CN108950587A - A kind of high surface area solids polymer membrane electrode and preparation method thereof - Google Patents

A kind of high surface area solids polymer membrane electrode and preparation method thereof Download PDF

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CN108950587A
CN108950587A CN201810744762.0A CN201810744762A CN108950587A CN 108950587 A CN108950587 A CN 108950587A CN 201810744762 A CN201810744762 A CN 201810744762A CN 108950587 A CN108950587 A CN 108950587A
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catalyst
preparation
solid polymer
proton exchange
polymer membrane
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CN108950587B (en
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田博元
刘锋
刘少名
梁丹曦
徐桂芝
邓占锋
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State Grid Corp of China SGCC
State Grid Shanxi Electric Power Co Ltd
Global Energy Interconnection Research Institute
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State Grid Corp of China SGCC
State Grid Shanxi Electric Power Co Ltd
Global Energy Interconnection Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—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
    • C25B11/097—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 comprising two or more noble metals or noble metal alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • 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

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Abstract

The invention belongs to electrolysis water technical fields, and in particular to a kind of preparation method of electrode film.The preparation method of solid polymer membrane electrode provided by the invention, initiative ground is first in Surface modification of proton exchange membrane painting catalyst, by the endless all standing of film surface；Then above-mentioned film surface is performed etching using anisotropic etching method under the protection of catalyst granules; painting catalyst again after hole or comb finger is formed, allow for film surface that catalyst granules is attached in hole in this way or is combed in the film surface of finger.Preparation method provided by the invention can significantly improve the electrochemically active specific surface area of membrane electrode anode catalyst, the multiphase for opening up aquaporin, electron channel, proton channel, gas passage of catalyst granules and electrochemical reaction etc. contacts, it has been finally reached raising catalyst utilization, catalyst loading is reduced, the purpose of membrane electrode preparation cost is greatly lowered.

Description

A kind of high surface area solids polymer membrane electrode and preparation method thereof
Technical field
The invention belongs to electrolysis water technical fields, and in particular to a kind of preparation method of electrode film.
Background technique
Energy Conversion Technology is dissolved in renewable energy to play a significant role with storage, and water electrolysis hydrogen production and oxygen are to compare Mature Energy Conversion Technology.In recent years, solid polymer water electrolysis (Solid polymer water electrolysis, SPE) technology is just gradually domestic because having many advantages, such as structure is simple, small in size, high-efficient, start and stop are fast and highly-safe It is outer to receive and realize preliminary commercialization.Solid polymer water electrolysis is to substitute conventional alkaline using solid polymer electrolyte Diaphragm and electrolyte in electrolysis water, and by being embedded in catalyst as a whole in solid polymer electrolyte two sides, shape At membrane electrode, which has the function of that catalysis reaction is transmitted with ion simultaneously.
In solid polymer water electrolysis technology, membrane electrode is the most key, to electrolysis performance with it is decisive from equipment life Effect.Currently used solid polymer electrolyte is mainly perfluorosulfonic acid proton exchange film (solid-state strong acid, chemical stability It is good).Cathod catalyst mainly uses Pt/C, i.e., carbon-supported Pt, the overpotential very little of cathode, and carbon will not be oxidized, and utilizes carbon High surface area and good electric conductivity, enable to the dosage of Pt relatively low.And the catalyst of anode-side mainly uses IrO2/ RuO2, overpotential is very high, and carbon can be oxidized under strong acid and high oxidation potential, so anode-side can not be using carbon come supported catalyst Agent, this causes the dosage of noble metal very high.
As it can be seen that there is also some disadvantages for SPE technology, such as the price of proton exchange membrane is higher, membrane electrode cost of manufacture is high, Catalyst is expensive etc., and Ir is one of element most rare on the earth, and annual global yield only has 3 tons, and serious limitation is solid The application scale of body polymer water electrolysis tech.In addition, deformation caused by proton exchange membrane heat expansion or swelling will also result in catalysis Layer unbalance stress and cause Catalytic Layer and proton exchange film stripping, make membrane electrode stability decline.So how to reduce membrane electrode Cost, and the stability for improving membrane electrode is the research hotspot of SPE membrane electrode research field.
Anode noble metal catalyst dosage is reduced, increasing reaction surface area is that a kind of membrane electrode cost that reduces there are efficacious prescriptions Method.Chinese patent literature CN105734606A discloses a kind of SPE hydrolysis ultrathin electrodes structure and preparation method thereof.The technology First using goldleaf as raw material, using going alloyage to obtain nanoporous gold thin film, then by this film transfer to ion exchange On film.It is catalyst-loaded as supporting layer using this layer of porous gold thin film again, it is prepared into ultra-thin membrane electrode.The technology utilizes nanogold The three-dimensional connection structure of film enhances the conveying of reactant, reduces noble metal dosage.However, goldleaf cost is high, it is comprehensive Manufacturing cost considers that finite thickness causes the three-dimensional connection structure space being capable of providing limited；And this method preparation process Complexity is not easy to carry out industrial production.
To sum up, a kind of reduction anode noble metal dosage how is developed, the solid polymer membrane electricity of reaction surface area is increased The cost effective method of pole is still those skilled in the art's technical problem urgently to be resolved.
Summary of the invention
It is an object of the invention to overcome, solid polymer membrane electrode higher cost, reaction surface area are lower in the prior art Defect, and then provide a kind of solid polymer membrane electrode novel preparation method.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
A kind of solid polymer membrane electrode, including proton exchange membrane body, and it is set to the proton exchange membrane body extremely Several proton exchange columns of few one side, the surface of the proton exchange column is provided with catalyst granules.
The length of the proton exchange column is 200~1000nm.
The proton exchange column is provided at least one catalyst granules far from the end face of the proton exchange membrane body.
It is identical with the material of the proton exchange column to form the proton exchange membrane body.
The material of the proton exchange membrane body and/or the proton exchange column is Nafion.
The catalyst granules includes Ir metal, Ru metal, IrO2、RuO2、RhO2And PtCoO2One of or it is a variety of.
A kind of preparation method of solid polymer membrane electrode, including,
(1) in a surface painting catalyst of proton exchange membrane, make the catalyst dispersion on said surface；
(2) Surface modification of proton exchange membrane obtained by step (1) is performed etching；
(3) painting catalyst again；
The etching is anisotropic etching；
The catalyst is the catalyst for electrolysis water, and will not be eliminated by the etching.
In step (1), the catalyst coverage rate on the surface is 5~40%.
In step (1), the catalyst coverage rate on the surface is 20~30%.
The anisotropic etching method is reactive ion etching method.
Etching gas is oxygen.
Vertically the Surface modification of proton exchange membrane carries out the etching.
The depth etched in step (2) is 200~1000nm.
The step (1) and/or the step (3) further include the steps that baking after completing painting catalyst.
The temperature of the baking is 85~95 DEG C, and the time of the baking is 8~12min.
The painting catalyst by the way of coating catalytic agent dispersing liquid.
Dispersing agent is isopropanol in the dispersion liquid.
The catalyst loading being coated in the step (1) is 0.1~0.5mg/cm2, what is be coated in the step (2) urges Agent loading is 1~4mg/cm2。
The proton exchange membrane is Nafion membrane.
The catalyst includes Ir metal, Ru metal, IrO2、RuO2、RhO2And PtCoO2One of or it is a variety of.
A kind of high surface area solids polymer electrode membrane, at least side of the electrode film are by above-mentioned preparation method system ?.
Technical solution of the present invention has the advantages that
1. solid polymer membrane electrode provided by the invention, by being arranged catalyst granules on proton exchange membrane body On several proton exchange columns of at least one side, more electrolysis water reaction channels can be obtained, improve catalyst and proton The utilization rate of exchange membrane, compared with traditional membrane electrode, carrier of the proton exchange column as catalyst can not only be constructed more Reaction channel, also improve the utilization rate of Nafion membrane；Also, it as a kind of flexible structure, is attached on proton exchange column Catalyst granules by proton exchange membrane occur heat expansion and swelling influenced it is smaller so that membrane electrode is able to maintain that preferable stabilization Property.
The preparation method of solid polymer membrane electrode provided by the invention, initiative ground are first coated in Surface modification of proton exchange membrane Catalyst, by the endless all standing of film surface；Then use anisotropic etching method to above-mentioned under the protection of catalyst granules Film surface performs etching, and forms painting catalyst again after hole or comb finger, allows for catalyst granules attachment in this way Film surface in hole is combed in the film surface of finger.Preparation method provided by the invention can significantly improve membrane electrode The electrochemically active specific surface area of anode catalyst opens up catalyst granules and the aquaporin of electrochemical reaction, electron channel, matter The multiphase of subchannel, gas passage etc. contacts, and has been finally reached raising catalyst utilization, reduces catalyst loading, substantially Degree reduces the purpose of membrane electrode preparation cost.
Preparation method provided by the invention is performed etching by using anisotropic etching method, can obtain being suitable for supporting The proton exchange membrane of the stereochemical structure of catalyst, it is and traditional catalyst coated in this way after the secondary coating for carrying out catalyst Mode is compared, and the contact area of catalyst and film greatly increases, and is attached in proton exchange membrane so that catalyst is more stable, Improve the stability of membrane electrode.Reduce catalyst loading.
2. high surface solid polymer electrode membrane preparation method provided by the invention, by selecting different top layer catalyst Coverage rate can obtain different proton exchange membrane structures, be that comb refers to structure when top layer catalyst coverage rate is 5~40%；When When top layer catalyst coverage rate is 60~95%, proton exchange membrane is pore structure；When coverage rate 40~60%, proton exchange The structure of film is therebetween；Wherein, preferably top layer catalyst coverage rate is (20~30%), enables to aquaporin, electricity Subchannel, proton channel and gas passage are opened to greatest extent, improve catalyst utilization.Also, work as top layer preferred catalytic When agent coverage rate is 20~30%, proton exchange membrane is comb finger, as the flexible supporter of catalyst, accordingly even when When it occurs heat expansion or is swollen, catalyst is also not easy to fall off from proton exchange membrane.Meanwhile catalyst granules is protected In three-dimensional, intensive membrane structure, additionally it is possible to weaken the hydrogen generated when electrolysis and oxygen to the souring of catalyst granules, So that membrane electrode is more stable.By increasing the step of baking after catalyst coated, catalyst and proton exchange can be promoted The adhesiveness of film surface further increases the stability and service life of membrane electrode.
3. high surface solid polymer membrane electrode preparation method provided by the invention, has further defined preferred etching Method and etch period.Reactive ion etching technology is the dry etching techniques that a kind of anisotropy is very strong, selectivity is high.Its benefit Made to be etched with the ion energy surface of layer forms the damaging layer for being easy etching and promotes chemical reaction.Energetic ion is certain Operating pressure under, vertically directive sample surfaces carry out physical bombardment, only perform etching along vertically sinking to the bottom surface direction.Benefit With reactive ion etching technology, three-dimensional structure can be formed in substrate surface, increase surface area.It is covered by preferred catalyst Rate, and complex reaction ion etching technology limit etching depth, and area increase reaches as high as 6000%, and ensure that simultaneously good Good aquaporin, electron channel, proton channel and gas passage.So that solid polymer electrode film provided by the present invention Compared with traditional electrode film, longer life expectancy, and electrolytic efficiency is also greatly improved.
Detailed description of the invention
In order to illustrate more clearly of the technical solution in the specific embodiment of the invention, specific embodiment will be retouched below Attached drawing needed in stating is briefly described, it should be apparent that, the accompanying drawings in the following description is some realities of the invention Mode is applied, it for those of ordinary skill in the art, without creative efforts, can also be attached according to these Figure obtains other attached drawings.
Fig. 1 is the preparation method schematic diagram for the high surface solid polymer electrode membrane that embodiment 1 provides；
Fig. 2 is the preparation method schematic diagram for the solid polymer electrode film that comparative example provides.
The reference numerals are as follows in above-mentioned attached drawing:
1- proton exchange membrane body；2- proton exchange column.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation Example is a part of the embodiment of the present invention, instead of all the embodiments.In addition, invention described below different embodiments Involved in technical characteristic can be combined with each other as long as they do not conflict with each other.
It should be noted that only describe the preparation method on a surface of electrode film in following embodiment, when only with When the method for the invention carries out the preparation of membrane electrode anode, cathode, example can be made on a surface of proton exchange membrane first It such as can first be recycled after the Pt/C catalyst of coated on one side hydrogen gas side (i.e. cathode plane) with conventional method provided by the present invention Method prepares anode-side, and due to blocking for substrate, cathode plane not will receive the influence of etching.Institute in following embodiment and comparative example Surface modification of proton exchange membrane product size is identical.
Embodiment 1
A kind of solid polymer membrane electrode is present embodiments provided, structure includes that material is that the proton of Nafion membrane is handed over Membrane body 1 and several proton exchange columns 2 for being set to 1 one sides of the proton exchange membrane body are changed, several proton exchange columns Material be also Nafion membrane, and be provided with IrO on proton exchange column2-RuO2Catalyst granules.
The present embodiment additionally provides a kind of preparation method of high surface polymer membrane electrode, as shown in Figure 1, specifically including Following steps,
Nafion membrane is taken, is coated with RuO in surface thereof2Isopropanol dispersion liquid, complete for the first time it is catalyst coated, support Amount is 0.1mg/cm2, duty ratio is about 10% at this time, then toasts 10min at 90 DEG C.
The above-mentioned film surface for being coated with catalyst is performed etching using reactive ion etching process, using oxygen as quarter Gas is lost, etching device chamber is extracted into 1torr vacuum below, then passes to oxygen, is excited oxygen for band using coil The plasma of electricity, then vertically Nafion membrane surface is arrived in bombardment under electric field action, using etching power 100W, etching depth D=a × t, a are the etch rate per minute of the Nafion membrane, and t is etch period, the etching speed of Nafion membrane in the present embodiment Rate is 50nm/min, etches 20min, and etching depth is micron at this time.In this way, being formed proton exchange membrane body 1 and several Proton exchange column 2.
It is catalyst coated to second of film surface progress after etching, still use IrO2-RuO2Isopropanol dispersion liquid carry out Coating, so that adhering to IrO on proton exchange column 22-RuO2Catalyst granules, loading 4mg/cm2, then toasted at 90 DEG C 30min。
Embodiment 2
The preparation method for present embodiments providing a kind of high surface polymer membrane electrode, specifically includes,
Nafion membrane is taken, is coated with IrO in surface thereof2Isopropanol dispersion liquid, complete for the first time it is catalyst coated, support Amount is 0.5mg/cm2, duty ratio is about 50% at this time, then toasts 10min at 90 DEG C.
The above-mentioned film surface for being coated with catalyst is performed etching using reactive ion etching process, using argon gas as quarter Gas is lost, etches 4min, etching depth is about 200nm at this time.
It is catalyst coated to second of film surface progress after etching, still use IrO2Isopropanol dispersion liquid applied Cloth, loading 1mg/cm2, then 30min is toasted at 90 DEG C.
Embodiment 3
The preparation method for present embodiments providing a kind of high surface polymer membrane electrode, specifically includes,
Nafion membrane is taken, in the isopropanol dispersion liquid of surface thereof coating Ir metallic particles, first time catalyst is completed and applies Cloth, loading 0.2mg/cm2, duty ratio is about 20% at this time, then toasts 10min at 90 DEG C.
The above-mentioned film surface for being coated with catalyst is performed etching using reactive ion etching process, using oxygen as quarter Gas is lost, 10min is etched, etching depth is 500nm at this time, and formation length is several proton exchange columns of 500nm.
Film surface after etching is carried out it is second catalyst coated, still using the isopropanol dispersion liquid of Ir metallic particles into Row coating, so that catalyst granules is attached on proton exchange column, Ir metallic particles loading is 3mg/cm2, then at 90 DEG C Lower baking 30min.
Embodiment 4
The preparation method for present embodiments providing a kind of high surface polymer membrane electrode, specifically includes,
Nafion membrane is taken, in the isopropanol dispersion liquid of surface thereof coating Ir metallic particles, first time catalyst is completed and applies Cloth, loading 0.3mg/cm2, duty ratio is about 30% at this time, then toasts 10min at 90 DEG C.
The above-mentioned film surface for being coated with catalyst is performed etching using reactive ion etching process, using argon gas as quarter Gas is lost, 15min is etched, etching depth is 750nm at this time, and formation length is the proton exchange column of 750nm, these proton exchanges Column and proton exchange membrane body collectively form comb finger.
Film surface after etching is carried out it is second catalyst coated, still using the isopropanol dispersion liquid of Ir metallic particles into Row coating, so that catalyst is attached on proton exchange column, catalyst loading 2mg/cm2, then toasted at 90 DEG C 30min。
Comparative example
This comparative example provides a kind of solid polymer method for preparing membrane electrode, as shown in Fig. 2, specifically including:
Nafion membrane is taken, and sprays IrO on its surface2And Nafion solution, the IrO after finally spraying twice2Loading is 1.5mg/cm2。
Using the resulting membrane electrode area of comparative example as standard, it is prepared using preparation method provided by the present invention Electrode film cooperates different duty and etching depth, the attainable surface area increase effect of institute when using different catalysts diameter Fruit is as shown in the table.
Wherein, coverage rate when duty ratio is first time painting catalyst, it may be assumed that area/proton of catalyst granules covering The surface area of exchange membrane；It is 100% calculating that membrane electrode area, which is with membrane electrode area obtained by comparative example,.
1 membrane electrode area of table is influenced by each parameter
Under identical Faradaic current, generates hydrogen and directly proportional to the rate of oxygen (2:1) to membrane electrode area, therefore film Electrode area is bigger, and gas production rate is higher.Since membrane electrode of the invention is three-dimensional structure, in identical equipment volume following table area Bigger, the yield of hydrogen and oxygen is higher.
Catalyst particle diameter is smaller, and the surface area for the electrode film that method provided by the invention is prepared is higher, with The raising of catalyst preparation level, the continuous reduction of catalyst size, this method still has the raising of electrode film properties puts at double Big effect.Duty ratio is bigger, and etching depth is bigger, theoretically for can obtain higher surface area.However, excessive duty Than can come technical difficulty, effect decline for the coating zone of second of catalyst with too deep etching depth.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or Variation is still in the protection scope of this invention.

Claims (21)

1. a kind of solid polymer membrane electrode, which is characterized in that including proton exchange membrane body (1), and be set to the proton Several proton exchange columns (2) of membrane body (1) at least one side are exchanged, the surface of the proton exchange column (2) is provided with catalysis Agent particle.
2. solid polymer membrane electrode according to claim 1, which is characterized in that the length of the proton exchange column (2) For 200~1000nm.
3. solid polymer membrane electrode according to claim 1 or 2, which is characterized in that the proton exchange column (2) is separate The end face of the proton exchange membrane body (1) is provided at least one catalyst granules.
4. solid polymer membrane electrode according to claim 1 to 3, which is characterized in that form the proton exchange membrane Ontology (1) is identical with the material of the proton exchange column (2).
5. solid polymer membrane electrode according to claim 1-4, which is characterized in that the proton exchange membrane sheet The material of body and/or the proton exchange column is Nafion.
6. solid polymer membrane electrode according to claim 1-5, which is characterized in that the catalyst granules packet Include Ir metal, Ru metal, IrO2、RuO2、RhO2And PtCoO2One of or it is a variety of.
7. a kind of preparation method of solid polymer membrane electrode, which is characterized in that including,
(1) in a surface painting catalyst of proton exchange membrane, make the catalyst dispersion on said surface；
(2) Surface modification of proton exchange membrane obtained by step (1) is performed etching；
(3) painting catalyst again；
The etching is anisotropic etching；
The catalyst is the catalyst for electrolysis water, and will not be eliminated by the etching.
8. the preparation method of solid polymer membrane electrode according to claim 7, which is characterized in that described in step (1) The catalyst coverage rate on surface is 5~40%.
9. the preparation method of solid polymer membrane electrode according to claim 7, which is characterized in that described in step (1) The catalyst coverage rate on surface is 20~30%.
10. according to the preparation method of the described in any item solid polymer membrane electrodes of claim 7-9, which is characterized in that described Anisotropic etching method is reactive ion etching method.
11. the preparation method of solid polymer membrane electrode according to claim 10, which is characterized in that etching gas is oxygen Gas.
12. according to the preparation method of the described in any item solid polymer membrane electrodes of claim 7-11, which is characterized in that described The vertical Surface modification of proton exchange membrane of etching carries out.
13. according to the preparation method of the described in any item solid polymer membrane electrodes of claim 7-12, which is characterized in that step (2) depth etched in is 200~1000nm.
14. according to the preparation method of the described in any item solid polymer membrane electrodes of claim 7-13, which is characterized in that described Step (1) and/or the step (3) further include the steps that baking after completing painting catalyst.
15. the preparation method of solid polymer membrane electrode according to claim 14, which is characterized in that the temperature of the baking Degree is 85~95 DEG C, and the time of the baking is 8~12min.
16. according to the preparation method of the described in any item solid polymer membrane electrodes of claim 7-15, which is characterized in that use The mode painting catalyst of coating catalytic agent dispersing liquid.
17. the preparation method of solid polymer membrane electrode according to claim 16, which is characterized in that in the dispersion liquid Dispersing agent is isopropanol.
18. according to the preparation method of the described in any item solid polymer membrane electrodes of claim 7-17, which is characterized in that described The catalyst loading being coated in step (1) is 0.1~0.5mg/cm2, the catalyst loading being coated in the step (2) is 1~4mg/cm2。
19. according to the preparation method of the described in any item solid polymer membrane electrodes of claim 7-18, which is characterized in that described Proton exchange membrane is Nafion membrane.
20. according to the preparation method of the described in any item solid polymer membrane electrodes of claim 7-19, which is characterized in that described Catalyst includes Ir metal, Ru metal, IrO2、RuO2、RhO2And PtCoO2One of or it is a variety of.
21. a kind of high surface area solids polymer electrode membrane, which is characterized in that at least side of the electrode film is by the power Benefit requires the described in any item preparation methods of 7-20 to be made.
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