CN102810677A - Fuel cell catalyst and preparation method thereof - Google Patents
Fuel cell catalyst and preparation method thereof Download PDFInfo
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- CN102810677A CN102810677A CN2012102951638A CN201210295163A CN102810677A CN 102810677 A CN102810677 A CN 102810677A CN 2012102951638 A CN2012102951638 A CN 2012102951638A CN 201210295163 A CN201210295163 A CN 201210295163A CN 102810677 A CN102810677 A CN 102810677A
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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
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Abstract
The invention discloses a fuel cell catalyst and a preparation method thereof. The fuel cell catalyst comprises a nanocarbon microsphere as a catalyst carrier and a metal catalyst loaded on the nanocarbon microsphere. By taking the nanocarbon microsphere with small particle size, high sphericity, large surface area and large pore size as the carrier to prepare the fuel cell catalyst, the obtained catalyst is not easy to migrate and aggregate in a catalytic layer and has high dispersion stability and the catalytic activity of the catalyst can be effectively improved; a membrane electrode prepared after adoption of the catalyst has a relatively high power of the membrane electrode per unit area; the catalyst has a relatively large three-phase reaction zone; the utilization ratio of the catalyst is sufficiently improved; and the resistance in various transfer processes and the loading capacity of a noble metal are reduced.
Description
Technical field
The present invention relates to the Proton Exchange Membrane Fuel Cells field, in particular to a kind of fuel-cell catalyst and preparation method thereof.
Background technology
Electrochemical redox reaction takes place in Proton Exchange Membrane Fuel Cells in energy conversion process, this reaction needed could realize under the effect of catalyst.Present widely used catalyst is main with precious metals pt, Pd, Ru, Ir etc. or Pt-M (M is Ru, Co, Ni, Mn etc.) alloy mainly.Pt is an example to use the most widely, in order to improve catalyst utilization, reduces noble metal dosage, reduces cost, and takes H usually
2Means such as PtCl direct-reduction process, colloid Pt sol method, ion-exchange with precious metals pt with the nanoparticle form high degree of dispersion on the bigger conduction of specific area, corrosion-resistant carrier; Like acetylene carbon black (Vulcan XC-72R; Average grain diameter 30nm, specific area 250m
2/ g), promptly make the Pt/C eelctro-catalyst of high dispersive.
Though primary carbon black particle particle diameter is very little; But the polarity of carbon blacksurface and nonpolar group mass contg are very low; And the affinity between other materials (like high molecular polymer, organic solvent, water etc.) far is weaker than the cohesiveness between the carbon black particle, so very difficult stable being scattered in the various media of carbon black, exists with larger-size aggregate mostly; Thereby significantly reduced its specific area; Reduce phase reaction zone in the Catalytic Layer, reduced catalyst utilization, caused the noble metal loading significantly to increase.Pt/C eelctro-catalyst with present widely used mass fraction 40% is an example, because the reunion of carbon black particle, specific area is reduced to 67.5m
2/ g only is about 25% of a theoretical value.Having put down in writing specific area among the patent CN1747785A " based on the improved polymer dielectric film fuel cell eelctro-catalyst that mixes carbon carrier " is 250m
2The Vulcan XC-72R carbon black of/g is that year Pt catalyst (catalyst 1) and the specific area of carrier is 600～1000m
2The Ketjen carbon black of/g is that the Pt catalyst (catalyst 2) that carries of carrier mixes use, has increased the specific area of conventional Pt/C (Vulcan XC-72R carbon black) catalyst, has improved catalyst activity.But the employed Ketjen carbon black of the Pt/C that is added (Ketjen carbon black) catalyst carrier specific area is big, and particle diameter is little, disperses difficulty more, and the regional shared ratio of effecting reaction is lower in the Catalytic Layer, and the utilance of noble metal is also lower; This catalyst also more is prone to migration and reunites simultaneously, and along with the carrying out of electrochemical reaction, the catalytic effect of catalyst weakens gradually, and battery efficiency reduces gradually.Therefore, how effectively to improve the effective ratio area of catalyst carrier, improve the decentralization of noble metal in the catalyst, it is active to improve catalyst, reduces the noble metal loading, has become the research direction that reduces the Proton Exchange Membrane Fuel Cells cost.
Summary of the invention
The present invention aims to provide a kind of fuel cell membrane electrode and preparation method thereof, to solve complicated process of preparation, the cost technical problems of high that exists in the prior art.
To achieve these goals, according to an aspect of the present invention, a kind of fuel-cell catalyst is provided, has comprised as the nanometer carbon microspheres of catalyst carrier and be carried on the metallic catalyst on the nanometer carbon microspheres.
Further, the average grain diameter of nanometer carbon microspheres is 20～50nm, and sphericity is 70～90%, and specific area is 150～300m
2/ g, pore size distribution is 10～100nm.
According to a further aspect in the invention, a kind of preparation method of fuel-cell catalyst is provided, has may further comprise the steps: prepared the nanometer carbon microspheres, and metallic catalyst is loaded on the nanometer carbon microspheres, obtain fuel-cell catalyst through infusion process; Perhaps will be used to prepare the amphipathic raw material of wood-charcoal material solution and the metallic catalyst formation mixed solution of nanometer carbon microspheres, and utilize the original position load method to prepare fuel-cell catalyst.
Further, the step of preparation nanometer carbon microspheres comprises: amphipathic raw material of wood-charcoal material solution is carried out freezing, dry, distillation, obtain Nano microsphere; Perhaps amphipathic raw material of wood-charcoal material solution is joined in the organic solvent, stir, standing demix separates, and oven dry obtains Nano microsphere; And Nano microsphere is carried out charing handle, obtain the nanometer carbon microspheres.
Further, infusion process comprises: the metal salt solution that will have catalytic action mixes with mass ratio 50:1～1000:1 with the nanometer carbon microspheres, stirs, and obtains mixed liquor A; In mixed liquor A, add formalin, stir, obtain mixed liquid B; Mixed liquid B is separated, and oven dry obtains solid; And solid heat-treated respectively at 200 ℃～400 ℃ and 800 ℃～1000 ℃, obtaining with the nanometer carbon microspheres is the fuel-cell catalyst of carrier.
Further, the original position load method comprises: the metal salt solution that will have catalytic action mixes with mass ratio 5:1～100:1 with amphipathic raw material of wood-charcoal material solution, stirs, and obtains mixed liquor C; In mixed liquor C, add formalin, stir, obtain mixed liquor D; With mixed liquor D freeze drying, vacuum treatment, oven dry obtains solid; Perhaps in mixed liquor D, add organic solvent, stir, standing demix separates, and oven dry obtains solid; And solid heat-treated respectively at 200 ℃～400 ℃ and 800 ℃～1000 ℃ under inert atmosphere, obtaining with the nanometer carbon microspheres is the fuel-cell catalyst of carrier.
Further, before mixed liquid B is separated, also comprise: the pH that in mixed liquid B, adds water-soluble alkali regulator solution system is 8～9, stirs 20～120 minutes.
Further, before mixed liquor D being carried out freeze drying or in mixed liquor D, adding organic solvent, also comprise: mixed liquor D is warming up to 60 ℃～90 ℃, kept 30～300 minutes and the step of natural cooling.
Further, metal salt solution is H
2PtCl
66H
2O solution, PdCl
2Solution, RuCl
2One or more mixing in the solution; The quality of said metal salt solution is 1%～20% than concentration.
Further, water-soluble alkali is one or more mixing in NaOH, potassium hydroxide, ethylenediamine, sodium carbonate, potash and the cesium hydroxide.
According to another aspect of the invention, the application of above-mentioned any catalyst in fuel cell membrane electrode is provided.
The nanometer carbon microspheres that particle diameter is little, sphericity is high through adopting in the present invention, surface area and aperture are big is as the preparing carriers fuel-cell catalyst; Making this catalyst in Catalytic Layer, be difficult for migration reunites; Dispersion stabilization with height; Can effectively improve the catalytic activity of catalyst, adopt the membrane electrode of this Preparation of Catalyst, have higher unit are membrane electrode power.Fuel-cell catalyst provided by the invention has bigger phase reaction district, has fully improved the utilance of catalyst, has reduced the load capacity of the resistance and the noble metal of various transmittance processs.
Description of drawings
The Figure of description that constitutes the application's a part is used to provide further understanding of the present invention, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, do not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 is the electron scanning micrograph of the nanometer carbon microspheres of exemplary embodiments of the present invention;
Fig. 2 is the transmission electron microscope photo of the nanometer carbon microspheres of exemplary embodiments of the present invention;
Fig. 3 shows the section structure sketch map of the three-decker membrane electrode of the exemplary embodiments according to the present invention; And
Fig. 4 shows the section structure sketch map of the five-layer structure membrane electrode of the exemplary embodiments according to the present invention.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the characteristic among the embodiment among the application can make up each other.Below with reference to accompanying drawing and combine embodiment to specify the present invention.
According to a kind of exemplary embodiment of the present invention, this fuel-cell catalyst comprises as the nanometer carbon microspheres of catalyst carrier and is carried on the metallic catalyst on the nanometer carbon microspheres.
Particle diameter is little, sphericity is high, the big advantage of surface area and aperture owing to the nanometer carbon microspheres as catalyst carrier has; The fuel-cell catalyst of carried metal particle has bigger phase reaction zone; Form the continuous passage of proton, electronics and reacting gas, improved ionomer and the interface continuity between the ionomer in the Catalytic Layer in the proton film, fully improved the utilance of catalyst; Reduce the resistance of various transmittance processs, reduced the load capacity of noble metal.The nanometer carbon microspheres is processed by the amphipathic raw material of wood-charcoal material of surface oxygen functional group, therefore with metallic catalyst good affinity is arranged.In addition, catalyst of the present invention is difficult for migration and reunites, and has the dispersion stabilization of height, can effectively improve the catalytic activity of catalyst, adopts the membrane electrode of this Preparation of Catalyst, has higher unit are membrane electrode power.
Metallic catalyst is the alloy that one or more metals in the metals such as Pt, Pd, Ru, Ir, Co, Ni, Mn are formed; And metallic catalyst can be one or more metallics at the existence of carrier surface, also can be one or more metal alloy particle.And prepare as raw material with amphipathic raw material of wood-charcoal material as the nanometer carbon microspheres of carrier, preferably, the particle diameter of nanometer carbon microspheres is 20～50nm, and sphericity is 70～90%, and specific area is 150～300m
2/ g, pore size distribution is 10～100nm.As depicted in figs. 1 and 2, can find out that from Fig. 1 and Fig. 2 the particle diameter of nanometer carbon microspheres is even, better dispersed, this is because the nanometer carbon microspheres is formed by the self assembly under capillary constraint of amphipathic raw material of wood-charcoal material.
Infusion process is meant preparation nanometer carbon microspheres earlier, and the method through dipping loads to metallic catalyst on the nanometer carbon microspheres again; The original position load method is meant earlier amphipathic raw material of wood-charcoal material solution and metallic catalyst is formed mixed solution, directly prepares the nanometer carbon microspheres that contains metallic catalyst then.
According to a further aspect in the invention, a kind of preparation method of fuel-cell catalyst is provided, has may further comprise the steps: prepared the nanometer carbon microspheres, and metallic catalyst is loaded on the nanometer carbon microspheres, obtain fuel-cell catalyst through infusion process; Perhaps will be used to prepare the amphipathic raw material of wood-charcoal material solution and the metallic catalyst formation mixed solution of nanometer carbon microspheres, and utilize the original position load method to prepare fuel-cell catalyst.
Through direct-reduction process the surface that noble metal is dispersed in the nanometer carbon microspheres is made fuel-cell catalyst; Perhaps the original position carried noble metal makes fuel-cell catalyst in the surface of nanometer carbon microspheres in the growth course of nanometer carbon microspheres.Preparation method's technology provided by the present invention is simple, does not need large-scale equipment or instrument, and raw material is easy to get and is cheap, greatly reduces production cost.
A preferred embodiment of the invention, the step of preparation nanometer carbon microspheres comprises: at first amphipathic raw material of wood-charcoal material solution is carried out freezing, dry, distillation, obtain Nano microsphere; Perhaps amphipathic raw material of wood-charcoal material solution is joined in the organic solvent, stir, standing demix separates, and oven dry obtains Nano microsphere; Again the Nano microsphere that obtains is carried out charing and handle, obtain the nanometer carbon microspheres.
Amphipathic raw material of wood-charcoal material solution among the present invention is to be formed by amphipathic raw material of wood-charcoal material preparation of raw material, and raw material is selected from one or more among the burnt base of coal tar pitch, the burnt base of petroleum asphalt, mesophase pitch Jiao base, petroleum coke base, needle coke base and the pitch coke base.The above-mentioned raw materials source is abundant, cheap, is easy to realize large-scale industrial production.Introduce the preparation process of nanometer carbon microspheres below in detail.
A, in the above-mentioned raw materials one or more are joined in the deionized water; And be 10～14 with the pH of water-soluble alkali (potassium hydroxide, NaOH, ethylenediamine, potash, sodium carbonate, cesium hydroxide etc.) regulator solution, be mixed with mass percent concentration and be 5～10% amphipathic raw material of wood-charcoal material solution;
B, above-mentioned amphipathic raw material of wood-charcoal material solution is put into freeze drier, under-10 ℃ ~-50 ℃, freeze, under the high vacuum condition of 1.3 ~ 60Pa, ice distillation is wherein removed for steam, obtain dark gray powder, i.e. the nanometer carbon microspheres;
C, without step B, the low boiling-point and polarity organic solvent that employing can be dissolved each other with water refers generally to ethanol, acetone or methyl alcohol etc. here; Percent by volume 20～500:1 according to the amphipathic raw material of wood-charcoal material solution that makes in organic solvent and the steps A; While stirring amphipathic raw material of wood-charcoal material solution is joined in the organic solvent, stir 5～30min, stir speed (S.S.) is 300～1500r/min; Obtain mixed liquor; With the mixed liquor standing demix, it is the molten altogether thing of organic solvent and water at the middle and upper levels, and the amphipathic raw material of wood-charcoal material particulate that does not dissolve is contained in lower floor;
The supernatant liquid of D, mixed liquor that step C is obtained separates through separatory funnel with lower floor, and supernatant liquid carries out rectifying separation, and the organic solvent that rectifying obtains can be recycled;
E, lower floor is contained amphipathic raw material of wood-charcoal material particulate part set by step the C cycle of treatment handle, then separate according to step D, so repeated treatments is 3～5 times, makes amphipathic raw material of wood-charcoal material particulate all dissolvings as far as possible of lower floor;
F, will pass through the mixture that contains amphipathic raw material of wood-charcoal material particulate that step e handles and place 50～70 ℃ of evaporate to dryness organic solvents, obtain the very thin grey black toner end of particle, be the nanometer carbon microspheres;
G, in retort (being generally tube furnace, box type furnace or rotary furnace etc.); The nanometer carbon microspheres that (nitrogen, argon gas or helium) makes step B or F under inert atmosphere rises to 900～2600 ℃ with the heating rate of 1～10 ℃/min and carries out charing or graphitization processing 1～2h; Naturally cool to room temperature then, obtaining particle diameter is the nanometer carbon microspheres of 20nm～50nm.The microscopic appearance of nanometer carbon microspheres is as depicted in figs. 1 and 2.
Wherein, In preparation has the process of water soluble amphiphilic raw material of wood-charcoal material solution, need not add any surfactant, the charcoal precursor is dispersed in the water, and has reduced the use of organic solvent to a certain extent; Make synthesis technique become simply, and environmental protection.Employed equipment is simple in the synthesis technique of this nanometer carbon microspheres and the building-up process, compared with the synthetic method such as the hydro thermal method of traditional nano material, and template etc., production cost is more cheap;
A preferred embodiment of the invention, infusion process comprises: the metal salt solution that will have catalytic action mixes with mass ratio 50:1～1000:1 with the nanometer carbon microspheres, stirs, and obtains mixed liquor A; In mixed liquor A, add formalin, stir, obtain mixed liquid B; Mixed liquid B is separated, and oven dry obtains solid; And solid heat-treated respectively at 200～400 ℃ and 800～1000 ℃, obtaining with the nanometer carbon microspheres is the fuel-cell catalyst of carrier.In the operation of reality, in the nanometer carbon microspheres, drip platinum acid chloride solution while stirring, stirred 20～300 minutes, after the adding formalin, stirred 10～60 minutes.Adopt infusion process can make more firm that metallic catalyst combines with the nanometer carbon microspheres, can also reduce the catalyst cost, raising catalyst efficiency, the useful life of prolongation catalyst.This preparation method has simple to operate and the high advantage of earning rate in addition.
Further preferably, before mixed liquid B is separated, also comprise: the pH that in mixed liquid B, adds water-soluble alkali regulator solution system is 8～9, stirs 20～120min.Water-soluble alkali is one or more mixing in NaOH, potassium hydroxide, ethylenediamine, sodium carbonate, potash and the cesium hydroxide.The purpose that the adding water-soluble alkali is regulated is because alkali condition more helps metal salt solution and is reduced into metallic particles.
According to another kind of preferred implementation of the present invention, the original position load method comprises: the metal salt solution that will have catalytic action mixes with mass ratio 5:1～100:1 with amphipathic raw material of wood-charcoal material solution, stirs, and obtains mixed liquor C; In mixed liquor C, add formalin, stir, obtain mixed liquor D; With mixed liquor D freeze drying, vacuum treatment, oven dry obtains solid; Perhaps in mixed liquor D, add organic solvent, stir, standing demix separates, and oven dry obtains solid; And solid heat-treated respectively at 200 ℃～400 ℃ and 800 ℃～1000 ℃ under inert atmosphere, obtaining with the nanometer carbon microspheres is the fuel-cell catalyst of carrier.
Through original position supported catalyst particles in the process of synthesis of nano carbon microspheres, can make the load of catalyst granules more even; Make the more even distribution of catalyst on carrier through the original position load method, practiced thrift the consumption of noble metal, improved catalytic efficiency.Further preferably, metal catalyst solution is H
2PtCl
66H
2O solution, PdCl
2Solution, RuCl
2One or more mixing in the solution; The quality of metal salt solution is 1%～20% than concentration.The preferred above-mentioned solution of the present invention is as catalyst but be not limited thereto, can also with in the metals such as Pd, Ru, Ir, Co, Ni and Mn one or more with contain the Pt catalyst mix.
The solid that obtains is at last heat-treated respectively at 200 ℃～400 ℃ and 800 ℃～1000 ℃ under inert atmosphere; Purpose is to make nanometer carbon microspheres catalyst have certain activity; Solid is handled in 200 ℃～400 ℃ of low-temperature zone and 800 ℃～1000 ℃ two stages of high temperature section respectively, handled the light component and the hetero-atom that make in the precursor in low-temperature zone and overflow, then in the high temperature section charing in low-temperature zone; Make structure more stable; Improve conductance, so after high-temperature process, activated catalytic activity, having obtained with the nanometer carbon microspheres is the fuel-cell catalyst of carrier.
Preferably, the mass concentration of amphipathic raw material of wood-charcoal material solution is 1%～30%; The addition of formalin is 5%～20% of a metal catalyst solution quality.The mass concentration of amphipathic raw material of wood-charcoal material solution being controlled in 1%～30% the scope is yield and the particle diameter of considering the nanometer carbon microspheres; Amphipathic raw material of wood-charcoal material solution in this mass concentration scope can be taken into account the yield and the particle size uniformity of nanometer carbon microspheres; If the too little meeting of concentration makes product yield low excessively, be unfavorable for volume production; If concentration too greatly raw material be prone to reunite, be difficult to obtain the nanometer carbon microspheres.
The purpose that wherein adds formaldehyde is that metal catalyst solution is reduced to metal simple-substance; So the amount according to metal catalyst solution is added formaldehyde; The addition of formaldehyde is that 5%～20% of metal catalyst solution quality just in time is reduced into metallic particles with metal catalyst solution fully, can not cause simultaneously formaldehyde too much and contaminated environment again.
According to a kind of exemplary embodiment of the present invention, before mixed liquor D being carried out freeze drying or in mixed liquor D, adding the organic solvent step, also comprise: mixed liquor D is warming up to 60～90 ℃, kept 30～300 minutes and the step of natural cooling.The purpose that heats up also is in order to promote the reduction of metallic catalyst, and temperature is controlled at 60～90 ℃ and keep making in 30～300 minutes formaldehyde to give full play to reproducibility and slaine is reduced.
According to another aspect of the invention, the application of above-mentioned any catalyst in fuel cell membrane electrode also is provided.Introduce the preparation method of membrane electrode of fuel batter with proton exchange film below in detail.
Nanometer carbon microspheres catalyst with supporting Pt is an example; With nanometer carbon microspheres catalyst, Polymer Solution, low boiling point organic solvent and the deionized water of supporting Pt according to (1～10): 1: (0～50): the volume ratio of (0～200) is mixed; Through sonic oscillation 1～100min, be adjusted to ink shape catalyst solution.This catalyst solution is uniformly coated on the PEM, and the temperature with PEM during spraying is controlled at 40～130 ℃, and catalyst thickness is 1～50 μ m, the PEM that is coated with catalyst is dried in vacuum drying oven remove solvent.Wherein the vacuum drying temperature is 40～100 ℃, and drying time is 1～100min.Another surface for preparing PEM after the same method promptly makes the membrane electrode of three-decker.The section structure sketch map of the membrane electrode of this three-decker is followed successively by catalyst layer, PEM, catalyst layer from top to bottom shown in 3.
With the upper and lower surfaces of the three-decker membrane electrode for preparing be covered with diaphragm preserve subsequent use, perhaps directly with two the gas diffusion layers handled of hydrophobization combine, obtain the membrane electrode of five-layer structure, as shown in Figure 4.The membrane electrode of this five-layer structure can directly be used for fuel cell.The gas diffusion layers here can be carbon fiber paper, carbon-fiber cloth etc., and its process for hydrophobicizing is that those skilled in the art are total to the technology of knowing.
The PEM that the present invention adopts can be perfluoro sulfonic acid membrane, sulfonated polystyrene film, sulfonated polyether-ether-ketone film, sulfonated polyether sulfone film, sulfonated polyimide film, sulfonated polyphenyl and imidazoles film etc.The mass percent concentration of the Polymer Solution that adopts is 0.1%～5%; Solute is and the corresponding resin of used PEM, for example perfluorinated sulfonic resin, sulfonated polystyrene ion exchange resin, sulfonated polyether-ether-ketone resin, sulfonated polyether sulphone resin, sulfonated polyimide resin, sulfonated polyphenyl and imidazoles resin etc.Solvent is the good solvent of the above-mentioned resin of solubilized or mixes good solvent; Like N, one or more in dinethylformamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, dimethylacetylamide, butyrolactone, ethylene glycol, sulfolane, triphenyl phosphoric acid, 2-methyl cellosolve, cellosolvo, glycol dimethyl ether, the diethylene glycol dimethyl ether equal solvent.Low boiling point organic solvent is meant one or more in ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, the glycerine equal solvent.PEM can be perfluoro sulfonic acid membrane, sulfonated polystyrene film, sulfonated polyether-ether-ketone film, sulfonated polyether sulfone film, sulfonated polyimide film, sulfonated polyphenyl and imidazoles film etc.
Polymer Solution concentration is mass fraction 0.1～5%; Solute is and the corresponding resin of used PEM, for example perfluorinated sulfonic resin, sulfonated polystyrene ion exchange resin, sulfonated polyether-ether-ketone resin, sulfonated polyether sulphone resin, sulfonated polyimide resin, sulfonated polyphenyl and imidazoles resin etc.Solvent is the good solvent of the above-mentioned resin of solubilized or mixes good solvent; Like N, one or more in dinethylformamide, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, dimethylacetylamide, butyrolactone, ethylene glycol, sulfolane, triphenyl phosphoric acid, 2-methyl cellosolve, cellosolvo, glycol dimethyl ether, the diethylene glycol dimethyl ether equal solvent.Low boiling point organic solvent can be in ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, the glycerine equal solvent one or more.
Introducing a kind of preparation below is the processing step of five layer proton exchange membrane fuel cell membrane electrodes of catalyst to carry Pt nanometer carbon microspheres:
Get and carry a Pt nanometer carbon microspheres catalyst, Polymer Solution, isopropyl alcohol and deionized water according to certain (1～10): 1: (0～50): (0～200) mixed through sonic oscillation 1～100min, is adjusted to ink shape catalyst solution.Cut out the gas diffusion layers of the hydrophobization processing of suitable area size, catalyst solution is evenly coated on the gas diffusion layers, catalyst thickness is 1～50 μ m, and oven dry is desolvated to remove in vacuum drying oven again.With two identical gas diffusion layers that spray catalyst and PEM according to " gas diffusion layers/catalyst/PEM/catalyst/gas diffusion layer " structure hot pressing 1～10min under 40～150 ℃, 1～100Mpa.Promptly obtain the five-layer structure membrane electrode, its section structure sketch map is as shown in Figure 4, is respectively gas diffusion layers, catalyst layer, PEM, catalyst layer, gas diffusion layers from top to bottom.
Further specify beneficial effect of the present invention below in conjunction with specific embodiment:
1, the needle coke based raw material is carried out preliminary treatment, the amphipathic raw material of wood-charcoal material of preparation needle coke base.
100mL nitration mixture (is that 65% red fuming nitric acid (RFNA) and concentration are that 98% concentrated sulfuric acid volume ratio is the 3:7 preparation with concentration) is heated to 80 ℃; Stir speed (S.S.) with 300r/min stirs; Add 10g needle coke based raw material, reaction 1h pours reactant in 1L deionized water cessation reaction; Adopt the filtration under diminished pressure device to filter, the washing of gained cakes with deionized water is to neutral.The solid matter that obtains is joined in the NaOH solution of 500mL concentration 1mol/L, the rotating speed with 300r/min under 80 ℃ stirs 1h, filtration under diminished pressure, and the pH value that in this process, keeps solution is all the time greater than 12; Collect filtrating, in the filtrating that obtains, drip the HCl of 1mol/L, regulate its pH value to 1, have this moment deposition to generate; Centrifugation, the sediment that obtains is extremely neutral with deionized water wash, and 100 ℃ of oven dry 10h promptly get the amphipathic raw material of wood-charcoal material of needle coke base in baking oven.
2, preparation nanometer carbon microspheres
Get the amphipathic raw material of wood-charcoal material of the needle coke base that makes in the 2g step 1 and join in the 18mL deionized water, regulate pH value to 12 with ethylenediamine, the stir speed (S.S.) stirring 30min with 200r/min obtains 30% amphipathic raw material of wood-charcoal material solution; 500mL acetone is stirred with the 1000r/min stir speed (S.S.), simultaneously the speed of amphipathic raw material of wood-charcoal material solution with 10mL/min is added in the acetone, stir 10min; Leave standstill; Demixing, upper strata are the molten altogether thing of acetone and water, and the amphipathic raw material of wood-charcoal material particulate that does not dissolve is contained in lower floor; Use separatory funnel with the mixture separation that obtains.The part that lower floor is contained amphipathic raw material of wood-charcoal material particulate is poured in the 500mL acetone, continues solvent exchange, repeated treatments 4 times; The mixture that then will contain amphipathic raw material of wood-charcoal material particulate obtains the very thin grey black toner end of particle in 50 ℃ of evaporate to dryness acetone, is amphipathic raw material of wood-charcoal material Nano microsphere.
The amphipathic raw material of wood-charcoal material Nano microsphere that makes is risen to 1100 ℃ of charings with the heating rate of 2 ℃/min handle 1h, naturally cool to room temperature then, obtain having the nanometer carbon microspheres of catalyst activity.
3, the nanometer carbon microspheres catalyst of preparation supporting Pt particle
Get the nanometer carbon microspheres of preparation in the 1g step 2, the interpolation quality is 1% H than concentration
2PtCl
6Solution 1000g stirs 60min, adds the formalin 2.5g of concentration 30% then; Stir 20min, then be warming up to 60 ℃, keep 30min; Naturally reduce to room temperature, centrifugation obtains the very thin grey black toner end of particle; With this powder under argon gas atmosphere respectively at 200 ℃, 800 ℃ heat treatment 60min, obtain the nanometer carbon microspheres of supporting Pt base eelctro-catalyst.
4, preparation nanometer carbon microspheres catalyst solution
Get the nanometer carbon microspheres catalyst of the supporting Pt that 1g step 3 makes; Deionized water 5g, isopropyl alcohol 20g, concentration is the Nafion solution 3g of 10wt%; Mix the back earlier with magnetic stirring apparatus with rotating speed 500r/min; At room temperature stir 8min, sonic oscillation 10s then, the nanometer carbon microspheres catalyst solution of the supporting Pt that obtains mixing.
5, preparation membrane electrode
Smooth being fixed on the electric boiling plate of Nafion115 film of cutting suitable dimension is warming up to 50 ℃.The nanometer carbon microspheres catalyst solution that carries Pt that step 4 is made evenly is sprayed on the Nafion115 film, and spray area is 100mm * 100mm, and coating thickness is 3～5 μ m.The Nafion115 film that will be coated with catalyst is then dried 30min down at 60 ℃, desolvates to remove.Handle the another side that catalyst is sprayed on PEM after the same method, promptly obtain the three-decker membrane electrode.
Embodiment 2
1, adopt the burnt base of coal tar pitch to carry out preliminary treatment as raw material and prepare amphipathic raw material of wood-charcoal material, preprocess method is identical with embodiment 1.
2, preparation nanometer carbon microspheres
Get the burnt basic amphipathic raw material of wood-charcoal material of 1g coal tar pitch and join in the 19mL deionized water, regulate pH value to 12,, obtain 1% amphipathic raw material of wood-charcoal material solution with the stir speed (S.S.) stirring of 200r/min 0.5 hour with ethylenediamine; In cryogenic temperature is-50 ℃, vacuum degree be under the 15Pa condition with the freeze drying of amphipathic raw material of wood-charcoal material solution, obtain dark gray powder, be amphipathic raw material of wood-charcoal material Nano microsphere.
The amphipathic raw material of wood-charcoal material Nano microsphere that makes is risen to 900 ℃ of charings with the heating rate of 10 ℃/min handle 2h, naturally cool to room temperature then, obtain having the nanometer carbon microspheres of catalyst activity.
3, the nanometer carbon microspheres catalyst granules of preparation load Ru
Get the nanometer carbon microspheres that 10g step 2 makes, the interpolation quality is 2% RuCl than concentration
2Solution 50g stirs 120min, adds the formalin 100g of concentration 40% then; Stir 120min, in mixed liquor, add potassium hydroxide solution make solution pH be 8, stir 20; Then be warming up to 90 ℃, keep 300min, reduce to room temperature naturally; Centrifugation obtains the very thin dark gray powder of particle.With this dark gray powder under argon gas atmosphere respectively at 400 ℃, 1000 ℃ heat treatment 120min, obtain the nanometer carbon microspheres catalyst granules of supporting Pt.
4, preparation nanometer carbon microspheres catalyst solution
Get year Pt nanometer carbon microspheres catalyst that 2g step 3 makes; Deionized water 10g, isopropyl alcohol 40g, concentration is the Nafion solution 6g of 10wt%; Mix the back earlier with magnetic stirring apparatus with rotating speed 500r/min; At room temperature stir 10min, sonic oscillation 15s then, what obtain mixing carries Pt nanometer carbon microspheres catalyst solution.
5, preparation membrane electrode
Smooth being fixed on the electric boiling plate of Nafion117 film of cutting suitable dimension is warming up to 45 ℃.The Pt nanometer carbon microspheres catalyst solution that carries that step 4 is made evenly is sprayed on the Nafion117 film, and spray area is 100mm * 100mm, and coating thickness is 3-5 μ m.The PEM that will be coated with catalyst is then dried 30min down at 60 ℃, desolvates to remove.Handle the another side that catalyst is sprayed on the Nafion117 film after the same method, promptly obtain the three-decker membrane electrode.
Embodiment 3
1, is raw material with the burnt base of petroleum asphalt, it carried out preliminary treatment prepare amphipathic raw material of wood-charcoal material that preprocess method is with embodiment 1.
2, utilize the original position load method to prepare the nanometer carbon microspheres catalyst of load P d
Get the burnt basic amphipathic raw material of wood-charcoal material of petroleum asphalt that 1g step 1 makes and join in the 15mL deionized water, regulate pH value to 12,, obtain 6.2% amphipathic raw material of wood-charcoal material solution 80g with the stir speed (S.S.) stirring of 200r/min 0.5 hour with ethylenediamine; Add quality while stirring and be 2% PdCl than concentration
2Solution 100g stirs 300min, adds the formalin 20g of concentration 40% then, stirs 20min; Then be warming up to 60 ℃, keep 300min, reduce to room temperature naturally; In cryogenic temperature is-10 ℃, vacuum degree be under the 60Pa condition with the freeze drying of amphipathic raw material of wood-charcoal material solution, obtain dark gray powder.With this powder under nitrogen atmosphere respectively at 400 ℃, 1000 ℃ heat treatment 60min, obtain the nanometer carbon microspheres catalyst of original position load P d, wherein the performance parameter of the carrier nanometer carbon microspheres in this nanometer carbon microspheres catalyst is seen table 1.
3, preparation nanometer carbon microspheres catalyst solution
Get the nanometer carbon microspheres catalyst of the load P d that 1g step 3 makes; Deionized water 5g, isopropyl alcohol 20g, concentration is the Nafion solution 3g of 10wt%; Mix the back earlier with magnetic stirring apparatus with rotating speed 500r/min; At room temperature stir 8min, sonic oscillation 10s then, the nanometer carbon microspheres catalyst solution of the load P d that obtains mixing.
4, preparation membrane electrode
The nanometer carbon microspheres catalyst solution of the load P d that step 3 is made evenly is sprayed on the carbon fiber paper that hydrophobization is handled, and spray area is 100mm * 100mm, and coating thickness is 20～50 μ m.The gas diffusion layers that will be coated with catalyst is then dried 40min down at 65 ℃, desolvates to remove.According to preparing 2 identical gas diffusion layers with quadrat method.Be coated with the gas diffusion layers of catalyst and the Nafion117 film of suitable dimension makes up according to " carbon fiber paper/catalyst/PEM/catalyst/carbon fibrous paper " structure with 2 that make, 135 ℃ with 6MPa pressure under hot pressing 90s.Promptly obtain the membrane electrode of 5 layers of structure.
Embodiment 4
1, according to embodiment 1 in identical method the needle coke based raw material is carried out preliminary treatment, obtain the amphipathic raw material of wood-charcoal material of needle coke base.
2, adopt the preparation of original position load method to contain the nanometer carbon microspheres catalyst of Ni.
Get the amphipathic raw material of wood-charcoal material of needle coke base that 2g step 1 makes and join in the 18mL deionized water, regulate pH value to 12,, obtain 10% amphipathic raw material of wood-charcoal material solution 2g with the stir speed (S.S.) stirring of 200r/min 0.5 hour with ethylenediamine; In amphipathic raw material of wood-charcoal material solution, add mass concentration while stirring and be 2% NiCl
2Solution 80g stirs 100min, adds mass concentration then and be 15% formalin 20g, stirs 60min, then is warming up to 70 ℃, keeps 100min, reduces to room temperature naturally; 600mL ethanol is stirred with the 1500r/min stir speed (S.S.), simultaneously the speed of mixed liquor with 10mL/min is added in the ethanol, stir 20min, leave standstill, demixing, the upper strata is the molten altogether thing of ethanol and water; Use separatory funnel with the mixture separation that obtains; Underclad portion is poured in the 600mL ethanol, continued solvent exchange, repeated treatments 5 times; Then with the solidliquid mixture of lower floor at 65 ℃ of following evaporate to dryness ethanol; Obtain the very thin grey black toner end of particle; With this powder under helium atmosphere respectively at 200 ℃, 800 ℃ heat treatment 90min; Obtain the nanometer carbon microspheres catalyst of original position load Ni base eelctro-catalyst, wherein the performance parameter of the carrier nanometer carbon microspheres in this nanometer carbon microspheres catalyst is seen table 1.
3, preparation nanometer carbon microspheres catalyst solution
Get the nanometer carbon microspheres catalyst of the load Ni that 2g step 3 makes; Deionized water 10g, isopropyl alcohol 40g, concentration is the Nafion solution 6g of 10wt%; Mix the back earlier with magnetic stirring apparatus with rotating speed 500 commentaries on classics/min; At room temperature stir 10min, sonic oscillation 15s then, what obtain mixing carries Pt nanometer carbon microspheres catalyst solution.
4, preparation membrane electrode
The Ni nanometer carbon microspheres catalyst solution that carries that step 3 is made evenly is sprayed on the carbon fiber paper that hydrophobization is handled, and spray area is 100mm * 100mm, and coating thickness is 20～50 μ m.The gas diffusion layers that will be coated with catalyst is then dried 40min down at 65 ℃, desolvates to remove.According to preparing 2 identical gas diffusion layers with quadrat method.Be coated with the gas diffusion layers of catalyst and the Nafion117 film of suitable dimension makes up according to " carbon fiber paper/catalyst/PEM/catalyst/carbon fibrous paper " structure with 2,135 ℃ with 6MPa pressure under hot pressing 90s.Promptly obtain the membrane electrode of 5 layers of structure.
Comparative Examples 1
1, preparation is the Pt catalyst of carrier with the carbon black
At first get the 75mL platinum acid chloride solution and join in the 250mL there-necked flask, add the 2mL mass concentration then successively and be 37% formalin and 2mL mass concentration and be 20% sodium hydroxide solution, add the Vulcan XC-72R carbon black that the 1g isopropyl alcohol disperses at last.Be warming up to 80～95 ℃, reaction 1.5h, cooling, filtration promptly obtain with carbon black at the Pt of carrier base eelctro-catalyst.
2, preparation nanometer carbon microspheres catalyst solution
Get that 1g step 1 makes with carbon black at the Pt of carrier base eelctro-catalyst; Deionized water 5g, isopropyl alcohol 20g, concentration is the Nafion solution 3g of 10wt%; Mix the back earlier with magnetic stirring apparatus with rotating speed 500r/min; At room temperature stir 8min, sonic oscillation 10s then, obtain mixing with carbon black at the Pt of carrier base eelctro-catalyst solution.
3, preparation membrane electrode
Smooth being fixed on the electric boiling plate of Nafion115 film of cutting suitable dimension is warming up to 50 ℃.What step 4 was made is that the Pt base eelctro-catalyst solution of carrier evenly is sprayed on the Nafion115 film with the carbon black, and spray area is 100mm * 100mm, and coating thickness is 3～5 μ m.The Nafion115 film that will be coated with catalyst is then dried 30min down at 60 ℃, desolvates to remove.Handle the another side that catalyst is sprayed on PEM after the same method, promptly obtain the three-decker membrane electrode.
The performance parameter of the Vulcan XC-72R carbon black carrier that obtains in nanometer carbon microspheres carrier that embodiment 1-4 is obtained and the Comparative Examples 1 and the performance parameter of membrane electrode compare, and concrete data are seen table 1.
Table 1
| |
Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | |
| Nanometer carbon microspheres average grain diameter (nm) | ?45 | ?30 | ?25 | ?20 | ?50 |
| Nanometer carbon microspheres sphericity (%) | ?70 | ?90 | ?80 | ?85 | ?65 |
| Nanometer carbon microspheres specific area (m 2/g） | ?150 | ?290 | ?275 | ?300 | ?124 |
| Nanometer carbon microspheres pore size distribution (nm) | ?30-80 | ?40-70 | ?35-85 | ?10-65 | ?20-50 |
| Unit are membrane electrode power (W/cm 2） | ?0.52 | ?0.50 | ?0.48 | ?0.47 | ?0.40 |
Can find out that from the data contrast of table 1 the nanometer carbon microspheres particle diameter of the carried metal particle for preparing among the application's the embodiment 1-4 is little, sphericity is high, has bigger specific area, and pore size distribution mainly concentrates between the 10-100nm.Employing has the nanometer carbon microspheres of performance parameter in the table 1 as the preparing carriers fuel-cell catalyst, and this catalyst evenly is sprayed on the PEM, makes the Catalytic Layer thickness membrane electrode all identical with response area.Because the three-dimensional netted polymer backbone that Nafion solution forms after solvent evaporates had both been fixed the nanocatalyst of dispersity; Prevent its migration reunion; Keep Catalytic Layer good active reaction zone and gas-liquid diffusion admittance, form good the contact with the Nafion film again, set up continuous proton transport passage; Form constitutionally stable phase reaction zone, helped carrying out smoothly of electrochemical redox reaction.The membrane electrode test result shows; With the unit are membrane electrode generated output of nanometer carbon microspheres Preparation of Catalyst is the unit are membrane electrode power of the Preparation of Catalyst of carrier with the conventional carbon black in the Comparative Examples 1 all; Show with the nanometer carbon microspheres to be that the eelctro-catalyst of carrier has higher catalytic activity, significantly improved the generating efficiency of fuel cell.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a fuel-cell catalyst is characterized in that, comprises as the nanometer carbon microspheres of catalyst carrier and is carried on the metallic catalyst on the said nanometer carbon microspheres.
2. catalyst according to claim 1 is characterized in that, the average grain diameter of said nanometer carbon microspheres is 20～50nm, and sphericity is 70%～90%, and specific area is 150～300m
2/ g, pore size distribution is 10～100nm.
3. the preparation method of a fuel-cell catalyst is characterized in that, may further comprise the steps:
Prepare the nanometer carbon microspheres, and metallic catalyst is loaded on the said nanometer carbon microspheres, obtain said fuel-cell catalyst through infusion process; Perhaps
To be used to prepare the amphipathic raw material of wood-charcoal material solution and the said metallic catalyst formation mixed solution of said nanometer carbon microspheres, and utilize the original position load method to prepare said fuel-cell catalyst.
4. preparation method according to claim 3 is characterized in that, the step for preparing said nanometer carbon microspheres comprises:
Amphipathic raw material of wood-charcoal material solution is carried out freezing, dry, distillation, obtain Nano microsphere; Perhaps said amphipathic raw material of wood-charcoal material solution is joined in the organic solvent, stir, standing demix separates, and oven dry obtains Nano microsphere; And said Nano microsphere is carried out charing handle, obtain said nanometer carbon microspheres.
5. preparation method according to claim 3 is characterized in that, said infusion process comprises:
The metal salt solution that will have catalytic action mixes with mass ratio 50:1～1000:1 with said nanometer carbon microspheres, stirs, and obtains mixed liquor A;
In said mixed liquor A, add formalin, stir, obtain mixed liquid B;
Said mixed liquid B is separated, and oven dry obtains solid; And
Said solid is heat-treated respectively at 200～400 ℃ and 800～1000 ℃, and obtaining with the nanometer carbon microspheres is the fuel-cell catalyst of carrier.
6. preparation method according to claim 3 is characterized in that, said original position load method comprises:
The metal salt solution that will have catalytic action mixes with mass ratio 5:1～100:1 with amphipathic raw material of wood-charcoal material solution, stirs, and obtains mixed liquor C;
In said mixed liquor C, add formalin, stir, obtain mixed liquor D;
With said mixed liquor D freeze drying, vacuum treatment, oven dry obtains solid; Perhaps in said mixed liquor D, add organic solvent, stir, standing demix separates, and oven dry obtains solid; And
Said solid is heat-treated respectively at 200 ℃～400 ℃ and 800 ℃～1000 ℃ under inert atmosphere, and obtaining with the nanometer carbon microspheres is the fuel-cell catalyst of carrier.
7. preparation method according to claim 5 is characterized in that, before said mixed liquid B is separated, also comprises: the pH that in said mixed liquid B, adds water-soluble alkali regulator solution system is 8～9, stirs 20～120 minutes.
8. preparation method according to claim 6 is characterized in that, before said mixed liquor D being carried out freeze drying or in said mixed liquor D, adding organic solvent, also comprises:
Said mixed liquor D is warming up to 60～90 ℃, kept 30～300 minutes and the step of natural cooling.
9. according to claim 5 or 6 described preparation methods, it is characterized in that said metal salt solution is H
2PtCl
66H
2O solution, PdCl
2Solution, RuCl
2One or more mixing in the solution; The quality of said metal salt solution is 1%～20% than concentration.
10. preparation method according to claim 7 is characterized in that, said water-soluble alkali is one or more mixing in NaOH, potassium hydroxide, ethylenediamine, sodium carbonate, potash and the cesium hydroxide.
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