CN102403516A - Preparation method of curved surface electrode catalyst layer - Google Patents

Preparation method of curved surface electrode catalyst layer Download PDF

Info

Publication number
CN102403516A
CN102403516A CN2011102212275A CN201110221227A CN102403516A CN 102403516 A CN102403516 A CN 102403516A CN 2011102212275 A CN2011102212275 A CN 2011102212275A CN 201110221227 A CN201110221227 A CN 201110221227A CN 102403516 A CN102403516 A CN 102403516A
Authority
CN
China
Prior art keywords
electrode
catalyst
matrix
electrochemical deposition
electrochemical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011102212275A
Other languages
Chinese (zh)
Other versions
CN102403516B (en
Inventor
叶丁丁
张彪
李俊
朱恂
廖强
王宏
王永忠
丁玉栋
陈蓉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chongqing University
Original Assignee
Chongqing University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chongqing University filed Critical Chongqing University
Priority to CN2011102212275A priority Critical patent/CN102403516B/en
Publication of CN102403516A publication Critical patent/CN102403516A/en
Application granted granted Critical
Publication of CN102403516B publication Critical patent/CN102403516B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02E60/50—Fuel cells

Landscapes

  • Inert Electrodes (AREA)
  • Catalysts (AREA)

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

Curved surface electrode catalyst layer preparation method
Technical field
The present invention relates to the electrode catalyst layer preparation method, be specifically related to curved surface electrode catalyst layer preparation method.
Background technology
Comprise that at various common electrochemical reactors electrode matrix commonly used in fuel cell, electrolytic cell, the electrochemical cell etc. mainly contains the stable and corrosion resistant material with carbon element of electrochemical properties such as carbon paper, carbon cloth, carbon felt, graphite cake.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 the performance and the volumetric power density of electrochemical reactor with respect to plane electrode.
In Proton Exchange Membrane Fuel Cells, use the membrane electrode Membrane Electrode Assembly of waveform waved; MEA can increase electrode surface area and strengthen the transmission of reactive material; Improve fuel cell performance and volumetric power density W.R. Merida, G. McLean, N. Djilali; Journal of Power Sources, 102 (2001) 178-185..Yet this waveform membrane electrode also is to use carbon paper as electrode matrix, and cost is higher, and is corroded easily with the 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 in the microfluid fuel cell, to use graphite rod as electrode matrix.Graphite rod low price, easy, the wide material sources of production use graphite rod can significantly reduce battery cost as electrode matrix.Use the such cylindrical surface electrode of graphite rod not only can increase the electro-chemical activity surface area of electrode in the battery as the place of electrochemical reaction generation; 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 microfluid fuel cell performance and fuel availability simultaneously.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; Need not 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 3Characteristics such as liquid fuels such as OH and formic acid HCOOH have wide material sources, are easy to produce, energy density height, environmental friendliness are the desirable fuel of fuel cell.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 Preparation of Catalyst mainly can be divided into electrochemical deposition method and two types of direct attachment methods in the method for curved surface electrode matrix.As adopting electrochemical deposition method to carry out the electrochemical deposition catalyst among the patent US2004072047-A1; Can cause catalyst crystal dendritic growth Dendritic growth; Make the catalyst crystal particle diameter increase, reduce the 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 evenly disperses it it being coated on electrode surface, with promptly forming catalyst layer after the thermolamp oven dry; Adopt the used nanoparticle catalyst activity of direct attachment method higher; But this preparation method only is applicable to the electrode structure on plane; Be difficult to evenly to distribute at curved surface electrode surface catalyst slurry, and owing to the curved surface unequal reason of being heated, directly the catalyst layer of attachment method preparation cracking, the aliquation that can occur causing by thermal stress, phenomenon such as come off; Cause catalyst waste, seriously even make catalyst complete failure.In addition,, also make the part catalyst not contact, can not produce catalytic effect, cause the utilance of noble metal catalyst limited with reactive material owing to the phenomenon of catalyst nano particle agglomeration in catalyst pulp, can occur; Like the direct attachment method of the catalyst that adopts among the 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 promptly 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 this 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: may further comprise the steps:
The first step: the electrode matrix preliminary treatment is used to remove the micro-grease and the metal oxide of electrode matrix surface attachment;
Second step: electrochemical deposition catalyst
To pass through pretreated electrode matrix inserts in the electrochemical cell; In electrochemical cell, pack into and contain the cationic electroplate liquid of catalyst; With electrode matrix as work electrode; With reference electrode, electrode is constituted three-electrode system, carry out electrochemical deposition with respect to standard hydrogen electrode SHE for-0.7～0.5 V through electrochemical workstation or potentiostat Control work electrode potential, catalyst loading reaches predetermined carrying capacity on electrode matrix; Then electrode matrix is taken out, with subsequent use behind the deionized water rinsing at air drying;
Utilization electrochemical method deposited catalyst; Can on curved surface electrode, carry out uniform electrochemical deposition; 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, problem such as come off;
The 3rd step: in perfluorinated sulfonic resin Nafion solution, flood
The electrode matrix that will pass through electrochemical deposition immerses the perfluorinated sulfonic resin Nafion solution 1～30 minute of 0.1～5 wt.%, then it is taken out at air drying;
This step can significantly reduce the overpotential in the 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 got into for the 5th step reach the catalyst loading of setting up to catalyst loading on the electrode matrix after;
Through repeating step two and step 3, can form multilayer Multi-layer structure at catalyst layer, this structure can increase the electro-chemical activity area of electrode, improves electrode performance;
The 5th step: activated electrode
The concentration of in electrochemical cell, packing into is 0.05～5 mol/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; Constitute three-electrode system with reference electrode with to electrode, then in the potential region that with respect to standard hydrogen electrode SHE is-0.20～1.70 V with electrochemical method activated electrode repeatedly, up to the curve that obtains to overlap fully; At last it is taken out, rinse the preparation of promptly accomplishing 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 pass through pretreated electrode matrix described in second step inserts in the electrochemical cell; In electrochemical cell, pack into and contain the cationic electroplate liquid of catalyst, the said cationic electroplate liquid of catalyst that contains is that the mass fraction that is dissolved among 0.1～3 mol/L watery hydrochloric acid HCl is 0.1～3 wt.% 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 4th step in the potential region that with respect to standard hydrogen electrode SHE is-0.20～1.70 V 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 graphite rod or 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 on curved surface electrode, carry out uniform electrochemical deposition, and the catalyst layer of formation is evenly distributed on curved surface; The present invention can significantly reduce the overpotential in the 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 electro-chemical activity 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 electron scanning micrograph that adopts method preparation among the patent US2004072047-A1.
Fig. 1 b is the curved surface electrode catalyst layer surface electron scanning micrograph that adopts method preparation among the patent US2006210867-A1.
Fig. 1 c is the curved surface electrode catalyst layer surface electron scanning micrograph 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 among the patent US2004072047-A1.
Fig. 2 b is the cross section electron scanning micrograph that adopts the curved surface electrode catalyst layer of method preparation among the 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 method makes among patent US2004072047-A1 and the patent US2006210867-A1.
Embodiment
The preparation method of curved surface electrode catalyst layer is characterized in: may further comprise the steps:
The first step: the electrode matrix preliminary treatment, be used to remove the micro-grease and the metal oxide of electrode matrix surface attachment, electrode matrix can be graphite rod or carbon-point or other contact rods; Concrete grammar can adopt: electrode matrix is put into the alkaline solution that concentration is 0.1～5 mol/L, and alkaline solution can be NaOH NaOH or potassium hydroxide KOH solution; Through constant temperature blender with magnetic force control solution temperature is 25～100 ℃; And stir; To remove the micro-grease of electrode matrix surface attachment, after 5～120 minutes, take out electrode matrix, rinse well with deionized water; Then electrode matrix being put into concentration is 0.1～5 mol/L acid solution, and this diluted acid property 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 drying for standby at room temperature with deionized water;
Second step: electrochemical deposition catalyst
To pass through pretreated electrode matrix and insert in the electrochemical cell, and in electrochemical cell, pack into and contain the cationic electroplate liquid of catalyst, the said cationic electroplate liquid of catalyst that contains is 0.1～3 wt.% palladium bichloride PdCl that is dissolved in 0.1～3 mol/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, electrode such as platinum Pt sheet or platinum filament or gauze platinum electrode are constituted three-electrode system; Carry out electrochemical deposition with respect to standard hydrogen electrode SHE for-0.7～0.5 V through electrochemical workstation or potentiostat Control work electrode potential; Catalyst loading reaches predetermined carrying capacity on electrode matrix, like 0.05～3.0 mg/cm 2, then electrode matrix is taken out, with subsequent use behind the deionized water rinsing at air drying;
The 3rd step: in perfluorinated sulfonic resin Nafion solution, flood
The electrode matrix that will pass through electrochemical deposition immerses the perfluorinated sulfonic resin Nafion solution 1～30 minute of 0.1～5 wt.%, then it is taken out at air drying;
The 4th step: repeating step two and step 3, catalyst loading reaches the catalyst loading of setting on electrode matrix, and can set catalyst loading is 0.1～10.0 mg/cm 2, got into for the 5th step then;
The 5th step: activated electrode
The concentration of in electrochemical cell, packing into is 0.05～5 mol/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, electrode is constituted three-electrode system, then in the potential region that with respect to standard hydrogen electrode SHE is-0.20～1.70 V 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; Linear volt-ampere scanning curve or cyclic voltammetry scan curve or step potential curve up to obtaining to overlap fully take out electrode at last, 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 made further specific descriptions, but execution mode of the present invention is not limited thereto.
Embodiment 1
The first step: with diameter be the graphite rod of 0.5 mm to immerse concentration be the NaOH NaOH solution of 1 mol/L, using constant temperature blender with magnetic force control temperature is 80 ℃, and stirs; After 30 minutes graphite rod is taken out, it is washed the back repeatedly at air drying with deionized water; Then it being immersed concentration is the watery hydrochloric acid HCl solution of 1 mol/L, stirs equally, after 3 hours graphite rod is got and removes, and it is subsequent use at air drying to rinse the back well with deionized water;
Second step: will pass through pretreated graphite rod and place the electrochemical deposition pond, and in the electrochemical deposition pond, pack into and contain the cationic electroplate liquid of catalyst, this electroplate liquid is to be dissolved in that mass fraction is the palladium bichloride PdCl of 1 wt.% in the watery hydrochloric acid that concentration is 1 mol/L 2Solution; As work electrode,, carry out electrochemical deposition with graphite rod with reference electrode, to electrode formation three-electrode system; Is that 0.1 V carries out the constant potential electrochemical deposition through electrochemical workstation Control work electrode potential with respect to standard hydrogen electrode SHE, and the Pd catalyst loading reaches 1 mg/cm on graphite rod 2The graphite rod that is coated with the Pd catalyst is taken out, subsequent use after rinsing well with deionized water at air drying;
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 5 wt.%, takes out after 5 minutes at air drying;
The 4th step: repeat electrochemical deposition step 2 and step 3; Totally 5 times; The Pd catalyst loading reaches 5mg/cm on graphite rod 2;
The 5th step: activated electrode
The concentration of in electrochemical cell, packing into is the sulfuric acid H of 0.5 mol/L 2SO 4Solution is put into electrochemical cell with the electrode that the 4th step obtained, and as work electrode; With reference electrode, to electrode formation three-electrode system; To be the potential region of-0.2～1.0 V, carry out cyclic voltammetry scan with the sweep speed of 50 mV/s and carry out electrode activation, up to the cyclic voltammetry curve that obtains to overlap fully with respect to standard hydrogen electrode SHE; With its taking-up, rinse well then with deionized water.
Embodiment 2:
The first step: with diameter be the carbon-point of 1.0 mm to immerse concentration be the potassium hydroxide KOH solution of 5 mol/L, using constant temperature blender with magnetic force control temperature is 25 ℃, and stirs; After 10 minutes carbon-point is taken out, it is washed the back repeatedly at air drying with deionized water; Then it being immersed concentration is the dilute sulfuric acid H of 5 mol/L 2SO 4Solution stirs equally, after 2 hours carbon-point is taken out, and is subsequent use at air drying after rinsing well with deionized water;
Second step: carbon-point is placed the electrochemical deposition pond, in the electrochemical deposition pond, pack into and contain the cationic electroplate liquid of catalyst, this electroplate liquid is to be dissolved in that mass fraction is the chloroplatinic acid H of 3 wt.% in the watery hydrochloric acid that concentration is 3 mol/L 2PtCl 6Solution; As work electrode,, carry out electrochemical deposition with carbon-point with reference electrode, to electrode formation three-electrode system; Is that 0.4 V carries out the constant potential electrochemical deposition through potentiostat Control work electrode potential with respect to standard hydrogen electrode SHE, and the Pt catalyst loading reaches 1.5 mg/cm on carbon-point 2The carbon-point that is coated with the Pt catalyst is taken out, subsequent use after rinsing well with deionized water at air drying;
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 0.5 wt.%, takes out after 30 minutes at air drying;
The 4th step: repeating step 2 and step 3; Totally 3 times; After accomplishing on the carbon rod Pt catalyst loading reach 4.5 mg/cm 2
The 5th step: the concentration of in electrochemical cell, packing into is the perchloric acid HClO of 5 mol/L 4Solution is put into electrochemical cell with the electrode that the 4th step obtained, and as work electrode; With reference electrode, to electrode formation three-electrode system; Be the potential region of 0.0～1.2 V with respect to standard hydrogen electrode SHE, carrying out linearity volt-ampere scanning carrying out electrode activation, up to the linear volt-ampere scanning curve that obtains to overlap fully with the sweep speed of 10 mV/s; With its taking-up, rinse well then with deionized water.
Embodiment 3:
Different with embodiment 1 first step is that electrode matrix is the titanium rod;
Second step: the titanium rod is placed the electrochemical deposition pond, in the electrochemical deposition pond, pack into and contain the cationic electroplate liquid of catalyst, this electroplate liquid is to be dissolved in that mass fraction is the nickel chloride NiCl of 1.5 wt.% in the watery hydrochloric acid that concentration is 2 mol/L 2Solution; As work electrode,, carry out electrochemical deposition with the titanium rod with reference electrode, to electrode formation three-electrode system; Carry out constant potential electrochemical deposition with respect to standard hydrogen electrode SHE for-0.2 V through electrochemical workstation Control work electrode potential, the Raney nickel carrying capacity reaches 1.0 mg/cm on the titanium rod 2The titanium rod that is coated with Raney nickel is taken out, subsequent use after rinsing well with deionized water at air drying;
The 3rd step: the titanium rod immersion mass fraction that will be coated with Raney nickel is the perfluorinated sulfonic resin Nafion solution of 2.5 wt.%, takes out after 15 minutes at air drying;
The 4th step: repeat electrochemical deposition step 2 and step 3; Totally 4 times; The Raney nickel carrying capacity reaches 4mg/cm on the titanium rod 2
The 5th step: activated electrode
The concentration of in electrochemical cell, packing into is the perchloric acid HClO of 2 mol/L 4Solution is put into electrochemical cell with the electrode that the 4th step obtained, and as work electrode; With reference electrode, to electrode formation three-electrode system; To be the potential region of 0.2～1.4 V, to carry out step potential scanning with the sweep speed of 20 mV/s and carry out electrode activation, up to the step potential scanning curve that obtains to overlap fully with respect to standard hydrogen electrode SHE; With its taking-up, rinse well then with deionized water.
Embodiment 4:
Different with embodiment 2 first steps is that electrode matrix is a copper rod;
Second step: copper rod is placed the electrochemical deposition pond, in the electrochemical deposition pond, pack into and contain the cationic electroplate liquid of catalyst, this electroplate liquid is to be dissolved in that mass fraction is the cobalt chloride CoCl of 2.0 wt.% in the watery hydrochloric acid that concentration is 0.5 mol/L 2Solution; As work electrode,, carry out electrochemical deposition with copper rod with reference electrode, to electrode formation three-electrode system; For to carry out the constant potential electrochemical deposition with respect to standard hydrogen electrode SHE for-0.4 V, the Co catalysts carrying capacity reaches 0.2 mg/cm on copper rod through electrochemical workstation Control work electrode potential 2The copper rod that is coated with Co catalysts is taken out, subsequent use after rinsing well with deionized water at air drying;
The 3rd step: the copper rod immersion mass fraction that will be coated with Co catalysts is the perfluorinated sulfonic resin Nafion solution of 1.0 wt.%, takes out after 20 minutes at air drying;
The 4th step: repeat electrochemical deposition step 2 and step 3; Totally 15 times; The Co catalysts carrying capacity reaches 3 mg/cm on copper rod 2
The 5th step: activated electrode
The concentration of in electrochemical cell, packing into is the perchloric acid HClO of 1.0 mol/L 4Solution is put into electrochemical cell with the electrode that the 4th step obtained, and as work electrode; With reference electrode, to electrode formation three-electrode system; Be the potential region of 0.0～1.5 V with respect to standard hydrogen electrode SHE, carrying out step potential scanning with the sweep speed of 40 mV/s and carry out electrode activation, up to the step potential scanning curve that obtains to overlap fully; With its taking-up, rinse well then with deionized water.
Embodiment 5:
Different with embodiment 1 first step is that the employing diameter is the graphite rod of 2 mm:
Second step: graphite rod is placed the electrochemical deposition pond, in the electrochemical deposition pond, pack into 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 1.5 mol/L is 0.5 wt.% 3With chloroplatinic acid H 2PtCl 6Mixed solution; As work electrode,, carry out electrochemical deposition with graphite rod with reference electrode, to electrode formation three-electrode system; Carry out constant potential electrochemical deposition with respect to standard hydrogen electrode SHE for-0.7 V through electrochemical workstation Control work electrode potential, platinum ruthenium catalyst carrying capacity reaches 0.8 mg/cm on graphite rod 2The graphite rod that is coated with platinum-ruthenium Pt-Ru catalyst is taken out, subsequent use after rinsing well with deionized water at air drying;
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 4.0 wt.%, takes out after 10 minutes at air drying;
The 4th step: repeat electrochemical deposition step 2 and step 3; Totally 6 times; The Pt-Ru catalyst loading reaches 4.8 mg/cm on graphite rod 2
The 5th step: activated electrode
The concentration of in electrochemical cell, packing into is the sulfuric acid H of 3 mol/L 2SO 4Solution is put into electrochemical cell with the electrode that the 4th step obtained, and as work electrode; With reference electrode, to electrode formation three-electrode system; Be the potential region of 0.0～1.7 V with respect to standard hydrogen electrode SHE, carrying out step potential scanning with the sweep speed of 30 mV/s and carry out electrode activation, up to the step potential scanning curve that obtains to overlap fully; With its taking-up, rinse well then with deionized water.
Embodiment 6:
Observe the curved surface electrode catalyst layer that embodiment 1,2 and 5 obtains with electronic scanner microscope, this curved surface electrode catalyst layer surface pattern is shown in Fig. 1 c, and the cross section pattern of this curved surface electrode catalyst layer is shown in Fig. 2 c.Dendritic growth does not appear in the electrode surface catalyst that from Fig. 1 c, can find out the inventive method preparation, but demonstrates the characteristic on " island ", can find out that from Fig. 2 c the catalyst layer that mode of the present invention prepares demonstrates sandwich construction.
Adopt that method prepares the curved surface electrode catalyst layer among the patent US2004072047-A1, observe with electronic scanner microscope, curved surface electrode catalyst layer surface pattern shown in Fig. 1 a, the cross section pattern 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 method prepares the curved surface electrode catalyst layer among the patent US2006210867-A1, observe with electronic scanner microscope, the electrode catalyst layer surface topography shown in Fig. 1 b, the cross section pattern 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 method makes among patent US2004072047-A1 and the patent US2006210867-A1 according to the curved surface electrode that the present invention obtains and relatively see Fig. 3 and following table; Visible by Fig. 3 and following table; Is 0.0～0.9 V at potential region with respect to standard hydrogen electrode SHE; When sweep speed was 10 mV/s, the curved surface electrode of the inventive method preparation had maximum formic acid oxidation peak current density.
 
Figure 75172DEST_PATH_IMAGE001

Claims (4)

1. the preparation method of curved surface electrode catalyst layer is characterized in that: may further comprise the steps:
The first step: the electrode matrix preliminary treatment is used to remove the micro-grease and the metal oxide of electrode matrix surface attachment;
Second step: electrochemical deposition catalyst
To pass through pretreated electrode matrix inserts in the electrochemical deposition pond; In the electrochemical deposition pond, pack into and contain the cationic electroplate liquid of catalyst, with electrode matrix as work electrode, with reference electrode, electrode is constituted three-electrode system; The Control work electrode potential is that-0.7 V～0.5 V carries out electrochemical deposition with respect to standard hydrogen electrode; Catalyst loading reaches predetermined carrying capacity on electrode matrix, then electrode matrix is taken out, with subsequent use at air drying behind the deionized water rinsing;
The 3rd step: in perfluor sulfoacid resin solution, flood
The electrode matrix that will pass through electrochemical deposition immerses the perfluor sulfoacid resin solution 1～30 minute of 0.1～5 wt.%, then it is taken out at air drying;
The 4th step: repeating step two and step 3 got into for the 5th step reach the catalyst loading of setting up to catalyst loading on the electrode matrix after;
The 5th step: activated electrode
The concentration of in electrochemical cell, packing into is 0.05～5 mol/L sulfuric acid or perchloric acid solution; The electrode that the 4th step obtained is put into electrochemical cell, and, constitute three-electrode system with reference electrode with to electrode as work electrode; Then in the potential region that with respect to standard hydrogen electrode is-0.20 V～1.70 V with electrochemical method activated electrode repeatedly; Up to the curve that obtains to overlap fully, with its taking-up, rinse well at last with deionized water.
2. the preparation method of curved surface electrode catalyst layer according to claim 1; It is characterized in that: will pass through pretreated electrode matrix described in second step and insert in the electrochemical deposition pond; In the electrochemical deposition pond, pack into and contain the cationic electroplate liquid of catalyst, the said cationic electroplate liquid of catalyst that contains is that the mass fraction that is dissolved in 0.1～3 mol/L watery hydrochloric acid is palladium bichloride or chloroplatinic acid or ruthenic chloride or cobalt chloride or the nickel chloride solution of 0.1～3 wt.%.
3. the preparation method of curved surface electrode catalyst layer according to claim 1; It is characterized in that: described in the 4th step with respect to standard hydrogen electrode in the potential region of-0.20 V～1.70 V with electrochemical method activated electrode repeatedly; Wherein, electrochemical method is linear volt-ampere scanning method or cyclic voltammetry scan method or step potential method.
4. according to the preparation method of claim 1 or 2 or 3 described curved surface electrode catalyst layers, it is characterized in that: electrode matrix is graphite rod or carbon-point or other contact rods.
CN2011102212275A 2011-08-04 2011-08-04 Preparation method of curved surface electrode catalyst layer Active CN102403516B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011102212275A CN102403516B (en) 2011-08-04 2011-08-04 Preparation method of curved surface electrode catalyst layer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011102212275A CN102403516B (en) 2011-08-04 2011-08-04 Preparation method of curved surface electrode catalyst layer

Publications (2)

Publication Number Publication Date
CN102403516A true CN102403516A (en) 2012-04-04
CN102403516B CN102403516B (en) 2013-11-06

Family

ID=45885489

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011102212275A Active CN102403516B (en) 2011-08-04 2011-08-04 Preparation method of curved surface electrode catalyst layer

Country Status (1)

Country Link
CN (1) CN102403516B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103093963A (en) * 2013-01-28 2013-05-08 北京大学 Flexible and light dye-sensitized solar cell with double faces specular
CN103219530A (en) * 2013-04-03 2013-07-24 胡国良 Treatment method of vanadium battery carbon felt electrode
CN107910559A (en) * 2017-09-27 2018-04-13 昆明理工大学 The preparation method of Ni-based ultralow platinum load catalyst for methanol in a kind of acid medium
CN107910562A (en) * 2017-11-08 2018-04-13 常州大学 A kind of inexpensive high activity tri-metal nano composite electrode preparation method
CN112786901A (en) * 2021-03-02 2021-05-11 上海交通大学 Preparation method of fuel cell membrane electrode with controllable surface buckling

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1472834A (en) * 2003-04-28 2004-02-04 重庆大学 Method for preparing proton interchange film fuel battery electrodes
CN1988226A (en) * 2005-12-21 2007-06-27 中国科学院大连化学物理研究所 Process for preparing integrated renewable fuel double effect oxygen electrode diffusion layer
CN101359744A (en) * 2008-09-08 2009-02-04 重庆大学 Method for carbon supported ultra-low platinum catalytic electrode preparation by indirect galvanic deposit

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1472834A (en) * 2003-04-28 2004-02-04 重庆大学 Method for preparing proton interchange film fuel battery electrodes
CN1988226A (en) * 2005-12-21 2007-06-27 中国科学院大连化学物理研究所 Process for preparing integrated renewable fuel double effect oxygen electrode diffusion layer
CN101359744A (en) * 2008-09-08 2009-02-04 重庆大学 Method for carbon supported ultra-low platinum catalytic electrode preparation by indirect galvanic deposit

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103093963A (en) * 2013-01-28 2013-05-08 北京大学 Flexible and light dye-sensitized solar cell with double faces specular
CN103219530A (en) * 2013-04-03 2013-07-24 胡国良 Treatment method of vanadium battery carbon felt electrode
CN107910559A (en) * 2017-09-27 2018-04-13 昆明理工大学 The preparation method of Ni-based ultralow platinum load catalyst for methanol in a kind of acid medium
CN107910559B (en) * 2017-09-27 2020-11-17 昆明理工大学 Preparation method of nickel-based ultralow platinum loaded methanol catalyst in acidic medium
CN107910562A (en) * 2017-11-08 2018-04-13 常州大学 A kind of inexpensive high activity tri-metal nano composite electrode preparation method
CN107910562B (en) * 2017-11-08 2020-06-12 常州大学 Low-cost high-activity trimetal nanocomposite electrode preparation method
CN112786901A (en) * 2021-03-02 2021-05-11 上海交通大学 Preparation method of fuel cell membrane electrode with controllable surface buckling

Also Published As

Publication number Publication date
CN102403516B (en) 2013-11-06

Similar Documents

Publication Publication Date Title
Abdullah et al. Ultrasonically surface-activated nickel foam as a highly efficient monolith electrode for the catalytic oxidation of methanol to formate
CN107858701B (en) A kind of titanium-based hydrogen-precipitating electrode and preparation method thereof for solid polymer water electrolyzer
CN102881916B (en) Gas diffusion electrode carried with double-shell core-shell catalyst and preparation and application thereof
CN105810957B (en) The preparation and application of a kind of platinum/nickel hydroxide cobalt hydroxide/graphene three-dimensional composite catalyst
CN100588018C (en) Preparation method for carbon supported ultra-low platinum catalytic electrode by indirect galvanic deposit
CN102806093B (en) Preparation method of high-efficiency low-platinum catalyst for direct methanol fuel cell
CN102403516B (en) Preparation method of curved surface electrode catalyst layer
Hosseini et al. Electrocatalytic oxidation of sodium borohydride on a nanoporous Ni/Zn-Ni electrode
CN105633425A (en) Pdx@Pt/C core-shell structure cathode catalyst for fuel cell and preparation method of Pdx@Pt/C core-shell structure cathode catalyst
CN102703953B (en) Method for preparing nanometer platinum/titanium dioxide nanotube electrode through cyclic voltammetry electrodeposition
Smiljanic et al. Electrochemical stability and degradation of commercial Pd/C catalyst in acidic media
CN113174600A (en) Porous nickel screen electrolytic water catalytic material and preparation method thereof
CN110592616A (en) Method for preparing platinum/titanium dioxide nanotube composite electrode by electroplating method
CN111763955A (en) Super-hydrophobic platinum hydrogen evolution electrode, preparation method thereof and preparation method of hydrogen
Paul et al. Electrochemical characterization of Ni-Co and Ni-Co-Fe for oxidation of methyl alcohol fuel with high energetic catalytic surface
Zhang et al. Boosting the performance of alkaline direct ethanol fuel cell with low-Pd-loading nickel foam electrode via mixed acid-etching
CN106328963A (en) Preparation method and application of self-supporting Pd-Ag-Ni ternary metal catalyst
CN104600332B (en) Without membrane cell catalyst pulp and prepare catalyst pulp and electrode method
CN108155391A (en) A kind of efficient nickel-base catalyst for promoting sodium borohydride direct oxidation
Kobayashi et al. Palladium deposition on nickel wire electrodes by a galvanic replacement reaction
CN105413679B (en) A kind of preparation method of graphene two-dimensional noble metal cluster composite
CN114481185B (en) Corrosion-resistant current collector and preparation method and application thereof
Jin et al. High catalytic activity of Pt-modified Ag electrodes for oxidation of glycerol and allyl alcohol
CN116282393A (en) Palladium-nickel phosphide-foam nickel composite electrode and preparation method and application thereof
CN102899684B (en) Preparation method for cathodic porous supported catalytic electrode used in electrolysis and hydro-liquefaction of coal

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant