CN110144599A - Membrane electrode and its preparation method and application is precipitated in a kind of efficient oxygen - Google Patents

Membrane electrode and its preparation method and application is precipitated in a kind of efficient oxygen Download PDF

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CN110144599A
CN110144599A CN201910422985.XA CN201910422985A CN110144599A CN 110144599 A CN110144599 A CN 110144599A CN 201910422985 A CN201910422985 A CN 201910422985A CN 110144599 A CN110144599 A CN 110144599A
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precipitated
membrane electrode
oxygen
prba
film
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陈燕
朱云敏
李菲
刘茜
朱惠钦
陈惠君
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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    • 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
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    • 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
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
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    • 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
    • C23C14/58—After-treatment
    • C23C14/5826—Treatment with charged particles
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
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    • C25B1/04—Hydrogen or oxygen by electrolysis of water
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    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • C25B11/0773—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide of the perovskite type
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8867—Vapour deposition
    • H01M4/8871—Sputtering
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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    • 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
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    • Y02E60/30—Hydrogen technology
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Abstract

The invention belongs to electrode material field, discloses a kind of efficient oxygen and membrane electrode and its preparation method and application is precipitated.The preparation method is that: golden collector is prepared by ion sputtering in the zirconia substrate of monocrystalline stabilized with yttrium oxide, PrBa is then prepared by the method that pulse laser deposits in gained gold collection liquid surface0.5Sr0.5Co1.5Fe0.5O5+αGained catalytically-active materials layer is carried out plasma surface treatment by catalytically-active materials layer, obtains the efficient oxygen and membrane electrode is precipitated.The present invention can efficiently reduce the overpotential that the oxygen of catalyst is precipitated by argon gas or hydrogen gas plasma processing, improve oxygen and the utilization rate of catalyst is precipitated and can largely reduce the energy consumption of electrolysis water.

Description

Membrane electrode and its preparation method and application is precipitated in a kind of efficient oxygen
Technical field
The invention belongs to electrode material fields, and in particular to a kind of efficient oxygen is precipitated membrane electrode and preparation method thereof and answers With.
Background technique
Currently, in the selection of new energy conversion equipment raw material, hydrogen feed because its in conversion process of energy absolutely not Pollution, which generates, has very big potential.In addition, the specific energy of Hydrogen Energy equipment is high, has a safety feature, set as new energy conversion It is standby that there is vast potential for future development.Currently, the optimal method of preparation hydrogen feed is electrolysis water, the hydrogen that electrolysis water generates Conversion equipment be can be applied to by oxidation regeneration Cheng Shui, be a green energy conversion.With advances in technology and market It continues to develop, the efficiency for promoting electrolysis water increasingly seems important and urgent.In electrolysis water, it is divided into oxygen and is precipitated and hydrogen precipitation two Process.Wherein, the theoretical decomposition voltage of electrolysis water is 1.23V (relative to reversible hydrogen electrode), but since oxygen precipitation process is Rate controlling step, is the main contributions step of overpotential in electrolysis water, and the voltage of electrolysis water is much higher than 1.23V in practice.Therefore it is electrolysed Generally require to use catalyst in water, wherein the overpotential for reducing the oxygen precipitation process in electrolysis water be the emphasis studied at present with Hot spot, other than the improvement of current material and electrolysis hydraulic art, the modification for existing oxygen being precipitated catalyst is that comparison is popular One of research direction, modification can improve the catalytic activity of catalyst by some better simply processing modes, to realize drop The energy consumption of low electrolysis water.
Presently found effective oxygen-separating catalyst has following several major class: (1) noble heavy metal oxide, such as IrO2And RuO2 Deng；(2) with the perovskite material of catalytic activity: LaCoO4, CaMnO3,La0.7Sr0.3CoO3+α, PrCoO4And PrMnO3Deng； (3) there are metal-doped double perovskite materials: Ba0.5Sr0.5Co0.8Fe0.2O3-α,La0.8Sr0.2MnO3-α, Ca1.5Sr0.5Co1.5Fe0.5O5+αAnd PrBa0.5Sr0.5Co1.5Fe0.5O5+αDeng；(4) transition metal oxide, such as Co3O4And NiO2 Deng.Since noble metal is expensive, especially IrO2And RuO2, have very big limitation in actual a wide range of use.Its In, perovskite material prepares relatively easy, and price is low, long catalytic life, low toxicity, and crystalline structure is stable and abundant raw material etc. is excellent Point is that one of material is precipitated in the oxygen of electrolysis water first choice.
But while preparing perovskite material oxygen catalyst be precipitated, calcium titanium of the high-crystallinity without miscellaneous phase in order to obtain Pit wood material, synthesis generally require high-temperature calcination on the way, and the active area of perovskite material can reduce after high-temperature calcination, and oxygen is precipitated The performance of catalytic activity is unfavorable.So catalytic performance is precipitated there is still a need for further increasing, on the one hand in the oxygen of perovskite material The reason is that perovskite material conductivity is lower, on the one hand the reason is that perovskite material active site exposes as far as possible, on the one hand It is on the other hand then that catalyst electrode and soda acid electrolyte is precipitated in oxygen the reason is that the specific surface area of perovskite material need to be improved as far as possible Matching problem.Conventional commercial electrolyte liquid is alkalinity, and electrolyte itself can also promote oxygen that catalyst material pattern is precipitated simultaneously The pernicious reactions such as change, structure collapses, material dissolution, active site reduction, to influence its catalytic activity.Conventional oxygen is precipitated Catalyst modification includes high-energy ball milling, and noble metal (Pt, Pd, Ag, Au etc.) adulterates, transition metal (Ca, Cr, Co, Cu, Ni, Fe, Mn etc.) doping, the doping of nonmetalloid (F, S, P, N etc.), graphene, the mixing etc. of the two-dimensional materials such as molybdenum disulfide, still Above-mentioned method of modifying preparation process is relatively complicated, so that the preparation cost of catalyst is higher.Therefore it develops a kind of efficient Oxygen precipitation membrane electrode prepares 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 efficient The preparation method of oxygen precipitation membrane electrode.
Another object of the present invention is to provide a kind of efficient oxygen being prepared by the above method, and membrane electrode is precipitated.
A further object of the present invention is to provide above-mentioned efficient oxygen, and application of the membrane electrode in electrolysis water is precipitated.
The object of the invention is achieved through the following technical solutions:
The preparation method of membrane electrode, including following preparation step is precipitated in a kind of efficient oxygen:
(1) golden collector is prepared by ion sputtering on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide；
(2) the golden collection liquid surface obtained by step (1) is prepared by the method that pulse laser deposits PrBa0.5Sr0.5Co1.5Fe0.5O5+αCatalytically-active materials layer；
(3) by PrBa obtained by step (2)0.5Sr0.5Co1.5Fe0.5O5+αCatalytically-active materials layer carries out at plasma surface Reason obtains the efficient oxygen and membrane electrode is precipitated.
Further, the monocrystalline crystal face of the zirconia substrate of monocrystalline stabilized with yttrium oxide described in step (1) be (100), (110) or (111)；Substrate dimension size is 2.5*2.5*0.5mm~20*20*0.5mm.
Further, the time of ion sputtering described in step (1) is 100~500s, more preferably 320s.
Further, catalytically-active materials PrBa in step (2)0.5Sr0.5Co1.5Fe0.5O5+αIn, α value range is 0 < α ≤1。
Further, the gas of plasma surface treatment described in step (3) be argon gas or hydrogen, air pressure be 10~ 100Pa, power are 50~500W, and the processing time is 5~120min.
Further, the external silver wire of golden collector in membrane electrode is precipitated in the efficient oxygen, and silver wire uses closed Glass tube encapsulation.
Further, the efficient oxygen is precipitated membrane electrode and removes PrBa0.5Sr0.5Co1.5Fe0.5O5+αCatalytically-active materials layer Part except (conversion zone) coats waterproof coating.
A kind of efficient oxygen precipitation membrane electrode, is prepared by the above method.
Application of the membrane electrode in electrolysis water is precipitated in above-mentioned efficient oxygen.
The principle of the present invention are as follows: PrBa0.5Sr0.5Co1.5Fe0.5O5+αAt argon gas or hydrogen plasma condition lower surface After reason, the oxygen in perovskite material is deprived by high-energy argon ion or high energy hydrogen ion, is caused containing oxygen vacancies perovskite material.It is suitable When oxygen vacancies introducing, do not influence the appearance structure of catalyst itself, the active site that oxygen is precipitated increases, and improves catalyst Catalytic activity.In addition, the film and electrolyte after corona treatment have better compatibility, it is easier to adsorb OH-, be conducive to The progress of oxygen evolution reaction.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) present invention improves the catalytic activity that catalyst is precipitated in oxygen, is embodied in relative to reversible hydrogen electrode, in electricity Current density is 10mA cm-2When, PrBa0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode is in 100W, the processing of 20Pa hydrogen gas plasma Oxygen deposition potential is 1.6706V after 15min, without the PrBa of corona treatment0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode Deposition potential be 1.7177V, hydrogen gas plasma processing can efficiently reduce catalyst oxygen be precipitated overpotential, improve oxygen The utilization rate of catalyst is precipitated and can largely reduce the energy consumption of electrolysis water.
(2) present invention improves the catalytic activity that catalyst is precipitated in oxygen, is embodied in relative to reversible hydrogen electrode, in electricity Current density is 10mA cm-2When, PrBa0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode is in 100W, the processing of 20Pa argon plasma Oxygen deposition potential is 1.6908V after 15min, without the PrBa of corona treatment0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode Deposition potential be 1.7177V, argon plasma processing can efficiently reduce catalyst oxygen be precipitated overpotential, improve oxygen The utilization rate of catalyst is precipitated and can largely reduce the energy consumption of electrolysis water.
(3) zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide that the present invention uses can be prepared into arbitrary shape and big Small membrane electrode, in addition, the good mechanical property of substrate, can make membrane electrode in practice preferably apply.
(4) present invention can be adapted for most using argon gas, the method on hydrogen plasma treatment membrane electrode surface Transition metal oxide material, and catalysis material is precipitated in the large batch of processing oxygen of energy, the consistency for handling sample is good.
Detailed description of the invention
Fig. 1 is the oxygen analysis that membrane electrode (PBSCF-Film-Ar100W20Pa5min) is precipitated in efficient oxygen prepared by embodiment 1 Cyclic voltammetry curve (dotted line) and the PrBa handled without argon plasma out0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Fig. 2 is the oxygen that membrane electrode (PBSCF-Film-Ar100W20Pa10min) is precipitated in efficient oxygen prepared by embodiment 2 The PrBa that cyclic voltammetry curve (dotted line) is precipitated and is handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Fig. 3 is the oxygen that membrane electrode (PBSCF-Film-Ar100W20Pa15min) is precipitated in efficient oxygen prepared by embodiment 3 The PrBa that cyclic voltammetry curve (dotted line) is precipitated and is handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Fig. 4 is the oxygen analysis that membrane electrode (PBSCF-Film-Ar50W20Pa15min) is precipitated in efficient oxygen prepared by embodiment 4 Cyclic voltammetry curve (dotted line) and the PrBa handled without argon plasma out0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Fig. 5 is the oxygen that membrane electrode (PBSCF-Film-Ar150W20Pa15min) is precipitated in efficient oxygen prepared by embodiment 5 The PrBa that cyclic voltammetry curve (dotted line) is precipitated and is handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Fig. 6 is the oxygen that membrane electrode (PBSCF-Film-Ar100W10Pa15min) is precipitated in efficient oxygen prepared by embodiment 6 The PrBa that cyclic voltammetry curve (dotted line) is precipitated and is handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Fig. 7 is the oxygen that membrane electrode (PBSCF-Film-Ar100W40Pa15min) is precipitated in efficient oxygen prepared by embodiment 7 The PrBa that cyclic voltammetry curve (dotted line) is precipitated and is handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Fig. 8 is that membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen prepared by embodiment 82Oxygen 100W20Pa15min) Cyclic voltammetry curve (dotted line) and the PrBa without hydrogen plasma treatment is precipitated0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Fig. 9 is that membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen prepared by embodiment 92Oxygen 100W20Pa10min) Cyclic voltammetry curve (dotted line) and the PrBa without hydrogen plasma treatment is precipitated0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Figure 10 is that membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen prepared by embodiment 102Oxygen 100W20Pa5min) Cyclic voltammetry curve (dotted line) and the PrBa without hydrogen plasma treatment is precipitated0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Figure 11 is that membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen prepared by embodiment 112Oxygen 50W20Pa15min) Cyclic voltammetry curve (dotted line) and the PrBa without hydrogen plasma treatment is precipitated0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Figure 12 is that membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen prepared by embodiment 122150W20Pa15min) Cyclic voltammetry curve (dotted line) and the PrBa without hydrogen plasma treatment is precipitated in oxygen0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Figure 13 is that membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen prepared by embodiment 132100W10Pa15min) Cyclic voltammetry curve (dotted line) and the PrBa without hydrogen plasma treatment is precipitated in oxygen0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Figure 14 is that membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen prepared by embodiment 142100W40Pa15min) Cyclic voltammetry curve (dotted line) and the PrBa without hydrogen plasma treatment is precipitated in oxygen0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Figure 15 is embodiment 3 (PBSCF-Film-Ar) and 8 (PBSCF-Film-H of embodiment2) preparation efficient oxygen be precipitated Membrane electrode and PrBa without plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αThe scanning electricity of membrane electrode (PBSCF-Film) Sub- microscope figure.
Figure 16 is embodiment 3 (PBSCF-Film-Ar) and 8 (PBSCF-Film-H of embodiment2) preparation efficient oxygen be precipitated Membrane electrode and PrBa without plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αThe contact angle of membrane electrode (PBSCF-Film) Test chart.
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) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) Catalytically-active materials layer is prepared in golden collection liquid surface, reserves 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress ar pressure is 20Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 5min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The efficient oxygen of preparation is precipitated membrane electrode and carries out oxygen precipitation active testing, and active testing condition is precipitated in oxygen are as follows: with 1mol L-1The electrolyte that KOH is precipitated as oxygen is passed through high pure oxygen half an hour so that up to electrolyte oxygen saturation, experimental temperature is room 25 DEG C of temperature is tested as three-electrode system, and platinized platinum is to electrode, and the purity of platinum is higher than 99.999%, and saturation Ag/AgCl is reference electricity Pole, test equipment are morning China 660.
The oxygen precipitation that membrane electrode (PBSCF-Film-Ar100W20Pa5min) is precipitated in efficient oxygen manufactured in the present embodiment follows Ring volt-ampere curve (dotted line) and the PrBa handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF- Film it is as shown in Figure 1 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen).
Embodiment 2
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress ar pressure is 20Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 10min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
The oxygen that membrane electrode (PBSCF-Film-Ar100W20Pa10min) is precipitated in efficient oxygen manufactured in the present embodiment is precipitated Cyclic voltammetry curve (dotted line) and the PrBa handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in Figure 2 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Embodiment 3
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress ar pressure is 20Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
The oxygen that membrane electrode (PBSCF-Film-Ar100W20Pa15min) is precipitated in efficient oxygen manufactured in the present embodiment is precipitated Cyclic voltammetry curve (dotted line) and the PrBa handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in Figure 3 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Embodiment 4
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress ar pressure is 20Pa, and radio-frequency power supply discharge power is 50W plasma Body handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
The oxygen precipitation that membrane electrode (PBSCF-Film-Ar50W20Pa15min) is precipitated in efficient oxygen manufactured in the present embodiment follows Ring volt-ampere curve (dotted line) and the PrBa handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF- Film it is as shown in Figure 4 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen).
Embodiment 5
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress ar pressure is 20Pa, radio-frequency power supply discharge power be 150W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
The oxygen that membrane electrode (PBSCF-Film-Ar150W20Pa15min) is precipitated in efficient oxygen manufactured in the present embodiment is precipitated Cyclic voltammetry curve (dotted line) and the PrBa handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in Figure 5 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Embodiment 6
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress ar pressure is 10Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
The oxygen that membrane electrode (PBSCF-Film-Ar100W10Pa15min) is precipitated in efficient oxygen manufactured in the present embodiment is precipitated Cyclic voltammetry curve (dotted line) and the PrBa handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in Figure 6 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Embodiment 7
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress ar pressure is 40Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
The oxygen that membrane electrode (PBSCF-Film-Ar100W40Pa15min) is precipitated in efficient oxygen manufactured in the present embodiment is precipitated Cyclic voltammetry curve (dotted line) and the PrBa handled without argon plasma0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in Figure 7 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Embodiment 8
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress hydrogen gas pressure is 20Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
Membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen manufactured in the present embodiment2Oxygen precipitation 100W20Pa5min) follows Ring volt-ampere curve (dotted line) and PrBa without hydrogen plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF- Film it is as shown in Figure 8 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen).
Embodiment 9
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress hydrogen gas pressure is 20Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 10min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
Membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen manufactured in the present embodiment2Oxygen 100W20Pa10min) is precipitated Cyclic voltammetry curve (dotted line) and PrBa without hydrogen plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in Figure 9 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Embodiment 10
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress hydrogen gas pressure is 20Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 5min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
Membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen manufactured in the present embodiment2Oxygen 100W20Pa15min) is precipitated Cyclic voltammetry curve (dotted line) and PrBa without hydrogen plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in Figure 10 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Embodiment 11
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress hydrogen gas pressure is 20Pa, and radio-frequency power supply discharge power is 50W plasma Body handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
Membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen manufactured in the present embodiment2Oxygen precipitation 50W20Pa15min) follows Ring volt-ampere curve (dotted line) and PrBa without hydrogen plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF- Film it is as shown in figure 11 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen).
Embodiment 12
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress hydrogen gas pressure is 20Pa, radio-frequency power supply discharge power be 150W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
Membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen manufactured in the present embodiment2Oxygen 150W20Pa15min) is precipitated Cyclic voltammetry curve (dotted line) and PrBa without hydrogen plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in figure 12 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Embodiment 13
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress hydrogen gas pressure is 10Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
Membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen manufactured in the present embodiment2Oxygen 100W10Pa15min) is precipitated Cyclic voltammetry curve (dotted line) and PrBa without hydrogen plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in figure 13 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Embodiment 14
(1) on zirconium oxide (YSZ) substrate of monocrystalline stabilized with yttrium oxide, the size of substrate is 5*5mm, is oriented to 100, is led to It crosses ion sputtering and prepares golden collector, (reserved clean substrates are conveniently used for observation film table to reserved 2.5*2.5mm clean substrates The variation of face pattern and the flatness of pld (pulsed laser deposition)), sputtering time 320s；
(2) by catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αBy pulse laser sediment method in step (1) institute It obtains golden collection liquid surface and catalytically-active materials layer is prepared, reserve 2*2mm gold collector as connecting wire region；
(3) by the membrane electrode of step (2), progress hydrogen gas pressure is 40Pa, radio-frequency power supply discharge power be 100W etc. from Daughter handles PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated；
(4) gold afflux body portion will be reserved in step (3) to connect with silver wire, silver wire is encapsulated using closed glass pipe；Then The part that conversion zone is removed on substrate is coated into epoxide-resin glue (E-44AB), air drying is fully cured to glue for 24 hours, obtains Membrane electrode is precipitated in the efficient oxygen of the present embodiment.
The catalysis oxygen of preparation is precipitated electrode and carries out oxygen precipitation active testing, and testing procedure is the same as embodiment 1.
Membrane electrode (PBSCF-Film-H is precipitated in efficient oxygen manufactured in the present embodiment2Oxygen 100W40Pa15min) is precipitated Cyclic voltammetry curve (dotted line) and PrBa without hydrogen plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode (PBSCF-Film) it is as shown in figure 14 that cyclic voltammetry curve (solid line) comparison diagram is precipitated in oxygen.
Above embodiments 3 (PBSCF-Film-Ar), 8 (PBSCF-Film-H of embodiment2) in efficiently oxygen be precipitated membrane electrode With the PrBa without plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αThe microscopic comparison of membrane electrode (PBSCF-Film) is as schemed Shown in 15.
Above embodiments 3 (PBSCF-Film-Ar), 8 (PBSCF-Film-H of embodiment2) in efficiently oxygen be precipitated membrane electrode With the PrBa without plasma treatment0.5Sr0.5Co1.5Fe0.5O5+αThe contact angle comparison diagram of membrane electrode (PBSCF-Film) is such as Shown in Figure 16.
By the microscopic comparison of Figure 15 as it can be seen that PrBa0.5Sr0.5Co1.5Fe0.5O5+αMembrane electrode is carrying out argon gas or hydrogen After plasma treatment, the structure of film surface is had no effect on, Film roughness is small and flat and smooth.In conjunction in Figure 16 argon gas or Electrolyte contacts angle figure after hydrogen plasma treatment, available following conclusion: after argon gas or hydrogen plasma treatment Membrane electrode reduces with the contact angle of electrolyte, it was confirmed that the film after plasma treatment is more advantageous to absorption OH-, be conducive to It improves oxygen and catalytic activity is precipitated.In conjunction with Fig. 1~7, available following conclusion: apply the time of argon plasma processing not Together, power is different, and air pressure is different, then the PrBa being prepared0.5Sr0.5Co1.5Fe0.5O5-αThe oxygen of membrane electrode is precipitated in efficient oxygen Precipitation activity is also different, but can obviously reduce the overpotential of oxygen precipitation.Progress ar pressure is 20Pa, and radio-frequency power supply is put Electrical power is 100W corona treatment PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains efficient oxygen and film is precipitated Oxygen to be precipitated activity maximum, be 10mA cm in current density-2Be 1.6908V relative to reversible hydrogen electrode potential, and without argon The potential of the membrane electrode of gas plasma treatment is up to 1.7177V.Progress hydrogen gas pressure is 20Pa, and radio-frequency power supply discharge power is 100W corona treatment PrBa0.5Sr0.5Co1.5Fe0.5O5+αFilm surface 15min obtains the oxygen precipitation that film is precipitated in efficient oxygen It is active maximum, it is 10mA cm in current density-2Be 1.6706V relative to reversible hydrogen electrode potential, and without hydrogen plasma The potential of the membrane electrode of processing is up to 1.7177V.
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 (9)

1. the preparation method that membrane electrode is precipitated in a kind of efficient oxygen, it is characterised in that including following preparation step:
(1) golden collector is prepared by ion sputtering in the zirconia substrate of monocrystalline stabilized with yttrium oxide；
(2) the golden collection liquid surface obtained by step (1) is prepared by the method that pulse laser deposits PrBa0.5Sr0.5Co1.5Fe0.5O5+αCatalytically-active materials layer；
(3) by PrBa obtained by step (2)0.5Sr0.5Co1.5Fe0.5O5+αCatalytically-active materials layer carries out plasma surface treatment, It obtains the efficient oxygen and membrane electrode is precipitated.
2. the preparation method that membrane electrode is precipitated in a kind of efficient oxygen according to claim 1, it is characterised in that: step (1) Described in monocrystalline stabilized with yttrium oxide zirconia substrate monocrystalline crystal face be (100), (110) or (111)；Substrate dimension size is 2.5*2.5*0.5mm~20*20*0.5mm.
3. the preparation method that membrane electrode is precipitated in a kind of efficient oxygen according to claim 1, it is characterised in that: step (1) Described in ion sputtering time be 100~500s.
4. the preparation method that membrane electrode is precipitated in a kind of efficient oxygen according to claim 1, it is characterised in that: step (2) Middle catalytically-active materials PrBa0.5Sr0.5Co1.5Fe0.5O5+αIn, α value range is 0 α≤1 <.
5. the preparation method that membrane electrode is precipitated in a kind of efficient oxygen according to claim 1, it is characterised in that: step (3) Described in plasma surface treatment gas be argon gas or hydrogen, air pressure be 10~100Pa, power be 50~500W, processing Time is 5~120min.
6. the preparation method that membrane electrode is precipitated in a kind of efficient oxygen according to claim 1, it is characterised in that: described efficient The external silver wire of golden collector in membrane electrode is precipitated in oxygen, and silver wire is encapsulated using closed glass pipe.
7. the preparation method that membrane electrode is precipitated in a kind of efficient oxygen according to claim 1, it is characterised in that: described efficient Oxygen is precipitated membrane electrode and removes PrBa0.5Sr0.5Co1.5Fe0.5O5+αPart except catalytically-active materials layer coats waterproof coating.
8. membrane electrode is precipitated in a kind of efficient oxygen, it is characterised in that: prepared by the described in any item methods of claim 1~7 It obtains.
9. application of the membrane electrode in electrolysis water is precipitated in a kind of efficient oxygen according to any one of claims 8.
CN201910422985.XA 2019-05-21 2019-05-21 Membrane electrode and its preparation method and application is precipitated in a kind of efficient oxygen Pending CN110144599A (en)

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