CN101462076A - Novel use of hydrophobing agent/conductive carbon material composite body - Google Patents
Novel use of hydrophobing agent/conductive carbon material composite body Download PDFInfo
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- CN101462076A CN101462076A CNA2009100449397A CN200910044939A CN101462076A CN 101462076 A CN101462076 A CN 101462076A CN A2009100449397 A CNA2009100449397 A CN A2009100449397A CN 200910044939 A CN200910044939 A CN 200910044939A CN 101462076 A CN101462076 A CN 101462076A
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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
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- 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 invention relates to the technical field of fuel batteries, and discloses novel use of a hydrophobing agent/conducting carbon material complex as an electro-catalyst carrier for a fuel battery. The complex can be taken as the electro-catalyst carrier for the fuel battery and used for preparing an electro-catalyst and an electrode. The invention also further discloses the electro-catalyst and the electrode prepared from the hydrophobing agent/conducting carbon material complex, and application thereof. As for the electro-catalyst prepared from the hydrophobing agent/conducting carbon material complex, the utilization rate of the catalyst is high; the transmission capability of reaction gas and reaction products is strong; the mass transfer polarization loss is small; the fuel battery assembled by the electro-catalyst has superior battery output performance; and the electro-catalyst is particularly suitable to be used in fuel batteries taking the air as an oxidant.
Description
Technical field
The present invention relates to fuel cell, be specifically related to application as the water-repelling agent/conductive carbon material complex of electrocatalyst for fuel cell carrier.
Background technology
Fuel cell as a kind of efficient, eco-friendly TRT, receives concern more and more widely.Low-temperature fuel cell (operating temperature≤80 ℃) comprises Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cell, PEMFC) and directly alcohol fuel battery (Direct alcohol fuel cell, DAFC), because of its energy transformation ratio height, advantage such as environmental friendliness, operating temperature are low is considered to have a wide range of applications at aspects such as automobile power, portable power source and small hydropower stations.
Electrode is the place that electrochemical reaction takes place in the fuel cell.The electrochemical reducting reaction that takes place as cathode side in PEMFC and DAFC is:
O
2+4H
++4e
-→H
2O
By the electrode reaction equation as can be known, carry out for guaranteeing successful reaction, the reflecting point place must possess simultaneously proton is arranged, the continuous transmission channel of electronics, reacting gas, and the timely eliminating of product-water simultaneously also is the necessary factor that guarantees that this reaction is carried out smoothly.Usually the electrical conductivity passage of reaction zone is realized by the eelctro-catalyst (as Pt/C) of electric conductivity.The proton conduction passage is made up by electrolyte (ion exchange resin is as Nafion).The transmission channels of reacting gas and product water is served as by the space that forms between each composition material.Usually will be called " phase reaction district " by the intersection of " catalyst/reacting gas/electrolyte ".At present, the research of electrode structure mainly concentrates on: how effectively to construct " phase reaction district ", improve the utilization rate of catalyst, reduce the activation polarization loss; How effectively to make up the three-dimensional porous network structure of electrode, improve the transmittability of reacting gas and product, reduce mass transfer polarization loss.
In the low-temperature fuel cell evolution, formed the preparation technology of multiple electrode, electrode structure also constantly changes, and the common objective of various technologies of preparing all is to improve catalyst utilization, the mass transfer of intensifier electrode inside.At present, the electrode structure that is widely adopted can be divided into four big classes substantially, that is: thick-layer hydrophobic type electrode, thin layer hydrophilic electrode, parent/hydrophobic compound electrode and superthin layer electrode.
Thick-layer hydrophobic type electrode production process is: Pt/C catalyst and a certain amount of PTFE are mixed the back preparation on diffusion layer, after realizing the bonding and hydrophobic effect of PTFE after the uniform temperature roasting, again at the Nafion solution of spray one deck in surface by the lower alcohol dilution.Such electrode hydrophobicity is better, and the mass transfer of reacting gas is relatively good.But because ionic conductive polymer (Nafion) is to enter on the Catalytic Layer surface by the mode that sprays into or immerse, so it is inner and fully contact with catalyst granules be difficult to guarantee that it fully penetrates into Catalytic Layer, so the utilization rate of electrode inner catalyst is very low, generally has only 10-20% (S.Srininvasan, O.A.Velev, A.Parthasarathy, et al..High energy efficiency and high power densityproton exchange membrane fuel cells-electrode kinetics and mass transport.J.Power Sources, 1991,36 (3): 299-320).In addition, PTFE can wrap the part catalyst particle in the preparation process, also is a reason that causes catalyst utilization low.
Thin layer hydrophilic electrode production process is: after at first the Nafion solution of 5wt.% and Pt/C eelctro-catalyst being mixed, or be prepared on the PTFE film, change being pressed onto on the PEM again; Or directly be prepared into the PEM surface, form electrode.The advantage of this electrode is catalyst and Nafion full contact, and catalyst utilization improves.Shortcoming is that the gas transfer resistance is bigger because electrode interior does not contain water-repelling agent, takes place easily " water logging ".
Parent/hydrophobic compound electrode production process is: the hydrophobicity catalysis individual layer that is made of PTFE and catalyst at diffusion layer surface preparation one deck at first, the hydrophily catalysis individual layer that is made of Nafion and catalyst at its surface preparation one deck again, two catalysis individual layers are common forms complete electrodes.Under the same catalyst consumption, combination electrode is compared with traditional hydrophilic or hydrophobic type electrode, shows mass-transfer performance and ionic conduction performance preferably, and catalyst utilization improves greatly, the corresponding raising of battery performance.Shortcoming is that preparation technology is loaded down with trivial details relatively, and Catalytic Layer is thicker.
The superthin layer electrode is to adopt the thin layer electrode of means such as physical/chemical vapour deposition or particle beams sputter in gas diffusion layers or the formation of PEM surface.Such electrode shows more excellent quality than power-performance, but the area specific power is also lower, is not suitable for practical application.
In sum, all there is certain drawback in the electrode structure that exists at present.The utilization rate height of exploitation catalyst, the transmittability of reacting gas and product is strong, and the electrode of the long service life of the little and electrode of mass transfer polarization loss has extremely important realistic meaning.
Summary of the invention
The objective of the invention is to solve in traditional hydrophobic thick-layer electrode production process, the polymer that part catalyst activity particle can be used as water-repelling agent wraps up and the problem of utilization rate reduction, and there is not water-repelling agent in traditional hydrophilic thin layer electrode, electrode is easily by the problem of " water logging ", provide a kind of novel electrocatalyst for fuel cell carrier, its preparation with and application on preparation eelctro-catalyst, low-temperature fuel cell catalyst electrode.
One aspect of the present invention discloses water-repelling agent/conductive carbon material complex powder and can be used as the new purposes of electrocatalyst for fuel cell carrier.
Above-mentioned water-repelling agent/conductive carbon material complex is water-repelling agent and the compound product of conductive carbon material, and based on water-repelling agent/conductive carbon material complex weight, the water-repelling agent weight percentage is 0.5～50%, is preferably 1～40%, is preferably 5～20%.
Above-mentioned water-repelling agent/conductive carbon material complex is water-repelling agent and the compound product of conductive carbon material, wherein, conductive carbon material is one or more the mixing that is selected from conductive carbon black, carbon fiber, CNT, activated carbon, carbosphere, carbon whisker or the graphite granule; Described conductive carbon material is particle diameter 5～100nm, is preferably 8～60nm, is preferably 10～40nm; Specific area 10～3000m
2/ g is preferably 30～2000m
2/ g is preferably 50～1500m
2/ g; Water-repelling agent is selected from polytetrafluoroethylene (PTFE), inclined to one side tetrafluoroethene (PVDF), polytetrafluoroethylene (PTFE)-perfluoroalkyl vinyl ether (PFA), FEP fluorinated ethylene propylene copolymer resin (FEP) or ethylene fluoride/tetrafluoroethylene copolymer resins (ETFE), is preferably PTFE.
The particle diameter of above-mentioned water-repelling agent/conductive carbon material complex is between 0.5～50 μ m.
Above-mentioned water-repelling agent/conductive carbon material complex can adopt the micro-wave dielectric heating technique to make, and its detailed process is:
1) at first that conductive carbon material is wetting with ethanol or isopropyl alcohol, add conductive carbon material quality 10-100 deionized water doubly subsequently, in ultrasonic wave, fully disperse, stir;
2) the water-repelling agent emulsion is dropwise joined in the suspension of the above-mentioned material with carbon element of abundant dispersion, this step water-repelling agent dripping quantity is 1.5～3 times of water-repelling agent actual content in the product, fully stirs, and material with carbon element is fully mixed with water-repelling agent contact;
3) above-mentioned mixed liquor is placed 70-100 ℃ of water-bath coacervation, and vapor away pure and mild deionized water as solvent;
4) water-repelling agent after will drying and the mixture of conductive carbon material place micro-wave oven, and carry out microwave heating treatment: microwave heating time is 0.5～30 minute, is generally 1～20 minute, is preferably 1.5～5 minutes; The power of microwave system is 500W～30KW; Obtain water-repelling agent/conductive carbon material complex powder.
Water-repelling agent/conductive carbon material complex the powder that obtains can be determined the content of final water-repelling agent by weight method; Prepared water-repelling agent/conductive carbon material complex particle diameter is between 0.5～50 μ m.
Above-mentioned water-repelling agent/conductive carbon material complex powder can be used as the electrocatalyst for fuel cell carrier.
Second aspect present invention, a kind of electrocatalyst for fuel cell is disclosed, be composited by catalyst activity particle and electro-catalyst carrier, wherein, based on the eelctro-catalyst gross weight, the weight percentage of catalyst activity particle is 5-80%, and is preferred 5-50%, and electro-catalyst carrier is above-mentioned water-repelling agent/conductive carbon material complex.
Above-mentioned catalyst activity particle is group VIII or the Cr that is selected from the periodic table of elements, Mo, Zr, the metallic element of one or more among the Ti, especially for being selected from Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cr, one or more metallic elements among Mo, Zr, the Ti.
Above-mentioned electrocatalyst for fuel cell can water-repelling agent/conductive carbon material complex be a carrier, by the preparation of microwave colloid reducing process, specifically comprises the following steps:
(1) the solubility predecessor with the catalyst activity particle is dissolved in the ethylene glycol, and ultrasonic dispersion also fully mixes, and obtains solution A;
(2) with carrier and ethylene glycol in 10～500ml ethylene glycol: the ratio of 1g carrier is mixed, ultrasonic dispersion and stir after, obtain slurry B;
(3) in the ratio calculating solution A of active particle in the eelctro-catalyst and carrier and the ratio of slurry B, solution A is dropwise joined among the slurry B, fully stir, make both mix pH value to 9～14 that the back adds alkali lye accent solution;
(4) heated 0.1～30 minute the mixed liquor microwave continuous or the intermittence that will mix up the pH value, be generally 0.5～10min, be preferably 0.5～5min, obtain slurry C; Described microwave frequency band is 1～3GHz, and the power output of microwave system is 500W～30KW;
(5) stir slurry C, and be cooled to room temperature, add acid solution and regulate pH value to 1～3, obtain slurry D;
(6) with slurry D centrifuge washing, 60-120 ℃ vacuum drying 4-12 hour, promptly get eelctro-catalyst of the present invention, active particle/(water-repelling agent/conductive carbon material) complex.
The solubility predecessor of above-mentioned catalyst activity particle is one or more the mixture in metal nitrate, oxalates, acetate or the metallate solution.
Above-mentioned electrocatalyst for fuel cell can be used for preparing electrode for fuel cell.
A third aspect of the present invention discloses a kind of low-temperature fuel cell electrode, comprises proton conductive polymer and above-mentioned electrocatalyst for fuel cell.
Above-mentioned low-temperature fuel cell specifically comprises the following steps: with the preparation method of electrode
(1) above-mentioned eelctro-catalyst is mixed with isopropyl alcohol, mechanical agitation or ultrasonic dispersion, general 10mg catalyst disperses with 1～20ml isopropyl alcohol;
(2) proton conductive polymer is joined in the above-mentioned eelctro-catalyst slurries, the addition of proton conductive polymer is 5%～40% of proton conductive polymer and a catalyst gross mass, is generally 10%～35%, is preferably 15%～30%, obtains catalyst pulp;
(3) with the above-mentioned catalyst pulp for preparing, adopt spraying, methods such as serigraphy or blade coating are prepared in gas diffusion layers or PEM surface, dry naturally, vapor away solvent, form electrode.
Above-mentioned proton conductive polymer is the perfluor high molecular polymer that side chain contains sulfonate group, and side chain contains the partially fluorinated high molecular polymer of sulfonate group or the non-fluorine high molecular polymer that side chain contains sulfonate group.
The electrode of this method preparation has been strengthened the aqueous vapor management of electrode interior, reduces mass transfer polarization loss, improves battery performance.
The present invention has following advantage:
At first, in catalyst preparation process, water-repelling agent is incorporated into carrier surface, and then the reducing activity particle thereon, effective like this active particle of having avoided is by the parcel of water-repelling agent, but increased the usable floor area of catalyst.
In addition, use in the process of this Preparation of Catalyst electrode, catalyst directly contacts with proton conductive polymer, has guaranteed making full use of of active component, and the proton conduction network is continuous.The hydrophobic carrier of catalyst can make up abundant hydrophobic channel again in electrode, help reacting gas and enter into electrode interior, reduces mass transfer polarization loss.Thereby the output performance of raising battery shows more excellent cell output by its fuel battery assembled, is particularly suitable for using in the fuel cell that with the air is oxidant.
Water-repelling agent in the invention/conductive carbon material composite granule can be used as separate material, produces, and preserves.Eelctro-catalyst and electrode production process are simple, and be easy to operate.
Description of drawings
Fig. 1 is the XRD spectra of Pt/ of the present invention (PTFE/C) catalyst;
Fig. 2 is the electrode surface of Pt/ of the present invention (PTFE/C) preparation and the SEM photo of the electrode surface that commercialization Pt/C prepares;
Fig. 3 is that the electrode of Pt/ of the present invention (PTFE/C) preparation and the PEMFC output performance of the electrode that commercialization Pt/C prepares compare (the solid I-V polarization curve that is illustrated as, the hollow power density curve that is illustrated as);
The specific embodiment
The present invention is described in further detail below by embodiment, should be understood that embodiment is used to limit the scope of the invention.
Embodiment 1:
The preparation of catalyst carrier:
Get 2.0g VulcanXC-72 conductive carbon black, after usefulness 4mL aqueous isopropanol is wetting, add the 60mL deionized water, mechanical agitation 15min carries out ultrasonic processing 30min subsequently again.Then, under mechanical agitation, slowly drip the 8.6g10wt.%PTFE aqueous emulsion, fully stir, carbon black is evenly mixed with PTFE.Place 90 ℃ of water-bath coacervations then, remove clear liquid after, the oven dry, making PTFE content is the PTFE/C complex predecessor of 30wt.%.With this predecessor put into micro-wave oven (700W, 2450MHz) in, carry out the heating schedule that heating using microwave 5s stops 20s, to remove residual moisture content in the sample.Heat the heating schedule that 10s stops 60s subsequently repeatedly, to PTFE content be 9wt%.Getting PTFE content is the PTFE/VXC composite granule of 9wt%, is designated as 9PTFE/VXC.
Preparation of catalysts:
Get 222.2mg 9PTFE/VXC composite granule, add 35ml ethylene glycol (EG) solution, behind the ultrasonic dispersion 15min, carry out magnetic agitation 30min.Get the H that 2.3mL concentration is 37mg Pt/mL
2PtCl
6/ ethylene glycol solution (H
2PtCl
6/ EG solution) be added drop-wise in the carrier slurry.Fully stir.Drip 2M NaOH/EG solution and regulate pH to 13.With the complex catalyst precursor thing solution that mixes up the pH value place micro-wave oven (700W, 2450MHz) in, heating using microwave 1.5min takes out, and stirs the cold of drying in the air.Drip 2M HNO
3Solution is regulated pH to 3.Leave standstill centrifugation behind the 2hr and wash the NaOH of EG and adding, HNO off
3Solids after the separation places 80 ℃ of vacuum drying chambers, dry 4hr, and based on the gross mass of VXC and Pt, obtaining Pt content is 29% catalyst, notes by abridging into 29Pt/ (9PTFE/VXC), its XRD spectra is referring to Fig. 1.
The preparation of electrode:
Get 25.6mg29Pt/ (9PTFE/VXC) catalyst, add the 3ml isopropyl alcohol, after the ultrasonic dispersion, add the 160mg5wt%Nafion water-alcohol solution, form the catalyst feed liquid that is uniformly dispersed behind the ultrasonic dispersion treatment 1hr.It is 18cm that this feed liquid is sprayed on area
2Nafion 212 film surfaces, dry the back naturally and form electrode.The loading of Pt is 0.4mg Pt cm in the electrode
2Electrode surface form SEM photo is shown in Fig. 2 a.
With this electrode is negative electrode, and anode is identical traditional hydrophobic thick-layer electrode, compacting membrane electrode and assembled battery.The battery performance curve is referring to Fig. 3.
The preparation of catalyst carrier:
Get 2.0g CNT (CNT), after usefulness 10mL aqueous isopropanol is wetting, add the 100mL deionized water, mechanical agitation 15min carries out ultrasonic processing 30min subsequently again.Then, under mechanical agitation, slowly drip 30g 5wt.%FEP aqueous emulsion, fully stir, nanotube is evenly mixed with FEP.Place 90 ℃ of water-bath coacervations then, remove clear liquid after, the oven dry, making FEP content is the FEP/CNT complex predecessor of 42wt.%.With this predecessor put into micro-wave oven (500W, 2450MHz) in, carry out the heating schedule that heating using microwave 5s stops 20s, to remove residual moisture content in the sample.Heat the heating schedule that 15s stops 60s subsequently repeatedly, to FEP content be 20wt%.Getting FEP content is the FEP/CNT composite granule of 20wt%, is designated as 20FEP/CNT.
Preparation of catalysts:
Get 250mg 20FEP/CNT composite granule, add 40ml ethylene glycol (EG) solution, behind the ultrasonic dispersion 15min, carry out magnetic agitation 30min.Get the H that 0.57mL concentration is 18.5mg Pt/mL
2PtCl
6/ ethylene glycol solution (H
2PtCl
6/ EG solution) be added drop-wise in the carrier slurry.Fully stir.Drip 2M NaOH/EG solution and regulate pH to 13.With the complex catalyst precursor thing solution that mixes up the pH value place micro-wave oven (500W, 2450MHz) in, heating using microwave 0.1min takes out, and stirs the cold of drying in the air.Drip 2M HNO
3Solution is regulated pH to 3.Leave standstill centrifugation behind the 2hr and wash the NaOH of EG and adding, HNO off
3Solids after the separation places 60 ℃ of vacuum drying chambers, dry 12hr.Based on the gross mass of CNT and Pt, obtaining Pt content is 5% catalyst, notes by abridging into 5Pt/ (20FEP/CNT).
The preparation of electrode:
Get 180mg5Pt/ (20FEP/CNT) catalyst, add the 18ml isopropyl alcohol, after the ultrasonic dispersion, add the 635mg5wt%Nafion water-alcohol solution, form the catalyst feed liquid that is uniformly dispersed behind the ultrasonic dispersion treatment 1hr.Is 18cm with this feed liquid blade coating at area
2The gas diffusion layers surface, dry the back naturally and form electrode.The loading of Pt is 0.4mg Pt cm in the electrode
2
The preparation of catalyst carrier:
(Black Pearls 2000 BP), after usefulness 30mL aqueous isopropanol is wetting, adds the 200mL deionized water, and mechanical agitation 15min carries out ultrasonic processing 30min subsequently again to get 2.0g pearl carbon black.Then, under mechanical agitation, slowly drip 7.1g 10wt.%PTFE aqueous emulsion, fully stir, the pearl carbon black is evenly mixed with PTFE.Place 90 ℃ of water-bath coacervations then, remove clear liquid after, the oven dry, making PTFE content is the PTFE/BP complex predecessor of 26wt.%.With this predecessor put into micro-wave oven (2KW, 2450MHz) in, carry out the heating schedule that heating using microwave 5s stops 20s, to remove residual moisture content in the sample.Heat the heating schedule that 10s stops 20s subsequently repeatedly, to PTFE content be 15wt%.Getting PTFE content is the PTFE/BP composite granule of 15wt%, is designated as 15PTFE/BP.
Preparation of catalysts:
Get 235mg 15PTFE/BP composite granule, add 60ml ethylene glycol (EG) solution, behind the ultrasonic dispersion 15min, carry out magnetic agitation 30min.Get the H that 7.2mL concentration is 18.5mg Pt/mL
2PtCl
6/ ethylene glycol solution (H
2PtCl
6/ EG solution) be added drop-wise in the carrier slurry.Fully stir.Drip 2M NaOH/EG solution and regulate pH to 13.With the complex catalyst precursor thing solution that mixes up the pH value place micro-wave oven (1KW, 2450MHz) in, heating using microwave 3min takes out, and stirs the cold of drying in the air.Drip 2M HNO
3Solution is regulated pH to 3.Leave standstill centrifugation behind the 2hr and wash the NaOH of EG and adding, HNO off
3Solids after the separation places 100 ℃ of vacuum drying chambers, dry 5hr.Based on the gross mass of BP and Pt, obtaining Pt content is 40% catalyst, notes by abridging into 40Pt/ (15PTFE/BP).
The preparation of electrode:
Get 19.9mg 40Pt/ (15PTFE/BP) catalyst, add the 2ml isopropyl alcohol, after the ultrasonic dispersion, add the 132.5mg10wt%Nafion water-alcohol solution, form the catalyst feed liquid that is uniformly dispersed behind the ultrasonic dispersion treatment 1hr.Is 18cm with this feed liquid blade coating at area
2The gas diffusion layers surface, dry the back naturally and form electrode.The loading of Pt is 0.4mg Ptcm in the electrode
2
The preparation of catalyst carrier:
Get 2.0g acetylene black (AB), after usefulness 6mL aqueous isopropanol is wetting, add the 120mL deionized water, mechanical agitation 15min carries out ultrasonic processing 30min subsequently again.Then, under mechanical agitation, slowly drip 14.3g 15wt.%ETFE aqueous emulsion, fully stir, acetylene black is evenly mixed with ETFE.Place 90 ℃ of water-bath coacervations then, remove clear liquid after, the oven dry, making ETFE content is the ETFE/AB complex predecessor of 52wt.%.With this predecessor put into micro-wave oven (2KW, 2450MHz) in, carry out the heating schedule that heating using microwave 5s stops 20s, to remove residual moisture content in the sample.Heat the heating schedule that 20s stops 60s subsequently repeatedly, to ETFE content be 30wt%.Getting ETFE content is the ETFE/AB composite granule of 30wt%, is designated as 30ETFE/AB.
Preparation of catalysts:
Get 285mg 30ETFE/AB composite granule, add 100ml ethylene glycol (EG) solution, behind the ultrasonic dispersion 15min, carry out magnetic agitation 30min.Get the H that 5.7mL concentration is 18.5mg Pt/mL
2PtCl
6/ ethylene glycol solution (H
2PtCl
6/ EG solution) and 3ml concentration be the Co (NO of 31.7mg Co/mL
3)
2/ ethylene glycol solution (Co (NO
3)
2/ EG solution) be added drop-wise in the carrier slurry.Fully stir.Drip 2M NaOH/EG solution and regulate pH to 13.With the complex catalyst precursor thing solution that mixes up the pH value place micro-wave oven (1KW, 2450MHz) in, heating using microwave 30min takes out, and stirs the cold of drying in the air.Drip 2M HNO
3Solution is regulated pH to 3.Leave standstill centrifugation behind the 2hr and wash the NaOH of EG and adding, HNO off
3Solids after the separation places 100 ℃ of vacuum drying chambers, dry 5hr.Based on AB and gross mass (Pt+Co), obtaining (Pt+Co) content is 50% catalyst, and brief note is 50 (PtCo
3)/(30ETFE/AB).
The preparation of electrode:
Get 17.5mg 50 (PtCo
3The catalyst of)/(30ETFE/AB) adds the 2.5ml isopropyl alcohol, after the ultrasonic dispersion, adds 18.4mg 5wt% Nafion water-alcohol solution, forms the catalyst feed liquid that is uniformly dispersed behind the ultrasonic dispersion treatment 1hr.It is 18cm that this feed liquid is sprayed on area
2Nafion film surface, dry the back naturally and form electrode.The loading of Pt is 0.4mg Pt cm in the electrode
2
Embodiment 5
The preparation of catalyst carrier:
Get 2.0g carbon fiber (CF), after usefulness 15mL aqueous isopropanol is wetting, add the 20mL deionized water, mechanical agitation 15min carries out ultrasonic processing 30min subsequently again.Then, under mechanical agitation, slowly drip 1.5g 1wt.%PVDF aqueous emulsion, fully stir, carbon fiber is evenly mixed with FEP.Place 90 ℃ of water-bath coacervations then, remove clear liquid after, the oven dry, making PVDF content is the PVDF/CF complex predecessor of 0.7wt.%.With this predecessor put into micro-wave oven (1KW, 2450MHz) in, carry out the heating schedule that heating using microwave 5s stops 20s, to remove residual moisture content in the sample.Heat the heating schedule that 5s stops 30s subsequently repeatedly, to PVDF content be 0.5wt%.Getting PVDF content is the PVDF/CF composite granule of 0.5wt%, is designated as 20PVDF/CF.
20PVDF/CF with preparation is a carrier, prepares catalyst according to embodiment 1 described method, and is the feedstock production electrode with this catalyst;
Embodiment 6
The preparation of catalyst carrier:
(Graphite Powder GP), after usefulness 50mL aqueous isopropanol is wetting, adds the 80mL deionized water, and mechanical agitation 15min carries out ultrasonic processing 30min subsequently again to get the 2.0g graphite powder.Then, under mechanical agitation, slowly drip 80g 5wt.%PTFE aqueous emulsion, fully stir, graphite powder is evenly mixed with PTFE.Place 90 ℃ of water-bath coacervations then, remove clear liquid after, the oven dry, making PTFE content is the PTFE/GP complex predecessor of 66wt.%.With this predecessor put into micro-wave oven (30KW, 2450MHz) in, carry out the heating schedule that heating using microwave 5s stops 20s, to remove residual moisture content in the sample.Heat the heating schedule that 10s stops 20s subsequently repeatedly, to PTFE content be 50wt%.Getting PTFE content is the PTFE/GP composite granule of 50wt%, is designated as 50PTFE/GP.
50PTFE/GP with preparation is a carrier, prepares catalyst according to embodiment 1 described method, and is the feedstock production electrode with this catalyst;
Embodiment 7
The preparation of catalyst carrier:
Get 1.0g acetylene black and 1.0g pearl carbon black respectively, evenly be mixed into mixed powder (AB+BP), after usefulness 20mL aqueous isopropanol is wetting, add the 120mL deionized water, mechanical agitation 15min carries out ultrasonic processing 30min subsequently again.Then, under mechanical agitation, slowly drip the 40g10wt.%FEP aqueous emulsion, fully stir, mixed powder is evenly mixed with FEP.Place 90 ℃ of water-bath coacervations then, remove clear liquid after, the oven dry, make the FEP/ that FEP content is 66wt.% (AB+BP) complex predecessor.With this predecessor put into micro-wave oven (500W, 2450MHz) in, carry out the heating schedule that heating using microwave 5s stops 20s, to remove residual moisture content in the sample.Heat the heating schedule that 15s stops 60s subsequently repeatedly, to FEP content be 40wt%.Getting FEP content is FEP/ (AB+BP) composite granule of 40wt%, is designated as 40FEP/ (AB+BP).
40FEP/ (AB+BP) with preparation is a carrier, prepares catalyst according to embodiment 1 described method, and is the feedstock production electrode with this catalyst;
Embodiment 8 performance comparative examples
Get 25.3mg commercialization 28.4%Pt/C catalyst, add the 3ml isopropyl alcohol, after the ultrasonic dispersion, add 160mg5wt%Nafion solution, form the catalyst feed liquid that is uniformly dispersed behind the ultrasonic dispersion treatment 1hr.It is 18cm that this feed liquid is sprayed on area
2Nafion 212 film surfaces, dry the back naturally and form electrode.The loading of Pt is 0.4mg Pt cm in the electrode
2Brief note is 28.4Pt/C-commercial.Electrode surface form SEM photo is shown in Fig. 2 b.
With this electrode is negative electrode, is assembled into monocell according to the method for embodiment 1.The battery performance curve is referring to Fig. 3.
As seen from Figure 3, at same catalyst load amount (0.4mg Pt cm
2) under the condition, the battery performance (29Pt/ (9PTFE/VXC)) that the present invention prepares electrode obviously is better than conventional electrodes (28.4Pt/C-commercial), reason is that the carrier of catalyst of the present invention has hydrophobicity, make prepared electrode also have certain hydrophobicity, help the mass transfer of electrode interior.
Claims (21)
1. water-repelling agent/conductive carbon material complex is as the electrocatalyst for fuel cell carrier.
2. electrocatalyst for fuel cell, be active particle/(water-repelling agent/conductive carbon material) complex, be as electro-catalyst carrier and the compound product of catalyst activity particle with water-repelling agent/conductive carbon material complex, wherein, active particle is group VIII or the Cr that is selected from the periodic table of elements, Mo, Zr, one or more metallic elements among the Ti.
3. as electrocatalyst for fuel cell as described in the claim 2, it is characterized in that described water-repelling agent/conductive carbon material complex is water-repelling agent and the compound product of conductive carbon material, based on water-repelling agent/conductive carbon material complex weight, the weight percentage of water-repelling agent is 0.5～50%.
4. as electrocatalyst for fuel cell as described in the claim 3, it is characterized in that the weight percentage of described water-repelling agent is 1～40%.
5. as electrocatalyst for fuel cell as described in the claim 4, it is characterized in that the weight percentage of described water-repelling agent is 5～20%.
6. as electrocatalyst for fuel cell as described in the claim 2, it is characterized in that the particle diameter of described water-repelling agent/conductive carbon material complex is between 0.5～50 μ m.
7. as electrocatalyst for fuel cell as described in the claim 2, it is characterized in that described conductive carbon material is one or more the mixing that is selected from conductive carbon black, carbon fiber, CNT, activated carbon, carbosphere, carbon whisker or the graphite granule.
8. as electrocatalyst for fuel cell as described in the claim 2, it is characterized in that described water-repelling agent is selected from polytetrafluoroethylene (PTFE), inclined to one side tetrafluoroethene, polytetrafluoroethylene (PTFE)-perfluoroalkyl vinyl ether, FEP fluorinated ethylene propylene copolymer resin or ethylene fluoride/tetrafluoroethylene copolymer resins.
9. as electrocatalyst for fuel cell as described in arbitrary claim in the claim 2-8, it is characterized in that described water-repelling agent/conductive carbon material complex is by making through the following steps:
(a) conductive carbon material is wetting with ethanol or isopropyl alcohol, add conductive carbon material quality 10-100 deionized water doubly subsequently, disperse and stir, obtain conductive carbon material suspension;
(b) the water-repelling agent emulsion is dropwise joined in the conductive carbon material suspension, stir, material with carbon element is fully mixed with water-repelling agent contact;
(c) above-mentioned mixed liquor is placed 70-100 ℃ of water-bath coacervation, and vapor away pure and mild deionized water;
(d) water-repelling agent after will drying and the mixture of conductive carbon material place micro-wave oven, carry out microwave heating treatment, obtain water-repelling agent/conductive carbon material complex powder.
10. as electrocatalyst for fuel cell as described in as described in the claim 9, it is characterized in that among the described step b, the water-repelling agent dripping quantity is 1.5～3 times of water-repelling agent content in water-repelling agent/conductive carbon material complex product.
11., it is characterized in that based on the eelctro-catalyst gross weight, the weight percentage of described active particle is 5-80% as electrocatalyst for fuel cell as described in arbitrary claim in the claim 2-8.
12., it is characterized in that described active particle is for being selected from Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cr, one or more metallic elements among Mo, Zr, the Ti as electrocatalyst for fuel cell as described in arbitrary claim in 2-8.
13. as the preparation method of electrocatalyst for fuel cell as described in arbitrary claim in the claim 2-12, with water-repelling agent/conductive carbon material complex as electro-catalyst carrier and catalyst activity particle by compound the obtaining of microwave colloid reducing process.
14. the preparation method as electrocatalyst for fuel cell as described in arbitrary claim in the claim 2-12 comprises the following steps:
(a) the solubility predecessor with active particle is dissolved in the ethylene glycol, disperses and mixes, and obtains solution A;
(b) with the described water-repelling agent of arbitrary claim in the claim 1-6/conductive carbon material complex as electro-catalyst carrier and ethylene glycol in 10～500ml ethylene glycol: the ratio of 1g carrier is mixed, and after disperseing and stirring, obtains slurry B;
(c) solution A is dropwise joined among the slurry B, stir, make both mix pH value to 9～14 that solution is transferred in the back;
(d) heated 0.1～30 minute the mixed liquor microwave continuous or the intermittence that will mix up the pH value, obtain slurry C;
(e) stir slurry C, and be cooled to room temperature, regulate pH value to 1～3, obtain slurry D;
(f) with slurry D centrifuge washing, 60-120 ℃ of vacuum drying promptly gets active particle/(water-repelling agent/conductive carbon material) complex.
15. be used to prepare electrode as electrocatalyst for fuel cell as described in arbitrary claim in the claim 2-12.
16. a low-temperature fuel cell electrode comprises proton conductive polymer and electrocatalyst for fuel cell, it is characterized in that, described fuel electrode eelctro-catalyst is the described electrocatalyst for fuel cell of arbitrary claim in the claim 2-12.
17., it is characterized in that based on proton conductive polymer and catalyst gross mass, the mass percent of proton conductive polymer is 5%～40% as low-temperature fuel cell electrode as described in the claim 15.
18., it is characterized in that based on proton conductive polymer and catalyst gross mass, the mass percent of proton conductive polymer is 10%～35% as low-temperature fuel cell electrode as described in the claim 16.
19., it is characterized in that based on proton conductive polymer and catalyst gross mass, the mass percent of proton conductive polymer is 15%～30% as low-temperature fuel cell electrode as described in the claim 17.
20., comprise the following steps: as the preparation method of low-temperature fuel cell as described in arbitrary claim in the claim 16-19 with electrode
(a) the described electrocatalyst for fuel cell of arbitrary claim in the claim 2-12 is mixed with isopropyl alcohol, mechanical agitation or ultrasonic dispersion make the eelctro-catalyst slurries;
(b) with proton conductive polymer, join in the above-mentioned eelctro-catalyst slurries, the addition of proton conductive polymer is 5%～40% of proton conductive polymer and a catalyst gross mass, obtains catalyst pulp;
(c) with the above-mentioned catalyst pulp for preparing, adopt spraying, the method for serigraphy or blade coating is prepared in gas diffusion layers or PEM surface, dries naturally, forms electrode.
21., it is characterized in that among the step a, in the eelctro-catalyst slurries, the concentration of electrocatalyst for fuel cell is 0.5～10mg/ml as the preparation method of low-temperature fuel cell as described in the claim 20 with electrode.
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