CN1186838C - Preparation method of proton-exchange membrane fuel cell electrode catalyst - Google Patents
Preparation method of proton-exchange membrane fuel cell electrode catalyst Download PDFInfo
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Abstract
The present invention relates to a method for preparing electrode catalysts for proton exchange membrane fuel batteries, which is characterized in that the processes for preparing catalysts are carried out in an identical solvent system, and a solvent is selected from one or several kinds of dibasic alcohol and trihydric alcohol of C2 to C8 or a water solution thereof, wherein the volume percentage content of water is from 0 to 95%. In the preparing process of catalysts, the solvent performs the functions of a reducing agent, a dispersing agent and a protecting agent. The method comprises the preparing steps of preparing solution, mixing the solution, regulating the pH value of the mixed solution to an alkaline pH value, rising the temperature for reduction and utilizing hydrochloric acid solution to regulate the pH value to an acid pH value. The method of the present invention can be used for preparing metal carried catalysts with high dispersion and fine and uniform distribution without the need of preprocessing metal precursors or any surface acting agent or other high molecular organic substances as a protecting agent, and the metal content of prepared carried catalysts can reach 90%.
Description
Technical field:
The present invention relates to support type list constituent element, double elements and multicomponent Preparation of catalysts method based on Pt, and this catalyst belongs to the technical field and the fuel cell field of producing catalyst with the chemical method as the application of electrode catalyst in Proton Exchange Membrane Fuel Cells.
Background technology:
Fuel cell has the energy conversion efficiency height, and is pollution-free, advantages such as noiselessness, it is green energy resource, receive people's very big concern in recent years, especially proton exchange membrane types of fuel cells (PEMFCs) has obtained very great development, and part has obtained application as the electrical source of power of motor vehicle.Make fuel with hydrogen, although battery performance is good, but fuel source is an a great problem, the cost of high-purity hydrogen is higher, all there is huge difficulty in deposit and transportation as gaseous fuel hydrogen simultaneously, comparatively desirable method is original position hydrogen manufacturing or liquid fuel such as gasoline or all kinds of alcohol catalysis decomposing hydrogen-production at present, but contain all kinds of secondary catabolites in the hydrogen of this kind method system inevitably, as carbon dioxide, carbon monoxide etc., although through strict purification, still contain a spot of carbon monoxide in the hydrogen and extremely be difficult to remove.Even also can cause the catalyst poisoning inactivation rapidly and contain trace amounts of CO in the fuel, reduced battery efficiency and life-span significantly, the anode catalyst of therefore developing high performance anti-CO is the key that PEMFCs is promoted and is used widely.Direct methanol fuel cell (DMFCs) can directly utilize methyl alcohol to make fuel, need not in the middle of reforming unit, have advantages such as system configuration is simple, volume energy density is high, fuel supplement is convenient, be especially suitable for use as removable power supply, as mobile phone, notebook computer and electric vehicle power sources etc.At present one of key problem that is electrolytical DMFCs with proton exchange membrane is that the catalytic oxidation activity of anode methyl alcohol under the low temperature is not high, and the catalysis serious polarization need overcome higher polarization potential and could guarantee certain reaction speed.With regard to DMFCs, loss in efficiency mainly comes from catalysis polarization, the just problem of electrode catalyst.This types of fuel cells that adopts other alcohol to make fuel also has similar even even more serious anode catalyst problem.Above-mentioned two class batteries all are low temperature batterys, activity of such catalysts there is very high requirement, the electrode catalyst that can keep certain catalytic activity at present at low temperatures is still based on noble metal especially metal platinum, these noble metal deposits are limited, scarcity of resources, cost an arm and a leg, need to improve the utilization ratio of noble metal, to promote the Proton Exchange Membrane Fuel Cells development beyond doubt necessary and prepare nano level finely dispersed supported catalyst.On the other hand, form double elements or multicomponent catalyst, also can increase the catalytic activity and the stability of noble metal effectively, and the adding of other metals also helps the raising of noble metal utilance with cheap metal and these noble metals.But how to improve the decentralization of noble metal effectively, how to improve the interaction between noble metal and other component effectively, it is active and stable to improve catalyst ground, improving the utilance of noble metal resource, is the pressing issues that comprise that all kinds of Preparation of Catalyst aspect of electrode catalyst is badly in need of solving.
At the problems referred to above and requirement, many research workers have attempted the noble metal catalyst that several different methods prepares and improve electrode catalyst and other type.With regard to present with regard to the various types of electrodes method for preparing catalyst of platinum, can being divided three classes roughly.
One class is that the colloid method prepares electrode catalyst.This method mainly is by preparing metastable metal oxide colloids, and short then sedimentation or transfer on the carrier handles making again through other process.Document 1[H.G.Retrow, R.G.Allen USP 3,992,331], document 2[M.Watanabe, J.Electroanal.Chem.229 (1987) 395] and document 3[A.K.Shukla, J.Appl.Electrochem., 29 (1999) 129] mainly preparing carbon by these class methods carries platinum and Pt-Ru/C catalyst.Document 1 at first is prepared into Na with chloroplatinic acid
6[Pt (SO
3)
4], then by ion-exchange, with Na
6[Pt (SO
3)
4] in sodium ion be exchanged into hydrogen ion, heating is boiled in the air, discharges unnecessary sulfite ion, the last dry at a certain temperature oxide black colloid that makes Pt, this colloid can be distributed in water or other solvent once more, thereby supports at an easy rate on all kinds of carriers.Utilize this method, can make the Pt catalyst of 1.5～2.5 nanometers, this method is owing to just fall chloride ions displace in advance simultaneously, thereby can effectively avoid trace chlorine in the catalyst to cause the loss of catalytic activity.The method for preparing catalyst in the document 2 is at first chloroplatinic acid to be prepared into Na
6[Pt (SO
3)
4], but what be different from document 1 is that this method is not with Na
6[Pt (SO
3)
4] separate separately, but directly add excessive hydrogen peroxide its oxidation Decomposition is formed a kind of stable platinum oxide colloid, take off unnecessary hydrogen peroxide rapid branches such as the compound of dropping ruthenium such as ruthenium trichloride in this colloid then, the oxide junction of also oxidized generation ruthenium-oxide of ruthenium and platinum is synthesized the oxide cluster simultaneously, by the adjusting of pH, they are deposited on the carriers such as active carbon; Can platinum wherein be reduced into metallic state by hydrogen.The catalyst that utilizes the preparation of this method be a kind of be core with the ruthenium-oxide, platinum is positioned at the metal cluster of outer surface.The method for preparing catalyst in the document 3 is at first the chloride of platinum and ruthenium all to be transformed into sulfurous acid network and thing, i.e. Na
6[Pt (SO
3)
4] and Na
6[Ru (SO
3)
4], and it is separated.Then they are mixed and resolve into the mixed oxide colloid with hydrogen peroxide oxidation again, support on the activated carbon again.Perhaps as in the document 2 earlier with hydrogen peroxide with Na
6[Pt (SO
3)
4] oxidation Decomposition, add Na then
6[Ru (SO
3)
4] divide and take off unnecessary hydrogen peroxide, while Na
6[Ru (SO
3)
4] being transformed into ruthenium-oxide, the modulation by pH makes two kinds of metal oxide co-precipitations to activated carbon.
Another kind of is to adopt surfactant or other organic macromolecule to prepare the nano-noble metal particle of high degree of dispersion as protective agent, perhaps supports on the carrier by the nano noble metal particles of other approach with preparation.Even these class methods also still can obtain very high metal dispersity under noble metal loading condition with higher.But these class methods are very high to solvent, surfactant or protective agent and operating condition requirement, the while complicated operation, and cost is higher.Document 4[H.B nnemann, et al, USP 5,641,723] adopt the boron hydracid quaternary ammonium salt NR that has long carbochain
4BR
3H makes reducing agent and protective agent reduction platinum ruthenium and other transition metal precursors, prepares the narrower nano level metal colloid of particle size distribution range.This method requires the anhydrous and oxygen-free system, and typical preparation process is finished in the oxolane system.Adopt the performance of the anti-carbon monoxide poisoning of platinum-ruthenium alloys catalyst in hydrogen-oxygen proton exchange membrane fuel cell of this method preparation slightly to be better than commercial catalyst.
The 3rd class preparation method's characteristic feature is the dipping of noble metal precursor at carrier surface.The key of these class methods is with noble metal precursor such as PtRu such as chloroplatinic acid, Ru by dipping
3CO
12Deng under the carrier surface deposition, then by liquid-phase reduction agent such as hydrazine hydrate, boron hydrohalogenic acid salt etc., perhaps vapour phase reduction agent such as hydrogen etc. reduce to the carrier that has flooded precursor, both can make all kinds of catalyst.Utilize these class methods can prepare the multicomponent catalyst, but these class methods require carrier to have higher specific surface area, and these class methods are not easy to make noble metal to realize high degree of dispersion.To the noble metal catalyst of high loadings, the effect of this class methods preparation is not very desirable.Document 5[P.Stonehart, M.Watanabe, USP5,208,207] introduced a kind of method for preparing the platinum ruthenium palladium three constituent element catalyst that active carbon supports.At first precursor such as the acid of chlorine palladium, chloroplatinic acid and the ruthenic chloride with three kinds of metals mixes, be reduced into opaque mixture with the more weak reducing agent of reducing power such as sodium thiosulfate etc. then, add carbon carrier then, vigorous stirring forms thick slurry, heating evaporation falls solvent between 75 to 80 degree, obtain black powder, again black powder is obtained the loaded catalyst of three constituent elements with the aqueous dispersion washing and filtering.Document 6[M.D.Moser, R.J.Lawson USP 4,677,094] introduced the Preparation of catalysts method that is used for the hydrocarbon reformation hydrogen production, its quick-reading flow sheets is the platinum ashbury metal catalyst that at first prepares support type, floods other elements such as ruthenium, cobalt, rhenium, nickel, iridium then respectively on its surface.This catalyst all is significantly improved at aspects such as active and stability with respect to other catalyst.Document 7[W.Roh, J.Cho, H.Kim, J.Appl.Electrochem.26 (1996) 623] further base metal such as dipping iron copper on the basis of the Pt/C of commodity catalyst, pass through high-temperature process then, make platinum and iron copper form alloy, this catalyst electrical catalyze reduction to oxygen in phosphoric acid fuel cell shows active high than the Pt/C catalyst.
Technology contents:
The invention provides a kind of method for preparing electrode catalyst, the electrode catalyst for preparing by this method is applicable to all kinds of Proton Exchange Membrane Fuel Cellss, it is characterized in that:
The Preparation of catalysts process is carried out under same dicyandiamide solution, and solvent is selected from C2 to the dihydroxylic alcohols of C8, in the trihydroxy alcohol one or more, perhaps its aqueous solution, and wherein the volumn concentration of water is 0～95%; In the Preparation of catalysts process, this solvent plays reducing agent, dispersant, protectant effect;
Preparation process may further comprise the steps:
A, precursor compound is dissolved in the above-mentioned solvent;
B, with above-mentioned solvent preparation NaOH or potassium hydroxide solution;
C, place above-mentioned solvent to disperse preparation carrier suspension in carrier;
D, step a precursor solution is transferred in the step c carrier suspension;
F, at-10～30 ℃, step b NaOH or potassium hydroxide solution are added in the steps d mixed solution, the pH value of regulating mixed solution is to alkaline;
E, under inert gas shielding, 40～250 ℃ keep down 0.5～12 hour heating reduction;
G, extremely acid with hydrochloric acid solution adjusting pH under 0～50 ℃;
H, mixture is filtered, washing, 40～200 ℃ of vacuumizes, the nanoscale support type Pt that obtains high degree of dispersion is catalyst based.
In the proton exchange membrane fuel cell electrode Preparation of catalysts method of the present invention, the solvent that is adopted is preferably ethylene glycol, or the mixed solution of ethylene glycol and water.
In the proton exchange membrane fuel cell electrode Preparation of catalysts method of the present invention, the pH value of regulating mixed solution among the step f is preferably in more than 9; The pH value of regulating mixed solution in the step g is preferably in below 5.
In the proton exchange membrane fuel cell electrode Preparation of catalysts method of the present invention, step f is preferably under the inert gas shielding and carries out; Can use ultrasonic dispersion among the step f; Can use ultrasonic mixing in the step g.
Use the catalyst of proton exchange membrane fuel cell electrode Preparation of catalysts method preparation of the present invention, before use, can be in all kinds of atmosphere, handled 0.5～24 hour for 60～1200 ℃.
The catalyst of the inventive method preparation is not limited only to the Pt element, can be based on Pt, add the support type double elements multicomponent nanocatalyst of more other kind metal preparations based on Pt, utilize this method can prepare anode catalyst and cathod catalyst, employed carrier all has excellent conducting performance, has the material of certain electric conductivity etc. as all kinds of material with carbon elements and other.
Difference of the present invention compared with prior art is:
1, preparation nanometer Pt and alloy catalyst thereof in the document 1,3, needs at first are transformed into hydrosulfide with the chloride of Pt and Ru, though this process can be eliminated the influence of trace chlorine to catalytic performance more effectively, cause certain precious metal losses easily.
2, it is similar that document 2 prepares the method and the document 1 of catalyst, but do not remove the chloride ion step midway, the catalyst yield is higher, but it is not very high utilizing the alloying level of two kinds of metals in the catalyst of this method preparation, cooperative interaction between the metal is not strong, and noble metal does not reach very desirable stage to the catalytic action of methyl alcohol etc.
3, document 4 adopts the boron hydracid quaternary ammonium salt NR that has long carbochain
4BR
3H makes reducing agent and protective agent reduction platinum ruthenium and other transition metal precursors, prepares the narrower nano level metal colloid of particle size distribution range.This method requires the anhydrous and oxygen-free system, and typical preparation process is finished in the oxolane system.Though this method can be prepared the very little noble metal catalyst of particle diameter; but make surperficial protective agent and reducing agent owing to adopt larger molecular organics; also must in the anhydrous and oxygen-free system, prepare simultaneously; complex operation; operating condition is very harsh; the Preparation of Catalyst cost is higher, and is not suitable for the batch process of catalyst.Compare with this method, the present invention does not adopt any larger molecular organics or other surfactant, need not extra reducing agent yet, and is simple to operate, becomes instinct to reduce significantly; And the catalyst granules of preparation is still very little.
4, the three constituent element catalyst that support of the active carbon of document 5 preparation have shown the ability of anti-CO preferably, but this method uses sulfur-containing compound to make reducing agent in preparation, and the reduction be over support finish after, do not have timely filtration washing, but disperse washing after dry again, intermediate reaction form the especially various chloride sulfide of multiple salinity all together absorption deposit on the active carbon, and be not easy to remove, and the existence of these materials all causes certain influence to the performance of catalyst inevitably.
Though 5, document 6 adopts dipping method can prepare the catalyst of multicomponent, and demonstrates catalytic activity preferably, dipping method can not prepare the higher load type metal catalyst of loading.Compare with this method, the present invention can not only prepare double elements, the multicomponent group load type metal catalyst of low loading, and can also prepare the higher double elements of loading, multicomponent group load type metal catalyst, and when the metal loading is very high, still can good dispersion be arranged guarantee fund's accessory.
6, the catalyst of document 7 preparations shows active preferably to the electrical catalyze reduction of oxygen, but auxiliary agent and main catalyst component platinum do not add simultaneously, but add auxiliary agent on the Pt/C that finishes again preparing, in order to guarantee to generate necessary alloy, realize intermetallic interaction, have to catalyst is carried out high-temperature process, this causes the noble metal sintering inevitably, the metallic radius is increased, and auxiliary agent covers the surface of platinum simultaneously, has reduced the utilance of noble metal.Utilize method of the present invention, can in the preparation process of beginning, can guarantee that platinum supports on the carrier with other kinds auxiliary agent, can under low slightly temperature, can realize interacting between the metal.
Generally speaking, the present invention is by changing the composition of solvent in the dispersion, improve the viscosity of solvent, can reduce the diffusion rate of metallic in solution effectively, prevent between the metallic polymerization mutually and increase, avoid the loaded nano level Pt that adopts molecules surfactant can make the high degree of dispersion high-load catalyst based again simultaneously, can reduce the cost of preparation nanocatalyst significantly, between the various metals,, interact obviously in the while catalyst in conjunction with closely.The anode catalyst that utilizes the preparation of this method demonstrates active preferably to the catalytic oxidation of low-carbon alcohols fuel such as methyl alcohol, ethanol etc., hydrogen/oxygen (air) PEMFCs is demonstrated the ability of stronger anti-CO; Utilize the cathod catalyst of this method preparation that oxygen is had electrical catalyze reduction activity preferably.
The present invention does not adopt any surfactant or other organic protective agent can prepare the nano level platinum based electrode catalyst of high degree of dispersion high-load.Solvent cost is low, preparation easily, and catalyst preparation process is succinctly efficient, and higher noble metal yield is arranged, even in the electrode catalyst of preparation higher tenor is arranged, can guarantee that also noble metal has higher decentralization.
Utilize good material with carbon element of various electric conductivities such as all kinds of activated carbon, carbon fiber, carbon nano-tube to make carrier, the nanoscale Pt based electrode catalyst by the present invention can prepare high degree of dispersion comprises all kinds of double elements and multicomponent electrode catalyst.Also platinum, platinum/other metal can be supported on other materials with electric conductivity by the present invention and to prepare electrode catalyst, both can prepare anode catalyst and also can prepare cathod catalyst.
With such Pt based electrode catalyst that supports on good carbon carrier of electric conductivity such as all kinds of activated carbon, carbon fiber, the carbon nano-tube etc., successfully be applied to low-temperature fuel cell PEMFCs, fuel can adopt all kinds of alcoholic solutions, glucose solution, hydrogen, hydrogen/CO gaseous mixture etc., demonstrates the ability of electro catalytic activity preferably and good anti-CO.
In a word; the inventive method does not need metal precursor is carried out preliminary treatment; also need not any generally acknowledged surfactant or other macromolecule organic and make the careful even metal loaded catalyst of distribution that protective agent can prepare high degree of dispersion, the loaded catalyst tenor of preparation can be up to 90%.
Description of drawings:
Monocell performance map (methyl alcohol is made fuel) when Fig. 1 makes anode catalyst for the catalyst that adopts the present invention's preparation;
The monocell operating condition:
Battery temperature: 90 ℃; Dielectric film: Nafion-115; Electrode area: 9cm
2
Methanol concentration: 1 mol; Methyl alcohol flow velocity: 1 ml/min; Negative electrode (oxygen electrode) oxygen pressure: 2 atmospheric pressure;
Negative electrode (oxygen electrode) catalyst: Pt/C (20Pt%, Johnson Matthey); Noble metal dosage: 1mgPt/cm
2
Anode catalyst: PtRu/C (20Pt10Ru%); Noble metal dosage: 2mgPtRu/cm
2
★: anode adopts self-control catalyst Pt Ru/C (20Pt10Ru%, embodiment 1, curve 1 and 3);
●: anode adopts commercial catalyst PtRu/C (20Pt10Ru%, Johnson Matthey, curve 2 and 4).
Monocell performance map (methyl alcohol is made fuel) when Fig. 2 makes anode catalyst for the catalyst that adopts the present invention's preparation;
The monocell operating condition:
Battery temperature: 75 ℃; Dielectric film: Nafion-115; Electrode area: 9cm
2
Methanol concentration: 1 mol, methyl alcohol flow velocity: 1 ml/min; Negative electrode (oxygen electrode) oxygen pressure: 2 atmospheric pressure;
Negative electrode (oxygen electrode) catalyst: Pt/C (20Pt%, Johnson Matthey); Noble metal dosage: 1mgPt/cm
2
Anode catalyst: PtRu/C (20Pt10Ru%); Noble metal dosage: 2mgPtRu/cm
2
★: anode adopts self-control catalyst Pt Ru/C (20Pt10Ru%, embodiment 1, curve 1 and 3);
●: anode adopts commercial catalyst PtRu/C (20Pt10Ru%, Johnson Matthey, curve 2 and 4).
Monocell performance map (methyl alcohol is made fuel) when the catalyst that Fig. 3 adopts the present invention to prepare is made anode catalyst;
The monocell operating condition:
Dielectric film: Nafion-115; Electrode area: 9cm
2
Methanol concentration: 1 mol; Methyl alcohol flow velocity: 1 ml/min;
Negative electrode (oxygen electrode) oxygen pressure: 2 atmospheric pressure;
Negative electrode (oxygen electrode) catalyst: Pt/C (20Pt%, Johnson Matthey); Noble metal dosage: 1mgPt/cm
2
Anode catalyst: self-control PtRu/C (60Pt30Ru%, embodiment 3); Noble metal dosage: 2mgPtRu/cm
2
■: the current/voltage curve when battery temperature is 25 ℃;
●: the current/voltage curve when battery temperature is 75 ℃;
▲: the current/voltage curve when battery temperature is 90 ℃.
Monocell performance map (methyl alcohol is made fuel) when the catalyst that Fig. 4 adopts the present invention to prepare is made anode catalyst;
The monocell operating condition:
Dielectric film: Nafion-115; Electrode area: 9cm
2:
Methanol concentration: 1 mol; Methyl alcohol flow velocity: 1 ml/min; Negative electrode (oxygen electrode) oxygen pressure: 2 atmospheric pressure;
Negative electrode (oxygen electrode) catalyst: Pt/C (20Pt%, Johnson Matthey); Noble metal dosage: 1mgPt/cm
2
Anode catalyst: self-control PtRu/C (40Pt20Ru%, embodiment 2); Noble metal dosage: 2mgPtRu/cm
2
■: the current/voltage curve when battery temperature is 25 ℃;
●: the current/voltage curve when battery temperature is 75 ℃;
▲: the current/voltage curve when battery temperature is 90 ℃.
Monocell performance map (ethanol is made fuel) when the catalyst that Fig. 5 adopts the present invention to prepare is made anode catalyst;
The monocell operating condition:
Dielectric film: Nafion-115; Electrode area: 9cm
2
Concentration of alcohol: 1 mol, ethanol flow velocity: 1 ml/min; Negative electrode (oxygen electrode) oxygen pressure: 2 atmospheric pressure;
Negative electrode (oxygen electrode) catalyst: Pt/C (20Pt%, Johnson Matthey); Noble metal dosage: 1mgPt/cm
2
Anode catalyst; PtRu/C (20Pt10Ru% embodiment 1); Noble metal dosage: 2mgPtRu/cm
2
●: the experimental result when battery temperature is 90 ℃ (1,3);
★: the experimental result when battery temperature is 75 ℃ (2,4).
Embodiment:
The particular content of embodiment of the invention technical scheme is as follows, does not limit the present invention certainly:
1, choice of Solvent: ethylene glycol, or the mixed solution of ethylene glycol and water, wherein the volumn concentration of water is 0～95%.
2, obtain solution:
(1), the precursor compound of Pt such as chloroplatinic acid or potassium chloroplatinate etc. are dissolved in the solvent in above-mentioned 1, preparation content is the solution of 0.01～500mgPt/ml.Also with solvent or directly water dissolving in above-mentioned 1, solution metal content is 0.01～500mg/ml with the precursor compound of other metal.These metals comprise ruthenium, tin, iridium, osmium, palladium, gold, silver, copper, iron, nickel, cobalt, chromium, molybdenum, tungsten, rhodium etc.Perhaps according to the requirement of preparation catalyst, by the metal ratio of demand Pt precursor and needed other metal precursor are dissolved into a kind of solvent and are mixed with mixed solution.
(2), utilize the solvent in above-mentioned 1, preparation NaOH or potassium hydroxide solution, its concentration is 0.01～4 mol.
3, with carrier before test 40～250 ℃ of air dryings 0.5～24 hour, with above-mentioned 1 in solvent or directly mix (wherein the solvent that requires of every milligram of carrier is 0.01～1000 milliliter) with water, sonic oscillation disperseed 5～60 minutes, preparation carrier suspension.Carrier comprises that all kinds of material with carbon elements with excellent conductive performance such as activated carbon, carbon nano-tube, carbon fiber and other have the material of certain electric conductivity, perhaps the mixture of above-mentioned carrier material.
4, require according to catalyst requirement and metallic atom ratio; measure platinum precursor solution or other metal precursor solutions (catalyst of preparation one-component) of preparation in above-mentioned 2; perhaps will be wherein two kinds or several solution that contain single metal precursor mix; the mixed solution (preparation double elements or multicomponent catalyst) that perhaps contains platinum and other metals; sonic oscillation mixed 5～180 minutes; transfer to then that sonic oscillation is after 5～250 minutes in the prepared carrier suspension of above-mentioned steps 3, inert gas shielding was stirred 0.5～24 hour down.
5, at-10～30 ℃; under the inert gas shielding, NaOH or potassium hydroxide solution in an amount of above-mentioned 3 are added in the prepared mixed solution of step 4, the pH value of regulating mixed solution is to alkalescence; particularly more than 9, sonic oscillation mixed 5～600 minutes.Inert gas shielding was stirred 0.5～24 hour down, kept 0.5～12 hour heating reduction down at 40～250 ℃.
6, under 0～50 ℃, regulate pH to acid,, stirred 0.5～24 hour, perhaps keep 0.5～24 hour to promote sedimentation at 50～170 ℃ particularly below 5 with hydrochloric acid solution.Mixture is filtered, a large amount of hot deionized water washings, 40～200 ℃ of vacuumizes, the nanoscale support type Pt that can obtain high degree of dispersion is catalyst based.
7, all kinds of platinum based catalysts that above-mentioned steps can be prepared were handled 0.5～24 hour for 60～1200 ℃, as oxidizing atmosphere, reducing atmosphere, inert gas etc. in all kinds of atmosphere.Also can use without handling directly.
9, the catalyst based catalyst that especially supports on all kinds of material with carbon elements of the load type platinum of above-mentioned steps preparation is applied on all kinds of supporters such as carbon paper, the carbon cloth etc. according to the program for preparing electrode, with each based solid electrolyte at 80～240 ℃, hot pressing is 10～1000 seconds under 2～50 atmospheric pressure, make membrane electrode assembly (MEA), be assembled into battery.
10, at the gaseous mixture of solution, hydrogen, hydrogen/CO gaseous mixture, hydrogen body and other gases of logical each class A fuel A of the anode-side of above-mentioned battery such as all kinds of alcohol or glucose etc., at logical oxygen of cathode side or air, discharge in the time of 0～170 ℃.
The preparation of embodiment 1:PtRu/C (20Pt10Ru%) anode catalyst
Activated carbon XC-72R handles with the salpeter solution of 5mol/L in advance, and 200 ℃ of dryings take by weighing 25 milliliters of ethylene glycol of 500 milligrams of usefulness and water after 4 hours mixed solvent (wherein the volume content of water is 5%) sonic oscillation disperses to make in 30 minutes carbon and starches.Measure 19.5 milliliters of chloroplatinic acid/ethylene glycol solutions (7.4 milligrams of platinum/milliliters), measure ruthenium trichloride/ethylene glycol+aqueous solution (volume content 10% of water wherein, 6.4 11.2 milliliters of mixing milligram ruthenium/milliliter), sonic oscillation is added drop-wise to after 20 minutes in the carbon slurry, logical argon gas deoxygenation was stirred after 10 hours, drip 15 milliliters of the NaOH/ethylene glycol solutions of 1 mol, continue to stir and be warming up to 185 ℃ of maintenances 4 hours after 5 hours, be cooled to 25 ℃ then, diluted hydrochloric acid aqueous solution adjust pH to 3 with 1 mol, stir after 3 hours, filter, filtrate is as clear as crystal.70 ℃ of vacuumizes of solid obtained the catalyst of 20%Pt-10Ru% in 8 hours, and yield is 98.8%.Transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 2.5 nanometers.
The preparation of embodiment 2:PtRu/C (40Pt20Ru%) anode catalyst
Activated carbon XC-72R handles with the salpeter solution of 5mol/L in advance, and 200 ℃ of dryings take by weighing 50 milliliters of ethylene glycol of 500 milligrams of usefulness and water after 4 hours mixed solvent (wherein the volume content of water is 5%) sonic oscillation disperses to make in 30 minutes carbon and starches.Measure 25 milliliters of chloroplatinic acid/ethylene glycol solutions (20 milligrams of platinum/milliliters), measure ruthenium trichloride/ethylene glycol+aqueous solution (volume content 10% of water wherein, 10 milligrams of ruthenium/milliliters) 25 milliliters of mixing, sonic oscillation is added drop-wise to after 20 minutes in the carbon slurry, logical argon gas deoxygenation was stirred after 10 hours, drip 15 milliliters of the NaOH/ethylene glycol solutions of 1 mol, continue to stir and be warming up to 180 ℃ of maintenances 4 hours after 5 hours, be cooled to 25 ℃ then, diluted hydrochloric acid aqueous solution adjust pH to 2.5 with 1.5 mol, stir after 5 hours, filter, filtrate is as clear as crystal.70 ℃ of vacuumizes of solid obtained the catalyst of 40%Pt-20Ru% in 8 hours.Yield 93%, transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 3.0 nanometers.
Embodiment 3:PtRu/C (60Pt30Ru%) Preparation of catalysts
Activated carbon XC-72R handles with the salpeter solution of 5mol/L in advance, and 200 ℃ of dryings take by weighing 20 milliliters of ethylene glycol of 200 milligrams of usefulness and water after 4 hours mixed solvent (wherein the volume content of water is 5%) sonic oscillation disperses to make in 30 minutes carbon and starches.Measure 24 milliliters of chloroplatinic acid/ethylene glycol solutions (50 milligrams of platinum/milliliters), measure 20 milliliters of mixing of ruthenium trichloride/ethylene glycol (30 milligrams of ruthenium/milliliters), sonic oscillation is added drop-wise to after 50 minutes in the carbon slurry, logical argon gas deoxygenation was stirred after 10 hours, drip 10 milliliters of the NaOH/ethylene glycol solutions of 2 mol, continue to stir and be warming up to 180 ℃ of maintenances 6 hours after 5 hours, be cooled to 25 ℃ then, diluted hydrochloric acid aqueous solution adjust pH to 2.5 with 1.5 mol, stir after 5 hours, filter, filtrate is as clear as crystal.70 ℃ of vacuumizes of solid obtained the catalyst of 60%Pt-30Ru% in 8 hours, yield 86%, and transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 3.0 nanometers.
Embodiment 4:PtRu/ carbon nano-tube (20Pt10Ru%) Preparation of catalysts
Carbon nano-tube is passed through sulfuric acid treatment in advance.200 ℃ of dryings take by weighing 25 milliliters of ethylene glycol of 500 milligrams of usefulness and water after 4 hours mixed solvent (wherein the volume content of water is 5%) sonic oscillation disperses to make in 30 minutes carbon nano tube suspension.Measure 19.5 milliliters of chloroplatinic acid/ethylene glycol solutions (7.4 milligrams of platinum/milliliters), measure ruthenium trichloride/ethylene glycol+aqueous solution (volume content 5% of water wherein, 6.4 11.2 milliliters of mixing milligram ruthenium/milliliter), sonic oscillation was added drop-wise in the carbon nano tube suspension after 20 minutes, logical argon gas deoxygenation was stirred after 10 hours, drip 15 milliliters of the NaOH/ethylene glycol solutions of 1 mol, continue to stir and be warming up to 185 ℃ of maintenances 4 hours after 5 hours, be cooled to 25 ℃ then, diluted hydrochloric acid aqueous solution adjust pH to 3 with 1 mol, stir after 3 hours, filter, filtrate is as clear as crystal.70 ℃ of vacuumizes of solid obtained the catalyst of 20%Pt-10Ru% in 8 hours.Yield 95%, transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 3.0 nanometers.
Embodiment 5:PtCo/C (20Pt%, Pt/Co=2: the 1) preparation of cathod catalyst
Activated carbon XC-72R disperses to make in 30 minutes the carbon slurry at 200 ℃ of dryings take by weighing 25 milliliters of ethylene glycol of 500 milligrams of usefulness and water after 4 hours mixed solvent (wherein the volume content of water is 4%) sonic oscillation in advance.Measure 19.5 milliliters of chloroplatinic acid/ethylene glycol solutions (7.4 milligrams of platinum/milliliters), measure cobalt nitrate/ethylene glycol+aqueous solution (volume content 5% of water wherein, 7.0 11.0 milliliters of mixing milligram cobalt/milliliter), sonic oscillation is added drop-wise to after 40 minutes in the carbon slurry, logical argon gas deoxygenation was stirred after 10 hours, drip 10 milliliters of the NaOH/ethylene glycol solutions of 1.5 mol, continue to stir and be warming up to 185 ℃ of maintenances 6 hours after 16 hours, be cooled to 25 ℃ then, diluted hydrochloric acid aqueous solution adjust pH to 3 with 1 mol, stir after 8 hours, filter, filtrate is as clear as crystal.70 ℃ of vacuumizes of solid obtained the PtCo/C catalyst in 8 hours.Yield 97.7%, transmission electron microscope and X-ray diffraction experiment result show that the double elements metal particle size is below 3.0 nanometers.
The preparation of embodiment 6:Pt/C (20Pt%) electrode catalyst
Activated carbon XC-72R disperses to make in 50 minutes the carbon slurry at 200 ℃ of dryings take by weighing 60 milliliters of ethylene glycol of 600 milligrams of usefulness and water after 10 hours mixed solvent (wherein the volume content of water is 10%) sonic oscillation in advance.Measure 15 milliliters of chloroplatinic acid/ethylene glycol solutions (10.0 milligrams of platinum/milliliters), be added drop-wise in the carbon slurry, logical argon gas deoxygenation was stirred after 12 hours, drip 5 milliliters of the NaOH/ethylene glycol solutions of 1.0 mol, continue to stir and be warming up to 170 ℃ after 16 hours and kept 3 hours, reduce to room temperature then, diluted hydrochloric acid aqueous solution adjust pH to 3.5 with 0.2 mol, stir after 8 hours, filter, filtrate is as clear as crystal.70 ℃ of vacuumizes of solid obtained the PtCo/C catalyst in 8 hours.Yield 97.0%, transmission electron microscope and X-ray diffraction experiment result show that the double elements metal particle size is below 3.0 nanometers.
Embodiment 7:PtRuIr/C (20Pt%, Pt/Ru/Ir=2: 1: 1) Preparation of catalysts
Activated carbon XC-72R takes by weighing 40 milliliters of ethylene glycol sonic oscillations of 650 milligrams of usefulness 200 ℃ of dryings in advance and disperses to make in 30 minutes the carbon slurry after 4 hours.Measure chloroplatinic acid/ethylene glycol+aqueous solution (volume content 2% of water wherein, 7.4 milligram platinum/milliliter) 27 milliliters, measure 5.8 milliliters of mixing of ruthenium trichloride/ethylene glycol (9 milligrams of ruthenium/milliliters), measure chloro-iridic acid/ethylene glycol+aqueous solution (volume content 10% of water wherein, 6 milligrams of iridium/milliliters) 16.5 milliliters, sonic oscillation is added drop-wise to after 30 minutes in the carbon slurry, logical argon gas deoxygenation was stirred after 10 hours, drip 15 milliliters of the NaOH/ethylene glycol solutions of 1 mol, continue to stir and be warming up to 180 ℃ after 12 hours and kept 8 hours, be cooled to 25 ℃ then, diluted hydrochloric acid aqueous solution adjust pH to 3.5 with 1.5 mol, stir after 5 hours, filter, filtrate is as clear as crystal.70 ℃ of vacuumizes of solid obtained the catalyst (total metal contents in soil is 35%) of 20%Pt-5.2Ru%-10% in 8 hours.Yield 98%, transmission electron microscope and X-ray diffraction experiment result show that three constituent element noble metal granule sizes are below 2.5 nanometers.
The preparation of embodiment 8:PtCuFe/C (20Pt%, Pt/Cu/Fe=2: 1: 1) cathod catalyst
1 gram chloroplatinic acid is dissolved into (7.4 milligrams of platinum/milliliters) in 50 milliliters of ethylene glycol, with 0.236 gram CuSO
45H
2O and 0.256 gram FeCl
36H
2O dissolves with 10 ml deionized water, and two kinds of solution are mixed, and sonic oscillation disperseed 120 minutes.Activated carbon XC-72R takes by weighing 1.36 mixed solvent (wherein the volume content of water the is 10%) sonic oscillations that restrain with 100 milliliters of ethylene glycol and water 200 ℃ of dryings in advance and disperses to make in 60 minutes the carbon slurry after 10 hours.The mixed solution of metal is added drop-wise in the carbon slurry, logical argon gas deoxygenation was stirred after 10 hours, drip 15 milliliters of the NaOH/ethylene glycol solutions of 1.0 mol, continue to stir and be warming up to 170 ℃ of maintenances 4 hours after 16 hours, reduce to room temperature then,, be warming up to 80 ℃ again and stir after 8 hours with the diluted hydrochloric acid aqueous solution adjust pH to 3.5 of 0.2 mol, filter, filtrate is as clear as crystal.70 ℃ of vacuumizes of solid obtained the PtCuFe/C cathod catalyst in 8 hours.Yield 98.7%, transmission electron microscope and X-ray diffraction experiment result show that the double elements metal particle size is below 3.0 nanometers.
Embodiment 9:PtNi/ carbon nano-tube (20Pt10Ni%) Preparation of catalysts
Carbon nano-tube is passed through sulfuric acid treatment in advance.200 ℃ of dryings take by weighing 25 milliliters of glycerol of 500 milligrams of usefulness and water after 4 hours mixed solvent (wherein the volume content of water is 20%) sonic oscillation disperses to make in 30 minutes carbon nano tube suspension.(wherein the volume content of water is 10% to measure the mixed solution of chloroplatinic acid/glycerol and water, 7.4 milligram platinum/milliliter) 19.5 milliliters, (wherein the volume content of water is 10% to measure the mixed solution of nickel nitrate/glycerol and water, 8 milligrams of nickel/milliliters) 9 milliliters of mixing, sonic oscillation was added drop-wise in the carbon nano tube suspension after 50 minutes, logical argon gas deoxygenation was stirred after 12 hours, drip 15 milliliters of the NaOH/ethylene glycol solutions of 1 mol, continue to stir and be warming up to 175 ℃ of maintenances 5 hours after 5 hours, be cooled to 25 ℃ then,, stir after 5 hours with the diluted hydrochloric acid aqueous solution adjust pH to 3.5 of 1 mol, filter, filtrate is as clear as crystal.70 ℃ of vacuumizes of solid obtained the catalyst of 20%Pt-10Ni% in 8 hours.Yield 95%, transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 3.0 nanometers.
Embodiment 10: the Application Example of the catalyst of preparation on fuel cell
Make the anode catalyst of DMFCs, assembling monocell with the PtRu/C catalyst of embodiment 1～9 preparation.The catalyst that for example adopts embodiment 1 to prepare is made oxygen agent catalyst and is done the monocell experiment: weigh the Pt-Ru/C (20Pt%wt, 10Ru%wt) 67mg and an amount of H that get in the balance
2After O and ethanol mix, add 5% Nafion 150mg, after ultrasonic oscillation is even, be coated onto 10cm
2Supporting layer on, the preparation anode, wherein the noble metal total content is 2mg/cm
2Weigh in the balance and get the Pt/C catalyst that content is 20%wt (Johnson Matthey commercial catalyst) 50mg and an amount of H
2After O and ethanol mix, add 20% polytetrafluoroethylene PTFE aqueous solution 62.5mg, after ultrasonic oscillation is even, be coated onto 10cm
2Supporting layer on, make negative electrode.With the Nafion solution of the negative electrode that makes and anode-catalyzed laminar surface spraying 5%, consumption is 1mg/cm
2Then with the Nafionl15 film 130 ℃ of 90 seconds of following hot pressing, promptly make membrane electrode assembly, one or several stainless (steel) wires are respectively put in the membrane electrode assembly both sides, the assembling monocell.Two pole plates of battery are corrosion resistant plate, and the battery effective area is 9cm
2Feed methanol aqueous solution in the anode-side, concentration is 1mol/L, and flow velocity is 1ml/min.Aerating oxygen in the cathode side, pressure are 0.2MPa.With after inserting heating rod in two pole plates battery temperature being raised to 75 ℃, begin the discharge running.After treating that cell discharge performance is stable, measure the voltage/current density curve of battery.Its performance curve is seen accompanying drawing.In addition, (20Pt%wt 10Ru%wt) makes anode electrocatalyst, prepares anode according to top step, assembling monocell, the test of making comparisons to adopt Johnson Matthey commercial catalyst PtRu/C.
Claims (7)
1, a kind of proton exchange membrane fuel cell electrode Preparation of catalysts method is characterized in that:
The Preparation of catalysts process is carried out under same dicyandiamide solution, and solvent is ethylene glycol, glycerol or its aqueous solution, and wherein the volumn concentration of water is 0～10%;
Preparation process may further comprise the steps:
A, Pt and other metal component are comprised that the precursor compound of ruthenium, iridium, osmium, palladium, gold, silver, copper, iron, nickel, cobalt, chromium, molybdenum, rhodium is dissolved in the above-mentioned solvent, perhaps that the precursor compound of copper, iron is directly soluble in water, Pt content is 0.01～500mg/ml in the solution, and other tenor is 0.01～500mg/ml;
B, with above-mentioned solvent preparation NaOH or potassium hydroxide solution, its concentration is 0.01～4 mol;
C, the material with carbon element carrier that conductivity is good place above-mentioned solvent to disperse preparation carrier suspension;
D, step a precursor solution is transferred in the step c carrier suspension;
F, at-10～30 ℃, the NaOH or the potassium hydroxide solution of step b preparation is added in the steps d mixed solution, the pH value of regulating mixed solution is to alkaline;
E, under inert gas shielding, 40～250 ℃ keep down 0.5～12 hour heating reduction;
G, extremely acid with hydrochloric acid solution adjusting pH value under 0～50 ℃;
H, mixture is filtered, washing, 40～200 ℃ of vacuumizes, the nanoscale support type Pt that obtains high degree of dispersion is catalyst based;
Above-mentioned preparation process is all under agitation carried out.
2, according to the described proton exchange membrane fuel cell electrode Preparation of catalysts of claim 1 method, it is characterized in that: regulate more than the pH value to 9 of mixed solution among the step f.
3, according to the described proton exchange membrane fuel cell electrode Preparation of catalysts of claim 2 method, it is characterized in that: regulate below the pH value to 5 of mixed solution in the step g.
4, according to the described proton exchange membrane fuel cell electrode Preparation of catalysts of claim 1 method, it is characterized in that: step f carries out under inert gas shielding.
5, according to the described proton exchange membrane fuel cell electrode Preparation of catalysts of claim 1 method, it is characterized in that: use ultrasonic dispersion among the step f.
6, according to the described proton exchange membrane fuel cell electrode Preparation of catalysts of claim 1 method, it is characterized in that: use ultrasonic mixing in the step g.
7, according to the described proton exchange membrane fuel cell electrode Preparation of catalysts of claim 1 method, it is characterized in that: before the use, the platinum based catalyst of preparation was handled 0.5～24 hour at 60～1200 ℃.
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| CN103000908A (en) * | 2011-09-08 | 2013-03-27 | 中国科学院过程工程研究所 | Metal/YSZ Composite electrode preparation method |
| CN103191726A (en) * | 2013-03-19 | 2013-07-10 | 燕山大学 | Preparation method of fuel-cell catalyst |
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