CN106159284A - A kind of ordered nano-structure membrane electrode and preparation method thereof - Google Patents
A kind of ordered nano-structure membrane electrode and preparation method thereof Download PDFInfo
- Publication number
- CN106159284A CN106159284A CN201510182054.9A CN201510182054A CN106159284A CN 106159284 A CN106159284 A CN 106159284A CN 201510182054 A CN201510182054 A CN 201510182054A CN 106159284 A CN106159284 A CN 106159284A
- Authority
- CN
- China
- Prior art keywords
- electrode
- preparation
- die plate
- nano
- ordered nano
- 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
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8896—Pressing, rolling, calendering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
The present invention provides a kind of ordered nano-structure membrane electrode and preparation method thereof, including the coating of microporous layers, the preparation of binding agent, the bonding of foraminous die plate and substrate, mixes the preparation of electroplate liquid, the preparation of nano-array, the post processing of product and the pressing of membrane electrode assembly.The core technology of the present invention is the preparation of ordered nano array catalysis electrode, mainly by template electro-deposition path, by platiniferous or platinum alloy nanostructure deposition in foraminous die plate, remove foraminous die plate and binding agent, obtain the one-dimensional orderly nano-array catalysis electrode being grown directly upon in microporous layers, and then pressing obtains membrane electrode.The present invention need not any transfer or the method turning pressure, ordered nano-structure can be applied in membrane electrode assembly, propose a kind of novel porous electrode structure, and reformed the preparation technology of membrane electrode assembly, catalysis activity and the utilization rate of noble metal of electrode are greatly improved, are further used for fuel cell and battery performance can be greatly improved.
Description
Technical field
The present invention relates to fuel cell correlative technology field, relate to a kind of ordered nano-structure membrane electrode and preparation method thereof, especially
Relate to a kind of ordered nano-structure membrane electrode being applied to fuel cell and preparation method thereof.
Background technology
Miscellaneous Portable mobile electronic device that has been born with rapid changepl. never-ending changes and improvements of science and technology, gradually becoming strong of its function directly results in biography
The capacity of system battery can not meet people's power consumption requirements for respective electronic equipment, therefore a kind of volume of exploitation little, light,
Persistent period, sufficiently long Portable power source was extremely urgent.The features such as the volume of fuel cell is little, capacity big, safety and stability
Making it show superiority in portable power source field, realize working long hours by adding fuel, its energy density is lithium ion
The several times of battery.In recent years, as the future developing trend of Novel mobile power source, passive direct methanol fuel cell (Direct
Methanol Fuel Cells, DMFC) it is one of portable power source technology of rather paying close attention to of people, utilize methanol as fuel to obtain electricity
And fuel feed pump and aerator can be eliminated, reduce the energy consumption of auxiliary equipment.It is so that equipment need not charging
On the premise of run the long period.
But, current passive type DMFC is still faced with some technical barriers in actual application aspect: (1) methanol is oozed by barrier film
Thoroughly, fuel availability and battery operating voltage is made to reduce；(2) methanol electrochemical reaction activity is the highest, i.e. the utilization rate of catalyst is low；
(3) low power density, fuel and oxidant are completely by free diffusing, it is difficult to methanol and oxygen are sent to catalysis by stable equilibrium ground
Agent surface participates in reaction, causes systematic function poor.Before the application that formally puts goods on the market, still face a lot of severe technology and choose
War.For the accreditation won the market early, many research work need the most deeply to ask with these existing for solution at present
Topic.
In current fuel cell studies, due to the plurality of advantages of methanol, and passive type need not external accessory, institute
A big study hotspot is become with the DMFC of passive type.The core of whole battery is membrane electrode assembly
(Membrane Electrode Assemblies, MEA), it be material transferring, electrochemical reaction, electronics and ion transmission with
And the place that energy transfer occurs, its performance quality directly influences the height of whole battery performance.Current research mainly collects
In on regulation and control anode, the supporting layer of negative electrode and Catalytic Layer and the film played an important role.Overall Development Trend is to develop high property
The ordered nano-structure MEA of energy.Therefore, how to prepare ultra-thin, nanostructured is controlled, (part) interface orderly, each is compatible
Property good membrane electrode assembly become the main target of research both at home and abroad, be also that DMFC obtains high-performance, realizes practical pass
Key.
Summary of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of ordered nano being applied to fuel cell
The preparation method of structure membrane electrode, for improving the performance of membrane electrode assembly in prior art.
For achieving the above object and other relevant purposes, the present invention provides the preparation method of a kind of ordered nano-structure membrane electrode, institute
State preparation method at least to comprise the following steps:
1) providing a substrate and a foraminous die plate, described substrate includes carbon paper and the electrode microporous layers coated on described carbon paper；
2) preparation binding agent, is bondd described foraminous die plate with described electrode microporous layers by binding agent；
3) preparation mixing electroplate liquid, utilization is electrodeposited in described electrode microporous layers surface and prepares nano-array；
4) sedimentation products post processing, including removing described foraminous die plate and binding agent, thus prepares the catalysis of ordered nano array
Electrode；
5) using described ordered nano array catalysis electrode as negative electrode and/or anode, between described negative electrode and anode, a matter is placed
Proton exchange hot pressing become membrane electrode.
Preferably, described step 1) in the method for coating of electrode microporous layers as follows:
By ultrasonic after carbon dust, polytetrafluoroethylsolution solution, isopropanol water solution mixing, described carbon paper coated and is mixed with described gathering
Tetrafluoroethene solution, the carbon dust of described isopropanol water solution, obtain described electrode microporous layers after sintering.
It is highly preferred that described carbon dust is carbon nano-tube material, carbon fibre material or carbosphere material.
It is highly preferred that ultrasonic time is set as 30～150min, the mass fraction of the politef on described carbon paper is 0～40%,
The carrying capacity of the carbon dust on described carbon paper is 0～2.0mg cm-2, the mass fraction of described electrode microporous layers politef is 0～50%,
Sintering temperature is set as 100～500 DEG C, and sintering time is set as 10～60min.
Preferably, described step 2) in the compound method of binding agent as follows:
Kynoar is mixed with N-Methyl pyrrolidone and magnetic agitation, obtain Kynoar solution as binding agent.
It is highly preferred that the temperature of magnetic agitation is set as 20～80 DEG C, the time of magnetic agitation is set as 1～10h, described poly-inclined fluorine
The mass fraction of vinyl solution is 2%～15%.
Preferably, described step 2) in foraminous die plate as follows with the adhesive method of described substrate:
Described binding agent is coated in described electrode microporous layers, then foraminous die plate is bonded in described electrode microporous layers and stands.
It is highly preferred that the consumption of described binding agent is set as 2.0～15.0mgcm-2, described foraminous die plate be anodic oxidation aluminium formwork,
Titania nanotube template or Merlon foraminous die plate, the bilateral aperture of described foraminous die plate is set as 50～400nm, quiet
The time of putting is set as 0～30min.
Preferably, described step 3) in mixing electroplate liquid compound method as follows:
It is prepared as described mixing electroplate liquid after platinum presoma or platinum presoma and precious metal chemical complex being mixed with acid solution, lead salt, and
Stand.
Receive or one or both combination in chloroplatinic acid it is highly preferred that described platinum presoma is chloroplatinic acid, described noble metal chemical combination
Thing is Palladous chloride., Nickel dichloride., Chlorizate chromium, nickel nitrate, chromic nitrate or ruthenium trichloride, and described acid solution is perchloric acid or dilute sulfuric acid,
Described lead salt is lead acetate or plumbi nitras.
It is highly preferred that platinum precursor concentration is 1～10mM in described mixing electroplate liquid, precious metal chemical complex concentration is 1～10mM,
Acid strength is 0.01～0.2M, and lead salt concentration is 0.02～0.4mM.
It is highly preferred that the time of repose of described mixing electroplate liquid is set as 0～24h.
Preferably, described step 3) in electro-deposition preparation method as follows:
3-1) by described substrate and the described foraminous die plate of bonding, and described mixing electroplate liquid loads precipitation equipment；
3-2) to be coated with the described carbon paper of electrode microporous layers as working electrode, electrode microporous layers side directly with mix electroplate liquid
Contact, platinum line is as to electrode, and saturated calomel electrode, as reference electrode, uses cyclic voltammetry to carry out electro-deposition；
Take described precipitation equipment apart after 3-3) electro-deposition is complete, deposition has the electrode microporous layers of nano-array stand.
It is highly preferred that electro-deposition voltage is set to-1.0～0V, electrodeposition time is set as 1000～15000s, and described deposition is received
The electrode microporous layers time of repose of rice array is set as 4～24h.
Preferably, described step 4) in sedimentation products post-processing approach as follows:
The method that described nano-array electro-deposition prepared dissolves removes described foraminous die plate, then uses N-Methyl pyrrolidone
Remove described binding agent, then with the alternately washing of water, ethanol for several times, obtain described ordered nano array under the conditions of vacuum drying afterwards
Catalysis electrode.
It is highly preferred that described foraminous die plate is alkalescence or both sexes template, then concentration is set as that the alkali liquor of 1.0～3.0M dissolves
Described foraminous die plate；Described foraminous die plate is Merlon foraminous die plate, then molten with carbon tetrachloride, chloroform or oxolane
Described foraminous die plate is dissolved in agent；When removing binding agent, N-Methyl pyrrolidone solution heating-up temperature is set as 20～90 DEG C, vacuum
The temperature being dried is set as 30～100 DEG C.
The present invention also provides for the ordered nano-structure membrane electrode that a kind of described preparation method prepares.
The present invention reoffers a kind of ordered nano catalysis electrode, and described catalysis electrode at least includes:
Substrate, described substrate includes carbon paper and the electrode microporous layers coated on described carbon paper；
Nano-array, is deposited on described electrode microporous layers surface.
The present invention additionally also provides for one and utilizes described ordered nano array catalysis electrode to be applied to film electricity as negative electrode and/or anode
The purposes of pole.
As it has been described above, the preparation method of the ordered nano array catalysis electrode of the present invention, have the advantages that the present invention's
The preparation method of the ordered nano array catalysis electrode being applied to fuel cell passes through template electro-deposition path, platiniferous or platinum is closed
Nanowires of gold or nanotube deposition, in foraminous die plate, remove foraminous die plate, obtain platinum or the platinum alloy of one-dimensional ordered nano-structure
Nano-array catalysis electrode, the present invention directly prepares nano wire or nano-tube array in substrate, thus prepares ordered nano knot
The catalysis electrode of structure, and form orderly nano-structure film electrode aggregate with the obtained direct pressing of ordered nano-structure electrode,
Reformed the electrode preparation method in battery core parts membrane electrode assembly, be greatly improved membrane electrode assembly catalysis activity,
The utilization rate of noble metal catalyst and the mass-transfer efficiency of electrode interior.
Accompanying drawing explanation
Fig. 1 is shown as the preparation method schematic flow sheet of the ordered nano array catalysis electrode being applied to fuel cell of the present invention.
Fig. 2 is shown as the electrode microporous layers of the present invention and the X-ray diffraction schematic diagram of Pt nanowires eelctro-catalyst.
Fig. 3 is shown as the electron scanning imaging schematic diagram of the Pt nanowires eelctro-catalyst of the present invention.
Fig. 4 is shown as the transmission electron microscope schematic diagram of the Pt nanowires eelctro-catalyst of the present invention.
Fig. 5 is shown as the DMFC assembly of the orderly Pt nanowires eelctro-catalyst electrode gained of the present invention and existing skill
The performance test collection of illustrative plates of the fuel cell of art.
Fig. 6 is shown as the electron scanning imaging schematic diagram of the platinum nanotube eelctro-catalyst of the present invention.
Element numbers explanation
S1～S5 step one～step 5
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by disclosed by this specification
Content understand other advantages and effect of the present invention easily.The present invention can also be added by the most different detailed description of the invention
To implement or application, the every details in this specification can also be based on different viewpoints and application, in the essence without departing from the present invention
Various modification or change is carried out under god.
Refer to Fig. 1～Fig. 6.It should be noted that the diagram provided in the present embodiment illustrates the present invention's the most in a schematic way
Basic conception, the most graphic in component count time only display with relevant assembly in the present invention rather than is implemented according to reality, shape and
Size is drawn, and during its actual enforcement, the kenel of each assembly, quantity and ratio can be a kind of random change, and its assembly layout type
State is likely to increasingly complex.
As it is shown in figure 1, the present invention provides the preparation method of a kind of ordered nano-structure membrane electrode being applied to fuel cell, described
The preparation method of ordered nano-structure membrane electrode at least comprises the following steps:
S1 a, it is provided that substrate and a foraminous die plate, described substrate includes carbon paper and the electrode microporous layers coated on described carbon paper；
S2, prepares binding agent, is bondd with described electrode microporous layers by described foraminous die plate by binding agent；
S3, preparation mixing electroplate liquid, utilization is electrodeposited in described electrode microporous layers surface and prepares nano-array；
S4, sedimentation products post processing, including removing described foraminous die plate and binding agent, thus prepare ordered nano array and urge
Polarizing electrode；
S5, using described ordered nano array catalysis electrode as negative electrode and/or anode, places a matter between described negative electrode and anode
Proton exchange hot pressing become membrane electrode.
The preparation method of the ordered nano-structure membrane electrode of the present invention is described in detail below.
Step S1 being first carried out: provide a substrate and a foraminous die plate, described substrate includes carbon paper and coats on described carbon paper
Electrode microporous layers.
The detailed process that coats of described electrode microporous layers is: by carbon dust, politef (Polytetrafluoro Ethylene, PTFE)
After solution, isopropanol (Iso-Propyl Alcohol, IPA) aqueous solution ultrasonic 30～150min, containing mass fraction it is being
Coating carrying capacity on the carbon paper of 0～40%PTFE is 0～2.0mg cm-2Be mixed with described PTFE solution, described IPA aqueous solution
Carbon dust, obtains described electrode microporous layers after sintering 10～60min under 100～500 DEG C of temperature conditionss.
Described carbon dust can be carbon nano-tube material, carbon fibre material or carbosphere material, and certainly, described carbon dust can also be it
His suitable material with carbon element, does not limits at this.
Described foraminous die plate is anodic oxidation aluminium formwork, titania nanotube template or Merlon foraminous die plate, certainly,
Described foraminous die plate can also be other suitable porous materials, does not limits at this.
Then perform step S2: prepare binding agent, by binding agent, described foraminous die plate is bondd with described electrode microporous layers.
The method of concrete configuration binding agent is: by Kynoar (Polyvinylidene Fluoride, PVDF) and N-methyl pyrrole
Pyrrolidone (N-Methyl Pyrrolidone, NMP) is mixed to be incorporated in magnetic agitation 1～10h under 20～80 DEG C of temperature conditionss and obtains matter
Amount mark is that the PVDF solution of 2%～15% is as binding agent.
By the method that described foraminous die plate and substrate bond it is specifically: by 2.0～15.0mg cm-2Described PVDF solution is coated in described
In electrode microporous layers, then bilateral aperture being set as, the foraminous die plate of 50～400nm is bonded in described electrode microporous layers and quiet
Set to 0～30min.
Then step S3 is performed: preparation mixing electroplate liquid, utilization is electrodeposited in described electrode microporous layers surface and prepares nano-array.
The compound method of described mixing electroplate liquid is: platinum presoma or platinum presoma and precious metal chemical complex are mixed with acid solution, lead salt
It is prepared as described mixing electroplate liquid after conjunction, and stands 0～24h.Wherein, described platinum presoma can be chloroplatinic acid receive, chloroplatinic acid
In one or both mixing, described precious metal chemical complex can be Palladous chloride., Nickel dichloride., Chlorizate chromium, nickel nitrate, nitric acid
Chromium or ruthenium trichloride, described acid solution can be perchloric acid or dilute sulfuric acid, and described lead salt can be then lead acetate or plumbi nitras.At this
In embodiment, described in described mixing electroplate liquid, platinum precursor concentration is 1～10mM, and described precious metal chemical complex concentration is
1～10mM, described acid concentration is 0.01～0.2M, and described lead salt concentration is 0.02～0.4mM.
In this step, the method for electro-deposition is: first, by described substrate and the described foraminous die plate of bonding, and described electroplate liquid
Load precipitation equipment；Then, using described carbon paper as working electrode, microporous layers side is directly and plating solution contacts, platinum line
As to electrode, saturated calomel electrode, as reference electrode, uses cyclic voltammetry to carry out electro-deposition；Electro-deposition voltage is set to
-1.0～0V, electrodeposition time is set as 1000～15000s；Electro-deposition is carried out under nitrogen protective condition；Tear open after electro-deposition is complete
Open described precipitation equipment, deposition has the electrode microporous layers of platinum or platinum alloy nano-array stand 4～24h.Described platinum or platinum alloy
The appearance and size of nano-array can be regulated and controled by sedimentation time and described mixing bath concentration, and the platinum or the platinum alloy that finally obtain are received
Rice array can be nano wire or nanotube etc..
It should be noted that the nano-array of deposition growth is grown in electrode microporous layers surface, and this nano-array is through institute
State the doubled via of foraminous die plate.
Then execution step S4: sedimentation products post processing；Including removing described foraminous die plate and binding agent, thus prepare
Sequence nano-array catalysis electrode.
Detailed process is: the method described foraminous die plate of removal that described nano-array electro-deposition prepared dissolves, such as, if
Foraminous die plate is the alkalescence such as anodic oxidation aluminium formwork or titania nanotube template or both sexes template, then concentration is set as
The alkali liquor of 1.0～3.0M dissolves described foraminous die plate；If described foraminous die plate is Merlon foraminous die plate, then with carbon tetrachloride,
Chloroform or tetrahydrofuran solvent dissolve described foraminous die plate, more alternately wash for several times with water, ethanol, and at 30～100 DEG C
It is vacuum dried under temperature conditions, obtains described ordered nano array catalysis electrode.Described ordered nano array catalysis electrode is directly
Methanol fuel cell membrane electrode uses as negative electrode and/or anode.
Finally perform step S5: using described ordered nano array catalysis electrode as negative electrode and/or anode, in described negative electrode and anode
Between place a PEM and hot pressing becomes membrane electrode.
By the mode of spraying or blade coating at one layer of Nafion resin of surface attachment of ordered nano array electrode, through drying and processing,
Under conditions of 130 DEG C, 3～6MPa, hot pressing forms cathode and anode and the membrane electrode assembly of PEM " three-in-one ".
The present invention also provides for a kind of ordered nano-structure membrane electrode, and this membrane electrode utilizes and prepares described in above-mentioned preparation method, institute
The structure stating membrane electrode includes: negative electrode, anode and hot pressing are formed at the PEM between described negative electrode and anode.Wherein,
Negative electrode and anode can be all ordered nano array catalysis electrode prepared by the present invention, or only anode or negative electrode are the present invention
The ordered nano array catalysis electrode of preparation.
Described ordered nano array catalysis electrode at least includes: substrate, and described substrate includes carbon paper and coats on described carbon paper
Electrode microporous layers；Nano-array, is deposited on described electrode microporous layers surface.
Embodiment one
The present embodiment provides the preparation method of a kind of orderly Pt nanowires membrane electrode, comprises the following steps:
Weigh the CNT of 20.0mg respectively, 40.4mg mass fraction be 12.39% politef (PTFE) solution,
Isopropanol (IPA) aqueous solution (IPA:H of 200mg2O=1:1), the ultrasonic 120min time and after being mixed；Containing
Mass fraction is to use scraper to smear carrying capacity 2.0mg cm on the carbon paper of 20%PTFE-2CNT；Enter at a temperature of 350 DEG C again
Row sintering 30min obtains cathode micro porous layer.
Weighing Kynoar (PVDF) and N-Methyl pyrrolidone (NMP), preparation PVDF mass fraction is 8.14%
Mixed solution；Magnetic agitation 8h under the conditions of 25 DEG C, obtains PVDF solution as binding agent.
The PVDF solution drawing about 50.0mg is coated in described cathode micro porous layer and makes to be coated in microporous layers by doctor blade
PVDF solution about 32.0mg, then bonds the porous anodic alumina template (AAO template) that bilateral aperture is 200nm
In described cathode micro porous layer and stand 10min, treat that described cathode micro porous layer bonds with described AAO template.
1.0g six is hydrated chloroplatinic acid (H2PtCl6·6H2O) 50ml volumetric flask the graduation mark that adds water are poured into, then with moving liquid
Tolerance takes 25.896ml to 100ml volumetric flask；Then 0.847ml perchloric acid is measured to 100ml volumetric flask；Weigh 7.6mg again
Lead acetate, to 100ml volumetric flask, is prepared by mixing into electroplate liquid, and stands 12h.
Described substrate after bonding is loaded precipitation equipment with described AAO template, takes the described electroplate liquid after 25ml stands and pour into
Precipitation equipment；Using described carbon paper as working electrode, microporous layers side directly and plating solution contacts, platinum line as to electrode,
Saturated calomel electrode makees reference electrode；Deposition voltage interval-0.5～0V, sedimentation time 10000s are set；Under nitrogen protective condition
Cyclic voltammetry is used to carry out electro-deposition；Stripping device after electro-deposition, has the described cathode micro porous layer carbon of Pt nanowires by deposition
Paper stands 12h.
Remove described deposition by the NaOH solution of 2.0M and have the AAO template on the cathode micro porous layer carbon paper of Pt nanowires, then
Remove PVDF binding agent with NMP, more alternately wash for several times with water, ethanol, and be vacuum dried under 75 DEG C of temperature conditionss
To Pt nanowires eelctro-catalyst electrode.
The Pt nanowires eelctro-catalyst that the present embodiment obtains is characterized, as shown in Figure 2, it is thus achieved that electrode microporous layers and platinum nanometer
The X-ray diffractogram (XRD figure) of line eelctro-catalyst, with the whole diffraction region of the angle scanning of 2 θ, as X-ray diffraction
The abscissa of spectrum；Using the intensity of the diffraction maximum of different diffraction angle (2 θ) as vertical coordinate.It is illustrated in figure 3 the platinum nanometer of the present embodiment
Electron scanning imaging figure (SEM figure) of line eelctro-catalyst, can measure from electron scanning imaging system and obtain described Pt nanowires
The diameter of eelctro-catalyst about 200nm.It is illustrated in figure 4 the transmission electron microscope picture (TEM of the Pt nanowires eelctro-catalyst of the present embodiment
Figure), a length of 3～5 μm obtaining described Pt nanowires eelctro-catalyst can be measured from transmission electron microscope system.
Pt nanowires catalysis electrode black with business-like Pt (Johnson Matthey) catalyst of the present embodiment is compared, will
The orderly Pt nanowires catalysis electrode of the present embodiment gained is used in cathode catalysis layer, obtains DMFC assembly；Will be existing
Fuel cell is formed by the Nafion115 film in technology:
(1) anode support: carbon paper TGPH060, mass fraction is the waterproof material (Toray) of 20%；Anode micro porous
Layer: carbon dust Vulcan XC-72R (1.0mg cm-2) (Cabot company) and PTFE (Dupont that mass fraction is 20%
Company)；Anode catalyst layer: Pt-Ru/C (4.0mg cm-2), mass fraction be 5.03% perfluorinated sulfonic acid-politef common
Polymers (Nafion) solution (Dupont company).
(2) cathode support layers: carbon paper TGPH060, the waterproof material of mass fraction 20%；Cathode micro porous layer: CNT
(2mg·cm-2) and mass fraction be the PTFE of 12.89%；The cathode catalysis layer of the present embodiment: the platinum nanometer of the present embodiment
Line and mass fraction are the Nafion solution of 5.03%；The cathode catalysis layer of prior art: nano platinum particle, mass fraction is 5.03%
Nafion solution.
(3) Nafion115 film (Dupont company).
Pt-Ru/C in above-mentioned anode catalyst layer all comes in Johnson Matthey company (writing a Chinese character in simplified form JM company)；Above-mentioned cathode catalysis
Pt/C in Ceng all comes in JM company.
DMFC assembly and prior art to the orderly Pt nanowires eelctro-catalyst electrode gained of the present embodiment gained
In Nafion115 film composition fuel cell test, being illustrated in figure 5 catalyst loading is 2.0mg cm-2、
1.5mg·cm-2、1.0mg·cm-2And 0.5mg cm-2Time performance test collection of illustrative plates, from this collection of illustrative plates understand: respectively by prepared film
Electrode aggregate carries out performance test on DMFC, uses the orderly Pt nanowires catalysis of the present embodiment gained
The power density of the DMFC of electrode is big, and its performance is better than using the direct methanol combustion of commercialized catalyst (JM)
Material battery.
Embodiment two
The present embodiment provides the preparation method of a kind of orderly platinum nanotube films electrode, comprises the following steps:
Weigh the CNT of 60.0mg respectively, 179.2mg mass fraction be 8.37% PTFE solution, the IPA of 600mg
Aqueous solution (IPA:H2O=1:1), the ultrasonic 120min time and after being mixed；It is being 20%PTFE's containing mass fraction
Scraper is used to smear carrying capacity 2.0mg cm on carbon paper-2CNT；At a temperature of 350 DEG C, it is sintered 30min again and obtains negative electrode
Microporous layers.
Weighing PVDF and NMP, preparation PVDF mass fraction is the mixed solution of 5.28%；Magnetic agitation under the conditions of 25 DEG C
8h, obtains PVDF solution as binding agent.
The PVDF solution drawing about 50mg is coated in described cathode micro porous layer and makes to be coated in PVDF in microporous layers by doctor blade
Solution about 32mg, is then bonded in the AAO template that bilateral aperture is 200nm in described cathode micro porous layer and stands 10min,
Treat that described cathode micro porous layer bonds with described AAO template.
By 1.0g H2PtCl6·6H2O pours 50ml volumetric flask the graduation mark that adds water into, then measures 7.769ml with pipettor and arrives
100ml volumetric flask；Then 0.254ml perchloric acid is measured to 100ml volumetric flask；Weigh 2.3mg lead acetate again to hold to 100ml
Measuring bottle, is prepared by mixing into electroplate liquid, and stands 12h.
Described substrate after bonding is loaded precipitation equipment with described AAO template, takes the described electroplate liquid after 25ml stands and pour into
Precipitation equipment；Using described carbon paper as working electrode, microporous layers side directly and plating solution contacts, platinum line as to electrode,
Saturated calomel electrode is as reference electrode；Deposition voltage interval-0.5～0V, sedimentation time 10000s are set；At nitrogen protective condition
Lower use cyclic voltammetry carries out electro-deposition；Stripping device after electro-deposition, has the described cathode micro porous layer of platinum nanotube by deposition
Carbon paper stands 12h.
Remove described deposition by the NaOH solution of 2.0M and have the AAO template on the cathode micro porous layer carbon paper of platinum nanotube, then
Remove PVDF binding agent with NMP, more alternately wash for several times with water, ethanol, and be vacuum dried under 75 DEG C of temperature conditionss
To platinum nanotube eelctro-catalyst electrode.
Being characterized by the Pt nanowires eelctro-catalyst that the present embodiment obtains, the Pt nanowires electricity being illustrated in figure 6 the present embodiment is urged
Electron scanning imaging figure (SEM figure) of agent, can measure from electron scanning imaging system and obtain described Pt nanowires electro-catalysis
The diameter of agent about 200nm.
Embodiment three
The present embodiment provides the preparation method of a kind of orderly platinum ruthenium nano-wire catalysis electrode, comprises the following steps:
Weigh the XC-72 carbon dust (Cabot company) of 80.0mg respectively, 161.4mg mass fraction be 12.39% PTFE molten
Liquid, the IPA aqueous solution (IPA:H of 800mg2And be mixed the ultrasonic 120min time O=1:1),；Containing mass fraction
For using scraper to smear carrying capacity 2.0mg cm on the carbon paper of 20%PTFE-2Carbon dust；It is sintered 30min again at a temperature of 350 DEG C
Obtain anode micro porous layer.
PVDF and NMP weighed, preparation PVDF mass fraction is 9.37% mixed solution；Magnetic agitation under the conditions of 25 DEG C
8h, obtains PVDF solution as binding agent.
The PVDF solution drawing 50.0mg is coated in described anode micro porous layer and makes to be coated in PVDF in microporous layers by doctor blade
Solution about 32.0mg；Then the AAO template that bilateral aperture is 400nm is bonded in described anode micro porous layer and stands
10min, treats that described anode micro porous layer bonds with described AAO template.
By 1.0g H2PtCl6·6H2O pours 50ml volumetric flask the graduation mark that adds water into, then measures 25.896ml with pipettor
To 100ml volumetric flask；Take 1.0g mono-hydrate ruthenium trichloride pour 50ml volumetric flask into and add water to graduation mark, then use pipettor
Measure 11.27ml and pour 100ml volumetric flask into；Then 0.847ml perchloric acid is measured to 100ml volumetric flask；Weigh 7.6mg again
Lead acetate, to 100ml volumetric flask, is prepared by mixing into electroplate liquid, stands 12h.
Described substrate after bonding is loaded precipitation equipment with described AAO template, takes the described mixing electroplate liquid after 25ml stands
Pour precipitation equipment into.Using carbon paper as working electrode, microporous layers side directly and plating solution contacts, platinum line as to electrode,
Saturated calomel electrode makees reference electrode；Deposition voltage interval-0.5～0V, sedimentation time 10000s are set；Under nitrogen protective condition
Cyclic voltammetry is used to start electro-deposition；Stripping device after electro-deposition, has the described anode micro porous layer of platinum ruthenium nano-wire by deposition
Carbon paper stands 12h.
Remove described deposition by the NaOH solution of 2.0M and have the AAO template on the anode micro porous layer carbon paper of platinum ruthenium nano-wire, so
Remove PVDF binding agent with NMP afterwards, more alternately wash for several times with water, ethanol, and be vacuum dried under 75 DEG C of temperature conditionss
Obtain platinum ruthenium nano-wire eelctro-catalyst electrode.
The present invention constitutes electrode microporous layers at one layer of material with carbon element of surface smear of carbon paper, prepares certain density PVDF solution conduct
Binding agent, is got up electrode microporous layers and foraminous die plate by binding agent bonding, then prepare certain density noble metal precursor,
The mixing electroplate liquid of the composition such as acid solution and lead salt, carries out electro-deposition under nitrogen protective condition, obtains diameter and length is controlled
Nano-array catalysis electrode, prepare membrane electrode assembly by the method for hot pressing, for DMFC.
The preparation method of the ordered nano array catalysis electrode being applied to fuel cell of the present invention passes through template electro-deposition path,
By platiniferous or platinum alloy nano wire or nanotube deposition in foraminous die plate, remove foraminous die plate, obtain one-dimensional ordered nano-structure
Platinum or platinum alloy nano-array catalysis electrode, platinum or the platinum alloy nano-array of ordered nano-structure are applied to fuel cell
Membrane electrode assembly, is greatly improved catalysis activity and the utilization rate of noble metal catalyst of membrane electrode assembly.Further, use
The performance of fuel cell can be improved in DMFC.
In sum, the present invention provides a kind of ordered nano-structure membrane electrode and preparation method thereof, including the coating of microporous layers, viscous
The knot preparation of agent, the bonding of foraminous die plate and substrate, mix the preparation of electroplate liquid, the preparation of nano-array, the post processing of product
And the pressing of membrane electrode assembly.The core technology of the present invention is the preparation of ordered nano array catalysis electrode, the most logical
Cross template electro-deposition path, by platiniferous or platinum alloy nanostructure deposition in foraminous die plate, remove foraminous die plate and binding agent,
Obtain the one-dimensional orderly nano-array catalysis electrode being grown directly upon in microporous layers, and then pressing obtains membrane electrode.The present invention is not
Need any transfer or the method turning pressure, ordered nano-structure can be applied in membrane electrode assembly, it is proposed that be a kind of novel
Porous electrode structure, and reformed the preparation technology of membrane electrode assembly, catalysis activity and the noble metal of electrode be greatly improved
Utilization rate, be further used for fuel cell and battery performance can be greatly improved.So, the present invention effectively overcomes in prior art
Various shortcoming and have high industrial utilization.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any it is familiar with this skill
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage of art.Therefore, such as
All that in art, tool usually intellectual is completed under without departing from disclosed spirit and technological thought etc.
Effect is modified or changes, and must be contained by the claim of the present invention.
Claims (16)
1. the preparation method of an ordered nano-structure membrane electrode, it is characterised in that described preparation method at least comprises the following steps:
1) providing a substrate and a foraminous die plate, described substrate includes carbon paper and the electrode microporous layers coated on described carbon paper；
2) preparation binding agent, is bondd described foraminous die plate with described electrode microporous layers by binding agent；
3) preparation mixing electroplate liquid, utilization is electrodeposited in described electrode microporous layers surface and prepares nano-array；
4) sedimentation products post processing, including removing described foraminous die plate and binding agent, thus prepares the catalysis of ordered nano array
Electrode；
5) using described ordered nano array catalysis electrode as negative electrode and/or anode, between described negative electrode and anode, a proton is placed
Exchange membrane hot pressing become membrane electrode.
The preparation method of ordered nano-structure membrane electrode the most according to claim 1, it is characterised in that: described step 1) in electricity
The method for coating of atomic aperture layer is as follows:
By ultrasonic after carbon dust, polytetrafluoroethylsolution solution, isopropanol water solution mixing, described carbon paper is coated described in being mixed with
Polytetrafluoroethylsolution solution, the carbon dust of described isopropanol water solution, obtain described electrode microporous layers after sintering.
The preparation method of ordered nano-structure membrane electrode the most according to claim 2, it is characterised in that: described carbon dust is carbon nanometer
Tube material, carbon fibre material or carbosphere material.
The preparation method of ordered nano-structure membrane electrode the most according to claim 2, it is characterised in that: ultrasonic time is set as
30～150min, the mass fraction of the politef on described carbon paper is 0～40%, and the carrying capacity of the carbon dust on described carbon paper is
0～2.0mg cm-2, the mass fraction of described electrode microporous layers politef is 0～50%, and sintering temperature is set as
100～500 DEG C, sintering time is set as 10～60min.
The preparation method of ordered nano-structure membrane electrode the most according to claim 1, it is characterised in that: described step 2) in viscous
The compound method of knot agent is as follows:
Kynoar is mixed with N-Methyl pyrrolidone and magnetic agitation, obtain Kynoar solution as binding agent.
The preparation method of ordered nano-structure membrane electrode the most according to claim 5, it is characterised in that: the temperature of magnetic agitation sets
Being set to 20～80 DEG C, the time of magnetic agitation is set as 1～10h, and the mass fraction of described Kynoar solution is
2%～15%.
The preparation method of ordered nano-structure membrane electrode the most according to claim 1, it is characterised in that: described step 2) in many
Casement plate is as follows with the adhesive method of described substrate:
Described binding agent is coated in described electrode microporous layers, then foraminous die plate is bonded in described electrode microporous layers and quiet
Put.
The preparation method of ordered nano-structure membrane electrode the most according to claim 7, it is characterised in that: the consumption of described binding agent
It is set as 2.0～15.0mg cm-2, described foraminous die plate is anodic oxidation aluminium formwork, titania nanotube template or poly-carbon
Acid esters foraminous die plate, the bilateral aperture of described foraminous die plate is set as 50～400nm, and time of repose is set as 0～30min.
The preparation method of ordered nano-structure membrane electrode the most according to claim 1, it is characterised in that: described step 3) in mixed
The compound method closing electroplate liquid is as follows:
It is prepared as described mixing electroplate liquid after platinum presoma or platinum presoma and precious metal chemical complex being mixed with acid solution, lead salt,
And stand.
The preparation method of ordered nano-structure membrane electrode the most according to claim 9, it is characterised in that: described platinum presoma is
Chloroplatinic acid is received or one or both combination in chloroplatinic acid, and the concentration of described platinum presoma is 1～10mM；Your gold described
Genus compound is Palladous chloride., Nickel dichloride., Chlorizate chromium, nickel nitrate, chromic nitrate or ruthenium trichloride, the concentration of precious metal chemical complex
It is 1～10mM；Described acid solution is perchloric acid or dilute sulfuric acid, and the concentration of described acid solution is 0.01～0.20M；Described lead salt is
Lead acetate or plumbi nitras, concentration is 0.02～0.40mM.
The preparation method of 11. ordered nano-structure membrane electrodes according to claim 1, it is characterised in that: described step 3) in
Electro-deposition preparation method is as follows:
3-1) by described substrate and the described foraminous die plate of bonding, and described mixing electroplate liquid loads precipitation equipment；
3-2) to be coated with the described carbon paper of electrode microporous layers as working electrode, electrode microporous layers side directly with mix electricity
Plating solution contacts, and platinum line is as to electrode, and saturated calomel electrode, as reference electrode, uses cyclic voltammetry to carry out electricity heavy
Long-pending；
Take described precipitation equipment apart after 3-3) electro-deposition is complete, deposition has the electrode microporous layers of nano-array stand.
The preparation method of 12. ordered nano-structure membrane electrodes according to claim 1, it is characterised in that: described step 4) in
Sedimentation products post-processing approach is as follows:
Described nano-array electro-deposition prepared first passes through the method for dissolving and removes described foraminous die plate, then uses N-methyl
Ketopyrrolidine removes described binding agent, then with the alternately washing of water, ethanol for several times, obtains described afterwards under the conditions of vacuum drying
Ordered nano array catalysis electrode.
The preparation method of 13. ordered nano-structure membrane electrodes according to claim 12, it is characterised in that: described foraminous die plate
For anodic oxidation aluminium formwork or titania nanotube template, then concentration is set as that the alkali liquor of 1.0～3.0M is to dissolve
State foraminous die plate；Described foraminous die plate is Merlon foraminous die plate, then molten with carbon tetrachloride, chloroform or oxolane
Described foraminous die plate is dissolved in agent；When removing binding agent, N-Methyl pyrrolidone solution heating-up temperature is set as 20～90 DEG C, very
The empty temperature being dried is set as 30～100 DEG C.
14. 1 kinds of ordered nano-structure membrane electrodes utilizing the preparation method described in claim 1 to prepare.
15. 1 kinds of ordered nano array catalysis electrodes, it is characterised in that described catalysis electrode at least includes:
Substrate, described substrate includes carbon paper and the electrode microporous layers coated on described carbon paper；
Nano-array, is deposited on described electrode microporous layers surface.
The ordered nano array catalysis electrode that 16. 1 kinds utilize described in claim 15 is applied to membrane electrode as negative electrode and/or anode
Purposes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510182054.9A CN106159284B (en) | 2015-04-17 | 2015-04-17 | A kind of ordered nano-structure membrane electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510182054.9A CN106159284B (en) | 2015-04-17 | 2015-04-17 | A kind of ordered nano-structure membrane electrode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106159284A true CN106159284A (en) | 2016-11-23 |
| CN106159284B CN106159284B (en) | 2019-08-30 |
Family
ID=58058574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510182054.9A Active CN106159284B (en) | 2015-04-17 | 2015-04-17 | A kind of ordered nano-structure membrane electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106159284B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108539206A (en) * | 2018-03-30 | 2018-09-14 | 江苏大学 | A kind of Catalytic Layer orderly fuel cell electrode and membrane electrode entirely |
| CN109440140A (en) * | 2018-11-22 | 2019-03-08 | 浙江大学 | A kind of manufacturing method of electrolytic copper foil |
| CN111740122A (en) * | 2020-07-06 | 2020-10-02 | 全球能源互联网研究院有限公司 | Ordered membrane electrode and preparation method thereof |
| CN112259747A (en) * | 2020-10-21 | 2021-01-22 | 成都新柯力化工科技有限公司 | Fuel cell membrane electrode assembly formed by growing whiskers and preparation method |
| CN112310416A (en) * | 2020-11-02 | 2021-02-02 | 马鞍山安慧智电子科技有限公司 | Method for preparing ordered fuel cell membrane electrode |
| CN112382767A (en) * | 2020-10-26 | 2021-02-19 | 江苏大学 | Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer |
| CN113862637A (en) * | 2020-06-30 | 2021-12-31 | 高丽大学校产学协力团 | Ruthenium-based nanowire and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911782A (en) * | 2006-07-21 | 2007-02-14 | 东莞理工学院 | Preparation method of palladium nanometer wire oldered array material |
| CN102864473A (en) * | 2012-10-22 | 2013-01-09 | 哈尔滨工业大学 | Preparation method of three-dimensional ordered macroporous silicon or germanium film |
| CN103303861A (en) * | 2013-05-14 | 2013-09-18 | 中国科学院上海硅酸盐研究所 | Three-dimensional ordered precious metal nanotube array electrode and preparation method thereof |
| CN103515633A (en) * | 2013-09-02 | 2014-01-15 | 清华大学 | Ordered solid oxide membrane electrode |
| CN103531826A (en) * | 2013-10-30 | 2014-01-22 | 中国科学院上海高等研究院 | Direct-methanol fuel cell nano-porous structural film electrode construction method based on sacrificial template method |
| CN103606687A (en) * | 2013-11-26 | 2014-02-26 | 华南师范大学 | Anode catalyst porous array Pt-p-HxMoO3 for direct methanol fuel cell and preparation method of anode catalyst porous array Pt-p-HxMoO3 |
-
2015
- 2015-04-17 CN CN201510182054.9A patent/CN106159284B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911782A (en) * | 2006-07-21 | 2007-02-14 | 东莞理工学院 | Preparation method of palladium nanometer wire oldered array material |
| CN102864473A (en) * | 2012-10-22 | 2013-01-09 | 哈尔滨工业大学 | Preparation method of three-dimensional ordered macroporous silicon or germanium film |
| CN103303861A (en) * | 2013-05-14 | 2013-09-18 | 中国科学院上海硅酸盐研究所 | Three-dimensional ordered precious metal nanotube array electrode and preparation method thereof |
| CN103515633A (en) * | 2013-09-02 | 2014-01-15 | 清华大学 | Ordered solid oxide membrane electrode |
| CN103531826A (en) * | 2013-10-30 | 2014-01-22 | 中国科学院上海高等研究院 | Direct-methanol fuel cell nano-porous structural film electrode construction method based on sacrificial template method |
| CN103606687A (en) * | 2013-11-26 | 2014-02-26 | 华南师范大学 | Anode catalyst porous array Pt-p-HxMoO3 for direct methanol fuel cell and preparation method of anode catalyst porous array Pt-p-HxMoO3 |
Non-Patent Citations (2)
| Title |
|---|
| 张敏 等: "Pt纳米线阵列的氧还原催化性能", 《物理化学学报》 * |
| 陈勇等: "一维铂纳米线阵列的模板电沉积及其表征", 《化学世界》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108539206A (en) * | 2018-03-30 | 2018-09-14 | 江苏大学 | A kind of Catalytic Layer orderly fuel cell electrode and membrane electrode entirely |
| CN109440140A (en) * | 2018-11-22 | 2019-03-08 | 浙江大学 | A kind of manufacturing method of electrolytic copper foil |
| CN113862637A (en) * | 2020-06-30 | 2021-12-31 | 高丽大学校产学协力团 | Ruthenium-based nanowire and preparation method thereof |
| CN113862637B (en) * | 2020-06-30 | 2024-04-16 | 高丽大学校产学协力团 | Ruthenium-based nanowire and preparation method thereof |
| CN111740122A (en) * | 2020-07-06 | 2020-10-02 | 全球能源互联网研究院有限公司 | Ordered membrane electrode and preparation method thereof |
| CN111740122B (en) * | 2020-07-06 | 2021-12-28 | 全球能源互联网研究院有限公司 | Ordered membrane electrode and preparation method thereof |
| CN112259747A (en) * | 2020-10-21 | 2021-01-22 | 成都新柯力化工科技有限公司 | Fuel cell membrane electrode assembly formed by growing whiskers and preparation method |
| CN112382767A (en) * | 2020-10-26 | 2021-02-19 | 江苏大学 | Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer |
| CN112382767B (en) * | 2020-10-26 | 2021-10-12 | 江苏大学 | Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer |
| CN112310416A (en) * | 2020-11-02 | 2021-02-02 | 马鞍山安慧智电子科技有限公司 | Method for preparing ordered fuel cell membrane electrode |
| CN112310416B (en) * | 2020-11-02 | 2021-09-28 | 马鞍山安慧智电子科技有限公司 | Method for preparing ordered fuel cell membrane electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106159284B (en) | 2019-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106159284B (en) | A kind of ordered nano-structure membrane electrode and preparation method thereof | |
| Du et al. | Advanced catalyst supports for PEM fuel cell cathodes | |
| Park et al. | Ultra-low loading of IrO2 with an inverse-opal structure in a polymer-exchange membrane water electrolysis | |
| Wu et al. | Highly dispersed ultrafine Pt nanoparticles on reduced graphene oxide nanosheets: in situ sacrificial template synthesis and superior electrocatalytic performance for methanol oxidation | |
| Kim et al. | Ordered macroporous platinum electrode and enhanced mass transfer in fuel cells using inverse opal structure | |
| Cai et al. | High-performance supercapacitor electrode based on the unique ZnO@ Co3O4 core/shell heterostructures on nickel foam | |
| Wang et al. | Pd nanowire arrays as electrocatalysts for ethanol electrooxidation | |
| Sharma et al. | Support materials for PEMFC and DMFC electrocatalysts—A review | |
| Zainoodin et al. | Electrode in direct methanol fuel cells | |
| Maiyalagan et al. | Nitrogen containing carbon nanotubes as supports for Pt–Alternate anodes for fuel cell applications | |
| Zheng et al. | In situ one-step method for preparing carbon nanotubes and Pt composite catalysts and their performance for methanol oxidation | |
| Yi et al. | Fabrication of novel porous Pd particles and their electroactivity towards ethanol oxidation in alkaline media | |
| Ghosh et al. | Facile in situ synthesis of multiwall carbon nanotube supported flowerlike Pt nanostructures: an efficient electrocatalyst for fuel cell application | |
| Xu et al. | High-performance polypyrrole functionalized PtPd electrocatalysts based on PtPd/PPy/PtPd three-layered nanotube arrays for the electrooxidation of small organic molecules | |
| Muthurasu et al. | Fabrication of nonmetal-modulated dual metal–organic platform for overall water splitting and rechargeable zinc–air batteries | |
| CN106430166A (en) | Preparation method of MOFs (Metal-Organic Frameworks)-graphene composite material | |
| CN106887598A (en) | A kind of ordering membrane electrode and its preparation and application | |
| CN105576264B (en) | A kind of gas-diffusion electrode and its preparation and application | |
| Dai et al. | Silver nanoparticle-induced growth of nanowire-covered porous MnO2 spheres with superior supercapacitance | |
| Jiang et al. | Recent advances in solid–liquid–gas three‐phase interfaces in electrocatalysis for energy conversion and storage | |
| He et al. | Pt nanoparticle-loaded graphene aerogel microspheres with excellent methanol electro-oxidation performance | |
| CN103028396A (en) | Preparation method of Pd@Pt core-shell structural catalyst for low-temperature fuel cell | |
| CN104685682B (en) | The manufacture method of catalyst for fuel cell and the fuel cell containing the catalyst for fuel cell manufactured using the manufacture method | |
| Jin et al. | Polyaniline hollow tubes loading tiny platinum nanoparticles for boosting methanol oxidation | |
| CN102881916A (en) | Gas diffusion electrode carried with double-shell core-shell catalyst and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230116 Address after: 201109 2nd floor, building 11, 988 Zhongchun Road, Minhang District, Shanghai Patentee after: Shanghai Hurui Technology Co.,Ltd. Address before: 201210 No. 99, Hai Ke Road, Pudong New Area, Pudong New Area, Shanghai. Patentee before: SHANGHAI ADVANCED Research Institute CHINESE ACADEMY OF SCIENCES |