CN114990604A - PEM water electrolysis cell catalyst loaded diffusion layer and preparation method thereof - Google Patents
PEM water electrolysis cell catalyst loaded diffusion layer and preparation method thereof Download PDFInfo
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 title claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 137
- 239000010936 titanium Substances 0.000 claims abstract description 137
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 137
- 239000011248 coating agent Substances 0.000 claims abstract description 85
- 238000000576 coating method Methods 0.000 claims abstract description 85
- 239000000835 fiber Substances 0.000 claims abstract description 75
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000011068 loading method Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 48
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000001680 brushing effect Effects 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000010422 painting Methods 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005238 degreasing Methods 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 2
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 2
- -1 tantalum butanediol Chemical compound 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
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 13
- 239000011247 coating layer Substances 0.000 abstract 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract 1
- 229910000457 iridium oxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 238000005303 weighing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- 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
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
A diffusion layer loaded by a PEM water electrolyzer catalyst and a preparation method thereof, wherein the diffusion layer comprises a metal diffusion layer substrate, an intermediate layer and a catalytic active layer; the preparation method comprises the following steps: 1) pretreating the surface of the titanium-based gas diffusion layer by using oxalic acid; 2) preparing the corrosion-resistant intermediate layer on the surface of the diffusion layer by a coating pyrolysis method 4) coating and sintering the intermediate layer to prepare the catalytic active layer. The invention prepares the double-layer coating layer on the diffusion layer, thereby not only ensuring the corrosion resistance and the conductivity of the metallic titanium as a gas diffusion layer, but also ensuring the binding force of a catalyst loading interface, simultaneously, the pretreated titanium fiber felt has larger specific surface area, effectively improving the effective catalytic activity area of the coating, effectively improving the electrochemical performance of noble metal oxide, and realizing the aim of reducing the load capacity of iridium oxide and keeping the stability of the PEM electrolytic water tank.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by electrolyzing water, and particularly relates to a diffusion layer loaded with a PEM water electrolyzer catalyst and a preparation method thereof.
Background
Facing increasingly severe energy shortage and environmental pollution, the wide application of hydrogen energy is considered as one of the important means for solving the problem. The hydrogen production by electrolyzing water is an important hydrogen production technology, and the hydrogen production mode is efficient and clean. Particularly, the water electrolysis technology of Proton Exchange Membrane (PEM) has good hydrogen production efficiency and high hydrogen purity (99.999 percent), and is the most promising water electrolysis hydrogen production mode. However, the proton exchange membrane electrolyzed water reaction tank must work in an acid environment, so that high requirements are imposed on the catalytic activity and stability of the catalyst in the acid environment.
When the electrolysis reaction in the PEM electrolysis cell is carried out, the anode of the cell is in an acid environment, the electrolysis voltage is usually higher than 1.6V, and therefore a titanium material with good stability must be selected. The common porous sintered titanium plate and titanium fiber felt of the anode diffusion layer have pore structures which can meet the mass transfer requirement of a PEM electrolytic cell and realize higher electrolytic performance, wherein the thickness of the titanium fiber felt is as low as 0.25mm, the porosity is as high as 70 percent, and the structure is more favorable for gas-liquid mass transfer. However, untreated metallic titanium generates a titanium dioxide film on the surface in an oxidizing environment, which results in a great reduction in conductivity. In order to maintain the conductivity of the coating, the surface is generally required to be plated with platinum for corrosion prevention, and the treatment mode has the problems of poor binding force, easy falling of the coating, passivation of a diffusion layer and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a diffusion layer loaded with a catalyst for a PEM water electrolysis cell and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a diffusion layer loaded by a catalyst of a PEM water electrolysis cell comprises a metal diffusion layer substrate, an intermediate layer and a catalytic active layer; the metal diffusion layer matrix is titanium fiber felt or porous titanium; the intermediate layer is Ta 2 O 5 And Pt, the catalytically active layer being IrO 2 And Ta 2 O 5 A mixed oxide coating.
The thickness of the metal diffusion layer substrate is 0.5-1.5 mm.
In the middle layer, the load amount of Pt is 0.2-2 mg cm -2 By Ta 2 O 5 The molar ratio of the element Ta in the form is 20-40%, and the thickness of the intermediate layer is 0.1-1 μm.
In the catalytic active layer, IrO is used 2 The loading capacity of the element Ir in the form is 1-3 mg cm -2 The molar ratio of the element Ta is 20-40%, and the thickness of the active layer is 0.5-5 μm.
The preparation method of the diffusion layer loaded on the PEM water electrolysis cell catalyst comprises the following specific preparation steps:
(1) pretreating the titanium fiber felt or the porous titanium;
(2) preparing a coating liquid A: dissolving 20-40 mol percent of tantalum source and 60-80 mol percent of platinum source in an organic solvent in sequence, and stirring at room temperature to form a base solution;
(3) preparing a coating liquid B: mixing and dissolving 60-80 mol percent of iridium source and 20-40 mol percent of tantalum source in an organic solvent, and stirring at room temperature to form active liquid;
(4) and coating and sintering: and (2) drying the pretreated titanium fiber felt in the step (1), then coating and sintering the surface by using a coating solution A, and then coating and sintering a coating solution B to obtain the catalytic diffusion layer of the PEM water electrolysis cell.
The step (1) of pretreating the surface of the titanium fiber felt or the porous titanium comprises the following steps:
(1.1) degreasing the surface of the titanium fiber felt or the porous titanium;
(1.2) soaking the titanium fiber felt or the porous titanium in dilute hydrochloric acid with the mass concentration of 3-15% for 3-5 min;
(1.3) boiling the titanium fibrofelt or the porous titanium in an oxalic acid solution with the mass concentration of 5-10% for 5-20 min;
(1.4) cleaning the titanium fiber felt or the porous titanium, and storing in absolute ethyl alcohol for later use.
The tantalum source in the step (2) and the step (3) is selected from any one of tantalum pentachloride n-butyl alcohol solution, tantalum butanediol and tantalum ethoxide.
The platinum source in the step (2) is selected from any one of chloroplatinic acid, platinum tetrachloride and platinum oxide.
The iridium source in the step (3) is selected from any one of chloroiridic acid, iridium trichloride and iridium bromide.
The organic solvent in the step (2) and the step (3) is the same, and any one or a mixture of n-butyl alcohol, isopropanol and ethanol is selected.
The step (4) of coating and sintering specifically comprises the following steps:
(4.1) coating the prepared coating liquid A on the pretreated titanium fiber felt, naturally airing, and putting in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.2) sintering the titanium fiber felt treated in the step (4.1) in a muffle furnace at 450-520 ℃ for 10-25 min, taking out, and cooling to room temperature;
(4.3) repeating the step (4.1) to ensure that the total coating thickness of the coating liquid A is 0.1-1 mu m, placing the treated titanium fiber felt in a muffle furnace at 450-520 ℃ for sintering for 50-75 min, taking out, and cooling to room temperature;
(4.4) coating the prepared coating liquid B on the titanium fibrofelt treated in the step (4.3), naturally airing, and putting the titanium fibrofelt in an oven at the temperature of 60-100 ℃ to completely volatilize the solvent;
(4.5) sintering the titanium fiber felt treated in the step (4.4) in a muffle furnace at 450-520 ℃ for 10-25 min, taking out, and cooling to room temperature;
(4.6) repeating the step (4.4) to ensure that the total painting thickness of the coating liquid B is 0.5-5 mu m; and (3) keeping the coated titanium fiber felt in a muffle furnace at 450-500 ℃ for 30-90min, taking out, and naturally cooling to room temperature.
Compared with the prior art, the invention has the beneficial effects that:
a platinum-containing intermediate layer with good conductivity is introduced on the surface of a commonly used titanium-based metal diffusion layer substrate, so that the titanium-based metal diffusion layer substrate has good electronic conductivity, an effective charge conduction channel exists between the titanium fibrofelt substrate and an oxide coating, the voltage is reduced, and titanium passivation caused by unfavorable charge conduction is inhibited; pretreatment of the titanium fibrofelt increases the area of coating adhesion, thereby increasing the effective catalytic activity area, reducing iridium loading by replacing iridium with a portion of platinum, while maintaining high catalytic activity of the electrode.
Drawings
FIG. 1 is a scanning electron microscope image of a PEM water electrolysis cell gas diffusion layer prepared by a thermal decomposition method according to the invention.
Fig. 2 is a scanning electron microscope image of the carbon fiber felt gas diffusion layer prepared in comparative example 1 of the present invention.
FIG. 3 is a scanning electron microscope image of the titanium fiber mat of comparative example 2 of the present invention (a) before acid washing, (b) after pretreatment).
FIG. 4 is a graph showing the electrocatalytic performance of example 1 of the present invention and comparative example 1.
FIG. 5 is an interface diagram of the gas diffusion layer of the PEM water electrolysis cell of the present invention, wherein 1 is a titanium fiber felt, 2 is a corrosion-resistant conductive intermediate layer, and 3 is a catalytic layer.
Detailed Description
The exemplary embodiments will be described herein in detail, and the embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of methods consistent with certain aspects of the invention, as detailed in the appended claims.
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings and examples.
Example one
A catalyst-loaded diffusion layer for a PEM water electrolyser as described in this example, with reference to figure 5,comprises a metal diffusion layer substrate, an intermediate layer and a catalytic active layer; the metal diffusion layer matrix is titanium fiber felt or porous titanium; the intermediate layer is Ta 2 O 5 And Pt, the catalytically active layer being IrO 2 And Ta 2 O 5 A mixed oxide coating.
The thickness of the metal diffusion layer substrate is 1 mm.
In the intermediate layer, the supported amount of Pt was 1.5mg cm -2 By Ta 2 O 5 The molar ratio of elemental Ta present as such is 30%.
In the catalytic active layer, IrO is used 2 The loading amount of the element Ir in the form is 2mg cm -2 The molar ratio of the element Ta was 30%.
The preparation method of the diffusion layer loaded with the catalyst for the PEM water electrolytic cell in the embodiment specifically comprises the following steps:
(1) pretreating a titanium fiber felt or porous titanium;
(1.1) degreasing the surface of the titanium fiber felt or the porous titanium;
(1.2) soaking the titanium fiber felt or the porous titanium in dilute hydrochloric acid with the mass concentration of 5% for 5 min;
(1.3) boiling a titanium fiber felt or porous titanium in a boiling oxalic acid solution with the mass concentration of 10% for 10 min;
(1.4) cleaning the titanium fiber felt or the porous titanium, and storing in absolute ethyl alcohol for later use.
2) Preparing a coating liquid A: weighing tantalum ethoxide solution, dissolving the tantalum ethoxide solution in n-butyl alcohol solvent, and stirring at room temperature until the tantalum ethoxide solution is completely dissolved to form solution I; weighing chloroplatinic acid according to the molar ratio of Ta to Pt which is 1:4, adding the chloroplatinic acid into the solution I, and stirring at room temperature until the chloroplatinic acid is completely dissolved to form coating liquid A;
3) preparing a coating liquid B: accurately weighing chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta to 7:3, mixing and dissolving the chloroiridic acid and the tantalum pentachloride n-butyl alcohol solution in a n-butyl alcohol solvent, and stirring at room temperature to form an active solution;
4) coating and sintering: and (2) drying the pretreated titanium fiber felt, brushing and sintering the coating liquid A on the surface, and then brushing and sintering the coating liquid B to obtain the catalytic diffusion layer of the PEM water electrolytic cell.
4.1) coating the prepared coating liquid A on the pretreated titanium fiber felt, naturally airing, and putting in an oven at 90-100 ℃ to completely volatilize the solvent;
4.2) placing the titanium fiber felt treated in the step 4.1) in a muffle furnace at 470-500 ℃ for sintering for 15min, taking out, and cooling to room temperature;
4.3) repeating the step 4.1) to ensure that the total painting thickness of the coating liquid A is 0.1 mu m, sintering the treated titanium fiber felt in a muffle furnace at 460-510 ℃ for 65min, taking out, and cooling to room temperature;
4.4) brushing the prepared coating liquid B on the titanium fibrofelt treated in the step 4.3), naturally airing, and putting in an oven at 70-100 ℃ to completely volatilize the solvent;
4.5) placing the titanium fiber felt treated in the step 4.4) in a muffle furnace at 450-520 ℃ for sintering for 25min, taking out, and cooling to room temperature;
4.6) repeating the step 4.4) to ensure that the total coating thickness of the coating liquid B is 0.5 mu m, keeping the temperature of the coated titanium fiber felt in a muffle furnace at 460-500 ℃ for 60min, taking out, and naturally cooling to room temperature.
The prepared PEM water electrolysis diffusion layer is loaded with a catalyst with a double-layer structure on a metal diffusion layer substrate. Referring to fig. 1, it can be seen that after the intermediate layer is uniformly attached to the surface of the metal diffusion layer substrate, the noble metal oxide active layer is uniformly attached to the surface of the diffusion layer, thereby reducing the exposure of the surface of the metal substrate. The uniform coating of the active layer is beneficial to improving the catalytic activity, can also effectively prevent the oxidation passivation of the titanium matrix, and plays a role in protecting the matrix.
Example two
The diffusion layer loaded with the catalyst for the PEM water electrolysis cell comprises a metal diffusion layer substrate, an intermediate layer and a catalytic active layer, and is shown in figure 5; the metal diffusion layer substrate is a titanium fiber felt or porous titanium; the intermediate layer is Ta 2 O 5 And Pt, the catalytic active layer is IrO 2 And Ta 2 O 5 A mixed oxide coating.
The thickness of the metal diffusion layer substrate is 1.2 mm.
In the intermediate layer, the supported amount of Pt was 0.2mg cm -2 By Ta 2 O 5 The molar ratio of the element Ta present is 20%.
In the catalytic active layer, IrO is used 2 The loading amount of the element Ir in the form is 1mg cm -2 The molar ratio of the element Ta was 20%.
The preparation method of the diffusion layer loaded with the catalyst for the PEM water electrolytic cell in the embodiment specifically comprises the following steps:
(1) pretreating a titanium fiber felt or porous titanium;
(1.1) degreasing the surface of the titanium fiber felt or the porous titanium;
(1.2) soaking the titanium fiber felt or the porous titanium in dilute hydrochloric acid with the mass concentration of 3% for 5 min;
(1.3) boiling a titanium fiber felt or porous titanium in a boiling oxalic acid solution with the mass concentration of 8% for 10 min;
and (1.4) cleaning the titanium fiber felt or the porous titanium, and storing the titanium fiber felt or the porous titanium in absolute ethyl alcohol for later use.
2) Preparing a coating liquid A: weighing tantalum ethoxide solution, dissolving the tantalum ethoxide solution in n-butyl alcohol solvent, and stirring at room temperature until the tantalum ethoxide solution is completely dissolved to form solution I; weighing chloroplatinic acid according to the molar ratio of Ta to Pt which is 2:3, adding the chloroplatinic acid into the solution I, and stirring at room temperature until the chloroplatinic acid is completely dissolved to form coating liquid A;
3) preparing a coating liquid B: accurately weighing chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta to 3:2, mixing and dissolving the chloroiridic acid and the tantalum pentachloride n-butyl alcohol solution in a n-butyl alcohol solvent, and stirring at room temperature to form an active solution;
4) coating and sintering: and (2) drying the pretreated titanium fiber felt, brushing and sintering the coating liquid A on the surface, and then brushing and sintering the coating liquid B to obtain the catalytic diffusion layer of the PEM water electrolytic cell.
4.1) coating the prepared coating liquid A on the pretreated titanium fiber felt, naturally airing, and putting in an oven at 60-100 ℃ to completely volatilize the solvent;
4.2) placing the titanium fiber felt treated in the step 4.1) in a muffle furnace at 450-520 ℃ for sintering for 10min, taking out, and cooling to room temperature;
4.3) repeating the step 4.1) to ensure that the total coating thickness of the coating liquid A is 1 mu m, placing the treated titanium fiber felt in a muffle furnace at 470-520 ℃ for sintering for 50min, taking out, and cooling to room temperature;
4.4) coating the prepared coating liquid B on the titanium fibrofelt treated in the step 4.3), naturally airing, and putting in an oven at 80-100 ℃ to completely volatilize the solvent;
4.5) placing the titanium fiber felt treated in the step 4.4) in a muffle furnace at 450-470 ℃ for sintering for 10min, taking out, and cooling to room temperature;
4.6) repeating the step 4.4) to ensure that the total coating thickness of the coating liquid B is 5 mu m, keeping the temperature of the coated titanium fiber felt in a muffle furnace at 480-500 ℃ for 30min, taking out, and naturally cooling to room temperature.
EXAMPLE III
The diffusion layer loaded with the catalyst for the PEM water electrolysis cell comprises a metal diffusion layer substrate, an intermediate layer and a catalytic active layer, and is described in the embodiment with reference to FIG. 5; the metal diffusion layer substrate is a titanium fiber felt or porous titanium; the intermediate layer is Ta 2 O 5 And Pt, the catalytically active layer being IrO 2 And Ta 2 O 5 A mixed oxide coating.
The thickness of the metal diffusion layer substrate is 1.5 mm.
In the intermediate layer, the loading amount of Pt is 2mg cm -2 From Ta 2 O 5 The molar ratio of the element Ta present is 40%.
In the catalytic active layer, IrO is used 2 The loading amount of the element Ir in the form is 2mg cm -2 The molar ratio of the element Ta is 40%.
The preparation method of the diffusion layer loaded with the catalyst for the PEM water electrolytic cell in the embodiment specifically comprises the following steps:
(1) pretreating a titanium fiber felt or porous titanium;
(1.1) degreasing the surface of the titanium fiber felt or the porous titanium;
(1.2) soaking the titanium fiber felt or the porous titanium in dilute hydrochloric acid with the mass concentration of 15% for 5 min;
(1.3) boiling the titanium fiber felt or the porous titanium in a boiling oxalic acid solution with the mass concentration of 8% for 10 min;
and (1.4) cleaning the titanium fiber felt or the porous titanium, and storing the titanium fiber felt or the porous titanium in absolute ethyl alcohol for later use.
2) Preparing a coating liquid A: weighing tantalum ethoxide solution, dissolving the tantalum ethoxide solution in n-butyl alcohol solvent, and stirring at room temperature until the tantalum ethoxide solution is completely dissolved to form solution I; weighing chloroplatinic acid according to the molar ratio of Ta to Pt which is 3 to 7, adding the chloroplatinic acid into the solution I, and stirring at room temperature until the chloroplatinic acid is completely dissolved to form coating liquid A;
3) preparing a coating liquid B: accurately weighing chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta to 4:1, mixing and dissolving the chloroiridic acid and the tantalum pentachloride n-butyl alcohol solution in a n-butyl alcohol solvent, and stirring at room temperature to form an active solution;
4) coating and sintering: and (2) drying the pretreated titanium fiber felt, painting and sintering the coating liquid A on the surface, and painting and sintering the coating liquid B to obtain the catalytic diffusion layer of the PEM water electrolysis cell.
4.1) coating the prepared coating liquid A on the pretreated titanium fiber felt, naturally drying the coating liquid A, and putting the dried coating liquid A in an oven at the temperature of 60-100 ℃ to completely volatilize the solvent;
4.2) placing the titanium fiber felt treated in the step 4.1) in a muffle furnace at 450-480 ℃ for sintering for 25min, taking out, and cooling to room temperature;
4.3) repeating the step 4.1) to ensure that the total coating thickness of the coating liquid A is 0.5 mu m, placing the treated titanium fiber felt in a muffle furnace at 450-500 ℃ for sintering for 75min, taking out, and cooling to room temperature;
4.4) brushing the prepared coating liquid B on the titanium fibrofelt treated in the step 4.3), naturally airing, and putting in an oven at 60-80 ℃ to completely volatilize the solvent;
4.5) placing the titanium fiber felt treated in the step 4.4) in a muffle furnace at 480-520 ℃ for sintering for 15min, taking out, and cooling to room temperature;
4.6) repeating steps 4.4) and 4.5) so that the total brushing thickness of the coating liquid B is 3 μm;
and (3) preserving the temperature of the coated titanium fibrofelt in a muffle furnace at 480-500 ℃ for 90min, taking out, and naturally cooling to room temperature.
Comparative example 1
Cutting a titanium fiber felt sample sheet with the size of (10 multiplied by 20) mm from a commercial titanium fiber felt, carrying out surface treatment on the titanium fiber felt by the pretreatment mode, and drying the titanium fiber felt sample sheet. Accurately weighing 40mg of commercial IrO 2 And adding the powder into a mixed solution consisting of 4mL of deionized water, 4mL of absolute ethyl alcohol and 40 mu L of naphthol, and performing ultrasonic dispersion for 2 hours to obtain a coating liquid. Dripping 186 μ L of coating liquid with a liquid-transfering gun for three times onto the titanium fiber felt, placing into an oven, and keeping the temperature at 120 deg.C for 2h to obtain iridium metal loading amount of 0.4mg/cm -2 The titanium fiber mat diffusion layer of (1) to obtain comparative example 1. FIG. 2 is an SEM image of a sample of comparative example 1.
Comparative example 2
The sample was cut out to a size of (10X 20) mm from a commercial titanium fiber mat, and the surface thereof was treated in the above-described pretreatment manner and then dried, to obtain comparative example 2. Fig. 3(a) is an SEM image of a titanium fiber mat without pretreatment, and fig. 3(b) is an SEM image after pretreatment.
H in the electrolyte of 0.5mol/L 2 SO 4 The Ag/AgCl electrode is used as a reference electrode, the Pt electrode is used as a counter electrode, the titanium fibrofelt diffusion layer prepared by the preparation method provided by the embodiment 1 and the comparative example 1 is used as a working electrode, and the electro-catalysis performance of the sample is tested in an electrochemical workstation under a three-electrode system. As can be seen from fig. 4, the titanium felt diffusion layer with double-layer catalyst support has better catalytic activity and lower overpotential of OER reaction.
Meanwhile, as can be seen from a comparison of fig. 1 and 2, the catalyst adhesion formed by the coating pyrolysis method is more uniform and dense than the coating obtained by the ink drop coating. Compared with fig. 3 and 4, the titanium fibrofelt treated by oxalic acid has a rougher surface, which is beneficial to forming a tight combination between the coating and the titanium substrate and preventing the titanium metal from being oxidized and passivated to cause the potential to rise.
In conclusion, the invention adopts a pyrolysis method to prepare the titanium fiber felt with a double-layer structure of the catalyst layer and the anticorrosive layer, has excellent corrosion resistance and conductivity and good oxygen evolution catalytic activity, and is suitable for the diffusion layer of the PEM water electrolyzer. The platinum is introduced between the titanium fibrofelt and the oxide catalyst layer, so that the charge conduction efficiency is increased, the stability of the electrode in use is increased, the load of the metal iridium is reduced, and the cost is reduced. The titanium fibrofelt pretreated by oxalic acid has larger specific surface area, and can effectively improve the catalytic activity area, thereby optimizing the electrochemical performance of the noble metal anode and prolonging the service life.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
It will be understood that the invention is not limited to what has been described above and that various modifications and changes can be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. A diffusion layer loaded by a catalyst of a PEM water electrolysis cell is characterized by comprising a metal diffusion layer substrate, an intermediate layer and a catalytic active layer; the metal diffusion layer matrix is titanium fiber felt or porous titanium; the intermediate layer is Ta 2 O 5 And Pt, the catalytically active layer being IrO 2 And Ta 2 O 5 A mixed oxide coating.
2. The catalyst-supported diffusion layer of the PEM water electrolyzer of claim 1 wherein the thickness of the metal diffusion layer substrate is 0.5-1.5 mm.
3. The diffusion layer loaded with the catalyst for the PEM water electrolyzer of claim 1, wherein the loading amount of Pt in the intermediate layer is 0.2-2 mg cm -2 By Ta 2 O 5 The molar ratio of the element Ta existing in the form is 20-40%, and the thickness of the middle layer is 0.1-1 mu m.
4. The PEM water electrolyzer catalyst-supported diffusion layer of claim 1 wherein said catalytically active layer is IrO 2 The loading capacity of the element Ir in the form is 1-3 mg cm -2 The molar ratio of the element Ta is 20-40%, and the thickness of the active layer is 0.5-5 μm.
5. The preparation method of the catalyst-supported diffusion layer of the PEM water electrolyzer based on claim 1 is characterized by comprising the following specific preparation steps:
(1) pretreating the titanium fiber felt or the porous titanium;
(2) preparing a coating liquid A: dissolving 20-40 mol percent of tantalum source and 60-80 mol percent of platinum source in an organic solvent in sequence, and stirring at room temperature to form a base solution;
(3) preparing a coating liquid B: mixing and dissolving 60-80 mol percent of iridium source and 20-40 mol percent of tantalum source in an organic solvent, and stirring at room temperature to form active liquid;
(4) and coating and sintering: and (2) drying the pretreated titanium fiber felt in the step (1), brushing and sintering the coating liquid A on the surface, and then brushing and sintering the coating liquid B to obtain the PEM water electrolysis cell catalytic diffusion layer.
6. The method for preparing the catalyst-supported diffusion layer of the PEM water electrolyzer of claim 5, wherein the step (1) of pretreating the surface of the titanium fiber felt or the porous titanium comprises the following steps:
(1.1) degreasing the surface of the titanium fiber felt or the porous titanium;
(1.2) soaking the titanium fiber felt or the porous titanium in dilute hydrochloric acid with the mass concentration of 3-15% for 3-5 min;
(1.3) boiling the titanium fibrofelt or the porous titanium in an oxalic acid solution with the mass concentration of 5-10% for 5-20 min;
(1.4) cleaning the titanium fiber felt or the porous titanium, and storing in absolute ethyl alcohol for later use.
7. The method for preparing the catalyst-supported diffusion layer of the PEM water electrolyzer of claim 5, wherein the tantalum source in the step (2) and the step (3) is selected from any one of tantalum pentachloride, tantalum butanediol and tantalum ethoxide.
8. The method for preparing the catalyst-supported diffusion layer of the PEM water electrolyzer of claim 5, wherein the platinum source of the step (2) is selected from any one of chloroplatinic acid, platinum tetrachloride and platinum oxide;
the iridium source in the step (3) is selected from any one of chloro-iridic acid, iridium trichloride and bromoiridic acid.
9. The method for preparing the catalyst-supported diffusion layer of the PEM water electrolyzer of claim 5, wherein the organic solvents in the step (2) and the step (3) are the same, and any one of n-butanol, isopropanol and ethanol or a mixture thereof is selected.
10. The method for preparing the catalyst-supported diffusion layer of the PEM water electrolyzer of claim 5, wherein the step (4) of painting and sintering specifically comprises the following steps:
(4.1) coating the prepared coating liquid A on the pretreated titanium fiber felt, naturally airing, and putting in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.2) sintering the titanium fiber felt treated in the step (4.1) in a muffle furnace at 450-520 ℃ for 10-25 min, taking out, and cooling to room temperature;
(4.3) repeating the step (4.1) to ensure that the total coating thickness of the coating liquid A is 0.1-1 mu m, placing the treated titanium fiber felt in a muffle furnace at 450-520 ℃ for sintering for 50-75 min, taking out, and cooling to room temperature;
(4.4) coating the prepared coating liquid B on the titanium fibrofelt treated in the step (4.3), naturally airing, and putting the titanium fibrofelt in an oven at the temperature of 60-100 ℃ to completely volatilize the solvent;
(4.5) sintering the titanium fiber felt treated in the step (4.4) in a muffle furnace at 450-520 ℃ for 10-25 min, taking out, and cooling to room temperature;
(4.6) repeating the step (4.4) to ensure that the total painting thickness of the coating liquid B is 0.5-5 mu m; and (3) keeping the coated titanium fiber felt in a muffle furnace at 450-500 ℃ for 30-90min, taking out, and naturally cooling to room temperature.
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