonged; furthermore, the cost and performance of the composite diffusion layer are at an upper level, and the composite diffusion layer has high cost performance.
In a word, the composite diffusion layer prepared by the invention has the characteristics of low development cost, high stability, high activity, large specific surface area, compact mesh of a diffusion base layer, high strength of a support base layer, flat surface and the like, can be effectively used for PEM electrolytic hydrogen production under a high-pressure reaction condition, can reduce the cost of using a pure titanium fiber felt diffusion layer, can greatly avoid the problem of corrosion and fragmentation of a carbon paper serving as a cathode diffusion layer, improves the design life of a PEM electrolytic hydrogen production system, reduces the operation and maintenance cost of the system, promotes the large-scale commercial application of PEM hydrogen production, and is worthy of popularization.
Drawings
FIG. 1 is an optical microscope image of the composite diffusion layer obtained in example 1.
Figure 2 is an XRD pattern of the composite diffusion layer obtained in example 1.
Fig. 3 is an optical microscope image of the composite diffusion layer obtained in example 2.
Fig. 4 is an XRD pattern of the composite diffusion layer obtained in example 2.
Fig. 5 is a surface view of a membrane electrode after operation of a titanium fiber blanket diffusion layer.
Fig. 6 is an optical microscope image of the carbon paper after the diffusion layer was run.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
A TA1 brand titanium wire with the wire diameter of 0.05mm is selected, a 200-mesh titanium woven wire mesh is formed by twill, meanwhile, a diamond-shaped mesh with the aperture of 2 x 4mm is formed by punching and stretching a titanium foil with the thickness of 0.1mm, wherein the 200-mesh titanium woven wire mesh is close to the membrane electrode side, and the diamond-shaped mesh is close to the bipolar plate side. The meshes of the 200-mesh titanium woven silk screen and the diamond-shaped mesh are reversely placed, so that welding with different sizes can not be locally generated between the 200-mesh titanium woven silk screen and the diamond-shaped mesh in order to ensure the structural consistency of the subsequent sintering process, and meanwhile, the original meshes do not occurThe method comprises the steps of obviously deforming, forming a micro mastoid structure on a 200-mesh titanium woven wire mesh and a diamond wire mesh surface by adopting a die before the 200-mesh titanium woven wire mesh and the diamond wire mesh are overlapped, fixing the micro mastoid structure together to form a whole by a mode of embedding the protrusions of the mastoid into the pits and static friction force between the 200-mesh titanium woven wire mesh and the diamond wire mesh, serving as a composite diffusion layer matrix, coating thermoplastic conductive polyethylene emulsion in a liquid state on the mastoid position, and removing oil stains on the surface of the composite diffusion layer matrix by ultrasonic washing of a 10% dilute hydrochloric acid solution and deionized water after the thermoplastic conductive polyethylene emulsion is cooled. After being sufficiently dried, the mixture is dried at 1200 ℃ and the vacuum degree is 2.5-10 -2 And (3) sintering at high temperature for 2 hours under the Pa condition, leveling the sintered composite diffusion layer matrix for multiple times by a leveling machine, annealing, cutting to 50mm, then putting into a mixed solution of chloroplatinic acid and urea, wherein the dosage of chloroplatinic acid is 0.5g, the dosage of urea is 10g, the dosage of deionized water is 20ml, placing into a muffle furnace for calcining at 550 ℃ after ultrasonic stirring uniformly, preserving the heat for 4 hours, and taking out for subsequent electrochemical performance test after cooling to room temperature. FIG. 1 is an optical microscope image of the obtained composite diffusion layer, FIG. 2 is an XRD spectrum of the obtained composite diffusion layer, and an obvious diffraction peak corresponding to 002 crystal face of g-C3N4 appears near 27.5 degrees, and simultaneously, an obvious characteristic peak appears at 25.3 degrees, 37.9 degrees, 53.7 degrees and 60 degrees, and the characteristic peak is similar to TiO 2 Substantially in agreement, specify g-C 3 N 4 And the surface thin layer of the nitrogen doped titanium oxide intercalation structure is successfully synthesized. In addition, no significant platinum diffraction peak was observed, indicating that a lower loading resulted in a weaker detection signal.
Example 2
Selecting a TA1 brand titanium wire with the wire diameter of 0.05mm, forming a 200-mesh titanium woven wire mesh by adopting a twill, and adopting a TA1 brand titanium wire with the wire diameter of 0.1mm, forming a 80-mesh titanium woven wire mesh by adopting a twill, and simultaneously selecting a titanium foil with the thickness of 0.1mm to punch and stretch to form a diamond-shaped mesh with the aperture of 2 x 4mm, wherein the 200-mesh titanium woven wire mesh is close to the membrane electrode side, the diamond-shaped mesh is close to the bipolar plate side, and the 80-mesh titanium woven wire mesh is positioned between the 200-mesh titanium woven wire mesh and the diamond-shaped mesh. The 200 mesh titanium woven silk screen, the 80 mesh titanium woven silk screen and the meshes of the diamond mesh are reversely placed, so as to ensure the structural consistency of the subsequent sintering process, and the 200 mesh titaniumThe method is characterized in that the mesh screen, the 80-mesh titanium mesh screen and the diamond mesh screen can not generate welding with different sizes locally, meanwhile, the original mesh is not obviously deformed, a die is adopted to form a micro mastoid structure on the surfaces of the 200-mesh titanium mesh screen, the 80-mesh titanium mesh screen and the diamond mesh screen before the 200-mesh titanium mesh screen, the 80-mesh titanium mesh screen and the diamond mesh screen are overlapped, the micro mastoid structure is fixed together to form a whole body through the mode that the protrusions of the mastoid are embedded into the pits and static friction force between the protrusions of the mastoid to serve as a composite diffusion layer matrix, and thermoplastic conductive polyethylene emulsion in liquid state is coated at the mastoid position, and after the thermoplastic conductive polyethylene emulsion is cooled, ultrasonic washing is carried out through 10% dilute hydrochloric acid solution and deionized water to remove oil stains on the surface of the composite diffusion layer matrix. After being sufficiently dried, the mixture is dried at 1200 ℃ and the vacuum degree is 2.5-10 -2 And (3) sintering at high temperature for 2 hours under the Pa condition, leveling the sintered composite diffusion layer matrix for multiple times by a leveling machine, annealing, cutting to 50mm, then putting into a mixed solution of chloroplatinic acid and urea, wherein the dosage of chloroplatinic acid is 0.5g, the dosage of urea is 10g, the dosage of deionized water is 20ml, placing into a muffle furnace for calcining at 550 ℃ after ultrasonic stirring uniformly, preserving the heat for 4 hours, and taking out for subsequent electrochemical performance test after cooling to room temperature. Fig. 3 is an optical microscope image of the obtained composite diffusion layer, and fig. 4 is an XRD pattern of the obtained composite diffusion layer, which is substantially identical to fig. 2, and also illustrates successful synthesis of the composite diffusion layer structure of this example.
Example 3
A TA1 brand titanium wire with the wire diameter of 0.05mm is selected, a 200-mesh titanium woven wire mesh is formed by plain weave, and meanwhile, a diamond-shaped mesh with the aperture of 1 x 2mm is formed by punching and stretching a titanium foil with the thickness of 0.1mm, wherein the 200-mesh titanium woven wire mesh is close to the membrane electrode side, and the diamond-shaped mesh is close to the bipolar plate side. The mesh openings of the 200-mesh titanium woven wire mesh and the diamond mesh are reversely placed, so that welding with different sizes can not be generated locally by the 200-mesh titanium woven wire mesh and the diamond mesh in order to ensure the structural consistency of the subsequent sintering process, meanwhile, the original mesh openings are not obviously deformed, a micro mastoid structure is formed on the 200-mesh titanium woven wire mesh and the diamond mesh surface by adopting a die before the 200-mesh titanium woven wire mesh and the diamond mesh are overlapped, and the mastoid is embedded into the concave mode by the protrusion of the mastoid and the 200-mesh titanium woven wire meshThe thermoplastic conductive polyethylene emulsion is fixed together with static friction force between diamond nets to form a whole body to be used as a composite diffusion layer matrix, the mastoid position is coated with the thermoplastic conductive polyethylene emulsion in liquid state, and after the thermoplastic conductive polyethylene emulsion is cooled, the thermoplastic conductive polyethylene emulsion is ultrasonically washed by 20% of dilute hydrochloric acid solution and deionized water to remove greasy dirt on the surface of the composite diffusion layer matrix. After being fully dried, the vacuum degree is 3 x 10 at 1500 DEG C -2 And (3) sintering at high temperature for 2 hours under the Pa condition, leveling the sintered composite diffusion layer matrix for multiple times by a leveling machine, annealing, cutting to 50mm, then putting into a mixed solution of chloroplatinic acid and urea, wherein the dosage of chloroplatinic acid is 0.5g, the dosage of urea is 10g, the dosage of deionized water is 20ml, placing into a muffle furnace for calcining at 550 ℃ after ultrasonic stirring uniformly, preserving heat for 5 hours, and taking out for subsequent electrochemical performance test after cooling to room temperature.
Example 4
A TA1 brand titanium wire with the wire diameter of 0.05mm is selected, a 200-mesh titanium woven wire mesh is formed by plain weave, and meanwhile, a diamond-shaped mesh with the aperture of 1 x 2mm is formed by punching and stretching a titanium foil with the thickness of 0.1mm, wherein the 200-mesh titanium woven wire mesh is close to the membrane electrode side, and the diamond-shaped mesh is close to the bipolar plate side. The method comprises the steps of reversely placing meshes of a 200-mesh titanium woven wire mesh and a diamond-shaped mesh, ensuring the structural consistency of the subsequent sintering process, enabling the 200-mesh titanium woven wire mesh and the diamond-shaped mesh not to generate welding with different sizes locally, enabling the original meshes not to generate obvious deformation, forming a micro mastoid structure on the surfaces of the 200-mesh titanium woven wire mesh and the diamond-shaped mesh by adopting a die before the 200-mesh titanium woven wire mesh and the diamond-shaped mesh are overlapped, enabling the 200-mesh titanium woven wire mesh and the diamond-shaped mesh to be fixed together to form a whole through a mode that protrusions of mastoids are embedded into the pits and static friction force between the 200-mesh titanium woven wire mesh and the diamond-shaped mesh, serving as a composite diffusion layer matrix, coating thermoplastic conductive polyethylene emulsion in a liquid state on the mastoid position, and removing greasy dirt on the surface of the composite diffusion layer matrix through ultrasonic washing of 20% diluted hydrochloric acid solution and deionized water after the thermoplastic conductive polyethylene emulsion is cooled. After being fully dried, the vacuum degree is 3 x 10 at 1000 DEG C -2 High-temperature sintering for 2h under Pa condition, leveling the sintered composite diffusion layer matrix by a leveling machine for multiple times, annealing, cutting to 50mm, and adding into mixed solution of chloroplatinic acid and urea, wherein the dosage of chloroplatinic acid0.5g of urea 10g and 20ml of deionized water, and placing the mixture in a muffle furnace for calcining at 450 ℃ after ultrasonic stirring uniformly, preserving the heat for 2h, and taking out the mixture after cooling to room temperature for subsequent electrochemical performance test.
Example 5
A TA1 brand titanium wire with the wire diameter of 0.05mm is selected, a 200-mesh titanium woven wire mesh is formed by plain weave, and meanwhile, a diamond-shaped mesh with the aperture of 1 x 2mm is formed by punching and stretching a titanium foil with the thickness of 0.1mm, wherein the 200-mesh titanium woven wire mesh is close to the membrane electrode side, and the diamond-shaped mesh is close to the bipolar plate side. The method comprises the steps of reversely placing meshes of a 200-mesh titanium woven wire mesh and a diamond-shaped mesh, ensuring the structural consistency of the subsequent sintering process, enabling the 200-mesh titanium woven wire mesh and the diamond-shaped mesh not to generate welding with different sizes locally, enabling the original meshes not to generate obvious deformation, forming a micro mastoid structure on the surfaces of the 200-mesh titanium woven wire mesh and the diamond-shaped mesh by adopting a die before the 200-mesh titanium woven wire mesh and the diamond-shaped mesh are overlapped, enabling the 200-mesh titanium woven wire mesh and the diamond-shaped mesh to be fixed together to form a whole through a mode that protrusions of mastoids are embedded into the pits and static friction force between the 200-mesh titanium woven wire mesh and the diamond-shaped mesh, serving as a composite diffusion layer matrix, coating thermoplastic conductive polyethylene emulsion in a liquid state on the mastoid position, and removing greasy dirt on the surface of the composite diffusion layer matrix through ultrasonic washing of 20% diluted hydrochloric acid solution and deionized water after the thermoplastic conductive polyethylene emulsion is cooled. After being fully dried, the vacuum degree is 3 x 10 at 1500 DEG C -2 And (3) sintering at high temperature for 2 hours under the Pa condition, leveling the sintered composite diffusion layer matrix for multiple times by a leveling machine, annealing, cutting to 50mm, then putting into a mixed solution of chloroplatinic acid and urea, wherein the dosage of chloroplatinic acid is 0.5g, the dosage of urea is 5g, the dosage of thiourea is 5g, the dosage of deionized water is 20ml, placing into a muffle furnace for calcining at 550 ℃ after ultrasonic stirring uniformly, preserving heat for 5 hours, and taking out for subsequent electrochemical performance test after cooling to room temperature.
Comparative example 1
Porous sintered titanium containing a coating with the same precious metal loading, titanium fiber felt, composite diffusion layer in the examples and carbon paper were evaluated sequentially using a PEM cell with an active area of 50 x 50mm, wherein the membrane electrode was a komu N117 membrane with an anode iridium loading of 1mg/cm 2 Cathode platinum supportIn an amount of 0.3mg/cm 2 The conductivity of pure water is less than 0.1uS/cm, the torsion of electrolysis Chi Xuanjin is 5Nm, the working temperature is 60 ℃, the working pressure of the cathode side is 1.6MPa, the compression amount of various materials is considered, the compensation is carried out by finely adjusting the thickness of the frame in the experiment, and the overall thickness of the diffusion layer is controlled to be between 0.4 and 0.5 mm. As can be seen from table 1 below, the overall performance of the composite diffusion layer is at an upper level, and the performance is further improved with the increase of porosity, so that the problems of damage to the surface of the membrane electrode by the titanium felt fiber (see fig. 5) and corrosion and cracking of the carbon paper during long-term operation (see fig. 6) can be well avoided. In addition, the composite diffusion layer formed by sintering titanium wire meshes with different mesh numbers and mechanical strength is obviously superior to the direct physical superposition performance, and the current trend is more uniform by fusion bonding among different titanium wires after sintering, so that better electrochemical performance is realized. It is also known that by designing the flow passage aperture in a gradient manner according to the Bernoulli (Venturi) principle, the pressure difference can be realized so as to improve the gas flow velocity, further increase the water permeability and the air permeability of the diffusion layer and improve the mass transfer efficiency.
TABLE 1 electrochemical Properties of different diffusion layers
The above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, so variations in shape and principles of the present invention should be covered.
Claims (10)
1. A PEM electrolytic hydrogen production composite diffusion layer is characterized in that metal reticular porous materials with different specifications and types are sequentially placed according to the order from a membrane electrode to a bipolar plate when the diffusion layer is used and the principles of gradually decreasing mesh number or specific surface area, gradually increasing thickness and gradually improving mechanical strength are adopted; the metal mesh porous material near the membrane electrode side serves as a diffusion base layer, the high-density small mesh of the metal mesh porous material serves as a protection membrane electrode surface catalytic layer and improves the gas transmission rate, the metal mesh porous material near the bipolar plate side serves as a support base layer, the high mechanical strength and the large mesh of the metal mesh porous material serve as an equilibrium reaction pressure to reduce the deformation of the diffusion layer, and meanwhile, the surface tension of water seepage on the cathode side of the bipolar plate is reduced, so that the water seepage along the bipolar plate flow channel is accelerated to flow out of the electrolytic stack.
2. A PEM electrolytically hydrogen production composite diffusion layer according to claim 1 wherein the metal mesh porous material between the diffusion substrate and support substrate acts as a reinforcing and/or finishing layer to further enhance the performance of the composite diffusion layer.
3. A PEM electrolytically active hydrogen composite diffusion layer according to claim 2 wherein the surface of each metal mesh-like porous material forms a micro-mastoid structure, and adjacent metal mesh-like porous materials are held together as a composite diffusion layer matrix by the mastoid protrusions being embedded in the concavities and by static friction forces between them.
4. A PEM electrolytically generated hydrogen composite diffusion layer in accordance with claim 3 wherein the surface of said composite diffusion layer substrate forms g-C 3 N 4 And a thin layer of an intercalation structure of the noble metal and the nitrogen doped titanium oxide, and embedding the noble metal into the thin layer in a punctiform form through high-temperature reduction to form the corrosion-resistant coating with stronger binding force.
5. A PEM electrolytically generated hydrogen composite diffusion layer in accordance with claim 4 wherein said metal mesh porous material is metallic titanium to mitigate electrochemical corrosion at high potential; the metal mesh porous material has a structure of one or a combination of a plurality of fiber felts, fiber meshes, foam metals and porous metals.
6. A PEM electrolytically generated hydrogen composite diffusion layer in accordance with claim 5 wherein said metallic titanium is of grade TA1 to reduce the cation content of impurities generated during the reaction; the fiber mat is a drawn or cut fiber mat and must be long fiber; the fiber net is a woven net or a punching stretching net, and the placing direction keeps the holes to be in the same direction or in different directions, and is overlapped or penetrated.
7. A PEM electrolytically active hydrogen composite diffusion layer according to claim 6 wherein said woven mesh has a wire diameter of 0.05-0.1mm and a mesh size of 80-200 mesh, formed by plain or twill; the hole patterns of the punching and stretching net are diamond or hexagon, and the aperture is 1-2 x 2-4mm; the maximum diameter of the mastoid is required to be adjusted according to the size of the diffusion layer, and the maximum diameter of the mastoid corresponding to the 50mm diffusion layer is not more than 5mm.
8. A method of preparing a PEM electrolytically generated hydrogen composite diffusion layer in accordance with any one of claims 1-7 comprising the steps of:
1) According to the order from the membrane electrode to the bipolar plate when the diffusion layer is used, the metal mesh porous materials with different specifications and models are sequentially placed according to the principles that the mesh number or the specific surface area is gradually reduced, the thickness is gradually increased and the mechanical strength is gradually improved; the metal reticular porous material close to the membrane electrode side serves as a diffusion base layer, the metal reticular porous material close to the bipolar plate side serves as a support base layer, and meanwhile, the metal reticular porous material can be added between the diffusion base layer and the support base layer as a reinforcing layer and/or a modifying layer according to requirements, so that the performance of the composite diffusion layer is further enhanced;
2) Before the metal mesh porous materials are overlapped, a micro mastoid structure is formed on the surface of each metal mesh porous material by adopting a die, when the metal mesh porous materials are overlapped, every two metal mesh porous materials are fixed together to form a whole by embedding the mastoid bulges into the concave mode and static friction force between the metal mesh porous materials, the metal mesh porous materials are used as a composite diffusion layer matrix, the mastoid positions are coated with liquid thermoplastic conductive materials, and then the thermoplastic conductive materials are cooled, so that the binding force between different layers is further improved; then, ultrasonic washing is carried out through dilute acid solution and deionized water to remove greasy dirt on the surface of the composite diffusion layer matrix, after full drying, the composite diffusion layer matrix is put into a vacuum sintering furnace or protective atmosphere with reducing property, after vacuum sintering, the surface flatness of the composite diffusion layer matrix is improved through a leveling and annealing stress-removing process, and the final composite diffusion layer matrix is obtained, wherein a thermoplastic conductive material breaks away from the composite diffusion layer matrix under the high-temperature condition, and a support base layer is arranged at the lowest part during sintering;
3) And (3) carrying out surface treatment on the final composite diffusion layer matrix obtained in the step (2): putting the composite diffusion layer matrix into a mixed solution containing a noble metal precursor and a carbon nitride precursor, fully stirring, putting the mixed solution into a muffle furnace for calcining, decomposing the carbon nitride precursor at high temperature to form gas molecules, inserting and impacting the surface of the composite diffusion layer matrix, and oxidizing the titanium material of the composite diffusion layer matrix at high temperature to form g-C 3 N 4 And the noble metal is embedded into the thin layer in a punctiform form through high-temperature reduction to form a corrosion-resistant coating with stronger binding force, so that the preparation is completed.
9. The method for preparing a PEM electrolytic hydrogen production composite diffusion layer according to claim 8, wherein in step 2), said thermoplastic conductive material is one or a combination of several of polyethylene emulsion, polypropylene emulsion, polyvinyl chloride emulsion, polystyrene emulsion, polyester emulsion, polyamide emulsion; the dilute acid solution is hydrochloric acid or sulfuric acid with the mass fraction of 10-20%; the temperature and pressure of the vacuum sintering are required to be customized for different wire diameters and structures, and the vacuum degree is less than 3 x 10 -2 Pa, sintering temperature is 1000-1500 ℃; and flattening the sintered composite diffusion layer matrix by adopting a flattening machine through multiple pressing rollers.
10. The method for preparing a PEM electrolytic hydrogen production composite diffusion layer according to claim 8, wherein in step 3), said noble metal precursor is any one of chloroplatinic acid, platinum tetrachloride, platinum nitrate, chloroiridium acid, iridium trichloride, bromoiridium acid; the mass feed ratio of the noble metal precursor is 5-10%; the carbon nitride precursor is any one of urea, thiourea, melamine and dicyandiamide; in the mixed solution, the mass ratio of the carbon nitride precursor to deionized water is 1:1-2; the high-temperature calcination temperature is 450-550 ℃, and the heat preservation time is 2-5h.
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