CN106159284B - 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
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- CN106159284B CN106159284B CN201510182054.9A CN201510182054A CN106159284B CN 106159284 B CN106159284 B CN 106159284B CN 201510182054 A CN201510182054 A CN 201510182054A CN 106159284 B CN106159284 B CN 106159284B
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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]
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- 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]
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- 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
Abstract
The present invention provides a kind of ordered nano-structure membrane electrode and preparation method thereof, coating including microporous layers, the preparation of binder, foraminous die plate and the bonding of substrate, the preparation for mixing electroplate liquid, the preparation of nano-array, the post-processing of product and the pressing of membrane electrode assembly.Core of the invention technology is the preparation of ordered nano array catalysis electrode, mainly pass through template electro-deposition path, by platiniferous or platinum alloy nanostructure deposition in foraminous die plate, remove foraminous die plate and binder, it obtains being grown directly upon the one-dimensional orderly nano-array catalysis electrode in microporous layers, and then presses and obtain membrane electrode.The present invention does not need any transfer or turns the method for pressure, ordered nano-structure can be applied in membrane electrode assembly, propose a kind of novel porous electrode structure, and the preparation process of membrane electrode assembly is reformed, the catalytic activity of electrode and the utilization rate of noble metal greatly improved, battery performance can be greatly improved by being further used for fuel cell.
Description
Technical field
The present invention relates to fuel cell correlative technology field, it is related to a kind of ordered nano-structure membrane electrode and its preparation side
Method, more particularly to a kind of ordered nano-structure membrane electrode and preparation method thereof applied to fuel cell.
Background technique
Miscellaneous Portable mobile electronic device with rapid changepl. never-ending changes and improvements that has been born of science and technology, function are gradually become strong directly
Cause the capacity of conventional batteries to be no longer satisfied people for the power consumption requirements of corresponding electronic equipment, therefore develops a kind of volume
It is small, light, duration sufficiently long portable mobile power supply is extremely urgent.The small in size of fuel cell, capacity are big, safety is steady
The features such as determining makes it show superiority in mobile power source field, is realized and is worked long hours by addition fuel, energy is close
Degree is the several times of lithium ion battery.In recent years, as the future developing trend of novel mobile power source, passive direct methanol fuel
Battery (Direct Methanol Fuel Cells, DMFC) is one of the mobile power source technology that people rather pay close attention to, and utilizes first
Alcohol obtains electric energy as fuel and eliminates fuel feed pump and air blower, reduces the energy consumption of ancillary equipment.It can make
It obtains equipment and runs the long period under the premise of not needing charging.
However, current passive type DMFC is still faced with some technical problems in terms of practical application: (1) methanol by every
Film infiltration reduces fuel availability and battery operating voltage；(2) methanol electrochemical reaction activity is not high, i.e. the benefit of catalyst
It is low with rate；(3) low power density, fuel and oxidant lean on free diffusing completely, it is difficult to stable equilibrium by methanol and oxygen
It is transmitted to catalyst surface and participates in reaction, cause system performance poor.Before the application that formally puts goods on the market, still face many tight
High technological challenge.For the approval won the market early, many research work need further deeply to solve current institute
Existing these problems.
In current fuel cell studies, set since the plurality of advantages and passive type of methanol do not need external auxiliary
It is standby, so the direct methanol fuel cell of passive type becomes a big research hotspot.The core of entire battery is membrane electrode assembly
(Membrane Electrode Assemblies, MEA), it is the transmission of material transferring, electrochemical reaction, electronics and ion
And the place that energy transfer occurs, its performance superiority and inferiority directly influence the height of entire battery performance.Current research master
It concentrates on the supporting layer and Catalytic Layer and the film to play an important role of regulation anode, cathode.Whole Development Trend is out
Send out ordered nano-structure MEA high performance.Therefore, how to prepare that ultra-thin, nanostructure is controllable, (part) is orderly, each interface
The good membrane electrode assembly of compatibility becomes the main target studied both at home and abroad and DMFC obtains high-performance, realizes functionization
Key.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of having applied to fuel cell
The preparation method of sequence nanostructure membrane electrode, for improving the performance of membrane electrode assembly in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of preparation side of ordered nano-structure membrane electrode
Method, the preparation method at least include the following steps:
1) substrate and a foraminous die plate are provided, the substrate includes carbon paper and coats the electrode micropore on the carbon paper
Layer；
2) binder is prepared, is bonded the foraminous die plate and the electrode microporous layers by binder；
3) mixing electroplate liquid is prepared, prepares nano-array using the electrode micropore layer surface is electrodeposited in；
4) sedimentation products post-process, including the removal foraminous die plate and binder, to prepare ordered nano battle array
Column catalysis electrode；
5) it using the ordered nano array catalysis electrode as cathode and/or anode, is put between Yu Suoshu cathode and anode
A proton exchange membrane and hot pressing are set into membrane electrode.
Preferably, the method for coating of electrode microporous layers is as follows in the step 1):
Ultrasound after carbon dust, polytetrafluoroethylsolution solution, isopropanol water solution are mixed, has coated mixing on the carbon paper
The carbon dust of polytetrafluoroethylsolution solution, the isopropanol water solution is stated, the electrode microporous layers are obtained after sintering.
It is highly preferred that the 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 polytetrafluoroethylene (PTFE) on the carbon paper is 0
~40%, the carrying capacity of the carbon dust on the carbon paper is 0~2.0mgcm-2, the quality point of the electrode microporous layers polytetrafluoroethylene (PTFE)
Number is 0~50%, and sintering temperature is set as 100~500 DEG C, and sintering time is set as 10~60min.
Preferably, the preparation method of binder is as follows in the step 2):
Kynoar is mixed to simultaneously magnetic agitation with N-Methyl pyrrolidone, obtains Kynoar solution as bonding
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
The mass fraction of Kynoar solution is 2%~15%.
Preferably, foraminous die plate and the adhesive method of the substrate are as follows in the step 2):
The binder is coated in the electrode microporous layers, then foraminous die plate is bonded in the electrode microporous layers
And it stands.
It is highly preferred that the dosage of the binder is set as 2.0~15.0mgcm-2, the foraminous die plate is anodic oxidation
The bilateral aperture of aluminum alloy pattern plate, titania nanotube template or polycarbonate foraminous die plate, the foraminous die plate is set as 50
~400nm, time of repose are set as 0~30min.
Preferably, the preparation method of mixing electroplate liquid is as follows in the step 3):
The mixing plating is prepared into after platinum presoma or platinum presoma and precious metal chemical complex are mixed with acid solution, lead salt
Liquid, and stand.
It is highly preferred that the platinum presoma is that chloroplatinic acid is received or the combination of one or both of chloroplatinic acid, your gold
Category compound is palladium chloride, nickel chloride, chromium chloride, nickel nitrate, chromic nitrate or ruthenium trichloride, and the acid solution is perchloric acid or dilute sulphur
Acid, the lead salt are lead acetate or plumbi nitras.
It is highly preferred that in the mixing electroplate liquid platinum precursor concentration be 1~10mM, precious metal chemical complex concentration be 1~
10mM, acid strength are 0.01~0.2M, and lead salt concentration is 0.02~0.4mM.
It is highly preferred that the time of repose of the mixing electroplate liquid be set as 0~for 24 hours.
Preferably, electro-deposition preparation method is as follows in the step 3):
The substrate of bonding and the foraminous die plate and the mixing electroplate liquid 3-1) are packed into precipitation equipment；
3-2) to be coated with the carbon papers of electrode microporous layers as working electrode, electrode microporous layers side directly with mix
Plating solution contacts, platinum line are used as to electrode, and saturated calomel electrode carries out electricity using cyclic voltammetry and sink as reference electrode
Product；
The precipitation equipment is dismantled after 3-3) electro-deposition is complete, the electrode microporous layers for being deposited with nano-array are stood.
It is highly preferred that electro-deposition voltage is set as -1.0~0V, electrodeposition time is set as 1000~15000s, described heavy
Product have the electrode microporous layers time of repose of nano-array be set as 4~for 24 hours.
Preferably, sedimentation products post-processing approach is as follows in the step 4):
The method of the nano-array dissolution of electro-deposition preparation is removed into the foraminous die plate, then uses N- methyl pyrrole
Pyrrolidone removes the binder, then alternately washing for several times, obtains described orderly receiving later under the conditions of vacuum drying with water, ethyl alcohol
Rice array catalysis electrode.
It is highly preferred that the foraminous die plate is alkalinity or both sexes template, then it is set as the lye of 1.0~3.0M using concentration
To dissolve the foraminous die plate；The foraminous die plate is polycarbonate foraminous die plate, then uses carbon tetrachloride, chloroform or tetrahydro
THF solvent dissolves the foraminous die plate；N-Methyl pyrrolidone solution heating temperature is set as 20~90 when except no-bonder
DEG C, vacuum drying temperature is set as 30~100 DEG C.
The present invention also provides the ordered nano-structure membrane electrodes that the preparation method described in one kind prepares.
The present invention provides a kind of ordered nano catalysis electrode again, and the catalysis electrode includes at least:
Substrate, the substrate include carbon paper and coat the electrode microporous layers on the carbon paper；
Nano-array is deposited on the electrode micropore layer surface.
In addition the present invention also provides a kind of using the ordered nano array catalysis electrode as cathode and/or anode application
In the purposes of membrane electrode.
As described above, the preparation method of ordered nano array catalysis electrode of the invention, has the advantages that this hair
The preparation method of the bright ordered nano array catalysis electrode applied to fuel cell is by template electro-deposition path, by platiniferous
Or platinum alloy nano wire or nanotube deposition remove foraminous die plate, obtain the platinum of one-dimensional ordered nano-structure in foraminous die plate
Or platinum alloy nano-array catalysis electrode, the present invention directly prepare nano wire or nano-tube array in substrate, to be made
The catalysis electrode of ordered nano-structure, and directly pressed with obtained ordered nano-structure electrode and form orderly nano-structure film
Electrode aggregate has reformed the electrode preparation method in battery core component membrane electrode assembly, membrane electrode collection greatly improved
Catalytic activity, the mass-transfer efficiency of the utilization rate of noble metal catalyst and electrode interior of zoarium.
Detailed description of the invention
The preparation method process that Fig. 1 is shown as the ordered nano array catalysis electrode applied to fuel cell of the invention is shown
It is intended to.
Fig. 2 is shown as the X-ray diffraction schematic diagram of electrode microporous layers and Pt nanowires elctro-catalyst of the invention.
Fig. 3 is shown as the electron scanning imaging schematic diagram of Pt nanowires elctro-catalyst of the invention.
Fig. 4 is shown as the transmission electron microscope schematic diagram of Pt nanowires elctro-catalyst of the invention.
Fig. 5 be shown as the resulting direct methanol fuel cell component of orderly Pt nanowires elctro-catalyst electrode of the invention with
The performance test map of the fuel cell of the prior art.
Fig. 6 is shown as the electron scanning imaging schematic diagram of platinum nanotube elctro-catalyst of the invention.
Component label instructions
S1~S5 step 1~step 5
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Please refer to FIG. 1 to FIG. 6.It should be noted that diagram provided in the present embodiment only illustrates this in a schematic way
The basic conception of invention, only shown in schema then with related component in the present invention rather than package count when according to actual implementation
Mesh, shape and size are drawn, when actual implementation kenel, quantity and the ratio of each component can arbitrarily change for one kind, and its
Assembly layout kenel may also be increasingly complex.
As shown in Figure 1, the present invention provides a kind of preparation method of ordered nano-structure membrane electrode applied to fuel cell,
The preparation method of the ordered nano-structure membrane electrode at least includes the following steps:
S1, provides a substrate and a foraminous die plate, and the substrate includes that carbon paper and the electrode coated on the carbon paper are micro-
Aperture layer；
S2 prepares binder, is bonded the foraminous die plate and the electrode microporous layers by binder；
S3 prepares mixing electroplate liquid, prepares nano-array using the electrode micropore layer surface is electrodeposited in；
S4, sedimentation products post-processing, including the removal foraminous die plate and binder, to prepare ordered nano battle array
Column catalysis electrode；
S5 is put between Yu Suoshu cathode and anode using the ordered nano array catalysis electrode as cathode and/or anode
A proton exchange membrane and hot pressing are set into membrane electrode.
The preparation method of ordered nano-structure membrane electrode of the invention is described in detail below.
Step S1 is first carried out: a substrate and a foraminous die plate are provided, the substrate includes carbon paper and coats in the carbon
Electrode microporous layers on paper.
The electrode microporous layers coat detailed process are as follows: by carbon dust, polytetrafluoroethylene (PTFE) (Polytetrafluoro
Ethylene, PTFE) solution, isopropanol (Iso-Propyl Alcohol, IPA) aqueous solution mixing after 30~150min of ultrasound,
It is 0~2.0mgcm that carrying capacity is coated on the carbon paper for being 0~40%PTFE containing mass fraction-2To be mixed with the PTFE molten
The carbon dust of liquid, the IPA aqueous solution obtains the electrode micropore after being sintered 10~60min under the conditions of 100~500 DEG C of temperature
Layer.
The carbon dust can be carbon nano-tube material, carbon fibre material or carbosphere material, and certainly, the carbon dust can also be with
It is other suitable carbon materials, it is unlimited herein.
The foraminous die plate be anodic oxidation aluminium formwork, titania nanotube template or polycarbonate foraminous die plate,
Certainly, the foraminous die plate is also possible to other suitable porous materials, unlimited herein.
Then it executes step S2: preparing binder, glued the foraminous die plate and the electrode microporous layers by binder
Knot.
The method of concrete configuration binder are as follows: by Kynoar (Polyvinylidene Fluoride, PVDF) and N-
Methyl pyrrolidone (N-Methyl Pyrrolidone, NMP) mixing and under the conditions of 20~80 DEG C of temperature magnetic agitation 1~
10h obtains the PVDF solution that mass fraction is 2%~15% as binder.
The method for specifically bonding the foraminous die plate and substrate are as follows: by 2.0~15.0mgcm-2The PVDF solution applies
In the electrode microporous layers, the foraminous die plate that bilateral aperture is set as 50~400nm is then bonded in the electrode micropore
On layer and stand 0~30min.
Then it executes step S3: preparing mixing electroplate liquid, prepare nanometer using the electrode micropore layer surface is electrodeposited in
Array.
The preparation method of the mixing electroplate liquid are as follows: by platinum presoma or platinum presoma and precious metal chemical complex and acid solution,
The mixing electroplate liquid is prepared into after lead salt mixing, and stand 0~for 24 hours.Wherein, the platinum presoma can be chloroplatinic acid receive,
The mixing of one or both of chloroplatinic acid, the precious metal chemical complex can be palladium chloride, nickel chloride, chromium chloride, nickel nitrate,
Chromic nitrate or ruthenium trichloride, the acid solution can be perchloric acid or dilute sulfuric acid, and the lead salt then can be lead acetate or plumbi nitras.
In the present embodiment, platinum precursor concentration described in the mixing electroplate liquid is 1~10mM, and the precious metal chemical complex concentration is
1~10mM, the acid concentration are 0.01~0.2M, and the lead salt concentration is 0.02~0.4mM.
The method of electro-deposition in this step are as follows: firstly, by the substrate of bonding and the foraminous die plate and the electricity
Plating solution is packed into precipitation equipment；Then, using the carbon paper as working electrode, microporous layers side directly and plating solution contacts, platinum
Belong to line to be used as to electrode, saturated calomel electrode carries out electro-deposition as reference electrode, using cyclic voltammetry；Electro-deposition voltage is set
It is set to -1.0~0V, electrodeposition time is set as 1000~15000s；Electro-deposition is carried out under the conditions of nitrogen protection；Electro-deposition is complete
Dismantle the precipitation equipment later, by be deposited with platinum or platinum alloy nano-array electrode microporous layers stand 4~for 24 hours.The platinum
Or the appearance and size of platinum alloy nano-array can be regulated and controled by sedimentation time and the mixing bath concentration, the platinum finally obtained
Or platinum alloy nano-array can be nano wire or nanotube etc..
It should be noted that the nano-array of deposition growth is grown in electrode micropore layer surface, and the nano-array
Across the doubled via of the foraminous die plate.
Then step S4: sedimentation products post-processing is executed；Including removing the foraminous die plate and binder, so that preparation obtains
Obtain ordered nano array catalysis electrode.
Detailed process are as follows: the method for the nano-array dissolution of electro-deposition preparation is removed into the foraminous die plate, example
Such as, if foraminous die plate is the alkalinity such as anodic oxidation aluminium formwork or titania nanotube template or both sexes template, concentration is used
It is set as the lye of 1.0~3.0M to dissolve the foraminous die plate；If the foraminous die plate is polycarbonate foraminous die plate, use
Carbon tetrachloride, chloroform or tetrahydrofuran solvent alternately wash for several times to dissolve the foraminous die plate, then with water, ethyl alcohol, and
It is dried in vacuo under the conditions of 30~100 DEG C of temperature, obtains the ordered nano array catalysis electrode.The ordered nano array is urged
Polarizing electrode uses in direct methanol fuel cell membrane electrode as cathode and/or anode.
Finally execute step S5: using the ordered nano array catalysis electrode as cathode and/or anode, Yu Suoshu cathode
A proton exchange membrane and hot pressing are placed between anode into membrane electrode.
The mode of spraying or blade coating is adhered into one layer of Nafion resin on the surface of ordered nano array electrode, by drying
Processing, under conditions of 130 DEG C, 3~6MPa, hot pressing forms the membrane electrode set of cathode and anode and proton exchange membrane " three-in-one "
Body.
The present invention also provides a kind of ordered nano-structure membrane electrode, which is obtained using preparation described in above-mentioned preparation method
, the structure of the membrane electrode includes: the proton exchange that cathode, anode and hot pressing are formed between the cathode and anode
Film.Wherein, cathode and anode can all be ordered nano array catalysis electrode prepared by the present invention, either only anode or yin
Ordered nano array catalysis electrode extremely prepared by the present invention.
The ordered nano array catalysis electrode includes at least: substrate, and the substrate includes carbon paper and coats in the carbon
Electrode microporous layers on paper；Nano-array is deposited on the electrode micropore layer surface.
Embodiment one
The present embodiment provides a kind of preparation methods of orderly Pt nanowires membrane electrode, comprising the following steps:
Carbon nanotube, the 40.4mg mass fraction for weighing 20.0mg respectively are molten for 12.39% polytetrafluoroethylene (PTFE) (PTFE)
Isopropanol (IPA) aqueous solution (IPA:H of liquid, 200mg2O=1:1), and it is mixed the rear ultrasound 120min time；Containing matter
It measures and smears carrying capacity 2.0mgcm using scraper on the carbon paper that score is 20%PTFE-2Carbon nanotube；Again at a temperature of 350 DEG C into
Row sintering 30min obtains cathode micro porous layer.
Kynoar (PVDF) and N-Methyl pyrrolidone (NMP) are weighed, preparing PVDF mass fraction is 8.14%
Mixed solution；Magnetic agitation 8h under the conditions of 25 DEG C obtains PVDF solution as binder.
The PVDF solution for drawing about 50.0mg is coated in the cathode micro porous layer and is made to be coated in microporous layers with doctor blade
Then bilateral aperture is bonded in institute for the porous anodic alumina template (AAO template) of 200nm by upper PVDF solution about 32.0mg
10min is stated in cathode micro porous layer and stood, is bonded to the cathode micro porous layer and the AAO template.
1.0g six is hydrated chloroplatinic acid (H2PtCl6·6H2O it) pours into 50ml volumetric flask and adds water to graduation mark, then with shifting
Liquid tolerance takes 25.896ml to 100ml volumetric flask；Then 0.847ml perchloric acid is measured to 100ml volumetric flask；7.6mg is weighed again
Lead acetate is prepared by mixing into electroplate liquid to 100ml volumetric flask, and stands 12h.
The electroplate liquid by the substrate and AAO template loading precipitation equipment after bonding, after taking 25ml to stand
Pour into precipitation equipment；Using the carbon paper as working electrode, microporous layers side directly and plating solution contacts, platinum line as pair
Electrode, saturated calomel electrode make reference electrode；- 0.5~0V of deposition voltage section, sedimentation time 10000s are set；It is protected in nitrogen
Electro-deposition is carried out using cyclic voltammetry under the conditions of shield；Stripping device after electro-deposition will be deposited with the yin of Pt nanowires
Atomic aperture layer carbon paper stands 12h.
The AAO template being deposited with described in the removing of the NaOH solution of 2.0M on the cathode micro porous layer carbon paper of Pt nanowires, so
PVDF binder is removed with NMP afterwards, then is alternately washed for several times with water, ethyl alcohol, and be dried in vacuo and obtain under the conditions of 75 DEG C of temperature
Pt nanowires elctro-catalyst electrode.
The Pt nanowires elctro-catalyst that the present embodiment obtains is characterized, as shown in Fig. 2, obtaining electrode microporous layers and platinum
The X-ray diffractogram (XRD diagram) of nano wire elctro-catalyst, with the entire diffraction region of the angle scanning of 2 θ, as X-ray diffraction spectrum
Abscissa；Using the intensity of the diffraction maximum of different angle of diffraction (2 θ) as ordinate.It is illustrated in figure 3 the platinum nanometer of the present embodiment
The electron scanning imaging figure (SEM figure) of line elctro-catalyst, can measure from electron scanning imaging system and obtains the Pt nanowires
The diameter of elctro-catalyst about 200nm.It is illustrated in figure 4 the transmission electron microscope picture (TEM of the Pt nanowires elctro-catalyst of the present embodiment
Figure), it can measure from transmission electron microscope system and obtain a length of 3~5 μm of the Pt nanowires elctro-catalyst.
Black (Johnson Matthey) catalyst of Pt nanowires catalysis electrode and commercialized Pt to the present embodiment carries out
Compare, the resulting orderly Pt nanowires catalysis electrode of the present embodiment is used in cathode catalysis layer, obtains direct methanol fuel cell
Component；Nafion115 film in the prior art is formed into fuel cell:
(1) anode support: carbon paper TGPH060, the waterproof material (Toray) that mass fraction is 20%；Anode micro porous
Layer: carbon dust Vulcan XC-72R (1.0mgcm-2) (Cabot company) and mass fraction be 20% PTFE (Dupont is public
Department)；Anode catalyst layer: Pt-Ru/C (4.0mgcm-2), perfluorinated sulfonic acid-polytetrafluorethylene copolymer that mass fraction is 5.03%
Object (Nafion) solution (Dupont company).
(2) cathode support layers: carbon paper TGPH060, the waterproof material of mass fraction 20%；Cathode micro porous layer: carbon nanotube
(2mg·cm-2) and mass fraction be 12.89% PTFE；The cathode catalysis layer of the present embodiment: the Pt nanowires of the present embodiment and
The Nafion solution that mass fraction is 5.03%；The cathode catalysis layer of the prior art: nano platinum particle, mass fraction 5.03%
Nafion solution.
(3) Nafion115 film (Dupont company).
Pt-Ru/C in above-mentioned anode catalyst layer is come in Johnson Matthey company (writing a Chinese character in simplified form JM company)；Above-mentioned yin
Pt/C in the Catalytic Layer of pole comes JM company.
The orderly resulting direct methanol fuel cell component of Pt nanowires elctro-catalyst electrode resulting to the present embodiment and
The fuel cell of Nafion115 film composition in the prior art is tested, and being illustrated in figure 5 catalyst loading is 2.0mg
cm-2、1.5mg·cm-2、1.0mg·cm-2And 0.5mgcm-2When performance test map, it was found from the map: respectively will
Membrane electrode assembly obtained in direct methanol fuel cell for being tested for the property, using the resulting orderly platinum of the present embodiment
The power density of the direct methanol fuel cell of nanowire catalytic electrode is big, and performance is better than using commercialized catalyst (JM)
Direct methanol fuel cell.
Embodiment two
The present embodiment provides a kind of preparation methods of orderly platinum nanotube films electrode, comprising the following steps:
The carbon nanotube of 60.0mg is weighed respectively, the IPA of the PTFE solution that 179.2mg mass fraction is 8.37%, 600mg
Aqueous solution (IPA:H2O=1:1), and it is mixed the rear ultrasound 120min time；In the carbon for being 20%PTFE containing mass fraction
Carrying capacity 2.0mgcm is smeared using scraper on paper-2Carbon nanotube；Being sintered 30min at a temperature of 350 DEG C again, to obtain cathode micro-
Aperture layer.
PVDF and NMP are weighed, the mixed solution that PVDF mass fraction is 5.28% is prepared；Magnetic agitation under the conditions of 25 DEG C
8h obtains PVDF solution as binder.
The PVDF solution for drawing about 50mg is coated in the cathode micro porous layer and to be coated in microporous layers with doctor blade
Then the AAO template that bilateral aperture is 200nm is bonded in the cathode micro porous layer and is stood by PVDF solution about 32mg
10min is bonded to the cathode micro porous layer and the AAO template.
By 1.0g H2PtCl6·6H2O pours into 50ml volumetric flask and adds water to graduation mark, is then measured with pipettor
7.769ml arriving 100ml volumetric flask；Then 0.254ml perchloric acid is measured to 100ml volumetric flask；2.3mg lead acetate is weighed again to arrive
100ml volumetric flask is prepared by mixing into electroplate liquid, and stands 12h.
The electroplate liquid by the substrate and AAO template loading precipitation equipment after bonding, after taking 25ml to stand
Pour into precipitation equipment；Using the carbon paper as working electrode, microporous layers side directly and plating solution contacts, platinum line as pair
Electrode, saturated calomel electrode is as reference electrode；- 0.5~0V of deposition voltage section, sedimentation time 10000s are set；In nitrogen
Electro-deposition is carried out using cyclic voltammetry under protective condition；Stripping device after electro-deposition will be deposited with described in platinum nanotube
Cathode micro porous layer carbon paper stands 12h.
The AAO template being deposited with described in the removing of the NaOH solution of 2.0M on the cathode micro porous layer carbon paper of platinum nanotube, so
PVDF binder is removed with NMP afterwards, then is alternately washed for several times with water, ethyl alcohol, and be dried in vacuo and obtain under the conditions of 75 DEG C of temperature
Platinum nanotube elctro-catalyst electrode.
The Pt nanowires elctro-catalyst that the present embodiment obtains is characterized, the platinum nanometer of the present embodiment is illustrated in figure 6
The electron scanning imaging figure (SEM figure) of line elctro-catalyst, can measure from electron scanning imaging system and obtains the Pt nanowires
The diameter of elctro-catalyst about 200nm.
Embodiment three
The present embodiment provides a kind of preparation methods of orderly platinum ruthenium nano-wire catalysis electrode, comprising the following steps:
XC-72 carbon dust (Cabot company), the 161.4mg mass fraction for weighing 80.0mg respectively are molten for 12.39% PTFE
IPA aqueous solution (the IPA:H of liquid, 800mg2O=1:1), and it is mixed the ultrasonic 120min time；It is being containing mass fraction
Carrying capacity 2.0mgcm is smeared using scraper on the carbon paper of 20%PTFE-2Carbon dust；30min is sintered at a temperature of 350 DEG C again to obtain
To anode micro porous layer.
Weighed PVDF and NMP, preparation PVDF mass fraction are 9.37% mixed solution；Magnetic agitation under the conditions of 25 DEG C
8h obtains PVDF solution as binder.
The PVDF solution for drawing 50.0mg is coated in the anode micro porous layer and to be coated in microporous layers with doctor blade
PVDF solution about 32.0mg；Then the AAO template that bilateral aperture is 400nm is bonded in the anode micro porous layer and is stood
10min is bonded to the anode micro porous layer and the AAO template.
By 1.0g H2PtCl6·6H2O pours into 50ml volumetric flask and adds water to graduation mark, is then measured with pipettor
25.896ml arriving 100ml volumetric flask；It takes mono- hydrate ruthenium trichloride of 1.0g to pour into 50ml volumetric flask and adds water to graduation mark, then use
Pipettor measures 11.27ml and pours into 100ml volumetric flask；Then 0.847ml perchloric acid is measured to 100ml volumetric flask；It weighs again
7.6mg lead acetate is prepared by mixing into electroplate liquid to 100ml volumetric flask, stands 12h.
Mixing electricity by the substrate and AAO template loading precipitation equipment after bonding, after taking 25ml to stand
Plating solution pours into precipitation equipment.Using carbon paper as working electrode, microporous layers side directly and plating solution contacts, platinum line as pair
Electrode, saturated calomel electrode make reference electrode；- 0.5~0V of deposition voltage section, sedimentation time 10000s are set；It is protected in nitrogen
Start electro-deposition using cyclic voltammetry under the conditions of shield；Stripping device after electro-deposition will be deposited with described in platinum ruthenium nano-wire
Anode micro porous layer carbon paper stands 12h.
The AAO template being deposited with described in the removing of the NaOH solution of 2.0M on the anode micro porous layer carbon paper of platinum ruthenium nano-wire,
Then PVDF binder is removed with NMP, then is alternately washed for several times with water, ethyl alcohol, and be dried in vacuo under the conditions of 75 DEG C of temperature
To platinum ruthenium nano-wire elctro-catalyst electrode.
The present invention smears one layer of carbon material on the surface of carbon paper and constitutes electrode microporous layers, prepares certain density PVDF solution
As binder, electrode microporous layers are got up with foraminous die plate by binder bonding, certain density noble metal is then prepared
The mixing electroplate liquid of the compositions such as precursor, acid solution and lead salt, carries out electro-deposition under the conditions of nitrogen protection, obtains diameter and length
The controllable nano-array catalysis electrode obtained is spent, membrane electrode assembly is made by the method for hot pressing, is used for direct methanol fuel cell.
The preparation method of ordered nano array catalysis electrode applied to fuel cell of the invention is heavy by template electricity
Product path removes foraminous die plate by platiniferous or platinum alloy nano wire or nanotube deposition in foraminous die plate, obtains one-dimensional orderly
The platinum or platinum alloy nano-array catalysis electrode of nanostructure, the platinum of ordered nano-structure or platinum alloy nano-array are applied to
The catalytic activity of membrane electrode assembly and the utilization of noble metal catalyst greatly improved in the membrane electrode assembly of fuel cell
Rate.Further, the performance of fuel cell can be improved for direct methanol fuel cell.
In conclusion the present invention provides a kind of ordered nano-structure membrane electrode and preparation method thereof, the painting including microporous layers
System, the preparation of binder, foraminous die plate with after the bonding of substrate, the preparation for mixing electroplate liquid, the preparation of nano-array, product
Processing and the pressing of membrane electrode assembly.Core of the invention technology is the preparation of ordered nano array catalysis electrode, main
If by platiniferous or platinum alloy nanostructure deposition in foraminous die plate, removing foraminous die plate by template electro-deposition path
And binder, obtain being grown directly upon the one-dimensional orderly nano-array catalysis electrode in microporous layers, and then press and obtain film electricity
Pole.The present invention does not need any transfer or turns the method for pressure, and ordered nano-structure can be applied in membrane electrode assembly, mentioned
A kind of novel porous electrode structure is gone out, and has reformed the preparation process of membrane electrode assembly, urging for electrode greatly improved
Change the utilization rate of activity and noble metal, battery performance can be greatly improved by being further used for fuel cell.So effective gram of the present invention
It has taken various shortcoming in the prior art and has had high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (15)
1. a kind of preparation method of ordered nano-structure membrane electrode, which is characterized in that the preparation method includes at least following step
It is rapid:
1) substrate and a foraminous die plate are provided, the substrate includes carbon paper and coats the electrode microporous layers on the carbon paper；
2) binder is prepared, is bonded the foraminous die plate and the electrode microporous layers by binder；
3) mixing electroplate liquid is prepared, prepares nano-array using the electrode micropore layer surface is electrodeposited in；
4) sedimentation products post-process, including the removal foraminous die plate and binder, urge to prepare ordered nano array
Polarizing electrode；
5) using the ordered nano array catalysis electrode as cathode and/or anode, one is placed between Yu Suoshu cathode and anode
Proton exchange membrane and hot pressing are at membrane electrode；
Wherein, electro-deposition preparation method is as follows in the step 3):
The substrate of bonding and the foraminous die plate and the mixing electroplate liquid 3-1) are packed into precipitation equipment；
3-2) to be coated with the carbon papers of electrode microporous layers as working electrode, electrode microporous layers side directly with mix plating
Liquid contact, platinum line are used as to electrode, and saturated calomel electrode carries out electro-deposition as reference electrode, using cyclic voltammetry；
The precipitation equipment is dismantled after 3-3) electro-deposition is complete, the electrode microporous layers for being deposited with nano-array are stood.
2. the preparation method of ordered nano-structure membrane electrode according to claim 1, it is characterised in that: in the step 1)
The method for coating of electrode microporous layers is as follows:
Ultrasound after carbon dust, polytetrafluoroethylsolution solution, isopropanol water solution are mixed is coated on the carbon paper and is mixed with described gather
The carbon dust of tetrafluoroethene solution, the isopropanol water solution obtains the electrode microporous layers after sintering.
3. the preparation method of ordered nano-structure membrane electrode according to claim 2, it is characterised in that: the carbon dust is carbon
Nano-tube material, carbon fibre material or carbosphere material.
4. the preparation method of ordered nano-structure membrane electrode according to claim 2, it is characterised in that: ultrasonic time setting
For 30~150min, the mass fraction of the polytetrafluoroethylene (PTFE) on the carbon paper is 0~40%, the carrying capacity of the carbon dust on the carbon paper
For 0~2.0mgcm-2, the mass fraction of the electrode microporous layers polytetrafluoroethylene (PTFE) is 0~50%, and sintering temperature is set as 100
~500 DEG C, sintering time is set as 10~60min.
5. the preparation method of ordered nano-structure membrane electrode according to claim 1, it is characterised in that: in the step 2)
The preparation method of binder is as follows:
Kynoar is mixed to simultaneously magnetic agitation with N-Methyl pyrrolidone, obtains Kynoar solution as binder.
6. the preparation method of ordered nano-structure membrane electrode according to claim 5, it is characterised in that: the temperature of magnetic agitation
Degree is set as 20~80 DEG C, and the time of magnetic agitation is set as 1~10h, and the mass fraction of the Kynoar solution is 2%
~15%.
7. the preparation method of ordered nano-structure membrane electrode according to claim 1, it is characterised in that: in the step 2)
Foraminous die plate and the adhesive method of the substrate are as follows:
The binder is coated in the electrode microporous layers, is then bonded in foraminous die plate in the electrode microporous layers and quiet
It sets.
8. the preparation method of ordered nano-structure membrane electrode according to claim 7, it is characterised in that: the binder
Dosage is set as 2.0~15.0mgcm-2, the foraminous die plate be anodic oxidation aluminium formwork, titania nanotube template or
Person's polycarbonate foraminous die plate, the bilateral aperture of the foraminous die plate are set as 50~400nm, and time of repose is set as 0~
30min。
9. the preparation method of ordered nano-structure membrane electrode according to claim 1, it is characterised in that: in the step 3)
The preparation method for mixing electroplate liquid is as follows:
The mixing electroplate liquid is prepared into after platinum presoma or platinum presoma and precious metal chemical complex are mixed with acid solution, lead salt,
And it stands.
10. the preparation method of ordered nano-structure membrane electrode according to claim 9, it is characterised in that: the platinum forerunner
Body is that chloroplatinic acid is received or the combination of one or both of chloroplatinic acid, the concentration of the platinum presoma are 1~10mM；Your gold
Category compound is palladium chloride, nickel chloride, chromium chloride, nickel nitrate, chromic nitrate or ruthenium trichloride, and the concentration of precious metal chemical complex is 1
~10mM；The acid solution is perchloric acid or dilute sulfuric acid, and the concentration of the acid solution is 0.01~0.20M；The lead salt is lead acetate
Or plumbi nitras, concentration are 0.02~0.40mM.
11. the preparation method of ordered nano-structure membrane electrode according to claim 1, it is characterised in that: the step 4)
Middle sedimentation products post-processing approach is as follows:
The method that the nano-array prepared by electro-deposition first passes through dissolution is removed into the foraminous die plate, then uses N- methyl pyrrole
Pyrrolidone removes the binder, then alternately washing for several times, obtains under the conditions of vacuum drying described orderly later with water, ethyl alcohol
Nano-array catalysis electrode.
12. the preparation method of ordered nano-structure membrane electrode according to claim 11, it is characterised in that: the multiple-hole die
Plate is anodic oxidation aluminium formwork or titania nanotube template, then is set as the lye of 1.0~3.0M using concentration to dissolve
The foraminous die plate；The foraminous die plate is polycarbonate foraminous die plate, then molten with carbon tetrachloride, chloroform or tetrahydrofuran
The foraminous die plate is dissolved in agent；N-Methyl pyrrolidone solution heating temperature is set as 20~90 DEG C when except no-bonder, very
The dry temperature of sky is set as 30~100 DEG C.
13. a kind of ordered nano-structure membrane electrode prepared using preparation method described in claim 1.
14. a kind of ordered nano array catalysis electrode prepared using preparation method described in claim 1, feature are existed
In the catalysis electrode includes at least:
Substrate, the substrate include carbon paper and coat the electrode microporous layers on the carbon paper；
Nano-array is deposited on the electrode micropore layer surface.
15. a kind of ordered nano array catalysis electrode using described in claim 14 is applied to film as cathode and/or anode
The purposes of electrode.
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| CN108539206B (en) * | 2018-03-30 | 2019-12-31 | 江苏大学 | Catalysis layer full-order fuel cell electrode and membrane electrode |
| CN109440140B (en) * | 2018-11-22 | 2020-08-11 | 浙江大学 | Method for manufacturing electrolytic copper foil |
| KR102370705B1 (en) * | 2020-06-30 | 2022-03-04 | 고려대학교 산학협력단 | Ruthenium-based nanowire and manufacturing 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 |
| CN112259747B (en) * | 2020-10-21 | 2021-08-03 | 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 |
| 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 |
| 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 |
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