JP5400413B2 - Electrolyzer - Google Patents

Description

  The present invention relates to an electrolytic device in which a power feeding body is provided on both sides of an electrolyte membrane, and a separator is stacked on the power feeding body.

  For example, in a polymer electrolyte fuel cell, a fuel gas (a gas containing mainly hydrogen, such as hydrogen gas) is supplied to the anode side electrode, while an oxidant gas (mainly containing oxygen) is supplied to the cathode side electrode. By supplying a gas (for example, air), direct current electric energy is obtained.

  One of the methods for producing hydrogen gas as a fuel gas is a solid polymer type water electrolysis apparatus. This water electrolysis apparatus uses a solid polymer electrolyte membrane in order to decompose water and generate hydrogen (and oxygen). Electrode catalyst layers are provided on both sides of the solid polymer electrolyte membrane to form an electrolyte membrane / electrode structure, and a power feeder is provided on both sides of the electrolyte membrane / electrode structure. It is configured. That is, the unit is configured substantially in the same manner as the above fuel cell.

  Therefore, in a state where a plurality of units are stacked, a voltage is applied to both ends in the stacking direction, and water is supplied to the anode-side power feeding body. As a result, water is decomposed and hydrogen ions (protons) are generated on the anode side of the electrolyte membrane / electrode structure, and the hydrogen ions permeate the solid polymer electrolyte membrane and move to the cathode side to bond with electrons. Thus, hydrogen is produced. On the other hand, on the anode side, oxygen produced together with hydrogen ions (protons) is discharged from the unit with excess water.

  As this type of equipment, for example, a power feeder disclosed in Patent Document 1 is known. In this patent document 1, as shown in FIG. 7, the double structure electric power feeding body 3 is comprised by couple | bonding the powder sintering part 1 and the fiber sintering part 2 integrally.

  The powder sintered part 1 is formed by sintering titanium powder, while the fiber sintered part 2 is formed by sintering a titanium fiber sheet. The double structure power feeder 3 is used in a state where the powder sintered portion 1 is in pressure contact with the solid electrolyte membrane 4 in the electrolytic cell of the hydrogen oxygen generator.

JP 2001-279482 A

  However, in Patent Document 1 described above, since the powder sintered portion 1 is formed by sintering titanium powder, the powder sintered portion 1 is likely to have variations in opening due to the aggregation state of the particles, and the diameter of the opening is small. The distribution becomes wide. For this reason, when the double structure power supply 3 is applied to a high pressure water electrolysis apparatus that generates high pressure hydrogen, when the solid electrolyte membrane 4 is brought into pressure contact with the powder sintered portion 1 due to a differential pressure between the anode side and the cathode side. There is a problem that damage such as damage occurs in the solid electrolyte membrane 4.

  The present invention solves this type of problem, and an object thereof is to provide an electrolysis apparatus capable of preventing damage to an electrolyte membrane as much as possible with a simple configuration.

  The present invention relates to an electrolytic apparatus in which a power feeding body is provided on both sides of an electrolyte membrane, and a separator is stacked on the power feeding body. In this electrolysis apparatus, a protective sheet member having a large number of through holes is interposed between the electrolyte membrane and the power supply body, and the through holes are tapered to reduce the diameter toward the electrolyte membrane. have.

  The power supply body includes an anode-side power supply body to which water is supplied, and a cathode-side power supply body from which hydrogen higher than normal pressure is obtained by electrolysis of the water, and the protective sheet member includes the electrolyte membrane and the above-mentioned It is preferable to interpose between the anode-side power feeder.

Furthermore, the electrolytic apparatus of the present invention, feeder, along with a number of through-holes having a tapered shape whose diameter decreases toward the electrolyte membrane is formed, and the anode current collector which water is supplied, transmural hole And a cathode-side power feeder that can obtain hydrogen higher than normal pressure by electrolysis of water, and the high-pressure hydrogen is generated during electrolysis operation. The electrolyte membrane is pressed against the anode-side power supply body by a pressure difference between the cathode flow path and the anode flow path through which the water and generated normal pressure oxygen flow .

  According to the present invention, the protective sheet member interposed between the electrolyte membrane and the power feeding body, or the power feeding body is provided with a plurality of through holes, and the through holes can be easily controlled in opening diameter. Done. Moreover, the through-hole has a tapered shape that decreases in diameter toward the electrolyte membrane. For this reason, water is smoothly introduced into the through hole, the water is satisfactorily supplied to the electrolyte membrane, and the generated gas can be easily detached.

  Accordingly, it is only necessary to provide a through-hole having a tapered shape that is reduced in diameter toward the electrolyte membrane. With a simple configuration, the electrolyte membrane is prevented from being damaged as much as possible, and water supply property and gas separation are prevented. It is possible to improve the performance.

It is a perspective explanatory view of a water electrolysis device concerning a 1st embodiment of the present invention. It is a partial cross section side view of the water electrolysis device. It is a disassembled perspective explanatory drawing of the unit cell which comprises the said water electrolysis apparatus. It is sectional explanatory drawing of the said unit cell. It is an expansion explanatory view of a protection sheet member. It is a section explanatory view of a unit cell which constitutes a water electrolysis device concerning a 2nd embodiment of the present invention. It is explanatory drawing of the electric power feeder currently disclosed by patent document 1. FIG.

  As shown in FIG.1 and FIG.2, the water electrolysis apparatus 10 which concerns on the 1st Embodiment of this invention comprises the high pressure hydrogen production apparatus, and the several unit cell 12 is horizontal (arrow A direction) or A laminate 14 is provided that is laminated in the vertical direction (arrow B direction). At one end in the stacking direction of the stacked body 14, a terminal plate 16a, an insulating plate 18a, and an end plate 20a are sequentially disposed upward. Similarly, a terminal plate 16b, an insulating plate 18b, and an end plate 20b are sequentially disposed on the other end in the stacking direction of the stacked body 14 downward.

  The water electrolysis apparatus 10 integrally clamps and holds the disk-shaped end plates 20a and 20b via a plurality of tie rods 22 extending in the direction of arrow A, for example. The water electrolysis apparatus 10 may employ a configuration in which the water electrolysis apparatus 10 is integrally held by a box-like casing (not shown) including the end plates 20a and 20b as end plates. Moreover, although the water electrolysis apparatus 10 has a substantially cylindrical shape as a whole, it can be set in various shapes such as a cubic shape.

  As shown in FIG. 1, terminal portions 24a and 24b are provided on the side portions of the terminal plates 16a and 16b so as to protrude outward. The terminal portions 24a and 24b are electrically connected to the power source 28 via the wirings 26a and 26b. The terminal portion 24 a on the anode (anode) side is connected to the positive pole of the power source 28, while the terminal portion 24 b on the cathode (cathode) side is connected to the negative pole of the power source 28.

  As shown in FIGS. 2 and 3, the unit cell 12 includes a disk-shaped electrolyte membrane / electrode structure 32, and an anode side separator 34 and a cathode side separator 36 that sandwich the electrolyte membrane / electrode structure 32. . The anode-side separator 34 and the cathode-side separator 36 have a disk shape, and are made of, for example, a carbon member or the like, or are used for corrosion protection on a steel plate, a stainless steel plate, a titanium plate, an aluminum plate, a plated steel plate, or a metal surface thereof. The metal plate that has been subjected to the above surface treatment is press-molded or cut and subjected to a corrosion-resistant surface treatment.

  The electrolyte membrane / electrode structure 32 includes, for example, a solid polymer electrolyte membrane 38 in which a perfluorosulfonic acid thin film is impregnated with water, and an anode-side power feeder 40 disposed on both sides of the solid polymer electrolyte membrane 38. And a cathode-side power feeder 42.

  An anode electrode catalyst layer 40a and a cathode electrode catalyst layer 42a are formed on both surfaces of the solid polymer electrolyte membrane 38. The anode electrode catalyst layer 40a uses, for example, a Ru (ruthenium) -based catalyst, while the cathode electrode catalyst layer 42a uses, for example, a platinum catalyst.

  The anode-side power supply body 40 and the cathode-side power supply body 42 are made of, for example, a sintered body (porous conductor) of spherical atomized titanium powder. The anode-side power supply body 40 and the cathode-side power supply body 42 are provided with a smooth surface portion that is etched after grinding, and the porosity is set within a range of 10% to 50%, more preferably 20% to 40%. Is done.

  As shown in FIGS. 3 and 4, a protective sheet member 44 in which a large number of through holes 44 a are formed is interposed between the solid polymer electrolyte membrane 38 and the anode-side power feeder 40. The protective sheet member 44 is made of, for example, a titanium sheet, and the thickness is set within a range of, for example, 20 μm to 500 μm. The surface roughness of the titanium sheet is set to 6.3 μm or less, preferably 3.2 μm or less. This titanium sheet is preferably formed by cold rolling.

  The through hole 44 a is set such that the distribution width of the through hole 44 a is smaller than the distribution width of the hole portion of the anode power feeding body 40, and the through hole 44 a is reduced in diameter toward the solid polymer electrolyte membrane 38. It has a tapered shape (see FIG. 4). The through hole 44a is formed by etching, drilling, electric discharge machining, electron beam, laser, pressing or the like.

  Specifically, in the through hole 44a, the opening diameter on the solid polymer electrolyte membrane 38 side is set in a range of 80 μm to 200 μm so that damage to the solid polymer electrolyte membrane 38 can be avoided, The opening diameter on the anode-side power feeding body 40 side is set within a range of 170 μm to 250 μm so that the water supply property and the oxygen release property can be improved.

  As shown in FIG. 3, the outer peripheral edge of the unit cell 12 communicates with each other in the direction of arrow A, which is the stacking direction, and a water supply communication hole 46 for supplying water (pure water) and produced by reaction. A discharge communication hole 48 for discharging the generated oxygen and unreacted water and a hydrogen communication hole 50 for flowing hydrogen generated by the reaction are provided.

  A surface 34 a of the anode separator 34 facing the electrolyte membrane / electrode structure 32 is provided with a supply passage 52 a communicating with the water supply communication hole 46 and a discharge passage 52 b communicating with the discharge communication hole 48. A first flow path 54 communicating with the supply passage 52a and the discharge passage 52b is provided on the surface 34a. The first flow path 54 is provided in a range corresponding to the surface area of the anode-side power feeding body 40, and includes a plurality of flow path grooves, a plurality of embosses, and the like (see FIGS. 2 and 3).

  As shown in FIG. 3, a discharge passage 56 that communicates with the hydrogen communication hole 50 is provided on the surface 36 a of the cathode separator 36 that faces the electrolyte membrane / electrode structure 32. A second flow path 58 communicating with the discharge passage 56 is formed on the surface 36a. The second flow path 58 is provided in a range corresponding to the surface area of the cathode power supply body 42 and is configured by a plurality of flow path grooves, a plurality of embosses, and the like (see FIGS. 2 and 3).

  The seal members 60a and 60b are integrated with each other around the outer peripheral ends of the anode side separator 34 and the cathode side separator 36. The seal members 60a and 60b include, for example, EPDM, NBR, fluorine rubber, silicone rubber, fluorosilicone rubber, butyl rubber, natural rubber, styrene rubber, chloroprene, acrylic rubber, or other seal materials, cushion materials, or packing materials. Used.

  As shown in FIG. 1, pipes 62a, 62b and 62c communicating with the water supply communication hole 46, the discharge communication hole 48 and the hydrogen communication hole 50 are connected to the end plate 20a. Although not shown, the pipe 62c is provided with a back pressure valve (or electromagnetic valve), and the pressure of hydrogen generated in the hydrogen communication hole 50 can be maintained at a high pressure.

  The operation of the water electrolysis apparatus 10 configured as described above will be described below.

  As shown in FIG. 1, water is supplied from a pipe 62a to the water supply communication hole 46 of the water electrolysis apparatus 10, and a power supply 28 electrically connected to the terminal portions 24a and 24b of the terminal plates 16a and 16b is connected. A voltage is applied via For this reason, as shown in FIG. 3, in each unit cell 12, water is supplied from the water supply communication hole 46 to the first flow path 54 of the anode separator 34, and this water flows along the anode power supply body 40. Moving.

  Accordingly, water is decomposed by electricity in the anode electrode catalyst layer 40a, and hydrogen ions, electrons, and oxygen are generated. Hydrogen ions generated by this anodic reaction permeate the solid polymer electrolyte membrane 38 and move to the cathode electrode catalyst layer 42a side, and combine with electrons to obtain hydrogen.

  For this reason, hydrogen flows along the second flow path 58 formed between the cathode side separator 36 and the cathode side power supply body 42. This hydrogen is maintained at a higher pressure than the water supply communication hole 46, and can flow out of the water electrolysis apparatus 10 through the hydrogen communication hole 50. On the other hand, oxygen generated by the reaction and unreacted water flow through the first flow path 54, and these are discharged to the outside of the water electrolysis apparatus 10 along the discharge communication hole 48. The second channel 58 has a higher pressure than the first channel 54.

  In this case, in the first embodiment, as shown in FIG. 4, a protective sheet member 44 provided with a plurality of through holes 44 a is interposed between the solid polymer electrolyte membrane 38 and the anode-side power feeder 40. ing. For this reason, the solid polymer electrolyte membrane 38 is transferred to the anode-side power supply body 40 by a pressure difference between the second flow path 58 in which high-pressure hydrogen gas is generated and the normal pressure first flow path 54 through which water and oxygen flow. The solid polymer electrolyte membrane 38 does not come into direct contact with the anode-side power feeder 40 when pressed toward the surface.

  Further, the opening diameter of the through hole 44a provided in the protective sheet member 44 can be easily controlled. Therefore, in the protective sheet member 44, the opening diameter of the through hole 44a can be set within a narrow range, and the distribution width can be set to be significantly narrower than the distribution width of the anode-side power feeding body 40. For this reason, the solid polymer electrolyte membrane 38 can be prevented from being pushed into the through hole 44a and being damaged as much as possible.

  In addition, the through hole 44 a has a tapered shape that decreases in diameter toward the solid polymer electrolyte membrane 38. As a result, as shown in FIG. 5, water is smoothly introduced from the anode-side power feeder 40 into the through hole 44a, and the water is satisfactorily supplied to the anode electrode catalyst layer 40a of the solid polymer electrolyte membrane 38. It becomes possible. On the other hand, oxygen generated in the anode electrode catalyst layer 40a smoothly moves to the anode-side power supply body 40 along the tapered shape of the through hole 44a, and the release of the oxygen is easily performed.

  As a result, in the first embodiment, it is only necessary to provide a through hole 44a having a tapered shape that is reduced in diameter toward the solid polymer electrolyte membrane 38, and the solid polymer electrolyte membrane 38 is damaged with a simple configuration. The effect that it can prevent as much as possible and can aim at the improvement of water supply property and gas detachability is acquired.

  FIG. 6 is an explanatory cross-sectional view of a unit cell 72 constituting a water electrolysis apparatus 70 according to the second embodiment of the present invention.

  In addition, the same referential mark is attached | subjected to the component same as the unit cell 12 which comprises the water electrolysis apparatus 10 which concerns on 1st Embodiment, and the detailed description is abbreviate | omitted.

  The unit cell 72 includes, for example, an anode side power feeding body 74 made of a titanium plate, and the anode side power feeding body 74 is provided with a large number of through holes 74a. The through-hole 74a includes a tapered portion 76a that decreases in diameter toward the solid polymer electrolyte membrane 38, and a linear portion 76b that extends straight from the end of the tapered portion 76a toward the first flow path 54. Have

  The through-hole 74a may have a tapered shape whose diameter decreases from the first flow channel 54 toward the solid polymer electrolyte membrane 38 as a whole.

  In the second embodiment configured as described above, the through-hole 74a provided in the anode-side power feeder 74 can be easily controlled in opening diameter, and the through-hole 74a is formed in the solid polymer electrolyte membrane 38. It has a taper-shaped portion 76a that decreases in diameter.

  Thus, with the simple configuration, the solid polymer electrolyte membrane 38 can be prevented from being damaged as much as possible, and the water supply property and gas detachability can be improved. The same effect can be obtained.

DESCRIPTION OF SYMBOLS 10, 70 ... Water electrolysis apparatus 12, 72 ... Unit cell 14 ... Laminated body 16a, 16b ... Terminal plate 18a, 18a ... Insulation plate 20a, 20b ... End plate 24a, 24b ... Terminal part 28 ... Power supply 32 ... Electrolyte membrane * electrode Structure 34... Anode separator 36. Cathode separator 38. Solid polymer electrolyte membrane 40. Discharge communication hole 50 ... Hydrogen communication hole 54, 58 ... Flow path

Claims (4)

An electrolytic device in which a power feeding body is provided on both sides of an electrolyte membrane, and a separator is stacked on the power feeding body,
Between the electrolyte membrane and the power feeder, a protective sheet member having a large number of through holes is interposed,
The electrolytic device according to claim 1, wherein the through hole has a tapered shape with a diameter decreasing toward the electrolyte membrane. The electrolyzer according to claim 1, wherein the power feeding body includes an anode power feeding body to which water is supplied;
A cathode-side power feeder that can obtain hydrogen at a pressure higher than normal pressure by electrolysis of the water;
With
The electrolysis apparatus, wherein the protective sheet member is interposed between the electrolyte membrane and the anode-side power feeding body. An electrolytic device in which a power feeding body is provided on both sides of an electrolyte membrane, and a separator is stacked on the power feeding body,
The power feeding body is formed with a large number of through holes having a tapered shape that is reduced in diameter toward the electrolyte membrane, and an anode side power feeding body to which water is supplied;
Together are formed by without porous conductive material providing a transmembrane hole, a cathode current collector to the high pressure hydrogen can be obtained than the normal pressure by electrolysis of the water,
With
During the electrolysis operation, the electrolyte membrane is pressed against the anode-side power supply body by a pressure difference between the cathode flow channel in which the high-pressure hydrogen is generated and the anode flow channel in which the water and generated normal-pressure oxygen flow. by electrolysis apparatus according to claim Rukoto. The electrolyzer according to claim 3, wherein the anode flow path is provided in a range corresponding to a surface area of the anode-side power supply body on a surface of the separator facing the anode-side power supply body ,
The cathode passage, an electrolytic device according to claim provided et the possible within a range corresponding to the surface area of the cathode current collector the cathode current collector to the surface facing to the separator.

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