CN106574382B - Electrode unit, electrolysis unit and the electrode for electrolysis unit - Google Patents
Electrode unit, electrolysis unit and the electrode for electrolysis unit Download PDFInfo
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- CN106574382B CN106574382B CN201580043799.5A CN201580043799A CN106574382B CN 106574382 B CN106574382 B CN 106574382B CN 201580043799 A CN201580043799 A CN 201580043799A CN 106574382 B CN106574382 B CN 106574382B
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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
- 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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Abstract
According to embodiment, the electrode unit of electrolysis unit has the 1st electrode (20), the 2nd electrode and diaphragm, 1st electrode (20) have the 1st surface (21a), positioned at the 1st surface opposite side the 2nd surface (21b) and respectively in multiple through holes (13) on the 1st surface and the 2nd surface opening, 1st surface of the 2nd electrode and the 1st electrode is oppositely arranged, the diaphragm is set between the 1st electrode and the 2nd electrode, at least penetrates ion.1st surface of the 1st electrode has the reaction non-active portion (52) for electrolysis.
Description
Technical field
Embodiments of the present invention are related to electrode unit, the electrolysis unit for having electrode unit, for the electricity of electrolysis unit
Pole.
Background technique
In recent years, it provides and water electrolysis is generated to electrolysis water with various functions, such as alkali ion water, ozone
The electrolysis unit of water or hypochloric acid water etc..As electrolysis unit, for example, propose the electrolytic cell with 3 Room types electrolysis it is aquatic
At device.Medial compartment is divided into, positioned at the two sides of the medial compartment by cation-exchange membrane and anion-exchange membrane in electrolytic cell
Anode chamber and this Room 3 of cathode chamber.The anode and yin of the porous structure with perforation are each configured in anode chamber and cathode chamber
Pole.These amberplexes and electrode constitute electrode unit.
In such electrolysis unit, for example, the salt water that circulates in medial compartment, flows respectively in anode chamber and cathode chamber
Water flowing.By with cathode and anode by the saline electrolysis of medial compartment, to generate hypochloric acid water by the chlorine that generates in anode,
Sodium hydroxide water is generated in cathode chamber simultaneously.Hypochloric acid water generated is used as sterilizing water, and sodium hydroxide water is used as
Washing water.
In the electrolytic cell of 3 Room types, anion-exchange membrane is easy to deteriorate because of chlorine, hypochlorous acid.Therefore, it is proposed to
Following technologies, the technology are inserted with the nothing of overlapping portion or notch between the anode and anion-exchange membrane of porous structure
Woven fabric reduces the deterioration of the amberplex as caused by chlorine.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-322053 bulletin
Summary of the invention
Problems to be solved by the invention
But in the case where sandwiching the multiple aperture plasma membrane of non-woven fabrics etc between electrode and amberplex, diffuse through electricity
Pressure rises, and electrolytic efficiency reduces.
Project to be solved by this invention be to provide a kind of long-life, efficient electrode unit, electrolysis unit and
Electrode for electrolysis unit.
The means used to solve the problem
According to embodiment, electrolysis unit has electrode unit.Electrode unit has the 1st electrode, the 2nd electrode and diaphragm,
1st electrode have the 1st surface, positioned at the 1st surface opposite side the 2nd surface and respectively on the 1st surface and
1st surface of multiple through holes of the 2nd surface opening, the 2nd electrode and the 1st electrode is oppositely arranged；The diaphragm is set
It is placed between the 1st electrode and the 2nd electrode, at least passes through anion, the 1st surface of the 1st electrode at least has pair
In the reaction non-active portion of electrolysis.
Detailed description of the invention
Fig. 1 is the sectional view for showing the electrolysis unit of the 1st embodiment.
Fig. 2 is the sectional view for showing the electrolytic cell of electrolysis unit of the 1st variation.
Fig. 3 is the sectional view for showing the electrolytic cell of the 2nd variation.
Fig. 4 is the exploded perspective view for showing the electrode unit of electrolysis unit of the 1st embodiment.
Fig. 5 is the perspective view for showing the 1st electrode of the electrode unit.
Fig. 6 is the sectional view shown in by the 1st electrode and diaphragm amplification.
Fig. 7 be show using the 1st surface of the 1st electrode as when active part to the 1st surface of the 1st electrode with every
The figure for the result that hypochlorous acid concentration's distribution between film is simulated.
Fig. 8 is the 1st table shown using the 1st surface of the 1st electrode as reaction non-active portion timesharing to the 1st electrode
The figure for the result that hypochlorous acid concentration's distribution between face and diaphragm is simulated.
Fig. 9 is the sectional view for showing the electrolysis unit of the 2nd embodiment.
Figure 10 is the exploded perspective view for showing the electrode unit of electrolysis unit of the 2nd embodiment.
Figure 11 is the perspective view for showing the 1st electrode of electrode unit of the 2nd embodiment.
Figure 12 is the sectional view of the electrolysis unit of the 3rd variation.
Figure 13 is the perspective view for schematically showing the 1st electrode of electrolysis unit of the 3rd embodiment.
Figure 14 is the sectional view for showing the 1st electrode and diaphragm of electrolysis unit of the 3rd embodiment.
Figure 15 is the sectional view for schematically showing the manufacturing process of the 1st electrode of the 3rd embodiment.
Figure 16 is the sectional view for showing the electrolysis unit of the 4th embodiment.
Figure 17 is the perspective view for showing the configuration example of the active evaluating apparatus of cell reaction.
Specific embodiment
In the following, being illustrated referring to attached drawing to various embodiments.It should be noted that in embodiments to common
Composition be accompanied by same symbol, and the repetitive description thereof will be omitted.In addition, each figure is embodiment and for promoting embodiment
The schematic diagram of understanding, shape, size, ratio etc. have difference with actual device, these can refer to the following description
Change is suitably designed with well-known technique.
(the 1st embodiment)
Fig. 1 is the sectional view for schematically showing the electrolysis unit of the 1st embodiment.Electrolysis unit 10 for example has Room 2
The electrolytic cell 11 of type and the electrode unit 12 being configured in electrolytic cell 11.Electrolytic cell 11 is formed as flat rectangular box, in
Portion is divided into anode chamber 16 and this Room 2 of cathode chamber 18 by electrode unit 12.
Electrode unit 12 includes the 1st electrode (anode) 20 in anode chamber 16；The 2nd electricity in cathode chamber 18
Pole (opposite electrode, cathode) 22；Be set to the 1st and the 2nd interelectrode diaphragm 24.Diaphragm 24 is at least to make anion-permeable
Film, the tank house in electrolytic cell 11 is divided by anode chamber 16 and cathode chamber 18 by the diaphragm 24.1st electrode 20 with every
Film 24 is opposed, and configures in face of anode chamber 16, and the 2nd electrode 22 is opposed with diaphragm 24, and matches in face of cathode chamber 18
It sets.
Electrolysis unit 10, which has, applies alive power supply 30, electricity for the 1st and the 2nd electrode 20,22 to electrode unit 12
Flowmeter, potentiometer and control device 36 that they are controlled etc..Liquid can also be set in anode chamber 16, cathode chamber 18
The flow path of body.It is also can connect in anode chamber 16, cathode chamber 18 for being externally supplied the liquid such as raw water or electrolyte or inciting somebody to action
The piping of their discharges or pump etc..It is porous alternatively, it is also possible to be arranged between electrode unit 12 and anode chamber 16 or cathode chamber 18
The spacer of matter.
In electrolysis unit 10, the two poles of the earth of power supply 30 are electrically connected 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 (not shown) and the 1st electrode 20 and the 2nd electrode
22 electrical connections, detect the voltage for being applied to electrode unit 12.Its detection information is supplied to control device 36.Do not scheme
The galvanometer shown is connect with the voltage applying circuit of electrode unit 12, is examined to the electric current to circulate in electrode unit 12
It surveys.Its detection information is supplied to control device 36.Control device 36 is according to the program for being stored in memory, according to the inspection
Measurement information, control power supply 30 applies to the voltage of electrode unit 12 or load.Electrolysis unit 10 is with to anode chamber 16 and cathode chamber
The state of 18 supply response object substances, application or load voltage between the 1st electrode 20 and the 2nd electrode 22, to be used in
The electrochemical reaction of electrolysis carries out.The electrolysis unit 10 of present embodiment is preferred for electric to halogen-containing electrolyte progress is wrapped
Solution generates system of the halogen compounds as electrolysate.
Fig. 2 is the sectional view for showing the electrolytic cell of electrolysis unit of the 1st variation.As shown in Fig. 2, the week of the 1st electrode 20
The peripheral portion of edge, the peripheral portion of the 2nd electrode 22 and diaphragm 24 is also used as sealing, and the sealing is for preventing from being electrolysed
Water leaks into outside electrolytic cell 11.Electrolytic cell 11 has the anode cap 11a for the rectangle for forming anode chamber 16 and forms cathode chamber
The cathode shield 11b of 18 rectangle, these anode caps 11a and cathode shield 11b hold the peripheral portion of the 1st electrode 20, the 2nd electrode
22 peripheral portion and the peripheral portion of diaphragm 24 and be connected with each other.That is, the peripheral portion of the peripheral portion of the 1st electrode 20, the 2nd electrode 22
And the peripheral portion of diaphragm 24 is held between anode cap 11a and cathode shield 11b, and is fixed in electrolytic cell 11.In addition,
The seal members 8a such as o-ring are equipped between the peripheral portion and anode cap 11a of 1st electrode 20.The 2nd electrode 22 peripheral portion with
The seal members 8b such as o-ring are equipped between cathode shield 11b.
Fig. 3 is the sectional view for showing the electrolytic cell of electrolysis unit of the 2nd variation.As the 2nd variation, in the 1st electricity
Such as the spacer film 25 constituted by non-woven fabrics can be set between pole 20 and diaphragm 24.
Then, the electrode unit 12 of electrolytic cell 11 is described in detail.Fig. 4 is the electrode shown in electrolysis unit 10
The exploded perspective view of unit, Fig. 5 are the perspective views for showing the 1st surface side of the 1st electrode.
As shown in Figure 1, Figure 2 and Figure 4, the 1st electrode 20 of plate is for example in the substrate being made of the metal plate of rectangle
The porous structure of a large amount of through holes 13 is formed in 21.Substrate 21 has the 1st surface 21a and substantially parallel with the 1st surface 21a
The 2nd opposed surface 21b.Interval, the i.e. plate thickness of 1st surface 21a and the 2nd surface 21b is formed as T1.1st surface 21a with every
Film 24 is opposed, and the 2nd surface 21b is opposed with anode chamber 16.
Through hole 13 is formed with rectangular arrangement and in large quantities in the almost entire surface of the 1st electrode 20.Each through hole 13
Such as section is formed as round, is open in the 1st surface 21a and the 2nd surface 21b.It should be noted that through hole 13 can be by
According to the 1st surface side 21a opening diameter be greater than the 2nd surface side 21b opening diameter mode by taper wall surface or bending
Wall surface formed.Through hole 13 is not limited to circle, and the various shapes such as rectangle, ellipse can be used.Through hole 13 is not limited to advise
It then arranges, randomly can also arrange to be formed.
As the substrate 21 of the 1st electrode 20, the valve metals, conductive metal such as titanium, chromium, aluminium or its alloy can be used.Its
In preferred titanium.According to the difference of cell reaction, in order to reduce activation overpotential, preferably the 1st surface 21a of the 1st electrode 20,
The side (inner surface) of 2nd surface 21b and through hole 13 forms electrolytic catalyst (catalyst layer).Catalyst layer is formed to electricity
Solution is active cell reaction active part 50.The thickness of catalyst layer is usually 0.5~5 μm or so.Electrode is being used as sun
In the case where pole, the substrate itself as electrode is, it is preferable to use the oxide catalysts such as the noble metal catalysts such as platinum, yttrium oxide
Agent.It can be formed according to the amount of the per unit area of electrolytic catalyst in the two sides of the 1st electrode 20 different mode.
According to the present embodiment, the 1st surface 21a of the 1st electrode 20 is generally flatly formed, and it is non-live for having to electrolysis
The cell reaction non-active portion 52 of property.About the cell reaction non-active portion 52, it is described in detail below.
As shown in Figure 1, Figure 2 and Figure 4, in present embodiment, the 22 and the 1st electrode 20 of the 2nd electrode (opposite electrode, cathode)
Similarly constitute.That is, the 2nd electrode 22 is for example with being formed with a large amount of perforations in the substrate 23 being made of the metal plate of rectangle
The porous structure in hole 15.Substrate 23 have the 1st surface 23a and with opposed the 2nd surface substantially in parallel the 1st surface 23a
23b.1st surface 23a is opposed with diaphragm 24, and the 2nd surface 23b is opposed with cathode chamber 18.
As diaphragm 24, various dielectric films or the multiple aperture plasma membrane with nano-pore can be used.As dielectric film,
Polyelectrolyte membrane, such as ion exchange solid polyelectrolyte membrane can be used, specifically, can be used yin from
The film of sub- exchangeability or the film of hydrocarbon system.As the film of anion exchange, Tokuyama Corporation system can be enumerated
AMX, the SELEMION manufactured by Asahi Glass Co., Ltd etc. for A201, ASTOM the Corporation manufacture made.As having
The multiple aperture plasma membrane of nano-pore has the porous ceramics, Porous such as porous glass, Porous aluminium oxide, Porous titanium oxide
Porous polymer such as polyethylene, Porous propylene etc..By the way that such diaphragm 24 is arranged, ion selectivity can be improved.
1st surface of the diaphragm 24 for example formed as the rectangle with the almost equal size of the 1st electrode 20, with the 1st electrode 20
The entire surface of 21a is opposed.In present embodiment, diaphragm 24 is held in the 1st surface 21a and the 2nd electrode 22 of the 1st electrode 20
The 1st surface 23a between.When 1st electrode 20 is directly contacted with diaphragm 24, the diffusion overpotential of ion is reduced, thus preferably,
However, you can also not must contact.Alternatively, the 2nd variation as shown in Figure 3 is such, can also the 1st electrode 20 and diaphragm 24 it
Between be equipped with the other structures body such as spacer film 25.In addition, the peripheral portion of the 1st electrode 20 and diaphragm 24 is also used as sealing, it should
Sealing is for preventing electrolysis water from leaking into outside electrolytic cell 11.2nd electrode 22 can not also directly be contacted with diaphragm 24, or
Other structures body can also be arranged in person between the 2nd electrode 22 and diaphragm 24.
In electrolysis unit 10, the electrolysates such as acid water, alkaline water, reaction gas for being generated by cell reaction pass through
2nd surface 21b of the 1st electrode 20 and the 2nd surface 23b for passing through the 2nd electrode 22, are discharged from anode chamber 16 and cathode chamber 18
To outside.But the flowing for the raw water or electrolyte being transported in anode chamber 16 is obstructed inside through hole 13, separately
Outside, it in the adjacent portions of the 1st surface 21a and diaphragm 24 of the 1st electrode 20, is become difficult using the discharge that flowing carries out.In addition,
Reaction product is stopped such as hypochlorous acid, chlorine, and reaction overvoltage rises, and can lead to the bad of diaphragm 24 because of free radical etc.
Change.In addition, diaphragm 24 sometimes also can be because of gas if the narrow zone between the 1st electrode 20 and diaphragm 24 generates gas
Pressure and rupture.
Then, according to the 1st embodiment, the 1st surface 21a of 1st electrode 20 opposed with diaphragm 24 at least partly has
The cell reaction non-active portion 52 that cell reaction does not occur, using other parts as cell reaction active part 50.As Fig. 1,
Shown in Fig. 3 and Fig. 5, such as in the 1st electrode 20 of punch metal shape, cell reaction active part 50 is formed in through hole
Around 13 side (inner surface) or each through hole 13 of the 2nd surface 21b or the 1st surface 21a, by the 1st surface 21a's
Other parts are as cell reaction non-active portion 52.Multiple rings around each through hole 13 for surrounding the 1st surface 21a
In the case that shape portion forms cell reaction active part 50, as shown in Fig. 6, the 1st surface 21a is set as D at a distance from diaphragm 24
When, it is preferably that the part L >=1.5 × D is anti-as electrolysis using the distance L on the periphery at least away from through hole 13 of the 1st surface 21a
Answer non-active portion 52.
It is simulated so that the electrolysis by sodium-chloride water solution generates hypochlorous acid as an example.As transmission diaphragm 24 by the 1st
20 electric attraction of electrode (anode) and reach anode chamber 16 chloride ion concentration distribution and the 1st electrode 20 current density point
The velocity flow profile of cloth and the fluid flowed in anode chamber 16 as a result, as shown in fig. 7, by the 1st surface of the 1st electrode 20
In the case that 21a is as cell reaction active part 50, it is known that hypochlorous acid stays in the 1st surface of the 1st electrode 20 with high concentration
Between 21a and diaphragm 24.In this way, it is believed that the phenomenon that region of generation high concentration is near the diaphragm 24 of the 1st electrode 20
It crosses diaphragm 24 and supplies the intrinsic phenomenon of electrolytic cell of ion.If the hypochlorous acid of high concentration stays in the surface of diaphragm 24, can
Cause the deterioration of diaphragm 24.In particular, the surface of diaphragm 24 forms the distance L that high concentration region is the periphery away from through hole 13
For the region L >=1.5 × D.Therefore, by will be nonactive as cell reaction with the electrode surface of the comparable part in the region
Part, it is believed that can inhibit hypochlorous generation, hypochlorous stop can be prevented.
Fig. 8 shows hypochlorous concentration distribution when keeping the 1st surface 21a of the 1st electrode 20 nonactive.By the figure
It is found that not generating time chlorine on the surface of diaphragm 24 using the 1st surface 21a as in the case where cell reaction non-active portion 52
Acid high concentration region.By the above content discovery, in the 1st surface 21a of the 1st electrode 20, by by the periphery away from through hole 13
Distance L be the part L >=1.5 × D as cell reaction non-active portion 52, the hypochlorous acid on 24 surface of diaphragm can be inhibited
The generation of high concentration region.
As described above, it is ideal for contacting electrode with diaphragm 24 in order to reduce diffusion overpotential as far as possible.The situation
Under, the 1st surface 21a and 24 distance D of diaphragm of the 1st electrode 20 are 0, thus the periphery of through hole 13 is non-live to cell reaction
Property part distance L be also 0, that is, preferably the almost entire surface of the 1st surface 21a be cell reaction non-active portion 52.It needs
Illustrate, is described below, in the case where the 1st surface 21a is not flat surface and has concave-convex, the not no limit
It is fixed.
1st variation as shown in Figure 2 is such, and the peripheral portion of the peripheral portion of the 1st electrode 20 and diaphragm 24 is used as sealing
In the case where portion, in sealing, occur fraction of cell reaction with the anion come is spread in diaphragm 24, but raw water or
The fluids such as electrolyte are shielded, thus the reaction products such as hypochlorous acid or chlorine are not discharged, and are easy to happen the deterioration of diaphragm.Cause
This, is preferably not provided with catalyst layer and anti-as electrolysis with the peripheral portion of the 1st surface 21a of comparable 1st electrode 20 of sealing
Answer non-active portion 52.
In present embodiment and variation, it is close that cell reaction non-active portion 52 is for example defined as usual revolution electric current
Spend range (30~300mA/cm2) under cell reaction overvoltage than 300mV or more the big portion of cell reaction active part 50
Point.
Therefore, " nonactive " described herein refers to that relatively activity degree is substantially low compared with " active part ", is not
Cell reaction does not occur completely for finger.
As the method for difference cell reaction active part 50 and cell reaction non-active portion 52, there are following methods: point
Each electrode is not made, and electrochemical reaction activity is evaluated.For example, being reacted using the generation of the chlorine as one of cell reaction
For the purpose of, it will be in a manner of becoming 0.25M (Ir) in iridium chloride (IrCl3·nH2O the solution leaching that n-butyl alcohol is added in) and prepares
Stain is applied to the titanium plate (electrode base material) for having carried out the 0.1mm of processing in 1 hour in 80 DEG C in 10wt% oxalic acid aqueous solution, it
After be dried, be burnt into 10 minutes at 450 DEG C.The coating and drying, firing are repeated 5 times, obtain being formed with yttrium oxide
The electrode of catalyst.The electrode is cut in such a way that reaction electrode area is 1cm × 1cm, as 3 pole formula electricity shown in Figure 17
The working electrode 71 in pond 80 is inserted into.3 pole formula batteries 80 use platinum guaze to electrode 74, and reference electrode 73 uses reversible hydrogen electrode
(RHE).The hydrochloric acid of 0.1M and the salt water of 1M are added in electrolyte 75, voltage is applied to working electrode 71 using potentiostat,
Obtain cyclic voltammogram.At this point, 125mA/cm2Current flowing when voltage be 1.6VvsRHE.
In contrast, instead of being coated with yttrium oxide, ethyl alcohol and diethanol is added into original four-isopropyl titanate under ice bath
Amine is added dropwise ethyl alcohol mixing water while stirring and makes colloidal sol, and is applied to titanium plate.Later, 7 minutes are burnt at 500 DEG C, instead
After carrying out 3 coatings and firing again, it is burnt into 1 hour at 450 DEG C, obtains the electrode for the insulating coating for being formed with titanium oxide.With
Reaction electrode area is that the mode of 1cm × 1cm cuts the electrode, is obtained in the electrolyte of the salt water of the hydrochloric acid and 1M of 0.1M
Cyclic voltammogram.At this point, 125mA/cm2Current flowing when voltage be 1.9VvsRHE.
If there are the insulating coatings of above-mentioned oxidation iridium catalyst and titanium oxide on same electrode, then such as above-mentioned knot
Fruit can generate the voltage difference of 300mV or more when introducing same electric current like that.It is therefore, although also different according to cell reaction,
Assuming that the difference of reaction speed is about 150 times when Tafel slope is 60mV/dec.That is, since reaction is substantially urged in yttrium oxide
The forming region for occurring in agent, thus aoxidizing iridium catalyst can be defined as cell reaction active part, and titanium oxide insulation is covered
The forming region of film can be defined as electrolysis non-active portion.
It should be noted that in the examples described above, although chlorine generation is referred to, but as long as being oxygen generation, hydrogen reduction, gold
Belong to the various electrochemical reactions such as oxidation, soda ash cell reaction, then cell reaction active part and cell reaction non-active portion are set
This method divided is exactly effective.
That is, cell reaction does not occur substantially in cell reaction non-active portion 52, thus by being set to the 1st electricity
The cell reaction product or gas at pole 20 and the interface of diaphragm 24 are easy the part stopped, can inhibit the deterioration of diaphragm 24.
As the forming method of cell reaction active part 50 and cell reaction non-active portion 52, as shown in figure 3, only
The 1st surface 21a of the 1st electrode 20 being made of valve metals such as titanium, chromium, aluminium and its alloys a part, herein only respectively passing through
Annulus around through-hole 13 is coated with the oxide catalysts such as the noble metal catalysts such as conductive platinum or yttrium oxide
Deng cell reaction active part 50 can be formed.In this case, activation overpotential is low to urge by suitably setting decomposition voltage
Agent coating part becomes cell reaction active part 50, and the part of the relatively high uncoated catalyst of activation overpotential becomes electricity
Solution reaction non-active portion 52.
It in addition to this, can also be after the entire surface of electrode forms catalyst, it would be desirable to the part for inhibiting gas to generate
Catalyst removes, to form cell reaction non-active portion 52.For example, the entire surface (of the Ti electrode in punch metal shape
The side of 1 surface 21a, the 2nd surface 21b, through hole 13) formed catalyst layer after, for the 1st surface comprising peripheral portion
21a is removed catalyst by grinding or injection processing, it is possible thereby to form non-active portion.The punch metal the case where
Under, if the face that turned-down edge (ダ レ) will be present carries out catalyst coated and utilization as the 1st surface 21a, and using the above method
The catalyst of grinding removes, then the catalyst for being attached to the part of turned-down edge will not be ground removing and remain, thus can be easy
Ground makes the electrode of structure shown in fig. 5.
As other forming methods of cell reaction non-active portion 52, such as can be on the 1st surface of the 1st electrode 20
It is formed on 21a by vinyl chloride resin, vinylidene chloride, polyvinyl alcohol, polyvinyl acetate, ABS, polyethylene, poly- terephthaldehyde
Sour glycol ester, polystyrene, polylactic acid, polyimides, polypropylene, polyisobutene, acrylic resin, polycarbonate, fluorine
The plastics such as resin, chlorinated polyether, methylpentene resin, epoxy resin, phenolic resin, natural rubber, butyl rubber, the third rubber of second
Ceramics such as the rubber such as glue, fluorubber, titanium oxide, silica, aluminium oxide, niobium oxide, tantalum oxide, nickel oxide, tungsten oxide etc. are constituted
Insulating layer, so as to form cell reaction non-active portion 52.
That is, constituting the surface of the conductive part of cell reaction active part 50 mainly by having 106The electricity of S/m or more
The material of conductance is formed, and constitutes the surface of the insulating properties part of cell reaction non-active portion 52 mainly by having 10-6S/m with
Under the material of conductivity formed.
In addition, the material as insulating layer, if using vinyl chloride, vinylidene chloride, polyethylene, poly terephthalic acid second
Diol ester, polystyrene, polylactic acid, polyimides, fluororesin, silica, tungsten oxide etc. are 2 or more and 6 areas below in pH
The material that Zeta-potential is negative in domain is then repelled by electricity and inhibits anion to the 1st electrode 20 and diaphragm (anion-exchange membrane) 24
Interface supply, can more effectively inhibit the deterioration of anion-exchange membrane caused by the stop of reaction gas, the long-life is provided
Electrode unit 12 and electrolysis unit 10.
It is generated in hypochlorous situation in anode chamber 16 by being electrolysed, it is contemplated that for hypochlorous durability, insulation
The preferred vinyl chloride of material, the vinylidene chloride, polyethylene, fluororesin, silica, tungsten oxide of layer.In particular, from stability and
It sets out in terms of insulation characterisitic, more preferable fluororesin, silica.
If using electrolysis unit as constructed as above and electrode unit, by with the diaphragm pair that at least passes through anion
Cell reaction non-active portion 52 is arranged in 1st surface of the 1st electrode set, and cell reaction product can be inhibited to be easy to stay in
The cell reaction of the part of membrane surface.The position of cell reaction non-active portion 52 is set according to the 1st surface of the 1st electrode
It is determined at a distance from diaphragm.It can inhibit the deterioration of diaphragm caused by reaction gas, such as anion-exchange membrane as a result, it can be with
Obtain the electrode unit and electrolysis unit of long-life.
In addition, by the way that cell reaction active part 50 and electrolysis is arranged on the 1st surface of 1st electrode opposed with diaphragm
Diffusion overpotential is suppressed to by reaction non-active portion 52 so that the 1st electrode 20 be made to contact with diaphragm (anion-exchange membrane)
It is lower, while reaction gas is difficult to discharged part as cell reaction non-active portion and inhibits cell reaction, it will be anti-
The discharge of gas is answered readily partially to generate cell reaction as cell reaction active part 50.It can inhibit reaction gas as a result,
The deterioration of diaphragm caused by body, such as anion-exchange membrane, the electrode unit and electrolysis unit of available long-life.In addition,
The raising of reaction efficiency may be implemented in the rising that can inhibit the diffusion overpotential of electrode.
In conclusion according to the present embodiment, the electrode list of the available long-life that can maintain electrolysis performance for a long time
Member, electrolysis unit and electrode.
Then, the electrode unit of other embodiment and electrolysis unit are illustrated.It should be noted that following
In the other embodiment of explanation, same reference marks is accompanied by for part identical with the first embodiment described above and omits it
It is described in detail, and is described in detail centered on the part different from the 1st embodiment.
(the 2nd embodiment)
Fig. 9 is the sectional view for schematically showing the electrolysis unit of the 2nd embodiment, and Figure 10 is the decomposition of electrode unit
Perspective view, Figure 11 are the perspective views for showing the 1st surface side of the 1st electrode.
In order to increase the response area for the electrode for carrying out cell reaction, it is preferable that electrode is constituted with fine screen mesh, but only use filament
When composition, the resistance overvoltage of Faradaic current is increased, the mechanical strength as electrode is also unable to ensure.Therefore, according to
2 embodiments, the 1st electrode 20 are eyed structure comprising the line width that the predominating path and intensity for taking into account electric current maintain is wider
Linear portion and thinner threadiness portion for ensuring cell reaction area.That is, the 1st electrode 20 has, there are two or more differences
The surface of the eyed structure in the linear portion of width, thin linear portion forms cell reaction active part.In addition, the 1st electrode
20 have porous structure, and through hole is different with the 2nd surface 21b side opening diameter in the 1st surface side 21a.
As shown in Figure 9 and Figure 10, the 1st electrode 20 in the substrate 21 being made of the metal plate of rectangle for example with forming
There are the porous structure and eyed structure of a large amount of through holes.Substrate 21 has the 1st surface 21a and substantially parallel with the 1st surface 21a
The 2nd opposed surface 21b.1st surface 21a is opposed with diaphragm 24, and the 2nd surface 21b is opposed with anode chamber 16.
Multiple 1st hole portions 40 are formed in the 1st surface 21a of substrate 21, are open in the 1st surface 21a.In addition, the 2nd
Surface 21b is formed with multiple 2nd hole portions 42, is open in the 2nd surface 21b.The opening of the 1st hole portion 40 as 24 side of diaphragm is straight
Diameter R1 less than the 2nd hole portion 42 opening diameter R2, in addition, the quantity about hole portion, more forms compared with the 2nd hole portion 42
1st hole portion 40.The depth of 1st hole portion 40 is T1, and the depth of the 2nd hole portion 42 is T2.In present embodiment, with the side of T1 < T2
Formula is formed.
2nd hole portion 42 is arranged with rectangular in the 2nd surface 21b for example formed as rectangle.Provide each 2nd hole portion 42
Peripheral wall can be from the bottom from hole portion to opening, i.e. the 2nd surface side of direction and the conical surface or flexure plane that diameter broadens are formed.
The width of the linear portion 60a at interval, i.e. electrode between the 2nd adjacent hole portion 42 is set as W2.It should be noted that the 2nd hole portion
42 are not limited to rectangle, or various other shapes.It, can also be in addition, the 2nd hole portion 42 is not limited to be regularly arranged
Arrange to be formed to machine.
1st hole portion 40 is arranged with rectangular in the 1st surface 21a for example formed as rectangle.Provide each 1st hole portion 40
Wall surface can be from the bottom from hole portion to opening, i.e. the 1st surface 21a of direction and the conical surface or flexure plane that diameter broadens are formed.
In present embodiment, multiple, such as 16 the 2nd hole portions 42 of the 1st hole portion 40 and 1 are oppositely arranged.This 16 the 1st hole portions 40 are divided
It is not connected to the 2nd hole portion 42, the through hole of perforation substrate 21 has been formed together with the 2nd hole portion 42.In the 1st adjacent hole portion 40
Between shape webbed threadiness portion 60b, the width W1 of linear portion 60b be set as the width less than the linear portion 60a between the 2nd hole portion 42
Spend W2.The number density of the 1st hole portion 40 of the 1st surface 21a is filled compared with the number density of the 2nd hole portion 42 of the 2nd surface 21b as a result,
Divide big.
It should be noted that the 1st hole portion 40 is not limited to rectangle, or other shapes.1st hole portion 40 is not limited to
It is regularly arranged, randomly can also arrange to be formed.In addition, being not limited to the structure that all 1st hole portions 40 are connected to the 2nd hole portion 42
At also may include the 1st hole portion not being connected to the 2nd hole portion 42.
As shown in figure 11, the 1st surface 21a of the 1st electrode 20 has cell reaction active part 50 and cell reaction non-live
Property part 52.In the 1st surface 21a, by with the contact width of diaphragm 24 is wide, generated gas be difficult to it is discharged wide
Linear portion 60a is as cell reaction non-active portion 52, the thin linear portion 60b of the line width that generation gas can be easily discharged
As cell reaction active part 50.The forming method of cell reaction active part 50 and cell reaction non-active portion 52 with
Above-mentioned 1st embodiment is identical.That is, such as that noble metal catalyst conductive platinum or yttrium oxide etc. can be aoxidized
Object catalyst etc. is applied to thin linear portion 60b, to form cell reaction active part 50.Alternatively, can be in wide threadiness
Insulating layer is formed on portion 60a, to form cell reaction non-active portion 52.
As shown in Figure 9 and Figure 10, according to the 2nd embodiment, the 2nd electrode (cathode) 22 is in the same manner as the 1st electrode 20 with more
Pore structure and eyed structure are constituted.That is, the 2nd electrode 22 is for example with the substrate 23 being made of the metal plate of rectangle, the tool of substrate 23
Have the 1st surface 23a and with substantially parallel the 2nd opposed surface 23b of the 1st surface 23a.1st surface 23a is opposed with diaphragm 24,
2nd surface 23b is opposed with cathode chamber 18.
Multiple 1st hole portions 44 are formed in the 1st surface 23a of substrate 23, are open in the 1st surface 23a.In addition, in the 2nd table
Face 23b forms multiple 2nd hole portions 46, is open in the 2nd surface 23b.The opening diameter of the 1st hole portion 44 as 24 side of diaphragm is small
In the opening of the 2nd hole portion 46, in addition, the quantity about hole portion, more forms the 1st hole portion 44 compared with the 2nd hole portion 46.1st
The depth of hole portion 44 forms smaller than the depth of the 2nd hole portion 46.
Multiple, such as 16 the 2nd hole portions 46 of the 1st hole portion 44 and 1 are oppositely arranged.This 16 the 1st hole portions 44 are respectively with
The connection of 2 hole portions 46, the through hole of perforation substrate 23 has been formed together with the 2nd hole portion 46.It is formed between the 1st adjacent hole portion 44
The thin netted linear portion of width, forms wide netted, clathrate the linear portion of width between the 2nd adjacent hole portion 46.
The number density of the 1st hole portion 44 of 1st surface 23a is sufficiently big compared with the number density of the 2nd hole portion 46 of the 2nd surface 23b.
By the way that the 1st electrode 20 formed as described above, diaphragm 24, the 2nd electrode 22 to be oppositely disposed, to obtain electrode
Unit 12.In the 2nd embodiment, other compositions of electrolysis unit 10 are identical as the first embodiment described above and the 1st variation.
It according to the 2nd embodiment, contacts the 1st electrode 20 with diaphragm 24, diffusion overpotential is suppressed to lower, while being difficult to be discharged
The wide linear portion inhibition cell reaction of the width of gas is generated, is occurred in the easy thin linear portion of discharge for generating gas electric
Thus solution reaction can inhibit the deterioration of diaphragm (amberplex) caused by generating gas, the electrode of available long-life
Unit and electrolysis unit.It is additionally possible to suppress the rising of the diffusion overpotential of electrode, may be implemented the raising of reaction efficiency.
It should be noted that making the 1st electrode 20 to make the deterioration that more smooth inhibition diaphragm is discharged for generating gas
The cell reaction active part 50 on the 1st surface is recessed to the 2nd surface side 21b, and it is effective that gap is arranged between diaphragm 24
's.
Figure 12 shows the electrolysis unit of the 3rd variation.
In electrolysis unit, in order to improve electrolytic efficiency, inhibit the pair carried out simultaneously with the main reaction for generating target product
Reaction is effective.For example, the main reaction of the 1st electrode (anode) is to pass through in the electrolysis unit of above-mentioned manufacture hypochloric acid water
The oxidation of chloride ion and generate hypochlorous acid, but can also generate oxygen by the oxidation of hydroxide ion as side reaction.Due to
Chloride ion is reached anode (the 1st electrode) by diaphragm, thus, on the 1st surface of the high electrode of chlorine ion concentration, (diaphragm is attached
Closely), the diffusion overpotential of chloride ion oxidation reaction is low, and hypochlorous formation efficiency is high.But in the back side of electrode (the 2nd table
Face), chlorine ion concentration is low, thus the diffusion overpotential of chloride ion oxidation reaction increases, and is easy to aoxidize by hydroxide ion
It reacts and generates oxygen, hypochlorous formation efficiency reduces.
In order to inhibit such side reaction, as shown in figure 12, it is electrolysed the 2nd surface (back side) 21b of the 1st electrode 20
It is effective for reacting non-active portion 54.For example, in the same manner as above embodiment, by formed on the 2nd surface 21b by
The insulating layer 62 of the compositions such as the ceramics such as titanium oxide, silica, aluminium oxide, niobium oxide, tantalum oxide, nickel oxide, can form electrolysis
React non-active portion 54.
In such 1st electrode 20, it can inhibit secondary anti-in the 2nd high surface 21b of the diffusion overpotential of main reaction
It should carry out, because can efficiently generate target electrolysate without consuming electric current in vain.
(the 3rd embodiment)
Figure 13 is the perspective view for showing the 1st surface side of the 1st electrode of electrolysis unit of the 3rd embodiment.According to this reality
Mode is applied, the 1st recess (bumps) of the 1st pattern is integrally formed in the 1st surface 21a of the 1st electrode 20, the of the 1st electrode 20
The 2nd recess (bumps) of 2nd pattern different from the 1st pattern is integrally formed in 2 surface 21b.
In present embodiment, the 1st recess of the 1st pattern has that the 1st surface 21a's for being formed in substrate 21 is multiple thin
The 1st linear recess portion 70, these the 1st recess portions 70 are open in the 1st surface 21a respectively.2nd recess of the 2nd pattern, which has, to be formed in
Multiple thick linear second recesses 72 of 2nd surface 21b of substrate 21, these second recesses 72 are opened in the 2nd surface 21b respectively
Mouthful.Other than the peripheral portion of substrate 21, these the 1st recess portions 70 and second recesses 72 are formed in the effective coverage of entire rectangle.
Also, multiple 1st recess portion 70 and 1 second recesses 72 are connected to, and have respectively constituted through hole 13.
Multiple 1st recess portions 70 are extended with elongated linear formation in the 1st direction X, such as horizontal direction.Multiple 1
Recess portion 70 is arranged in parallel to each other.Each 1st recess portion 70 is formed longerly than the opening width W3 of second recesses 72.This implementation
In mode, the 1st recess portion 70 is from the effective coverage (middle section of the rectangle in addition to the peripheral portion on the 1st surface) of the 1st surface 21a
One end continuously extend to the other end.The depth D1 of each 1st recess portion 70 is more shallow than the half of the plate thickness T of substrate 21, such as
Be formed as 0.1~0.2mm.In present embodiment, each 1st recess portion 70 from bottom side to the 1st surface 21a width according to broadening
Mode is formed, that is, the cross sectional shape with approximate trapezoid.As a result, a part of 1st recess portion 70 with the perforation width W2 of 0.2mm with
Multiple second recesses 72 are connected to.
Multiple second recesses 72 of the 2nd surface side 21b are formed in elongated linear formation, are intersected with the 1st direction X
Direction, for example vertical with the 1st direction X the 2nd direction Y extends.Multiple second recesses 72 are arranged in parallel to each other.Each
2 recess portions 72 are from one end of the effective coverage (middle section of the rectangle in addition to the peripheral portion on the 2nd surface) of the 2nd surface 21b to another
One end continuously extends.The opening width W3 of each second recesses 72 is greater than the opening width W1 of the 1st recess portion 70, for example formed as
The depth D2 of 1.6mm, second recesses 72 are deeper than the half of the plate thickness T of substrate 21, for example formed as 0.6~0.7mm.This implementation
In mode, each second recesses 72 are formed in the way of broadening from bottom side to the 2nd surface 21b width, with approximate trapezoid
Cross sectional shape.
As shown in figure 14, other than with the elongated remaining 1st surface 21a of threadiness, each 1st recess portion 70 side and
Bottom surface, the 2nd surface 21b entire surface formed catalyst layer, such as iridium oxide catalyst layer, as cell reaction active portion
Divide 50.1st surface 21a does not form catalyst, constitutes cell reaction non-active portion 52.1st electrode 20 is with the 1st surface 21a
The state contacted with diaphragm 24 is configured.
As shown in Figure 15 (a), the 1st electrode 20 as constructed as above is for example to the 1st surface 21a of substrate 21 and the 2nd surface
21b is etched and part eliminates, and forms the 1st recess with the 1st pattern and the 2nd recess with the 2nd pattern.Then, it uses
Catalyst layer is coated the entirety of the 1st surface 21a, the 2nd surface 21b, the 1st recess portion 70 and second recesses 72.
Then, as shown in Figure 15 (b), the 1st surface 21a for becoming protrusion is ground, by urging on the 1st surface 21a
Agent layer removes.As a result, using the 1st surface 21a of the 1st electrode 20 as cell reaction non-active portion 52.1st recess portion, 70 He
The cross sectional shape of second recesses 72 is not limited to trapezoidal, can be the various shapes such as rectangle, semicircle, ellipse, arc-shaped.Separately
Outside, the angle that the 1st recess portion 70 intersects with second recesses 72 is not limited to right angle, can be other arbitrary angles.
The 1st electrode 20 according to the above configuration, the fluid to circulate in the 1st thin-line-shaped recess portion 70 are logical from through hole 13
It crosses linear second recesses 72 and circulates to anode chamber 16 or cathode chamber.Main cell reaction from diaphragm 24 slightly from
The region for opening the bottom surface of the 1st recess portion 70 of depth D1 occurs, and the hypochlorous acid as product forms small from the 1st recess portion 70
Gap is recovered to anode chamber 16 by through hole 13.Thus, it is possible to take into account high formation efficiency and prevent diaphragm from deteriorating.?
Using this shape 1 electrode 20 when, electrolysate be easy stop be the 1st surface 21a most adjacent with diaphragm 24
Region.It is therefore preferable that will be using the remaining 1st surface 21a of convex as cell reaction non-active portion 52, by the 1st recess portion 70
Side and bottom surface are as cell reaction active part 50.In the case where this 1 electrode, using the peripheral portion of electrode as close
When envelope portion, it is also preferred that using the 1st surface of the peripheral portion as cell reaction non-active portion.
(the 4th embodiment)
Figure 16 is the sectional view for schematically showing the electrolysis unit of the 4th embodiment.In 4th embodiment, electrolysis dress
Set 10 electrolytic cells 11 and electrode unit 12 for having 3 Room types.Electrolytic cell 11 is formed as flat rectangular box, inside it (electricity
Solve room) it is configured with electrode unit 12.Electrolytic cell 11 has the rectangular box-like middle boxes 11c for forming medial compartment 19, forms anode
The substantially rectangular anode cap 11a of the room 16 and cathode shield 11b for forming cathode chamber 18, in anode cap 11a and cathode shield 11b
Between clamp middle boxes 11c state they are connected with each other, thus constitute electrolytic cell 11.
Electrode unit 12 has: the 1st diaphragm of anode chamber 16 and medial compartment 19 will be divided into the tank house of electrolytic cell 11
24a；The 2nd diaphragm 24b of medial compartment 19 and cathode chamber 18 will be divided into tank house；In anode chamber 16 and with the 1st diaphragm
The 1st 24a opposed electrode (anode) 20；Be located in cathode chamber 18 and 2nd electrode (cathode) opposed with the 2nd diaphragm 24b
22.1st diaphragm 24a and the 2nd diaphragm 24b is parallel to each other opposed across gap, forms between these diaphragms 24a, 24b
Compartment 19.The spacer of Porous also can be set in medial compartment 19 as keeping the keeping body of electrolyte.
Electrolysis unit 10, which has, applies alive power supply 30, electricity for the 1st and the 2nd electrode 20,22 to electrode unit 12
Flowmeter 32, potentiometer 34 and the control device 36 that they are controlled.It can also be arranged in anode chamber 16, cathode chamber 18
The flow path of liquid.It is also can connect in anode chamber 16, cathode chamber 18 for being externally supplied liquid or matching liquid discharge
Pipe or pump etc..In addition, according to circumstances, Porous can also be arranged between electrode unit 12 and anode chamber 16 or cathode chamber 18
Spacer.
In electrode unit 12, the 1st electrode 20 and 22 use of the 2nd electrode are real in the first embodiment described above or the 2nd, the 3rd
Apply the 1st electrode and the 2nd electrode shown in mode.That is, the 1st electrode 20 and the 2nd electrode 22 have, there are the more of a large amount of through holes
Pore structure.In addition, the 1st surface 21a of 1st electrode 20 opposed with the 1st diaphragm 24a has cell reaction non-active portion 52.
Catalyst layer is formed in the 2nd surface 21b of the 1st electrode 20 and the side (inner surface) of each through hole 13, so as to form electricity
Solve reactivity part 50.
1st diaphragm 24a is the diaphragm for making anion-permeable, and the 2nd diaphragm 24b is the diaphragm for making cation permeable.1st every
Film 24a is opposed with the 1st surface 21a of the 1st electrode 20 for example formed as the rectangle with the almost equal size of the 1st electrode 20.2nd
Diaphragm 24b is opposed with the 1st surface 23a of the 2nd electrode 22 for example formed as the rectangle with the almost equal size of the 2nd electrode 22.
As the 1st diaphragm 24a and the 2nd diaphragm 24b, the various electrolysis illustrated in the first embodiment described above can be used
Plasma membrane or multiple aperture plasma membrane with nano-pore.
Peripheral portion, the peripheral portion of the 2nd electrode 22 and the peripheral portion of the 1st and the 2nd diaphragm 24a, 24b of 1st electrode 20
It can be used as the sealing for preventing electrolysis water to be leaked to outside electrolytic cell 11 to utilize.That is, the peripheral portion of the 1st electrode 20 and
The peripheral portion of 1st diaphragm 24a is held between middle boxes 11c and the end face of anode cap 11a, and is fixed in electrolytic cell 11.
The seal members 8a1 such as o-ring are equipped between the peripheral portion and anode cap 11a of the 1st electrode 20.On the periphery of the 1st diaphragm 24a
The seal members 8a2 such as o-ring are equipped between portion and middle boxes 11c.
The peripheral portion of 2nd electrode 22 and the peripheral portion of the 2nd diaphragm 24b are held in middle boxes 11c's and cathode shield 11b
Between end face, and it is fixed in electrolytic cell 11.It is close that o-ring etc. is equipped between the peripheral portion and cathode shield 11b of the 2nd electrode 22
Seal component 8b1.The seal members 8b2 such as o-ring are equipped between the peripheral portion and middle boxes 11c of the 2nd diaphragm 24b.
Although the flowing of fluid does not occur for sealing, electrolysis can be generated between the ion and electrode contained in diaphragm
Reaction, thus electrolysate or gas stop, and are easy to produce the deterioration of diaphragm.Therefore, in sealing, the of the 1st electrode 20
1 surface 21a is as cell reaction non-active portion 52.Similarly, in sealing, the 1st surface 23a conduct of the 2nd electrode 22
Cell reaction non-active portion.
Such electrolysis unit 10 is preferably electrolysed the halogen-containing electrolyte of packet.For example, for generate hypochloric acid water
Electrolysis unit 10 in the case where, include electrolyte, such as salt water of chloride ion, anode to the left and right to the circulation of medial compartment 19
Room 16 and cathode chamber 18 circulate water, using the 20 and the 2nd electrode (anode) 22 of the 1st electrode (cathode) by the salt water power of medial compartment 19
Solution.Hypochloric acid water is generated in anode chamber 16 as a result, and generates sodium hydroxide water in cathode chamber 18.
In the electrolysis unit 10 of the electrolytic cell 11 with 3 Room types, hypochlorous acid and chlorine are generated in the 1st electrode (anode) side
Gas, but the anion-exchange membrane used as the 1st diaphragm 24a is easy to deteriorate because of hypochlorous acid or chlorine.Therefore, make to have
There is the 1st electrode 20 of cell reaction non-active portion 52 adjacent with the 1st diaphragm (anion-exchange membrane) 24a, by diffusion overpotential
It is suppressed to lower, while the part that hypochlorous acid or chlorine are easy to stop inhibits to be electrolysed as cell reaction non-active portion 52
Reaction, the discharge of hypochlorous acid or chlorine readily partially generate cell reaction as cell reaction active part 50.As a result,
The deterioration of 1st diaphragm (anion-exchange membrane) 24a, electrode unit, the electricity of available long-life caused by can inhibit because of chlorine
Solve device.
Then, various embodiments and comparative example are illustrated.
(embodiment 1)
The flat titanium plate that electrode base material 21 is 0.5mm using plate thickness T1, is etched the titanium plate, to make Fig. 4
~the 1st electrode 20 shown in fig. 6.In electrode, the thickness (depth of the 1st hole portion) in the region of the 1st hole portion 40 comprising path
T1 is 0.15mm, and thickness (depth of the 2nd hole portion) T2 in the region of the 2nd hole portion 42 comprising major diameter is 0.35mm.1st hole portion
40 be rectangle, and aperture R1 is 0.57mm, and the 2nd hole portion 42 is rectangle, and aperture R2 is 2mm.Between the 1st adjacent hole portion 40
The width W1 of the netted linear portion 60b formed is 0.1mm, the wide linear portion 60a formed between the 2nd adjacent hole portion 42
Width W2 be 1.0mm.
1st electrode 20 is handled 1 hour in 10wt% oxalic acid aqueous solution in 80 DEG C.In a manner of 0.25M (Ir)
Iridium chloride (IrCl3·nH2O n-butyl alcohol is added in), after the 1st surface 21a of prepared solution coating to electrode base material 21,
It is dried, is burnt into.In this case, dry carry out 10 minutes at 80 DEG C, firing carries out 10 minutes at 450 DEG C.It will be such
It is coated and dried, is burnt into repetition 5 times, obtain the electrode base material for being formed with oxidation iridium catalyst.With reaction electrode area for 3cm ×
The mode of the size of 4cm cuts the electrode base material, forms the 1st electrode (anode) 20.
Ethyl alcohol and diethanol amine is added into original four-isopropyl titanate under ice bath, ethyl alcohol mixing water is added dropwise under stiring
And make colloidal sol.The colloidal sol is restored to room temperature, in the 1st surface 21a of the 1st electrode 20, to cover thin linear portion 60b
State, wide linear portion 60a is applied to hairbrush.The film being coated with is burnt into 7 minutes at 500 DEG C.It is repeated 3 times
After coating and firing, it is burnt into 1 hour at 500 DEG C, obtains the insulating layer being made of titanium oxide.In above-mentioned electrode fabrication, generation
Platinum is sputtered on the surface of electrode base material for production yttrium oxide, forms the 2nd electrode (cathode) 22.
Using these the 1st electrodes 20 and 22 electrode of the 2nd electrode, electrode unit 12 and electrolytic cell 11 shown in fig. 6 are made.
It is used as the A201 that the 1st diaphragm 24a, the Tokuyama used as anion-exchange membrane are manufactured as the 2nd diaphragm 24b
Nafion 117.As the keeping body for keeping electrolyte, the Porous polystyrene of thickness 5mm is used.Use silicone sealant
The diaphragm of these the 1st and the 2nd electrodes, the 1st and the 2nd, Porous polystyrene are overlapped and are fixed with screw, forms electrode unit
12。
The anode chamber 16 of electrolytic cell 11 and cathode chamber 18 are respectively by being formed with the container shape of the vinyl chloride of straight line flow path
At.Control device 36, power supply 30, potentiometer, galvanometer are set.It will be used to supply tap water to anode chamber 16 and cathode chamber 18
Piping and pump be connected to electrolytic cell 11, will be used for the keeping body (Porous polystyrene) of electrode unit 12 recycle supply
The saturated salt water pot of saturated brine and piping, pump are connected to electrolytic cell 11.
It using electrolysis unit 10, is electrolysed with electric current 1.5A, generates hypochloric acid water in 20 side of the 1st electrode (anode),
2nd electrode (cathode), 22 side generates sodium hydroxide water.Even if electrolytic efficiency is also higher after 1000 hours continuously run
It is maintained 70% or more, the salt concentration in acid water maintains 0.05% or less.The hardly seen deterioration to the 1st diaphragm, can be with
Carry out stable electrolysis processing.
(embodiment 2)
For foring the electrode base material of oxidation iridium catalyst similarly to Example 1, it is being blinded by the 1st surface 21a's
In the state of thin linear portion 60b, the oxidation iridium catalyst on the wide linear portion 60a of the 1st surface 21a is removed by sandblasting,
Produce the 1st electrode 20.Other than the 1st electrode 20, electrolysis unit 10 is produced similarly to Example 1.
It using the electrolysis unit, is electrolysed with electric current 1.5A, generates hypochloric acid water in 20 side of the 1st electrode (anode),
2nd electrode (cathode), 22 side generates sodium hydroxide water.Even if electrolytic efficiency is also higher after 1000 hours continuously run
It is maintained 70% or more, the salt concentration in acid water maintains 0.05% or less.The hardly seen deterioration to the 1st diaphragm, can be with
Carry out stable electrolysis processing.
(embodiment 3)
Titanium-based material is etched similarly to Example 1, produces the electrode base material of porous structure.By the electrode base
Material is handled 1 hour in 10wt% oxalic acid aqueous solution in 80 DEG C in advance.In iridium chloride (IrCl in a manner of 0.25M (Ir)3·
nH2O) in be added n-butyl alcohol, by prepared solution the 1st surface 21a and the 2nd surface 21b for being blinded by electrode base material width
Linear portion 60a in the state of, be applied to the 1st surface 21a and the 2nd surface 21b, be repeated similarly to Example 1 later
Dry and firing, obtains to two sides and is formed with the electrode base material of oxidation iridium catalyst.It is 3cm × 4cm's with reaction electrode area
The mode of size cuts the electrode base material, forms the 1st electrode (anode) 20.
Other than the 1st electrode (anode) 20, electrolysis unit 10 is produced similarly to Example 1.
It using the electrolysis unit, is electrolysed with electric current 1.5A, generates hypochloric acid water in 20 side of the 1st electrode (anode),
2nd electrode (cathode), 22 side generates sodium hydroxide water.Even if electrolytic efficiency is also higher after 1000 hours continuously run
It is maintained 70% or more, the salt concentration in acid water maintains 0.05% or less.The hardly seen deterioration to the 1st diaphragm, can be with
Carry out stable electrolysis processing.
(embodiment 4)
The flat titanium plate that electrode base material 21 is 1mm using plate thickness T1, is etched the titanium plate, thus makes Figure 13
Shown in the 1st electrode 20.
As shown in figure 13, multiple 1st recess portions 70 are with elongated linear formation, in the 1st direction X, such as horizontal vertical side
To extension.Multiple 1st recess portions 70 are arranged in parallel to each other.The opening width W1 of each 1st recess portion 70 is such as 0.4mm, the
The spacing P1 of the orientation Y of 1 recess portion 70 is 0.5mm, and the half of the depth D1 of the 1st recess portion 70 than the plate thickness T of substrate 21 is more
Shallowly, for example formed as 0.1~0.2mm.
Multiple second recesses 72 of the 2nd surface side 21b are formed in elongated linear formation, are intersected with the 1st direction X
Direction, for example vertical with the 1st direction X the 2nd direction Y extends.The opening width W3 of each second recesses 72 and the 1st recess portion 70
Opening width W1 compares sufficiently large, for example, 2.4mm, and the spacing P2 of the orientation X of second recesses 72 is 3mm, second recesses 72
Depth D2 it is deeper than the half of the plate thickness T of substrate 21, for example formed as 0.6~0.7mm.2nd the passing through with 1.2mm of recess portion 72
Logical width Opening length is connected to multiple 1st recess portions 70.
The electrode base material 21 for foring the 1st recess portion 70 and second recesses 72 as described above is water-soluble in 10wt% oxalic acid in advance
It is handled 1 hour in liquid in 80 DEG C.In iridium chloride (IrCl in a manner of becoming 0.25M (Ir)3·nH2O n-butyl alcohol is added in), it will
After electrode base material is impregnated into prepared solution, dry and firing is repeated similarly to Example 1, obtains entire
Face is formed with the electrode base material of oxidation iridium catalyst.Later, the 1st surface 21a is ground, catalyst is removed.With reaction
Electrode area is that the mode of the size of 3cm × 4cm cuts the electrode base material, forms the 1st electrode (anode) 20.
Other than the 1st electrode (anode) 20, electrolysis unit 10 is produced similarly to Example 1.
It using the electrolysis unit, is electrolysed with electric current 1.5A, generates hypochloric acid water in 20 side of the 1st electrode (anode),
2nd electrode (cathode), 22 side generates sodium hydroxide water.Even if electrolytic efficiency is also higher after 1000 hours continuously run
It is maintained 70% or more, the salt concentration in acid water maintains 0.05% or less.The hardly seen deterioration to the 1st diaphragm, can be with
Carry out stable electrolysis processing.
(comparative example 1)
Other than the insulating coating for being not provided with titanium oxide, the 1st electrode and electrolysis dress are produced similarly to Example 1
It sets.It using the electrolysis unit, is electrolysed with electric current 1.5A, generates hypochloric acid water in anode-side, generate hydroxide in cathode side
Sodium water.After 1000 hours continuously run, electrolytic efficiency is reduced to 50% hereinafter, the salt concentration in acid water is more than
1%, the 1st diaphragm (dielectric film) is deteriorated.
(comparative example 2)
In addition between the 1st electrode (anode) and the 1st diaphragm (anion-exchange membrane) be arranged 80 μm of thickness non-woven fabrics with
Outside, electrolysis unit is produced in the same manner as comparative example 1.Using the electrolysis unit, it is electrolysed with electric current 1.5A, in anode-side
Hypochloric acid water is generated, generates sodium hydroxide water in cathode side.After 1000 hours continuously run, electrolytic efficiency is reduced to
50% hereinafter, the salt concentration in acid water is more than 1%, and the 1st diaphragm is deteriorated.
(comparative example 3)
Other than not removing the catalyst of the 1st surface 21a, the 1st electrode and electrolysis are produced similarly to Example 4
Device.It using the electrolysis unit, is electrolysed with electric current 1.5A, generates hypochloric acid water in anode-side, generate hydrogen-oxygen in cathode side
Change sodium water.After 1000 hours continuously run, electrolytic efficiency is reduced to 50% hereinafter, the salt concentration in acid water is more than
1%, the 1st diaphragm (dielectric film) is deteriorated.
The present invention is not limited by above embodiment original state, can model without departing from its main purpose in implementation phase
It encloses and interior embodies constituent element deformation.In addition, passing through appropriate group of multiple constituent elements disclosed in above embodiment
It closes, is capable of forming various inventions.It is wanted for example, it is also possible to delete several compositions from whole constituent element shown in embodiment
Element.It in turn, can be with the constituent element in appropriately combined different embodiments.
For example, the 1st electrode and the 2nd electrode are not limited to rectangle, it can choose various other shapes.The 1st of 1st electrode
Hole portion and the 2nd hole portion are not limited to rectangle, or various other shapes such as circle, ellipse.The material of each component parts
Above-mentioned embodiments and examples are not limited to, other materials can be suitably selected.
Claims (27)
1. a kind of electrode unit, has:
1st electrode, the 1st electrode have the 1st surface, positioned at the 1st surface opposite side the 2nd surface and respectively the 1st
Multiple through holes on surface and the 2nd surface opening；
1st surface of the 2nd electrode, the 2nd electrode and the 1st electrode is oppositely arranged；With
Diaphragm, the diaphragm are set between the 1st electrode and the 2nd electrode, at least pass through anion,
1st surface of the 1st electrode at least has the reaction non-active portion for electrolysis,
When the 1st surface is set as D at a distance from the diaphragm, the week at least away from the through hole on the 1st surface
The distance L on side is that the part L >=1.5 × D is reaction non-active portion.
2. electrode unit as described in claim 1, wherein the reaction non-active portion is made of insulating properties part.
3. electrode unit as claimed in claim 2, wherein the reaction non-active portion by the 1st surface at least
The insulating layer forming portion that a part is formed with insulating layer is constituted.
4. electrode unit as claimed in claim 3, wherein the insulating layer is by being ζ-in 2 or more and 6 regions below in pH
The material that current potential is negative is formed.
5. electrode unit as described in claim 1, wherein the non-active portion that reacts is by the part structure of unsupported catalyst
At.
6. electrode unit as described in claim 1, wherein the 2nd surface of the 1st electrode has for the anti-of electrolysis
Answer non-active portion.
7. electrode unit as described in claim 1, wherein the 1st surface of the 1st electrode has the reaction for electrolysis living
Property part and reaction non-active portion.
8. electrode unit as claimed in claim 7, wherein the reactivity part is by least the one of the 1st surface
The catalyst coated portion that conductive metallic catalyst or oxide catalyst are coated on part is constituted.
9. electrode unit as claimed in claim 7 or 8, wherein in the 1st surface, the reactivity part is located at
Around each through hole.
10. electrode unit as claimed in claim 7 or 8, wherein the 1st electrode, which has, includes two or more different in width
The eyed structure in linear portion, the surface in most thin linear portion constitute the reactivity part.
11. electrode unit as claimed in claim 7 or 8, wherein the 1st electrode, which has, is formed in the more of the 1st surface
A recess portion, the 1st surface constitute the reaction non-active portion, and the bottom surface of each recess portion constitutes the reactivity portion
Point.
12. electrode unit as described in claim 1, which is characterized in that the peripheral portion on the 1st surface of the 1st electrode
To react non-active portion.
13. a kind of electrolysis unit, has:
Electrolytic cell with tank house；With
It is configured at electrode unit described in any one of described indoor claim 1~12 of electrolysis.
14. electrolysis unit as claimed in claim 13, wherein be filled with the electrolysis comprising halogens in the tank house
Matter liquid passes through electrolytically generated halogen compounds.
15. electrolysis unit as claimed in claim 13, wherein the electrode unit has the 1st diaphragm, and the 1st diaphragm will
The anode chamber that the tank house is divided into the cathode chamber for being supplied to electrolyte and is supplied to water, at least passes through anion,
1st electrode and the 1st diaphragm are relatively configured in the anode chamber, the 2nd electrode and the 1st diaphragm
It is relatively configured in the cathode chamber.
16. electrolysis unit as claimed in claim 13, wherein the electrode unit has the 1st diaphragm and the 2nd diaphragm, described
The tank house is divided into the medial compartment for being supplied to electrolyte solution and the anode chamber that is supplied to water by the 1st diaphragm, at least make yin from
Son passes through, and the tank house is divided into the medial compartment and is supplied to the cathode chamber of water by the 2nd diaphragm, at least makes cation
Pass through, the 1st electrode and the 1st diaphragm are relatively configured in the anode chamber, the 2nd electrode with the described 2nd every
Film is relatively configured in the cathode chamber.
17. the electrolysis unit as described in claim 15 or 16, wherein having for the 1st surface of the 1st electrode is described
The peripheral portion in the region of through hole is reaction non-active portion.
18. a kind of electrode, for the electrode for electrolysis unit, have the 1st surface, the opposite side positioned at the 1st surface
2nd surface and respectively in multiple through holes on the 1st surface and the 2nd surface opening,
1st surface has reactivity part and reaction non-active portion for electrolysis,
When the 1st surface is set as D at a distance from diaphragm, the periphery at least away from the through hole on the 1st surface
Distance L is that the part L >=1.5 × D is reaction non-active portion.
19. electrode as claimed in claim 18, wherein the reactivity part and the reaction non-active portion are by conduction
Property part and insulating properties part respectively constitute.
20. electrode as claimed in claim 19, wherein the reaction non-active portion is by least the one of the 1st surface
The insulating layer forming portion that insulating layer is formed on part is constituted.
21. electrode as claimed in claim 20, wherein the insulating layer is by being ζ-electricity in 2 or more and 6 regions below in pH
The material that position is negative is formed.
22. electrode as claimed in claim 18, wherein the reactivity part and the reaction non-active portion are by loading
The part of the part and unsupported catalyst that have catalyst respectively constitutes.
23. electrode as claimed in claim 22, wherein the reactivity part is by least one of the 1st surface
The catalyst coated portion that conductive metallic catalyst or oxide catalyst are coated on point is constituted.
24. the electrode as described in any one of claim 18~23, wherein in the 1st surface, the reactivity portion
Quartile is around each through hole.
25. the electrode as described in any one of claim 18~23, wherein have the threadiness comprising two or more different in width
The eyed structure in portion, the surface in most thin linear portion constitute the reactivity part.
26. the electrode as described in any one of claim 18~23, wherein have and be formed in the multiple recessed of the 1st surface
Portion, the 1st surface constitute the reaction non-active portion, and the bottom surface of each recess portion constitutes the reactivity part.
27. the electrode as described in any one of claim 18~23, wherein the 2nd surface has the reaction for electrolysis
Non-active portion.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014191591 | 2014-09-19 | ||
| JP2014-191591 | 2014-09-19 | ||
| PCT/JP2015/075827 WO2016043134A1 (en) | 2014-09-19 | 2015-09-11 | Electrode unit, electrolysis device, and electrode used in electrolysis device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106574382A CN106574382A (en) | 2017-04-19 |
| CN106574382B true CN106574382B (en) | 2018-12-04 |
Family
ID=55533172
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580043799.5A Expired - Fee Related CN106574382B (en) | 2014-09-19 | 2015-09-11 | Electrode unit, electrolysis unit and the electrode for electrolysis unit |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6258515B2 (en) |
| CN (1) | CN106574382B (en) |
| WO (1) | WO2016043134A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6554622B2 (en) * | 2015-08-18 | 2019-07-31 | 黒谷 信征 | Method for producing water by face-to-face electrolysis of electrode box that can have auxiliary electrode and electrode box that has auxiliary electrode |
| JP6639638B2 (en) * | 2016-03-18 | 2020-02-05 | 株式会社東芝 | Electrolysis electrode, electrode unit, and electrolyzed water generator |
| KR101804979B1 (en) * | 2017-07-31 | 2018-01-11 | 주식회사 이앤에프 | Device for spraying hydroxyl radical water |
| KR102313539B1 (en) * | 2018-11-21 | 2021-10-15 | 이연주 | Sterilizing electrode and method thereof and sterilizer using same |
| US11339480B2 (en) | 2019-03-06 | 2022-05-24 | Kabushiki Kaisha Toshiba | Electrolytic cell and hydrogen production apparatus |
| JP7470931B2 (en) * | 2021-02-09 | 2024-04-19 | パナソニックＩｐマネジメント株式会社 | Gas generator |
| CN113044933A (en) * | 2021-04-07 | 2021-06-29 | 湖南满缘红水科技有限公司 | Low-salt EOW electrolytic cell, low-salt EOW electrolytic device and low-salt EOW preparation method |
| JP2023065251A (en) * | 2021-10-27 | 2023-05-12 | 株式会社イープラン | Hydrogen generation device |
| CN114318391B (en) * | 2021-11-30 | 2023-06-27 | 中国华能集团清洁能源技术研究院有限公司 | Novel electrolytic tank electrode plate with optimized structure, electrolytic unit and application |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6258515B2 (en) | 2018-01-10 |
| JPWO2016043134A1 (en) | 2017-04-27 |
| WO2016043134A1 (en) | 2016-03-24 |
| CN106574382A (en) | 2017-04-19 |
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