JP2012144778A - Electrolysis electrode and device for generating ozone using the electrolysis electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolysis electrode capable of generating an ozone water at high efficiency and to provide a device for generating the ozone water using the electrolysis electrode.SOLUTION: The electrolysis electrode 1 is composed by forming a groove 13 on at least one surface of a substrate 11 and forming a conductive diamond film along the groove 13. The electrolysis electrode 1 is used as the anode 1P of an electrolytic cell in the ozone generation device 10. The groove 13 functions as the flow path of a liquid to be treated, the flow rate of the liquid to be treated which is supplied to the electrolytic cell increases, and the ozone water can be generated at high efficiency.

Description

  The present invention relates to an electrode for electrolysis and an ozone generator having the electrode for electrolysis as an anode.

  Ozone is a substance having a very strong oxidizing power, and sterilization, decolorization and deodorizing action derived from the oxidizing power are applied in various fields. The sterilization method and the decolorization method using ozone are safe treatment methods free from secondary contamination because ozone itself is easily decomposed naturally into oxygen, and has attracted attention in recent years. Ozone water in which ozone is dissolved in water has further improved oxidizing power and is generally used for sterilization and the like. For these purposes, development of a simpler and more efficient generation method of ozone water is required.

  As means for obtaining ozone water, a method of generating ozone gas and dissolving the ozone gas in water and an electrolytic method of directly generating ozone water are known. In the method of dissolving ozone gas in water, ozone gas is generated by a silent discharge method and is dissolved in water through a gas-liquid dissolution tower, so that the apparatus configuration becomes large and complicated.

  On the other hand, in the electrolysis method, an electrolytic cell is configured by sandwiching a solid polymer film between a porous or net-like anode and cathode, and ozone water is obtained by flowing tap water or pure water through the electrolytic cell. The device configuration becomes smaller.

  As an anode of an electrolysis cell used in this electrolysis method, for example, Patent Document 1 discloses one using a porous graphite plate in which a diamond thin film is attached to one side of a base material. However, when a diamond thin film is attached to the substrate, there is a problem that the diamond peels off. Also, when diamond is formed on a mesh-like substrate, the electrolytic distribution is not uniform when diamond is deposited, and there is a concern of plasma concentration causing damage due to local heating and pinholes. Is done.

  Thus, Patent Document 2 discloses a technique in which a diamond plate surface processed into a porous or reticulated structure by laser processing is used as an anode of an electrolytic cell.

JP-A-9-268395 JP-A-2005-336607

  However, in Patent Document 2, since the gap between the holes formed on the surface of the anode is as large as about 1 mm, it is possible to sufficiently secure the region of the three-phase interface where the anode, the solid polymer film, and water are in contact at the same time. However, there is a problem that ozone cannot be generated with high efficiency.

  Further, in both Patent Documents 1 and 2, since no measures are taken to facilitate the flow of the liquid to be treated on the surface of the anode, there is room for further improvement in order to generate ozone with high efficiency.

  An object of the present invention is to provide an electrode for electrolysis that can generate ozone water with high efficiency, and an ozone generator using the electrode for electrolysis.

  (1) An electrode for electrolysis according to the present invention is formed on a substrate having a substantially flat plate shape, a conductive diamond film formed on at least one surface of the substrate, and a surface on which the conductive diamond film is formed. And a groove that is a flow path of the liquid to be processed.

  According to this configuration, since the substrate has a substantially flat plate shape, when conductive diamond is formed on the surface of the substrate using the plasma CVD method, plasma concentration is avoided, and the conductive diamond is uniform. The film can be formed with excellent adhesion.

  On the other hand, if the surface of the electrode for electrolysis is flat, when this anode is applied to an ozone generator, it is difficult to secure a three-phase interface region where the anode, the solid polymer film, and water contact. Therefore, good electrolysis cannot be performed.

  Therefore, in this configuration, a groove is formed on the surface of the electrolysis electrode, which is a flow path for flowing the liquid to be processed. Therefore, the flow rate of the liquid to be treated can be increased at the same time as securing the three-phase interface, and ozone water can be generated with high efficiency.

  (2) It is preferable that a plurality of the grooves are formed substantially in parallel. According to this configuration, the flow rate can be increased by arranging the longitudinal direction of the groove from the upstream side to the downstream side of the liquid to be processed, so that more ozone water can be generated.

  (3) It is preferable that a plurality of the grooves are formed so as to be connected to each other. According to this configuration, the liquid to be treated can be smoothly flowed by connecting the grooves to each other, and the three-phase interface can be increased. Specific examples of connecting the grooves to each other include, for example, a lattice shape and a mesh shape. As the lattice shape, a mode in which a plurality of grooves are formed in parallel at regular intervals in the longitudinal direction of the electrode for electrolysis and a plurality of grooves is formed in parallel in the lateral direction of the electrode for electrolysis at a certain interval. That's fine. Alternatively, the plurality of grooves are formed in parallel at a predetermined interval in a predetermined first oblique direction of the electrode for electrolysis, and the plurality of grooves are parallel in the second oblique direction intersecting the first oblique direction. What is necessary is just to employ | adopt the aspect to form. As the mesh shape, for example, a mode in which grooves are formed like tile joints may be employed. In addition, examples of the groove include a bowl shape and a triangular shape. In any case, the shape of the groove is arbitrary as long as it does not affect the surroundings of the diamond. Furthermore, the aspect which provides an unevenness | corrugation in the inner wall of a groove | channel is preferable. As a result, the three-phase interface that contributes to the reaction increases, and ozone generated on the electrode surface can be quickly dissolved using turbulent flow, so that ozone water can be generated with higher efficiency.

  (4) It is preferable that the base material is silicon.

  According to this configuration, since the silicon that is most proven and does not easily adhere to scale (precipitates containing calcium oxide, phosphate, silica, etc.) is used, the electrode for electrolysis has high durability. Can be provided. Note that when silicon is used as the base material and conductive diamond is formed by CVD, carbides are formed at the interface during the film formation, so that the adhesion degree of the conductive diamond can be further improved.

  (5) The base material is preferably titanium, niobium, tantalum, titanium carbide, niobium carbide, or tantalum carbide. According to this configuration, since titanium, niobium, tantalum, or a carbide thereof is used as the base material, the groove can be easily formed by machining.

  (6) The conductive diamond film is preferably manufactured by a plasma CVD method. As a CVD method, a method using a hot filament and a plasma CVD method are known. However, when the plasma CVD method is used, the inside of the groove can be reliably coated with the conductive diamond film. Further, the plasma CVD method has the merits of being the most industrially stable and excellent in reproducibility of doping. Therefore, in this configuration, it is preferable to use a plasma CVD method.

  (7) An ozone generator according to the present invention is an ozone generator that electrolyzes water to generate ozone, and includes a solid polymer film, and a cathode and an anode disposed with the solid polymer film interposed therebetween. The anode is configured using the electrode for electrolysis according to any one of (1) to (6), the surface on which the groove is formed is disposed in close contact with the solid polymer film, And a supply unit for supplying a liquid to be processed to the groove.

  According to this configuration, since the electrolysis electrode of any one of (1) to (6) is used as the anode, ozone water can be generated with high efficiency. In addition, since the anode has a grooved surface that is in close contact with the solid polymer film, the distance between the anode and the solid polymer film is shortened, ozone generated by electrolysis can be moved quickly, and Water flow that does not contribute to decomposition can be minimized. Further, the device configuration can be made compact by bringing the anode and the solid polymer film into close contact with each other. Furthermore, since the anode is provided with a groove, even if the solid polymer film and the groove are brought into close contact with each other, a three-phase interface is ensured, and ozone water can be generated with high efficiency.

  (8) The supply unit includes a supply path that supplies the liquid to be processed to the groove, and a drain path that discharges the liquid to be processed so that the liquid to be processed that has passed through the groove does not return to the supply path. It is preferable to provide.

  According to this configuration, the discharged liquid to be treated is prevented from being supplied to the anode again, and ozone water can be generated with high efficiency.

  (9) It is preferable that the anode has a length in a direction in which the liquid to be processed flows is longer than a length in the direction of the solid polymer film.

  According to this configuration, the liquid to be treated can be smoothly flowed from upstream to downstream, and ozone water can be generated with high efficiency.

  (10) It is preferable that the anode has a length in a direction in which the liquid to be processed flows is shorter than a length in the direction of the solid polymer film.

  According to this configuration, since the length of the anode flowing in the liquid to be processed is longer than the length of the solid polymer film in the same direction, the supply port and the discharge port are arranged facing the anode. Can be set and the degree of freedom of setting is expanded. Moreover, a conductive diamond film and a groove can be formed on both surfaces of the anode, and the liquid to be treated can be flowed on both surfaces of the anode, so that ozone generation efficiency can be further increased.

  (11) The cathode preferably has a mesh structure. Here, as the mesh structure, for example, a porous structure in which water can easily enter and exit may be employed.

  According to this configuration, since the cathode has a mesh structure, even when the cathode is brought into close contact with the solid polymer film, ion exchange on the cathode side can be performed efficiently.

  According to the present invention, it is possible to provide an electrode for electrolysis and an ozone generator that generate ozone water with high efficiency.

It is a block diagram of the electrode for electrolysis by embodiment of this invention. It is a top view of the electrode for electrolysis when a plurality of grooves are provided in parallel to the surface of the electrode for electrolysis. It is a top view of the electrode for electrolysis at the time of connecting a plurality of grooves mutually. 1 is an overall configuration diagram of an ozone generator according to an embodiment of the present invention. (A) is a whole block diagram of the ozone generator when the ozone generator of FIG. 4 is placed in the horizontal direction, and (B) is the anode, solid polymer film, and cathode of (A) along the groove. It is sectional drawing when cut. It is a whole block diagram of an ozone production | generation apparatus at the time of using the electrode for electrolysis in which the groove | channel was formed in both surfaces as an anode. In the ozone generator shown in FIG. 5, the whole block diagram of the ozone generator when the length of the solid polymer film 2 in the direction L1 is made longer than the length of the anode is shown. It is sectional drawing when the ozone production | generation apparatus of FIG. 7 is cut | disconnected along a groove | channel. FIG. 3 shows a configuration diagram of an electrolysis cell when a groove is formed on both surfaces of an anode and a cathode is brought into close contact with a solid polymer film. FIG. 3 shows a configuration diagram of an electrolysis cell in which a groove is formed only on one surface of an anode and a cathode is attached to a solid polymer membrane via a spacer.

  Hereinafter, the electrode for electrolysis by embodiment of this invention is demonstrated. FIG. 1 is a configuration diagram of an electrode 1 for electrolysis according to an embodiment of the present invention, (A) is a configuration diagram of a groove 13, and (B) to (E) show modified examples of the groove 13. It is a block diagram.

  As shown in FIG. 1A, the electrode 1 for electrolysis includes a base material 11, a conductive diamond film 12, and a groove 13 (an example of a flow path). The base material 11 has a substantially flat plate shape, and has a quadrangular shape when viewed from above. As the base material 11, it is preferable to employ silicon having high adhesion to diamond.

  As described later, since the conductive diamond film 12 is formed at a high temperature of 800 ° C. and then cooled, the conductive diamond film 12 is peeled off when a material having a high thermal expansion coefficient is used as the substrate 11. There is a fear. Therefore, as the base material 11, a carbide forming metal (carbide growth metal) such as titanium, niobium, or tantalum, which is a substance having a low thermal expansion coefficient, may be employed.

  Further, when titanium, niobium, or tantalum is carbonized, the coefficient of thermal expansion further decreases. Therefore, from the viewpoint of reducing the coefficient of thermal expansion, it is preferable to employ a carbide of titanium, a carbide of niobium, or a carbide of tantalum.

  The conductive diamond film 12 is formed on the upper surface of the base material 11. The groove 13 is formed on the surface on which the conductive diamond film 12 is formed. As described above, since the groove 13 is formed on the surface of the electrode 1 for electrolysis, when the electrode 1 for electrolysis is used as the anode 1P of the ozone generator shown in FIG. Can generate ozone water with high efficiency.

  In the example of FIG. 1, the electrode 1 for electrolysis has the conductive diamond film 12 and the groove 13 only on the upper surface, but may have the conductive diamond film 12 and the groove 13 on both surfaces. In this way, when the electrolysis electrode 1 is used as the anode 1P of the ozone generator, the liquid to be treated can be flowed on both surfaces of the anode to generate more ozone water.

  The height h of the groove 13 is, for example, about 0.2 to 1.2 mm, preferably about 0.25 to 1.1 mm, and more preferably about 1 mm. In order to avoid this, it is desirable to suppress it to about 1/2 of the thickness. The width w of the groove 13 is, for example, 0.5 mm to 2.2 mm, preferably 0.8 mm to 2.1 mm, and more preferably about 2 mm. From the viewpoint of increasing the number of three-phase interfaces where the anode, water, and the solid polymer film are simultaneously in contact with each other to generate ozone with high efficiency, it is preferable to provide small grooves 13 with high density. However, in the present embodiment, the groove 13 also has a function as a flow path for flowing the liquid to be processed. Therefore, if the groove 13 is made larger, the flow rate of the liquid to be treated increases, so that the groove 13 is preferably made larger from the viewpoint of making the groove 13 function as a flow path. Therefore, in the present embodiment, the above values are adopted as the height h and the width w of the groove 13 in order to ensure the three-phase interface and simultaneously function the groove 13 as a flow path.

  In FIG. 1A, the groove 13 has a cross-sectional shape with a flat bottom surface and an inner wall orthogonal to the bottom surface. However, as shown in FIG. It is good. Further, as shown in FIG. 1C, the cross-sectional shape of the groove 13 may be a semicircular shape.

  Further, as shown in FIG. 1D, the groove 13 may have a cross-sectional shape provided with irregularities on the bottom surface. For example, in the case where a single crystal silicon substrate is used, this unevenness can be formed by performing anisotropic etching with KOH or TMAH or by partially cutting with a dicing saw. By doing so, the surface area of the groove 13 is increased, the three-phase interface is increased, and ozone water can be generated with high efficiency. Further, as shown in FIG. 1E, the groove 13 may be provided with unevenness in a top view. In this case, the three-phase interface can be further increased.

  FIG. 2 is a top view of the electrolysis electrode 1 when a plurality of grooves 13 are provided in parallel to the surface of the electrolysis electrode 1. In the example of FIG. 2, a plurality of grooves 13 are provided in parallel at a constant interval d. Here, the distance d is preferably high from the viewpoint of securing the three-phase interface and the flow path function, but there is a certain limit to the high density from the viewpoint of manufacturing. Therefore, in the present embodiment, a value taking into consideration both viewpoints is adopted as the interval d. The distance d is, for example, 0.5 mm to 2.2 mm, preferably 0.8 mm to 2.1 mm, and more preferably about 1 mm.

  3A and 3B are top views of the electrode 1 for electrolysis when a plurality of grooves 13 are connected to each other. FIGS. 3A and 3B show the case where the grooves 13 are formed in a lattice shape. C) shows a case where the grooves 13 are formed in a mesh shape, and FIG. 3D shows a case where the grooves 13 are formed in a honeycomb shape.

  In FIG. 3A, a plurality of grooves 13 are formed in parallel in the horizontal direction of the electrode 1 for electrolysis with a distance d1, and a plurality of grooves 13 are formed in parallel in the vertical direction of the electrode for electrolysis with a distance d2. ing. Note that the same value may be adopted as the intervals d1 and d2, or different values may be adopted. Further, the size may be changed between the vertical groove 13 and the horizontal groove 13.

  In FIG. 3B, a plurality of grooves 13 are formed substantially parallel to a predetermined first oblique direction dr1 of the electrode 1 for electrolysis, and substantially parallel to a second oblique direction dr2 intersecting the first oblique direction dr1. A plurality of grooves 13 are formed. Here, as the angle θ between the first oblique direction dr1 and the second oblique direction dr2, various angles can be adopted, but for example, about 90 degrees is adopted in FIG. 3B. In the example of FIG. 3B, the interval between the grooves 13 in the first oblique direction dr1 and the interval between the grooves 13 in the second oblique direction dr2 are substantially constant, but may not be constant. Further, some variation may be given to the direction of the groove 13 in the first and second oblique directions dr1 and dr2.

  In FIG. 3C, the groove 13 is formed like a tile joint, and the groove 13 is formed in a mesh shape. In FIG. 3D, a plurality of substantially hexagonal grooves 13 are arranged so that the upper side and the lower side are in contact with each other. When a plurality of grooves 13 are formed in at least two directions as shown in FIGS. 3A to 3D, the flow rate of the liquid to be processed can be increased simultaneously with increasing the three-phase interface.

  FIG. 4 is an overall configuration diagram of the ozone generator 10 according to the embodiment of the present invention. The ozone generator 10 includes an anode 1P, a solid polymer film 2, a cathode 3, a supply path 41 (an example of a supply unit), a drainage path 42 (an example of a supply unit), a fixed jig 5, an anode holder 6, and a packing 7. I have.

  As the anode 1P, the electrode 1 for electrolysis shown in any of FIGS. 1 to 3 is employed. In the anode 1P, the surface on which the groove 13 is formed is disposed in close contact with one surface of the solid polymer film 2.

  The solid polymer film 2 has a flat plate shape and is sandwiched between the anode 1P and the cathode 3. As the solid polymer film 2, for example, Nafion (registered trademark) manufactured by DuPont is adopted. The solid polymer film 2 is fitted and fixed to the lower surface (the right surface in the figure) of the fixing jig 5. The solid polymer film 2 is provided between the supply port 41x and the discharge port 42x. Thereby, the supply channel 41 and the drainage channel 42 are isolated by the solid polymer film 2 and the anode 1P, and the liquid to be treated discharged from the drainage channel 42 can be prevented from returning again to the anode 1P side. .

  The cathode 3 is composed of a flat plate-like member, and is disposed on the upper surface of the fixed jig 5 (surface opposite to the surface on which the anode 1P is disposed).

  A spacer 51 is fitted in the center of the fixed jig 5, and the cathode 3 is in close contact with the spacer 51. The spacer 51 is made of a porous material. Therefore, the cathode 3 is arranged somewhat apart from the solid polymer film 2.

  Instead of using the spacer 51, the cathode 3 may be installed at a distance from the solid polymer film 2. Alternatively, if a cathode 3 having a mesh structure is employed, the cathode 3 can be brought into close contact with the solid polymer film 2 without the spacer 51 interposed therebetween. In this case, ion exchange on the cathode 3 side can be performed more efficiently.

  The length of the anode 1P in the direction L1 (vertical direction) in which the liquid to be processed flows is longer than the length in the direction L1 of the solid polymer film 2. In addition, the solid polymer film 2 is disposed substantially at the center of the anode 1P. Therefore, areas D1 and D2 exposed from the solid polymer film 2 are secured on the upstream side and the downstream side in the direction L1 of the anode 1P. Thereby, the supply path 41 can be arrange | positioned to the area | region D1, and the drainage path 42 can be arrange | positioned to the area | region D2, and the supply path 41 and the drainage path 42 can be provided only in the cathode 3 side. As a result, the apparatus configuration can be made more compact than when the supply path 41 is provided on the anode 1P side and the drainage path 42 is provided on the cathode 3 side.

  The supply path 41 is formed of a tubular member in which the supply port 41x is located at a position facing the region D1 of the anode 1P, and is arranged on the upper surface side of the fixed jig 5, and is connected to the upper side of the not-shown object. The liquid to be processed supplied from the processing liquid supply unit is supplied to the anode 1P. Tap water or soft water is used as the liquid to be treated. The supply path 41 is configured by a hole that communicates with the fixed jig 5 at a part of the downstream side.

  The drainage channel 42 is a hole formed in the fixed jig 5 so that the discharge port 42x is located at a position facing the region D2 of the anode 1P. The packing 7 is interposed between the outer periphery of the anode holder 6 and the outer periphery of the fixed jig 5. As a result, the liquid to be processed can be prevented from flowing outside the fixed jig 5. The waste water containing ozone is mixed in the tank 20, but a tubular member may be disposed in the same manner as the supply path 41 and drawn out without being mixed into the tank 20 or the like. In this case, higher density ozone water can be obtained.

  The tank 20 has a size capable of accommodating about 4/3 of the lower part of the ozone generator 10 and is constituted by a bottomed box body whose upper side is open, and stores a liquid to be processed. The ozone generator 10 is immersed in the liquid to be processed in the tank 20 so that at least the cathode 3 is immersed in water. The tank 20 stores the liquid to be processed discharged from the drainage channel 42.

In the ozone generation apparatus 10 configured as described above, the liquid to be processed is supplied from the supply path 41 and flows to the groove 13 of the anode 1P, the drainage path 42, and the tank 20. In this state, a voltage is applied between the anode 1P and the cathode 3. Then, the reaction of 2H ₂ O → O ₂ + 4H ⁺ + 4e ⁻ and 3H ₂ O → O ₃ + 6H ⁺ + 6e ⁻ occurs at the anode 1 P, and nH ⁺ + ne ⁻ → (n / 2) H ₂ occurs at the cathode 3. (However, n = 4 or 6) occurs and ozone is generated. Then, this ozone is dissolved in the water to be treated and becomes ozone water, which is discharged from the drainage channel 42.

  Thus, in the ozone generator 10 according to the present embodiment, the electrolysis electrode 1 having a plurality of grooves 13 on the surface is used as the anode 1P, and therefore ozone water can be generated with high efficiency.

  5A is an overall configuration diagram of the ozone generation device 10 when the ozone generation device 10 of FIG. 4 is placed in the horizontal direction, and FIG. 5B is a diagram illustrating the anode 1P and the solid in FIG. 3 is a cross-sectional view of an electrolytic cell including a polymer film 2 and a cathode 3 cut along a groove 13. FIG.

  The anode holder 6 includes a recess 61, and the anode 1P is fitted into the recess 61. An electrode plate 1x is attached to the center of the bottom surface of the anode holder 6. A conductive wire LN1 is connected to the electrode plate 1x. A conductive wire LN2 is connected to the cathode 3.

  FIG. 6 is an overall configuration diagram of the ozone generator 10 when the electrode 1 for electrolysis having grooves 13 formed on both surfaces is used as the anode 1P. As shown in FIG. 6, the anode 1P has grooves 13a and 13b formed on both sides. In FIG. 5, the anode 1P is sandwiched between the fixed jig 5 and the anode holder 6. However, in FIG. 6, the anode 1P is sandwiched between the pair of fixed jigs 5a and 5b. Conductor LN1 is connected to anode 1P, and a positive voltage is applied via conductor LN1. A conductive wire LN2 is connected to each of the cathodes 3 and 3, and a negative voltage is applied via the conductive wire LN2.

  The fixed jig 5a and the fixed jig 5b have the same shape as the fixed jig 5 in FIG. 5, and sandwich the anode 1P so that the supply paths 41a and 41b and the drain paths 42a and 42b face each other. Similarly to FIG. 4, the ozone generator 10 shown in FIG. 6 is immersed in the tank 20 for storing the liquid to be processed, and the liquid to be processed is supplied simultaneously from the supply path 41a and the supply path 41b. And the to-be-processed liquid supplied from the supply path 41a is discharged | emitted from the drainage path 42a through the groove | channel 13a. Further, the liquid to be treated supplied from the supply path 41b passes through the groove 13b and is discharged from the drainage path 42b.

  In this state, a voltage is supplied between the anode 1P and the cathode 3 of the fixed jig 5a, and a voltage is supplied between the anode 1P and the cathode 3 of the fixed jig 5b. Then, ozone is generated in each of the grooves 13a and 13b, and the generated ozone is dissolved in water to become ozone water and discharged from the drains 42a and 42b.

  Therefore, the ozone generator 10 shown in FIG. 6 can generate twice as much ozone as the ozone generator 10 shown in FIG. 5, and can generate ozone water with higher efficiency.

  FIG. 7 shows an overall configuration diagram of the ozone generator 10 in the case where the length of the solid polymer film 2 in the direction L1 is longer than the length of the anode 1P in the ozone generator 10 shown in FIG. FIG. 8 is a cross-sectional view when the ozone generator 10 of FIG. 7 is cut along the groove 13.

  In the case of FIG. 7, the solid polymer film 2 is arranged so that the length in the direction L <b> 1 is longer than that of the anode 1 </ b> P and substantially covers the upper surface of the anode holder 6. Therefore, the supply path 41 and the drainage path 42 are provided not on the fixed jig 5 but on the anode holder 6. Specifically, the supply channel 41 and the drain channel 42 are provided symmetrically with respect to the anode holder 6.

  The ozone generator 10 configured in this way is immersed in the liquid to be treated in the tank 20 in the same manner as in FIG. When the liquid to be processed is supplied from the supply path 41, the liquid to be processed is discharged from the drain path 42 through the groove 13. In this state, when a positive voltage is applied to the cathode plate 1x and a negative voltage is applied to the cathode 3, ozone is generated at the anode 1P, and this ozone is dissolved in water as the liquid to be treated to become ozone water. Discharged from.

  FIG. 9 shows a configuration diagram of an electrolysis cell in the case where the grooves 13 are formed on both surfaces of the anode 1P in the ozone generator 10 of FIG. The electrolytic cell shown in FIG. 9 shows a state viewed from the longitudinal direction of the groove 13. As shown in FIG. 9, the cathode 3 is in close contact with the solid polymer film 2. Therefore, the spacer 51 shown in FIG. 6 becomes unnecessary, and the height of the ozone generator 10 can be reduced and downsizing can be achieved. Further, since the grooves 13 are provided on both surfaces of the anode 1P, more ozone can be generated as compared with the case where the grooves 13 are provided only on one surface as in FIG.

  FIG. 10 shows the ozone generator 10 shown in FIG. 9 in which the groove 13 is formed only on one surface of the anode 1P, and the cathode 3 is attached to the solid polymer film 2 via the porous spacer 51. The block diagram of the electrolytic cell in the case is shown. Note that the electrolytic cell shown in FIG. 10 shows a state viewed from the direction of the groove 13. In this way, ozone water can be generated with high efficiency by providing the cathode 3 through the porous spacer 51 through which water can freely flow to the electrode portion.

  Next, the manufacturing method of the electrode 1 for electrolysis is demonstrated. First, a substrate 11 having a groove 13 having a depth of, for example, 250 μm on the surface is prepared. Here, the groove 13 is formed by cutting a silicon substrate having a thickness of, for example, 500 μm with a dicing saw.

  Next, powder processing is performed on the substrate 11 on which the grooves 13 are formed. Here, the powder treatment is a treatment in which the substrate 11 is immersed in ethanol containing diamond powder and ultrasonic waves are applied.

  Next, the conductive diamond film 12 is formed on the surface of the substrate 11 on the side where the grooves 13 are formed by a plasma CVD method. Here, the conductive diamond film 12 is formed using a microwave plasma CVD apparatus. The microwave plasma CVD apparatus includes a stainless steel chamber in which a molybdenum substrate holder is installed.

  The base material 11 is installed in this substrate holder. Then, a mixed gas obtained by diluting 0.5 vol% of methane with hydrogen is flowed into the chamber under the conditions of a pressure of 50 Torr and a flow rate of 100 scm, and at the same time, plasma is generated in the chamber by radiating microwaves into the chamber. Further, 10 ppm of siborane is added into the chamber in order to make the diamond film conductive. And the output of a microwave is adjusted so that the temperature of the base material 11 may be hold | maintained at 800 degreeC, and about 3 hours are made to pass. Thereby, the conductive diamond film 12 is formed on the surface of the substrate 11. Next, the microwave emission is stopped, and the substrate 11 is naturally cooled to take out the substrate 11 from the chamber. As described above, the conductive diamond film 12 in which diamond is doped with boron is formed so as to follow the shape of the groove 13, and the electrode 1 for electrolysis is completed.

DESCRIPTION OF SYMBOLS 1 Electrode for electrolysis 1P Anode 1x Electrode plate 2 Solid polymer film 3 Cathode 5, 5a, 5b Fixed jig 6 Anode holder 7 Packing 10 Ozone generator 11 Base material 12 Conductive diamond film 13, 13a, 13b Groove 20 Tank 41 41a, 41b Supply channel 42, 42a, 42b Drain channel 51 Spacer

Claims (11)

A base material having a substantially flat plate shape;
A conductive diamond film formed on at least one surface of the substrate;
An electrode for electrolysis provided with a groove which is formed on a surface on which the conductive diamond film is formed and which is a flow path of a liquid to be processed.   The electrode for electrolysis according to claim 1, wherein a plurality of the grooves are formed substantially in parallel.   The electrode for electrolysis according to claim 1 or 2, wherein a plurality of the grooves are formed so as to be connected to each other.   The electrode for electrolysis according to claim 1, wherein the base material is silicon.   The electrode for electrolysis according to any one of claims 1 to 3, wherein the base material is titanium, niobium, tantalum, titanium carbide, niobium carbide, or tantalum carbide.   The electrode for electrolysis according to claim 1, wherein the conductive diamond film is manufactured by a plasma CVD method. An ozone generator that electrolyzes water to generate ozone,
A solid polymer membrane;
A cathode and an anode disposed with the solid polymer membrane interposed therebetween,
The anode is configured using the electrode for electrolysis according to any one of claims 1 to 6, and the surface on which the groove is formed is disposed in close contact with the solid polymer film,
An ozone generator comprising: a supply unit that supplies a liquid to be processed to the groove.   The said supply part is provided with the supply path which supplies the said to-be-processed liquid to the said groove | channel, and the drainage path which discharges | emits the said to-be-processed liquid so that the to-be-processed liquid which passed the said groove | channel does not return to the said supply path. Item 8. The ozone generator according to Item 7.   The ozone generator according to claim 7 or 8, wherein the anode has a length in a direction in which the liquid to be treated flows is longer than a length in the direction of the solid polymer film.   The ozone generator according to claim 7 or 8, wherein the anode has a length in a direction in which the liquid to be treated flows is shorter than a length in the direction of the solid polymer film.   The ozone generator according to any one of claims 7 to 10, wherein the cathode has a mesh structure.

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