CN106011922B - Electrode and preparation method thereof containing cerium - Google Patents
Electrode and preparation method thereof containing cerium Download PDFInfo
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- CN106011922B CN106011922B CN201610525048.3A CN201610525048A CN106011922B CN 106011922 B CN106011922 B CN 106011922B CN 201610525048 A CN201610525048 A CN 201610525048A CN 106011922 B CN106011922 B CN 106011922B
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C20/00—Chemical coating by decomposition of either solid compounds or suspensions of the coating forming compounds, without leaving reaction products of surface material in the coating
- C23C20/06—Coating with inorganic material, other than metallic material
- C23C20/08—Coating with inorganic material, other than metallic material with compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/324—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of electrode and preparation method thereof containing cerium.The preparation method of the present invention includes the following steps：Stainless steel substrate is polished, carries out oil removing, then etch activates to obtain pretreating substrates in an acidic solution；The electronickelling on the pretreating substrates, to form the electrode containing nickel coating；Coating of titanium dioxide is formed on the electrode containing nickel coating, to obtain the electrode containing coating of titanium dioxide；It is anode using the electrode containing coating of titanium dioxide as cathode, platinum guaze, using the solution comprising cerium compound and platinum compounds as electroplate liquid, the platinum coating containing cerium is formed on the electrode containing coating of titanium dioxide, to obtain the electrode containing cerium.The present invention uses cheap stainless steel substrate, by being formed on nickel coating, coating of titanium dioxide and platinum coating containing cerium, more ensure that the stability in use of electrode.
Description
Technical field
The present invention relates to a kind of electrodes and preparation method thereof, especially can be applied to electrode and its preparation side of electrolysis water
Method.
Background technology
Electrolytic water generating device can generate electrolysis water, include mainly alkaline water, slightly acidic water, strong oxidized water etc..Electrode
All it is the core equipment of electrolytic water generating device with seperation film, there are close relationships for their quality with electrolysis water.In order to carry
The service life of high electrolytic water generating device, and water pollution is avoided, generally use platinum Ti electrode is as electrolytic water generating device
Anode.But platinum Ti electrode is expensive, this causes the production cost of electrolytic water generating device high, serious to restrict
Its popularization and application.
Based on this, some researchers begin look for the substitute of platinum Ti electrode.For example, application No. is
The Chinese patent application of 201120553451.X discloses a kind of device for tap water electrolytic separation, by amberplex,
Ti-alloy anode, stainless steel cathode, tank house, upper end cover, bottom end cover are constituted, and amberplex is mounted on Ti-alloy anode and not
It becomes rusty between steel cathode, Ti-alloy anode is mounted on the side of tank house, and stainless steel cathode is mounted on the other side of tank house, electrolysis
Room is fixed between upper end cover and bottom end cover.The patent document has ruthenium iridium metals layer in the surface burn-back of Ti-alloy anode, instead of
The platinum being electroplated on Ti-alloy anode, has saved cost, but its price is still higher.For another example, application No. is
201410818169.8 Chinese patent application discloses a kind of electrode for electrolysis, the electrode for electrolysis include conductive substrate and
Active coating, the conductive substrate be the base material comprising titanium or titanium alloy, the active coating include at least primer coating and
Face coat, the primer coating include titanium oxide, iridium oxide and ru oxide, and the face coat is aoxidized comprising iridium
The metal or oxide of one or both of object, ru oxide, titanium oxide and palladium, platinum element.The electricity of the patent document
Solution uses duplex coating with electrode, and compared to the signal layer coating for containing only ruthenium, iridium, titanium, electrode activity is more preferable, and the analysis of electrode
Chloride potential is low, and oxygen evolution potential is high, and the service life is longer for electrode, and electrolysis stability is more preferable.But still make in the patent document
It uses titanium or titanium alloy as base material, causes the cost of electrode still higher.
Therefore, at present there is an urgent need to a kind of electrode, production cost is relatively low, and stability in use is very good.
Invention content
One of the objects of the present invention is to provide a kind of preparation method of the electrode containing cerium, can process to obtain cost compared with
Low, the extraordinary electrode of stability in use.
It is another object of the present invention to provide a kind of electrodes containing cerium, can reduce production cost, and use
Stability is very good.
The inventor of the present application discovered that above-mentioned purpose may be implemented in following technical solution.
The present invention provides a kind of preparation method of the electrode containing cerium, and the preparation method includes the following steps：
(1) pre-treatment step of stainless steel substrate：
Stainless steel substrate is polished, carries out oil removing, then etch activates to obtain pretreating substrates in an acidic solution；
(2) forming step of nickel coating：
The electronickelling on the pretreating substrates, to form the electrode containing nickel coating；
(3) forming step of coating of titanium dioxide：
Coating of titanium dioxide is formed on the electrode containing nickel coating, to obtain the electrode containing coating of titanium dioxide；
(4) forming step of the platinum coating containing cerium：
It is anode using the electrode containing coating of titanium dioxide as cathode, platinum guaze, to include cerium compound and platinum chemical combination
The solution of object is electroplate liquid, the platinum coating containing cerium is formed on the electrode containing coating of titanium dioxide, to obtain containing cerium
Electrode.
Preparation method according to the present invention, it is preferable that in step (1), stainless steel substrate is used into 80~110 mesh
Sand paper polishing, by the stainless steel substrate after polishing at 30~45 DEG C with alkaline degreaser immersion carry out oil removing, then in acid
Property solution in etch activate and obtain pretreating substrates in 60~80 seconds；Wherein, the alkaline degreaser is containing 10~35g/L tricresyl phosphates
The aqueous solution of sodium and 5~13g/L sodium metasilicate；The acid solution includes 10~20wt% nitric acid, 30~40wt% hydrochloric acid and 45
~55wt% water.
Preparation method according to the present invention, it is preferable that in step (2), using the pretreating substrates as cathode,
Stainless steel is as anode, using the solution comprising nickel compound as electroplate liquid, the electronickelling on the pretreating substrates, to be formed
Electrode containing nickel coating.
Preparation method according to the present invention, it is preferable that the electroplate liquid in step (2) includes following component：
Plating conditions in step (2) are：Cathode-current density is 5~10A/dm2, electroplating temperature is 40~60 DEG C, and
Electroplating time 1~10 minute.
Preparation method according to the present invention, it is preferable that in step (3), the electrode containing nickel coating is placed in
In the mixed solution that ammonium hexa-fluorotitanate and boric acid are formed, takes out and dry after being impregnated 10~50 hours at 35~55 DEG C, then exist
It is heat-treated 50~80 minutes under inert gas shielding, at 500~700 DEG C, is obtained containing coating of titanium dioxide after natural cooling
Electrode；Wherein, a concentration of 0.2~0.35mol/L of ammonium hexa-fluorotitanate in the mixed solution and boric acid concentration be 0.2~
0.35mol/L。
Preparation method according to the present invention, it is preferable that in step (4), the cerium compound is selected from cerous sulfate, nitre
Sour cerium or cerium chloride；The platinum compounds is selected from two ammino platinum of dinitroso or chloroplatinic acid.
Preparation method according to the present invention, it is preferable that the electroplate liquid in step (4) includes following component：
Preparation method according to the present invention, it is preferable that the electroplate liquid in step (4) includes following component：
Preparation method according to the present invention, it is preferable that in step (4), cathode-current density is 1~3A/dm2,
Anode and cathode spacing is 0.6~1.5cm, and tank voltage is 2~5V, and the pH value of electroplate liquid is 9.5~11.5, and electroplating temperature is 80~95
DEG C and electroplating time be 10~50 hours.
The present invention also provides a kind of electrode containing cerium, the electrode includes stainless steel substrate, nickel coating, titanium dioxide painting
Layer and the platinum coating containing cerium；In stainless steel substrate outer surface, thickness is 5~25 microns for the nickel coating setting；Described
In nickel coating outer surface, thickness is 5~10 microns for coating of titanium dioxide setting；The platinum coating containing cerium is arranged in dioxy
Change titanium coating outer surface, thickness is 3~10 microns；Based on the total weight of the platinum coating containing cerium, the platinum coating containing cerium
Cerium containing 0.5~10wt%.
The base material of the present invention is stainless steel, cheap many relative to titanium or titanium alloy.The present invention is in stainless steel
The nickel coating with microcellular structure is formed outside base material, to promote the generation of nanometer titanium dioxide coating, and then improves electricity
The anticorrosive and oxidation resistance of pole.In addition, the present invention also forms platinum coating outside stainless steel substrate, and Ce elements are added,
It more ensure that the stability in use of electrode in this way, such as ensure during prolonged use Cr VI in stainless steel not
It can penetrate into electrolysis water.
Specific implementation mode
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
The electrode of the present invention is preferably electrode for electrolysis, and " electrode for electrolysis " indicates the electrode used in electrolysis process,
The electrode preferably used in electrolytic water generating device.
In the present invention, " stainless steel " indicates that erosion-resisting steel alloy can be supported in air or in chemical attack medium,
Including but not limited to martensitic stain less steel, ferritic stainless steels, austenitic stainless steels, martensitic stain less steel, iron element
Body-austenitic stainless steels.Chromium can be contained in the stainless steel of the present invention, content can be 12% or more.Other than chromium, this
The elements such as nickel, the molybdenum that steel can be made to be passivated can be added in the stainless steel of invention.
In the present invention, so-called " A is arranged in the outer surface of B ", is not that proper A is fully wrapped around by B, A, B
Between there may be relationships that is overlapped, intersecting, interpenetrate.
The preparation method of the electrode containing cerium of the present invention includes the following steps：(1) pre-treatment step of stainless steel substrate；
(2) forming step of nickel coating；(3) forming step of the forming step of coating of titanium dioxide and the platinum coating of (4) containing cerium.Below
It will be illustrated respectively.
<The pre-treatment step of stainless steel substrate>
The pre-treatment step of stainless steel substrate of the present invention includes：Stainless steel substrate is polished, oil removing is carried out, then in acid
Etch activates to obtain pretreating substrates in property solution.The bruting process of stainless steel substrate can be polished with sand paper, can also be used thin
Sand is polished.When polishing using sand paper, the sand paper of 80~110 mesh may be used, it is preferred to use the sand paper of 90~100 mesh.
Stainless steel substrate alkaline degreaser after polishing is impregnated to remove the oily matter on surface.Soaking temperature can be with
Control is at 30~45 DEG C, preferably 35~40 DEG C.Soaking time is not particularly limited, by the oiliness on stainless steel substrate surface
Substance removal is totally limited.The alkaline degreaser of the present invention can be containing 10~35g/L tertiary sodium phosphates and 5~13g/L sodium metasilicate
Aqueous solution, preferably contain 15~30g/L tertiary sodium phosphates and 6~11g/L sodium metasilicate aqueous solution, more preferably contain 20~25g/
The aqueous solution of L tertiary sodium phosphates and 8~10g/L sodium metasilicate.The present invention acid solution include 10~20wt% nitric acid, 30~
40wt% hydrochloric acid and 45~55wt% water preferably include 12~18wt% nitric acid, 32~38wt% hydrochloric acid and 46~52wt% water,
More preferably include 15~17wt% nitric acid, 33~35wt% hydrochloric acid and 49~51wt% water.Wherein, the weight percent of nitric acid
With HNO3It calculates, the weight percent of hydrochloric acid is calculated with HCl.A specific implementation mode according to the present invention, acid of the invention
Property solution is made of 10~20wt% nitric acid, 30~40wt% hydrochloric acid and 45~55wt% water.
By the stainless steel substrate after oil removal treatment, etch activates in an acidic solution, and etch activation temperature can be at room temperature
It carries out.Etch soak time can be controlled at 60~80 seconds, preferably 65~75 seconds.The purpose of etch activation is so that stainless
Steel surface is easy the quasi- solution for forming coating of titanium dioxide of attachment.
<The forming step of nickel coating>
The forming step of the nickel coating of the present invention is the electronickelling on above-mentioned pretreating substrates, to be formed containing nickel coating
Electrode.Specifically, using pretreating substrates as cathode, stainless steel (substrate or base material) is used as anode, to include nickel compound
Solution is electroplate liquid, the electronickelling on the pretreating substrates, to form the electrode containing nickel coating.The present invention is in stainless base steel
The nickel coating with microcellular structure is formed outside material, to promote the generation of nanometer titanium dioxide coating, and then improves electrode
Anticorrosive and oxidation resistance.
" solution " of the present invention indicates the mixture that plated material is formed with solvent.The solvent of the present invention can be water.Electricity
Nickel plating can use electroplate liquid those of known in the art.Preferably, the electroplate liquid in the step may include following component：
A preferred embodiment according to the present invention, the electroplate liquid in the step are made of said components.
As further preferred embodiment, the electroplate liquid in the step may include following component：
A preferred embodiment according to the present invention, the electroplate liquid in the step are made of said components.
Embodiment more preferably, the electroplate liquid in the step may include following component：
A preferred embodiment according to the present invention, the electroplate liquid in the step are made of said components.
In the present invention, include plated material nickel sulfate in electroplate liquid, can be added in a manner of seven water nickel sulfates
Add.The sodium alkyl sulfate of the present invention can be selected from sodium hexadecyl sulfate, sodium tetradecyl sulfate, lauryl sodium sulfate, just
Sodium decyl sulfate, n-octyl sodium sulphate etc.；Preferably lauryl sodium sulfate or n-octyl sodium sulphate.
In the present invention, the plating conditions of the step are：Cathode-current density is 5~10A/dm2, preferably 6~8A/
dm2；Electroplating temperature is 40~60 DEG C, preferably 50~55 DEG C；Electroplating time 1~10 minute, preferably 2~5 minutes.
<The forming step of coating of titanium dioxide>
The forming step of coating of titanium dioxide of the present invention includes：The shape on the electrode containing nickel coating that above-mentioned steps obtain
At coating of titanium dioxide, to obtain the electrode containing coating of titanium dioxide.In the present invention, intend forming the molten of coating of titanium dioxide
The specific example of liquid is ammonium hexa-fluorotitanate and the mixed solution that boric acid is formed, but the present invention is not limited thereto.With it is above-mentioned mix it is molten
The similar solution that can form coating of titanium dioxide of liquid also belongs to the scope of the present invention.
According to embodiment of the present invention, the electrode containing nickel coating is placed in ammonium hexa-fluorotitanate and boric acid is formed
Mixed solution in, take out and dry after being impregnated 10~50 hours at 35~55 DEG C, then under inert gas protection, 500
It is heat-treated 50~80 minutes at~700 DEG C, the electrode containing coating of titanium dioxide is obtained after natural cooling.
In the present invention, hexafluorotitanic acid ammonium concentration can be 0.2~0.35mol/L, preferably 0.25~0.3mol/L；Boron
Acid concentration can be 0.2~0.35mol/L, preferably 0.25~0.3mol/L.In the present invention, soaking temperature be preferably 38~
52 DEG C, more preferably 40~45 DEG C；Soaking time is preferably 15~30 hours, more preferably 20~25 hours.
In order to ensure that coating of titanium dioxide is evenly distributed on the nickel coating of stainless steel substrate, above-mentioned heat treatment can be lazy
It is carried out under property gas shield.Inert gas can be selected from nitrogen, argon gas and helium etc..The temperature of heat treatment is preferably 550~650
DEG C, more preferably 580~600 DEG C；Heat treatment time is preferably 55~75 minutes, more preferably 60~70 minutes.
By the stainless steel substrate cooled to room temperature after heat treatment, the electrode containing coating of titanium dioxide is obtained.Such
The more dense uniform containing coating of titanium dioxide arrived.
<The forming step of platinum coating containing cerium>
The forming step of the platinum coating containing cerium of the present invention includes：The electricity containing coating of titanium dioxide that above-mentioned steps are obtained
Pole is anode as cathode, platinum guaze, using the solution comprising cerium compound and platinum compounds as electroplate liquid, contains titanium dioxide described
The platinum coating containing cerium is formed on the electrode of coating, to obtain the electrode containing cerium.
The electroplate liquid of the present invention is the solution comprising cerium compound and platinum compounds." solution " of the present invention indicates plating material
The mixture that material is formed with solvent.The solvent of the present invention can be water.Above-mentioned cerium compound is water-soluble cerium salt, can be selected from
Cerous sulfate, cerous nitrate or cerium chloride, preferably cerous sulfate.Above-mentioned platinum compounds is water-soluble platinum salt, can be selected from two nitrous
Two ammino platinum (NH of base3)2Pt(NO2)2·H2O, chloroplatinic acid H2PtCl6·6H2O etc., preferably two ammino platinum of dinitroso.
A specific implementation mode according to the present invention, the electroplate liquid include following component：
Specific implementation mode according to another preferred, the electroplate liquid are grouped as by following group：
According to the preferred embodiments of the disclosure, the electroplate liquid includes following component：
Preferred embodiment according to another preferred, the electroplate liquid are made of said components.
According to the further preferred specific implementation mode of the present invention, the electroplate liquid includes following component：
Specific implementation mode further preferred according to another preferred, the electroplate liquid is by said components group
At.
The forming step of the platinum coating containing cerium of the present invention can carry out in the electroplating device of this field routine, here not
It repeats again.In the forming step of the platinum coating containing cerium of the present invention, cathode-current density can be 1~3A/dm2, preferably 1.5
~2A/dm2；Anode and cathode spacing can be 0.6~1.5cm, preferably 0.8~1.0cm；Tank voltage can be 2~5V, be preferably
3~3.5V；The pH value of electroplate liquid can be 9.5~11.5, preferably 10~11；Electroplating temperature is 80~95 DEG C, is preferably 85
~90 DEG C；Electroplating time can be 10~50 hours, preferably 20~30 hours.
<Electrode>
The electrode of the present invention includes stainless steel substrate, nickel coating, coating of titanium dioxide and the platinum coating containing cerium.In the present invention
In, in stainless steel substrate outer surface, thickness is 5~25 microns, preferably 10~20 microns for nickel coating setting.It is described
Coating of titanium dioxide setting in nickel coating outer surface, thickness is 5~10 microns, preferably 6~8 microns.Described contains cerium
The setting of platinum coating in coating of titanium dioxide outer surface, thickness is 3~10 microns, preferably 5~8 microns, more preferably 5.5
~7.5 microns.In the present invention, the total weight based on the platinum coating containing cerium, the platinum coating containing cerium contains 0.5~
10wt%, preferably 1~8wt%, the more preferably cerium of 3~6wt%.Present inventor is it was unexpectedly observed that stainless base steel
Increase nickel coating and coating of titanium dioxide on material, and increase a certain amount of Ce elements in platinum coating, can more significantly increase
Add the stability in use of stainless steel substrate so that main material is the application of electrode of stainless steel becomes existing in electrolytic water generating device
It is real.
<The measurement of content of 6-valence Cr ions in water>
(1) content of 6-valence Cr ions in the diphenyl carbazide spectrophotometry detection water of GB7467-1987 is used；
(2) content of 6-valence Cr ions in water with ion chromatography is used, specific steps are referring to " ion-chromatographic determination is drunk
Cr VI in water ", Hu Zhongyang etc., the 14th national ion chromatography symposium collection of thesis, on September 17th, 2012.
Embodiment 1
(1) pre-treatment step of stainless steel substrate：
Stainless steel substrate is polished using the sand paper of 90 mesh, the stainless steel substrate after polishing is used into alkaline degreasing at 35 DEG C
Agent, which is impregnated, carries out oil removing.Alkaline degreaser is the aqueous solution of tertiary sodium phosphate containing 22g/L and 9g/L sodium metasilicate.It will be stainless after oil removing
Steel substrate obtains pretreating substrates after etch activates 70 seconds in an acidic solution.Acid solution is 17wt% nitric acid, 33wt% salt
The solution that acid and 50wt% water are formed.
(2) forming step of nickel coating
Using the pretreating substrates as cathode, stainless steel substrate is as anode, using following solution as electroplate liquid, described
Electronickelling on pretreating substrates, to form the electrode containing nickel coating：
Plating conditions are：Cathode-current density is 8A/dm2, electroplating temperature is 50 DEG C, electroplating time 2 minutes.
(3) forming step of coating of titanium dioxide：
By the mixing that the electrode containing nickel coating is placed in 0.25mol/L ammonium hexa-fluorotitanates and 0.25mol/L boric acid is formed
It in solution, takes out and dries after being impregnated 25 hours at 40 DEG C, be then heat-treated 60 minutes under nitrogen protection, at 600 DEG C, from
So the electrode containing coating of titanium dioxide is obtained after cooling.
(4) forming step of the platinum coating containing cerium：
It is anode using the electrode containing coating of titanium dioxide as cathode, platinum guaze, using following solution as electroplate liquid, containing dioxy
Change and forms the platinum coating containing cerium on the electrode of titanium coating：
Plating conditions are as follows：Cathode-current density is 2A/dm2, anode and cathode spacing be 1cm, tank voltage 3V, electroplate liquid
PH value is 10, and electroplating temperature is 85 DEG C and electroplating time is 20 hours.
Electrode A 1 is prepared by embodiment 1.The electrode is by stainless steel substrate, nickel coating, coating of titanium dioxide and contains
The platinum coating of cerium forms.After testing, the thickness of nickel coating is 25 microns, and the thickness of coating of titanium dioxide is 7 microns, the platinum containing cerium
The thickness of coating is 6 microns, wherein the cerium containing 5wt%.
Disclosed in application No. is the Chinese patent literature of 201120553451.X (Authorization Notice No. CN202440350U)
Electrolytic Water Experiment is carried out on electrolytic water generating device (Ti-alloy anode is replaced using electrode A 1；Voltage is 5.2V, electric current 25A,
Water source is tap water).Using the content of 6-valence Cr ions in diphenyl carbazide spectrophotometry and water with ion chromatography.It is holding
After continuous electrolysis water carries out 2000 hours, Cr VI is still not detected in the water of generation.
Embodiment 2
The cerous sulfate dosage of embodiment 1 is replaced with into 1.8g/L by 2.0g/L, remaining condition is same as Example 1, prepares
Obtain electrode A 2.The electrode is made of stainless steel substrate, nickel coating, coating of titanium dioxide and platinum coating containing cerium.After testing, nickel
The thickness of coating is 25 microns, and the thickness of coating of titanium dioxide is 7 microns, and the thickness of the platinum coating containing cerium is 6 microns, wherein containing
There is the cerium of 4.5wt%.
Disclosed in application No. is the Chinese patent literature of 201120553451.X (Authorization Notice No. CN202440350U)
Electrolytic Water Experiment is carried out on electrolytic water generating device (Ti-alloy anode is replaced using electrode A 2；Voltage is 5.2V, electric current 25A,
Water source is tap water).Using the content of 6-valence Cr ions in diphenyl carbazide spectrophotometry and water with ion chromatography.It is holding
After continuous electrolysis water carries out 2000 hours, Cr VI is still not detected in the water of generation.
Embodiment 3
By the hexafluorotitanic acid ammonium concentration of embodiment 1 replaces with 0.2mol/L, boric acid concentration replaces with 0.2mol/L, remaining
Part is same as Example 1, and electrode A 3 is prepared.The electrode is by stainless steel substrate, nickel coating, coating of titanium dioxide and containing cerium
Platinum coating forms.After testing, the thickness of nickel coating is 25 microns, and the thickness of coating of titanium dioxide is 6 microns, the platinum coating containing cerium
Thickness be 6 microns, wherein the cerium containing 5wt%.
Disclosed in application No. is the Chinese patent literature of 201120553451.X (Authorization Notice No. CN202440350U)
Electrolytic Water Experiment is carried out on electrolytic water generating device (Ti-alloy anode is replaced using electrode A 3；Voltage is 5.2V, electric current 25A,
Water source is tap water).Using the content of 6-valence Cr ions in diphenyl carbazide spectrophotometry and water with ion chromatography.It is holding
After continuous electrolysis water carries out 2000 hours, Cr VI is still not detected in the water of generation.
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (2)
1. a kind of preparation method of the electrode containing cerium, which is characterized in that the preparation method includes the following steps：
(1) pre-treatment step of stainless steel substrate：
Stainless steel substrate is polished using the sand paper of 80~110 mesh, the stainless steel substrate after polishing is used into alkali at 30~45 DEG C
Property degreaser impregnate and carry out oil removing, then etch activates and obtains pretreating substrates in 60~80 seconds in an acidic solution；Wherein, described
Alkaline degreaser is the aqueous solution containing 10~35g/L tertiary sodium phosphates and 5~13g/L sodium metasilicate；The acid solution include 10~
20wt% nitric acid, 30~40wt% hydrochloric acid and 45~55wt% water；
(2) forming step of nickel coating：
Using the pretreating substrates as cathode, stainless steel is as anode, using the solution comprising nickel compound as electroplate liquid, in institute
Electronickelling on pretreating substrates is stated, to form the electrode containing nickel coating；Electroplate liquid in step (2) includes following component：
Plating conditions in step (2) are：Cathode-current density is 5~10A/dm2, electroplating temperature is 40~60 DEG C, and when plating
Between 1~10 minute；
(3) forming step of coating of titanium dioxide：
The electrode containing nickel coating is placed in the mixed solution of ammonium hexa-fluorotitanate and boric acid formation, is impregnated at 35~55 DEG C
It takes out and dries after 20~25 hours, be then heat-treated 60~70 minutes under inert gas protection, at 580~600 DEG C, it is natural
The electrode containing coating of titanium dioxide is obtained after cooling；Wherein, the ammonium hexa-fluorotitanate a concentration of 0.2 in the mixed solution~
0.35mol/L and boric acid concentration are 0.2~0.35mol/L；
(4) forming step of the platinum coating containing cerium：
Using the electrode containing coating of titanium dioxide as cathode, platinum guaze it is anode, with comprising cerium compound and platinum compounds
Solution is electroplate liquid, the platinum coating containing cerium is formed on the electrode containing coating of titanium dioxide, to obtain the electrode containing cerium；
Electroplate liquid in step (4) includes following component：
In step (4), cathode-current density is 1~3A/dm2, anode and cathode spacing is 0.6~1.5cm, and tank voltage is 2~5V,
The pH value of electroplate liquid is 9.5~11.5, and electroplating temperature is 80~95 DEG C and electroplating time is 10~50 hours.
2. according to the method described in claim 1, it is characterized in that, the setting of the described nickel coating in stainless steel substrate outer surface,
Its thickness is 5~25 microns；In nickel coating outer surface, thickness is 5~10 microns for the coating of titanium dioxide setting；It is described
The platinum coating setting containing cerium in coating of titanium dioxide outer surface, thickness is 3~10 microns；Based on the total of the platinum coating containing cerium
Weight, the platinum coating containing cerium contain the cerium of 0.5~10wt%.
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