CN206768237U - Electrode, electrode unit and electrolysis unit - Google Patents
Electrode, electrode unit and electrolysis unit Download PDFInfo
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- CN206768237U CN206768237U CN201690000258.4U CN201690000258U CN206768237U CN 206768237 U CN206768237 U CN 206768237U CN 201690000258 U CN201690000258 U CN 201690000258U CN 206768237 U CN206768237 U CN 206768237U
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract
The electrode of embodiment is the same electrode of the substrate with the 1st surface, with the electrolysis of the 2nd surface of the 1st opposing surface and the multiple through holes penetrated from the 1st surface to the 2nd surface, it has in multiple 1st recesses of the 1st surface opening and is wider than multiple second recesses of the 1st recess in the 2nd surface opening and aperture area, and the radius of curvature of the edge part of the base material after the removing catalyst of the opening of the 1st recess is more than 0.01mm.
Description
Technical field
Embodiment of the present utility model is related to electrode, electrode unit and electrolysis unit.
Background technology
In recent years, there is provided water electrolysis is generated to the electrolysis water with various functions, such as alkali ion water, Ozone Water
Or the electrolysis unit of hypochloric acid water etc..In electrolysis water, hypochloric acid water has excellent sterilizing power, while safe to the human body, makees
Also approved for food additives.In addition, electrolysis unit is additionally operable to hydrogen manufacture etc..
As electrolysis unit, such as propose the electrolytic water generating device of the electrolytic cell with 3 Room types.It is positive in electrolytic cell
Amberplex and anion-exchange membrane are divided into medial compartment, positioned at the anode chamber of the both sides of the medial compartment and this Room 3 of cathode chamber.
Anode and negative electrode are respectively equipped with anode chamber and cathode chamber.As electrode, use and passed through expansion to metal plate substrate
(expand), etching or punching and machined the electrode of the loose structure in multiple holes.
In such electrolysis unit, for example, the salt solution that circulated in medial compartment, circulates respectively in anode chamber and cathode chamber
Water.By using negative electrode and anode by the saline electrolysis of medial compartment, so that hypochloric acid water, chlorine are generated in anode, while in cathode chamber
Generate sodium hydroxide water, hydrogen.The hypochloric acid water generated is utilized as sterilizing water, and sodium hydroxide water is as washings
Etc. being utilized.Hydrogen is utilized as hydrogen water or fuel.Particularly, in the case of mainly manufacture chlorine, hydrogen, entered with bigger electric current
Row electrolysis.
The high current that circulated in these electrolysis and in the case of being electrolysed in large quantities, if current convergence is in one of electrode
Point, then catalyst of the part etc. can be stripped, or the multiple aperture plasma membrane or dielectric film that are contacted with this easily deteriorate,
Decomposition voltage rises, the lost of life.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-101549 publications
Patent document 2：No. 4746629 publications of Japanese Patent No.
Utility model content
Utility model will solve the problems, such as
The problem of embodiment of the present utility model is to provide the electrolysis electricity also grown in a kind of life-span at higher current densities
Pole, electrode unit and electrolysis unit.
The means used to solve the problem
The electrode of embodiment has base material, multiple 1st recesses and a multiple second recesses, the base material have the 1st surface,
Penetrated with the 2nd surface of the 1st opposing surface and from the 1st surface to multiple through holes on the 2nd surface, it is described
Multiple 1st recesses are wider than in the 1st surface opening, the multiple second recesses in the 2nd surface opening and aperture area
1st recess, the radius of curvature of the opening of the 1st recess is more than 0.01mm.
Brief description of the drawings
Fig. 1 is the figure of one of the electrolysis unit for schematically showing embodiment.
Fig. 2A is the schematic diagram of one of the shape for the electrode for showing embodiment.
Fig. 2 B are the schematic diagrames of one of the shape of the minimum sectional area of the through hole for the electrode for showing embodiment.
Fig. 2 C are the figures for schematically showing the cut surface at Fig. 2A line A-A.
Fig. 2 D are the figures for illustrating the radius of curvature of the edge part of the 1st recess.
Fig. 3 A be show can application implementation mode electrode electrode unit the exploded perspective view of one.
Fig. 3 B are the schematic diagrames of one of the shape of the minimum sectional area of the through hole for the electrode for showing embodiment.
Fig. 3 C are the schematic diagrames for the cut surface for showing the line B-B shown in Fig. 3 A.
Fig. 3 D are the schematic diagrames for the cut surface for showing the line C-C shown in Fig. 3 A.
Fig. 4 A be show can application implementation mode electrode electrode unit the exploded perspective view of one.
Fig. 4 B are the schematic diagrames of the cut surface for the line D-D for showing Fig. 4 A.
Fig. 5 is the figure of another of the electrolysis unit for schematically showing embodiment.
Fig. 6 A are the figures of one of the manufacture method for showing electrode used in embodiment.
Fig. 6 B are the figures of one of the manufacture method for showing electrode used in embodiment.
Fig. 6 C are the figures of one of the manufacture method for showing electrode used in embodiment.
Fig. 6 D are the figures of one of the manufacture method for showing electrode used in embodiment.
Fig. 6 E are the figures of one of the manufacture method for showing electrode used in embodiment.
Fig. 6 F are the figures of one of the manufacture method for showing electrode used in embodiment.
Fig. 7 is the schematic diagram of one of the composition for showing electrode used in embodiment and Porous barrier film.
Fig. 8 is the figure of one of the electrolysis unit for schematically showing embodiment.
Fig. 9 is the figure of one of the electrolysis unit for schematically showing embodiment.
Embodiment
The electrode of embodiment has base material, multiple 1st recesses and a multiple second recesses, the base material have the 1st surface,
Penetrated with the 2nd surface of the 1st opposing surface and from the 1st surface to multiple through holes on the 2nd surface, the multiple 1st recess exists
1st surface opening, the multiple second recesses are wider than the 1st recess, the opening of the 1st recess in the 2nd surface opening and aperture area
The radius of curvature of edge part be more than 0.01mm.
The electrode unit of embodiment is the electrode unit for using above-mentioned electrode as the 1st electrode, and it has：In the presence of the 1st
Surface and the 1st electrode on the 2nd surface；The 2nd electrode being oppositely disposed with the 1st surface of the 1st electrode；It is arranged at the 1st of the 1st electrode the
The Porous barrier film on surface；The electrolyte holding structure being arranged between Porous barrier film and the 2nd electrode.
In addition, the electrolysis unit of embodiment is the electricity for the electrode unit for applying above-mentioned electrode and having used above-mentioned electrode
Solve one of device.The electrolysis unit has electrolytic cell and the electrode unit for being loaded into electrolytic cell, formed by electrode unit division
The 1st electrode chamber and the 2nd electrode chamber.It can carry and alive mechanism is applied to electrode unit, for example for applying electricity to electrode
Power supply and control device of pressure etc..
1st electrode chamber is, for example, anode chamber, and the 2nd electrode chamber is, for example, cathode chamber, can further set to electrolytic cell and lead
Enter the pipeline of the electrolyte solution comprising chloride ion, take out the pipeline of acidic electrolytic water from anode chamber and taken from cathode chamber
Go out the pipeline of electrolyzed alkaline water.The water quality sensor of monitoring water quality can also be set on pipeline.Particularly, it is acid for taking out
For the pipeline of electrolysis water, preferably conductivity sensor and/or pH sensors, for the pipeline for taking out electrolyzed alkaline water,
It is preferred that pH sensors and/or sodium ion sensor.For conductivity sensor, 0~20mS/cm or so electricity can be determined
Conductivity sensor, due to being mixed into a small amount of ionic impurity in acidic electrolytic water in the case of can be detected, thus
Particularly preferably.
Below, embodiment is illustrated referring to the drawings.
It should be noted that same symbol is accompanied by being commonly constructed in embodiments, and the repetitive description thereof will be omitted.Separately
Outside, each figure is the schematic diagram, its shape, size, ratio etc. and reality of embodiment and the understanding for promoting embodiment
Device has difference, and they may be referred to the following description and known technology and are suitably designed change.For example, in figure
Electrode is described in the plane, but can also be bent according to the shape of electrode unit, can also be cylindrical shape.
Fig. 1 is the figure of one of the electrolysis unit for schematically showing embodiment.
Electrolysis unit 10 possesses the electrolytic cell 11 and electrode unit 12 of 3 Room types.Electrolytic cell 11 is formed as flat rectangular box
Shape, anode chamber 16, cathode chamber 18 are divided into by spaced walls 14 and electrode unit 12 inside it and is formed at interelectrode medial compartment
19 this Room 3.
Electrode unit 12 is with the 1st electrode 20 in anode chamber 16 and in cathode chamber 18 and with as defined in
2nd electrode (opposite electrode) 22 of multiple through holes, formed with catalyst layer 28 on the 1st surface 21a of the 1st electrode 20, and
And there is Porous barrier film (can use dielectric film) 24 thereon.Can have on the 1st surface 23a of the 2nd electrode 22
Other Porous barrier films 27.1st electrode 20 and the 2nd electrode 22 separate gap and opposed in parallel to each other, porous at these
Formed with the medial compartment (electrolyte liquor chamber) 19 for keeping electrolyte between matter barrier film 24,27.Use can be set in medial compartment 19
In the keeping body 25 for keeping electrolyte.1st electrode 20 and the 2nd electrode 22 can be by multiple bridges 60 with insulating properties and mutual
Connection.
Electrolysis unit 10 possesses for applying the alive and of power supply 30 to the 1st and the 2nd electrode 20,22 of electrode unit 12
The control device 36 being controlled to power supply 30.Can also possess galvanometer 32, potentiometer 34.
As illustrated, the 1st electrode 20 for example with the base material 21 being made up of the metallic plate of rectangle formed with largely passing through
The loose structure of through hole.Base material 21 have the 1st surface 21a and with almost parallel the 2nd opposed surface 21b of the 1st surface 21a.The
1 surface 21a and the 2nd surface 21b interval, i.e. thickness of slab is formed as T1.1st surface 21a is opposed with Porous barrier film 24, the 2nd table
Face 21b is opposed with anode chamber 16.Can also be formed with anode oxide film (not shown) on the 21a of surface.
Multiple 1st recesses 40 are formed at the 1st surface 21a of base material 21, and are open in the 1st surface 21a.In addition, multiple 2
Recess 42 is formed in the 2nd surface 21b, and is open in the 2nd surface 21b.Opened as the 1st recess 40 of Porous barrier film 24 side
Mouth diameter R1 is less than the opening diameter R2 of second recesses 42.In addition, the quantity on recess, more preferably compared with second recesses 42
Ground forms the 1st recess 40.The depth of 1st recess 40 is T2, and the depth of second recesses 42 is T3, the shape in a manner of T2+T3=T1
Into.In addition, in embodiments, such as with T2<T3 mode is formed.In figure, form the 1st recess 40 and connect with second recesses 42
The through hole connect, but can also be not connected recess or the recess partly connected.Base material 21 is same base material, no
It is that different substrate materials are subjected to part welding etc. and the electrode being laminated.In the case where different substrate materials are laminated, hypochlorous acid holds
Base material contact surface is easily stayed in, formation efficiency reduces.Also, current convergence easily occurs in junction, easily causes catalysis
Agent deteriorates.
It is less than the opening diameter R2 of second recesses 42 as the opening diameter R1 of the 1st recess 40 of the side of Porous barrier film 24.Close
In the quantity of recess, the 1st recess 40 is more formed preferably compared with second recesses 42.For Porous barrier film by recess
Stress is relaxed caused by end, the life of Porous barrier film.Further, since the quantity of second recesses can be reduced,
Resistance thus can be reduced, the replacement, machinery for distribution keep also favourable.
At least one of the 1st electrode 20 and the 2nd electrode 22 used in the electrolysis unit 10 of embodiment have rule
Fixed multiple through holes.
The schematic diagram of one of the electrode for the 1st electrode 20 that can be used as Fig. 1 is illustrated that in Fig. 2A, Fig. 2 B and Fig. 2 C.
Fig. 2A is the figure of the 1st electrode 20 from the 2nd surface 21b.
Fig. 2 B are the schematic diagrames of the shape for the minimum sectional area parallel with base material for showing through hole.
Fig. 2 C are the figures for schematically showing the cut surface at Fig. 2A line A-A.
Fig. 2 D are the figures for illustrating the radius of curvature of the edge part of the 1st recess.
In figure, through hole is connected to the 1st recess 40 and second recesses 42.
As illustrated, the defined multiple through holes being arranged in the 1st electrode 20 are rhombus of the corner for circle.Opening can
To be measured using light microscope.In this case, it is circular that the shape of the 1st recess 40, which is also corner in the same manner as through hole,
Rhombus.Recess cross section can be the internal taper to narrow or curve-like.
Fig. 2 D show the figure for amplifying the edge part 48 of Fig. 2 C the 1st recess, and C1 is the radius of curvature of edge part 48.
As shown in Figure 2 C and 2 D shown in FIG., in embodiment, on the edge part 48 after the removing catalyst of the 1st recess, by it
Radius of curvature is defined as more than 0.01mm.
Thus, there is following effect.First, the current convergence of edge part is relaxed, and the stripping of catalyst reduces, can
Prevent voltage from rising, while the deterioration of the Porous barrier film near electrode is lowered.In addition, also easily formed uniformly in edge part
Catalyst.In addition, in the case of for negative electrode, the embrittlement caused by caused hydrogen can also be relaxed.It is further, it is also possible to slow
Rupture of abrasion or Porous barrier film with electrode caused by the Mechanical Contact of electrode and Porous barrier film etc..Especially it is possible to
The deterioration for relaxing in the operation start that hydraulic pressure easily changes and occurring when stopping.
If radius of curvature is less than 0.01mm, the effect above is insufficient.Radius of curvature is preferably more than 0.02mm.Further
Preferably more than 0.04mm.If but be more than 2mm, become too small tendency with through hole.In addition, the curvature of catalyst layer
Radius is preferably also more than 0.01mm.If being less than 0.01mm, there is the tendency for the lost of life for making barrier film because of current convergence.
The thickness of catalyst layer is preferably 0.1 μm~12 μm.If it is thinner than 0.1 μm, the lost of life.If being thicker than 12 μm, unit catalysis
The efficiency of dosage reduces, cost rise.More preferably more than 0.4 μm and less than 8 μm, more preferably more than 1 μm and 4 μm with
Under.
1st recess can be made in the entire surface on the 1st surface.In this case, exist non-through to the of the 2nd surface
1 recess.The 1st non-through recess is because the holding of chloride ion is excellent, thus in the low condition of chloride ion concentration, example
Such as be held in the chloride of medial compartment 19 concentration is low or the pressure of medial compartment 19 less than the pressure of anode chamber 16 situation
Under, hypochlorous formation efficiency can be improved or reduce driving voltage, thus be effective.
As shown in Figure 2 B, the opening of the through hole used in embodiment is on the basis of the section at sectional area minimum.
As the shape of second recesses 42, the rhombus for accommodating multiple 1st recesses 40 can be used.
Or the other shapes for accommodating multiple 1st recesses 40 can be used.When the summit of taper or curve is circular, water
The flowing of stream is smooth, and can prevent current convergence, is preferably more than 0.01mm as curvature.
As shown in Figure 2 A, multiple 1st recesses 40 mutually have roughly the same size, still, by from forming through hole
The opening of 1st recess 40 centrally through minimum opening diameter be formed on electrode base board.In these multiple through holes,
The aperture opening ratio of the through hole of the central part positioned at electrode base board and opening for the through hole of the periphery positioned at electrode base board can be made
Mouth rate is different.If the aperture opening ratio positioned at the through hole of central part is less than periphery, the resistance of central part diminishes, for central part
Electric current supply become easy.On the other hand, if the aperture opening ratio positioned at the through hole of central part is more than periphery, gas is easy
Discharge.Aperture opening ratio on any one in increase central part and periphery, it may be considered that operating condition or with other parts
Relation selects.
On generating the fundamental reaction at hypochlorous anode, using M as catalyst,
M+H2O→M-OH+H+e- (1)
M-OH→M-O+H++e- (2)
M-O+Cl-+H+→M+HClO (3)
Add up to
H2O+Cl-→HClO+H++2e- (4)。
On the other hand, it is at negative electrode
2H2O+2e-→H2+2OH- (5)
Total overall reaction also includes cation, is
2NaCl+3H2O→HClO+HCl+2NaOH+H2 (6)。
On the other hand, the side reaction of the generation oxygen at anode also occurs simultaneously sometimes, its reaction is
M+H2O→M-OH+H++e- (1)
M-OH→M-O+H++e- (2)
2M-O→2M+O2 (7)
Add up to
2H2O→O2+2H++2e- (8)。
If the concentration of the chloride ion required for reaction is small, the reaction for formula (7) that easily react.Therefore, in order to
Hypochlorous acid is efficiently generated, it is necessary to improve the concentration of chloride ion.Chloride ion is supplied to from Porous barrier film side, in electricity
The shielding portion of pole is stockpiled, and outside is flowed out to by spreading from opening.Therefore, in order to improve the concentration of chloride ion, spread away from
From critically important.And from reaction equation, in order to react, it is necessary to take out electronics, easily generation is electric under high current conditions
Current density it is uneven.
Fig. 3 A schematically show represent can the decomposition of one of other electrode units of electrode of application implementation mode stand
Body figure.
Fig. 3 B are the schematic diagrames of the shape for the minimum sectional area parallel with base material for showing through hole.
Fig. 3 C are the schematic diagrames for the cut surface for showing the line B-B shown in Fig. 3 A.
Fig. 3 D are the schematic diagrames for the cut surface for showing the line C-C shown in Fig. 3 A.
As illustrated, 6 the 1st recesses 63 are respectively from the right-hand member of the electrode 223 in addition to sealing 224 to reaching left end
Rectangle, the 1st recess 63 have what is do not connected with the 2nd surface 221b, 223b recesses connected and with the 2nd surface 221b, 223b
Opening portion (through hole) 61.Compartment of terrain is spaced one from the 1st recess 63 and configures 3 through holes 61.The depth ratio of 1st recess
2 recesses 62 are shallow.Be respectively arranged on the 1st electrode 220, the upper end of the 2nd electrode 222 64 is voltage applying mouth, thick beam 65 is towards electricity
Pressure applies direction.1st electrode and the 2nd electrode are same shape, and different surfaces is represented in figure.
3 second recesses 62 are respectively from the upper end of the electrode 221 in addition to sealing to the rectangle for reaching lower end.Not
6 through holes being respectively configured in 6 the 1st recesses of diagram connect with 1 second recesses 62.The 1st in 1st surface 221a is recessed
The number density in portion 61 is fully big compared with the number density of the second recesses 62 in the 2nd surface 221b.In Fig. 3 A, in order to make it easy to understand,
The quantity of opening portion is expressively less, but the number of actually opening portion is more.
Can be any shape as the shape of the through hole of embodiment, but preferably end for circular rectangle or
Person is oval or corner is circular rhombus.On the shape of through hole, there may also be bumps for profile.In addition, end is also can
With the set of the different multiple circular arcs of diameter.A part for electrode is shown in Fig. 3 A.In the case of this shape, due to end
Portion is circle, thus is not susceptible to the stress concentration for barrier film.Moreover, if open space can be made closeer, can improve
Aperture opening ratio.
In the case of Fig. 3 A electrode shape, due to the 1st recess 63, the hypochlorous acid of generation easily moves, thus easily
Outside is flowed out to from through hole.If hypochlorous acid does not flow out, chlorine can be produced, or is diffused into Porous barrier film side, efficiency drop
It is low.Such case easily occurs when the concentration of chloride ion is high, in the chloride concentration height or medial compartment 19 of medial compartment 19
Pressure be higher than anode chamber 16 in the case of easily occur.Therefore, chloride of the electrode structure shown in Fig. 3 A in medial compartment 19
Concentration is high or the pressure of medial compartment 19 is especially effective higher than in the case of anode chamber 16.
The aperture area of through hole can be 0.01mm2~4mm2.If it is less than 0.01mm2, then gas, hypochlorous acid etc. react
Discharge of the product to outside is difficult, deterioration of easy generation part etc..If it is more than 4mm2, then resistance change is big, has electrode reaction
Efficiency reduce tendency.Preferably 0.1mm2~1.5mm2.More preferably 0.2mm2~1mm2。
The aperture area of second recesses 62 can be 1~1600mm2.Preferably 4mm2~900mm2, more preferably 9mm2~
400mm2.Can also be to extend as rectangle or ellipse and connected from one end of the electrode in addition to sealing in one direction
To the recess of the other end.
The aperture area of 1st recess 63 can in the range of the aperture area less than second recesses 62 and more than through hole 61
Think 0.01mm2~1600mm2.The area of 1st recess is smaller, quantity is more, then the length of edge part is bigger, thus edge
The influence of curvature is bigger.It is therefore preferable that it is 0.2mm2~400mm2。
The opening of second recesses 62 can use square, rectangle, rhombus, circle, ellipse etc. variously-shaped.Second recesses 62
Opening diameter it is big when, hypochlorous acid, gas can be discharged preferably, but resistance becomes big, thus can not be too big.As second recesses
62 opening, as shown in the figure, or extended in one direction and from the electricity in addition to sealing as rectangle or ellipse
One end of pole is connected to the recess of the other end.
In addition, the opening of the 1st recess 63 can also use square, rectangle, rhombus, circle, ellipse etc. variously-shaped.Such as
Shown in figure, or extend as rectangle or ellipse and connected from one end of the electrode in addition to sealing in one direction
To the opening of the other end.
1st recess and 2 recesses that the other end is connected to from one end of second recesses can be vertical, can also be parallel.If hang down
Straight then gas easily spreads.Chloride ion is easily stockpiled if parallel.Vertically refer to 87 degree~93 degree of angular cross, put down
Row refers to that the angle of the crossing is within 3 degree.
It should be noted that the end that has that the electrode shown in Fig. 3 A possesses the composition as the 2nd embodiment is circle
Rectangular through hole and as the 1st and the 3rd embodiment composition have be arranged at the 1st surface from except sealing
One end of outer electrode is connected to both recesses of the other end, but can also be not provided with any structure in the 3rd embodiment
Into.
In addition, Fig. 3 A split sheds 61 arrange in the direction of voltage applying mouth 64.Thus, the beam that thickness of electrode is big, resistance is small
65 apply direction arrangement in voltage, thus power supply is easy, can reduce driving voltage.
The radius of curvature of the edge part 68 of base material after the removing catalyst of the 1st recess 63 shown in Fig. 3 C is respectively
More than 0.01mm.In addition, the radius of curvature of the edge part 69 of second recesses 62 shown in Fig. 3 D is respectively more than 0.01mm.
Thus, the current convergence of edge part is relaxed, and the stripping of catalyst reduces, at the same the Porous near electrode every
The deterioration of film is lowered.In addition, also easily form uniform catalyst in edge part.Moreover, in the case of for negative electrode, also
Embrittlement caused by can relaxing caused by hydrogen.Further, it is also possible to caused by relaxing the Mechanical Contact of electrode and Porous barrier film
The abrasion of electrode or the rupture of Porous barrier film etc..Especially it is possible to relax in the operation start that hydraulic pressure easily changes and stop
Caused deterioration when only.
Radius of curvature is preferably more than 0.01mm.If being less than 0.01mm, the effect above is small.Preferably more than 0.02mm.
More preferably more than 0.04mm.If but be more than 2mm, opening become it is too much.Preferably below 1mm, further preferably
For below 0.5mm.
Fig. 4 A schematically show represent can the decomposition of one of other electrode units of electrode of application implementation mode stand
Body figure.
Fig. 4 B are the schematic diagrames of the cut surface for the line D-D for showing Fig. 4 A.
Fig. 4 A split sheds 61 ' arrange in the direction of voltage applying mouth 64 '.Thus, the beam 65 ' that thickness of electrode is big, resistance is small
Apply direction arrangement in voltage, thus power supply is easy, can reduce driving voltage.1st electrode is phase similar shape with the 2nd electrode
Shape, the two sides of each electrode is identical structure.In addition, in the electrode unit 212 ', the 1st recess and second recesses are formd and passed through
Through hole 61 '.
In the same manner as Fig. 3 B the 1st recess 61, in Fig. 4 A electrode 221 ' and electrode 223 ', the 1st of through hole is formed
Recess 61 ' has elliptical shape.
Schematically show electrode structure in Fig. 4 A, but actually the 1st recess, second recesses, the quantity of through hole is more
It is more.
In the 1st electrode 20 of loose structure, it is wider than the conical surface or the bending on the 1st surface by using the opening of the 2nd face side
Face forms through hole 61 ', and the opening of through hole 61 ' is changed into obtuse angle with the contact angle of Porous barrier film 24, can also reduced to more
The stress concentration of hole matter barrier film 24.
As shown in Figure 4 B, the 1st recess remove catalyst after base material edge part 72 radius of curvature for 0.01mm with
On.Thus, the current convergence of edge part 72 is relaxed, and the stripping of catalyst reduces, while the Porous barrier film near electrode
Deterioration be lowered.In addition, also easily form uniform catalyst in edge part.Moreover, in the case of for negative electrode, may be used also
With the embrittlement caused by hydrogen caused by mitigation.Further, it is also possible to relax electrode and electricity caused by the Mechanical Contact of Porous barrier film
The abrasion of pole or the rupture of Porous barrier film etc..Especially it is possible to relax in the operation start that hydraulic pressure easily changes and stopping
When caused deterioration.Radius of curvature is preferably more than 0.01mm.If being less than 0.01mm, incline with what the effect above diminished
To.More preferably more than 0.02mm, more preferably more than 0.04mm.If but be more than 2mm, becoming big with opening inclines
To.
Fig. 5 is the figure of another of the electrolysis unit for schematically showing embodiment.
As shown in figure 5, in addition to Fig. 1 composition, the stream of liquid can also be set in anode chamber 16, cathode chamber 18
Road.In addition, according to circumstances, the interval of multiple aperture plasma membrane can be set between electrode unit 12 and anode chamber 16 or cathode chamber 18
Thing.Furthermore it is possible to further set to electrolytic cell 11 import the pipeline L1 of electrolyte comprising chloride ion, brine pit 107,
The pipeline L2 and L3 of water are supplied to electrolytic cell, the pipeline L4 of acidic electrolytic water is taken out from electrolytic cell and takes out alkalescence from electrolytic cell
The pipeline L5 of electrolysis water.And it is possible to be provided for the pipeline L7 of electrolyte of the circulation comprising chloride ion, can also set
Pipeline for discharge.Furthermore it is possible to further set water softener 109 and for from acidic electrolysis pond 106 to water softener
The pipeline L6 of the acidic electrolytic water of 109 supply adsorbent reactivations.Water softening device can be only used for being supplied to the water of cathode side.This
Outside, it can also be provided for storing the tank of electrolyzed alkaline water.Also, it may be provided for giving up the waste liquid of acidity and alkaline
Liquid mixes and is close to the tank of neutrality.Each pipeline can set water quality sensor 70.
Below, one of the manufacture method of the 1st electrode 20 to above-mentioned composition and Porous barrier film 24 illustrates.Scheming
The figure of one of the manufacture method of the electrode of embodiment is illustrated that in 6A~Fig. 6 F.
1st electrode 20 can for example be made by using the etching method of mask.
As shown in Figure 6 A and 6 B, 1 flat base material 21 is prepared.
Etchant resist 50a, 50b are coated with the 1st surface 21a of base material 21 and the 2nd surface 21b.
As shown in Figure 6 C, etchant resist 50a, 50b are exposed using optical mask (not shown), makes covering for etching respectively
Mould 52a, 52b.By optical mask come regulation aperture area, aperture opening ratio.
As shown in Figure 6 D, across these masks 52a, 52b, using solution to the 1st surface 21a of base material 21 and the 2nd surface
21b carries out Wet-type etching, is consequently formed multiple 1st recesses 40 and multiple second recesses 42.Afterwards, mask 52a, 52b are removed,
Thus the 1st electrode 20 is obtained.The flat shape of 1st recess 40 and second recesses 42 can by optical mask and etching condition come
Control.By designing mask, aperture opening ratio that can be freely in coordination electrode, aperture area, opening shape etc..
1st and the taper of second recesses 40,42 or the shape and curvature of flexure plane can pass through the material of base material 21, etching
Condition controls.When being set to T2 by the depth of the 1st recess 40, the depth of second recesses 42 is set into T3, according to T2<T3 mode
Form the 1st and second recesses.It should be noted that in etching, the two sides of base material 21 can be etched simultaneously, or can also one
Individual one face in face it is etched.The species of etching is not limited to Wet-type etching, can also use dry-etching etc..It is in addition, unlimited
In etching, the 1st electrode 20 can also be manufactured by expansion method, punching method or using the processing of laser or precision cutting etc., but
Most preferably wet etching.It should be noted that other method pre-production electrodes can also be utilized, pass through Wet-type etching afterwards
The radius of curvature of 1st recess or the edge part of second recesses is adjusted to specifically to be worth.When the speed of Wet-type etching is slow, curvature half
Footpath easily becomes big.
As the base material 21 of the 1st electrode 20 used in embodiment, the valves such as titanium, chromium, aluminium or its alloy gold can be used
Category, conductive metal.In titanium, chromium, aluminium, preferred titanium.In the case of for negative electrode, preferably titanium, chromium, aluminium, other alloys or
Stainless steel.Wherein, the stainless steel that more preferably resistant to hydrogen is brittle, rust quality is strong, particularly preferred SUS316L, SUS310S.
Electrolytic catalyst (catalyst layer) 28 is formed in the 1st surface 21a and the 2nd surface 21b of the 1st electrode 20.As sun
Electrode catalyst, preferably using oxide catalysts such as the noble metal catalysts such as platinum, yttrium oxides.From improving the close of catalyst and base material
Set out in terms of conjunction property, by the way that electrode is carried out into anodic oxidation to make small oxide-film preferably before anode catalyst is made
Bumps.
Catalyst layer can be at least provided with the part on the 1st surface.
The 1st catalyst layer and the 2nd catalyst layer are may further include, the 1st catalyst layer is arranged at the 1st electrode and
Between 1 Porous barrier film, it is made up of electrolytic catalyst, the 2nd catalyst layer is arranged at the 1st of the opposite side of the 1st catalyst layer
The surface of electrode, the amount of per unit area are different from the 1st catalyst layer.
It can also be formed according to the amount of the per unit area of the electrolytic catalyst mode different on the two sides of the 1st electrode.By
This, can suppress side reaction etc..
Surface (the 1st surface) general planar preferably in addition to recess of the Porous barrier film side of positive electrode.The surface of flat part
Roughness is preferably 0.01 μm~3 μm.If less than 0.01 μm, the tendency of the substantive surface area reduction with electrode, if greatly
In 3 μm, then there is the tendency that the stress for Porous barrier film easily concentrates on the convex portion of electrode.More preferably 0.02 μm~2 μ
M, it is more preferably 0.03 μm~1 μm.
Porous barrier film 24 for example formed as the size roughly equal with the 1st electrode 20 rectangle, with the 1st surface 21a's
Entire surface is opposed.Porous barrier film 27 is formed as the rectangle of the size roughly equal with the 2nd electrode 22, whole with the 1st surface 23a
Individual face is opposed.
As Porous barrier film 24,27, for example, can use the 1st porous layer with the 1st aperture and with the 1st hole
The layered product of 2nd porous layer in the 2nd different aperture of footpath.
As the film for Porous barrier film, can use the film with ion selectivity, such as hydrocarbon system polymer from
The ion permeable film of sub- permeability film or fluorine system polymer.
Inorganic oxide is preferably comprised in Porous barrier film.Particularly, it is excellent for the Porous barrier film of positive electrode side
It is positive inorganic oxide to be selected in Zeta-potential in the region that pH is 2~6.Thus, chemically stable, can increase in faintly acid region
Transportation performance of the big Porous barrier film for anion.
As inorganic oxide, such as zirconium oxide, titanium oxide, aluminum oxide, tin oxide, zircon, cupric oxide, oxygen can be used
Change iron and their mixed oxide.The inorganic oxide good as chemical stability, it can preferably use zirconium oxide, oxidation
Titanium, aluminum oxide or zircon.Wherein, the inorganic oxide good as resistance to bend(ing), further preferred zirconium oxide.Inorganic oxide
Hydroxide, alkoxide, oxyhalide, hydrate can be included.If by metal halide, metal alkoxide hydrolysis and make nothing
Machine oxide, it is different according to the temperature of post processing, their mixture is formed sometimes.
The presence ratio of inorganic oxide in Porous barrier film can be according to position and different.For example, around hole,
Surface can increase the presence ratio of inorganic oxide.
Inorganic oxide can use the mixture of composite oxides or different inorganic oxides as zircon.Separately
Outside, Porous barrier film can also further include different oxide of more than two kinds, and the presence ratio of each oxide is according to porous
The position of matter barrier film and it is different.For example, there can be the region containing the big zirconium oxide of bending strength on surface, internally exist
The region of the big titanium oxide of absolute value containing positive potential.
As the Zeta-potential on the surface of Porous barrier film, -30mV can be more than in the case of pH4.If being less than -30mV,
Even if voltage then is applied to Porous barrier film, it may have chlorion is difficult to the tendency entered.And then the surface of Porous barrier film
Zeta-potential can be more than -15mV.
In embodiment, Porous barrier film can be configured in the positive electrode side in negative electrode.
It is negative inorganic that the Porous barrier film being arranged in negative electrode, which can contain the Zeta-potential in the region that pH is 8~10,
Oxide.Thus, the transportation performance of cation can be increased near the negative electrode in alkalescent region.As such inorganic oxide
Thing, the Zeta-potential in basic region can be used easily to be changed into negative material, as such inorganic oxide, such as can made
With zirconium oxide, titanium oxide, aluminum oxide, tungsten oxide, zircon, silica and zeolite.It can be made using above-mentioned hopcalite
For inorganic oxide.In addition, the presence ratio of the inorganic oxide in Porous barrier film can be according to position and different.For example,
There can be the region containing the big zirconium oxide of bending strength on surface, the wide oxygen of the pH scopes containing negative potential internally be present
The region of SiClx.
On the Porous barrier film 24 of inorganic oxide, film can be formed by coated nanoparticle, or by using
Sol-gel is made, so as in face and three-dimensionally have irregular hole.In this case, Porous barrier film
24 bending resistance etc. also strengthens.In addition to inorganic oxide, polymer can also be included in Porous barrier film 24.Polymer
Film flexibility can be assigned.As such polymer, the chemically stable polymer for having halogen atom in main chain substitution can be used,
Such as polyvinylidene chloride, polyvinylidene fluoride, Teflon (registration mark) etc. can be enumerated.Wherein, chemically and thermostabilization
Property is set out, preferably Teflon.As other polymer, such as the hydrocarbon polymers such as polyethylene, polypropylene can be enumerated.Wherein, gather
Ethene because chemical stability and low cost and it is preferred that.It is in addition, so-called such as can use polyimides, polysulfones, polyphenylene sulfide
Engineering plastics.
On the aperture of Porous barrier film 24, the opening diameter of the side of the 1st electrode 20 and the opening diameter of the side of the 2nd electrode 22 can
With difference.It by the opening diameter for the side of the 2nd electrode 22 for further increasing hole, can be easier the movement of ion, while can
Further to reduce stress concentration caused by the through hole 40 of the 1st electrode 20.Because when the opening of the side of electrode 22 is big, expand
Ion movement becomes easy caused by dissipating.Even if the aperture of the side of electrode 20 is small, anion is also easier to be attracted by electrode.Phase
Instead, if the aperture of the side of electrode 20 is big, there is the tendency that chlorine of generation etc. readily diffuses into Porous barrier film side.
The aperture on the surface of Porous barrier film can be measured using high resolution scanning type electron microscope (SEM).
In addition, internal hole can be observed by section SEM to determine.
The schematic diagram of one of the composition of the electrode used in embodiment and Porous barrier film is illustrated that in Fig. 7.
As illustrated, Porous barrier film 24 have covering the 1st electrode 20 the 1st surface 21a parts the 1st region 24a and
Cover the 2nd region 24b of the opening of multiple 1st recesses 40 connected with the 2nd hole portion 42.In 21a parts, the gas such as caused chlorine
Body is difficult to be discharged.Therefore, electrode unit 12 easily deteriorates.Then, in Porous barrier film 24, by eliminating the 1st region
Surface holes, formed in a manner of non-porous, or the aperture of the surface holes in the 1st region 24a is less than the hole in the hole in the 2nd region
Footpath, the cell reaction with the 1st region 24a regions contacted can be suppressed, prevent the deterioration of electrode unit 12.In order to non-porous
Mode forms or reduced the aperture in hole, thin nothing can be additionally formed by silk-screen printing etc. in the 1st surface 21a of the 1st electrode
The small Porous barrier film of pore membrane or aperture.But because the response area of electrode is reduced, therefore in the part that gas is easily drained
Electrode zone in can sufficiently be reacted.In addition, the electrically insulating film being not through by using liquid covers the 1st electrode 20
Porous barrier film 24 opposite side the 2nd surface 21b, side reaction can be reduced.It should be noted that also illustrate in the figure 7
It is not the 1st recess 40 of through hole.As Porous barrier film 24, can use the different multiple Porous membrane layers in aperture
The multilayer film that product forms.In this case, by making the aperture of the Porous barrier film positioned at the side of the 2nd electrode 22 be more than positioned at the 1st electricity
The aperture of the Porous barrier film of the side of pole 20, can be more prone to the movement of ion, while the through hole that can reduce electrode is led
The stress concentration of cause.
Porous barrier film 24 is clamped between the 1st electrode 20 formed as described above and the 2nd electrode 22, with the state to it
Suppressed, thus the 1st electrode 20, Porous barrier film 24, the 2nd electrode 22 contact, and obtain electrode unit 12.
As shown in fig. 1, electrode unit 12 is disposed in electrolytic cell 11, is installed at spaced walls 14.Pass through spaced walls 14
With electrode unit 12, anode chamber 16 and cathode chamber 18 will be divided into electrolytic cell 11.Thus, electrode unit 12 is according to component parts
Configuration direction be, for example, that the mode of horizontal direction is disposed in electrolytic cell 11.1st electrode 20 of electrode unit 12 faces anode
Room 16 and configure, the 2nd electrode 22 in face of cathode chamber 18 and configure.
In electrolysis unit 10, the two poles of the earth of power supply 30 electrically connect with the 1st electrode 20 and the 2nd electrode 22.Power supply 30 is controlling
Voltage is applied to the 1st and the 2nd electrode 20,22 under the control of device 36.Potentiometer 34 is electrically connected with the 1st electrode 20 and the 2nd electrode 22
Connect, detect the voltage applied to electrode unit 12.Its detection information is supplied to control device 36.Galvanometer 32 and electrode
The voltage applying circuit connection of unit 12, detects the electric current to be circulated in electrode unit 12.Its detection information is supplied to control
Device 36 processed.Control device 36 is according to the program for being stored in memory, and according to detection information, control is using power supply 30 to electrode
The voltage of unit 12 applies or load.Electrolysis unit 10 is with to the shape of anode chamber 16 and the supply response object material of cathode chamber 18
State, application or load voltage between the 1st electrode 20 and the 2nd electrode 22, carry out the electrochemical reaction for electrolysis.
One as the formation Porous barrier film 24 on 1st surface 21a of the surface of the 1st electrode 20 formed with catalyst 28
Example, first, as illustrated in fig. 6e, by the solution coating containing inorganic oxide particle and/or precursors of inorganic oxides to the 1st surface
21a, make pre-treatment film 24c.Then, as fig 6 f illustrates, pre-treatment film 24c is sintered, made with porous porous
Matter barrier film 24.
As the method for making the solution containing precursors of inorganic oxides, for example, the alkoxide of metal can be dissolved in into alcohol
In, easily occur oxidation when the high boiling solvent such as glycerine is added to make porous structure, or being blended in sintering and
The organic matters such as the aliphatic acid of carbon dioxide are formed, so as to make solution.In addition, in order to cover the porous of electrode, it is molten
Liquid can add a small amount of water and make metal alkoxide partial hydrolysis, viscosity is increased.
As the method for forming Porous barrier film 24, before can containing inorganic oxide particle and/or inorganic oxide
The solution coating of body is to other multiple aperture plasma membranes.Or it can be pre-formed on the 1st surface 21a of the 1st electrode 20 with big
The multiple aperture plasma membrane in hole, and its surface and hole are covered with inorganic oxide particle and/or precursors of inorganic oxides.Or
The above method can be utilized to form the Porous barrier film with inorganic oxide in the keeping body 25 for keeping electrolyte.In addition,
They can be combined.
As the method for solution of the coating containing inorganic oxide particle and/or precursors of inorganic oxides, brush can be used
Apply, spray, impregnating.Porous process is made being sintered to pre-treatment film 24c, sintering temperature can be 100~
600 DEG C or so.
Composition and manufacture method more than etc., the longevity for the electrolysis performance that can remain stable for a long time can be provided
The electrode unit of life and the electrolysis unit for having used the electrode unit.
Embodiment is illustrated below, embodiment is specifically described.
Embodiment
(embodiment 1)
As the base material 21 of the 1st electrode, prepare the flat titanium plate that thickness of slab T1 is 0.5mm.
In the same manner as the process shown in Fig. 6 A~Fig. 6 F, the titanium plate is etched, makes in the 1st embodiment and can be used
The 1st electrode 20.Electrode the length of water (flow) direction be 15cm, width 10cm.
In the 1st electrode 20, the thickness (depth of the 1st recess) in the region comprising the 1st small recess 40 of area is
0.1mm, the thickness (depth of second recesses) in the region comprising the big second recesses 42 of area is 0.4mm.1st recess 40 is Fig. 2A
It is circular rhombus with such corner shown in Fig. 2 B (angle on the summit of rhombus obtained from extrapolation is 60 ° and 120 °).Pass through
Through hole is also rhombus of the corner for circle.Second recesses 42 are also rhombus, and one side of rhombus is about 3.6mm.
The etched electrode base material 21 is handled 1 hour in 10wt% oxalic acid aqueous solutions in 80 DEG C.And then in 1M sulphur
Sour ammonium with 10V in the mixed aqueous solution of 0.5M ammonium fluorides with carrying out anodic oxidation in 2 hours.Then, according to reaching 0.25M's (Ir)
Mode is to iridium chloride (IrCl3·nH2O n-butyl alcohol is added in), by the 1st surface of prepared solution coating to electrode base material 21
After 21a, it is dried, burns till, produces catalyst layer 28.Carry out 10 minutes, burn till 450 at 80 DEG C in this case, drying
DEG C carry out 10 minutes.Being coated with, drying and burn till for such iridium chloride butanol solution is repeated 5 times, by resulting electrode base material
As the 1st electrode (anode) 20.The thickness of catalyst layer is 2 μm.
The titanium oxide microparticle that particle diameter 100nm is coated with the glass cloth as 100 μm of the thickness of Porous barrier film is inclined with gathering
The moisture of difluoroethylene particle dissipates mixed liquor, and is dried.In addition, it is impregnated into 5% isopropanol of zirconium tetraisopropoxide (IV)
In solution, it is then lifted out in air.Dried 1 hour in 80 DEG C in an atmosphere, make Porous barrier film.The Porous barrier film table
Zeta-potential of the face when pH is 4 is -15mV.
Instead of making yttrium oxide catalyst layer 28, sputtering platinum is as catalyst layer, in addition in the same manner as the 1st electrode 21
Form the 2nd electrode (opposite electrode, negative electrode) 22.In the same manner as above-mentioned Porous barrier film 24, made thereon by oxidation titanium film structure
Into Porous barrier film 27.The thickness of catalyst layer is 0.2 μm.
As the keeping body 25 for keeping electrolyte, thickness 5mm Porous polystyrene is used.Utilize silicone sealant material
With screw by these the 1st electrode 20, Porous barrier film 24, Porous polystyrene 25, Porous barrier film 27 and the weights of the 2nd electrode 22
Merge and fix, produce electrode unit 12.The electrode unit 12 is positioned in electrolytic cell 11, passes through spaced walls 14 and electrode list
Electrolytic cell 11 is divided into anode chamber 16, cathode chamber 18 and provided with being configured at interelectrode Porous polystyrene 25 by member 12
This Room 3 of medial compartment 19.
The anode chamber 16 of electrolytic cell 11 and cathode chamber 18 are formed by the container of the vinyl chloride formed with straight line stream respectively.
Control device 36, power supply 30, potentiometer 34, galvanometer 32 are set.It will be used for from water-supply source 106 to anode chamber 16 and cathode chamber 18
The pipe arrangement and pump for supplying water are connected to electrolytic cell 11, it is ensured that water-supply line 104,105.Taken furthermore, it is possible to set from anode chamber 16
Go out the pipeline L4 of hypochloric acid water and the pipeline L5 of alkaline water is taken out from cathode chamber 18.By for the keeping body of electrode unit 12
The saturated common salt water pot 107 and pipe arrangement, pump of the circulation supply saturated aqueous common salt of (Porous polystyrene) 25 are connected to electrode unit,
Ensure to import the pipeline L1 of the electrolyte comprising chlorion and the pipeline 108 of the remaining electrolyte of recovery to electrolytic cell.In addition,
As water quality sensor 70, conductivity sensor is set in the outlet line of acidic electrolytic water, in the outlet of electrolyzed alkaline water
PH sensors are set in pipeline.Thus, the electrolysis unit with the composition same with Fig. 5 is obtained.
Using electrolysis unit 10, it is electrolysed with flow 2L/ minutes, voltage 5.7V, electric current 10A, in the 1st electrode (anode)
20 sides generate hypochloric acid water, and hydrogen and sodium hydroxide water are generated in the side of the 2nd electrode (negative electrode) 22.
The device does not find the rising of voltage in being continuously run at 2000 hours.
Afterwards, take out electrode, pair cross-section SEM is observed, calculate the 1st recess, second recesses section edges curvature
Radius, as a result it is respectively averagely 0.02mm and average 0.04mm.
(embodiment 2~6, comparative example 1)
In addition to pattern, etching condition except change mask, it is that corner is circular to obtain through hole similarly to Example 1
Diamond opening or oval opening electrolysis electrode.
(embodiment 7)
As the base material 21 of the 1st electrode, prepare the flat titanium plate that thickness of slab T1 is 0.5mm.
In the same manner as the process shown in Fig. 6 A~Fig. 6 F, the titanium plate is etched, so as to make embodiment
Workable 1st electrode 20 in electrolysis unit.Electrode the length of water (flow) direction be 15cm, width 10cm.
In the 1st electrode 20, the thickness (depth of the 1st recess) in the region comprising the 1st small recess 40 of area is
0.1mm, the thickness (depth of second recesses) in the region comprising the big second recesses 42 of area is 0.4mm.As shown in Figure 3A, the 1st
Recess 40 is the rectangle that the other end is connected to from one end in addition to sealing of electrode, and second recesses 42 are also removing from electrode
One end outside sealing is connected to the rectangle of the other end, and vertical with the first recess.Through hole is such end shown in Fig. 3 B
Portion is circular rectangle.
In addition to using the 1st above-mentioned electrode and the 2nd electrode equally made, electrode is made similarly to Example 1
Unit and electrolysis unit.
Using the electrolysis unit, it is electrolysed with flow 2L/ minutes, voltage 6.2V, electric current 10A, in the 1st electrode (anode)
20 sides generate hypochloric acid water, and hydrogen and sodium hydroxide water are generated in the side of the 2nd electrode (negative electrode) 22.The device continuous fortune at 2000 hours
The rising of voltage is not found in turning.Afterwards, electrode is taken out, from section SEM observation, the song of the section edges of the 1st recess
Rate is average 0.03mm.
(embodiment 8~12, comparative example 2)
In addition to pattern, etching condition except change mask, electrode is obtained similarly to Example 7.Similarly to Example 1
Ground makes electrode unit and electrolysis unit.
(embodiment 13)
As the base material 21 of the 1st electrode, prepare the flat titanium plate that thickness of slab T1 is 1mm.
In the same manner as the process shown in Fig. 6 A~Fig. 6 F, the titanium plate is etched, so as to make embodiment
Workable 1st electrode 20 in electrolysis unit.Electrode the length of water (flow) direction be 15cm, width 10cm.
In the 1st electrode 20, the thickness (depth of the 1st recess) in the region comprising the 1st small recess 40 of area is
0.4mm, the thickness (depth of second recesses) in the region comprising the big second recesses 42 of area is 0.6mm.As shown in Figure 4 A, the 1st
Recess 40 is that the end shown in Fig. 4 B is circular rectangle.
In addition to using the 1st above-mentioned electrode and the 2nd electrode equally made, electrode is made similarly to Example 1
Unit and electrolysis unit.
The through hole of 1st electrode is that the end shown in Fig. 4 B is circular rectangle.Except using the 1st above-mentioned electrode and
Beyond 2nd electrode, electrode unit and electrolysis unit are made similarly to Example 1.
Using the electrolysis unit, it is electrolysed with flow 2L/ minutes, voltage 6.0V, electric current 10A, in the 1st electrode (anode)
Side generates hypochloric acid water, and hydrogen and sodium hydroxide water are generated in the side of the 2nd electrode (negative electrode) 22.The device was continuously run at 2000 hours
In, voltage rises to 2%.Afterwards, electrode is taken out, from section SEM observation, the curvature of the section edges of the 1st recess
For average 0.04mm.
(embodiment 14~15, comparative example 3)
In addition to pattern, etching condition except change mask, electrode is obtained similarly to Example 13.It is same with embodiment 1
Make electrode unit and electrolysis unit sample.
(embodiment 16)
Another example of the electrolysis unit of embodiment is schematically shown in Fig. 8.
As shown in figure 8, the electrolysis unit 310 replaces electrolytic cell 11 using the electrolytic cell 311 of batch-type, the electrolytic cell
311 have cathode chamber 318 and the anode chamber 316 configured in a manner of surrounding cathode chamber 318, without stream and pipe arrangement, pass through
Free convection and form current, there is the composition same with Fig. 1 in addition.The capacity of anode chamber 316 and cathode chamber 318 is distinguished
For 2L, 0.1L, the electrode made similarly to Example 1 is used.Wherein, the size of electrode is 4 × 3cm.
Using the electrolysis unit 310, with voltage 7V, electric current 2A be electrolysed within 5 minutes, generated in the 1st electrode (anode) side
Hypochloric acid water, hydrogen and sodium hydroxide water are generated in the 2nd electrode (negative electrode) side.The electrolysis unit 310 operated at total 2000 hours
The rising of voltage is not found afterwards yet.Afterwards, electrode is taken out, from section SEM observation, the song of the section edges of the 1st recess
Rate is average 0.01mm.
(embodiment 17~21)
In addition to pattern, etching condition except change mask, electrode is obtained similarly to Example 16.It is same with embodiment 1
Make electrode unit and electrolysis unit sample.
(embodiment 22)
Another example of the electrolysis unit of embodiment is schematically shown in Fig. 9.
As shown in figure 9, electrolysis unit 310 has as interval between the electrode 20 of Porous barrier film 24 and the 1st in fig. 8
The multiple aperture plasma membrane 29 of thing.Using 76 μm of thickness glass cloth as the multiple aperture plasma membrane, it is identical with embodiment 16 in addition.
The electrolysis unit 310 does not find the rising of voltage after operating in total 2000 hours yet.Afterwards, electrode is taken out, by
Section SEM observation understands that the curvature of the section edges of the 1st recess is average 0.02mm.
In table 1 below, on embodiment 1~22 and comparative example 1~3, the radius of curvature of the edge part of the 1st recess is shown
Radius of curvature C2 (mm), the 1st recess of the edge part of voltage build-up rate (%), the 1st recess after C1 (mm), operating in 2000 hours
The thickness of catalyst layer and the sectional area (mm of through hole2)。
Table 1
As shown in Table 1 above, when the curvature at edge is more than 0.01mm, 2000 hours operating after voltage rise it is small or
Do not find that voltage rises.On the other hand, in embodiment 20,21, if being more than 2mm, the hypochlorous acid generation effect at initial stage is observed
The reduction of rate.
Several embodiments of the present utility model are illustrated, but these embodiments are intended only as example and shown
, not limit utility model scope.These new embodiments can by it is other it is various in a manner of implement, can not depart from
Various omissions are carried out in the range of utility model main points, are replaced, change.These embodiments and its deformation are included in utility model
Scope and purport in, while be included in the utility model described in claims and its impartial scope.
Symbol description
10 ... electrolysis units, 11 ... electrolytic cells, 12 ... electrode units, 14 ... spaced walls, 16 ... anode chambers, 18 ... negative electrodes
Room, 19 ... medial compartments, 20 ... the 1st electrodes, 21,23 ... base materials, 22 ... the 2nd electrode, 21a, 23a ... the 1st surface, 21b,
23b ... the 2nd surface, 24,27 ... Porous barrier films, 25 ... keeping bodies, 26,26a, 26b ... barrier films, 28 ... catalyst layers, 29 ...
Multiple aperture plasma membrane, 30 ... power supplys, 32 ... galvanometer, 34 ... potentiometers, 40,44,61,63 ... through holes (the 1st recess), 42,46,
62 ... second recesses, 50 ... etchant resists, 60 ... bridges, 64 ... voltage applying mouths, 65 ... beams, 70 ... water quality sensors.
Claims (20)
1. a kind of electrode, it is characterised in that it has base material, multiple 1st recesses and multiple second recesses, and the base material has the 1st
Surface, with the 2nd surface of the 1st opposing surface and being penetrated from the 1st surface to multiple through holes on the 2nd surface,
The multiple 1st recess is in the 1st surface opening, and the multiple second recesses are in the 2nd surface opening and aperture area
It is wider than the 1st recess,
The radius of curvature of the edge part of the opening of 1st recess is more than 0.01mm.
2. electrode as claimed in claim 1, wherein, the radius of curvature of the edge part of the opening of the 1st recess for 2mm with
Under.
3. electrode as claimed in claim 1 or 2, wherein, the radius of curvature of the edge part of the opening of the second recesses is
More than 0.01mm.
4. electrode as claimed in claim 1, wherein, a part and the second recesses of multiple openings of the 1st recess
Part insertion.
5. electrode as claimed in claim 1, wherein, the part in the region of the 1st recess with one of the second recesses
Divide insertion.
6. electrode as claimed in claim 1, wherein, the quantity of the 1st recess is more than the quantity of the second recesses.
7. electrode as claimed in claim 1, wherein, the smallest cross-sectional in the direction parallel with the base material of the through hole is
End is circular rectangle.
8. electrode as claimed in claim 1, wherein, the smallest cross-sectional in the direction parallel with the base material of the through hole is
Oval or corner is circular rhombus.
9. electrode as claimed in claim 1, wherein, the second recesses connect from one end of the base material in addition to sealing
To the other end.
10. electrode as claimed in claim 1, wherein, the 1st recess connects from one end of the base material in addition to sealing
To the other end.
11. electrode as claimed in claim 1, wherein, the smallest cross-sectional in the direction parallel with the base material of the through hole
Product is 0.01~4mm2。
12. electrode as claimed in claim 1, wherein, the region in addition to the 1st recess on the 1st surface is by flatly
Formed.
13. electrode as claimed in claim 11, wherein, the mean roughness of the flat part of the base material is 0.01 μm~3 μm.
14. electrode as claimed in claim 1, wherein, the through hole of the central part positioned at the base material of the base material is opened
Mouth rate is less than the aperture opening ratio of the through hole of the periphery positioned at the base material.
15. a kind of electrode unit, it is characterised in that it possesses：
The 1st electrode being made up of the electrode any one of claim 1~14；
It is configured on the 1st surface and through the Porous barrier film of ion；
It is arranged at the 2nd electrode of the 1st face side of the 1st electrode；With
The electrolyte holding structure being arranged between the Porous barrier film and the 2nd electrode.
16. electrode unit as claimed in claim 15, wherein, it is further equipped with being arranged at the 1st table of the 1st electrode
Multiple aperture plasma membrane between face and the 2nd electrode, the multiple aperture plasma membrane be held in the 1st surface of the 1st electrode with
Between the Porous barrier film.
A kind of 17. electrolysis unit, it is characterised in that it include electrolytic cell and the claim 15 that is loaded into the electrolytic cell or
Electrode unit described in 16, the 1st electrode chamber and the 2nd electrode chamber formed by electrode unit division.
18. electrolysis unit as claimed in claim 17, wherein, the 1st electrode chamber is anode chamber, and the 2nd electrode chamber is
Cathode chamber, the electrolysis unit be further equipped with to the electrolytic cell import comprising chloride ion electrolyte solution pipeline,
The pipeline of acidic electrolytic water is taken out from the anode chamber and the pipeline of electrolyzed alkaline water is taken out from the cathode chamber.
19. electrolysis unit as claimed in claim 18, wherein, the pipeline for taking out acidic electrolytic water is further equipped with determining
The sensor of electrical conductivity.
20. electrolysis unit as claimed in claim 17, wherein, the 1st electrode chamber surrounds the 2nd electrode chamber.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-181500 | 2015-09-15 | ||
| JP2015181500 | 2015-09-15 | ||
| PCT/JP2016/056801 WO2017047129A1 (en) | 2015-09-15 | 2016-03-04 | Electrode, electrode unit, and electrolysis device |
Publications (1)
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| WO2021153406A1 (en) * | 2020-01-27 | 2021-08-05 | 住友電気工業株式会社 | Metal porous body sheet and water electrolysis device |
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| US4260469A (en) * | 1978-09-05 | 1981-04-07 | The Dow Chemical Company | Massive dual porosity gas electrodes |
| JPS5741387A (en) * | 1980-08-26 | 1982-03-08 | Asahi Glass Co Ltd | Electrode body for electrolytic cell |
| JPS57149477A (en) * | 1981-03-09 | 1982-09-16 | Toagosei Chem Ind Co Ltd | Electrolytic cell with ion-exchange membrane |
| JP2756628B2 (en) * | 1992-10-16 | 1998-05-25 | 治 三宅 | Electrolytic ionic water generator |
| US6884745B2 (en) * | 2002-06-28 | 2005-04-26 | Advanced Energy Technology Inc. | Perforated cylindrical fuel cells |
| JP4220978B2 (en) * | 2004-04-28 | 2009-02-04 | 東海旅客鉄道株式会社 | Electrode, ozone generator, and ozone generation method |
| EP1953271A4 (en) * | 2005-11-24 | 2011-08-31 | Sumitomo Elec Hardmetal Corp | Diamond electrode, method for producing same, and electrolytic cell |
| JP2009026511A (en) * | 2007-07-18 | 2009-02-05 | Toyota Motor Corp | Fuel cell |
| KR20110073461A (en) * | 2008-09-24 | 2011-06-29 | 쿠리타 고교 가부시키가이샤 | Diamond electrode and method for manufacturing diamond electrode |
| US20110003233A1 (en) * | 2009-06-19 | 2011-01-06 | Donald Bennet Hilliard | Solid oxide electrolytic device |
| JP5480542B2 (en) * | 2009-06-23 | 2014-04-23 | クロリンエンジニアズ株式会社 | Conductive diamond electrode and ozone generator using conductive diamond electrode |
| GB0913836D0 (en) * | 2009-08-07 | 2009-09-16 | Afc Energy Plc | Fuel cell |
| JP2012057229A (en) * | 2010-09-10 | 2012-03-22 | Japan Organo Co Ltd | Scale prevention method for three-compartment electrolytic water generator, and three-compartment electrolytic water generator |
| JP2012144779A (en) * | 2011-01-12 | 2012-08-02 | Kobe Steel Ltd | Method for production of electrolysis electrode |
| JP5936626B2 (en) * | 2011-02-04 | 2016-06-22 | エイエフシー エナジー ピーエルシー | Fuel cell |
| JP6038604B2 (en) * | 2012-11-20 | 2016-12-07 | 株式会社東芝 | Electrochemical cell, oxygen reduction device using the cell, and refrigerator using the oxygen reduction device |
| WO2016042802A1 (en) * | 2014-09-19 | 2016-03-24 | 株式会社 東芝 | Electrode unit, electrolytic bath provided with electrode unit, and electrolysis device |
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| JPWO2017047129A1 (en) | 2018-02-01 |
| JP6585176B2 (en) | 2019-10-02 |
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