JP5457951B2 - Electrolytic cell - Google Patents

Description

  The present invention relates to an electrolytic cell used for electrolysis of an electrolytic solution.

  Various electrolyzers are provided that electrolyze an electrolyte to produce gas. In recent years, an electrolyzer for water electrolysis in which water (aqueous solution) is electrolyzed to generate hydrogen gas and oxygen gas has been proposed. As this type of electrolytic cell, one that holds an electrolytic solution between a pair of electrodes is known. Specifically, electrodes are joined to both surfaces of a solid polymer electrolyte membrane, and water is supplied to the electrolyte membrane to energize it (Patent Document 1), and electrodes are joined to both surfaces of a hollow frame (gasket). In addition, it is known that an electrolytic solution is stored in a space between them and energized (Patent Document 2).

  In a conventional electrolytic cell, a hard plate-like electrode having high bending rigidity has been used as an electrode for sandwiching an electrolytic solution. A hard electrode is pressed against the solid polymer electrolyte membrane or gasket at a high pressure so that the contact state between the electrode and the electrolyte is maintained against the gas generation pressure generated at the interface between the electrode and the electrolyte. This is because.

For example, Patent Document 1 describes a bolt-fixed electrolytic cell integrally with a separator plate and a fixed plate in a state where an electrode is joined to a solid polymer electrolyte membrane and a pressing force is urged by a pressing material.
Patent Document 2 describes an electrolytic cell in which an electrode made of a plate such as graphite or nickel and a gasket are press-contacted with bolts and nuts and laminated in multiple layers.

JP 2006-291329 A JP-A-10-88380

However, various problems have arisen because the electrode itself is a hard plate or the electrode is fixed to another hard member and the electrolytic cell is inflexible (rigid).
First, since the degree of freedom in structural design of the electrolytic cell was poor, the shape and installation position of the electrolytic cell were limited. Second, the impact resistance was low due to inflexibility, and there was a problem with the durability of the electrolytic cell when exposed outdoors. For example, when an electrolytic cell is installed outdoors and used in a hydrogen gas generator for home use, there is a risk that cracks or chips may easily occur when foreign matter such as wind and rain or pebbles collide with the electrolytic cell.

  The present invention has been made in view of the above problems, and provides an electrolytic cell having a high degree of freedom in structural design and suitable for outdoor installation.

The electrolytic cell of the present invention includes an electrode pair in which both a planar first electrode and a second electrode are arranged to face each other, and a liquid supply means for supplying an electrolytic solution between the electrode pair, An electrolytic cell that electrolyzes an electrolytic solution to generate a gas, and the electrode pair is flexible so that it can be bent or bent in a perpendicular direction, and an insulating property is maintained between the electrode pair. A liquid sheet is sandwiched, and the liquid retaining sheet is a fiber sheet formed body made of a hydrophilic polymer .

  Note that the various components of the present invention do not have to be individually independent, that a plurality of components are formed as one member, and one component is formed of a plurality of members. That a certain component is a part of another component, a part of a certain component overlaps a part of another component, and the like.

  In the electrolytic cell of the present invention, the electrode pair sandwiching the electrolytic solution is flexible so that it can be bent or bent in the direction perpendicular to the surface. For this reason, the structural design of the electrolytic cell of various shapes according to the purpose of use is possible, and since the electrode pair is excellent in impact resistance, the electrolytic cell can be suitably installed in an outdoor exposure environment.

It is a perspective view which shows the electrolytic cell concerning 1st embodiment. It is a disassembled perspective view of an electrolytic cell. (A) is a schematic diagram of a gas production | generation apparatus, (b) is the elements on larger scale. (A) is a perspective view of the electrode pair concerning 2nd embodiment, (b) is the elements on larger scale. (A) is a top view of the electrode concerning 3rd embodiment, (b) is a top view which shows the modification. It is explanatory drawing of the holder used for the measurement of water pressure resistance. It is a graph which shows the measurement result of the electric current value of Example 1 and Comparative Examples 1-3. It is a graph which shows the measurement result of the electric current value of Example 2. 10 is a graph showing measurement results of current values in Comparative Example 4.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

<First embodiment>
FIG. 1 is a perspective view showing an electrolytic cell 100 according to the first embodiment of the present invention. FIG. 2 is an exploded perspective view of the electrolytic cell 100.
First, the outline | summary of the electrolytic cell 100 of this embodiment is demonstrated.

  The electrolytic cell 100 of the present embodiment includes an electrode pair 30 in which both the planar first electrode 10 and the second electrode 20 are disposed to face each other, and a liquid supply unit that supplies the electrolyte ES between the electrode pair 30. 40, and electrolyzes the electrolytic solution ES to generate the gas G. The electrolytic cell 100 is characterized in that the electrode pair 30 is flexible enough to bend or bend in a direction perpendicular to the surface.

Next, the electrolytic cell 100 of this embodiment will be described in detail.
The electrolytic bath 100 is a gas generating device that electrolyzes the electrolytic solution ES to generate a gas G. The electrolytic solution ES and the gas G are not particularly limited, but in this embodiment, hydrogen gas is used as one of the gases G. That is, the electrolytic cell 100 of this embodiment constitutes a hydrogen gas generator by water electrolysis.

Electrolyte ES should just be water, and in order to perform electrolysis with high efficiency, it is good to add a non-volatile base or acid with a high degree of dissociation. Examples of the base include sodium hydroxide and potassium hydroxide, and examples of the acid include sulfuric acid.
The hydrogen generator including the electrolytic cell 100 of this embodiment can be used for hydrogen automobiles and household appliances in addition to household hydrogen production for fuel cells. When hydrogen gas generated in the electrolytic cell 100 is used as a power source, it may be combined with other natural energy.

  The first electrode 10 and the second electrode 20 are flexible conductive films. This conductive film is one in which the film itself or the surface thereof is conductive. Examples of the conductive material include metals such as gold, silver, copper, platinum, nickel, titanium, and iron, metal oxides such as ITO (indium tin oxide), tin oxide, and zinc oxide, or carbon. These conductive materials may be used as a single substance, or may be combined in the form of an alloy. As a thickness of the film which comprises the 1st electrode 10 and the 2nd electrode 20, the thing of the range of 1 micrometer-10 mm is preferable. When the thickness is 1 μm or more, sufficient strength is obtained when used as an electrode, and processing is easy. Moreover, a softness | flexibility is acquired by setting it as 10 mm or less, and size reduction and weight reduction of the electrolytic cell 100 are achieved.

  The composition of the conductive film may be a single composition, or a non-conductive base film formed by depositing the above conductive material. Although the method of film formation is not particularly limited, a method of forming the metal itself into an arbitrary film thickness by sputtering, vapor deposition, CVD (Chemical Vapor Deposition) method, sol-gel method, PLD (Pulse Laser Deposition) method or the like can be mentioned. It is done. Non-conductive substrate film is not particularly limited, but polyimide, polyethylene, polypropylene, polyvinylidene chloride, polylactic acid, polyamide, polycarbonate, polytetrafluoroethylene, polyurethane, polystyrene, polyester, ABS (acrylonitrile / butadiene / styrene) resin, Resin materials such as acrylic resin and polyacetal resin can be used.

  As shown in FIG. 2, an interelectrode spacer 32 is sandwiched between the first electrode 10 and the second electrode 20. The inter-electrode spacer 32 has a plate shape and is a frame body having a rectangular hollow portion 33 at substantially the center. The hollow portion 33 is a space where the electrolytic solution ES is supplied and electrolyzed. A hydrophilic liquid retaining sheet 50 is fitted in the hollow portion 33 of the present embodiment.

  For convenience, the lower right direction in FIGS. 1 and 2 is referred to as the surface side of the electrolytic cell 100, and the upper left direction is referred to as the back side of the electrolytic cell 100. Also, as shown in the figure, the vertical direction is defined, but this is defined for convenience in order to explain the relative relationship of the constituent elements, and the direction at the time of manufacturing and using the electrolytic cell 100 is not necessarily limited. Not what you want.

  The liquid retaining sheet 50 is made of a hydrophilic and insulating material, and is a sheet material that retains the electrolytic solution ES by wettability with respect to the electrolytic solution ES. The electrolytic cell 100 of the present embodiment uses the liquid retaining sheet 50 between the first electrode 10 and the second electrode 20, thereby preventing contact (short circuit) between the electrodes and the entire thin gap between the electrodes. It is possible to spread the electrolyte solution ES. That is, even when the flexible electrode pair 30 is bent or curved three-dimensionally by sandwiching the hydrophilic liquid retaining sheet 50 between the electrode pair 30, the first electrode 10 and the second electrode 20 Are not in contact with each other, and there is no shortage of electrolyte ES.

The material of the liquid retaining sheet 50 is not particularly limited, but a material that is hydrophilic and does not undergo electrolysis is used. For example, in addition to natural fiber materials such as cellulose, cupra, cotton, and silk, a porous sheet or nonwoven fabric made of a synthetic polymer such as polyvinylidene difluoride or hydrophilized polytetrafluoroethylene can be used. The thickness of the liquid retaining sheet 50 is preferably 1 mm or less. Further, the bulk (bulk) density of the liquid retaining sheet 50 is preferably 0.5 g / cm ³ or less. In these cases, since the electrical resistance given to the electrolytic solution ES by the liquid retaining sheet 50 is suppressed, the electrolytic solution ES can be efficiently electrolyzed.

  The plate thickness of the interelectrode spacer 32 corresponds to the distance between the first electrode 10 and the second electrode 20, that is, the distance between the electrodes. The thickness of the liquid retaining sheet 50 is equal to or smaller than the thickness of the interelectrode spacer 32. That is, the electrolytic solution ES can be stored in the hollow portion 33 in which the liquid retaining sheet 50 is fitted. The facing distance between the first electrode 10 and the second electrode 20 is preferably uniform over the entire electrode pair 30, but is not limited thereto.

  Since the liquid retaining sheet 50 is made of a fiber material, the liquid retaining sheet 50 has a high capillary force. Further, the liquid retaining sheet 50 may be provided over the entire surface in the hollow portion 33 to which the electrolytic solution ES is supplied. Thereby, the electrolyte solution ES can be spread over the entirety between the first electrode 10 and the second electrode 20. The liquid retaining sheet 50 has higher flexibility than the interelectrode spacer 32.

  The hollow portion 33 is provided with an electrolyte solution feed line 41 and an electrolyte solution discharge line 51 that communicate with each other. The electrolyte solution supply line 41 constitutes a part of the liquid supply unit 40.

The first electrode 10 and the second electrode 20 are attached to electrode holders 35 and 36, respectively.
The electrode holder 35 has a plate shape, and a hollow recess 351 for fitting the first electrode 10 is formed through the thickness direction. One end of the conducting wire 353 is exposed in the hollow recess 351, and the first electrode 10 and the conducting wire 353 are connected by fitting the first electrode 10 into the hollow recess 351.
On the back side of the hollow concave portion 351, an electrolytic solution feeding line 43 and an electrolytic solution discharge line 53 are formed as concave grooves, respectively. When the inter-electrode spacer 32 and the electrode holder 35 are joined, the electrolyte solution feeding lines 41 and 43 and the electrolyte solution discharge lines 51 and 53 coincide with each other.

  On the other hand, the electrode holder 36 is also plate-shaped, and a hollow recess 361 for fitting the second electrode 20 is formed through the thickness direction. One end of the conducting wire 363 is exposed in the hollow recess 361, and the second electrode 20 and the conducting wire 363 are connected by fitting the second electrode 20 into the hollow recess 361. Either a positive electrode or a negative electrode of a power feeding unit 90 (see FIG. 3A) that supplies a DC voltage to the electrode pair 30 is connected to the conductive wires 353 and 363.

  The conducting wires 353 and 363 are made of a conductive material, and are preferably a metal material, particularly platinum, gold, copper, nickel, or the like having a low electric resistance.

  On the surface side of the hollow recess 361, an electrolyte solution feed line 44 and an electrolyte solution discharge line 54 are formed as recessed grooves, respectively. When the inter-electrode spacer 32 and the electrode holder 36 are joined, the electrolyte solution feed lines 41 and 44 and the electrolyte solution discharge lines 51 and 54 respectively coincide with each other.

  The inter-electrode spacer 32 and the electrode holders 35 and 36 are both made of insulating thin plates, and the plate thickness is preferably 1 mm or less. The interelectrode spacer 32 and the electrode holders 35 and 36 are made of an insulating resin material such as PTFE (polytetrafluoroethylene), acrylic resin, polycarbonate, polyimide, or the like. Thereby, the flexibility of the electrode pair 30 is not impaired.

The liquid supply unit 40 includes a liquid supply pipe 46, a drainage pipe 47, a liquid storage tank 48, and a liquid feed pump 49 (see FIG. 3A).
The electrolyte solution supply lines 41, 43, 44 are connected to each other to form a pipe line, and a liquid supply pipe 46 is attached to the pipe line. The liquid supply pipe 46 is a pipe for supplying the electrolytic solution ES to the hollow portion 33 at a predetermined pressure, and communicates the hollow portion 33 and the liquid storage tank 48.
Moreover, the electrolyte solution discharge lines 51, 53, and 54 form another pipe line, and a drain pipe 47 is attached to the other pipe line. The drainage pipe 47 is a pipe for discharging the electrolytic solution ES electrolyzed in the hollow portion 33 and communicates with the hollow portion 33.

Gas recovery holders 37 and 38 are provided on the front and back surfaces of the electrode holders 35 and 36 with the inter-electrode spacer 32 as the center. As will be described later, the first electrode 10 and the second electrode 20 allow the gas G generated by electrolysis to pass in the thickness direction.
On the back side of the gas recovery holder 37, there are a cavity-shaped gas recovery chamber 371, a recovery gas passage 373 having one end communicating with the gas recovery chamber 371, and a gas extraction connected to the other end of the recovery gas passage 373. A line 375 is provided. The recovery gas channel 373 is provided in a concave groove shape on the back side of the gas recovery holder 37. However, the recovery gas flow path 373 may be formed as a through hole that penetrates the inside of the thickness of the gas recovery holder 37. The gas extraction line 375 is a tubular member that is airtightly connected to the recovery gas passage 373.

  On the other hand, on the surface side of the gas recovery holder 38, a cavity-shaped gas recovery chamber 381, a recovery gas passage 383 having one end communicating with the gas recovery chamber 381, and the other end of the recovery gas passage 383 are airtight. A gas extraction line 385 comprising a connected tubular member is provided. The recovery gas flow path 383 is formed in the shape of a concave groove on the surface side of the gas recovery holder 38 or as a through hole penetrating the inside of the plate thickness of the gas recovery holder 38.

  As a result, the gas G generated at the first electrode 10 fed through the conducting wire 353 is recovered from the gas extraction line 375 through the gas recovery chamber 371 and the recovery gas passage 373. Further, the other gas G generated in the second electrode 20 fed through the conducting wire 363 is also recovered from the gas extraction line 385 through the gas recovery chamber 381 and the recovery gas channel 383.

  The gas recovery holders 37 and 38 of this embodiment are made of insulating thin plates, and the gas recovery chambers 371 and 381 are formed in a cavity shape by injection molding or press molding. The flat plate portions 372 and 382 of the gas recovery holders 37 and 38 can be easily bent individually by a human hand.

  As shown in FIGS. 1 and 2, the interelectrode spacer 32, the electrode holders 35 and 36, and the gas recovery holders 37 and 38 are all three-dimensionally curved with substantially the same curvature. Specifically, the inter-electrode spacer 32, the electrode holders 35 and 36, and the gas recovery holders 37 and 38 are curved in a convex shape in the thickness direction toward the surface side. Thereby, the interelectrode spacer 32, the electrode holders 35 and 36, and the gas recovery holders 37 and 38 can be overlapped with each other.

  In addition, screw holes 391 are formed at the four corners of the gas recovery holders 37 and 38 and the electrode holders 35 and 36, respectively, and are fastened in close contact with each other by fixing screws 39.

Hereinafter, a structure formed by stacking the inter-electrode spacer 32 and the electrode holders 35 and 36 is referred to as an electrolytic cell main body 110. The electrolytic cell main body 110 includes a hollow portion 33 to which the electrolytic solution ES is supplied, the first electrode 10 and the second electrode 20 on both sides thereof, and a member (electrode holder 35) that opposes the first electrode 10 and the second electrode 20. 36).
In other words, the electrolytic cell 100 includes an electrolytic cell main body 110 and members (gas recovery holders 37 and 38) constituting a flow path for taking out the gas G from the electrolytic cell main body 110.

  The electrode pair 30 refers to the first electrode 10 and the second electrode 20 disposed to face each other with the inter-electrode spacer 32 interposed therebetween. The electrode pair 30 of the present embodiment has flexibility that can be bent or bent in the direction perpendicular to the plane. Here, the electrode pair 30 has flexibility means that the first electrode 10 and the second electrode 20 in a state of being opposed to each other have flexibility enough to bend and deform by a human hand. Say. In the case of this embodiment, the first electrode 10 and the second electrode 20 are opposed to each other by the electrode holders 35 and 36, and a bending load can be applied to the first electrode 10 and the second electrode 20 from the outside. The minimum configuration corresponds to the electrolytic cell main body 110. Therefore, in the case of this embodiment, the electrode pair 30 having flexibility means that the electrolytic cell body 110 including the electrode holders 35 and 36 can be bent and deformed by a human hand.

  Hereinafter, there is a case where the curve and the bending are not distinguished and are collectively referred to as a curve. That is, in a state in which at least one of the first electrode 10 or the second electrode 20 is bent in a direction intersecting with the planar direction of the electrode pair 30, the electrode pair 30 is tertiary regardless of the radius of curvature. It is originally curved.

  More specifically, in the case where the first electrode 10 and the second electrode 20 are metal films, the electrode pair 30 is flexible as an electrolysis molded into the shape of the No. 3 test piece defined in JIS Z 2248. It means that the first electrode 10 and the second electrode 20 are not torn when the tank body 110 is bent by a bending method with a bending angle of 170 degrees. In addition, when the first electrode 10 and the second electrode 20 are non-conductive base films in which a metal material is formed, the electrode pair 30 is flexible. (JIS K 7171) means that the first electrode 10 and the second electrode 20 are not torn or cracked when the bending angle is 170 degrees.

  Further, the flexural modulus (JIS K 7171) of the electrode pair 30 is preferably 0.1 MPa or more and 2000 MPa or less, and more preferably 1 MPa or more and 1000 MPa or less. Here, the bending elastic modulus of the electrode pair 30 is obtained by obtaining a bending moment per unit width of the electrolytic cell main body 110 including the electrode holders 35 and 36 and the inter-electrode spacer 32 by a three-point bending test. In addition, in the electrolytic cell 100 of this embodiment, you may use what was baked and carbonized in the state which shape | molded the flexible electrode pair 30 in the predetermined curve or bending shape. That is, after the user forms the flexible electrode pair 30 into an arbitrary shape, the electrode pair 30 may be cured and used in the electrolytic cell 100.

  The electrolytic cell 100 shown in FIGS. 1 and 2 is configured by mounting gas recovery holders 37 and 38 on both sides of an electrolytic cell main body 110 formed by opposingly arranging a pair of first electrode 10 and second electrode 20. Here, by overlapping the electrolytic cell main bodies 110 in multiple stages, the contact area between the electrode pair 30 and the electrolytic solution ES can be increased while suppressing the installation area of the electrolytic cell 100.

  FIG. 3A is a schematic diagram of a gas generation device 200 including a three-stage electrolytic cell main body 110. The electrolytic cell 100 includes an electrolytic cell main body 110 that is stacked in three stages, and gas recovery holders 37 and 38 that are provided on both the front and back surfaces, respectively. A gas recovery holder 37 or 38 is also sandwiched between the electrolytic cell bodies 110. In the same figure, regarding the electrolytic cell 100, a plan view is shown and only an end face in the thickness direction is shown.

  The gas generation device 200 of the present embodiment includes an electrolytic cell 100 and a liquid supply unit 40 that supplies an electrolytic solution ES thereto. The liquid supply unit 40 includes a liquid supply pipe 46 and a liquid feed pump 49 that supply the electrolytic solution ES to the hollow portions 33 of the three-stage electrolytic cell main body 110, and a liquid storage tank 48 in which the electrolytic solution ES is stored. It consists of The gas generating apparatus 200 of the present embodiment is an apparatus that generates hydrogen gas and oxygen gas by water electrolysis, and the electrolytic solution ES stored in the liquid storage tank 48 is mainly composed of water. The liquid supply unit 40 is optionally provided with a drain pipe 47 for discharging the electrolytic solution ES from the electrolytic cell main body 110.

  The positive electrode of the power feeding unit 90 is connected to the electrode (first electrode 10) in contact with the gas recovery holder 37. Further, the negative electrode of the power feeding unit 90 is connected to the electrode (second electrode 20) in contact with the gas recovery holder 38. That is, the first electrodes 10 are provided on both the front and back surfaces of the gas recovery holder 37 (37a) sandwiched between the electrolytic cell bodies 110, respectively. And the 2nd electrode 20 is each provided in the front and back both surfaces side of the gas collection holder 38 (38a) clamped between the electrolytic cell main bodies 110.

  A gas extraction line 375 is provided in communication with the two types of gas recovery holders 37 and 37a, and oxygen gas generated at the anode (first electrode 10) is recovered. On the other hand, a gas extraction line 385 is provided in communication with the two types of gas recovery holders 38 and 38a, and hydrogen gas generated at the cathode (second electrode 20) is recovered.

  In the gas generating apparatus 200 of the present embodiment, the electrolytic cell 100 is configured by superposing three-dimensionally curved electrolytic cell bodies 110 in multiple stages. Thereby, it is possible to install the electrolytic cell 100 in multiple stages on the curved installation surface. For this reason, for example, hydrogen gas can be generated by the gas generation device 200 using a space that has conventionally been a dead space, such as a pipe installed in a house or factory, as an installation location. In addition, each stage of the electrolytic cell main body 110 (electrode pair 30) and the gas recovery holder 37 or 38 of the present embodiment individually have flexibility that can be bent or bent in a perpendicular direction. For this reason, it is possible to freely adjust the curvature of the electrolytic cell 100 according to the shape of the installation place.

  The 1st electrode 10 and the 2nd electrode 20 of this embodiment are provided with the through-holes 12 and 22 which penetrate these in the thickness direction. The gas recovery path 60 configured by the gas extraction line 375 and the gas extraction line 385 recovers the gas G generated by electrolysis through the through holes 12 and 22.

  Moreover, in the electrolytic cell 100 of this embodiment, the insulating liquid retention sheet 50 is sandwiched between the electrode pair 30 in which the first electrode 10 and the second electrode 20 are arranged to face each other. Hereinafter, the first electrode 10, the second electrode 20, and the liquid retaining sheet 50 will be further described.

  In the electrolytic cell 100 of this embodiment, at least a part of the electrode pair 30 is three-dimensionally curved or bent. In the electrode pair 30 of the present embodiment, the same region of the first electrode 10 and the second electrode 20 facing each other is curved three-dimensionally. Thereby, the electrode pair 30 is three-dimensionally curved while the first electrode 10 and the second electrode 20 maintain a predetermined facing distance.

  FIG. 3B is a partially enlarged view of a curved top portion of the electrode pair 30 in FIG. As shown in FIGS. 3A and 3B, a liquid retaining sheet 50 is interposed between the first electrode 10 and the second electrode 20. The liquid retaining sheet 50 of the present embodiment is a fiber sheet formed body made of a hydrophilic polymer. By using the liquid retaining sheet 50, even when the supply pressure of the electrolytic solution ES by the liquid supply unit 40 is normal pressure, the electrolytic solution ES can be spread over the entire hollow portion 33 at the top of the curved portion.

  The hydrophilic polymer is cellulose, wool, cotton, polyvinylidene difluoride, or tetrafluoroethylene subjected to hydrophilic treatment. And the thickness of the liquid retention sheet | seat 50 of this embodiment is 1 mm or less.

  As shown in FIG.3 (b), the 1st electrode 10 and the 2nd electrode 20 are each provided with the 1 or more through-holes 12 and 22 which penetrate these in the thickness direction. The decomposed hydrogen gas and oxygen gas are taken out of the electrode pair 30 through the through holes 12 and 22. The electrolytic cell 100 is provided with a hydrogen gas extraction line 385 (see FIG. 1A) in contact with the back surface 25 of the electrolysis surface 24 of the second electrode 20. Similarly, the electrolytic cell 100 is provided with a gas extraction line 375 (see FIG. 1A) for oxygen gas in contact with the back surface 15 of the electrolysis surface 14 of the first electrode 10.

  The inner wall surfaces 13 and 23 of the through holes 12 and 22 are preferably hydrophobic, and the electrolytic surfaces 14 and 24 in contact with the electrolytic solution ES of the first electrode 10 and the second electrode 20 are preferably hydrophilic. Moreover, as for the 1st electrode 10 and the 2nd electrode 20, it is preferable that the back surfaces 15 and 25 of the electrolysis surfaces 14 and 24 are hydrophobic.

  The first electrode 10 and the second electrode 20 are formed by laminating electrolytic surfaces 14 and 24 with a conductive material such as a metal, metal oxide, or carbon on a film-like conductive member or an insulating base sheet. It is a laminated member. The electrolytic surfaces 14 and 24 are inner main surfaces exposed to the hollow portion 33.

  The purpose of the through holes 12 and 22 is to immediately collect the gas G (hydrogen and oxygen) generated on the surfaces of the first electrode 10 and the second electrode 20 on the back surface of each electrode. Thereby, even if the electrolytic solution ES is decomposed and the gas G is generated, the first electrode 10 and the second electrode 20 are not covered with the gas G. For this reason, the contact area (effective electrolysis area) between the electrode pair 30 and the electrolytic solution ES does not decrease.

  In addition, since the hydrogen gas and oxygen gas generated respectively at the first electrode 10 and the second electrode 20 are separated and recovered by the first electrode 10 and the second electrode 20 themselves, the hollow portion 33 has a gas separation gas. It is not necessary to provide an airtight plate-like skirt (separator). For this reason, according to this embodiment, it is possible to reduce the distance between the electrodes by reducing the thickness of the hollow portion 33, and it is possible to increase the electrolytic efficiency and reduce the thickness of the electrode pair 30.

  Here, by increasing the water resistance (electrolyte) pressure of the through holes 12 and 22, or by setting it to at least 0, the electrolyte ES does not enter the through holes 12 and 22, and only the gas G passes. It becomes possible. Thereby, gas-liquid separation becomes possible without the electrolyte solution ES leaking from the electrode pair 30. The water pressure resistance (P) is expressed by the following Young Laplace equation (1).

P = 4 · γ · sin (θ−90 °) / r (1)
γ: Surface tension of water (electrolyte) θ: Water (electrolyte) contact angle of the hole wall r: Hole diameter

As a method of increasing the water resistance (electrolyte) pressure (P), it is preferable to reduce the hole diameter or increase the contact angle as shown in the equation (1).
Moreover, by using the liquid retention sheet 50 made of a fiber material as in the present embodiment, the electrolyte solution ES is held in the hollow portion 33 by the capillary force of the liquid retention sheet 50, and the electrolyte solution ES is retained in the through holes 12 and 22. Infiltration is suppressed.

  The shape of the through holes 12 and 22 is not particularly limited. When using a fibrous film for the first electrode 10 and the second electrode 20, the eyes can be used as the through holes 12 and 22. Alternatively, the first electrode 10 and the second electrode 20 may be drilled. The method for drilling is not particularly limited, but a method using lithography and chemical etching may be used in addition to a method for physically drilling using an apparatus such as a laser or an NC (Numerical Control) processing machine.

  The diameters of the through holes 12 and 22 are 300 μm or less, preferably 200 μm or less. By setting it within this range, even if the supply pressure by the liquid feed pump 49 is sufficiently increased in practice, the water pressure (P) of the formula (1) is prevented from exceeding and the leakage of the electrolyte ES is prevented. it can.

  The distance between the centers of the adjacent through holes 12 and 22, that is, the pitch is preferably 1 mm or less. The smaller the pitch value, the greater the number of holes on the electrode surface, and the generated gas G tends to escape to the back surface.

The inner wall surfaces 13 and 23 of the through holes 12 and 22 are hydrophobic, that is, the water contact angle is 90 ° or more. On the other hand, the electrolysis surfaces 14 and 24 of the first electrode 10 and the second electrode 20 are hydrophilic, that is, the water contact angle is less than 90 °. When the water contact angle of the inner wall surfaces (hole walls) 13 and 23 of the through holes 12 and 22 is 90 ° or more as in this embodiment, the water pressure resistance of the through holes 12 and 22 is expressed by the formula (1). (P) becomes positive, and the electrolyte solution ES is prevented from entering the through holes 12 and 22.
In addition, since the water contact angle of the electrolytic surfaces 14 and 24 is less than 90 °, the affinity between the electrolytic solution ES and the first electrode 10 and the second electrode 20 is improved, and the gas G bubbles are generated on the electrolytic surface 14, 24 is prevented from remaining on. Thereby, the gas-liquid separation effect by the through-holes 12 and 22 is fully exhibited, and high electrolysis efficiency can be obtained.
A method for making the surfaces of the first electrode 10 and the second electrode 20 site-selective hydrophilic or hydrophobic is not particularly limited. As an example, a method of drilling the through holes 12 and 22 after providing a metal thin film (hydrophilicity) on the entire surface of a hydrophobic film of polyolefin such as polyethylene can be mentioned. In addition, it is possible to use a method in which a mask is attached to the upper surface of the perforated metal film, and then a hydrophobic treatment is performed by a CVD method or the like, and the mask is removed after the treatment.

The facing distance (distance between electrodes) between the first electrode 10 and the second electrode 20 is preferably 50 mm or less. Thereby, the water pressure applied to the through hole (for example, the through hole 22 of the second electrode 20) of the electrode on the lower surface side of the installed electrolytic cell 100 is suppressed to a predetermined value or less, and the electrolyte ES leaks from the through hole. Is suppressed.
Note that the through hole on the lower surface side (for example, the through hole 22 of the second electrode 20) has a greater water pressure load than the through hole on the upper surface side (for example, the through hole 12 of the first electrode 10). The diameter may be smaller than the through hole on the upper surface side.

This embodiment includes the following technical ideas.
Both the planar first electrode 10 and the second electrode 20 are disposed so as to face each other, and at least a part thereof is curved or bent in the direction perpendicular to the surface. And an electrolytic cell 100 that generates a gas G by electrolyzing the electrolytic solution ES.
According to the electrolytic cell 100, since the electrode pair 30 is curved or bent in the direction perpendicular to the surface, the electrode area per installation area can be increased, and the electrolytic cell 100 can be installed on an uneven installation surface. Is also possible.

  In such an electrolytic cell 100, electrodes (first electrode 10 and second electrode 20) made of a material having a high bending elastic modulus and formed in a curved or bent shape in advance can be used. Specifically, it is possible to exemplify an electrode which is cured by baking (carbonizing) the plate-like resin material in a curved state or a hemispherical shape. Such an electrode may have a bending elasticity that is not bent by the user with one hand.

<Second embodiment>
FIG. 4A is a perspective view of the electrode pair 30 according to the present embodiment, and FIG. 4B is a partially enlarged view thereof. Specifically, FIG. 4B is an enlarged view of a partial region surrounded by a circle B in FIG.

  The electrode pair 30 of this embodiment is wound in a roll shape.

  The first electrode 10 and the second electrode 20 of the present embodiment each include a gap portion 62 formed therein and through holes 12 and 22 communicating with the gap portion 62. And hydrogen gas and oxygen gas obtained by electrolyzing electrolyte solution ES can be collect | recovered from the back surface 15 and 25 side through the inside of the 1st electrode 10 and the 2nd electrode 20, respectively.

  More specifically, hydrogen gas is generated by electrolysis of the electrolytic solution ES on the electrolysis surface 14 of the first electrode 10 connected to the negative electrode of the power feeding unit 90 (not shown). This hydrogen gas is introduced into the gap 62 (62 a) of the first electrode 10 through the through hole 12. This is because the outside of the first electrode 10 is filled with the electrolytic solution ES at a predetermined supply pressure equal to or higher than atmospheric pressure, whereas the gap 62a is maintained at atmospheric pressure.

  On the other hand, oxygen gas is generated by electrolysis of the electrolytic solution ES on the electrolytic surface 24 of the second electrode 20 connected to the positive electrode of the power supply unit 90 (not shown). This oxygen gas is also introduced into the gap 62 b of the second electrode 20 through the through hole 22 and taken out of the electrode pair 30.

  The first electrode 10 and the second electrode 20 are electrode films having a large number of through holes 12 and 22 facing each other with a spacer (not shown) interposed therebetween. Ends on the innermost circumferential side in the winding direction of the first electrode 10 and the second electrode 20 are closed in a liquid-tight manner so that the electrolyte solution ES does not enter the gaps 62a and 62b.

  A hydrophilic liquid retaining sheet 50 is provided between the first electrode 10 and the second electrode 20 and outside of at least one of the first electrode 10 or the second electrode 20. In a state where these are laminated, the first electrode 10 and the second electrode 20 do not come into contact (short-circuit) with each other by being wound around an arbitrary axis (winding axis). Pair 30 can be obtained. The electrode pair 30 of this embodiment can be installed vertically with the winding axis in the vertical direction, and the installation space for the electrode pair 30 can be reduced. In addition, by using the liquid retaining sheet 50, the electrolytic solution ES can be spread over the entire hollow portion 33 between the first electrode 10 and the second electrode 20.

The electrolytic solution ES is supplied to the inside of the wound roll-shaped electrode pair 30. In other words, the electrolytic solution ES is supplied to both surfaces of the first electrode 10 and the second electrode 20 each having a two-layer structure.
The electrode pair 30 of the present embodiment is wound with the second electrode 20 inside, and the first electrode 10 is located on the outermost surface.

A sealing member 92 that prevents the electrolyte solution ES from leaking in the winding direction (circumferential direction) is provided at the winding end of the electrode pair 30. Further, a bottom plate (not shown) for preventing the electrolyte solution ES from leaking in the axial direction is provided at at least one axial end portion (roll end 94) of the roll-shaped electrode pair 30.
The seal member 92 is liquid-tight between the outermost first electrode 10 and the second electrode 20 that are wound in multiple layers and between the outermost second electrode 20 and the inner electrode 1. It is a member to be sealed.

  In addition, although the roll-shaped electrode pair 30 was illustrated in this embodiment, this invention is not limited to this. As a modified example of the electrode pair 30, a folded shape by Miura folding (registered trademark: double wave type developable curved surface) or other folding methods may be used.

<Third embodiment>
FIG. 5A is a plan view of an electrode (first electrode 10 or second electrode 20) of the present embodiment.
The first electrode 10 or the second electrode 20 of this embodiment includes mesh members 16 and 26 and conductive electrode members 18 and 28 attached to the mesh members 16 and 26.

The mesh members 16 and 26 are members that impart shape retention to the first electrode 10 and the second electrode 20, and may be meshes of braided fine wires or fiber entanglements. Further, the mesh members 16 and 26 may be conductive or insulating.
More specifically, the mesh members 16 and 26 of the present embodiment are wire meshes in which metal wires are braided in a lattice shape. The lattice shape may be an orthogonal lattice or an oblique lattice.

  That is, the net members 16 and 26 include a plurality of partitioned regions 17 and 27 arranged. The electrode members 18 and 28 have one or more through holes 12 and 22 penetrating in the thickness direction in the partition regions 17 and 27, respectively.

  The electrode members 18 and 28 of this embodiment are individually provided for each of the partition regions 17 and 27. That is, the first electrode 10 and the second electrode 20 of the present embodiment are formed by collecting a large number of minute electrode members 18 and 28 in a patchwork shape by the mesh members 16 and 26 (metal mesh). Since the mesh members 16 and 26 are conductive, the adjacent electrode members 18 and 28 are electrically connected to each other. The first electrode 10 and the second electrode 20 are rectangular.

  The electrode members 18 and 28 may be laminated on the upper surface of the mesh members 16 and 26, or may be fitted inside the partition regions 17 and 27.

  The electrode members 18 and 28 have a rectangular plate shape with a side length of 1 mm or less, preferably 500 μm or less, and a through hole 12 or 22 is formed in the approximate center thereof. One or more through holes 12 and 22 are provided in each electrode member 18 and 28. However, some of the electrode members 18 and 28 constituting the first electrode 10 and the second electrode 20 may not be provided with the through holes 12 and 22.

  In the first electrode 10 and the second electrode 20 of the present embodiment, the net members 16 and 26, which are wire nets, have shape retention and flexibility. For this reason, even if the electrode members 18 and 28 are non-flexible board | plate materials which have predetermined | prescribed board thickness, the 1st electrode 10 and the 2nd electrode 20 have flexibility as a whole. Thereby, while ensuring the mechanical strength of the electrode members 18 and 28 to predetermined, the flexibility of the 1st electrode 10 and the 2nd electrode 20 can fully be acquired.

  The first electrode 10 and the second electrode 20 of the present embodiment are configured in a tortoiseshell shape by gathering a large number of micro-sized electrode members 18 and 28 each having a side length of 1 mm or less. It can be easily formed into a curved shape.

  Instead of this embodiment, the electrode members 18 and 28 may be formed in a sheet shape extending over the plurality of partition regions 17 and 27.

  FIG. 5B is a plan view showing a modification of the first electrode 10 and the second electrode 20 of the present embodiment. The first electrode 10 and the second electrode 20 of the present modification are different from the present embodiment of FIG. Further, the first electrode 10 and the second electrode 20 of the present modification are formed by connecting a large number of rectangular electrode members 18 and 28 provided with through holes 12 and 22 in a planar shape with mesh members 16 and 26. In this respect, this embodiment is common to the embodiment of FIG.

The first electrode 10 and the second electrode 20 of the present modification can be easily formed into a prominent saddle shape (dome shape) by pressing the substantial center thereof in the direction perpendicular to the surface.
Hereinafter, examples of the reference form will be added.
1. An electrode pair in which both the planar first electrode and the second electrode are arranged to face each other, and a liquid supply means for supplying an electrolyte between the electrode pairs, and electrolyzing the electrolyte An electrolytic cell for generating gas,
The electrolytic cell is characterized in that the electrode pair has flexibility capable of bending or bending in a direction perpendicular to the surface.
2. 1. An insulating liquid retaining sheet is sandwiched between the electrode pair. The electrolytic cell described in 1.
3. 1. The liquid retaining sheet is a fiber sheet formed body made of a hydrophilic polymer. The electrolytic cell described in 1.
4). A through hole penetrating the first electrode or the second electrode in the thickness direction;
A gas recovery path for recovering the generated gas through the through hole; To 3. The electrolytic cell as described in any one of these.
5). 3. The inner wall surface of the through hole is hydrophobic, and the electrolytic surface in contact with the electrolytic solution of the first electrode and the second electrode is hydrophilic. The electrolytic cell described in 1.
6). 1. At least a part of the electrode pair is curved or bent three-dimensionally. To 5. The electrolytic cell as described in any one of these.
7). 5. The electrode pair is wound in a roll shape. The electrolytic cell described in 1.
8). 6. Said 1st electrode and said 2nd electrode are each provided with the space | gap part formed in the inside, and the through-hole connected to the said space | gap part, respectively. The electrolytic cell described in 1.
9. The first electrode or the second electrode includes a mesh member and a conductive electrode member attached to the mesh member. To 8. The electrolytic cell as described in any one of these.
10. The mesh member comprises a plurality of partitioned regions arranged,
Each of the electrode members has at least one through hole penetrating in the thickness direction in the partition region. The electrolytic cell described in 1.
11. 1. The bending elastic modulus of the electrode pair is 0.1 MPa or more and 2000 MPa or less. To 10. The electrolytic cell as described in any one of these.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.

Example 1
<Method for creating conductive film electrode>
1. Carbon electrode A 15 mm side square and 30 μm thick polyimide kapton film with a hole diameter of 30 μm and a close 3 hole pitch (distance between hole centers) equilateral triangle of 50 μm combined with lithography pattern printing and chemical etching Created. Thereafter, this polyimide film was carbonized by firing at 2000 ° C. for 3 hours in a nitrogen gas atmosphere. This was used as a conductive electrode film. After firing, the film thickness was changed to 28 μm, the hole diameter was 28 μm, and the adjacent three hole pitch was 46 μm.

2. Electrode film single side hydrophilization, single side hydrophobization The water contact angle of this electrode film was measured and found to be 60 °. In order to make the hole wall of the electrode film hydrophobic, first, an aluminum film having a thickness of 5 nm was formed on one surface, and a silica film having a thickness of 50 nm was formed on the back surface thereof by sputtering. Then, this electrode film was exposed to a 50 ° C. HMDS (hexamethyldisilazane) atmosphere for 3 hours. After removal, the aluminum film was removed by dissolving in 38% hydrochloric acid. And the water contact angle of the surface covered with the aluminum film and the surface not covered was measured.
As a result, the water contact angle of the portion covered with the aluminum film was 43 °, and the water contact angle of the uncovered surface was 120 °. Thereby, it was confirmed that the part which was not covered with the aluminum film was hydrophobized.
Moreover, when the water pressure resistance of this electrode film was measured with the hydrophilic surface having a contact angle of 43 ° facing upward by the water pressure resistance measuring method described below, it was confirmed that the water pressure was 27 g / cm ² or more.

3. Measuring method of water pressure resistance An electrode film 410 having a through hole was placed horizontally on the holder 400 shown in FIG. On this electrode film 410, the transparent tube 420 was installed in an upright state. Water (electrolytic solution ES) was gradually dropped into the transparent tube 420. The height from the surface of the electrode film 410 to the liquid surface 430 is measured at a different time immediately before the water leaks from the through hole. From this height and the tube inner diameter of the transparent tube 420, the height per unit area of the electrode film 410 is measured. The pressure applied to was calculated. This was used as the water pressure resistance of the through hole of the electrode film 410.

4). Electrolyzer assembly This electrode film was attached to the electrode holder 35 shown in FIGS.
Moreover, the interelectrode spacer 32 was prepared. As the inter-electrode spacer 32, a polyimide kapton film (film thickness: 500 μm) having a square hollow portion 33 with a side length of 10 mm in the center was used. In the hollow portion 33, a hydrophilic liquid retaining sheet 50 made of cellulose (10 mm square, dry thickness: 50 μm, bulk density: 0.075 g / cm ³ ) was placed.
The other electrode film prepared in the same manner was attached to the electrode holder 36, the interelectrode spacer 32 was sandwiched between the electrode holder 35 and the electrode holder 36, and these were clamped to prepare the electrolytic cell body 110. .
The spacing between the electrode films 410 was 500 μm, which is the thickness of the interelectrode spacer 32.
The electrode holders 35 and 36, the inter-electrode spacer 32, and the electrode film 410 were individually subjected to a bending test before use. Specifically, when these members are bent to a central angle of 150 to 170 °, it is visually confirmed that there is no cracking or breakage and that they have bending elasticity to return to their original state. did.

5. Electrolytic experiment An electrolytic solution (25% KOH) was injected into the electrolytic cell main body 110 at a rate of 0.0025 ml / min. A CV (cyclic voltammogram) curve was measured when the electrolyte was sufficiently filled and the electrolyte was seen from the drain pipe 47 in the outlet line.
The CV curve was measured using an electrochemical measurement system HZ-3000 (manufactured by Hokuto Denko Corporation). Specifically, the current values flowing between the electrode films 410 while increasing the voltage by setting the two electrode films 410 as an anode and a cathode, applying a voltage of 50 mV / sec, and applying a voltage of 0 to 2.5 V, respectively. Was measured. The results are shown in FIG.

Here, it was determined that the higher the current value in the CV curve, the more the electrolysis progressed and the greater the amount of gas generated. In addition, current values at two points of applied voltages of 2.0 V and 2.5 V were read from the CV curve, and compared with comparative examples and examples described later (see Table 3).

( Comparative Example 1)
The same operation as in Example 1 was performed except that only the electrode film on the anode side had no through hole.

( Comparative Example 2)
The same operation as in Example 1 was performed except that both the anode and cathode electrode films were made without through holes.

( Comparative Example 3)
The same operation as in Example 1 was performed except that the entire surfaces of the anode and cathode electrode films were exposed in an HMDS atmosphere and the water contact angle was 110 °.

The results of Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 are shown in FIG. From this result, it was confirmed that the current efficiency was significantly increased by using the porous electrode.

(Example 2)
The thickness of the inter-electrode spacer 32 is 120 μm, and an electrolytic cell main body similar to that of Example 1 is used using a hydrophilic liquid retaining sheet 50 (dry thickness: 20 μm, bulk density: 0.08 g / cm ³ ) made of cupra. 110 was created.
Next, the electrolytic cell main body 110 was curved in a direction perpendicular to the surface by 60 ° from the center in the longitudinal direction to a central angle of 120 °, and the electrolytic cell main body 110 was placed horizontally with the convex portion upward.

  In this state, the same CV curve as in Example 1 was repeatedly measured three times. As a result, the repeated stability of the current value was confirmed.

  FIG. 8 shows the results of three measurements. Table 3 shows current values at applied voltages of 2.0 V and 2.5 V in the third measurement result.

( Comparative Example 4)
The operation was performed three times in the same manner as in Example 2 except that the hydrophilic liquid retaining sheet 50 was not put between the electrode films. As a result, it was confirmed that the current value decreased with each measurement. The results are shown in FIG.

(Example 3)
An Ni foil (purity 99.99% or more, thickness 5 μm) was used as an electrode film, and a large number of through-holes having a diameter of 120 μm and adjacent three hole pitches (distance between hole centers) of 240 μm were processed using an NC processing machine. And one side of this electrode film was washed with concentrated sulfuric acid. The water contact angle of this cleaning surface was 35 °, and the water contact angle of the back surface was 120 °. This electrode film was used for an anode and a cathode. On the other hand, an electrolytic cell main body 110 having a curved shape similar to that of Example 2 was prepared using a liquid holding sheet 50 made of cupra similar to that of Example 2.
A CV curve was measured when an electrolytic solution (25% KOH) was used for the electrolytic cell main body 110. As a result, it was confirmed that water electrolysis was performed satisfactorily even when the electrode film was changed from carbon to Ni foil.

Example 4
A platinum (Pt) film having a thickness of 10 nm was formed by sputtering on a 17 μm thick PEN (Polyethylene Naphthalate) film (product name: OTEC, manufactured by Tobi Co., Ltd.) having an ITO film formed on the surface.
Next, through holes with a hole diameter of 120 μm and a close three hole pitch (hole center distance) of 240 μm were created by an NC processing machine. Then, using the Pt surface as an electrolytic surface, the electrolytic cell main body 110 having a curved shape similar to that in Example 3 was prepared using the liquid retaining sheet 50 similar to that in Example 3, and the CV curve was measured.
As a result, it was confirmed that good electrolysis was performed even when used as an electrode film in which a metal was formed on an organic (PEN) film.

(Example 5)
The electrolytic cell main body 110 of Example 1 was bent by 30 ° from the central portion in the longitudinal direction until a central angle of 150 ° was obtained as shown in FIG. A multilayer electrolytic cell in which three sets of electrolytic cell main bodies 110 were overlapped with each other was created, and the CV curve was measured.
As a result, it was confirmed that good electrolysis was performed even in a three-layer electrolytic cell having a curved surface.

(Example 6)
The distance between the electrode films is 120 μm, the electrolytic solution is changed to 1N sulfuric acid (H ₂ SO ₄ ), and the electrolytic cell main body is changed from the central portion in the longitudinal direction to a central angle of 150 ° as shown in FIG. Electrolysis was performed for 64 hours at an applied voltage of 2.5 V in the same apparatus as in Example 1 except that the film was bent by only °. As a result, it was confirmed that a rapid decrease in current value was not observed and stable water electrolysis operation was performed. In this case, it was confirmed by visual inspection before applying the voltage that no cracks or cracks were generated by bending the electrolytic cell body at a central angle of 150 °, and that no electrolyte leakage occurred. .

The characteristics of the electrode films (anode and cathode) used in Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Tables 1 and 2. Table 3 shows the distance between the electrodes, the electrode curve, the characteristics of the liquid retaining sheet, the electrolytic solution, and the current value of the measurement result.

  From these results, it was found that good electrolysis was possible by inserting a hydrophilic liquid-holding sheet between the electrode films and by providing through holes in the electrode film.

DESCRIPTION OF SYMBOLS 10 1st electrode 20 2nd electrode 12, 22 Through-hole 13, 23 Inner wall surface 14, 24 Electrolytic surface 15, 25 Back surface 16, 26 Net-like member 17, 27 Partition area | region 18, 28 Electrode member 30 Electrode pair 32 Interelectrode spacer 33 Hollow portion 35, 36 Electrode holder 351, 361 Hollow recess 353, 363 Conductor wire 37, 38 Gas recovery holder 371, 381 Gas recovery chamber 372, 382 Flat plate portion 373, 383 Recovery gas flow path 375, 385 Gas extraction line 39 Fixing screw 391 Screw hole 40 Liquid supply parts 41, 43, 44 Electrolyte liquid supply line 46 Liquid supply pipe 47 Drainage pipe 48 Liquid storage tank 49 Liquid supply pump 50 Liquid retention sheets 51, 53, 54 Electrolyte discharge line 60 Gas recovery path 62 void portion 90 power supply portion 92 seal member 94 roll end 100 electrolytic cell 110 electrolytic cell main body 200 gas generator 400 holder 41 Electrode film 420 transparent tube 430 liquid level ES electrolyte G Gas

Claims (9)

An electrode pair in which both the planar first electrode and the second electrode are arranged to face each other, and a liquid supply means for supplying an electrolyte between the electrode pairs, and electrolyzing the electrolyte An electrolytic cell for generating gas,
The electrode pair has flexibility that can be bent or bent in a perpendicular direction ,
An insulating liquid retaining sheet is sandwiched between the electrode pair,
The electrolytic tank , wherein the liquid retaining sheet is a sheet formed body of a fiber material made of a hydrophilic polymer . A through hole penetrating the first electrode or the second electrode in the thickness direction;
The electrolytic cell according to claim 1, further comprising a gas recovery path for recovering the generated gas through the through hole. The electrolytic cell according to claim 2 , wherein an inner wall surface of the through hole is hydrophobic, and an electrolytic surface in contact with the electrolytic solution of the first electrode and the second electrode is hydrophilic. The electrolytic cell according to any one of claims 1 to 3 , wherein at least a part of the electrode pair is three-dimensionally curved or bent. The electrolytic cell according to claim 4 , wherein the electrode pair is wound in a roll shape. 6. The electrolytic cell according to claim 5 , wherein the first electrode and the second electrode each include a void portion formed therein and a through hole communicating with the void portion. Wherein the first electrode or the second electrode, and the net-like member, the electrolytic cell as claimed in any one of 6 claim 1 comprising an electrode member of the deposited electrically conductive to said mesh member. The mesh member comprises a plurality of partitioned regions arranged,
The electrolytic cell according to claim 7 , wherein each of the electrode members has at least one through hole penetrating in a thickness direction in the partition region. The electrolytic cell according to any one of claims 1 to 8 , wherein the bending elastic modulus of the electrode pair is 0.1 MPa or more and 2000 MPa or less.

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