CN109536990A - A kind of flat thin-film electro catalyst operation electrode and its preparation method and application - Google Patents

A kind of flat thin-film electro catalyst operation electrode and its preparation method and application Download PDF

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Publication number
CN109536990A
CN109536990A CN201811194350.0A CN201811194350A CN109536990A CN 109536990 A CN109536990 A CN 109536990A CN 201811194350 A CN201811194350 A CN 201811194350A CN 109536990 A CN109536990 A CN 109536990A
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flat thin
film electro
catalyst operation
operation electrode
electro catalyst
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陈燕
朱云敏
刘茜
刘江
刘美林
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South China University of Technology SCUT
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South China University of Technology SCUT
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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
    • 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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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C23C14/042—Coating on selected surface areas, e.g. using masks using masks
    • 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
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • 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
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 belongs to electrocatalysis material technical field, a kind of flat thin-film electro catalyst operation electrode and its preparation method and application is disclosed.The flat thin-film electro catalyst operation electrode includes the catalytically-active materials layer on quartzy polycrystalline wafers substrate and substrate；An at least deblocking reaction region is reserved on the catalytically-active materials layer, the part on catalytically-active materials layer in addition to conversion zone covers golden collector, golden collector external wire.The response area and shape of flat thin-film electro catalyst operation electrode of the invention can arbitrarily regulate and control, and the oxygen at 1~2V is precipitated stability and is very significantly improved, and long service life, durability is good, and application prospect is good.

Description

A kind of flat thin-film electro catalyst operation electrode and its preparation method and application
Technical field
The invention belongs to electrocatalysis material technical fields, and in particular to a kind of flat thin-film electro catalyst operation electrode and its Preparation method and application.
Background technique
Currently, hydrogen feed has very big potential in the selection of new energy conversion equipment raw material.The ratio of Hydrogen Energy equipment Energy is high, has a safety feature, and because absolutely not pollution generates in conversion process of energy for it, as new energy conversion equipment With vast potential for future development.Currently, the optimal method of hydrogen preparation is electrolysis water.With advances in technology and market It continues to develop, the efficiency for promoting electrolysis water increasingly seems important and urgent.Therefore a set of perfect electrolysis wetting system is to grind at present The emphasis studied carefully works to existing electro-catalysis electric other than promoting energy consumption of the catalytic activity of electrode to realize electrolysis water The modification of pole one of research direction popular compared with optimization is also, is mainly imitated by effective catalysis of raising system electrolysis water The stability of rate and electrolysis system.
Presently found effective oxygen-separating catalyst: (1) noble heavy metal oxide, such as IrO2And RuO2Deng；(2) there is gold Belong to the perovskite material of doping: Ca1.5Sr0.5Co1.5Fe0.5O5+α, La0.7Sr0.3CoO3And PrBa0.5Sr0.5Co1.5Fe0.5O5+αDeng； (3) metal oxide, such as Co3O4With NiO etc..Due to noble metal, the catalytic activity of double perovskite materials and metal oxide is strong, Relatively easy, especially metal oxide is prepared, for double perovskite materials there are also long catalytic life, low toxicity and abundant raw material etc. are excellent Point is that one of material is precipitated in the oxygen of electrolysis water first choice.
But noble metal is being prepared, while electrode is precipitated in metal oxide and double perovskite materials catalysis oxygen, oxygen is precipitated The performance of working electrode is there is still a need for further increasing, on the one hand the reason is that the conductivity of above-mentioned catalyst is lower, one side reason It is the service life of working electrode, is on the other hand then the matching problem of catalyst and working electrode.Conventional commercial electrolyte The pernicious reactions such as liquid is alkalinity, and electrolyte itself can also promote electro-catalysis working electrode to damage simultaneously, and collector destroys, thus shadow Ring the catalytic activity of catalyst and the service life of working electrode.
Conventional electro-catalysis working electrode is to use glass carbon plate as supported active material substrate, but this kind of working electrode Plane is easy to damage, and smooth or special shape glass carbon plate is expensive；In addition a kind of common electro-catalysis working electrode is to make With carbon cloth, carbon paper, metal nickel screen etc. is used as supported active material substrate, but this kind of working electrode stability and mechanical strength compared with Difference.
Therefore develop that a kind of preparation process is simple, the good flat thin-film electro catalyst operation electrode of stability is extremely urgent.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of plate Formula thin-film electro catalyst operation electrode.
Another object of the present invention is to provide the preparation methods of above-mentioned flat thin-film electro catalyst operation electrode.
A further object of the present invention is to provide application of the above-mentioned flat thin-film electro catalyst operation electrode in electrolysis water.
The object of the invention is achieved through the following technical solutions:
A kind of flat thin-film electro catalyst operation electrode, including the catalytic activity material on quartzy polycrystalline wafers substrate and substrate The bed of material；An at least deblocking reaction region is reserved on the catalytically-active materials layer, on catalytically-active materials layer in addition to conversion zone Part cover golden collector, golden collector external wire.
Further, the catalytically-active materials refer to La0.7Sr0.3CoO3Or PrBa0.5Sr0.5Co1.5Fe0.5O5+αMaterial, Wherein α value range is 0~1.
Further, the size of the quartzy polycrystalline wafers substrate is 2.5*2.5*0.5mm~20*20*0.5mm； The gross area of the conversion zone is 1.25*1.25mm~10*5mm.
Further, the conducting wire refers to silver wire.
Further, part of the quartzy polycrystalline wafers substrate in addition to conversion zone coats waterproof coating.
Further, the conducting wire is encapsulated using closed casing.
The preparation method of above-mentioned flat thin-film electro catalyst operation electrode, includes the following steps:
(1) catalytically-active materials layer is prepared by the method that pulse laser deposits on quartzy polycrystalline wafers substrate；
(2) an at least deblocking reaction region is reserved obtained by the step (1) on catalytically-active materials layer, on catalytically-active materials layer Part in addition to conversion zone prepares golden collector by ion sputtering；
(3) by the golden collector partial circumscription conducting wire of step (2), the flat thin-film electro catalyst operation electrode is obtained.
Further, the time of ion sputtering described in step (2) is 100~500s.
Further, part of the flat thin-film electro catalyst operation electrode surface in addition to conversion zone coats waterproof Coating carries out water-proofing treatment, and the material of the waterproof coating is epoxide-resin glue, PVC-U adhesive or neutral silicone weather-resistant glue.
Application of the above-mentioned flat thin-film electro catalyst operation electrode in electrolysis water.
Compared with the existing technology, flat thin-film electro catalyst operation electrode of the invention has the following advantages that and beneficial to effect Fruit:
(1) response area of flat thin-film electro catalyst operation electrode of the invention and shape can arbitrarily regulate and control, and can make Flat thin-film electro catalyst operation electrode is preferably applied in practice.
(2) present invention improves the service life of flat thin-film electro catalyst operation electrode, and durability is good, is embodied in Flat thin-film electro catalyst operation electrode is just swept after carrying out macrocyclic oxygen and cyclic voltammetry is precipitated, negative to sweep cyclic voltammetric The almost coincidence of figure curve.
(3) the oxygen analysis of flat thin-film electro catalyst operation electrode of the invention under 1~2V (relative to reversible hydrogen electrode) Stability is very significantly improved out, and after testing 1000 circle cyclic voltammetries, cyclic voltammetry curve has almost no change.
(4) present invention improves the current-responsive of flat thin-film electro catalyst operation electrode, is embodied in flat thin For film electro-catalysis working electrode after the optimization for carrying out work area, the current-responsive maximum value of cyclic voltammogram curve is available It improves.
(5) flat thin-film electro catalyst operation electrode preparation cost of the invention is low and preparation process is relatively easy, unanimously Property is good.
(6) flat thin-film electro catalyst operation electrode of the invention can be adapted for most of oxide catalyst activity material Material, it is widely applicable.
Detailed description of the invention
Fig. 1 be in Examples 1 to 3 the shape assumption diagram of the flat thin-film electro catalyst operation electrode of gained and conversion zone and The structural schematic diagram of golden collector.
Fig. 2 is that the flat thin-film electro catalyst operation electrode of gained carries out stability test is precipitated in oxygen the in Examples 1 to 3 2 circle cyclic voltammetry curve figures.
Fig. 3 is that the flat thin-film electro catalyst operation electrode of gained carries out the 2nd circle that stability test is precipitated in oxygen in embodiment 3 (solid line) and the cyclic voltammetry curve figure after 1000 circles (dotted line) is recycled.
Fig. 4 is that the flat thin-film electro catalyst operation electrode of gained carries out the 2nd circle that stability test is precipitated in oxygen in embodiment 4 (solid line) and the cyclic voltammetry curve figure after 200 circles (dotted line) is recycled.
Fig. 5 is that the flat thin-film electro catalyst operation electrode of gained carries out the 2nd circle that stability test is precipitated in oxygen in embodiment 5 (solid line) and the cyclic voltammetry curve figure after 200 circles (dotted line) is recycled.
Fig. 6 is that the flat thin-film electro catalyst operation electrode of gained carries out the 2nd circle that stability test is precipitated in oxygen in embodiment 6 (solid line) and the cyclic voltammetry curve figure after 200 circles (dotted line) is recycled.
Fig. 7 is that the flat thin-film electro catalyst operation electrode of gained carries out the 2nd circle that stability test is precipitated in oxygen in embodiment 7 (solid line) and the cyclic voltammetry curve figure after 200 circles (dotted line) is recycled.
Fig. 8 is that the flat thin-film electro catalyst operation electrode of gained carries out the 2nd circle that stability test is precipitated in oxygen in embodiment 8 (solid line) and the cyclic voltammetry curve figure after 200 circles (dotted line) is recycled.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited In this.
Embodiment 1
(1) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in 10*10* Catalytically-active materials layer is prepared in the quartz substrate of 0.5mm；
(2) step (1) preparation catalytically-active materials layer on reserve 10*5mm conversion zone, remaining area gold from Golden collector (sputtering time 320s) is prepared on sub- sputter；
(3) afflux body portion golden in step (2) is connect with silver wire, then coats the part for removing conversion zone on substrate Epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains the flat film electro-catalysis work of the present embodiment Make electrode.
The shape assumption diagram of flat thin-film electro catalyst operation electrode and conversion zone obtained by the present embodiment and golden collector Structural schematic diagram as shown in figure 1 shown in (a).
Flat thin-film electro catalyst operation electrode obtained by the present embodiment carries out oxygen and stability test is precipitated, and oxygen is precipitated activity and surveys Strip part: with 1mol L-1The electrolyte that KOH is precipitated as oxygen is passed through high pure oxygen to electrolyte oxygen saturation, and experimental temperature is room 25 DEG C of temperature is tested as three-electrode system, and platinum filament is to electrode, and the purity of platinum is higher than 99.999%, and saturation Ag/AgCl is reference electricity Pole, flat thin-film electro catalyst operation electrode are working electrode, and test equipment is morning China 660.The flat film electro-catalysis of gained In the 2nd circle cyclic voltammetry curve such as Fig. 2 of working electrode shown in (a).
Embodiment 2
(1) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in 10*10* Catalytically-active materials layer is prepared in the quartz substrate of 0.5mm；
(2) step (1) preparation catalytically-active materials layer on reserve 5*5mm conversion zone, remaining area gold from Golden collector (sputtering time 320s) is prepared on sub- sputter；
(3) afflux body portion golden in step (2) is connect with silver wire, then coats the part for removing conversion zone on substrate Epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains the flat film electro-catalysis work of the present embodiment Make electrode.
The shape assumption diagram of flat thin-film electro catalyst operation electrode and conversion zone obtained by the present embodiment and golden collector Structural schematic diagram as shown in figure 1 shown in (b).
Flat thin-film electro catalyst operation electrode obtained by the present embodiment carries out oxygen and stability test is precipitated, and test process is the same as real Apply example 1.In the 2nd circle cyclic voltammetry curve such as Fig. 2 of the flat thin-film electro catalyst operation electrode of gained shown in (b).
Embodiment 3
(1) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in 10*10* Catalytically-active materials layer is prepared in the quartz substrate of 0.5mm；
(2) conversion zone of 2.5*2.5mm is reserved on the catalytically-active materials layer of step (1) preparation, remaining area exists Golden collector (sputtering time 320s) is prepared on gold ion sputter；
(3) afflux body portion golden in step (2) is connect with silver wire, then coats the part for removing conversion zone on substrate Epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains the flat film electro-catalysis work of the present embodiment Make electrode.
The shape assumption diagram of flat thin-film electro catalyst operation electrode and conversion zone obtained by the present embodiment and golden collector Structural schematic diagram as shown in figure 1 shown in (c).
Flat thin-film electro catalyst operation electrode obtained by the present embodiment carries out oxygen and stability test is precipitated, and test process is the same as real Apply example 1.In the 2nd circle cyclic voltammetry curve such as Fig. 2 of the flat thin-film electro catalyst operation electrode of gained shown in (c).Gained plate The 2nd of formula thin-film electro catalyst operation electrode encloses (solid line) and has recycled the cyclic voltammetric after 1000 circle (dotted line) cyclic voltammetries Curve comparison figure is as shown in Figure 3.
By Fig. 2 the results show that work area is in the flat thin-film electro catalyst operation electrode of different work areas Electric current maximum is precipitated in the oxygen of 2.5*2.5mm, can most show that catalytic performance is precipitated in the oxygen of thin-film material.By Fig. 3 the results show that system Standby flat thin-film electro catalyst operation electrode has splendid stability, after testing 1000 circle cyclic voltammetries, circulation Volt-ampere curve has almost no change.
Embodiment 4
(1) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in 10*10* Catalytically-active materials layer is prepared in the quartz substrate of 0.5mm；
(2) step (1) preparation catalytically-active materials layer on reserve 5*5mm conversion zone, remaining area gold from Golden collector (sputtering time 320s) is prepared on sub- sputter；
(3) afflux body portion golden in step (2) is connect with silver wire, then coats the part for removing conversion zone on substrate PVC-U adhesive, air drying are fully cured to glue for 24 hours, obtain the flat thin-film electro catalyst operation electrode of the present embodiment.
Flat thin-film electro catalyst operation electrode obtained by the present embodiment carries out oxygen and stability test is precipitated, and test process is the same as real Apply example 1.Test results are shown in figure 4.Solid line corresponds to the 2nd circle cyclic voltammetric song of flat thin-film electro catalyst operation electrode in figure Line chart, the corresponding cyclic voltammetry curve figure recycled after 200 circle cyclic voltammetries of dotted line.
Embodiment 5
(1) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in 10*10* Catalytically-active materials layer is prepared in the quartz substrate of 0.5mm；
(2) step (1) preparation catalytically-active materials layer on reserve 5*5mm conversion zone, remaining area gold from Golden collector (sputtering time 320s) is prepared on sub- sputter；
(3) afflux body portion golden in step (2) is connect with silver wire, then coats the part for removing conversion zone on substrate 793 neutral silicone weather-resistant glues, air drying are fully cured to glue for 24 hours, obtain the flat film electro-catalysis work of the present embodiment Make electrode.
Flat thin-film electro catalyst operation electrode obtained by the present embodiment carries out oxygen and stability test is precipitated, and test process is the same as real Apply example 1.Test results are shown in figure 5.Solid line corresponds to the 2nd circle cyclic voltammetric song of flat thin-film electro catalyst operation electrode in figure Line chart, the corresponding cyclic voltammetry curve figure recycled after 200 circle cyclic voltammetries of dotted line.
Embodiment 6
(1) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in 10*10* Catalytically-active materials layer is prepared in the quartz substrate of 0.5mm；
(2) step (1) preparation catalytically-active materials layer on reserve 5*5mm conversion zone, remaining area gold from Golden collector (sputtering time 320s) is prepared on sub- sputter；
(3) afflux body portion golden in step (2) is connect with silver wire, then coats the part for removing conversion zone on substrate Epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains the flat film electro-catalysis work of the present embodiment Make electrode.
Flat thin-film electro catalyst operation electrode obtained by the present embodiment carries out oxygen and stability test is precipitated, and test process is the same as real Apply example 1.Test results are shown in figure 6.Solid line corresponds to the 2nd circle cyclic voltammetric song of flat thin-film electro catalyst operation electrode in figure Line chart, the corresponding cyclic voltammetry curve figure recycled after 200 circle cyclic voltammetries of dotted line.
In conjunction with Fig. 4~6, available following conclusion: different waterproof glues is applied, identical work area has close Electrochemical behavior, the flat thin-film electro catalyst operation of different waterproof layers electricity different to the electro-catalysis stability of electrode Stability is precipitated most in the oxygen of flat thin-film electro catalyst operation electrode of the extremely middle epoxide-resin glue (E-44AB) as waterproof coating Greatly.
Embodiment 7
(1) by catalytically-active materials La0.7Sr0.3CoO3By pulse laser sediment method 10*10*0.5mm quartz Catalytically-active materials layer is prepared on substrate；
(2) step (1) preparation catalytically-active materials layer on reserve 5*5mm conversion zone, remaining area gold from Golden collector (sputtering time 320s) is prepared on sub- sputter；
(3) afflux body portion golden in step (2) is connect with silver wire, then coats the part for removing conversion zone on substrate Epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains the flat film electro-catalysis work of the present embodiment Make electrode.
Flat thin-film electro catalyst operation electrode obtained by the present embodiment carries out oxygen and stability test is precipitated, and test process is the same as real Apply example 1.Test results are shown in figure 7.Solid line corresponds to the 2nd circle cyclic voltammetric song of flat thin-film electro catalyst operation electrode in figure Line chart, the corresponding cyclic voltammetry curve figure recycled after 200 circle cyclic voltammetries of dotted line.
Embodiment 8
(1) by catalytically-active materials La0.7Sr0.3CoO3By pulse laser sediment method 10*10*0.5mm quartz Catalytically-active materials layer is prepared on substrate；
(2) conversion zone of 2.5*2.5mm is reserved on the catalytically-active materials layer of step (1) preparation, remaining area exists Golden collector (sputtering time 320s) is prepared on gold ion sputter；
(3) afflux body portion golden in step (2) is connect with silver wire, then coats the part for removing conversion zone on substrate Epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains the flat film electro-catalysis work of the present embodiment Make electrode.
Flat thin-film electro catalyst operation electrode obtained by the present embodiment carries out oxygen and stability test is precipitated, and test process is the same as real Apply example 1.Test results are shown in figure 8.Solid line corresponds to the 2nd circle cyclic voltammetric song of flat thin-film electro catalyst operation electrode in figure Line chart, the corresponding cyclic voltammetry curve figure recycled after 200 circle cyclic voltammetries of dotted line.
In conjunction with Fig. 6~8 the results show that flat thin-film electro catalyst operation electrode prepared by the present invention has wider be applicable in Range is suitable for most of oxide catalyst active material.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of flat thin-film electro catalyst operation electrode, it is characterised in that: the flat thin-film electro catalyst operation electrode packet Include the catalytically-active materials layer on quartzy polycrystalline wafers substrate and substrate；At least one piece is reserved on the catalytically-active materials layer instead Answer region, the part on catalytically-active materials layer in addition to conversion zone covers golden collector, golden collector external wire.
2. a kind of flat thin-film electro catalyst operation electrode according to claim 1, it is characterised in that: the catalytic activity Material refers to La0.7Sr0.3CoO3Or PrBa0.5Sr0.5Co1.5Fe0.5O5+αMaterial, wherein α value range is 0~1.
3. a kind of flat thin-film electro catalyst operation electrode according to claim 1, it is characterised in that: the quartz polycrystalline The size of wafer substrates is 2.5*2.5*0.5mm~20*20*0.5mm；The gross area of the conversion zone is 1.25* 1.25mm~10*5mm.
4. a kind of flat thin-film electro catalyst operation electrode according to claim 1, it is characterised in that: the conducting wire refers to Silver wire.
5. a kind of flat thin-film electro catalyst operation electrode according to claim 1, it is characterised in that: the quartz polycrystalline Part of the wafer substrates in addition to conversion zone coats waterproof coating.
6. a kind of flat thin-film electro catalyst operation electrode according to claim 1, it is characterised in that: the conducting wire uses Closed casing encapsulation.
7. a kind of described in any item preparation methods of flat thin-film electro catalyst operation electrode of claim 1~6, feature exist In including the following steps:
(1) catalytically-active materials layer is prepared by the method that pulse laser deposits on quartzy polycrystalline wafers substrate；
(2) an at least deblocking reaction region is reserved on the catalytically-active materials layer obtained by step (1), is removed on catalytically-active materials layer anti- The part except region is answered to prepare golden collector by ion sputtering；
(3) by the golden collector partial circumscription conducting wire of step (2), the flat thin-film electro catalyst operation electrode is obtained.
8. a kind of preparation method of flat thin-film electro catalyst operation electrode according to claim 7, it is characterised in that: step Suddenly the time of ion sputtering described in (2) is 100~500s.
9. a kind of preparation method of flat thin-film electro catalyst operation electrode according to claim 7, it is characterised in that: institute It states part coating waterproof coating of the flat thin-film electro catalyst operation electrode surface in addition to conversion zone and carries out water-proofing treatment, institute The material for stating waterproof coating is epoxide-resin glue, PVC-U adhesive or neutral silicone weather-resistant glue.
10. application of the described in any item flat thin-film electro catalyst operation electrodes of claim 1~6 in electrolysis water.
CN201811194350.0A 2018-10-15 2018-10-15 A kind of flat thin-film electro catalyst operation electrode and its preparation method and application Pending CN109536990A (en)

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Application publication date: 20190329