CN102403516B - Preparation method of curved surface electrode catalyst layer - Google Patents

Preparation method of curved surface electrode catalyst layer Download PDF

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CN102403516B
CN102403516B CN2011102212275A CN201110221227A CN102403516B CN 102403516 B CN102403516 B CN 102403516B CN 2011102212275 A CN2011102212275 A CN 2011102212275A CN 201110221227 A CN201110221227 A CN 201110221227A CN 102403516 B CN102403516 B CN 102403516B
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CN102403516A (en
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叶丁丁
张彪
李俊
朱恂
廖强
王宏
王永忠
丁玉栋
陈蓉
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Chongqing University
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Abstract

The invention provides a preparation method of a curved surface electrode catalyst layer, which is characterized by comprising the following steps of: 1, preprocessing an electrode matrix; 2, carrying out electrochemical deposition on a catalyst: inserting the preprocessed electrode matrix into an electrochemical deposition pool, loading an electroplating bath containing catalyst cations in the electrochemical deposition pool, forming a three-electrode system with a reference electrode and a counter electrode with the electrode matrix as a working electrode, controlling the potential of the working electrode to be -0.7-0.5V relative to a standard hydrogen electrode for carrying out electrochemical deposition until the loading capacity of the catalyst on the electrode matrix reaches a preset loading capacity, then taking the electrode matrix out, rinsing with deionized water for drying in air for later use; 3, dipping in a perfluorinated sulfonic acid resin solution; 4, repeating the step 2 and the step 3 until the loading capacity of the catalyst on the electrode matrix reaches the set loading capacity of the catalyst, entering the step 5; and 5, activating an electrode.

Description

The curved surface electrode catalyst layer preparation method
Technical field
The present invention relates to the electrode catalyst layer preparation method, be specifically related to the curved surface electrode catalyst layer preparation method.
Background technology
The electrode matrix of commonly using in various common electrochemical reactors comprise fuel cell, electrolytic cell, electrochemical cell etc. mainly contains the electrochemical properties such as carbon paper, carbon cloth, carbon felt, graphite cake and stablizes and corrosion resistant material with carbon element.The price of carbon paper, carbon cloth, carbon felt, graphite cake is all higher, has caused the cost of electrochemical reactor high.Carbon paper, carbon cloth, carbon felt, graphite cake etc. generally all are used as plane electrode, yet research W.R.Merida, G.McLean, N.Djilali, Journal of Power Sources, 102 (2001) 178-185. are verified, and curved surface electrode can significantly improve performance and the volumetric power density of electrochemical reactor with respect to plane electrode.
Use the membrane electrode Membrane Electrode Assembly of waveform waved in Proton Exchange Membrane Fuel Cells, MEA can increase electrode surface area and strengthen the transmission of reactive material, improve performance and the volumetric power density W.R.Merida of fuel cell, G.McLean, N.Djilali, Journal of Power Sources, 102 (2001) 178-185..Yet this waveform membrane electrode still uses carbon paper as electrode matrix, and cost is higher, and easily is corroded with support and the collector of stainless steel material as membrane electrode.Foreign study person E.Kjeang, J.McKechnie, D.Sinton, N.Djilali, Journal of Power Sources, 168 (2007) 379-390. propose to use graphite rod as electrode matrix in the microfluid fuel cell.The graphite rod low price, produce easily, wide material sources, use graphite rod can significantly reduce the cost of battery as electrode matrix.The place of using the such cylindrical surface electrode of graphite rod to occur as electrochemical reaction not only can increase the electro-chemical activity surface area of electrode in battery, and also can produce small sample perturbations during fluid flow-disturbing cylindrical electrode surface, the reinforcement reactive material replenishes electrode surface depletion boundaries layer Depletion boundary layer's, can improve simultaneously performance and the fuel availability of microfluid fuel cell.This kind uses graphite rod to use the vanadium oxide reduction electricity to V as the microfluid fuel cell of electrode 2+/ V 3+And VO 2+/ VO 2 +Act as a fuel respectively and oxidant, its advantage is the vanadium oxide reduction electricity to can be directly in the graphite rod surface reaction, do not need to use noble metal catalyst, however vanadium can to environment especially soil cause severe contamination and in liquid solubility lower, therefore limited it and be widely used.
Methyl alcohol CH 3The liquid fuels such as OH and formic acid HCOOH have wide material sources, are easy to produce, the characteristics such as energy density is high, environmental friendliness, are the desirable fuel of fuel cell.The liquid fuel such as methyl alcohol and formic acid can not directly reaction on carbon base body such as carbon paper, carbon cloth, graphite cake, graphite rod etc., must use catalyst to carry out catalysis.In order to make reliable fuel cell curved surface electrode, must the preparation method of curved surface electrode surface catalyst layer be studied.
At present the catalyst preparation mainly can be divided into electrochemical deposition method and direct attachment method two classes in the method for curved surface electrode matrix.As adopting electrochemical deposition method to carry out the electrochemical deposition catalyst in patent US2004072047-A1, can cause catalyst crystal dendritic growth Dendritic growth, make the catalyst crystal particle diameter increase, reduce electro-chemical activity surface area Electroactive surface area and the catalytic activity of catalyst; Directly adhering to rule is that catalyst nano particle such as Pd black or Pd/C etc. are mixed into catalyst pulp Catalyst ink by a certain percentage with deionized water and perfluorinated sulfonic resin Nafion solution, carry out after sonic oscillation makes its Uniform Dispersion, it being coated on electrode surface, with namely forming catalyst layer after the thermolamp oven dry; Adopt direct attachment method nanoparticle catalyst activity used higher, but this preparation method is only applicable to the electrode structure on plane, be difficult to evenly distribute at curved surface electrode surface catalyst slurry, and due to the curved surface unequal reason of being heated, directly the catalyst layer of attachment method preparation cracking, the aliquation that can occur being caused by thermal stress, the phenomenon such as come off, cause the catalyst waste, seriously even make catalyst complete failure.In addition, owing to the phenomenon of catalyst nano particle agglomeration can occur in catalyst pulp, also make the partially catalyzed agent not contact with reactive material, can not produce catalytic effect, cause the utilance of noble metal catalyst limited; Attachment method as direct in the catalyst that adopts in patent US2006210867-A1 is palladium black Pd black catalyst nano particle and Nafion solution and deionized water to be mixed sonic oscillation by a certain percentage drop in the carbon substrate surface after evenly, with namely making plane electrode after the thermolamp oven dry.This method not only can cause catalyst agglomeration but also and not be suitable for the curved surface electrode surface.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of curved surface electrode surface catalyst layer, and the method can reduce the dendritic growth of catalyst crystal, and can form sandwich construction, to improve the electrode electro Chemical active surface area.
In order to solve the problems of the technologies described above, technical scheme of the present invention is that the preparation method of curved surface electrode surface catalyst layer is characterized in: comprise the following steps:
The first step: the electrode matrix preliminary treatment is used for removing micro-grease and the metal oxide of electrode matrix surface attachment;
Second step: electrochemical deposition catalyst
To insert in electrochemical cell through pretreated electrode matrix, pack in electrochemical cell and contain the cationic electroplate liquid of catalyst, with electrode matrix as work electrode, with reference electrode, consist of three-electrode system together with electrode, control the work electrode current potential by electrochemical workstation or potentiostat and carry out electrochemical deposition with respect to standard hydrogen electrode SHE for-0.7～0.5V, until on electrode matrix, catalyst loading reaches predetermined carrying capacity, then electrode matrix is taken out, with standby at air drying after deionized water rinsing;
Use the electrochemical method deposited catalyst, can carry out uniform electrochemical deposition on curved surface electrode, the catalyst layer that forms is evenly distributed on curved surface, and the catalyst distribution of having avoided adopting the direct adherence method of catalyst very easily to occur inhomogeneous or crackle, aliquation, the problem such as come off;
The 3rd step: flood in perfluorinated sulfonic resin Nafion solution
To immerse the perfluorinated sulfonic resin Nafion solution 1～30 minute of 0.1～5wt.% through the electrode matrix of electrochemical deposition, then it be taken out at air drying;
This step can significantly reduce the overpotential in electrochemical deposition process, eliminate the dendritic growth of catalyst crystal, impel the catalyst crystal to carry out the growth of " island island " type, reduce catalyst particle size, and the crystal orientation that the catalyst crystal shows has very high catalytic activity and is difficult for oxidized;
The 4th step: repeating step two and step 3, until on electrode matrix, catalyst loading entered for the 5th step after reaching the catalyst loading of setting;
By repeating step two and step 3, can form multilayer Multi-layer structure at catalyst layer, this structure can increase the electrochemical surface area of electrode, improves electrode performance;
The 5th step: activated electrode
The concentration of packing in electrochemical cell is 0.05～5mol/L sulfuric acid H 2SO 4Perhaps perchloric acid HClO 4Solution, the electrode that the 4th step obtained is put into electrochemical cell as work electrode, consist of three-electrode system with reference electrode with together with electrode, then in the potential region that with respect to standard hydrogen electrode SHE is-0.20～1.70V with electrochemical method activated electrode repeatedly, until obtain the curve of coincidence fully, at last it is taken out, rinse the preparation of namely completing curved surface electrode surface catalyst layer with deionized water well.
Preferred version according to the preparation method of curved surface electrode surface catalyst layer of the present invention, to insert in electrochemical cell through pretreated electrode matrix described in second step, pack in electrochemical cell and contain the cationic electroplate liquid of catalyst, the described cationic electroplate liquid of catalyst that contains is that the mass fraction that is dissolved in 0.1～3mol/L watery hydrochloric acid HCl is 0.1～3wt.% palladium bichloride PdCl 2Perhaps chloroplatinic acid H 2PtCl 6Perhaps cobalt chloride CoCl 2Perhaps nickel chloride NiCl 2Perhaps ruthenic chloride RuCl 3Solution.
Preferred version according to the preparation method of curved surface electrode catalyst layer of the present invention, described in the 5th step in the potential region that with respect to standard hydrogen electrode SHE is-0.20～1.70V with electrochemical method activated electrode repeatedly, wherein, electrochemical method comprises linear volt-ampere scanning method or cyclic voltammetry scan method or step potential method.
According to the preparation method's of curved surface electrode catalyst layer of the present invention preferred version, electrode matrix is carbon-point or other contact rods.
The preparation method's of curved surface electrode catalyst layer of the present invention beneficial effect is: the present invention uses the electrochemical method deposited catalyst, can carry out uniform electrochemical deposition on curved surface electrode, and the catalyst layer of formation is evenly distributed on curved surface; The present invention can significantly reduce the overpotential in electrochemical deposition process, eliminates the dendritic growth of catalyst crystal, and impels the catalyst crystal to carry out the growth of " island island " type, reduces catalyst particle size; The crystal orientation of the catalyst crystal performance of the present invention preparation has very high catalytic activity and is difficult for oxidizedly, is best suited for the catalyst crystal orientation of fuel cell; Adopt the present invention, can form sandwich construction at catalyst layer, this structure can increase the electrochemical surface area of electrode, improves electrode performance; The present invention has a good application prospect.
Description of drawings
Fig. 1 a is the curved surface electrode catalyst layer surface electronic flying-spot microscope photo that adopts method preparation in patent US2004072047-A1.
Fig. 1 b is the curved surface electrode catalyst layer surface electronic flying-spot microscope photo that adopts method preparation in patent US2006210867-A1.
Fig. 1 c is the curved surface electrode catalyst layer surface electronic flying-spot microscope photo of preparation method's preparation of the present invention.
Fig. 2 a is the cross section electron scanning micrograph that adopts the curved surface electrode catalyst layer of method preparation in patent US2004072047-A1.
Fig. 2 b is the cross section electron scanning micrograph that adopts the curved surface electrode catalyst layer of method preparation in patent US2006210867-A1.
Fig. 2 c is the cross section electron scanning micrograph of the curved surface electrode catalyst layer of preparation method's preparation of the present invention.
Fig. 3 adopts the present invention curved surface electrode that obtains and the performance comparison diagram that adopts the curved surface electrode that in patent US2004072047-A1 and patent US2006210867-A1, method makes.
Embodiment
The preparation method of curved surface electrode catalyst layer is characterized in: comprise the following steps:
The first step: the electrode matrix preliminary treatment, be used for removing micro-grease and the metal oxide of electrode matrix surface attachment, electrode matrix can be carbon-point or other contact rods; Concrete grammar can adopt: electrode matrix is put into the alkaline solution that concentration is 0.1～5mol/L, and alkaline solution can be NaOH NaOH or potassium hydroxide KOH solution; Controlling solution temperature by constant temperature blender with magnetic force is 25～100 ℃, and stirred, to remove the micro-grease of electrode matrix surface attachment, took out electrode matrix after 5～120 minutes, rinse well with deionized water, then electrode matrix being put into concentration is 0.1～5mol/L acid solution, and this diluted acid solution can be hydrochloric acid HCl or dilute sulfuric acid H 2SO 4Solution etc.; Removing the metal oxide of electrode matrix surface attachment, after will again its taking-up be rinsed well with deionized water, drying for standby at room temperature;
Second step: electrochemical deposition catalyst
To insert in electrochemical cell through pretreated electrode matrix, and pack in electrochemical cell and contain the cationic electroplate liquid of catalyst, the described cationic electroplate liquid of catalyst that contains is the 0.1～3wt.% palladium bichloride PdCl that is dissolved in 0.1～3mol/L watery hydrochloric acid 2Perhaps chloroplatinic acid H 2PtCl 6Perhaps cobalt chloride CoCl 2Perhaps nickel chloride NiCl 2Perhaps ruthenic chloride RuCl 3Solution; With electrode matrix as work electrode, with reference electrode such as silver/silver chloride electrode Ag/AgCl or saturated calomel electrode SCE or standard hydrogen electrode SHE, consist of three-electrode system together with electrode such as platinum Pt sheet or platinum filament or gauze platinum electrode, control the work electrode current potential by electrochemical workstation or potentiostat and carry out electrochemical deposition with respect to standard hydrogen electrode SHE for-0.7～0.5V, until on electrode matrix, catalyst loading reaches predetermined carrying capacity, as 0.05～3.0mg/cm 2, then electrode matrix is taken out, with standby at air drying after deionized water rinsing;
The 3rd step: flood in perfluorinated sulfonic resin Nafion solution
To immerse the perfluorinated sulfonic resin Nafion solution 1～30 minute of 0.1～5wt.% through the electrode matrix of electrochemical deposition, then it be taken out at air drying;
The 4th step: repeating step two and step 3, until on electrode matrix, catalyst loading reaches the catalyst loading of setting, can set catalyst loading is 0.1～10.0mg/cm 2, then entered for the 5th step;
The 5th step: activated electrode
The concentration of packing in electrochemical cell is 0.05～5mol/L sulfuric acid H 2SO 4Perhaps perchloric acid HClO 4Solution, the electrode that the 4th step obtained is put into electrochemical cell, and as work electrode, with reference electrode, consist of three-electrode system together with electrode, then in the potential region that with respect to standard hydrogen electrode SHE is-0.20～1.70V with electrochemical method activated electrode repeatedly, this electrochemical method can adopt linear volt-ampere scanning method or cyclic voltammetry scan method or step potential method, until the linear volt-ampere scanning curve or cyclic voltammetry scan curve or the step potential curve that obtain to overlap fully, at last electrode is taken out, rinse well with deionized water.
Wherein, reference electrode can adopt silver/silver chloride electrode Ag/AgCl or saturated calomel electrode SCE or standard hydrogen electrode SHE, can adopt platinum Pt sheet or platinum filament or gauze platinum electrode to electrode.
Below in conjunction with embodiment, the present invention is further described specifically, but embodiments of the present invention are not limited to this.
Embodiment 1
The first step: the graphite rod immersion concentration that is 0.5mm with diameter is the NaOH NaOH solution of 1mol/L, and using constant temperature blender with magnetic force to control temperature is 80 ℃, and is stirred; After 30 minutes, graphite rod is taken out, it is rinsed repeatedly rear at air drying with deionized water; Then it being immersed concentration is the watery hydrochloric acid HCl solution of 1mol/L, is stirred equally, after 3 hours, graphite rod is got and is removed, standby at air drying after rinsing well with deionized water;
Second step: will be placed in the electrochemical deposition pond through pretreated graphite rod, and pack in the electrochemical deposition pond and contain the cationic electroplate liquid of catalyst, this electroplate liquid is to be dissolved in that in the watery hydrochloric acid that concentration is 1mol/L, mass fraction is the palladium bichloride PdCl of 1wt.% 2Solution; As work electrode, with reference electrode, to electrode formation three-electrode system, carry out electrochemical deposition with graphite rod; Controlling the work electrode current potential by electrochemical workstation is that 0.1V carries out the constant potential electrochemical deposition with respect to standard hydrogen electrode SHE, until on graphite rod, the Pd catalyst loading reaches 1mg/cm 2The graphite rod that is coated with the Pd catalyst is taken out, standby at air drying after rinsing well with deionized water;
The 3rd step: the graphite rod immersion mass fraction that will be coated with the Pd catalyst is the perfluorinated sulfonic resin Nafion solution of 5wt.%, takes out at air drying after 5 minutes;
The 4th step: repeat electrochemical deposition step 2 and step 3; Totally 5 times; Until on graphite rod, the Pd catalyst loading reaches 5mg/cm 2;
The 5th step: activated electrode
The concentration of packing in electrochemical cell is the sulfuric acid H of 0.5mol/L 2SO 4Solution, the electrode that the 4th step obtained is put into electrochemical cell, and as work electrode, with reference electrode, to electrode formation three-electrode system, take with respect to the potential region of standard hydrogen electrode SHE as-0.2～1.0V, carry out cyclic voltammetry scan with the sweep speed of 50mV/s and carry out electrode activation, until obtain the cyclic voltammetry curve of coincidence fully, then with its taking-up, rinse well with deionized water.
Embodiment 2:
The first step: the carbon-point immersion concentration that is 1.0mm with diameter is the potassium hydroxide KOH solution of 5mol/L, and using constant temperature blender with magnetic force to control temperature is 25 ℃, and is stirred; After 10 minutes, carbon-point is taken out, it is rinsed repeatedly rear at air drying with deionized water; Then it being immersed concentration is the dilute sulfuric acid H of 5mol/L 2SO 4Solution is stirred equally, after 2 hours, carbon-point is taken out, and is standby at air drying after rinsing well with deionized water;
Second step: carbon-point is placed in the electrochemical deposition pond, packs in the electrochemical deposition pond and contain the cationic electroplate liquid of catalyst, this electroplate liquid is to be dissolved in that in the watery hydrochloric acid that concentration is 3mol/L, mass fraction is the chloroplatinic acid H of 3wt.% 2PtCl 6Solution; As work electrode, with reference electrode, to electrode formation three-electrode system, carry out electrochemical deposition with carbon-point; Controlling the work electrode current potential by potentiostat is that 0.4V carries out the constant potential electrochemical deposition with respect to standard hydrogen electrode SHE, until on carbon-point, the Pt catalyst loading reaches 1.5mg/cm 2The carbon-point that is coated with the Pt catalyst is taken out, standby at air drying after rinsing well with deionized water;
The 3rd step: the carbon rod immersion mass fraction that will be coated with the Pt catalyst is the perfluorinated sulfonic resin Nafion solution of 0.5wt.%, takes out at air drying after 30 minutes;
The 4th step: repeating step 2 and step 3; Totally 3 times; After completing on carbon rod the Pt catalyst loading reach 4.5mg/cm 2
The 5th step: the concentration of packing in electrochemical cell is the perchloric acid HClO of 5mol/L 4Solution, the electrode that the 4th step obtained is put into electrochemical cell, and as work electrode, with reference electrode, to electrode formation three-electrode system, be the potential region of 0.0～1.2V with respect to standard hydrogen electrode SHE, carrying out the linearity volt-ampere with the sweep speed of 10mV/s and be scanned into the column electrode activation, until the linear volt-ampere scanning curve that obtains to overlap fully, then with its taking-up, rinse well with deionized water.
Embodiment 3:
Different from embodiment 1 first step is that electrode matrix is the titanium rod;
Second step: the titanium rod is placed in the electrochemical deposition pond, packs in the electrochemical deposition pond and contain the cationic electroplate liquid of catalyst, this electroplate liquid is to be dissolved in that in the watery hydrochloric acid that concentration is 2mol/L, mass fraction is the nickel chloride NiCl of 1.5wt.% 2Solution; As work electrode, with reference electrode, to electrode formation three-electrode system, carry out electrochemical deposition with the titanium rod; By electrochemical workstation control the work electrode current potential with respect to standard hydrogen electrode SHE for-0.2V carries out the constant potential electrochemical deposition, until on the titanium rod, the Raney nickel carrying capacity reaches 1.0mg/cm 2The titanium rod that is coated with Raney nickel is taken out, standby at air drying after rinsing well with deionized water;
The 3rd step: the titanium rod immersion mass fraction that will be coated with Raney nickel is the perfluorinated sulfonic resin Nafion solution of 2.5wt.%, takes out at air drying after 15 minutes;
The 4th step: repeat electrochemical deposition step 2 and step 3; Totally 4 times; Until on the titanium rod, the Raney nickel carrying capacity reaches 4mg/cm 2
The 5th step: activated electrode
The concentration of packing in electrochemical cell is the perchloric acid HClO of 2mol/L 4Solution, the electrode that the 4th step obtained is put into electrochemical cell, and as work electrode, with reference electrode, to electrode formation three-electrode system, take with respect to the potential region of standard hydrogen electrode SHE as 0.2～1.4V, carry out step potential with the sweep speed of 20mV/s and be scanned into the column electrode activation, until obtain the step potential scanning curve of coincidence fully, then with its taking-up, rinse well with deionized water.
Embodiment 4:
Different from embodiment 2 first steps is that electrode matrix is copper rod;
Second step: copper rod is placed in the electrochemical deposition pond, packs in the electrochemical deposition pond and contain the cationic electroplate liquid of catalyst, this electroplate liquid is to be dissolved in that in the watery hydrochloric acid that concentration is 0.5mol/L, mass fraction is the cobalt chloride CoCl of 2.0wt.% 2Solution; As work electrode, with reference electrode, to electrode formation three-electrode system, carry out electrochemical deposition with copper rod; By electrochemical workstation control the work electrode current potential for respect to standard hydrogen electrode SHE for-0.4V carries out the constant potential electrochemical deposition, until on copper rod, the Co catalysts carrying capacity reaches 0.2mg/cm 2The copper rod that is coated with Co catalysts is taken out, standby at air drying after rinsing well with deionized water;
The 3rd step: the copper rod immersion mass fraction that will be coated with Co catalysts is the perfluorinated sulfonic resin Nafion solution of 1.0wt.%, takes out at air drying after 20 minutes;
The 4th step: repeat electrochemical deposition step 2 and step 3; Totally 15 times; Until on copper rod, the Co catalysts carrying capacity reaches 3mg/cm 2
The 5th step: activated electrode
The concentration of packing in electrochemical cell is the perchloric acid HClO of 1.0mol/L 4Solution, the electrode that the 4th step obtained is put into electrochemical cell, and as work electrode, with reference electrode, to electrode formation three-electrode system, be the potential region of 0.0～1.5V with respect to standard hydrogen electrode SHE, carrying out step potential with the sweep speed of 40mV/s and be scanned into the column electrode activation, until obtain the step potential scanning curve of coincidence fully, then with its taking-up, rinse well with deionized water.
Embodiment 5:
Different from embodiment 1 first step is that the employing diameter is the graphite rod of 2mm:
Second step: graphite rod is placed in the electrochemical deposition pond, packs in the electrochemical deposition pond and contain the cationic electroplate liquid of catalyst, this electroplate liquid is to be dissolved in the ruthenic chloride RuCl that mass fraction in the watery hydrochloric acid that concentration is 1.5mol/L is 0.5wt.% 3With chloroplatinic acid H 2PtCl 6Mixed solution; As work electrode, with reference electrode, to electrode formation three-electrode system, carry out electrochemical deposition with graphite rod; By electrochemical workstation control the work electrode current potential with respect to standard hydrogen electrode SHE for-0.7V carries out the constant potential electrochemical deposition, until on graphite rod, platinum ruthenium catalyst carrying capacity reaches 0.8mg/cm 2The graphite rod that is coated with platinum-ruthenium Pt-Ru catalyst is taken out, standby at air drying after rinsing well with deionized water;
The 3rd step: the graphite rod immersion mass fraction that will be coated with platinum-ruthenium catalyst is the perfluorinated sulfonic resin Nafion solution of 4.0wt.%, takes out at air drying after 10 minutes;
The 4th step: repeat electrochemical deposition step 2 and step 3; Totally 6 times; Until on graphite rod, the Pt-Ru catalyst loading reaches 4.8mg/cm 2
The 5th step: activated electrode
The concentration of packing in electrochemical cell is the sulfuric acid H of 3mol/L 2SO 4Solution, the electrode that the 4th step obtained is put into electrochemical cell, and as work electrode, with reference electrode, to electrode formation three-electrode system, be the potential region of 0.0～1.7V with respect to standard hydrogen electrode SHE, carrying out step potential with the sweep speed of 30mV/s and be scanned into the column electrode activation, until obtain the step potential scanning curve of coincidence fully, then with its taking-up, rinse well with deionized water.
Embodiment 6:
Observe embodiment 1,2 and 5 curved surface electrode catalyst layers that obtain with electronic scanner microscope, this curved surface electrode catalyst layer surface topography is as shown in Fig. 1 c, and the cross-sectional morphology of this curved surface electrode catalyst layer is as shown in Fig. 2 c.Dendritic growth does not appear in the electrode surface catalyst that can find out the inventive method preparation from Fig. 1 c, but presents the feature on " island ", can find out that from Fig. 2 c the catalyst layer that mode of the present invention prepares presents sandwich construction.
Adopt that in patent US2004072047-A1, method prepares curved surface electrode catalyst layer, observe with electronic scanner microscope, the curved surface electrode catalyst layer surface topography as shown in Figure 1a, the cross-sectional morphology of this curved surface electrode catalyst layer such as Fig. 2 a.Can find out that from Fig. 1 a and Fig. 2 a the electrode surface catalyst presents dendritic growth.
Adopt that in patent US2006210867-A1, method prepares curved surface electrode catalyst layer, observe with electronic scanner microscope, the electrode catalyst layer surface topography as shown in Fig. 1 b, the cross-sectional morphology of electrode catalyst layer such as Fig. 2 b.Can find out that from Fig. 1 b and Fig. 2 b the electrode surface catalyst cracking, aliquation occur, comes off, the catalyst agglomeration phenomenon.
And will see with the performance that adopts the curved surface electrode that in patent US2004072047-A1 and patent US2006210867-A1, method makes according to the curved surface electrode that the present invention obtains and relatively see Fig. 3 and following table, by Fig. 3 and following table as seen, be 0.0～0.9V at potential region with respect to standard hydrogen electrode SHE, when sweep speed was 10mV/s, the curved surface electrode of the inventive method preparation had maximum Oxidation of Formic Acid peak current density.
Figure GDA00003336448200131

Claims (4)

1. the preparation method of curved surface electrode catalyst layer is characterized in that: comprise the following steps:
The first step: the electrode matrix preliminary treatment is used for removing micro-grease and the metal oxide of electrode matrix surface attachment;
Second step: electrochemical deposition catalyst
To insert in the electrochemical deposition pond through pretreated electrode matrix, pack in the electrochemical deposition pond and contain the cationic electroplate liquid of catalyst, with electrode matrix as work electrode, with reference electrode, consist of three-electrode system together with electrode, control the work electrode current potential and carry out electrochemical deposition with respect to standard hydrogen electrode for-0.7V～0.5V, until on electrode matrix, catalyst loading reaches predetermined carrying capacity, then electrode matrix is taken out, with standby at air drying after deionized water rinsing;
The 3rd step: flood in perfluor sulfoacid resin solution
To immerse the perfluor sulfoacid resin solution 1～30 minute of 0.1～5wt.% through the electrode matrix of electrochemical deposition, then it be taken out at air drying;
The 4th step: repeating step two and step 3, until on electrode matrix, catalyst loading entered for the 5th step after reaching the catalyst loading of setting;
The 5th step: activated electrode
The concentration of packing in electrochemical cell is 0.05～5mol/L sulfuric acid or perchloric acid solution, the electrode that the 4th step obtained is put into electrochemical cell, and as work electrode, consist of three-electrode system with reference electrode with together with electrode, then with respect to standard hydrogen electrode be-potential region of 0.20V～1.70V in electrochemical method activated electrode repeatedly, until obtain the curve of coincidence fully, with its taking-up, rinse well with deionized water at last.
2. the preparation method of curved surface electrode catalyst layer according to claim 1, it is characterized in that: will insert in the electrochemical deposition pond through pretreated electrode matrix described in second step, pack in the electrochemical deposition pond and contain the cationic electroplate liquid of catalyst, the described cationic electroplate liquid of catalyst that contains is that the mass fraction that is dissolved in 0.1～3mol/L watery hydrochloric acid is palladium bichloride or chloroplatinic acid or ruthenic chloride or cobalt chloride or the nickel chloride solution of 0.1～3wt.%.
3. the preparation method of curved surface electrode catalyst layer according to claim 1, it is characterized in that: described in the 5th step with respect to standard hydrogen electrode for the potential region of-0.20V～1.70V in electrochemical method activated electrode repeatedly, wherein, electrochemical method is linear volt-ampere scanning method or cyclic voltammetry scan method or step potential method.
4. the preparation method of according to claim 1 and 2 or 3 described curved surface electrode catalyst layers, it is characterized in that: electrode matrix is carbon-point or other contact rods.
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