CN102810677B - Fuel cell catalyst and preparation method thereof - Google Patents
Fuel cell catalyst and preparation method thereof Download PDFInfo
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- CN102810677B CN102810677B CN201210295163.8A CN201210295163A CN102810677B CN 102810677 B CN102810677 B CN 102810677B CN 201210295163 A CN201210295163 A CN 201210295163A CN 102810677 B CN102810677 B CN 102810677B
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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 Proton Exchange Membrane Fuel Cells field, in particular to a kind of fuel-cell catalyst and preparation method thereof.
Background technology
There is electrochemical redox reaction in Proton Exchange Membrane Fuel Cells, this reaction needed could realize under the effect of catalyst in energy conversion process.Now widely used catalyst mainly based on precious metals pt, Pd, Ru, Ir etc. or Pt-M(M for Ru, Co, Ni, Mn etc.) alloy.For the Pt be most widely used, in order to improve catalyst utilization, reducing noble metal dosage, reducing costs, usually take H
2precious metals pt is highly dispersed on the larger conduction of specific area, corrosion-resistant carrier with nanoparticle form by the means such as PtCl direct-reduction process, colloid Pt sol method, ion-exchange, as acetylene carbon black (Vulcan XC-72R, average grain diameter 30nm, specific area 250m
2/ g), i.e. the Pt/C eelctro-catalyst of obtained high dispersive.
Although primary carbon black particle particle diameter is very little, but the polarity of carbon blacksurface and nonpolar group mass contg very low, and the affinity between other materials (as high molecular polymer, organic solvent, water etc.) is far weaker than the cohesiveness between carbon black particle, therefore carbon black is difficult to stable be scattered in various medium, exist mainly with larger-size aggregate greatly, thus significantly reduce its specific area, reduce phase reaction region in Catalytic Layer, reduce catalyst utilization, cause noble metal loadings significantly to increase.For the Pt/C eelctro-catalyst of now widely used mass fraction 40%, due to the reunion of carbon black particle, specific area is reduced to 67.5m
2/ g is only about 25% of theoretical value.Describing specific area in patent CN1747785A " the polymer dielectric film fuel cell eelctro-catalyst based on the improvement of mixing carbon carrier " is 250m
2the Vulcan XC-72R carbon black of/g be carrier carry Pt catalyst (catalyst 1) and specific area is 600 ~ 1000m
2the Ketjen carbon black of/g be carrier to carry Pt catalyst (catalyst 2) used in combination, add the specific area of conventional Pt/C (Vulcan XC-72R carbon black) catalyst, improve catalyst activity.But the Ketjen carbon black-supported specific area that the Pt/C added (Ketjen carbon black) catalyst uses is large, and particle diameter is little, and disperse more difficult, the ratio in Catalytic Layer shared by effecting reaction region is lower, and the utilance of noble metal is also lower; This catalyst also more easily moves 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 catalyst, improve catalyst activity, reduce noble metal loadings, become the important research direction reducing 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 the complicated process of preparation existed in prior art, the technical problem that cost is higher.
To achieve these goals, according to an aspect of the present invention, provide a kind of fuel-cell catalyst, comprise the Nano carbon microballoon as catalyst carrier and the metallic catalyst that is carried on Nano carbon microballoon.
Further, the average grain diameter of Nano carbon microballoon 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, provide a kind of preparation method of fuel-cell catalyst, comprise the following steps: prepare Nano carbon microballoon, and by infusion process, metallic catalyst is loaded on Nano carbon microballoon, obtain fuel-cell catalyst; Or form mixed solution by for the preparation of the amphipathic Carbon Materials solution of Nano carbon microballoon and metallic catalyst, utilize original position load method to prepare fuel-cell catalyst.
Further, the step preparing Nano carbon microballoon comprises: amphipathic Carbon Materials solution is carried out freezing, dry, distillation, obtain Nano microsphere; Or amphipathic Carbon Materials solution is joined in organic solvent, stirs, stratification, be separated, dry, obtain Nano microsphere; And Nano microsphere is carried out charing process, obtain Nano carbon microballoon.
Further, infusion process comprises: mixed with mass ratio 50:1 ~ 1000:1 with Nano carbon microballoon by the metal salt solution with catalytic action, stirs, obtains mixed liquor A; In mixed liquor A, add formalin, stir, obtain mixed liquid B; Mixed liquid B is separated, dries, obtain solid; And solid is heat-treated respectively at 200 DEG C ~ 400 DEG C and 800 DEG C ~ 1000 DEG C, the fuel-cell catalyst that to obtain with Nano carbon microballoon be carrier.
Further, original position load method comprises: mixed with mass ratio 5:1 ~ 100:1 with amphipathic Carbon Materials solution by the metal salt solution with catalytic action, stirs, obtains mixed liquor C; In mixed liquor C, add formalin, stir, obtain mixed liquor D; By mixed liquor D freeze drying, vacuum treatment, dries, obtains solid; Or in mixed liquor D, add organic solvent, stir, stratification, be separated, dry, obtain solid; And solid is heat-treated respectively at 200 DEG C ~ 400 DEG C and 800 DEG C ~ 1000 DEG C under an inert atmosphere, the fuel-cell catalyst that to obtain with Nano carbon microballoon be carrier.
Further, also comprise before mixed liquid B is separated: in mixed liquid B, add water-soluble alkali regulate the pH of solution system to be 8 ~ 9, stir 20 ~ 120 minutes.
Further, also comprised before mixed liquor D being carried out to freeze drying or add organic solvent in mixed liquor D: mixed liquor D is warming up to 60 DEG C ~ 90 DEG C, the step keeping 30 ~ 300 minutes and naturally cool.
Further, metal salt solution is H
2ptCl
66H
2o solution, PdCl
2solution, RuCl
2one or more mixing in solution; The quality of described 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 cesium hydroxide.
According to another aspect of the invention, the application of any one catalyst above-mentioned in fuel cell membrane electrode is provided.
By adopting, particle diameter is little, sphericity is high in the present invention, the large Nano carbon microballoon of surface area and aperture prepares fuel-cell catalyst as carrier, this catalyst is made not easily to move reunion in Catalytic Layer, there is the dispersion stabilization of height, effectively can improve the catalytic activity of catalyst, adopt the membrane electrode of this catalyst preparing, there is higher unit are membrane electrode power.Fuel-cell catalyst provided by the invention has larger phase reaction district, substantially increases the utilance of catalyst, decreases the resistance of various transmittance process and the load capacity of noble metal.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the electron scanning micrograph of the Nano carbon microballoon of exemplary embodiments of the present invention;
Fig. 2 is the transmission electron microscope photo of the Nano carbon microballoon of exemplary embodiments of the present invention;
Fig. 3 shows the section structure schematic diagram of the three-decker membrane electrode according to exemplary embodiments of the present invention; And
Fig. 4 shows the section structure schematic diagram of the five-layer structure membrane electrode according to exemplary embodiments of the present invention.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
According to a kind of exemplary embodiment of the present invention, this fuel-cell catalyst comprises Nano carbon microballoon as catalyst carrier and the metallic catalyst that is carried on Nano carbon microballoon.
Owing to having as the Nano carbon microballoon of catalyst carrier, particle diameter is little, sphericity is high, the large advantage of surface area and aperture, the fuel-cell catalyst of carried metal particle has larger phase reaction region, define the continuous passage of proton, electronics and reacting gas, improve the interface continuity between the ionomer in proton membrane and the ionomer in Catalytic Layer, substantially increase the utilance of catalyst, decrease the resistance of various transmittance process, decrease the load capacity of noble metal.Nano carbon microballoon is made up of the amphipathic Carbon Materials of surface oxygen functional group, therefore has good affinity with metallic catalyst.In addition, catalyst of the present invention not easily moves reunion, has the dispersion stabilization of height, effectively can improve the catalytic activity of catalyst, adopt the membrane electrode of this catalyst preparing, have higher unit are membrane electrode power.
Metallic catalyst is the alloy of one or more metals composition in the metals such as Pt, Pd, Ru, Ir, Co, Ni, Mn; 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 be prepared using amphipathic Carbon Materials as raw material as the Nano carbon microballoon of carrier, preferably, the particle diameter of Nano carbon microballoon 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, as can be seen from Fig. 1 and Fig. 2, the uniform particle sizes of Nano carbon microballoon, better dispersed, this is because Nano carbon microballoon is formed by the self assembly under capillary constraint of amphipathic Carbon Materials.
Infusion process refers to first prepares Nano carbon microballoon, then loads on Nano carbon microballoon by the method for dipping by metallic catalyst; Original position load method refers to and first amphipathic Carbon Materials solution and metallic catalyst is formed mixed solution, and then directly preparation contains the Nano carbon microballoon of metallic catalyst.
According to a further aspect in the invention, provide a kind of preparation method of fuel-cell catalyst, comprise the following steps: prepare Nano carbon microballoon, and by infusion process, metallic catalyst is loaded on Nano carbon microballoon, obtain fuel-cell catalyst; Or form mixed solution by for the preparation of the amphipathic Carbon Materials solution of Nano carbon microballoon and metallic catalyst, utilize original position load method to prepare fuel-cell catalyst.
By direct-reduction process, noble metal dispersion is obtained fuel-cell catalyst on the surface of Nano carbon microballoon; Or obtain fuel-cell catalyst at the growth course situ carried noble metal of Nano carbon microballoon in the surface of Nano carbon microballoon.Preparation method's technique provided by the present invention is simple, does not need large-scale equipment or instrument, and raw material is easy to get and cheap, greatly reduces production cost.
A preferred embodiment of the invention, the step preparing Nano carbon microballoon comprises: first amphipathic Carbon Materials solution is carried out freezing, dry, distillation, obtain Nano microsphere; Or amphipathic Carbon Materials solution is joined in organic solvent, stirs, stratification, be separated, dry, obtain Nano microsphere; Again the Nano microsphere obtained is carried out charing process, obtain Nano carbon microballoon.
Amphipathic Carbon Materials solution in the present invention is formulated by amphipathic Carbon Materials 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 burnt base, petroleum coke base, needle coke base and pitch coke base.Above-mentioned raw materials abundance, cheap, be easy to realize large-scale industrial and produce.Introduce the preparation process of Nano carbon microballoon below in detail.
A, one or more in above-mentioned raw materials are joined in deionized water, and regulate the pH of solution to be 10 ~ 14 with water-soluble alkali (potassium hydroxide, NaOH, ethylenediamine, potash, sodium carbonate, cesium hydroxide etc.), be mixed with the amphipathic Carbon Materials solution that mass percent concentration is 5 ~ 10%;
B, above-mentioned amphipathic Carbon Materials solution is put into freeze drier, freeze at-10 DEG C ~-50 DEG C, be steam and removing by ice distillation wherein under the high vacuum condition of 1.3 ~ 60Pa, obtain dark gray powder, i.e. Nano carbon microballoon;
C, without step B, the low boiling-point and polarity organic solvent that employing can be dissolved each other with water, refer generally to ethanol, acetone or methyl alcohol etc. herein, according to the percent by volume 20 ~ 500:1 of amphipathic Carbon Materials solution obtained in organic solvent and steps A, while stirring amphipathic Carbon Materials solution is joined in organic solvent, stir 5 ~ 30min, stir speed (S.S.) is 300 ~ 1500r/min, obtain mixed liquor, by mixed liquor stratification, it is the common molten thing of organic solvent and water at the middle and upper levels, and not molten amphipathic Carbon Materials particulate is contained in lower floor;
D, the supernatant liquid of mixed liquor obtained by step C are separated by separatory funnel with lower floor, and supernatant liquid carries out rectifying separation, and the organic solvent that rectifying obtains can be recycled;
E, by lower floor containing the part of amphipathic Carbon Materials particulate by the process of step C cycle for the treatment of, be then separated according to step D, so repeatedly process 3 ~ 5 times, the amphipathic Carbon Materials particulate of lower floor is all dissolved as far as possible;
F, 50 ~ 70 DEG C of evaporate to dryness organic solvents will be placed in through step e process containing the mixture of amphipathic Carbon Materials particulate, obtain the black gray expandable powder that particle is very thin, be Nano carbon microballoon;
G, in retort (being generally tube furnace, box type furnace or rotary furnace etc.), Nano carbon microballoon obtained for step B or F is risen to 900 ~ 2600 DEG C with the heating rate of 1 ~ 10 DEG C/min and carries out carbonizing or graphitization processing 1 ~ 2h by (nitrogen, argon gas or helium) under an inert atmosphere, then naturally cool to room temperature, obtain the Nano carbon microballoon that particle diameter is 20nm ~ 50nm.The microscopic appearance of Nano carbon microballoon as depicted in figs. 1 and 2.
Wherein, have in the process of water miscible amphipathic Carbon Materials solution in preparation and do not need to add any surfactant, charcoal precursor can be made to be dispersed in water, and decrease the use of organic solvent to a certain extent, synthesis technique is made to become simple, and environmental protection.The equipment used in the synthesis technique of this Nano carbon microballoon and building-up process is simple, compared with the synthetic method of Conventional nano material as hydro thermal method, and template etc., production cost is more cheap;
A preferred embodiment of the invention, infusion process comprises: mixed with mass ratio 50:1 ~ 1000:1 with Nano carbon microballoon by the metal salt solution with catalytic action, stirs, obtains mixed liquor A; In mixed liquor A, add formalin, stir, obtain mixed liquid B; Mixed liquid B is separated, and dries, obtains solid; And solid is heat-treated respectively at 200 ~ 400 DEG C and 800 ~ 1000 DEG C, the fuel-cell catalyst that to obtain with Nano carbon microballoon be carrier.In the operation of reality, in Nano carbon microballoon, drip platinum acid chloride solution while stirring, stir 20 ~ 300 minutes, after adding formalin, stir 10 ~ 60 minutes.What adopt infusion process that metallic catalyst can be made to be combined with Nano carbon microballoon is more firm, can also reduce catalyst cost, improve catalyst efficiency, the useful life of extending catalyst.In addition this preparation method has simple to operate and that earning rate is high advantage.
Further preferably, also comprise before mixed liquid B is separated: in mixed liquid B, add water-soluble alkali regulate the pH of solution system to be 8 ~ 9, stir 20 ~ 120min.Water-soluble alkali is one or more mixing in NaOH, potassium hydroxide, ethylenediamine, sodium carbonate, potash and cesium hydroxide.Adding the object that water-soluble alkali carries out regulating is because alkali condition is more conducive to metal salt solution and is reduced into metallic particles.
According to another kind of preferred implementation of the present invention, original position load method comprises: mixed with mass ratio 5:1 ~ 100:1 with amphipathic Carbon Materials solution by the metal salt solution with catalytic action, stirs, obtains mixed liquor C; In mixed liquor C, add formalin, stir, obtain mixed liquor D; By mixed liquor D freeze drying, vacuum treatment, dries, obtains solid; Or in mixed liquor D, add organic solvent, stir, stratification, be separated, dry, obtain solid; And solid is heat-treated respectively at 200 DEG C ~ 400 DEG C and 800 DEG C ~ 1000 DEG C under an inert atmosphere, the fuel-cell catalyst that to obtain with Nano carbon microballoon be carrier.
By the process situ supported catalyst particles at synthesis of nano carbon microspheres, the load of catalyst granules can be made more even; Make the distribution of catalyst on carrier more even by original position load method, saved the consumption of noble metal, improve catalytic efficiency.Further preferably, metal catalyst solution is H
2ptCl
66H
2o solution, PdCl
2solution, RuCl
2one or more mixing in 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 by one or more in the metals such as Pd, Ru, Ir, Co, Ni and Mn with containing Pt catalyst mix.
The solid finally obtained is heat-treated respectively at 200 DEG C ~ 400 DEG C and 800 DEG C ~ 1000 DEG C under an inert atmosphere, object makes Nano carbon microspherical catalyst have certain activity, solid is processed in low-temperature zone 200 DEG C ~ 400 DEG C and high temperature section 800 DEG C ~ 1000 DEG C two stages respectively, carrying out processing in low-temperature zone makes the light component in precursor and hetero-atom overflow in low-temperature zone, then carbonize in high temperature section, make structure more stable, improve conductance, so have activated catalytic activity after high-temperature process, the fuel-cell catalyst that to obtain with Nano carbon microballoon be carrier.
Preferably, the mass concentration of amphipathic Carbon Materials solution is 1% ~ 30%; The addition of formalin is 5% ~ 20% of metal catalyst solution quality.The mass concentration of amphipathic Carbon Materials solution is controlled be yield and the particle diameter of considering Nano carbon microballoon in the scope of 1% ~ 30%, amphipathic Carbon Materials solution within the scope of this mass concentration can take into account yield and the particle size uniformity of Nano carbon microballoon, if the too little meeting of concentration makes product yield too low, be unfavorable for volume production; If concentration is too large, raw material is easily reunited, and is difficult to obtain Nano carbon microballoon.
The object wherein adding formaldehyde is that metal catalyst solution is reduced to metal simple-substance, so add formaldehyde according to the amount of metal catalyst solution, the addition of formaldehyde is that metal catalyst solution is just in time reduced into metallic particles by 5% ~ 20% of metal catalyst solution quality completely, can not cause again formaldehyde too much contaminated environment simultaneously.
According to a kind of exemplary embodiment of the present invention, also comprised before mixed liquor D being carried out to freeze drying or add organic solvent step in mixed liquor D: mixed liquor D is warming up to 60 ~ 90 DEG C, the step keeping 30 ~ 300 minutes and naturally cool.The object heated up also is reduction in order to promote metallic catalyst, temperature is controlled at 60 ~ 90 DEG C and keeps making formaldehyde give full play to reproducibility in 30 ~ 300 minutes and by metal salt back.
According to another aspect of the invention, the application of any one catalyst above-mentioned in fuel cell membrane electrode is additionally provided.Introduce the preparation method of membrane electrode of fuel batter with proton exchange film below in detail.
For the Nano carbon microspherical catalyst of supporting Pt, by the Nano carbon microspherical catalyst of supporting Pt, Polymer Solution, low boiling point organic solvent and deionized water according to (1 ~ 10): 1:(0 ~ 50): the volume ratio mixing of (0 ~ 200), through sonic oscillation 1 ~ 100min, be adjusted to ink shape catalyst solution.Be uniformly coated in proton exchange membrane by this catalyst solution, control at 40 ~ 130 DEG C during spraying by the temperature of proton exchange membrane, catalyst thickness is 1 ~ 50 μm, the proton exchange membrane being coated with catalyst is dried in vacuum drying oven and removes solvent.Wherein vacuum drying temperature is 40 ~ 100 DEG C, and drying time is 1 ~ 100min.Prepare another surface of proton exchange membrane after the same method, i.e. the membrane electrode of obtained three-decker.The section structure schematic diagram of the membrane electrode of this three-decker as indicated at 3, is followed successively by catalyst layer, proton exchange membrane, catalyst layer from top to bottom.
The upper and lower surface of the three-decker membrane electrode prepared is covered with diaphragm save backup, or directly and the gas diffusion layers of two hydrophobization process combine, obtain the membrane electrode of five-layer structure, as shown in Figure 4.The membrane electrode of this five-layer structure can be directly used in fuel cell.Gas diffusion layers herein can be carbon fiber paper, carbon-fiber cloth etc., and its process for hydrophobicizing is those skilled in the art's technology in common knowledge.
The proton exchange membrane 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, sulfonate polybenzimidazole film etc.The mass percent concentration of the Polymer Solution adopted is 0.1% ~ 5%, solute is the resin corresponding with proton exchange membrane used, such as perfluorinated sulfonic resin, sulfonated polystyrene ion exchange resin, sulfonated polyether-ether-ketone resin, sulfonated polyether sulphone resin, sulfonated polyimide resin, sulfonate polybenzimidazole resin etc.Solvent is good solvent or the mixing good solvent of the above-mentioned resin of solubilized, as one or more in DMF, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, dimethylacetylamide, butyrolactone, ethylene glycol, sulfolane, triphenyl phosphoric acid, 2-methyl cellosolve, cellosolvo, glycol dimethyl ether, diethylene glycol dimethyl ether equal solvent.Low boiling point organic solvent refers to one or more in ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, glycerol equal solvent.Proton exchange membrane can be perfluoro sulfonic acid membrane, sulfonated polystyrene film, sulfonated polyether-ether-ketone film, sulfonated polyether sulfone film, sulfonated polyimide film, sulfonate polybenzimidazole film etc.
Polymer Solution concentration is mass fraction 0.1 ~ 5%, solute is the resin corresponding with proton exchange membrane used, such as perfluorinated sulfonic resin, sulfonated polystyrene ion exchange resin, sulfonated polyether-ether-ketone resin, sulfonated polyether sulphone resin, sulfonated polyimide resin, sulfonate polybenzimidazole resin etc.Solvent is good solvent or the mixing good solvent of the above-mentioned resin of solubilized, as one or more in DMF, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, dimethylacetylamide, butyrolactone, ethylene glycol, sulfolane, triphenyl phosphoric acid, 2-methyl cellosolve, cellosolvo, glycol dimethyl ether, diethylene glycol dimethyl ether equal solvent.Low boiling point organic solvent can be one or more in ethanol, propyl alcohol, ethylene glycol, isopropyl alcohol, glycerol equal solvent.
Introduce a kind of processing step prepared to carry the five layer proton exchange membrane fuel cell membrane electrodes that Pt Nano carbon microballoon is catalyst below:
Get and carry Pt Nano carbon microspherical catalyst, Polymer Solution, isopropyl alcohol and deionized water according to certain (1 ~ 10): 1:(0 ~ 50): (0 ~ 200) ratio mixes, and through sonic oscillation 1 ~ 100min, is adjusted to ink shape catalyst solution.Cut out the gas diffusion layers of the hydrophobization process of suitable area size, be spread evenly across by catalyst solution on gas diffusion layers, catalyst thickness is 1 ~ 50 μm, then in vacuum drying oven, dry to remove desolventizing.By two identical gas diffusion layers spraying catalyst and proton exchange membrane according to " gas diffusion layers/catalyst/proton exchange membrane/catalyst/gas diffusion layer " structure in 40 ~ 150 DEG C, hot pressing 1 ~ 10min under 1 ~ 100Mpa.Namely obtain five-layer structure membrane electrode, its section structure schematic diagram as shown in Figure 4, is respectively gas diffusion layers, catalyst layer, proton exchange membrane, catalyst layer, gas diffusion layers from top to bottom.
Beneficial effect of the present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1
1, preliminary treatment is carried out to needle coke based raw material, prepare the amphipathic Carbon Materials of needle coke base.
By 100mL nitration mixture (with concentration be 65% red fuming nitric acid (RFNA) and concentration be 98% concentrated sulfuric acid volume ratio prepare for 3:7) be heated to 80 DEG C, stir with the stir speed (S.S.) of 300r/min, add 10g needle coke based raw material, reaction 1h, reactant is poured into cessation reaction in 1L deionized water, adopt pressure-reducing filter to filter, gained filter cake spends deionized water to neutral.Joined by the solid matter obtained in the NaOH solution of 500mL concentration 1mol/L, at 80 DEG C, stir 1h with the rotating speed of 300r/min, filtration under diminished pressure, keeps the pH value of solution to be greater than 12 all the time in the process; Collect filtrate, in the filtrate obtained, drip the HCl of 1mol/L, regulate its pH value to 1, now have precipitation to generate; Centrifugation, spends deionized water to neutral, dries 10h for 100 DEG C in an oven, obtain the amphipathic Carbon Materials of needle coke base by the sediment obtained.
2, Nano carbon microballoon is prepared
Getting the amphipathic Carbon Materials of needle coke base obtained in 2g step 1 joins in 18mL deionized water, by ethylenediamine adjust ph to 12, stirs 30min, obtain the amphipathic Carbon Materials solution of 30% with the stir speed (S.S.) of 200r/min; 500mL acetone is stirred with 1000r/min stir speed (S.S.), amphipathic Carbon Materials solution is added in acetone with the speed of 10mL/min simultaneously, stir 10min, leave standstill, demixing, upper strata is the common molten thing of acetone and water, and not molten amphipathic Carbon Materials particulate is contained in lower floor; Separatory funnel is used to be separated by the mixture obtained.Lower floor is poured in 500mL acetone containing the part of amphipathic Carbon Materials particulate, continues solvent exchange, repeatedly process 4 times; Then by containing the mixture of amphipathic Carbon Materials particulate in 50 DEG C of evaporate to dryness acetone, obtaining the black gray expandable powder that particle is very thin, being amphipathic Carbon Materials Nano microsphere.
Obtained amphipathic Carbon Materials Nano microsphere is risen to 1100 DEG C of charing process 1h with the heating rate of 2 DEG C/min, then naturally cools to room temperature, obtain the Nano carbon microballoon with catalyst activity.
3, the Nano carbon microspherical catalyst of supporting Pt particle is prepared
Get the Nano carbon microballoon of preparation in 1g step 2, adding quality is the H of 1% than concentration
2ptCl
6solution 1000g, stir 60min, then add the formalin 2.5g of concentration 30%, stir 20min, be then warming up to 60 DEG C, maintain 30min, naturally be down to room temperature, centrifugation, obtain the black gray expandable powder that particle is very thin, by this powder under an argon atmosphere respectively at 200 DEG C, 800 DEG C heat treatment 60min, obtain the Nano carbon microballoon of supporting Pt base eelctro-catalyst.
4, Nano carbon microspherical catalyst solution is prepared
Get the Nano carbon microspherical catalyst of the obtained supporting Pt of 1g step 3, deionized water 5g, isopropyl alcohol 20g, concentration is the Nafion solution 3g of 10wt%, first use magnetic stirring apparatus with rotating speed 500r/min after mixing, at room temperature stir 8min, then sonic oscillation 10s, obtain the Nano carbon microspherical catalyst solution of the supporting Pt mixed.
5, membrane electrode is prepared
The Nafion115 film of cutting suitable dimension is smooth to be fixed on electric boiling plate, is warming up to 50 DEG C.Be sprayed on Nafion115 film by the Nano carbon microspherical catalyst dissolution homogeneity carrying Pt obtained for step 4, spray area is 100mm × 100mm, and coating thickness is 3 ~ 5 μm.Then the Nafion115 film being coated with catalyst is dried 30min at 60 DEG C, to remove desolventizing.Process another side catalyst being sprayed on proton exchange membrane after the same method, namely obtain three-decker membrane electrode.
Embodiment 2
1, adopt the burnt base of coal tar pitch to carry out preliminary treatment to prepare amphipathic Carbon Materials as raw material, preprocess method is identical with embodiment 1.
2, Nano carbon microballoon is prepared
Getting the amphipathic Carbon Materials of the burnt base of 1g coal tar pitch joins in 19mL deionized water, by ethylenediamine adjust ph to 12, stirs 0.5 hour with the stir speed (S.S.) of 200r/min, obtains the amphipathic Carbon Materials solution of 1%; Be-50 DEG C in cryogenic temperature, vacuum degree be under 15Pa condition by the freeze drying of amphipathic Carbon Materials solution, obtain dark gray powder, be amphipathic Carbon Materials Nano microsphere.
Obtained amphipathic Carbon Materials Nano microsphere is risen to 900 DEG C of charing process 2h with the heating rate of 10 DEG C/min, then naturally cools to room temperature, obtain the Nano carbon microballoon with catalyst activity.
3, the Nano carbon microspherical catalyst particle of load Ru is prepared
Get the Nano carbon microballoon that 10g step 2 is obtained, adding quality is the RuCl of 2% than concentration
2solution 50g, stir 120min, then add the formalin 100g of concentration 40%, stir 120min, add in mixed liquor potassium hydroxide solution make solution pH be 8, stir 20, then be warming up to 90 DEG C, maintain 300min, be naturally down to room temperature, centrifugation, obtains the dark gray powder that particle is very thin.By this dark gray powder under an argon atmosphere respectively at 400 DEG C, 1000 DEG C heat treatment 120min, obtain the Nano carbon microspherical catalyst particle of supporting Pt.
4, Nano carbon microspherical catalyst solution is prepared
Get year Pt Nano carbon microspherical catalyst that 2g step 3 is obtained, deionized water 10g, isopropyl alcohol 40g, concentration is the Nafion solution 6g of 10wt%, first use magnetic stirring apparatus with rotating speed 500r/min after mixing, at room temperature stir 10min, then sonic oscillation 15s, obtain year Pt Nano carbon microspherical catalyst solution mixed.
5, membrane electrode is prepared
The Nafion117 film of cutting suitable dimension is smooth to be fixed on electric boiling plate, is warming up to 45 DEG C.Be sprayed on Nafion117 film by the Pt Nano carbon microspherical catalyst dissolution homogeneity that carries obtained for step 4, spray area is 100mm × 100mm, and coating thickness is 3-5 μm.Then the proton exchange membrane being coated with catalyst is dried 30min at 60 DEG C, to remove desolventizing.Process another side catalyst being sprayed on Nafion117 film after the same method, namely obtain three-decker membrane electrode.
Embodiment 3
1, with the burnt base of petroleum asphalt for raw material, carry out preliminary treatment to it and prepare amphipathic Carbon Materials, preprocess method is with embodiment 1.
2, original position load method is utilized to prepare the Nano carbon microspherical catalyst of load P d
Getting the amphipathic Carbon Materials of the burnt base of the obtained petroleum asphalt of 1g step 1 joins in 15mL deionized water, by ethylenediamine adjust ph to 12, stirs 0.5 hour with the stir speed (S.S.) of 200r/min, obtains the amphipathic Carbon Materials solution 80g of 6.2%; Adding quality while stirring than concentration is the PdCl of 2%
2solution 100g, stirs 300min, then adds the formalin 20g of concentration 40%, stirs 20min, then be warming up to 60 DEG C, maintain 300min, be naturally down to room temperature, be-10 DEG C in cryogenic temperature, vacuum degree be under 60Pa condition by the freeze drying of amphipathic Carbon Materials solution, obtain dark gray powder.By this powder in a nitrogen atmosphere respectively at 400 DEG C, 1000 DEG C heat treatment 60min, obtain the Nano carbon microspherical catalyst of original position load P d, the performance parameter of the carrier Nano carbon microballoon wherein in this Nano carbon microspherical catalyst is in table 1.
3, Nano carbon microspherical catalyst solution is prepared
Get the Nano carbon microspherical catalyst of the obtained load P d of 1g step 3, deionized water 5g, isopropyl alcohol 20g, concentration is the Nafion solution 3g of 10wt%, first use magnetic stirring apparatus with rotating speed 500r/min after mixing, at room temperature stir 8min, then sonic oscillation 10s, obtain the Nano carbon microspherical catalyst solution of the load P d mixed.
4, membrane electrode is prepared
Be sprayed on the carbon fiber paper of hydrophobization process by the Nano carbon microspherical catalyst dissolution homogeneity of load P d obtained for step 3, spray area is 100mm × 100mm, and coating thickness is 20 ~ 50 μm.Then the gas diffusion layers being coated with catalyst is dried 40min at 65 DEG C, to remove desolventizing.2 identical gas diffusion layers are prepared according to same method.The gas diffusion layers of catalyst is coated with the Nafion117 film of suitable dimension combines according to " carbon fiber paper/catalyst/proton exchange membrane/catalyst/carbon fibrous paper " structure, hot pressing 90s under 135 DEG C with 6MPa pressure by obtained 2.Namely the membrane electrode of 5 Rotating fields is obtained.
Embodiment 4
1, according to method in the same manner as in Example 1, preliminary treatment is carried out to needle coke based raw material, obtain the amphipathic Carbon Materials of needle coke base.
2, adopt the preparation of original position load method containing the Nano carbon microspherical catalyst of Ni.
The amphipathic Carbon Materials of needle coke base getting 2g step 1 obtained joins in 18mL deionized water, by ethylenediamine adjust ph to 12, stirs 0.5 hour with the stir speed (S.S.) of 200r/min, obtains the amphipathic Carbon Materials solution 2g of 10%; The NiCl that mass concentration is 2% is added while stirring in amphipathic Carbon Materials solution
2solution 80g, stirs 100min, then adds the formalin 20g that mass concentration is 15%, stirs 60min, is then warming up to 70 DEG C, maintains 100min, is naturally down to room temperature; Stirred with 1500r/min stir speed (S.S.) by 600mL ethanol, add in ethanol simultaneously by mixed liquor with the speed of 10mL/min, stir 20min, leave standstill, demixing, upper strata is the common molten thing of ethanol and water; Separatory funnel is used to be separated by the mixture obtained; Underclad portion is poured in 600mL ethanol, continue solvent exchange, repeatedly process 5 times; Then by the solidliquid mixture of lower floor evaporate to dryness ethanol at 65 DEG C, obtain the black gray expandable powder that particle is very thin, by this powder under helium atmosphere respectively at 200 DEG C, 800 DEG C heat treatment 90min, obtain the Nano carbon microspherical catalyst of original position load Ni base eelctro-catalyst, the performance parameter of the carrier Nano carbon microballoon wherein in this Nano carbon microspherical catalyst is in table 1.
3, Nano carbon microspherical catalyst solution is prepared
Get the Nano carbon microspherical catalyst of the obtained load Ni of 2g step 3, deionized water 10g, isopropyl alcohol 40g, concentration is the Nafion solution 6g of 10wt%, first use magnetic stirring apparatus with rotating speed 500 turns/min after mixing, at room temperature stir 10min, then sonic oscillation 15s, obtain year Pt Nano carbon microspherical catalyst solution mixed.
4, membrane electrode is prepared
Be sprayed on the carbon fiber paper of hydrophobization process by the Ni Nano carbon microspherical catalyst dissolution homogeneity that carries obtained for step 3, spray area is 100mm × 100mm, and coating thickness is 20 ~ 50 μm.Then the gas diffusion layers being coated with catalyst is dried 40min at 65 DEG C, to remove desolventizing.2 identical gas diffusion layers are prepared according to same method.2 are coated with the gas diffusion layers of catalyst and the Nafion117 film of suitable dimension combines according to " carbon fiber paper/catalyst/proton exchange membrane/catalyst/carbon fibrous paper " structure, hot pressing 90s under 135 DEG C and 6MPa pressure.Namely the membrane electrode of 5 Rotating fields is obtained.
Comparative example 1
1, preparing with carbon black is the Pt catalyst of carrier
First getting 75mL platinum acid chloride solution joins in 250mL there-necked flask, then add successively 2mL mass concentration be 37% formalin and 2mL mass concentration be the sodium hydroxide solution of 20%, finally add 1g isopropyl alcohol dispersion Vulcan XC-72R carbon black.Be warming up to 80 ~ 95 DEG C, reaction 1.5h, cooling, filtration, namely obtain with the Pt base eelctro-catalyst of carbon black at carrier.
2, Nano carbon microspherical catalyst solution is prepared
Get 1g step 1 obtained with the Pt base eelctro-catalyst of carbon black at carrier, deionized water 5g, isopropyl alcohol 20g, concentration is the Nafion solution 3g of 10wt%, first use magnetic stirring apparatus with rotating speed 500r/min after mixing, at room temperature stir 8min, then sonic oscillation 10s, obtain mixing with the Pt base eelctro-catalyst solution of carbon black at carrier.
3, membrane electrode is prepared
The Nafion115 film of cutting suitable dimension is smooth to be fixed on electric boiling plate, is warming up to 50 DEG C.By obtained for step 4 be that the Pt base eelctro-catalyst dissolution homogeneity of carrier is sprayed on Nafion115 film with carbon black, spray area is 100mm × 100mm, and coating thickness is 3 ~ 5 μm.Then the Nafion115 film being coated with catalyst is dried 30min at 60 DEG C, to remove desolventizing.Process another side catalyst being sprayed on proton exchange membrane after the same method, namely obtain three-decker membrane electrode.
The performance parameter of Vulcan XC-72R carbon black-supported obtained in the microsphere supported and comparative example 1 of the Nano carbon obtained by embodiment 1-4 and the performance parameter of membrane electrode contrast, and concrete data are in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Nano carbon microsphere average grain diameter (nm) | ?45 | ?30 | ?25 | ?20 | ?50 |
| Nano carbon microballoon sphericity (%) | ?70 | ?90 | ?80 | ?85 | ?65 |
| Nano carbon microballoon specific area (m 2/g） | ?150 | ?290 | ?275 | ?300 | ?124 |
| Nano carbon microballoon 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 |
As can be seen from the Data Comparison of table 1, the Nano carbon microspherulite diameter of the carried metal particle prepared in the embodiment 1-4 of the application is little, and sphericity is high, has larger specific area, and pore size distribution mainly concentrates between 10-100nm.The Nano carbon microballoon with performance parameter in table 1 is adopted to prepare fuel-cell catalyst as carrier, by this catalyst even application in proton exchange membrane, the membrane electrode that obtained Catalytic Layer thickness is all identical with response area.The three-dimensional network polymer skeleton formed after evaporation of the solvent due to Nafion solution had both secured the nanocatalyst of dispersity, prevent its migration from reuniting, the active reaction region keeping Catalytic Layer good and gas-liquid diffusion admittance, good contact is formed again with Nafion film, establish continuous print proton transmitting channel, define constitutionally stable phase reaction region, be conducive to carrying out smoothly of electrochemical redox reaction.Membrane electrode test result shows, the unit are membrane electrode generated output prepared with Nano carbon microspherical catalyst is all the unit are membrane electrode power of the catalyst preparing of carrier with conventional carbon black in comparative example 1, the eelctro-catalyst that to show with Nano carbon microballoon be carrier has higher catalytic activity, significantly improves the generating efficiency of fuel cell.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a fuel-cell catalyst, is characterized in that, comprises the Nano carbon microballoon as catalyst carrier and the metallic catalyst that is carried on described Nano carbon microballoon; The average grain diameter of described Nano carbon microballoon is 20 ~ 50nm, and sphericity is 70% ~ 90%, and specific area is 150 ~ 300m
2/ g, pore size distribution is 10 ~ 100nm.
2. a preparation method for fuel-cell catalyst, is characterized in that, comprises the following steps:
Prepare Nano carbon microballoon, make the average grain diameter of described Nano carbon microballoon be 20 ~ 50nm, sphericity is 70% ~ 90%, and specific area is 150 ~ 300m
2/ g, pore size distribution is 10 ~ 100nm, is then loaded on described Nano carbon microballoon by metallic catalyst by infusion process, obtains described fuel-cell catalyst; Or
Form mixed solution by for the preparation of the amphipathic Carbon Materials solution of described Nano carbon microballoon and described metallic catalyst, utilize original position load method to prepare described fuel-cell catalyst.
3. preparation method according to claim 2, is characterized in that, the step preparing described Nano carbon microballoon comprises:
Amphipathic Carbon Materials solution is carried out freezing, dry, distillation, obtain Nano microsphere; Or described amphipathic Carbon Materials solution is joined in organic solvent, stirs, stratification, be separated, dry, obtain Nano microsphere; And
Described Nano microsphere is carried out charing process, obtain described Nano carbon microballoon.
4. preparation method according to claim 2, is characterized in that, described infusion process comprises:
The metal salt solution with catalytic action is mixed with mass ratio 50:1 ~ 1000:1 with described Nano carbon microballoon, stirs, obtain mixed liquor A;
In described mixed liquor A, add formalin, stir, obtain mixed liquid B;
Described mixed liquid B is separated, dries, obtain solid; And
Described solid is heat-treated respectively at 200 ~ 400 DEG C and 800 ~ 1000 DEG C, the fuel-cell catalyst that to obtain with Nano carbon microballoon be carrier.
5. preparation method according to claim 2, is characterized in that, described original position load method comprises:
The metal salt solution with catalytic action is mixed with mass ratio 5:1 ~ 100:1 with amphipathic Carbon Materials solution, stirs, obtain mixed liquor C;
In described mixed liquor C, add formalin, stir, obtain mixed liquor D;
By described mixed liquor D freeze drying, vacuum treatment, dries, obtains solid; Or in described mixed liquor D, add organic solvent, stir, stratification, be separated, dry, obtain solid; And
Described solid is heat-treated respectively at 200 DEG C ~ 400 DEG C and 800 DEG C ~ 1000 DEG C under an inert atmosphere, the fuel-cell catalyst that to obtain with Nano carbon microballoon be carrier.
6. preparation method according to claim 4, is characterized in that, also comprises before described mixed liquid B being separated:
In described mixed liquid B, add water-soluble alkali regulates the pH of solution system to be 8 ~ 9, stirs 20 ~ 120 minutes.
7. preparation method according to claim 5, is characterized in that, also comprises before described mixed liquor D being carried out to freeze drying or add organic solvent in described mixed liquor D:
Described mixed liquor D is warming up to 60 ~ 90 DEG C, the step keeping 30 ~ 300 minutes and naturally cool.
8. the preparation method according to claim 4 or 5, is characterized in that, described metal salt solution is H
2ptCl
66H
2o solution, PdCl
2solution, RuCl
2one or more mixing in solution; The quality of described metal salt solution is 1% ~ 20% than concentration.
9. preparation method according to claim 6, is characterized in that, described water-soluble alkali is one or more mixing in NaOH, potassium hydroxide, ethylenediamine, sodium carbonate, potash and cesium hydroxide.
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| CN105655600A (en) * | 2016-03-22 | 2016-06-08 | 陈波 | Preparation method of Pt-Mn-graphene catalyst for fuel cell |
| CN106025293B (en) * | 2016-07-08 | 2019-08-13 | 青岛大学 | A kind of preparation of platinum/carbon ball@zinc-iron layered double hydroxide composite material |
| CN109728267B (en) * | 2018-12-11 | 2021-09-07 | 温州大学 | Preparation method and application of composite material of phosphorus-containing micromolecule functionalized carbon nanotube |
| CN111313031B (en) * | 2020-02-26 | 2021-03-26 | 深圳氢时代新能源科技有限公司 | Composite catalyst particles, and preparation method and application thereof |
| US11772089B2 (en) * | 2021-06-03 | 2023-10-03 | University Of South Carolina | Scalable method for production of supported catalysts |
| CN114188582A (en) * | 2021-12-10 | 2022-03-15 | 东方电气(成都)氢燃料电池科技有限公司 | Fuel cell membrane electrode ionomer pretreatment method |
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| CN1817456A (en) * | 2006-03-07 | 2006-08-16 | 太原理工大学 | Production of fuel battery catalyst carrier |
| CN102351163A (en) * | 2011-07-11 | 2012-02-15 | 中国东方电气集团有限公司 | Nano carbon microsphere cathode material of lithium ion cell and its preparation method |
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| CN1817456A (en) * | 2006-03-07 | 2006-08-16 | 太原理工大学 | Production of fuel battery catalyst carrier |
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