WO2023037755A1 - Pompe à hydrogène électrochimique - Google Patents

Pompe à hydrogène électrochimique Download PDF

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Publication number
WO2023037755A1
WO2023037755A1 PCT/JP2022/027348 JP2022027348W WO2023037755A1 WO 2023037755 A1 WO2023037755 A1 WO 2023037755A1 JP 2022027348 W JP2022027348 W JP 2022027348W WO 2023037755 A1 WO2023037755 A1 WO 2023037755A1
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Prior art keywords
anode
cathode
diffusion layer
gas diffusion
main surface
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PCT/JP2022/027348
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English (en)
Japanese (ja)
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貴之 中植
幸宗 可児
修 酒井
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パナソニックＩｐマネジメント株式会社
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Publication of WO2023037755A1 publication Critical patent/WO2023037755A1/fr

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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • 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
    • Y02E60/50—Fuel cells

Definitions

  • This disclosure relates to an electrochemical hydrogen pump.
  • Hydrogen has attracted attention as a clean alternative energy source to replace fossil fuels.
  • Hydrogen is expected to be a clean energy because it basically produces only water even if it is burned, does not emit carbon dioxide that causes global warming, and hardly emits nitrogen oxides.
  • a fuel cell which is being developed and spread for use as a power source for automobiles and for domestic private power generation.
  • Patent Document 1 describes an electrochemical hydrogen pump in which the anode gas diffusion layer is composed of a metal porous sheet.
  • Patent Document 2 describes an electrochemical cell in which a porous metal flow structure is composed of a titanium powder sintered body. It has been proposed to reduce the surface roughness of the main surface of this titanium powder sintered body by polishing or etching.
  • An object of one aspect of the present disclosure is to provide, as an example, an electrochemical hydrogen pump that can reduce the problems caused by the differential pressure between the anode and cathode more than ever before.
  • an electrochemical hydrogen pump includes an electrolyte membrane, an anode provided on one main surface of the electrolyte membrane, and an anode provided on the other main surface of the electrolyte membrane.
  • a cathode for applying a voltage between the anode and the cathode, wherein the voltage applicator applies the voltage to move hydrogen in the hydrogen-containing gas supplied to the anode through the electrolyte membrane to the cathode to generate compressed hydrogen
  • the anode is includes an anode catalyst layer and an anode gas diffusion layer, wherein the anode gas diffusion layer has a surface roughness on the anode separator side larger than that on the anode catalyst layer side.
  • the electrochemical hydrogen pump of one aspect of the present disclosure has the effect of being able to reduce problems caused by differential pressure between the anode and the cathode more than ever before.
  • FIG. 1A is a diagram showing an example of an electrochemical hydrogen pump according to an embodiment
  • FIG. FIG. 1B is an enlarged view of section B of the electrochemical hydrogen pump of FIG. 1A
  • FIG. 2A is a diagram showing an example of an electrochemical hydrogen pump according to an embodiment
  • FIG. 2B is an enlarged view of portion B of the electrochemical hydrogen pump of FIG. 2A.
  • FIG. 3 is a photograph showing an example of experimental results for verifying the relationship between the surface roughness of the main surface of the anode gas diffusion layer and water repellency.
  • the water present at the cathode of the electrochemical hydrogen pump penetrates the anode through the electrolyte membrane due to the differential pressure between the cathode and anode. Then, in such an electrochemical hydrogen pump, there is a possibility that the efficiency of the hydrogen compression operation decreases due to the occurrence of water clogging (flooding) in the gas flow path of the anode separator.
  • the present inventors have found that by appropriately setting the surface roughness of the pair of main surfaces of the anode gas diffusion layer, the cathode and anode of an electrochemical hydrogen pump Having found that it is possible to alleviate the problems caused by the differential pressure between the two, the following aspect of the present disclosure was conceived.
  • Patent Document 2 it is proposed to reduce the surface roughness of the main surface of the main sintered body by polishing or etching the titanium powder sintered body. This is a process performed to reduce contact resistance between constituent members in a chemical cell.
  • Patent Literature 2 does not discuss the magnitude relationship between the surface roughness of the pair of main surfaces of the anode gas diffusion layer.
  • the electrochemical hydrogen pump of the first aspect of the present disclosure includes an electrolyte membrane, an anode provided on one main surface of the electrolyte membrane, a cathode provided on the other main surface of the electrolyte membrane, and an anode separator provided on the cathode, a cathode separator provided on the cathode, and a voltage applicator that applies a voltage between the anode and the cathode, and the voltage applicator applies the voltage to the anode
  • the electrochemical hydrogen pump of this aspect can alleviate problems caused by the differential pressure between the anode and cathode more than before.
  • the surface roughness of the main surface of the anode gas diffusion layer on the anode separator side is reduced.
  • the wettability of the main surface of the anode gas diffusion layer on the side of the anode separator is reduced, that is, the water repellency is improved, compared to the case where the magnitude relationship is reversed.
  • the water repellent action of the main surface of the anode gas diffusion layer on the anode separator side causes water existing on the main surface on the anode separator side to be drained to the outside together with the hydrogen-containing gas.
  • the electrochemical hydrogen pump of this aspect can suppress a decrease in the efficiency of the hydrogen compression operation.
  • the surface roughness of the main surface of the anode gas diffusion layer on the anode catalyst layer side smaller than the surface roughness of the main surface of the anode gas diffusion layer on the anode separator side, the magnitude relationship between the surface roughnesses of both main surfaces is Compared to the opposite case, the hydrophilicity (wettability) of the main surface of the anode gas diffusion layer on the anode catalyst layer side is improved.
  • the electrochemical hydrogen pump of this aspect even if water permeates from the cathode to the anode due to the pressure difference between the anode and the cathode, the permeated water is retained on the main surface of the anode gas diffusion layer on the anode catalyst layer side.
  • flooding in the gas flow path of the anode separator can be suppressed by appropriately setting the magnitude relationship of the surface roughness of both main surfaces of the anode gas diffusion layer. can be done.
  • the electrochemical hydrogen pump of the second aspect of the present disclosure may be the electrochemical hydrogen pump of the first aspect, wherein the anode gas diffusion layer is a member containing a metal porous sheet.
  • the electrochemical hydrogen pump of the third aspect of the present disclosure may be the electrochemical hydrogen pump of the second aspect, wherein the metal porous sheet is a metal particle sintered sheet.
  • An electrochemical hydrogen pump of a fourth aspect of the present disclosure is the electrochemical hydrogen pump of any one of the first to third aspects, wherein the anode gas diffusion layer has a main surface on the anode catalyst layer side with a surface roughness Ra of It may be 4.5 ⁇ m or less, or the surface roughness Rz of the main surface on the anode catalyst layer side may be 20 ⁇ m or less.
  • the surface roughness Ra of the main surface of the anode gas diffusion layer on the anode catalyst layer side is 4.5 ⁇ m or less, or the main surface of the anode gas diffusion layer on the anode catalyst layer side
  • the anode gas diffusion layer can appropriately reduce the unevenness of the main surface on the anode catalyst layer side compared to the case where the surface roughness of the main surface exceeds the above value. can be made smaller.
  • An electrochemical hydrogen pump of a fifth aspect of the present disclosure is the electrochemical hydrogen pump of any one of the first to fourth aspects, wherein the anode gas diffusion layer has a surface roughness Ra of 6 ⁇ m on the main surface on the anode separator side. or more, or the surface roughness Rz of the main surface on the anode separator side may be 25 ⁇ m or more.
  • the surface roughness Ra of the main surface of the anode gas diffusion layer on the anode separator side is 6 ⁇ m or more, or the surface roughness Ra of the main surface of the anode gas diffusion layer on the anode separator side is 6 ⁇ m or more.
  • the anode gas diffusion layer can appropriately improve the water repellency of the main surface on the anode separator side compared to the case where the surface roughness of this main surface is below the above value. can.
  • FIG. 1A and 2A are diagrams showing an example of an electrochemical hydrogen pump according to an embodiment.
  • FIG. 1B is an enlarged view of section B of the electrochemical hydrogen pump of FIG. 1A.
  • FIG. 2B is an enlarged view of portion B of the electrochemical hydrogen pump of FIG. 2A.
  • FIG. 1A shows a vertical cross section of the electrochemical hydrogen pump 100 including a straight line passing through the center of the electrochemical hydrogen pump 100 and the center of the cathode gas outlet manifold 50 in plan view.
  • 2A also shows a vertical line of the electrochemical hydrogen pump 100 including a straight line passing through the center of the electrochemical hydrogen pump 100, the center of the anode gas inlet manifold 27, and the center of the anode gas outlet manifold 30 in plan view.
  • a cross section is shown.
  • the electrochemical hydrogen pump 100 includes at least one hydrogen pump unit 100A.
  • the electrochemical hydrogen pump 100 has a plurality of stacked hydrogen pump units 100A.
  • the number of hydrogen pump units 100A is not limited to this. In other words, the number of hydrogen pump units 100A can be set to an appropriate number based on operating conditions such as the amount of hydrogen that the electrochemical hydrogen pump 100 compresses.
  • the hydrogen pump unit 100A includes an electrolyte membrane 11, an anode AN, a cathode CA, a cathode separator 16, an anode separator 17, and an insulator 21.
  • electrolyte membrane 11, anode catalyst layer 13, cathode catalyst layer 12, anode gas diffusion layer 15, cathode gas diffusion layer 14, anode separator 17 and cathode separator 16 are laminated.
  • the anode AN is provided on one main surface of the electrolyte membrane 11 .
  • Anode AN is an electrode including anode catalyst layer 13 and anode gas diffusion layer 15 .
  • an annular sealing member 43 is provided so as to surround the anode catalyst layer 13 , and the anode catalyst layer 13 is properly sealed with the sealing member 43 .
  • the cathode CA is provided on the other main surface of the electrolyte membrane 11 .
  • Cathode CA is an electrode that includes a cathode catalyst layer 12 and a cathode gas diffusion layer 14 .
  • an annular sealing member 42 is provided so as to surround the cathode catalyst layer 12 , and the cathode catalyst layer 12 is properly sealed with the sealing member 42 .
  • MEA Membrane Electrode Assembly
  • the electrolyte membrane 11 has proton conductivity.
  • the electrolyte membrane 11 may have any configuration as long as it has proton conductivity.
  • Examples of the electrolyte membrane 11 include a fluorine-based polymer electrolyte membrane and a hydrocarbon-based polymer electrolyte membrane, but the electrolyte membrane 11 is not limited to these.
  • Nafion registered trademark, manufactured by DuPont
  • Aciplex registered trademark, manufactured by Asahi Kasei Corporation
  • the thickness of the electrolyte membrane 11 may be, for example, 7 ⁇ m or more and 100 ⁇ m or less.
  • the anode catalyst layer 13 is provided on one main surface of the electrolyte membrane 11 . Specifically, the main surface of the anode catalyst layer 13 and the main surface of the electrolyte membrane are in contact with each other.
  • the anode catalyst layer 13 contains, for example, platinum as a catalyst metal, but is not limited to this.
  • the cathode catalyst layer 12 is provided on the other main surface of the electrolyte membrane 11 . Specifically, the main surface of the cathode catalyst layer 12 and the main surface of the electrolyte membrane 11 are in contact with each other.
  • the cathode catalyst layer 12 contains, for example, platinum as a catalyst metal, but is not limited to this.
  • catalyst carriers for the cathode catalyst layer 12 and the anode catalyst layer 13 include, but are not limited to, carbon particles such as carbon black and graphite, and conductive oxide particles.
  • the cathode catalyst layer 12 and the anode catalyst layer 13 fine particles of catalyst metal are supported on the catalyst carrier in a highly dispersed manner.
  • a proton-conducting ionomer component is generally added to the cathode catalyst layer 12 and anode catalyst layer 13 in order to increase the electrode reaction field.
  • the cathode gas diffusion layer 14 is provided on the cathode catalyst layer 12 . Specifically, the main surface of the cathode gas diffusion layer 14 and the main surface of the cathode catalyst layer 12 are in contact with each other. Also, the cathode gas diffusion layer 14 is made of a porous material and has electrical conductivity and gas diffusion properties. Furthermore, it is desirable that the cathode gas diffusion layer 14 have elasticity so as to appropriately follow the displacement and deformation of the constituent members caused by the differential pressure between the cathode CA and the anode AN during operation of the electrochemical hydrogen pump 100 .
  • the cathode gas diffusion layer 14 may be a carbon porous sheet made of carbon fiber.
  • the porous carbon sheet may be a porous carbon fiber sheet such as carbon paper, carbon cloth, or carbon felt, but is not limited to these.
  • the anode gas diffusion layer 15 is provided on the anode catalyst layer 13 . Specifically, the main surface of the anode gas diffusion layer 15 and the main surface of the anode catalyst layer 13 are in contact with each other. Also, the anode gas diffusion layer 15 is made of a porous material and has electrical conductivity and gas diffusion properties. Furthermore, it is desirable that the anode gas diffusion layer 15 have high rigidity capable of suppressing the displacement and deformation of the constituent members caused by the differential pressure between the cathode CA and the anode AN during operation of the electrochemical hydrogen pump 100 .
  • the anode gas diffusion layer 15 is a member provided with a porous sheet 15S.
  • the porous sheet 15S may be a metal porous sheet or a carbon porous sheet.
  • metal porous sheets include metal particle sintered sheets made of titanium particles, stainless steel particles, and the like.
  • carbon porous sheet include a carbon particle sintered sheet.
  • the thickness of the anode gas diffusion layer 15 (porous sheet 15S) may be, for example, 0.1 mm or more and 1 mm or less.
  • the main surface 15A of the anode gas diffusion layer 15 on the anode separator 17 side has a larger surface roughness than the main surface 15B on the anode catalyst layer 13 side.
  • both main surfaces 15A , 15B, the water repellency of the main surface 15A of the anode gas diffusion layer 15 on the side of the anode separator 17 is improved compared to the case where the magnitude relationship of the surface roughnesses of 15B is reversed.
  • the reason for this is as follows.
  • the water repellency of a solid surface is formulated by the magnitude of the contact angle corresponding to the angle formed by the liquid surface and the solid surface when the surface of the liquid stationary on the solid surface contacts the solid surface.
  • An example of the relationship between the contact angle ⁇ A when the solid surface is rough and the contact angle ⁇ B when the solid surface is smooth is expressed by Wenzel's formula (1) below.
  • ⁇ SG , ⁇ LG and ⁇ SL represent interfacial free energies between solid-gas, liquid-gas and solid-liquid, respectively.
  • ⁇ in formula (1) is called roughness factor, which indicates the ratio of the apparent area of the solid surface to which surface roughness is imparted, and has a value of "1" or more.
  • the surface energy of the solid appears to be ⁇ times larger on the solid surface with the larger surface roughness, and the solid on the solid surface with the larger surface roughness - It can be seen that the increased contact area between the liquids emphasizes the water repellency compared to the solid surface with less surface roughness.
  • both main surfaces 15A, The main surface 15B of the anode gas diffusion layer 15 on the anode catalyst layer 13 side can be made smoother than when the magnitude relationship of the surface roughness of 15B is reversed.
  • anode gas diffusion layer 15 is provided with a conductive coating on at least both main surfaces of the porous sheet 15S in order to ensure desired conductivity between the anode catalyst layer 13 and the anode separator 17.
  • both main surfaces of the porous sheet 15S may be coated with highly conductive sheet-like coating films, or the surfaces of the electrode particles that constitute the porous sheet 15S may be coated. may be covered with a highly conductive coating film.
  • a platinum plating film with a small resistance can be mentioned, but it is not limited to this.
  • other than platinum other precious metals such as gold and ruthenium, diamond-like carbon, metal carbides, and metal nitrides can be used as materials for the coating film.
  • the thickness of the coating film may be set to 1/100 or less of the thickness of the porous sheet 15S.
  • the thickness of such a coating film can be measured by, for example, fluorescent X-ray analysis.
  • the anode separator 17 is provided on the anode gas diffusion layer 15 of the anode AN.
  • a cathode separator 16 is provided on the cathode gas diffusion layer 14 of the cathode CA.
  • a concave portion is provided in each central portion of the cathode separator 16 and the anode separator 17 .
  • a cathode gas diffusion layer 14 and an anode gas diffusion layer 15 are accommodated in each of these recesses.
  • the hydrogen pump unit 100A is formed.
  • the main surface of the cathode separator 16 that is in contact with the cathode gas diffusion layer 14 is a flat surface without any cathode gas flow path.
  • the contact area between the cathode gas diffusion layer 14 and the cathode separator 16 can be increased as compared with the case where the cathode gas flow path is provided on the main surface of the cathode separator 16 .
  • Electrochemical hydrogen pump 100 can then reduce the contact resistance between cathode gas diffusion layer 14 and cathode separator 16 .
  • the main surface of the anode separator 17 in contact with the anode gas diffusion layer 15 has, in plan view, a serpentine anode gas flow including, for example, a plurality of U-shaped folded portions and a plurality of straight portions.
  • a path 33 is provided. The linear portion of the anode gas channel 33 extends in the direction perpendicular to the paper surface of FIG. 2A.
  • an anode gas flow path 33 is an example and is not limited to this example.
  • the anode gas channel may be composed of a plurality of linear channels.
  • the anode gas flow path does not necessarily have to be formed by flow grooves provided on the surface of the metal sheet.
  • the anode gas flow path may be composed of a plurality of pores penetrating through the metal sheet in the thickness direction.
  • This metal sheet may be a support plate such as punching metal for supporting the anode gas diffusion layer 15 .
  • the hydrogen-containing gas flows in the plane of the metal sheet from the central portion of the metal sheet toward the peripheral edge of the metal sheet, part of the hydrogen-containing gas diffuses through the pores to the anode gas. Layer 15 is supplied.
  • annular and flat insulator 21 is sandwiched so as to surround the MEA. This prevents the cathode separator 16 and the anode separator 17 from short-circuiting.
  • the electrochemical hydrogen pump 100 includes a first end plate and a second end plate provided on both ends in the stacking direction of the hydrogen pump unit 100A, the hydrogen pump unit 100A, the first end plate and the second end plate. and a fastener 25 that fastens in the stacking direction.
  • the cathode end plate 24C and the anode end plate 24A respectively correspond to the above-described first end plate and second end plate. That is, the anode end plate 24A is an end plate provided on the anode separator 17 located at one end in the stacking direction in which the members of the hydrogen pump unit 100A are stacked. Also, the cathode end plate 24C is an end plate provided on the cathode separator 16 located at the other end in the stacking direction in which the members of the hydrogen pump unit 100A are stacked.
  • the fastener 25 may have any configuration as long as it can fasten the hydrogen pump unit 100A, the cathode end plate 24C and the anode end plate 24A in the stacking direction.
  • the fastener 25 may include a bolt and a nut with a disc spring.
  • the bolts of the fastener 25 may be configured to penetrate only the anode end plate 24A and the cathode end plate 24C. It penetrates each member of the hydrogen pump unit 100A, the cathode power supply plate 22C, the cathode insulating plate 23C, the anode power supply plate 22A, the anode insulating plate 23A, the anode end plate 24A and the cathode end plate 24C.
  • the end face of the cathode separator 16 located at the other end in the stacking direction and the end face of the anode separator 17 located at one end in the stacking direction are respectively connected to the cathode feeder plate 22C, the cathode insulating plate 23C, and the cathode separator 17.
  • a desired fastening pressure is applied to the hydrogen pump unit 100A by the fastener 25 so as to be sandwiched between the cathode end plate 24C and the anode end plate 24A through the anode power supply plate 22A and the anode insulating plate 23A.
  • the three-stage hydrogen pump units 100A are appropriately held in a stacked state by the fastening pressure of the fasteners 25 in the stacking direction, and the electrochemical hydrogen pump Since the bolt of the fastener 25 penetrates each member of 100, the movement of each member in the in-plane direction can be appropriately suppressed.
  • the cathode gas diffusion layers 14 of the hydrogen pump units 100A are communicated with each other.
  • the configuration in which the cathode gas diffusion layers 14 communicate with each other will be described below with reference to the drawings.
  • the cathode gas outlet manifold 50 includes through holes provided in each member of the three-stage hydrogen pump unit 100A and the cathode end plate 24C, and non-through holes provided in the anode end plate 24A. is composed of a sequence of A cathode gas lead-out path 26 is provided in the cathode end plate 24C.
  • the cathode gas lead-out path 26 may be composed of a pipe through which hydrogen (H 2 ) discharged from the cathode CA flows.
  • the cathode gas lead-out path 26 communicates with the cathode gas lead-out manifold 50 described above.
  • the cathode gas lead-out manifold 50 communicates with respective cathode gas diffusion layers 14 of the hydrogen pump unit 100A through respective cathode gas passages 34 .
  • the hydrogen that has passed through the cathode gas diffusion layers 14 and the cathode gas passages 34 of the hydrogen pump unit 100 ⁇ /b>A joins at the cathode gas outlet manifold 50 .
  • the merged hydrogen is guided to the cathode gas lead-out path 26 .
  • the cathode gas diffusion layers 14 of the hydrogen pump units 100A communicate with each other via the cathode gas passages 34 and the cathode gas outlet manifolds 50 of the hydrogen pump units 100A.
  • O-rings are provided between the cathode separator 16 and the anode separator 17, between the cathode separator 16 and the cathode power supply plate 22C, and between the anode separator 17 and the anode power supply plate 22A so as to surround the cathode gas outlet manifold 50 in plan view.
  • An annular sealing member 40 such as a sealing member 40 is provided, and the cathode gas outlet manifold 50 is properly sealed with this sealing member 40 .
  • an anode gas introduction path 29 is provided in the anode end plate 24A.
  • the anode gas introduction path 29 may be configured by a pipe through which the hydrogen-containing gas supplied to the anode AN flows.
  • hydrogen-containing gas examples include city gas containing methane gas and the like, LPG containing propane as a main component, and the like. Hydrogen gas etc. can be mentioned.
  • the anode gas introduction path 29 communicates with the tubular anode gas introduction manifold 27 .
  • the anode gas introduction manifold 27 is composed of a series of through holes provided in each member of the three-stage hydrogen pump unit 100A and the anode end plate 24A.
  • the anode gas introduction manifold 27 communicates with one end of each anode gas passage 33 of the hydrogen pump unit 100A via each of the first anode gas passages 35 .
  • the hydrogen-containing gas supplied from the anode gas introduction path 29 to the anode gas introduction manifold 27 is distributed to each of the hydrogen pump units 100A through the first anode gas passages 35 of the hydrogen pump units 100A. While the distributed hydrogen-containing gas passes through the anode gas flow path 33 , the hydrogen-containing gas is supplied from the anode gas diffusion layer 15 to the anode catalyst layer 13 .
  • the anode end plate 24A is provided with an anode gas lead-out path 31.
  • the anode gas lead-out path 31 may be composed of a pipe through which the hydrogen-containing gas discharged from the anode AN flows.
  • the anode gas lead-out path 31 communicates with the tubular anode gas lead-out manifold 30 .
  • the anode gas lead-out manifold 30 is composed of a series of through holes provided in each member of the three-stage hydrogen pump unit 100A and the anode end plate 24A.
  • the anode gas lead-out manifold 30 communicates with the other end of each anode gas passage 33 of the hydrogen pump unit 100A via each of the second anode gas passages 36 .
  • the hydrogen-containing gas that has passed through each of the anode gas passages 33 of the hydrogen pump unit 100A is supplied to the anode gas outlet manifold 30 through each of the second anode gas passages 36, where it joins. Then, the combined hydrogen-containing gas is led to the anode gas lead-out path 31 .
  • an anode gas introduction manifold 27 and an anode gas discharge manifold 30 are provided.
  • An annular sealing member 40 such as an O-ring is provided so as to surround the anode gas inlet manifold 27 and the anode gas outlet manifold 30, and the sealing member 40 appropriately seals them.
  • the electrochemical hydrogen pump 100 includes a voltage applicator 102.
  • the voltage applicator 102 is a device that applies a voltage between the anode AN and the cathode CA. That is, the electrochemical hydrogen pump 100 moves hydrogen in the hydrogen-containing gas supplied to the anode AN onto the cathode catalyst layer 12 via the electrolyte membrane 11 by applying the voltage from the voltage applicator 102 . , a device that produces compressed hydrogen.
  • the high potential of the voltage applicator 102 is applied to the anode AN, and the low potential of the voltage applicator 102 is applied to the cathode CA.
  • Voltage applicator 102 may have any configuration as long as it can apply a voltage between anode AN and cathode CA.
  • voltage applicator 102 may be a device that adjusts the voltage applied between anode AN and cathode CA.
  • the voltage applicator 102 includes a DC/DC converter when connected to a DC power supply such as a battery, a solar battery, or a fuel cell, and an AC power supply when connected to an AC power supply such as a commercial power supply. /DC converter.
  • the voltage applicator 102 adjusts the voltage applied between the anode AN and the cathode CA and the current flowing between the anode AN and the cathode CA so that the power supplied to the hydrogen pump unit 100A becomes a predetermined set value. It may also be a regulated power type power source.
  • the low potential side terminal of the voltage applicator 102 is connected to the cathode feed plate 22C, and the high potential side terminal of the voltage applicator 102 is connected to the anode feed plate 22A. It is The cathode feed plate 22C is in electrical contact with the cathode separator 16 located at the other end in the stacking direction, and the anode feed plate 22A is in electrical contact with the anode separator 17 located at one end in the stacking direction. are in electrical contact.
  • a hydrogen system including the electrochemical hydrogen pump 100 can also be constructed. In this case, equipment necessary for the hydrogen compression operation of the hydrogen system is appropriately provided.
  • the hydrogen system includes a highly humidified hydrogen-containing gas discharged from the anode AN through the anode gas lead-out path 31 and a low-humidified hydrogen-containing gas supplied from an external hydrogen supply source through the anode gas lead-in path 29.
  • a dew point adjuster eg, a humidifier
  • the hydrogen system includes, for example, a temperature detector that detects the temperature of the electrochemical hydrogen pump 100, a hydrogen reservoir that temporarily stores hydrogen discharged from the cathode CA of the electrochemical hydrogen pump 100, A pressure detector or the like for detecting the hydrogen gas pressure may be provided.
  • the following operations may be performed, for example, by an arithmetic circuit (not shown) of the controller reading out the control program from the storage circuit of the controller. However, it is not essential that the controller perform the following operations. The operator may perform some of the operations. In the following example, the case where the operation is controlled by the controller will be described.
  • a low-pressure hydrogen-containing gas is supplied to the anode AN of the electrochemical hydrogen pump 100 and the voltage of the voltage applicator 102 is supplied to the electrochemical hydrogen pump 100 .
  • the hydrogen-containing gas is often humidified by a humidifier (not shown).
  • the hydrogen (H 2 ) generated at the cathode CA can be compressed by increasing the pressure loss of a suitable hydrogen lead-out path using a flow rate regulator (not shown).
  • a flow rate regulator not shown
  • the cathode gas lead-out path 26 in FIG. 2A can be cited.
  • the flow rate regulator include a back pressure valve, a regulation valve, etc. provided in the cathode gas lead-out path 26 .
  • increasing the pressure loss in the cathode gas lead-out path 26 corresponds to reducing the opening degrees of the back pressure valve and the adjustment valve provided in the cathode gas lead-out path 26 .
  • the voltage applicator 102 applies the above voltage, thereby compressing hydrogen in the hydrogen-containing gas supplied to the anode AN at the cathode CA.
  • the hydrogen compression operation of the electrochemical hydrogen pump 100 is performed.
  • the amount of hydrogen in the hydrogen-containing gas decreases at the anode AN, and water vapor in the hydrogen-containing gas tends to condense.
  • water present in the cathode CA permeates into the anode AN through the electrolyte membrane 11 due to the differential pressure between the cathode CA and the anode AN. That is, in the electrochemical hydrogen pump 100 of this embodiment, flooding is likely to occur in the vicinity of the hydrogen-containing gas outlet of the anode AN.
  • the hydrogen compressed by the cathode CA is timely supplied to a hydrogen consumer (not shown).
  • hydrogen demanders include a hydrogen storage device for temporarily storing hydrogen, piping for hydrogen infrastructure, and a fuel cell for generating electricity using hydrogen.
  • hydrogen stored in a hydrogen storage device which is an example of a hydrogen consumer, may be supplied to a fuel cell, which is an example of a hydrogen consumer, in a timely manner.
  • the electrochemical hydrogen pump 100 of this embodiment can alleviate problems caused by the differential pressure between the anode AN and the cathode CA more than ever before.
  • the surface roughness of the main surface 15A of the anode gas diffusion layer 15 on the anode separator 17 side is improved as compared with the case where the surface roughness of the surfaces 15A and 15B is reversed.
  • water present on the main surface of the anode separator 17 side becomes hydrogen-containing due to the water-repellent effect of the main surface 15A of the anode gas diffusion layer 15 on the anode separator 17 side.
  • the electrochemical hydrogen pump 100 of the present embodiment can suppress a decrease in the efficiency of the hydrogen compression operation.
  • both main surfaces 15A The hydrophilicity (wettability) of the main surface 15B of the anode gas diffusion layer 15 on the anode catalyst layer 13 side can be improved compared to the case where the surface roughness of the surface 15B is reversed.
  • the electrochemical hydrogen pump 100 of the present embodiment even if water permeates from the cathode to the anode, the permeated water is easily retained on the main surface of the anode gas diffusion layer on the anode catalyst layer side, and the anode separator is formed. reduces the amount of permeated water reaching the gas flow path of the Therefore, the occurrence of flooding in the gas flow path of the anode separator due to permeated water from the cathode to the anode is suppressed.
  • the electrochemical hydrogen pump 100 of the present embodiment suppresses flooding in the anode AN by appropriately setting the magnitude relationship between the surface roughnesses of the main surfaces 15A and 15B of the anode gas diffusion layer 15. can do.
  • the surface roughness Ra of the main surface 15B of the anode gas diffusion layer 15 on the anode catalyst layer 13 side is 4.5 ⁇ m or less, or the main surface 15B of the anode gas diffusion layer 15 on the anode catalyst layer 13 side is suitable to have a surface roughness Rz of 20 ⁇ m or less.
  • the surface roughness Ra of the main surface 15B of the anode gas diffusion layer 15 on the anode catalyst layer 13 side is 4.5 ⁇ m or less, or the anode gas on the anode catalyst layer 13 side
  • the surface roughness Rz of the main surface 15B of the diffusion layer 15 is 20 ⁇ m or less
  • the anode gas diffusion layer 15 has a higher surface roughness than the anode catalyst layer 13 compared to the case where the surface roughness of the main surface 15B exceeds the above value.
  • the unevenness of the side main surface 15B can be appropriately reduced.
  • the permeated water is easily retained on the main surface of the anode gas diffusion layer on the anode catalyst layer side, and the amount of permeated water reaching the gas flow path of the anode separator is reduced. Therefore, the occurrence of flooding in the gas flow path of the anode separator due to permeated water from the cathode to the anode is suppressed.
  • the surface roughness Ra of the main surface 15B of the anode gas diffusion layer 15 on the anode catalyst layer 13 side is 2 ⁇ m or more, or the surface roughness Rz of the main surface 15B of the anode gas diffusion layer 15 on the anode catalyst layer 13 side is 10 ⁇ m. It is desirable to be above. If the surface roughness of the main surface 15B is made smaller than this, the hole diameter of the anode gas diffusion layer 15 needs to be made small, making it difficult for the hydrogen-containing gas supplied to the anode AN to be appropriately supplied to the anode catalyst layer 13. It is for the sake of becoming.
  • the electrochemical hydrogen pump 100 of this embodiment may be the same as the electrochemical hydrogen pump 100 of the embodiment except for the features described above.
  • the surface roughness of the main surface 15A of the anode gas diffusion layer 15 on the anode separator 17 side is greater than the surface roughness of the main surface 15B of the anode gas diffusion layer 15 on the anode catalyst layer 13 side.
  • the surface roughness Ra of the main surface 15A of the anode gas diffusion layer 15 on the anode separator 17 side is 6 ⁇ m or more, or the surface roughness of the main surface 15A of the anode gas diffusion layer 15 on the anode separator 17 side is It is suitable that Rz is 25 ⁇ m or more.
  • the surface roughness Ra of the main surface 15A of the anode gas diffusion layer 15 on the anode separator 17 side is set to 6 ⁇ m or more, or the surface roughness Ra of the anode gas diffusion layer 15 on the anode separator 17 side is By setting the surface roughness Rz of the main surface 15A to 25 ⁇ m or more, the anode gas diffusion layer 15 has a higher surface roughness on the anode separator 17 side than when the surface roughness of the main surface 15A is below the above value.
  • the surface roughness Ra of the main surface 15A of the anode gas diffusion layer 15 on the anode separator 17 side is 20 ⁇ m or less, or the surface roughness Rz of the main surface 15A of the anode gas diffusion layer 15 on the anode separator 17 side is 100 ⁇ m or less. It is desirable to have This is because the greater the surface roughness of the main surface 15A, the worse the contact resistance with the anode separator 17 and the lower the efficiency of the electrochemical hydrogen pump 100.
  • the electrochemical hydrogen pump 100 of this embodiment may be the same as the electrochemical hydrogen pump 100 of the embodiment or the first embodiment except for the features described above.
  • the anode gas diffusion layer 15 includes a porous sheet 15S, and an example of the porous sheet 15S is a metal particle sintered sheet.
  • a molding method for such a metal particle sintered body sheet for example, a press molding method can be mentioned.
  • a press molding method can be mentioned.
  • the surface roughness of the upper and lower molds for processing the metal particle base material by press molding is different, a metal particle sintered body sheet having main surfaces with different surface roughness can be obtained.
  • the molding method of the metal particle sintered body sheet is not limited to the press molding method.
  • molding of the metal particle sintered body sheet may be performed by, for example, a metal particle injection molding method.
  • Examples of materials for the metal particles used in the above press molding method or metal particle injection molding method include titanium and stainless steel.
  • methods for producing the titanium particles include a hydrodehydrogenation method, a gas atomization method, and the like.
  • FIG. 3 is a photograph showing an example of experimental results for verifying the relationship between the surface roughness of the main surface of the anode gas diffusion layer and water repellency.
  • a bird's-eye view photograph is shown in the upper part of FIG. 3, and a perspective photograph is shown in the lower part.
  • the "arithmetic mean roughness” and “maximum height” for expressing the surface roughness of surface A and surface B are measured by a contact surface roughness measuring machine ("Surftest SJ-210" manufactured by Mitutoyo Co., Ltd.). was measured based on JIS B0601:2001 using , and the results of these measurements were as follows.
  • the water in the petri dish permeated the titanium particle sintered body sheet, but part of it overflowed so as to wet the respective surfaces A and B of the titanium particle sintered body sheet.
  • the wettability of water on the surfaces A and B of the titanium particle sintered body sheet was observed.
  • the embodiment and the first and second examples of the first embodiment may be combined with each other as long as they do not exclude each other.
  • One aspect of the present disclosure can be used for an electrochemical hydrogen pump that can reduce problems caused by differential pressure between the anode and cathode more than ever before.
  • Electrolyte membrane 12 Cathode catalyst layer 13 : Anode catalyst layer 14 : Cathode gas diffusion layer 15 : Anode gas diffusion layer 15A : Main surface 15B : Main surface 15S : Porous sheet 16 : Cathode separator 17 : Anode separator 21 : Insulation Body 22A: Anode power supply plate 22C: Cathode power supply plate 23A: Anode insulating plate 23C: Cathode insulating plate 24A: Anode end plate 24C: Cathode end plate 25: Fastener 26: Cathode gas lead-out path 27: Anode gas introduction manifold 29: Anode Gas introduction path 30 : Anode gas outlet manifold 31 : Anode gas outlet path 33 : Anode gas flow path 34 : Cathode gas passage 35 : First anode gas passage 36 : Second anode gas passage 40 : Seal Member 43: Sealing member 50: Cathode gas

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Abstract

L'invention concerne une pompe à hydrogène électrochimique comportant une membrane électrolytique, une anode disposée sur l'une des surfaces principales de la membrane électrolytique, une cathode disposée sur l'autre des surfaces principales de la membrane électrolytique, et un séparateur d'anode disposé sur l'anode, un séparateur de cathode disposé sur la cathode, et un dispositif d'application de tension servant à appliquer une tension entre l'anode et la cathode. La pompe à hydrogène électrochimique est un appareil conçu de façon à ce que l'hydrogène présent dans un gaz contenant de l'hydrogène fourni à l'anode soit transféré à la cathode à travers la membrane électrolytique par application de la tension au moyen du dispositif d'application de tension, ce qui permet de générer de l'hydrogène comprimé. L'anode comprend une couche de catalyseur d'anode et une couche de diffusion de gaz d'anode, dans laquelle, dans la couche de diffusion de gaz d'anode, la rugosité de surface de la surface principale côté séparateur d'anode est supérieure à la rugosité de surface de la surface principale côté couche de catalyseur d'anode.
PCT/JP2022/027348 2021-09-07 2022-07-12 Pompe à hydrogène électrochimique WO2023037755A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09302493A (ja) * 1996-05-14 1997-11-25 Permelec Electrode Ltd ソーダ電解用ガス拡散陰極、その製造方法及び該陰極を使用するソーダ電解用電解槽
WO2020129513A1 (fr) * 2018-12-19 2020-06-25 パナソニックＩｐマネジメント株式会社 Pompe à hydrogène électrochimique
JP2020128561A (ja) * 2019-02-07 2020-08-27 パナソニックＩｐマネジメント株式会社 水素生成システム
JP2020152958A (ja) * 2019-03-20 2020-09-24 パナソニックＩｐマネジメント株式会社 電気化学式水素ポンプ
WO2020250508A1 (fr) * 2019-06-11 2020-12-17 パナソニックＩｐマネジメント株式会社 Pompe à hydrogène électrochimique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09302493A (ja) * 1996-05-14 1997-11-25 Permelec Electrode Ltd ソーダ電解用ガス拡散陰極、その製造方法及び該陰極を使用するソーダ電解用電解槽
WO2020129513A1 (fr) * 2018-12-19 2020-06-25 パナソニックＩｐマネジメント株式会社 Pompe à hydrogène électrochimique
JP2020128561A (ja) * 2019-02-07 2020-08-27 パナソニックＩｐマネジメント株式会社 水素生成システム
JP2020152958A (ja) * 2019-03-20 2020-09-24 パナソニックＩｐマネジメント株式会社 電気化学式水素ポンプ
WO2020250508A1 (fr) * 2019-06-11 2020-12-17 パナソニックＩｐマネジメント株式会社 Pompe à hydrogène électrochimique

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