An ordered electrode suitable for use in an electrolytic device and a method of making the same

Abstract

The application provides an ordered electrode for an electrolysis device and a preparation method thereof. The ordered electrode comprises a support structure, an ion transport layer and a catalyst layer, wherein the ion transport layer at least partially covers the surface of the support structure, and the catalyst layer at least partially covers the ion transport layer. The ordered electrode of the application provides an ordered support structure, which can facilitate material transport, reduce the loading of noble metal catalysts, and improve the utilization rate of catalyst active sites. In addition, the electronic transport layer between the support structure and the catalyst layer can effectively improve the migration rate of ions to the catalyst surface during the reaction process and reduce the mass transfer resistance.

Description

Technical Field

[0001] This application belongs to the field of electrode technology, specifically, it relates to an ordered electrode suitable for electrolysis devices and a method for preparing the same. Background Technology

[0002] Hydrogen plays a vital role as a secondary energy source, and green hydrogen is generally produced through water electrolysis. Currently, the high cost of green hydrogen production severely restricts its commercial application. Proton exchange membrane (PEM) water electrolysis technology requires large quantities of rare and precious metals such as iridium or ruthenium. Due to their scarcity on Earth, these elements are expensive, contributing to the high cost of PEM water electrolysis for hydrogen production. Therefore, reducing the amount of iridium or ruthenium used in the electrolyzer is crucial for lowering the cost of water electrolysis for hydrogen production.

[0003] In traditional membrane electrode structures, the loading of iridium or ruthenium, the active metals in the catalyst layer, is typically increased to 2-3 mg / cm³. 2 The catalyst layer is prepared by mixing and dispersing the catalyst and binder in a solvent and then applying them to the surface of the gas diffusion layer or the proton exchange membrane by spraying, brushing, or scraping. The catalyst layer prepared by this method exhibits a disordered stacking structure of catalyst powder particles, and the catalyst particles are prone to agglomeration under the action of the binder. Its disordered pore structure is not conducive to the transport of substances during the reaction process, resulting in the waste of a large number of active sites of the catalyst. The activity of the catalyst layer cannot be guaranteed by simply reducing the loading, thus leading to a high catalyst loading in traditional membrane electrodes.

[0004] The technology of ordering electrode preparation has been extensively studied in fuel cells. The ordering support in the catalyst layer of the ordered electrode used in fuel cells is usually carbon-based material or conductive polymer material. However, since the anode potential of PEM water electrolysis is much higher than that of the cathode electrode of the fuel cell during operation, traditional carbon-based materials and conductive polymer materials are easily oxidized during the operation of PEM water electrolysis equipment, and therefore cannot be used on the anode side of the water electrolysis equipment. Summary of the Invention

[0005] To address the problems existing in the prior art, this application provides an ordered electrode suitable for electrolysis devices and a method for preparing the same.

[0006] Specifically, this application relates to the following aspects:

[0007] An ordered electrode suitable for an electrolysis device, the ordered electrode comprising a support structure, an ion transport layer and a catalyst layer, wherein the ion transport layer at least partially covers the surface of the support structure and the catalyst layer at least partially covers the ion transport layer.

[0008] Optionally, the material of the ion transport layer is a proton transport material or anion transport material, preferably one or more of the following: perfluorosulfonic acid polymer, perfluorocarboxylic acid polymer, perfluorophosphate polymer, partially fluoropolymer, non-fluoropolymer, organic-inorganic complex, ionic polyphenylene ether (PPO), ionic polyarylene ether sulfone (PAES), ionic polyarylene ether ketone (PAEK), ionic polyolefin, ionic polybenzimidazole (PBI), and ionic polyaromatic hydrocarbon, wherein the ionic ions are selected from one or more of the following: quaternary phosphonium cation, guanidine salt ion, imidazole cation, quaternary ammonium cation, and metallocene cation; the partially fluoropolymer, the non-fluoropolymer, and the organic-inorganic complex have sulfonic acid groups, phosphate groups, or carboxylic acid groups.

[0009] Optionally, the material of the ion transport layer is selected from perfluorosulfonic acid polymers, preferably Nafion.

[0010] Optionally, the material of the ion transport layer is selected from partially fluoropolymers, wherein the side chains of the partially fluoropolymers have sulfonic acid groups, phosphate groups or carboxylic acid groups.

[0011] Optionally, the material of the ion transport layer is selected from non-fluoropolymers, which are selected from sulfonated or phosphorylated hydrocarbon polymers.

[0012] Optionally, the ion transport layer is a thin film.

[0013] Optionally, the thickness of the ion transport layer is 1 nm-10 μm, preferably 50 nm-1 μm.

[0014] Optionally, the support structure is a plurality of ordered nanowires or nanotubes.

[0015] Optionally, the diameter of the nanowire is 1-5000 nm, preferably 10-500 nm.

[0016] Optionally, the diameter of the nanotube is 5-10000 nm and the wall thickness is 0.5-100 nm.

[0017] Optionally, the material of the support structure is selected from one or more of metal oxides, metal hydroxides, basic metal carbonates, silicon, silicon dioxide, and carbon, preferably WO3. x MnO y TiO z NbO l One or more of layered bimetallic hydroxides and carbon, wherein x is 2-3, y is 1-2, z is 1-2, and l is 1-3.

[0018] Optionally, the material of the catalyst layer is selected from one or more of Pt, Ru, Ir, Rh, Au, Ni, Fe, Mo, Co, Pd, Re, Os, Nb, Sn, Ta, Sb or their oxides.

[0019] Optionally, the thickness of the catalyst layer is 0.1-50 μm, preferably 0.1-10 μm.

[0020] Optionally, the ordered electrode further includes an ion exchange membrane or a gas diffusion layer, and the support structure is disposed on the ion exchange membrane or the gas diffusion layer.

[0021] Optionally, the electrolysis device is a proton exchange membrane water electrolysis device, an anion exchange membrane water electrolysis device, or an alkaline water electrolysis device.

[0022] A method for preparing an ordered electrode suitable for an electrolysis device, the method comprising the following steps: preparing a support structure, preparing an ion transport layer on the surface of the support structure, and preparing a catalyst layer on the ion transport layer.

[0023] Optionally, the method for preparing the ion transport layer is selected from one or more of the following methods: spraying, vapor deposition, screen printing, immersion, and blade coating, with spraying being preferred.

[0024] Optionally, in the spraying method, the concentration of the spraying solution is 0.05%-5%, the spraying height is 5mm-150mm, the liquid flow rate is 0.1-8ml / min, and the nozzle moving speed is 50-2000mm / min.

[0025] Optionally, the preparation method of the support structure is selected from one or more of the following: hydrothermal method, electrochemical method, template method, spinning method, and gas phase synthesis method, preferably the electrochemical method.

[0026] Optionally, the method for preparing the catalyst layer is selected from one or more of the following methods: spraying, vapor deposition, sputtering, impregnation, and blade coating.

[0027] Optionally, the ordered electrode suitable for the electrolysis device is any of the ordered electrodes described above.

[0028] An electrolysis apparatus, the electrolysis apparatus comprising any of the above-described ordered electrodes.

[0029] The ordered electrode of this application provides an ordered support structure, which facilitates mass transport, reduces the loading of noble metal catalysts, and improves the utilization rate of catalyst active sites. Furthermore, the ion transport layer between the support structure and the catalyst layer effectively increases the migration rate of ions to the catalyst surface during the reaction, reducing mass transfer resistance. Compared with existing technologies, the ordered electrode of this application can effectively reduce the amount of noble metal catalyst while maintaining the activity of the catalyst layer. Moreover, the preparation method of this application is simple and controllable, and easy to scale up and mass-produce. Attached Figure Description

[0030] Figure 1 These are electron microscope images of the nanotubes prepared in Example 2;

[0031] Figure 2 These are electron microscope images of the ordered electrode prepared in Example 2;

[0032] Figure 3 This is a comparison diagram of the electrode performance prepared by patent CN114481196A and the ordered electrode performance prepared according to Example 2 of this patent.

[0033] Figure 4 This is the chemical structure of sPEPOF. Detailed Implementation

[0034] The present application is further illustrated below with reference to embodiments. It should be understood that the embodiments are only used to further illustrate and explain the present application and are not intended to limit the present application.

[0035] Unless otherwise defined, technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. While similar or identical methods and materials may be applied in experimental or practical applications, materials and methods are described herein. In case of conflict, the definitions included herein shall prevail. Furthermore, materials, methods, and examples are for illustrative purposes only and are not intended to be limiting. The present application is further described below with reference to specific embodiments, but is not intended to limit the scope of the application.

[0036] As mentioned above, existing ordered electrodes suffer from limitations in the application of traditional carbon-based materials and conductive polymer materials. Furthermore, existing ordered electrodes generally exhibit limited ion transport in water electrolysis devices. For example, patent CN114481196A describes a method for preparing IrO2 nanolayers on the surface of an ordered nanoarray support via electrochemical deposition. While this method improves the electronic conductivity of the electrode, the electrode structure relies solely on water for ion conduction. During the electrolysis of water to produce hydrogen and oxygen, the anode undergoes an oxidation reaction that generates a large amount of oxygen, while the cathode undergoes a reduction reaction that generates a large amount of hydrogen. Especially at high current densities, the rapidly and continuously generated gas bubbles accumulate on the catalyst surface, forming a bubble layer. This results in a lack of effective ion conductors on the catalyst surface, limiting the ion transport required for the electrode reaction process. When ion transport is impeded, in a PEM water electrolysis device, the outward transport of protons generated in the reaction is hindered at the anode, and the transport of protons to the catalyst surface is hindered at the cathode, thus hindering the formation of the three-phase reaction interface during the electrode reaction; in an AEM water electrolysis device, the transport of OH- is hindered at the anode. - Transport to the catalyst surface hinders the formation of the three-phase reaction interface during the electrode reaction, while for the cathode it hinders the generation of OH. - Because it transmits data externally, its performance will be significantly limited.

[0037] To address the problems existing in the prior art, this application provides an ordered electrode suitable for an electrolysis device, comprising a support structure, an ion transport layer, and a catalyst layer, wherein the ion transport layer at least partially covers the surface of the support structure, and the catalyst layer at least partially covers the ion transport layer.

[0038] The supporting structure is arranged in an ordered manner at the macroscopic or microscopic level. For example, the supporting structure can be multiple ordered nanowires or multiple ordered nanotubes, that is, multiple nanowires or nanotubes are regularly arranged along the same direction.

[0039] In one specific embodiment, the support structure is a plurality of ordered nanowires.

[0040] The diameter of the nanowire is 1-5000nm, for example, it can be 1nm, 5nm, 10nm, 20nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000nm, 3500nm, 4000nm, 4500nm, or 5000nm.

[0041] In one specific embodiment, the diameter of the nanowire is 10-500 nm.

[0042] In one specific embodiment, the support structure is a plurality of ordered nanotubes.

[0043] The diameter of the nanotube is 5-10000nm, for example, it can be 5nm, 10nm, 20nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1500nm, 2000nm, 2500nm, 3000nm, 3500nm, 4000nm, 4500nm, 5000nm, 5500nm, 6000nm, 6500nm, 7000nm, 7500nm, 8000nm, 8500nm, 9000nm, 9500nm, or 10000nm.

[0044] The wall thickness of the nanotube is 0.5-100nm, for example, it can be 0.5nm, 1nm, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, or 100nm.

[0045] In one specific embodiment, the nanotube has a diameter of 5-10000 nm and a wall thickness of 0.5-100 nm.

[0046] In one specific embodiment, the material of the support structure is selected from one or more of the following: metal oxides, metal hydroxides, basic metal carbonates, silicon, silicon dioxide, and carbon.

[0047] In one specific embodiment, the material of the support structure is selected from WO4. x MnO y TiO z NbO l One or more of the following: layered bimetallic hydroxides and carbon. Among them, WO3... x MnO y TiO z NbO l In this system, x represents 2-3, y represents 1-2, z represents 1-2, and l represents 1-3. The supporting structure can be made of materials such as WO3, MnO, MnO2, TiO2, or NbO.

[0048] Layered bimetallic hydroxides can be selected from one or more of nickel-iron hydrotalcite, cobalt-aluminum hydrotalcite, and MOF (metal-organic framework) derived metal hydroxides (such as Co-Ni-MOF).

[0049] The ion transport layer partially or completely covers the surface of the support structure.

[0050] The material of the ion transport layer may be the same as or different from that of the ion exchange membrane in the electrolysis equipment. When the material is different from that of the ion exchange membrane, it should have the corresponding ion transport capability. For example, when the ion exchange membrane is a proton exchange membrane, the ion transport layer must have proton transport capability, and when the ion exchange membrane is an anion exchange membrane, the ion transport layer must have anion transport capability.

[0051] In one specific embodiment, the material of the ion transport layer is selected from one or more of the following: perfluorosulfonic acid polymers, perfluorocarboxylic acid polymers, perfluorophosphate polymers, partially fluoropolymers, non-fluoropolymers, organic-inorganic complexes, ionic polyphenylene ethers (PPO), ionic polyarylene ether sulfones (PAES), ionic polyarylene ether ketones (PAEK), ionic polyolefins, ionic polybenzimidazoles (PBI), and ionic polyaromatics (aromatics without heteroatoms and having an aromatic hydrocarbon ring structure). The ions are selected from one or more of the following: quaternary phosphonium cations, guanidine salt ions, imidazole cations, quaternary ammonium cations, and metallocene cations, wherein the metallocene cations can be, for example, substituted or unsubstituted cobaltene cations, substituted or unsubstituted ferrocene cations, or substituted or unsubstituted nickelene cations. Partially fluoropolymers, non-fluoropolymers, and organic-inorganic complexes have sulfonic acid groups, phosphate groups, or carboxylic acid groups.

[0052] Perfluorosulfonic acid polymers can be prepared from perfluorosulfonic acid polymer dispersions, specifically DuPont's D520 and D2020, or Solvay's DFPSA-2179, DFSA-2079, DFPSA-2172, and DFSA-2072.

[0053] Some fluoropolymers can be polymers with some CF bonds and some CH bonds in their molecular chain structure, and the polymer side chains have sulfonic acid groups, phosphate groups or carboxylic acid groups, which enable them to transport protons. For example, they can be BAM membranes.

[0054] Non-fluoropolymers can be sulfonated or phosphorylated hydrocarbon polymers, such as sulfonated aromatic polymers, like sulfonated polybenzimidazole, polyimide, polysulfone, polyarylether, and polyketide.

[0055] Organic-inorganic complexes refer to complexes of inorganic compounds and organic polymers with cationic or anionic conductivity. The organic polymers with cationic or anionic conductivity can be perfluorosulfonic acid polymers, perfluorocarboxylic acid polymers, perfluorophosphate polymers, some fluorinated polymers, and non-fluorinated polymers. Some fluorinated polymers and non-fluorinated polymers have sulfonic acid groups, phosphate groups, or carboxyl groups. The inorganic compounds are metal oxides, inorganic acids, heteropoly acids, zeolites, phosphates (such as zirconium phosphate), silicon oxide, etc.

[0056] The ion transport layer is a thin film, preferably a polymer thin film, and the ion transport layer partially or completely covers the support structure.

[0057] The thickness of the ion transport layer can be 1nm-10μm, for example, 1nm, 5nm, 10nm, 20nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, 10μm.

[0058] In one specific embodiment, the thickness of the ion transport layer is 50 nm to 1 μm.

[0059] The ion transport layer can effectively improve the migration rate of ions to the catalyst surface during the reaction, especially at higher current densities. The ion transport layer must possess specific ion transport characteristics. For example, in PEM water electrolysis, the ion transport layer must have proton transport capability and its transport rate (ionic conductivity) should be in the range of 1–8000 mS / cm; when used in AEM water electrolysis, the ion transport layer must have OH... - The transmission capacity and its transmission rate (ionic conductivity) should be in the range of 0.5 to 5000 mS / cm.

[0060] This application, by setting an ion transport layer, avoids the problem in the prior art where ion transport around the catalyst is blocked when the electrode reaction rate is fast and gas bubbles are continuously generated, and can significantly improve the efficiency of the electrolyzer under high current density operating conditions.

[0061] The catalyst layer partially or completely covers the ion transport layer.

[0062] The catalyst layer material can be selected from one or more of Pt, Ru, Ir, Rh, Au, Ni, Fe, Mo, Co, Pd, Re, Os, Nb, Sn, Ta, Sb or their oxides.

[0063] The thickness of the catalyst layer can be adjusted according to the catalyst loading. Generally, the minimum catalyst loading should ensure that it forms a continuous structure, and the maximum loading should ensure that it does not fill the gaps between nanotubes or nanowires.

[0064] In one specific embodiment, the thickness of the catalyst layer is 0.1-50 μm, for example, it can be 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, etc. 22μm, 23μm, 24μm, 25μm, 26μm, 27μm, 28μm, 29μm, 30μm, 31μm, 32μm, 33μm, 34μm, 35μm, 36 μm, 37μm, 38μm, 39μm, 40μm, 41μm, 42μm, 43μm, 44μm, 45μm, 46μm, 47μm, 48μm, 49μm, 50μm.

[0065] In one specific embodiment, the thickness of the catalyst layer is 0.1-10 μm.

[0066] In one specific embodiment, the ordered electrode comprises a plurality of ordered nanowires, an ion transport layer, and a catalyst layer, wherein the ion transport layer at least partially covers the surface of the nanowires, and the catalyst layer at least partially covers the ion transport layer. The material of the ion transport layer is selected from one or more of the following: perfluorosulfonic acid polymers, perfluorocarboxylic acid polymers, perfluorophosphate polymers, partially fluorinated polymers, non-fluorinated polymers, organic-inorganic composites, ionic polyphenylene ether (PPO), ionic polyarylene ether sulfone (PAES), ionic polyarylene ether ketone (PAEK), ionic polyolefins, ionic polybenzimidazole (PBI), and ionic polyaromatic hydrocarbons. The ions are selected from one or more of the following: quaternary phosphonium cations, guanidine salt ions, imidazole cations, quaternary ammonium cations, and metallocene cations. The partially fluorinated polymer, the non-fluorinated polymer, and the organic-inorganic composite have sulfonic acid groups, phosphate groups, or carboxylic acid groups. The thickness of the ion transport layer is 50 nm-1 μm. The diameter of the nanowires is 10-500 nm. The material of the nanowires is selected from WO3. x MnO y TiO z NbO lThe catalyst layer comprises one or more of the following: layered bimetallic hydroxide, carbon, etc., wherein x is 2-3, y is 1-2, z is 1-2, and l is 1-3. The material of the catalyst layer is selected from one or more of Pt, Ru, Ir, Rh, Au, Ni, Fe, Mo, Co, Pd, Re, Os, Nb, Sn, Ta, Sb, or their oxides. The thickness of the catalyst layer is 0.1-10 μm.

[0067] In one specific embodiment, the ordered electrode comprises a plurality of ordered nanotubes, an ion transport layer, and a catalyst layer, wherein the ion transport layer at least partially covers the surface of the nanotubes, and the catalyst layer at least partially covers the ion transport layer. The material of the ion transport layer is selected from one or more of the following: perfluorosulfonic acid polymers, perfluorocarboxylic acid polymers, perfluorophosphate polymers, partially fluoropolymers, non-fluoropolymers, organic-inorganic composites, ionic polyphenylene ether (PPO), ionic polyarylene ether sulfone (PAES), ionic polyarylene ether ketone (PAEK), ionic polyolefins, ionic polybenzimidazole (PBI), and ionic polyaromatics. The ions are selected from one or more of the following: quaternary phosphonium cations, guanidine salt ions, imidazole cations, quaternary ammonium cations, and metallocene cations. The partially fluoropolymer, the non-fluoropolymer, and the organic-inorganic composite have sulfonic acid groups, phosphate groups, or carboxylic acid groups. The thickness of the ion transport layer is 50 nm to 1 μm. The nanotubes have a diameter of 5-10000 nm and a wall thickness of 0.5-100 nm. The material of the nanotubes is selected from WO3. x MnO y TiO z NbO l The catalyst layer comprises one or more of the following: layered bimetallic hydroxide, carbon, etc., wherein x is 2-3, y is 1-2, z is 1-2, and l is 1-3. The material of the catalyst layer is selected from one or more of Pt, Ru, Ir, Rh, Au, Ni, Fe, Mo, Co, Pd, Re, Os, Nb, Sn, Ta, Sb, or their oxides. The thickness of the catalyst layer is 0.1-10 μm.

[0068] The ordered electrode of this application may further include an ion exchange membrane or a gas diffusion layer, and the support structure is disposed on the ion exchange membrane or the gas diffusion layer.

[0069] The ion exchange membrane can be either a proton exchange membrane or an anion exchange membrane, and the gas diffusion layer structure can be a conductive porous material such as carbon paper, carbon cloth, metal felt, or metal mesh.

[0070] The ordered electrode of this application can be used in proton exchange membrane water electrolysis devices, anion exchange membrane water electrolysis devices, or alkaline water electrolysis devices, etc.

[0071] This application also provides a method for preparing an ordered electrode suitable for an electrolysis device, which includes the following steps:

[0072] Fabrication of support structure,

[0073] An ion transport layer is prepared on the surface of the support structure.

[0074] A catalyst layer is prepared on the ion transport layer.

[0075] The support structure can be fabricated on an ion exchange membrane or a gas diffusion layer. The fabrication method of the support structure is selected from one or more of the following: hydrothermal method, electrochemical method, template method, spinning method, and gas-phase synthesis method. The gas-phase synthesis method may include gas-phase oxidation, gas-phase decomposition, and atomized hydrolysis.

[0076] Those skilled in the art will understand that the specific process parameters used in methods such as hydrothermal synthesis, electrochemical synthesis, template synthesis, spinning synthesis, and vapor phase synthesis can be adjusted according to the actual type, material, and size of the support structure.

[0077] For example, when using an electrochemical method to prepare TiO2 nanotubes as a supporting structure, the electrode substrate is placed in an F-containing environment during the preparation process. - In electrolytes containing substances such as NH4F and KF, F... - The concentration is usually controlled between 0.05wt% and 2wt%. To adjust the electrolyte parameters, solvents such as ethylene glycol and isopropanol can be added to the electrolyte, with a concentration range of 30wt% to 95wt%, or salts such as (NH4)2SO4 and NaHSO4 can be added, with a concentration of 0.1 to 1 mol / L. During the oxidation process, the oxidation voltage is generally controlled between 5 and 80V, and the oxidation time is 10 min to 10 h.

[0078] The method for preparing the ion transport layer may be selected from one or more of the following: spraying, vapor deposition, screen printing, immersion, and blade coating.

[0079] Those skilled in the art will understand that the specific process parameters used in methods such as spraying, vapor deposition, screen printing, immersion, and blade coating can be adjusted according to the actual material and size of the ion transport layer.

[0080] Among them, spraying is the simplest and most effective method for preparing ion transport layers. For example, during the preparation process, the solution concentration can be controlled within the range of 0.05% to 5%, the spraying height can be set within the range of 5 mm to 150 mm, the liquid flow rate can be set within the range of 0.1 to 8 ml / min, the nozzle moving speed can be set within the range of 50 to 2000 mm / min, and the same position can be sprayed repeatedly multiple times.

[0081] The preparation method of the catalyst layer can be selected from one or more of the following methods: spraying, vapor deposition, sputtering, impregnation, and blade coating.

[0082] Those skilled in the art will understand that the specific process parameters used in methods such as spraying, vapor deposition, sputtering, impregnation, and blade coating can be adjusted according to the actual material and size of the catalyst layer.

[0083] In one specific embodiment, the ordered electrode suitable for the electrolysis device is any of the ordered electrodes described above. That is, the structure, material, and dimensions of the support structure, ion transport layer, and catalyst layer are as described above.

[0084] In one specific embodiment, the method for preparing an ordered electrode suitable for an electrolysis device includes the following steps:

[0085] The support structure was prepared using an electrochemical method.

[0086] An ion transport layer was prepared on the surface of the support structure using a spraying method.

[0087] A catalyst layer was prepared on the ion transport layer using a sputtering method.

[0088] This application also provides an electrolysis apparatus including any of the above-described ordered electrodes.

[0089] Example

[0090] Example 1

[0091] Regular, flat porous titanium plates were placed in containers containing distilled water, anhydrous ethanol, and acetone, respectively, and cleaned in an ultrasonic cleaning device for more than 30 minutes.

[0092] Electrochemical oxidation was carried out using a solution with a composition of 0.3 wt% NH4F, 10 wt% deionized water and 89.7 wt% ethylene glycol. The oxidation voltage was 50 V and the oxidation time was 5.5 h, thus preparing a titanium dioxide nanotube array structure.

[0093] A Nafion film with proton transport properties was fabricated on the titanium dioxide nanotube array prepared above. This Nafion film was prepared by ultrasonic spraying. During the preparation process, the concentration of the Nafion solution (specifically, a Nafion D520 dispersion manufactured by DuPont) was controlled at 0.1%, the spraying height was set to 50 mm, the liquid flow rate was 2 ml / min, the nozzle movement speed was 800 mm / min, and the same position was sprayed three times.

[0094] The sample prepared above was used to prepare a continuous IrO2 layer by reactive sputtering. During the preparation process, iridium metal was used as the target material, the ambient temperature was controlled at 25℃, and the process was carried out in a mixed atmosphere of Ar and O2, with an oxygen partial pressure of 35%, a gas flow rate of 100 sccm, a vacuum degree of 0.003 Pa, a target-substrate distance of 100 mm, a pulse power of 125 W, a frequency of 140 kHz, and a pulse width of 2 μs. This method can be used to prepare an ordered anodic electrode suitable for PEM water electrolysis.

[0095] Example 2

[0096] Regular, flat porous titanium plates were placed in containers containing distilled water, anhydrous ethanol, and acetone, respectively, and cleaned in an ultrasonic cleaning device for more than 30 minutes.

[0097] Electrochemical oxidation was carried out using a solution with a composition of 0.5 wt% NH4F, 10 wt% deionized water and 89.5 wt% ethylene glycol. The oxidation voltage was 55 V and the oxidation time was 3.5 h, thus preparing a titanium dioxide nanotube array structure.

[0098] A Nafion film with proton transport properties was fabricated on the titanium dioxide nanotube array prepared above. The Nafion film was mainly prepared by ultrasonic spraying. During the preparation process, the concentration of the Nafion solution (specifically, a Nafion D520 dispersion manufactured by DuPont) was controlled at 0.1%, the spraying height was set to 50 mm, the liquid flow rate was 2 ml / min, the nozzle movement speed was 800 mm / min, and the same position was sprayed three times.

[0099] The sample prepared above was used to prepare a continuous IrO2 layer by reactive sputtering. During the preparation process, iridium metal was used as the target material, the ambient temperature was controlled at 25℃, and the process was carried out in a mixed atmosphere of Ar and O2, with an oxygen partial pressure of 35%, a gas flow rate of 100 sccm, a vacuum degree of 0.003 Pa, a target-substrate distance of 100 mm, a pulse power of 125 W, a frequency of 140 kHz, and a pulse width of 2 μs. This method can be used to prepare an ordered anodic electrode suitable for PEM water electrolysis.

[0100] Example 3

[0101] Regular, flat porous titanium plates were placed in containers containing distilled water, anhydrous ethanol, and acetone, respectively, and cleaned in an ultrasonic cleaning device for more than 30 minutes.

[0102] Electrochemical oxidation was carried out using a solution with a composition of 0.5 wt% NH4F, 10 wt% deionized water and 89.5 wt% ethylene glycol. The oxidation voltage was 55 V and the oxidation time was 3.5 h, thus preparing a titanium dioxide nanotube array structure.

[0103] A layer of sPEPOF (sulfonated poly(diazanaphthyl ether phosphine)) with proton transport properties was prepared on the titanium dioxide nanotube array above. The molecular structure is as follows: Figure 4 (As shown) The sPEPOF membrane was mainly prepared by ultrasonic spraying. During the preparation process, the concentration of the sPEPOF solution was controlled at 0.1%, the spraying height was set at 50 mm, the liquid flow rate was 2 ml / min, the nozzle moving speed was 800 mm / min, and the same position was sprayed three times.

[0104] The sample prepared above was used to prepare a continuous IrO2 layer by reactive sputtering. During the preparation process, iridium metal was used as the target material, the ambient temperature was controlled at 25℃, and the process was carried out in a mixed atmosphere of Ar and O2, with an oxygen partial pressure of 35%, a gas flow rate of 100 sccm, a vacuum degree of 0.003 Pa, a target-substrate distance of 100 mm, a pulse power of 125 W, a frequency of 140 kHz, and a pulse width of 2 μs. This method can be used to prepare an ordered anodic electrode suitable for PEM water electrolysis.

[0105] Example 4

[0106] Regularly flat 5μm thick aluminum foil was placed in containers containing distilled water, anhydrous ethanol and acetone respectively, and cleaned in an ultrasonic cleaning device for more than 30 minutes; then it was fixed on the surface of a flat Pt sheet.

[0107] A Ti metal layer was prepared on the surface of aluminum foil by vapor deposition.

[0108] Electrochemical oxidation was carried out using a solution with a composition of 0.5 wt% NH4F, 10 wt% deionized water and 89.5 wt% ethylene glycol. The oxidation voltage was 55 V and the oxidation time was 3.5 h, thus preparing a titanium dioxide nanotube array structure.

[0109] A Nafion film with proton transport properties was fabricated onto the titanium dioxide nanotube array prepared above. This Nafion film was primarily prepared by ultrasonic spraying. During the preparation process, the concentration of the Nafion solution (specifically, a Nafion D520 dispersion manufactured by DuPont) was controlled at 0.1%, the spraying height was set to 50 mm, the liquid flow rate was 2 ml / min, the nozzle movement speed was 800 mm / min, and the same location was sprayed repeatedly 5 times.

[0110] The obtained structure was hot-pressed onto a Nafion 115 film, ensuring that the prepared titanium dioxide nanotubes remained in contact with the Nafion 115 film during the hot-pressing process. The hot-pressing pressure was controlled at 60 kPa and the hot-pressing temperature at 120 °C.

[0111] The obtained sample was placed in a 2M H2SO4 solution to etch away the aluminum foil substrate, thereby separating the platinum sheet from the sample and obtaining an ordered electrode structure integrating titanium dioxide nanotubes and Nafion 115 film.

[0112] The sample prepared above was used to prepare a continuous IrO2 layer by reactive sputtering. During the preparation process, iridium metal was used as the target material, the ambient temperature was controlled at 25℃, and the process was carried out in a mixed atmosphere of Ar and O2, with an oxygen partial pressure of 35%, a gas flow rate of 100 sccm, a vacuum degree of 0.003 Pa, a target-substrate distance of 75 mm, a pulse power of 125 W, a frequency of 140 kHz, and a pulse width of 2 μs. This method can be used to prepare an ordered anodic electrode suitable for PEM water electrolysis.

[0113] Example 5

[0114] Regularly flat 5μm thick aluminum foil was placed in containers containing distilled water, anhydrous ethanol and acetone respectively, and cleaned in an ultrasonic cleaning device for more than 30 minutes; then it was fixed on the surface of a flat Pt sheet.

[0115] A Ti metal layer was prepared on the surface of aluminum foil by vapor deposition.

[0116] Electrochemical oxidation was carried out using a solution with a composition of 0.5 wt% NH4F, 10 wt% deionized water and 89.5 wt% ethylene glycol. The oxidation voltage was 55 V and the oxidation time was 3.5 h, thus preparing a titanium dioxide nanotube array structure.

[0117] A Nafion film with proton transport properties was fabricated onto the titanium dioxide nanotube array prepared above. This Nafion film was primarily prepared by ultrasonic spraying. During the preparation process, the concentration of the Nafion solution (specifically, a Nafion D520 dispersion manufactured by DuPont) was controlled at 0.1%, the spraying height was set to 50 mm, the liquid flow rate was 2 ml / min, the nozzle movement speed was 800 mm / min, and the same location was sprayed four times.

[0118] The obtained structure was hot-pressed onto a Nafion 115 film, ensuring that the prepared titanium dioxide nanotubes remained in contact with the Nafion 115 film during the hot-pressing process. The hot-pressing pressure was controlled at 60 kPa and the hot-pressing temperature at 120 °C.

[0119] The obtained sample was placed in a 2M H2SO4 solution to etch away the aluminum foil substrate, thereby separating the platinum sheet from the sample and obtaining an ordered electrode structure integrating titanium dioxide nanotubes and Nafion 115 film.

[0120] The sample prepared above was used to prepare a continuous RuO2 layer by reactive sputtering. During the preparation process, ruthenium metal was used as the target material, the ambient temperature was controlled at 25℃, and the process was carried out in a mixed atmosphere of Ar and O2, with an oxygen partial pressure of 30%, a gas flow rate of 70 sccm, a vacuum degree of 0.003 Pa, a target-substrate distance of 100 mm, a pulse power of 125 W, a frequency of 140 kHz, and a pulse width of 2 μs. This method can be used to prepare an ordered anodic electrode suitable for PEM water electrolysis.

[0121] Example 6

[0122] Spinning solution: Weigh 9g of DMF (N,N-dimethylformamide) and 1g of PAN (peroxyacetyl nitrate) and dissolve them in a beaker. Weigh 0.3g of Nb2O5 and dissolve it in the above solution to obtain the spinning solution.

[0123] The above spinning solution was placed in a 5 mL syringe, with the needle voltage set to 15 kV, the spinning solution flow rate to 0.1 mm / min, and the distance between the needle and the receiver to 20 cm. Electrospinning was then performed on the spinning solution. The resulting spun film was calcined at 580 °C for 2 h to obtain Nb₂O₅ nanofibers.

[0124] The obtained structure was hot-pressed with a Nafion 115 film. During the hot-pressing process, the hot-pressing pressure was controlled at 60 kPa and the hot-pressing temperature was controlled at 120°C.

[0125] A Nafion film with proton transport properties was prepared from the Nb₂O₅ nanofibers described above. The Nafion film was primarily prepared by ultrasonic spraying. During the preparation process, the concentration of the Nafion solution (specifically, Nafion D520 dispersion manufactured by DuPont) was controlled at 0.1%, the spraying height was set to 50 mm, the liquid flow rate was 2 ml / min, the nozzle movement speed was 800 mm / min, and the same location was sprayed repeatedly 5 times.

[0126] The sample prepared above was used to prepare a continuous IrO2 layer by reactive sputtering. During the preparation process, iridium metal was used as the target material, the ambient temperature was controlled at 25℃, and the process was carried out in a mixed atmosphere of Ar and O2, with an oxygen partial pressure of 35%, a gas flow rate of 100 sccm, a vacuum degree of 0.003 Pa, a target-substrate distance of 75 mm, a pulse power of 125 W, a frequency of 140 kHz, and a pulse width of 2 μs. This method can be used to prepare an ordered anodic electrode suitable for PEM water electrolysis.

[0127] Example 7

[0128] Regular, flat porous titanium plates were placed in containers containing distilled water, anhydrous ethanol, and acetone, respectively, and cleaned in an ultrasonic cleaning device for more than 30 minutes.

[0129] Electrochemical oxidation was carried out using a solution with a composition of 0.5 wt% NH4F, 10 wt% deionized water and 89.5 wt% ethylene glycol. The oxidation voltage was 55 V and the oxidation time was 3.5 h, thus preparing a titanium dioxide nanotube array structure.

[0130] A polymer film layer (XC-1 produced by Sustainion) with anion transport properties was fabricated on the titanium dioxide nanotube array prepared above. The polymer film layer was mainly prepared by ultrasonic spraying. During the preparation process, the concentration of XC-1 solution was controlled at 0.1%, the spraying height was set at 50 mm, the liquid flow rate was 2 ml / min, the nozzle moving speed was 800 mm / min, and the same position was sprayed three times.

[0131] Prepare the acidic electroplating solution: The electroplating solution consists of 1M NiSO4 + 0.5M NiCl2 + 1.5M H3BO3.

[0132] The electroplating process employs a three-electrode system, with a pulse current of 50 mA / cm² during the process. 2 The pulse duration was 1 ms, the pulse interval was 5 ms, and the electrodeposition time was 40 s, while the electrolyte temperature was maintained at 25 °C throughout the process. This process allows for the preparation of an ordered electrode structure with deposited Ni particles.

[0133] The ordered electrode structure prepared by this method can be used as the anode catalyst layer in an anion electrolyte membrane water electrolysis device.

[0134] Comparative Example 1

[0135] Regular, flat porous titanium plates were placed in containers containing distilled water, anhydrous ethanol, and acetone, respectively, and cleaned in an ultrasonic cleaning device for more than 30 minutes.

[0136] Electrochemical oxidation was carried out using a solution with a composition of 0.5 wt% NH4F, 10 wt% deionized water and 89.5 wt% ethylene glycol. The oxidation voltage was 55 V and the oxidation time was 3.5 h, thus preparing a titanium dioxide nanotube array structure.

[0137] The sample prepared above was used to prepare a continuous IrO2 layer by reactive sputtering. During the preparation process, iridium metal was used as the target material, the ambient temperature was controlled at 25℃, and the process was carried out in a mixed atmosphere of Ar and O2, with an oxygen partial pressure of 35%, a gas flow rate of 100 sccm, a vacuum degree of 0.003 Pa, a target-substrate distance of 100 mm, a pulse power of 125 W, a frequency of 140 kHz, and a pulse width of 2 μs. This method can prepare an ordered anodic electrode suitable for PEM water electrolysis.

[0138] The main parameters used in the above embodiments and comparative examples are shown in Table 1.

[0139] Table 1

[0140]

[0141]

[0142]

[0143] The prepared electrodes can be characterized by scanning electron microscopy and elemental analysis to determine their structure and dimensional properties.

[0144] Figure 1 and Figure 2 The images show, respectively, the titanium dioxide nanotube array prepared in Example 2 obtained by scanning electron microscopy, and the titanium dioxide nanotubes after the preparation of the ion transport layer and catalytic layer. Figure 1 It can be seen that uniformly arranged and dense titanium dioxide nanotube arrays can be obtained through the above preparation methods. Figure 2 It can be seen that the preparation of the ion transport layer and the catalytic layer has formed a uniform structure on the surface of the nanotube.

[0145] The dimensions of each layer prepared in the above embodiments and comparative examples are shown in Table 2.

[0146] Table 2

[0147]

[0148]

[0149] Test Example 1 Performance Test

[0150] The electrodes prepared in the above embodiments and comparative examples were assembled into an electrolysis device for performance testing.

[0151] Test conditions: Comparative Example 1 and Examples 1-6 operated at 80°C, using a Nafion 115 membrane as the proton exchange membrane, with both anode and cathode gases at atmospheric pressure, Pt / C as the cathode, silica gel as the sealing gasket, and deionized water flowing through the anode; Example 7 operated at 50°C, using a Sustainion 37-50 membrane as the anion exchange membrane, with both anode and cathode gases at atmospheric pressure, Ni as the anode, PTFE as the sealing gasket, and 1% KOH electrolyte flowing through the anode.

[0152] The performance comparison between the electrode prepared in Example 1 of Patent CN114481196A (as a comparative patent) and the electrode prepared in Example 2 of this invention is as follows: Figure 3 As shown.

[0153] The voltage results obtained from the tests of each embodiment and comparative example are shown in Table 3, where the current concentration is 1 A / cm. 2 .

[0154] Table 3

[0155]

Claims

1. An ordered electrode suitable for use in an electrolytic device, characterized in that, The ordered electrode comprises a support structure, an ion transport layer and a catalyst layer, wherein the ion transport layer at least partially covers the surface of the support structure, and the catalyst layer at least partially covers the ion transport layer. The material of the support structure is selected from one or more of metal oxides, metal hydroxides, basic metal carbonates, silicon, and silicon dioxide. The material of the ion transport layer is selected from one or more of perfluorosulfonic acid polymers, perfluorocarboxylic acid polymers, perfluorophosphonic acid polymers, partially fluorine-containing polymers, non-fluorine polymers, organic-inorganic composites, polyphenylene oxide (PPO) with ions, polyarylether sulfone (PAES) with ions, polyarylether ketone (PAEK) with ions, polyolefin with ions, polybenzimidazole (PBI) with ions, and polyaromatic hydrocarbon with ions. The ions carried by the ion transport layer are selected from one or more of quaternary phosphonium cations, guanidinium ions, imidazole cations, quaternary ammonium cations, and metallocene cations.

2. The ordered electrode of claim 1, wherein The material of the ion transport layer is selected from perfluorosulfonic acid polymers.

3. The ordered electrode of claim 2, wherein, The material of the ion transport layer is Nafion.

4. The ordered electrode of claim 1, wherein The material of the ion transport layer is selected from partially fluorine-containing polymers, and the branched chains of the partially fluorine-containing polymers have sulfonic acid groups, phosphoric acid groups, or carboxylic acid groups.

5. The ordered electrode of claim 1, wherein The material of the ion transport layer is selected from non-fluorine polymers, and the non-fluorine polymers are selected from sulfonated or phosphonated hydrocarbon polymers.

6. The ordered electrode of claim 1, wherein The ion transport layer is a thin film.

7. The ordered electrode of claim 1, wherein The thickness of the ion transport layer is 1 nm to 10 μm.

8. The ordered electrode of claim 7, wherein, The thickness of the ion transport layer is 50 nm to 1 μm.

9. The ordered electrode of claim 1, wherein The support structure is a plurality of orderly arranged nanowires or nanotubes.

10. The ordered electrode of claim 9, wherein The diameter of the nanowires is 1 nm to 5000 nm.

11. The ordered electrode of claim 10, wherein, The diameter of the nanowires is 10 nm to 500 nm.

12. The ordered electrode of claim 9, wherein, The tube diameter of the nanotubes is 5 nm to 10000 nm, and the tube wall thickness is 0.5 nm to 100 nm.

13. The ordered electrode of claim 1, wherein The material of the support structure is selected from one or more of WO x , MnO y , TiO z , NbO l , and a layered double hydroxide, wherein x is 2-3, y is 1-2, z is 1-2, and 1 is 1-3.

14. The ordered electrode of claim 1, wherein The material of the catalyst layer is selected from one or more of Pt, Ru, Ir, Rh, Au, Ni, Fe, Mo, Co, Pd, Re, Os, Nb, Sn, Ta, Sb, and oxides thereof.

15. The ordered electrode of claim 1, wherein The thickness of the catalyst layer is 0.1 μm to 50 μm.

16. The ordered electrode of claim 15, wherein, The thickness of the catalyst layer is 0.1 μm to 10 μm.

17. The ordered electrode of claim 1, wherein The ordered electrode further comprises an ion exchange membrane or a gas diffusion layer, and the support structure is arranged on the ion exchange membrane or the gas diffusion layer.

18. The ordered electrode of claim 1, wherein, The electrolytic device is a proton exchange membrane water electrolysis device, an anion exchange membrane water electrolysis device, or an alkaline water electrolysis device.

19. A method for the preparation of the ordered electrode according to any one of claims 1-18 suitable for use in an electrolytic device, characterized by, The preparation method comprises the following steps: preparing a support structure, preparing an ion transport layer on the surface of the support structure, preparing a catalyst layer on the ion transport layer.

20. The method of claim 19, wherein, The preparation method of the ion transport layer is selected from one or more of spraying, vapor deposition, screen printing, dipping, and blade coating.

21. The method of claim 20, wherein, The preparation method of the ion transport layer is spraying.

22. The preparation method according to claim 20, characterized in that, In the spraying method, the concentration of the spraying solution is 0.05%-5%, the spraying height is 5mm-150mm, the liquid flow rate is 0.1-8ml / min, and the nozzle moving speed is 50-2000mm / min.

23. The preparation method according to claim 19, characterized in that, The preparation method of the support structure is selected from one or more of a hydrothermal method, an electrochemical method, a template method, a spinning method, and a gas phase synthesis method.

24. The method of claim 23, wherein, The preparation method of the support structure is an electrochemical method.

25. The preparation method according to claim 19, characterized in that, The preparation method of the catalyst layer is selected from one or more of a spraying method, a gas phase deposition method, a sputtering method, an impregnation method, and a blade coating method.

26. An electrolysis device, characterized by The electrolysis device comprises the ordered electrode according to any one of claims 1-18.

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