JPWO2016043109A1 - Electrolyzer and electrode - Google Patents

Abstract

According to the embodiment, the electrolytic cell of the electrolysis apparatus 10 includes a first electrode, a diaphragm, and a second electrode. The first electrode 14 includes a first surface 17a facing the diaphragm, a second surface 17b located on the opposite side of the first surface, a first recess 42 formed in a first pattern on the first surface, respectively. And a plurality of through-holes opened in the first surface and the first recess.

Description

  Embodiments described herein relate generally to an electrolysis apparatus and an electrode used in the electrolysis apparatus.

  As an electrolyzer, an electrolyzed water generator that generates alkaline ionized water, ozone water, hypochlorous acid water, or the like is known. As this electrolyzed water generating apparatus, an apparatus having a three-chamber type electrolytic cell (electrolytic cell) has been proposed. The interior of the three-chamber type electrolytic cell is divided into three chambers, an anode chamber, an intermediate chamber, and a cathode chamber, by a diaphragm. In such an electrolysis device, for example, chlorine gas generated in the anode chamber is obtained by flowing salt water in the intermediate chamber, flowing water in the left and right cathode chambers and the anode chamber, and electrolyzing the salt water in the intermediate chamber with the cathode and the anode. From this, hypochlorous acid water is generated and sodium hydroxide water is generated in the cathode chamber. The produced hypochlorous acid water is used as sterilizing / disinfecting water, and sodium hydroxide water is used as washing water.

Japanese Patent No. 3500173 Published patent publication 2011-256431 Japanese Patent No. 4705190 Published Patent Publication No. 2006-176835 Published Patent Publication No. 2014-101549

However, in such a three-chamber type electrolytic cell, the reaction around the anode is complicated as chlorine ion⇒chlorine gas⇒hypochlorous acid, and if this reaction system is not performed well, competing oxygen gas It produces | generates and the production | generation efficiency of hypochlorous acid falls. In addition, since the generated chlorine gas and hypochlorous acid are strong oxidizing agents, there is a risk of causing deterioration of the diaphragm.
The problem to be solved by the present invention is to provide a long-life and high-efficiency electrolysis apparatus and an electrode used for the electrolysis apparatus, which suppress the deterioration of the diaphragm.

  According to the embodiment, the electrolysis device includes a first electrode, a second electrode facing the first electrode, and at least one diaphragm disposed between the first electrode and the second electrode. It has an electrolytic cell. The first electrode includes a first surface facing the diaphragm, a second surface located on the opposite side of the first surface, a first recess formed in a first pattern on the first surface, and a second surface and a first surface, respectively. And a plurality of through holes opened in one recess.

FIG. 1 is a block diagram schematically showing an electrolysis apparatus according to the first embodiment. FIG. 2 is an exploded perspective view showing the electrolytic cell of the electrolysis apparatus according to the first embodiment. FIG. 3 is a sectional view of the electrolytic cell. FIG. 4 is an enlarged perspective view showing a first electrode and an anode cover of the electrolytic cell. FIG. 5 is a perspective view showing a first surface side of the first electrode. FIG. 6 is a perspective view showing a second surface side of the first electrode. FIG. 7 is an enlarged perspective view showing a part of the first electrode. FIG. 8 is a plan view of the first electrode when the first electrode is viewed from the first surface side. 9 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line AA in FIG. 10 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line BB in FIG. FIG. 11 is an enlarged perspective view showing a part of the first electrode of the electrolysis apparatus according to the first modification. FIG. 12 is a plan view of the first electrode when the first electrode according to the first modification is viewed from the first surface side. 13 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line CC in FIG. 14 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line DD of FIG. FIG. 15 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to a second modification. FIG. 16 is a plan view of the first electrode when the first electrode according to the second modification is viewed from the first surface side. FIG. 17 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line EE of FIG. 18 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line FF in FIG. FIG. 19 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to a third modification. FIG. 20 is a plan view of the first electrode when the first electrode according to the third modification is viewed from the first surface side. FIG. 21 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line GG in FIG. 20. 22 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line HH in FIG. 20. FIG. 23 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to a fourth modification. FIG. 24 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to a fifth modification. FIG. 25 is an enlarged perspective view showing a part of the first electrode of the electrolysis apparatus according to the sixth modification. FIG. 26 is an enlarged perspective view showing a part of the first electrode of the electrolysis apparatus according to the seventh modification. FIG. 27 is a plan view of the first electrode when the first electrode according to the seventh modification is viewed from the first surface side. 28 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line II of FIG. FIG. 29 is an enlarged perspective view showing a part of a first electrode of an electrolysis apparatus according to an eighth modification. FIG. 30 is a plan view of the first electrode when the first electrode according to the eighth modification is viewed from the first surface side. 31 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line JJ in FIG. 30. FIG.

  Various embodiments will be described below with reference to the drawings. In addition, the same code | symbol shall be attached | subjected to a common structure through embodiment, and the overlapping description is abbreviate | omitted. In addition, each drawing is a schematic diagram for promoting the embodiment and its understanding, and its shape, dimensions, ratio, etc. are different from the actual device, but these are considered in consideration of the following description and known techniques. The design can be changed as appropriate.

(First embodiment)
FIG. 1 is a diagram schematically showing an electrolysis apparatus according to the first embodiment. In the present embodiment, the electrolyzer 10 is configured as an electrolyzed water generator. As shown in FIG. 1, the electrolyzer 10 includes a so-called three-chamber type electrolytic cell 11. The electrolytic cell 11 is formed in a flat rectangular box shape, and the inside thereof includes an intermediate chamber 15a and an intermediate chamber 15a by an anion exchange membrane 16 as a first diaphragm and a cation exchange membrane 18 as a second diaphragm. It is partitioned into an anode chamber 15b and a cathode chamber 15c located on both sides. A first electrode (anode) 14 is provided in the anode chamber 15 b and faces the anion exchange membrane 16. A second electrode (cathode) 20 is provided in the cathode chamber 15 c and faces the cation exchange membrane 18.

  The electrolyzer 10 includes an electrolytic solution supply unit 19 that supplies an electrolytic solution, for example, saturated saline, to the intermediate chamber 15a of the electrolytic cell 11, and water that supplies electrolyzed water, for example, water to the anode chamber 15b and the cathode chamber 15c. A supply unit 21 and a power supply 23 for applying a positive voltage and a negative voltage to the first electrode 14 and the second electrode 20 are provided.

  The electrolyte supply unit 19 includes a salt water tank 25 that generates saturated saline, a supply pipe 19a that guides the saturated saline from the salt water tank 25 to the lower portion of the intermediate chamber 15a, and a liquid feed pump 29 provided in the supply pipe 19a. And a drain pipe 19b for sending the electrolytic solution flowing in the intermediate chamber 15a from the upper portion of the intermediate chamber 15a to the salt water tank 25.

  The water supply unit 21 includes a water supply source (not shown) that supplies water, a water supply pipe 21a that guides water from the water supply source to the lower portions of the anode chamber 15b and the cathode chamber 15c, and water that flows through the anode chamber 15b. A first drain pipe 21b that discharges from the cathode chamber 15c, a second drain pipe 21c that drains water flowing through the cathode chamber 15c from the upper part of the cathode chamber 15c, a gas-liquid separator 27 provided in the second drain pipe 21c, It has.

  A description will be given of an operation of generating acidic water (hypochlorous acid water and hydrochloric acid) and alkaline water (sodium hydroxide) by actually electrolyzing a saline solution by the electrolysis apparatus 10 configured as described above.

  As shown in FIG. 1, the liquid feed pump 29 is operated to supply saturated saline to the intermediate chamber 15a of the electrolytic cell 11, and supply water to the anode chamber 15b and the cathode chamber 15c. At the same time, a positive voltage and a negative voltage are applied from the power source 23 to the first electrode 14 and the second electrode 20, respectively. Sodium ions ionized in the brine flowing into the intermediate chamber 15a are attracted to the second electrode 20, pass through the cation exchange membrane 18, and flow into the cathode chamber 15c. And in the cathode chamber 15c, water is electrolyzed by the 2nd electrode 20, and hydrogen gas and sodium hydroxide aqueous solution are obtained. The sodium hydroxide aqueous solution and hydrogen gas generated in this way flow out from the cathode chamber 15c to the second drain pipe 21c, and are separated into the sodium hydroxide aqueous solution and hydrogen gas by the gas-liquid separator 27. The separated sodium hydroxide aqueous solution (alkaline water) is discharged through the second drain pipe 21c.

  Moreover, the chlorine ion ionized in the salt water in the intermediate chamber 15a is attracted to the first electrode 14, passes through the anion exchange membrane 16, and flows into the anode chamber 15b. Then, chlorine ions give electrons to the anode at the first electrode 14 to generate chlorine gas. Thereafter, the chlorine gas reacts with water in the anode chamber 15b to produce hypochlorous acid and hydrochloric acid. The acidic water (hypochlorous acid water and hydrochloric acid) thus generated is discharged from the anode chamber 15b through the first drain pipe 21b.

Next, the configuration of the electrolytic cell 11 will be described in more detail. FIG. 2 is an exploded perspective view of the electrolytic cell, and FIG. 3 is a cross-sectional view of the electrolytic cell.
As shown in FIGS. 2 and 3, the electrolytic cell 11 has a rectangular frame-shaped intermediate frame 22 that functions as a partition, and a rectangular plate shape that has an outer diameter dimension substantially equal to that of the intermediate frame 22 and covers one side surface of the intermediate frame. An anode cover (first cover member) 24 and a rectangular plate-like cathode cover (second cover member) 26 having an outer diameter dimension substantially equal to that of the intermediate frame 22 and covering the other side surface of the intermediate frame. Yes.

  An anion exchange membrane 16 is disposed between the intermediate frame 22 and the anode cover 24 as a first diaphragm that separates the intermediate chamber 15a and the anode chamber 15b. The anode chamber 15b is adjacent to the anion exchange membrane 16 in a first manner. An electrode (anode) 14 is disposed. Between the intermediate frame 22 and the cathode cover 26, a cation exchange membrane 18 is disposed as a second diaphragm separating the intermediate chamber 15a and the cathode chamber 15c, and the cathode chamber 15c is adjacent to the cation exchange membrane 18 in the second region. An electrode (cathode) 20 is disposed.

  A first inflow port 34 communicating with the intermediate chamber 15a is formed at the lower end of the intermediate frame 22, and a first outflow port 36 communicating with the intermediate chamber 15a is provided at the upper end. A supply pipe 19a and a drain pipe 19b are connected to the first inlet 34 and the first outlet 36, respectively.

  As shown in FIGS. 2 to 4, a plurality of linear ribs 33 project from the inner surface of the anode cover 24 and extend, for example, in the vertical direction (second direction Y). These ribs 33 are provided in parallel to each other and at a predetermined interval. Between these ribs 33, flow grooves 32 a extending in the vertical direction are formed. In addition, a pair of upper and lower horizontal grooves that communicate the ends of the flow grooves 32 a are formed on the inner surface of the anode cover 24. An anode chamber 15 b is defined by the flow grooves 32 a and the lateral grooves and the anion exchange membrane 16. Further, the flow groove 32a and the lateral groove form a flow path for flowing water.

  A second inflow port 37 that communicates with the lower end of the flow groove 32 a is formed in the lower part of the anode cover 24, and a second outflow port 38 that communicates with the upper end of the flow groove 32 a is provided in the upper part of the anode cover 24. A water supply pipe 21a and a first drain pipe 21b are connected to the second inlet 37 and the second outlet 38, respectively.

  On the inner surface of the cathode cover 26, a plurality of ribs 35, a plurality of flow grooves 32b, and lateral grooves that extend in the vertical direction (second direction Y) are formed. A cathode chamber 15 c is defined by the flow grooves 32 b and the lateral grooves and the cation exchange membrane 18. Further, the flow groove 32b and the lateral groove form a flow path for flowing water.

  A third inflow port 39 communicating with the lower end of the flow groove 32b is formed in the lower part of the cathode cover 26, and a third outflow port 41 communicating with the upper end of the flow groove 32b is provided in the upper part. A water supply pipe 21a and a second drain pipe 21c are connected to the third inlet 39 and the third outlet 41, respectively.

  As shown in FIGS. 2 and 3, between the constituent members, that is, between the peripheral edge of the anode cover 24 and the peripheral edge of the first electrode 14, and between the peripheral edge of the first electrode 14 and the anion exchange membrane 16. Water leakage between the frame 22, between the intermediate frame 22 and the peripheral edge of the second electrode 20 and the cation exchange membrane 18, and between the peripheral edge of the second electrode 20 and the peripheral edge of the cathode cover 26. A frame-shaped sealing material 40 for preventing the above is disposed.

  A plurality of fixing bolts 50 are inserted through the peripheral edge of each constituent member, for example, inserted from the anode cover 24 side, and the leading end thereof protrudes from the cathode cover 26. A nut 52 is screwed into the tip of each fixing bolt 50. The peripheral portions of the constituent members are fastened to each other by the fixing bolt 50 and the nut 52 as fastening members, and the water tightness of the intermediate chamber 15a, the anode chamber 15b, and the cathode chamber 15c is maintained.

  2 and 3, each of the anion exchange membrane 16 and the cation exchange membrane 18 has an outer diameter substantially equal to that of the intermediate frame 22 and is formed in a thin rectangular plate shape having a thickness of about 100 to 200 μm. Is formed. The anion exchange membrane 16 and the cation exchange membrane 18 have a characteristic of allowing only specific ions to pass therethrough. A plurality of through holes through which the fixing bolts 50 are inserted are formed in the peripheral portions of the anion exchange membrane 16 and the cation exchange membrane 18.

  The anion exchange membrane 16 is disposed to face one side of the intermediate frame 22, and the peripheral edge thereof is in close contact with the intermediate frame 22 via the sealing material 40. Similarly, the cation exchange membrane 18 is disposed to face the other surface side of the intermediate frame 22, and the peripheral edge thereof is in close contact with the intermediate frame 22 via the sealing material 40. The first diaphragm and the second diaphragm are not limited to ion exchange membranes, and may be porous membranes having water permeability.

  The first electrode 14 and the second electrode 20 are formed of a metal flat plate having a thickness of about 1 mm, and are formed in a rectangular shape having an outer diameter substantially the same as the outer diameter of the intermediate frame 22. A fine through hole for allowing liquid to pass through is formed in the central portion (effective region) of the first electrode 14 and the second electrode 20, and a plurality of through holes for inserting the fixing bolt 50 are formed in the peripheral portion. Has been. The 1st electrode 14 has the connecting terminal 14b which protrudes from the one side edge. Similarly, the 2nd electrode 20 has the connecting terminal 20b which protrudes from the one side edge.

  The first electrode 14 is disposed to face the anion exchange membrane 16 and is in close contact with the anion exchange membrane 16. The second electrode 20 is disposed opposite the cation exchange membrane 18 and is in close contact with the cation exchange membrane 18.

Next, the configuration of the first electrode (anode) 14 will be described in more detail on behalf of the electrode.
4 is an enlarged perspective view showing the first electrode and the anode cover, FIG. 5 is a perspective view showing the first surface side of the first electrode, and FIG. 6 is a perspective view showing the second surface side of the first electrode. 7 is an enlarged perspective view of a part of the first electrode, FIG. 8 is a plan view of the first electrode when the first electrode is viewed from the first surface side, and FIG. 9 is a line of FIG. FIG. 10 is a cross-sectional view of the first electrode and the anion exchange membrane along AA, and FIG. 10 is a cross-sectional view of the first electrode and the anion exchange membrane along line BB in FIG.

  As shown in FIGS. 4 to 7, the first electrode 14 has a porous structure and a mesh structure in which a large number of recesses and through holes are formed in a base material 17 made of, for example, a rectangular metal plate. The base material 17 has the 1st surface 17a and the 2nd surface 17b which opposes substantially parallel to the 1st surface 17a. The distance between the first surface 17a and the second surface 17b, that is, the plate thickness T is, for example, 0.8 mm. The first surface 17 a faces the first diaphragm 16, and the second surface 17 b faces the anode cover 24. As the base material 17, a metal such as titanium can be used.

  The first surface 17a of the base material 17 is formed with a first recess R1 having the first pattern over the entire surface, and the second surface 17b of the base material 17 has a second pattern different from the first pattern. A second recess R2 is formed over the entire surface.

  In the present embodiment, the first pattern first recess R1 includes a plurality of thin linear first recesses 42 formed on the first surface 17a of the base material 17, and each of these first recesses 42 is a first recess. Opened to the surface 17a. The second recess R2 of the second pattern has a plurality of thick or rough linear second recesses 44 formed on the second surface 17b of the base material 17, and each of these second recesses 44 is a second surface 17b. Is open. The first recess 42 and the second recess 44 are formed in the entire rectangular effective region except for the peripheral edge of the base material 17. A plurality of first recesses 42 communicate with one second recess 44, and each form a through hole 46. The entire surface of the first electrode 14 is coated with an iridium oxide catalyst. The iridium oxide catalyst has a lower overvoltage for chlorine gas generation than competing oxygen gas generation, and selectively generates chlorine gas if there is a certain amount of chlorine ions around the anode.

  As shown in FIGS. 4 to 10, in the present embodiment, the plurality of first recesses 42 are formed in an elongated linear shape and extend in the first direction X, for example, the horizontal direction. The plurality of first recesses 42 are provided in parallel with each other. Each first recess 42 is formed longer than an opening width W3 of a second recess 44 described later. In the present embodiment, the first recess 42 continuously extends from one end to the other end of the effective area of the first surface 17a (rectangular central area excluding the peripheral edge of the first surface). The opening width W1 of each first recess 42 is, for example, 0.4 mm, the pitch P1 in the arrangement direction Y of the first recesses 42 is 0.5 mm, and the depth D1 of the first recesses 42 is half the plate thickness T of the substrate 17. It is formed shallower, for example, 0.1 to 0.2 mm. In the present embodiment, each first recess 42 is formed so as to increase in width from the bottom side toward the first surface 17a, that is, has a substantially trapezoidal cross-sectional shape. Both side surfaces defining the first recess 42 extend with an inclination with respect to the first surface 17a. Thereby, some 1st recessed parts 42 are connected to the several 2nd recessed part 44 with the penetration width W2 of 0.2 mm.

  In the present embodiment, the plurality of second recesses 44 formed on the second surface 17b side is formed in an elongated linear shape, and intersects the first direction X, for example, the second direction orthogonal to the first direction X. It extends to Y. The plurality of second recesses 44 are provided in parallel with each other. Each second recess 44 extends continuously from one end to the other end of the effective area of the second surface 17b (a rectangular central area excluding the peripheral edge of the second surface). The opening width W3 of each second recess 44 is sufficiently larger than the opening width W1 of the first recess 42, for example, 2.4 mm, the pitch P2 in the arrangement direction X of the second recess 44 is 3 mm, and the depth of the second recess 44 The depth D2 is deeper than half the plate thickness T of the base material 17, and is formed to be 0.6 to 0.7 mm, for example. In the present embodiment, each second recess 44 is formed so as to increase in width from the bottom side toward the second surface 17b and has a substantially trapezoidal cross-sectional shape. Both side surfaces defining the second recess 44 extend inclining with respect to the second surface 17b. Thereby, the 2nd recessed part 44 is connected to the some 1st recessed part 42 by 1.2 mm of penetration width W4.

  The first electrode 14 configured as described above, for example, etches the first surface 17a and the second surface 17b of the base material 17 to partially scrape the first recess R1 and the second pattern having the first pattern. It can produce by forming 2nd dent R2 which has. The cross-sectional shapes of the first concave portion 42 and the second concave portion 44 are not limited to a trapezoidal shape, and may be various shapes such as a rectangular shape, a semicircular shape, an elliptical shape, and an arc shape. Further, the angle at which the first recess 42 and the second recess 44 intersect is not limited to a right angle, and may be any other angle.

With the above structure, the first recess 42 and the second recess 44 of the first electrode 14 communicate with each other at the intersections, thereby forming a large number of through holes 46. In the first surface 17a facing the first diaphragm 16, an opening is formed in a majority of 80% of the surface by the first recess 42, and the area of the communication opening is 16% of the area of the electrode surface. Keep it low. Further, considering the recovery of bubbles from the through hole 46, the flow of water is in the width direction of the through hole 46 (second direction Y). Thus, in the electrode which etched the base material 17 from both surfaces of the first and second surfaces 17a and 17b, the aperture ratio on each surface can be changed, and the same aperture ratio on both surfaces formed by die cutting or the like. The function which cannot be achieved by the conventional electrode of can be exhibited. The ratio of the opening area to the entire area of the first surface 17a of the first surface 17a of the through hole 46 formed by communicating the first recess 42 and the second recess 44 is the ratio of the opening area ratio to the entire area of the first surface 17a of the first recess 42. It is desirable to be less than half.
In the present embodiment, the second electrode (cathode) 20 is configured in the same manner as the first electrode 14.

  As shown in FIGS. 3 and 4, the first electrode 14 is arranged in a direction in which the extending direction Y of the second recess 44 and the extending direction of the flow groove (flow path) 32 a of the anode cover 24 are substantially coincident. ing. The second surface 17 b of the first electrode 14 faces the inner surface of the anode cover 24 and is in contact with the tip surface of the rib 33. Thereby, the water supplied to the anode chamber 15 b flows along the flow groove 32 a and the second recess 44 of the first electrode 14, that is, in a direction intersecting with the first recess 42 of the first electrode 14.

  As shown in FIGS. 3, 9, and 10, the first surface 17 a of the first electrode 14 faces the first diaphragm 16 and is in close contact with the first diaphragm 16. Since the first recesses 42 are formed in about 80% of the effective area of the first surface 17a, the first recesses 16 are formed in the first diaphragm 16 by a depth of 0.1 to 0.2 mm. It is away from. As shown in FIG. 10, the main reaction occurs in the bottom region of the first recess 42 slightly away from the first diaphragm 16, and the product hypochlorous acid is generated from a slight gap formed by the first recess 42. It is collected in the anode chamber through the through hole 46. Thereby, it is possible to achieve both high generation efficiency and prevention of diaphragm deterioration.

  According to the electrolysis apparatus 10 according to the first embodiment, by using the first electrode 14 having the above-described configuration, it is formed by a conventional punching (punching process) or cutting and extending (expanding / lass process) manufacturing method. Compared with the case where the made electrode is used, the outstanding effect can be acquired. In other words, the first electrode 14 and the first diaphragm 16 can be formed without providing a separate member such as a spacer by forming a large number of first recesses 42 in the first surface 17a of the first electrode 14 facing the first diaphragm 16. A small distance can be separated from each other, and as a result, both production efficiency and diaphragm deterioration can be improved.

  Since the conventional electrodes for die cutting can basically only form through holes that penetrate the first and second surfaces 17a and 17b in the same area, the main reaction is caused when the first electrode 14 and the first diaphragm 16 are brought into close contact with each other. It occurs on the first surface 17a facing the first diaphragm 16. Since the first surface is in close contact with the first diaphragm, there is a problem that the diaphragm 16 is deteriorated by the reaction product. In addition, when the first surface and the first diaphragm are in close contact with each other, there is a problem in that the product produced by the electrolytic reaction here cannot be recovered and efficiency is deteriorated.

  In the present embodiment, since the first recess 42 (first recess R1) having an area ratio of 80% is formed on the first surface 17a, which is the main reaction site, the reaction product has a slight gap D1 and through-holes. 46 is promptly collected in the flow groove 32a, and deterioration of the first diaphragm 16 can be suppressed.

  Ideally, the first recess 42 has a large opening area occupancy, but practically, the above-described effects can be sufficiently obtained if 60% or more of the effective area of the first surface 17a is used. Further, the finer the arrangement pitch P1 of the first recesses 42 is, the more advantageous is the product recovery from the portion in contact with the first diaphragm 16, but practically the effect is sufficiently exhibited if the pitch P1 is 0.8 mm or less. can do. The depth D1 of the first recess 42 is ideally shallow, but in practice, the effect can be exhibited if it is 0.5 mm or less. The minimum width of the region forming the first surface 17a of the first electrode 14 is 0.3 mm or less, that is, the value obtained by subtracting the opening width W1 of the first recess 42 from the arrangement pitch P1 of the first recess 42 is 0. If it is 3 mm or less, the substance produced | generated by the electrolytic reaction from the 1st surface 17a closely_contact | adhered with the diaphragm becomes easy, and the above-mentioned effect can be exhibited.

  One of the roles of the second recess 44 of the first electrode 14 is to form a through hole 46 for collecting the product from the first recess 42 formed shallow with high definition to the anode chamber 15b side. Another role of the second recess 44 is to collect the current electrolyzed in the first recess 42 with a low resistance. For this reason, the second recess 44 is a rough linear recess that intersects the first recess 42. By making the first recess 42 and the second recess 44 orthogonal to each other, the intersection of the first recess 42 and the second recess 44 communicates, and hypochlorous acid or the like generated in the first recess 42 is transmitted from the through hole 46. The anode chamber 15b is taken out. In addition, the area ratio of the through-hole 46 with respect to the area of the 1st electrode 14 is made low with 16%. This is to make the first recess 42 region lost by the through hole 46 as small as possible. As the area of the through hole 46 increases, more chlorine ions are diffused through the through hole 46. Therefore, the area of the through hole 46 is desirably within 30% of the electrode area.

  Moreover, in this embodiment, the 1st recessed part 42 and the 2nd recessed part 44 are linear, The longitudinal direction is mutually orthogonally crossed. For this reason, one first recess 42 communicates with a plurality of second recesses 44 to form a through hole 46, compared with a case where the first recess 42 and the second recess 44 penetrate one-to-one. Thus, drainage of the first recess 42 is improved. That is, a plurality of through-holes 46 are provided in one second recess 44 without becoming a narrow path, so that a reaction product, in particular, bubbles are easily removed. Further, by making the linear second recesses 44 orthogonal to the first recesses 42 at a rough pitch, the area ratio of the through holes 46 is set to 16 while keeping the opening area ratio of the first recesses 42 as high as 80%. It is as small as%. This prevents the reaction product from deteriorating the first diaphragm 16 and the electrolyte from diffusing from the through hole 46 to lower the concentration.

The second recess 44 has a rough pitch P2 of several mm, for example, 3 mm, leaving a large volume of the base material 17 so that the electric current generated by electrolysis can be supplied with low resistance, and the strength of the electrode itself. Is maintained. In practice, a sufficient feed resistance can be obtained by setting the pitch P2 to 1 mm or more.
From the above, according to the first embodiment, it is possible to provide a long-life and high-efficiency electrolysis device and electrode that suppress the deterioration of the diaphragm.

  Next, electrodes of the electrolysis apparatus according to various modifications will be described. In the modification described below, the same parts as those of the first embodiment described above are denoted by the same reference numerals, and the detailed description thereof is omitted, and the parts different from those of the first embodiment are mainly described. This will be explained in detail.

(First modification)
11 is an enlarged perspective view showing a part of the first electrode according to the first modification, FIG. 12 is a plan view of the first electrode when the first electrode is viewed from the first surface side, and FIG. FIG. 14 is a cross-sectional view of the first electrode and the anion exchange membrane along line CC in FIG. 12, and FIG. 14 is a cross-sectional view of the first electrode and the anion exchange membrane along line DD in FIG.

  As shown in FIGS. 11 to 14, according to the first modification, the basic specification of the first electrode 14 is the same as that of the first electrode 14 of the first embodiment shown in FIGS. 4 to 10. However, the second recesses 44 of the second recesses R2 are formed in narrow recesses having an opening width W3 of 1.6 mm and a through width W4 of 0.4 mm while the arrangement pitch P2 remains 3 mm.

  According to the said structure, the area ratio of the through-hole 46 can be lowered to about 5%, and it can suppress further that the chlorine ion which passed the 1st diaphragm 16 diffuses into the distribution | circulation groove | channel 32a. Thereby, the chlorine ion concentration on the first surface 17a of the first electrode 14 is increased to suppress the generation of oxygen gas, and the generation efficiency of acidic water is improved.

(Second modification)
FIG. 15 is an enlarged perspective view showing a part of the first electrode according to the second modification, FIG. 16 is a plan view of the first electrode when the first electrode is viewed from the first surface side, and FIG. FIG. 18 is a cross-sectional view of the first electrode and the anion exchange membrane along line EE in FIG. 16, and FIG. 18 is a cross-sectional view of the first electrode and the anion exchange membrane along line FF in FIG.

  As shown in FIGS. 15 to 18, according to the second modification, the plurality of second recesses 44 constituting the second recess R <b> 2 formed on the second surface 17 b of the first electrode 14 are arranged in the first direction X. Are extending in a second direction Y orthogonal to each other, but are not continuous in the second direction, but are divided into a plurality of parts. That is, the second recesses 44 in each row include a plurality of second recesses 44 that are arranged at a predetermined interval in the second direction Y. The length along the second direction Y of each second recess 44 is formed to be equal to or greater than the width of the first recess 42. Further, the length of the first recess 42 is longer than the width W3 of the second recess 44. As a result, the intersections of the first recess 42 and the second recess 44 communicate with each other to form a plurality of through holes 46. A plurality of first recesses 42 communicate with one second recess 44.

  According to the second modification of the above configuration, the second recesses 44 in each row are divided into a plurality of portions, and a wide linear portion is left between these second recesses. Thereby, mechanical strength improves in all the surface directions of the 1st electrode 14, and anisotropy can be relieve | moderated also about the feeding resistance of a 1st electrode.

  In the above-described first embodiment, the second recess 44 is configured in parallel with the flow groove 32a. However, the first electrode 14 may be installed in a direction in which the second recess 44 is orthogonal to the flow groove 32a. Good.

(Third Modification)
FIG. 19 is an enlarged perspective view showing a part of the first electrode according to the second modification, FIG. 20 is a plan view of the first electrode when the first electrode is viewed from the first surface side, and FIG. 20 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line GG in FIG. 20, and FIG. 22 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line HH in FIG.

According to the third modification, the first electrode 14 has a large number of first recesses 42 formed on the first surface 17a and constituting the first recess R1. The second recess formed in the second surface 17 b of the first electrode 14 is formed by the through hole 47. That is, a plurality of through holes 47 are opened in the first surface 17 a and the second surface 17 b of the base material 17. The through hole 47 is formed, for example, in a circular shape having a larger diameter than the width W1 of the first recess 42, that is, the through hole 47 has an opening length in the second direction Y longer than the width W1 of the first recess 42. Is formed. A plurality of first recesses 42 communicate with one through hole 47.
The first recess 42 of the first electrode 14 is formed by etching or photolithography because high definition is required, but the through hole 47 as the second recess is low-definition and may be formed by existing punching.

(Fourth modification)
FIG. 23 is an enlarged perspective view showing a part of the first electrode according to the fourth modification. According to the fourth modification, the plurality of first recesses 42 formed on the first surface 17a of the first electrode 14 and constituting the first recess R1 are not continuous in the first direction X but are divided into a plurality of parts. Has been. That is, the first recesses 42 in each row include a plurality of first recesses 42 arranged in the first direction X at a predetermined interval. The length of each first recess 42 is longer than the width W <b> 3 of the second recess 44. As a result, the intersections of the first recess 42 and the second recess 44 communicate with each other to form a plurality of through holes 46. A plurality of first recesses 42 communicate with one second recess 44.

  According to the 4th modification of the above-mentioned composition, the 1st crevice 42 of each line is divided into a plurality, and the linear part is left between these 1st crevice. Thereby, mechanical strength improves in all the surface directions of the 1st electrode 14, and anisotropy can be relieve | moderated also about the feeding resistance of a 1st electrode.

(5th modification)
FIG. 24 is an enlarged perspective view showing a part of the first electrode according to the fifth modification. The 1st recessed part 42 formed in the 1st surface 17a of the 1st electrode 14 is not restricted to linear form, It is good also as another shape. According to the fifth modification, the plurality of first recesses 42 formed on the first surface 17a of the first electrode 14 are not linear but extend along the first direction X and are bent at a plurality of locations. It is formed in a shape.

(Sixth Modification)
FIG. 25 is an enlarged perspective view showing a part of the first electrode according to the fifth modification. According to the fifth modification, the plurality of first recesses 42 formed on the first surface 17 a of the first electrode 14 and constituting the first recess R <b> 1 extend along the first direction X and are curved at a plurality of locations. It is formed in a linear or wavy shape.

(Seventh Modification)
FIG. 26 is an enlarged perspective view showing a part of the first electrode according to the seventh modification, FIG. 27 is a plan view of the first electrode when the first electrode is viewed from the first surface side, and FIG. FIG. 27 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line II in FIG. 26.

  As shown in FIGS. 26 to 28, according to the seventh modification, the first recess R1 formed on the first surface 17a of the first electrode 14 includes a plurality of third recesses in addition to the plurality of first recesses 42. A recess 45 is provided. The third recess 45 is formed by providing a notch in at least a part of the wall that separates the adjacent first recesses 42. The plurality of third recesses 45 open to the first surface 17a in regions other than the through-holes 46, and the adjacent first recesses 42 communicate with each other. In the present modification, each third recess 45 extends over most of the region between two through holes 46 adjacent in the first direction X.

  According to the seventh modification of the above configuration, the area of the first surface 17a that contacts the diaphragm can be further reduced by providing a plurality of third recesses. Further, the main reaction region of the electrode is the bottom surface of the first recess R1, and the area of the reaction region can be increased by providing the third recess.

(Eighth modification)
FIG. 29 is an enlarged perspective view showing a part of the first electrode according to the eighth modification, FIG. 30 is a plan view of the first electrode when the first electrode is viewed from the first surface side, and FIG. FIG. 31 is a cross-sectional view of the first electrode and the anion exchange membrane taken along line JJ in FIG. 30.

  As shown in FIGS. 29 to 30, according to the eighth modification, the basic configuration of the first electrode 14 is the same as that of the seventh modification described above, but the plurality of third recesses 45 are formed in the first direction X. Are intermittently provided in a plurality of locations in the first direction X in a region between two through holes 46 adjacent to each other. That is, the plurality of third recesses 45 are formed so as to partially leave wall portions separating the adjacent first recesses 42. In the present modification, for example, four third recesses 45 are provided in a region between two through holes 46 adjacent to each other in the first direction X. The plurality of third recesses 45 are provided in a line along the second direction Y.

  In the eighth modified example having the above-described configuration, the diaphragm that bends along the first recess R1 by intermittently providing a plurality of third recesses, that is, by reducing the length or width of each third recess. The amount of deformation can be reduced, and the diaphragm, electrode, and position can be defined more accurately.

  Furthermore, according to the eighth modification, as shown in FIG. 31, the first electrode 14 includes the catalyst layer 54 formed on the first recess R1 except for the first surface 17a. That is, in the first electrode 14, no catalyst is formed only on the first surface 17a, which is a region in contact with the diaphragm. As a result, the first surface in contact with the diaphragm does not undergo an electrolytic reaction, and the life of the diaphragm can be extended.

  In the eighth modification, the plurality of third recesses are arranged in a straight line in the second direction Y. However, the present invention is not limited to this, and the plurality of third recesses are arranged in the first direction. They may be arranged so as to be shifted from each other. For example, they may be arranged in a staggered manner.

The present invention is not limited to the above-described embodiments and modifications as they are, and can be embodied by modifying the components without departing from the scope of the invention in the implementation stage. In addition, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment and the modified examples. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, constituent elements over different embodiments and modifications may be appropriately combined.
For example, the first electrode and the second electrode are not limited to a rectangular shape, and other various shapes can be selected. The material of each constituent member is not limited to the above-described embodiments and modifications, and other materials can be appropriately selected. The electrode structure described above may be applied not only to the first electrode but also to the second electrode (cathode). The electrolyzer of the electrolyzer is not limited to a three-chamber type electrolyzer, and can be applied to a two-chamber or one-chamber electrolyzer and other electrolyzers using electrodes. Electrolytes and products are not limited to salts and hypochlorous acid, and may be applied to various electrolytes and products.

According to the embodiment, the electrolysis device includes a first electrode, a second electrode facing the first electrode, and at least one diaphragm disposed between the first electrode and the second electrode. It has an electrolytic cell. The first electrode is formed in a single plate shape having a first surface facing the diaphragm and a second surface located on the opposite side of the diaphragm, and a plurality of first electrodes formed in a first pattern on the first surface. It has a 1st crevice, and the 1st crevice has a bottom face spaced apart from the 1st surface, and a penetration hole opened in a part of the 2nd surface and the bottom face .

According to the embodiment, the electrolysis device includes a first electrode, a second electrode facing the first electrode, and at least one diaphragm disposed between the first electrode and the second electrode. It has an electrolytic cell. The first electrode is formed in a single plate shape having a first surface facing the diaphragm and a second surface located on the opposite side of the diaphragm, and is formed in a first pattern on the first surface. A plurality of first recesses and a plurality of second recesses formed on the second surface in a second pattern different from the first pattern, the first recesses being parallel to the first surface, respectively. A bottom surface extending along the first direction and spaced from the first surface, and a through hole opening in the second surface and a part of the bottom surface, wherein the second recesses are respectively The first surface of the first recess has an opening length larger than the width of the first recess in a second direction that opens to the second surface and is parallel to the first surface and intersects the first direction. The length in the direction is longer than the width of the second recess in the first direction. It said first recess having forms respectively communicating the through hole.

Claims (29)

An electrolytic cell having a first electrode, a second electrode facing the first electrode, and at least one diaphragm disposed between the first electrode and the second electrode;
The first electrode includes a first surface facing the diaphragm, a second surface located on the opposite side of the diaphragm, a first recess formed in a first pattern on the first surface, and the second surface. An electrolyzer having a surface and a plurality of through holes opened in the first recess.   The first electrode has a second recess formed in a second pattern different from the first pattern on the second surface, and a plurality of locations of the second recess communicate with the first recess and pass through the through hole. The electrolyzer according to claim 1, wherein Each of the first recesses has a plurality of first recesses that open in the first surface and extend in a first direction, and each of the second recesses opens in the second surface and intersects the first direction, respectively. A plurality of second recesses having an opening length larger than the width of the first recess in the second direction.
A length of the first recess in the first direction is longer than a width of the second recess in the first direction, and a plurality of the first recesses communicate with one second recess, and each of the through holes has a through hole. The electrolyzer according to claim 2, wherein   The plurality of first recesses are provided at a first pitch in the width direction, and the second recesses are provided at a second pitch in the width direction, and the second pitch is larger than the first pitch. Item 4. The electrolytic apparatus according to Item 3.   The electrolysis apparatus according to claim 4, wherein the first pitch of the first recesses is 0.8 mm or less.   The electrolysis apparatus according to claim 4 or 5, wherein the second pitch of the second recesses is 1 mm or more.   4. The electrolysis apparatus according to claim 3, wherein the plurality of first recesses have an opening area opening on a first surface of the first electrode of 60% or more with respect to an area of the first surface.   The electrolysis apparatus according to any one of claims 4 to 7, wherein a value obtained by subtracting an opening width W1 of the first recess from the arrangement pitch P1 of the first recess is 0.3 mm or less.   The electrolysis apparatus according to any one of claims 1 to 8, wherein an aperture ratio of the plurality of through holes is 30% or less of an area of the first surface of the first electrode.   The opening area ratio of the through hole formed by communicating the first recess and the second recess to the entire area of the first surface is less than half of the opening area ratio of the first recess to the entire area of the first surface. The electrolyzer according to any one of claims 3 to 8.   The depth of the said 1st recessed part is an electrolytic device of any one of Claim 3 thru | or 10 currently formed shallower than the half of the thickness of the said 1st electrode.   The electrolysis apparatus according to any one of claims 3 to 11, wherein the depth of the second recess is formed deeper than half of the thickness of the first electrode.   The depth of the said 1st recessed part is the electrolysis apparatus of Claim 11 or 12 which is less than 0.5 mm.   The electrolytic device according to claim 3, wherein the second recess extends along a second direction different from the first direction.   The electrolysis apparatus according to claim 14, wherein a plurality of the second recesses communicate with one first recess to form a through hole, respectively.   The first recess extends continuously along the first direction from one end to the other end of the effective area of the first electrode, and the second recess extends from one end to the other end of the effective area of the first electrode. The electrolyzer according to claim 14, which extends continuously along the second direction.   The electrolysis apparatus according to claim 16, wherein the first recess and the second recess extend linearly.   The electrolysis apparatus according to claim 17, wherein the first recess is divided into a plurality with a gap in the first direction.   The electrolytic device according to claim 17, wherein the second recess is divided into a plurality with a gap in the second direction.   The electrolysis apparatus according to claim 3, wherein the second recess is configured by a through-hole penetrating the first electrode.   The first recess includes a plurality of third recesses that open to the first surface in regions other than the through-holes and communicate with the adjacent first recesses, respectively. 2. The electrolysis apparatus according to item 1.   The electrolysis apparatus according to any one of claims 1 to 21, wherein the first electrode includes a catalyst layer formed on the first recess except for the first surface. An electrode used in an electrolysis device,
A first surface facing the diaphragm;
A second surface located opposite the first surface;
A first dent formed in a first pattern on the first surface;
A plurality of through holes each opened in the second surface and the first recess;
Electrode.   The second surface has a second recess formed in a second pattern different from the first pattern, and a plurality of portions of the second recess communicate with the first recess to form the through hole. Item 24. The electrode according to Item 23. Each of the first recesses has a plurality of first recesses that open in the first surface and extend in a first direction, and each of the second recesses opens in the second surface and intersects the first direction, respectively. A plurality of second recesses having an opening length larger than the width of the first recess in the second direction.
A length of the first recess in the first direction is longer than a width of the second recess in the first direction, and a plurality of the first recesses communicate with one second recess, and each of the through holes has a through hole. The electrode according to claim 24, wherein the electrode is formed.   25. The electrode according to claim 23 or 24, wherein the plurality of first recesses have an opening area opened to the first surface of 60% or more with respect to an area of the first surface.   The electrode according to claim 24 or 25, wherein an aperture ratio of a through hole formed by communicating the first recess and the second recess is 30% or less of the area of the first surface.   28. The any one of claims 25 to 27, wherein the first recess includes a plurality of third recesses that open to the first surface in regions other than the through holes and communicate with the adjacent first recesses. 2. The electrode according to item 1.   The electrode according to any one of claims 23 to 28, further comprising a catalyst layer formed on the first recess except for the first surface.

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