CN100511789C - Anode catalyst of high active PtNi base proton exchange film fuel cell - Google Patents
Anode catalyst of high active PtNi base proton exchange film fuel cell Download PDFInfo
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- CN100511789C CN100511789C CNB2005100459899A CN200510045989A CN100511789C CN 100511789 C CN100511789 C CN 100511789C CN B2005100459899 A CNB2005100459899 A CN B2005100459899A CN 200510045989 A CN200510045989 A CN 200510045989A CN 100511789 C CN100511789 C CN 100511789C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
This invention relates to an anode catalyst of a high active PtNi-base proton exchange membrane fuel batteries, in which, the active components include Pt and Ni at least, which recovers a precursor of an active component and carries it to a conductive carbon carrier, then synthesizes them under the recovery atmosphere, when the invented catalyst is used as an anode catalyst, it can either reduce the adsorption of CO on Pt or oxidate CO on the Pt to the rich H2 gas fuel containing CO to show an excellent anti-CO ability and active hydroxide.
Description
Technical field
The present invention relates to Proton Exchange Membrane Fuel Cells, specifically a kind of anode catalyst of high active PtNi base proton exchange film fuel cell.
Background technology
Fuel cell is a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) that can directly chemical energy be converted into electric energy.Because be not subjected to the restriction of Carnot cycle, fuel cell has the high advantage of energy conversion efficiency, fuel cell also has eco-friendly characteristics simultaneously, thereby is subject to people's attention day by day.Particularly Proton Exchange Membrane Fuel Cells because working temperature is low, starts soon, and specific power density is big, and volume and weight is all smaller, is well suited for the power supply as compact power and electric automobile, has caused the concern that people are increasingly extensive in recent years.
Hydrogen is the optimal fuel of Proton Exchange Membrane Fuel Cells (PEMFC), and the Pt/C catalyst is the highest active at present hydroxide reaction (HOR) catalyst.But the trace amounts of CO that contains in the hydrogen that makes by reformation natural gas, methyl alcohol and other liquid fuel has strong poisoning effect to Pt, and the performance of battery is descended greatly.This poisoning effect of CO is a key factor that hinders PEMFC commercialization process.
CO poisons Pt and mainly comes from the adsorption free energy of CO on Pt less than H
2Adsorption free energy on Pt, thereby most Pt active sites are occupied by CO and can not be used for HOR reaction.
In recent years, people have reported the Pt based alloy catalyst that some anti-CO poison, as PtRu/C, and PtNi/C, PtSn/C, PtIr/C, binary catalyst and three-way catalysts such as PtRuW/C, PtRuMo/C, PtRuSn/C and PtRuNi/C such as PtRh/C.
People such as M.Gotz (document 1: " Binary and ternary anode catalyst formulations includingthe elements W; Sn and Mo for PEMFCs operated on methanol oer reformategas ", Electrochimica Acta.43 (1998) 3637) report, have good CO resistance performance in the binary catalyst in the PtRu/C catalyst.
People such as Kyung-Won Park (document 2: " Chemical and effects of Niin Pt/Ni and Pt/Ru/Nialloy nanoparticles in methanol electrooxidation ", J.Phys.Chem.B106 (2002) 1869) reported that the PtRuNi/C catalyst has the CO resistance performance that is higher than PtRu/C.
However, the performance of CO-resistance catalyst still has big gap from the business-like requirement of fuel cell at present.Improve existing technology or develop new technology, when improving the anti-CO ability of catalyst, further increase its HOR activity, and then the performance of raising PEMFC is to realize its business-like important prerequisite.
For alloy catalyst, satisfy that active component is approaching on atomic scale, particle size is nanoscale and granularity and forming when distributing all uniformly condition, catalyst can show excellent performance.CO-resistance catalyst particularly, when reaching this and requiring, not only the absorption of CO on Pt weakens, and since other component that adds on atomic scale near Pt, can when hanging down overpotential, dissociate and adsorb the H2O molecule, the formation activation-OH functional group, oxidize away thereby can easily Pt be gone up the CO that adsorbs, for the HOR reaction discharges a large amount of active sites, thereby can improve the CO resistance performance of fuel cell greatly.
Hard people's (the document 3: " preparation method of a kind of high loadings double elements or multicomponent noble metal catalyst " that waits; CN1171670C) with polyalcohol simultaneously as solvent, reducing agent and protective agent; by the viscosity of regulation and control reaction medium, prepare the binary or the polynary noble metal catalyst of high content of metal.This scheme adopts common Convective Heating, exists the inhomogeneous and slow shortcoming of reaction rate of heating.
People's (documents 4: " Catalyst material " such as Lindsey Keck, US 5068161) disclosed a kind of with the active component predecessor in the alkali condition deposit to carbon carrier, reduce then and carry out high-temperature alloy and handle the platinum base alloy Preparation of catalysts method obtain high platinum content.But this procedure is long, and is consuming time many, and has a large amount of gases to produce in the preparation, occurs the accident of material splash easily.
As seen, develop safe, simple and easy, preparation technology fast and efficiently, the synthetic high activity CO-resistance catalyst that satisfies aforementioned requirement also is a factor that realizes that the Catalyst Production industrialization must be considered.
In recent years, with microwave applications in Preparation of catalysts, utilize microwave can be fast, equably to the characteristics of reactant heating, the multicomponent catalyst that obtain that particle diameter is little, granularity and composition is evenly distributed has caused people's extensive concern.
People such as Shen Peikang (document 5: " preparation method of low-temperature fuel cell nanocatalyst ", CN 1395335A) have reported that a kind of the utilization microwave inducedly once is carried on technology on the carrier with active component.Adopt the catalyst of this technology preparation have granularity little, be evenly distributed and characteristics that electro-chemical activity is high.But this technology has adopted poisonous or mordant chemicals such as formaldehyde, formic acid or sodium borohydride to make reducing agent.
People's (documents 6: " Physical and elevtrochemical characterizations ofmicrowave-assisted polyol preparation of carbon-supported PtRu nanoparticles " such as Zhaolin Liu, Langmuir 20 (2004) 181) reported that microwave-assisted polyalcohol legal system is equipped with the PtRu/C catalyst, during as the direct methanol fuel cell anode catalyst, has preferable performance.
Ito Yusuke (document 7: " Method for reforming complex metal particle ", JP2003286509) report a kind of method of improving multicomponent precious metal colloid particle composition non-uniform phenomenon with microwave, obtained forming catalyst even, performance improvement.Yet this arts demand uses polyacrylic acid, polypropylene amine, polyvinyl alcohol isocolloid stabilizer, has not only increased the catalyst cost, has also introduced impurity inevitably in product.
Summary of the invention
The object of the present invention is to provide a kind of PtNi matrix proton exchange film fuel cell anode catalyst, its preparation process technological process is simple, consuming time few, cost is low, active component once can be carried on the carrier simultaneously, can obtain the catalyst of high metal loading; Simultaneously, the solvent that uses in the catalyst preparation process, reducing agent and dispersant safety, nontoxic.
For achieving the above object, the technical solution used in the present invention is:
A kind of anode catalyst of high active PtNi base proton exchange film fuel cell, at least contain two kinds of metallic elements of Pt and Ni in the active component, the atomic ratio of Pt and Ni is 1:1, and the weight metal percentage composition is 30-80% in the catalyst, described Preparation of catalysts process is as follows
1) soluble metal active component predecessor is dissolved in the solvent, obtains solution A;
2) with electroconductive carbon carrier and dispersant mixed, obtain slurry B by 20～100ml dispersant/g carrier;
3) solution A and slurry B are mixed, stirring hydroxide, carbonate or bicarbonate (as: solution of solvent described in the aqueous solution of hydroxide, carbonate or the bicarbonate of powder, 0.1～3M alkali metal or alkaline-earth metal and/or the step 1)) the accent pH value that adds alkali metal or alkaline-earth metal is 10～14, obtains slurry C;
4) with slurry C with microwave continuous or intermittently heating (is prerequisite so that bumping not to take place) 1～30 minute, be cooled to room temperature, add hydrochloric acid, oxalic acid, acetic acid, sulfuric acid or nitric acid then to pH value≤6, obtain slurry D;
5) slurry D is carried out Separation of Solid and Liquid, and water, ethanol and/or isopropyl alcohol (but mixing of arbitrary proportion) washing solid is mutually to neutral and do not have a Cl
-, drying obtains pressed powder E;
6) with pressed powder E at reproducibility air-flow (as: H
2/ N
2, H
2/ Ar, CH
4/ N
2, CH
4/ Ar etc.) handled 1～8 hour down for 300～800 ℃ in, be cooled to room temperature after, promptly get catalyst of the present invention.
Can also contain IIIB in the periodic table of elements, IVB, VB in the described catalyst, VIB, VIIB, the metallic element of one or more in VIIIB and the IB family is as active component (other element can add by arbitrary proportion), and wherein Pt and Ni account for 30% of total weight metal content at least; The active component that can add usually in the catalyst is one or more among Ru, Rh, Pd, Os, Ir, Au, Ag, Ti, Mo, W, Fe and the Re; Be preferably among Ru, Rh, Pd, Os, Ir, Au and the Ag one or more; The weight content of the active component in the catalyst is generally 30-60%;
Soluble inorganic salts such as the nitrate that described soluble metal active component predecessor is a respective metal, sulfate, acetate, halide, or solubility organic compounds such as dinitroso two amine salt, acetylacetonate, or encircle in complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and the polymer thereof one or more greatly; Electroconductive carbon carrier can be graphitic carbon, carbon nano-tube, carbon fiber, carbosphere and/or carbon aerogels; Solvent can be water, C
2～C
8Monohydric alcohol (as: ethanol, isopropyl alcohol), C
2～C
8Dihydroxylic alcohols (as: ethylene glycol) and/or C
2～C
8Trihydroxy alcohol (it can be the mixed solution that mixes by arbitrary proportion); Dispersant can be water, C
2～C
8Monohydric alcohol, C
2～C
8Dihydroxylic alcohols, C
2～C
8Trihydroxy alcohol and/or the carboxylate (it can be the mixed solution that mixes by arbitrary proportion) of deriving by these alcohol;
The frequency of oscillation of described microwave is 1～50 Gigahertz (being generally 2～20 Gigahertzs), and microwave output power is 400～1000W (being generally 500-800W); The reproducibility component is (as H in the reproducibility air-flow
2, CH
4) percentage by volume be generally 0.5-10%, be preferably 1-5%.
The present invention has following advantage:
1. formed alloy between the activity of such catalysts component.The present invention is even by microwave, Fast Heating, a large amount of metal crystal seeds approaching on atomic scale have been generated at short notice, and in follow-up heat treatment, form alloy, the absorption of CO on Pt is weakened, thereby the feasible quantity that can be used for the Pt active sites of HOR increases greatly, has improved CO resistance performance.
2. in the application process, the CO of the last absorption of Pt can be oxidized away effectively.Catalyst of the present invention in use, H
2The O molecule can be than dissociating under the electronegative potential and forming the oxygen-containing functional group that is adsorbed on Ni and other metal (as: OH).Because active component is close on atomic scale in the catalyst, has formed alloy, the CO that adsorbs on the Pt active sites can generate the CO nontoxic to the Pt active sites at an easy rate by contiguous Ni and the oxygen-containing functional group oxidation on other metal
2Thereby, further improved CO resistance performance.
3. has high activity to HOR.Because microwave heating has evenly, characteristics fast, the average grain diameter of activity of such catalysts component on carrier little (less than 4nm) of preparation, and even particle size distribution, narrow distribution range, thereby have high activity to HOR.
4. metal loading height.The present invention can prepare the catalyst of high metal loading, and the metal loading can be up to 80%.
5. simple, consuming time less, the safety of preparation method.Preparation method's cost of the present invention is low, and technological process is simple, consuming time few, can realize once being carried on the carrier simultaneously active component; Simultaneously, the solvent that uses in the preparation process, reducing agent and dispersant safety, nontoxic.
In a word, the catalyst of the present invention's preparation is for the rich H that contains CO
2Gas meter reveals excellent activity, when being used for the Proton Exchange Membrane Fuel Cells anode, has substantially exceeded present widely used E-TEK commercialization catalyst.
Description of drawings
Fig. 1 is a tenor 40% of the present invention, and platinum ruthenium nickel mol ratio is the catalyst 40%Pt of 1:1:1
1Ru
1Ni
1The transmission electron microscope of/C (TEM) figure;
Fig. 2 is a tenor 40% of the present invention, and platinum ruthenium nickel mol ratio is the catalyst 40%Pt of 1:1:1
1Ru
1Ni
1The X-ray diffraction of/C (XRD) figure;
Fig. 3 is a tenor 40% of the present invention, and platinum ruthenium nickel mol ratio is the catalyst 40%Pt of 1:1:1
1Ru
1Ni
1/ C and tenor 40%, platinum ruthenium mol ratio are the commercial catalyst 40%Pt of E-TEK company of 1:1
1Ru
1The monocell performance comparison figure of/C.Wherein, catalyst is used for galvanic anode, and negative electrode all adopts the Pt/C catalyst; Anode and negative electrode feed 100ppmCO/H respectively
2Gas and O
2Carry out performance evaluation.
Embodiment
Below by embodiment the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1: 1g XC-72 carbon dust is added in the glycol water of 100ml 95%vol., stir, obtain slurry A; With 12.4ml concentration is that the nickel nitrate aqueous solution that the chloroplatinic acid hexahydrate ethylene glycol solution of 29.6mgPt/ml, ruthenium trichloride ethylene glycol solution that 51.35ml concentration is 3.7mgRu/ml and 11ml concentration are 10mgNi/ml mixes, and obtains mixed solution B; Slurry A is mixed with solution B, stir and add 2.5M NaOH ethylene glycol solution to PH=12, and be 2.45 Gigahertzs with frequency of oscillation, power output is the microwave heating 1.5min of 700W, be cooled to room temperature, add the 3M aqueous hydrochloric acid solution to PH=0.5, be filtered to neutrality and do not have Cl with deionized water wash
-, after the drying, feed 5%H
2/ N
2Mixed airflow 500 ℃ of following heat treatments 4 hours, is cooled to room temperature, obtains tenor 40%, and platinum ruthenium nickel mol ratio is the catalyst 40%Pt of 1:1:1
1Ru
1Ni
1/ XC-72.
As can be seen from Figure 1, catalyst metals particle little (3.4nm), (1.5-5.5nm) is evenly distributed.
Only show the diffraction maximum of Ptfcc structure among Fig. 2, do not have the peak of Ru and Ni.Calculating can get the lattice parameter of Pt crystallite
, less than Pt/C (
) and Pt
1Ru
1/ C (
), showing that catalyst has formed alloy, the absorption of CO on Pt weakens.
As can be seen from Figure 3, catalyst of the present invention is to containing the rich H of CO
2Gas has excellent HOR activity.In current density is 500 and 1000mA/cm
2The place, catalyst of the present invention is than the high 30mV and 77mV of E-TEK company catalyst difference.Battery is at 500mA/cm
2Gas chromatographic analysis during following stable discharging shows that 54% CO is oxidized to CO in the gas
2, show that Pt goes up the CO that adsorbs and can be oxidized away effectively.
Embodiment 2: 1g XC-72 carbon dust is added in the glycol water of 20ml 95%vol., stir, obtain slurry A; With 27.86ml concentration is that the nickel nitrate aqueous solution that the chloroplatinic acid hexahydrate ethylene glycol solution of 29.6mgPt/ml, ruthenium trichloride ethylene glycol solution that 115.47ml concentration is 3.7mgRu/ml and 24.81ml concentration are 10mgNi/ml mixes, stir, obtain mixed solution B; Above-mentioned slurry A is mixed with solution B, stir adding Na
2CO
3To PH=10, and be 2.45 Gigahertzs with frequency of oscillation, power output is the microwave heating 15min of 700W, is cooled to room temperature, adds the 3M aqueous solution of nitric acid to PH=0.5, washes with water to be filtered to neutrality and not have Cl
-, after the drying, feed 5%CH
4/ N
2Mixed airflow 500 ℃ of following heat treatments 4 hours, is cooled to room temperature, obtains tenor 60%, and platinum ruthenium nickel mol ratio is the catalyst 60%Pt of 1:1:1
1Ru
1Ni
1/ XC-72.
Embodiment 3: the 1gXC-72 carbon dust is added in the 100ml deionized water, stir, obtain slurry A; With 6.89ml concentration is that the chloro-iridic acid hexahydrate ethylene glycol solution that the chloroplatinic acid hexahydrate ethylene glycol solution of 29.6mgPt/ml, nickel nitrate aqueous solution that 6.13ml concentration is 10mgNi/ml and 11.48ml concentration are 35mgIr/ml mixes, stir, obtain mixed solution B; Slurry A is mixed with solution B, stir adding NaOH to PH=12, after fully mixing, with frequency of oscillation is 48.2 Gigahertzs, and power output is the microwave ethylene glycol solution heating 30min of 400W, is cooled to room temperature, add the 3M aqueous hydrochloric acid solution to PH=2, and wash with water and be filtered to neutrality and do not have Cl
-, after the drying, feed 0.5%H
2/ N
2Mixed airflow 600 ℃ of following heat treatments 3 hours, is cooled to room temperature, obtains tenor 40%, and platinum nickel iridium mol ratio is the catalyst 40%Pt of 1:1:1
1Ni
1Ir
2/ XC-72.
Embodiment 4: 1g XC-72 carbon dust is added in the glycol water of 100ml 95%vol., fully stir, obtain slurry A; With 11.14ml concentration is that the hexahydrated ethylene glycol solution of chloroplatinic acid of 29.6mgPt/ml and nickel nitrate aqueous solution that 9.92ml concentration is 10mgNi/ml mix, and stirs, and obtains mixed solution B; Slurries A is mixed with solution B, stir to add NaOH to PH=13, and be 2.45 Gigahertzs with frequency of oscillation, power output is the microwave heating 1.5min of 700W, is cooled to room temperature, and adding 3M aqueous hydrochloric acid solution is to PH=1, washes with water to be filtered to neutrality and not have Cl
-, after the drying, feed 1%CH
4/ Ar mixed airflow 300 ℃ of following heat treatments 8 hours, is cooled to room temperature, obtains tenor 30%, and platinum nickel mol ratio is the catalyst 30%Pt of 1:1
1Ni
1/ XC-72.
Embodiment 5: 1g XC-72 carbon dust is added in the 100ml ethylene glycol, stir, obtain slurry A; With 14.20ml concentration is that the iron nitrate aqueous solution that the hexahydrated ethylene glycol solution of chloroplatinic acid of 29.6mgPt/ml, nickel nitrate aqueous solution that 12.64ml concentration is 10mgNi/ml and 12.03ml concentration are 10mgFe/ml mixes, and stirs, and obtains mixed solution B; Slurry A is mixed with solution B, stir to add NaOH to PH=12, and be 48.2 Gigahertzs with frequency of oscillation, power output is the microwave heating 30min of 400W, is cooled to room temperature, and adding 3M aqueous hydrochloric acid solution is to PH=1, washes with water to be filtered to neutrality and not have Cl
-, after the drying, feed 5%H
2/ Ar mixed airflow 800 ℃ of following heat treatments 1 hour, is cooled to room temperature, obtains tenor 40%, and platinum ferronickel mol ratio is the catalyst 40%Pt of 1:1:1
1Ni
1Fe
1/ XC-72.
Embodiment 6: 1g carbon nano-tube (CNT) is added in the 100ml glycol water, stir, obtain slurry A; With 12.4ml concentration is that the nickel nitrate aqueous solution that the chloroplatinic acid hexahydrate ethylene glycol solution of 29.6mgPt/ml, ruthenium trichloride ethylene glycol solution that 51.35ml concentration is 3.7mgRu/ml and 11ml concentration are 10mgNi/ml mixes, and stirs, and obtains mixed solution B; Above-mentioned slurry A is mixed with solution B, stir to add NaOH to PH=12, and be 2.45 Gigahertzs with frequency of oscillation, power output is the microwave heating 1.5min of 700W, be cooled to room temperature, add the 3M aqueous hydrochloric acid solution, wash with water and be filtered to neutrality and do not have Cl to PH=0.5
-, after the drying, feed 10%H
2/ N
2Mixed airflow 500 ℃ of following heat treatments 4 hours, is cooled to room temperature, obtains tenor 40%, and platinum ruthenium nickel mol ratio is the catalyst 40%Pt of 1:1:1
1Ru
1Ni
1/ CNT.
Embodiment 7: 1g XC-72 carbon dust is added in the glycol water of 100ml 95%vol., stir, obtain slurry A; With 14.32ml concentration is that the nickel nitrate aqueous solution that the chloroplatinic acid hexahydrate ethylene glycol solution of 29.6mgPt/ml, palladium chloride ethylene glycol solution that 12.75ml concentration is 30mgPd/ml and 3.85ml concentration are 10mgNi/ml mixes, and obtains mixed solution B; Slurry A is mixed with solution B, stir to add NaOH to PH=12, and be 2.45 Gigahertzs with frequency of oscillation, power output is the microwave heating 15min of 700W, be cooled to room temperature, add the 3M aqueous hydrochloric acid solution, be filtered to neutrality and do not have Cl with deionized water wash to PH=0.5
-, after the drying, feed 10%CH
4/ Ar mixed airflow 500 ℃ of following heat treatments 4 hours, is cooled to room temperature, obtains tenor 40%, and platinum nickel palladium mol ratio is the catalyst 40%Pt of 1:1:0.5
1Ni
1Pd
0.5/ XC-72.
Embodiment 8: 1g XC-72 carbon dust is added in the glycol water of 100ml 95%vol., stir, obtain slurry A; With 7.53ml concentration is that the nickel nitrate aqueous solution that the chloroplatinic acid hexahydrate ethylene glycol solution of 29.6mgPt/ml, the sodium tungstate aqueous solution that 1.15ml concentration is 1M and 6.71ml concentration are 10mgNi/ml mixes, and obtains mixed solution B; Slurry A is mixed with solution B, stir to add NaOH to PH=12, and be 2.45 Gigahertzs with frequency of oscillation, power output is the microwave heating 15min of 700W, be cooled to room temperature, add the 3M aqueous hydrochloric acid solution, be filtered to neutrality and do not have Cl with deionized water wash to PH=0.5
-, after the drying, feed 1%H
2/ Ar mixed airflow 500 ℃ of following heat treatments 4 hours, is cooled to room temperature, obtains tenor 50%, and platinum nickel tungsten mol ratio is the catalyst 50%Pt of 1:1:1
1Ni
1W
1/ XC-72.
Embodiment 9: 1g XC-72 carbon dust is added in the glycol water of 50ml 95%vol., stir, obtain slurry A; With 12.48ml concentration is that the nickel nitrate aqueous solution that the chloroplatinic acid hexahydrate ethylene glycol solution of 29.6mgPt/ml, gold chloride hexahydrate ethylene glycol solution that 6.22ml concentration is 30mgAu/ml and 11.11ml concentration are 10mgNi/ml mixes, and obtains mixed solution B; Slurry A is mixed with solution B, stir to add the 2.5MNaOH ethylene glycol solution, and be 2.45 Gigahertzs with frequency of oscillation to PH=12, power output is the microwave heating 1.5min of 700W, be cooled to room temperature, add the 3M aqueous hydrochloric acid solution, be filtered to neutrality and do not have Cl with deionized water wash to PH=0.5
-, after the drying, feed 5%H
2/ N
2Mixed airflow 500 ℃ of following heat treatments 4 hours, is cooled to room temperature, obtains tenor 40%, and platinum nickel gold mol ratio is the catalyst 40%Pt of 1:1:0.5
1Ni
1Au
0.5/ XC-72.
Embodiment 10: be to prepare tenor 80% with the difference of embodiment 1, platinum nickel ruthenium mol ratio is the catalyst 80%Pt of 1:1:1
1Ni
1Ru
1/ XC-72.
Embodiment 11: be to prepare tenor 30% with the difference of embodiment 1, platinum nickel ruthenium mol ratio is the catalyst 30%Pt of 1:1:1
1Ni
1Ru
1/ XC-72.
Claims (10)
1. anode catalyst of high active PtNi base proton exchange film fuel cell, at least contain two kinds of metallic elements of Pt and Ni in the active component, the atomic ratio of Pt and Ni is 1:1, and weight metal content is 30-80% in the catalyst, it is characterized in that: described Preparation of catalysts process is as follows
1) soluble metal active component predecessor is dissolved in the solvent, obtains solution A;
2) with electroconductive carbon carrier and dispersant mixed, obtain slurry B by 20～100m1 dispersant/g carrier;
3) solution A and slurry B are mixed, stirring the hydroxide, carbonate or the bicarbonate accent pH value that add alkali metal or alkaline-earth metal is 10～14, obtains slurry C;
4) with slurry C with microwave continuous or intermittently heated 1～30 minute, be cooled to room temperature, add hydrochloric acid, oxalic acid, acetic acid, sulfuric acid or nitric acid then to pH value≤6, obtain slurry D;
5) slurry D is carried out Separation of Solid and Liquid, and one or more washing solids in water, ethanol and the isopropyl alcohol are mutually to neutrality and there is not a Cl
-, drying obtains pressed powder E;
6) with pressed powder E in the reproducibility air-flow 300～800 ℃ handled 1～8 hour down, be cooled to room temperature after, promptly get catalyst of the present invention.
2. according to the described catalyst of claim 1, it is characterized in that: also contain IIIB in the periodic table of elements in the described catalyst, IVB, VB, VIB, VIIB, the metallic element of one or more in VIIIB and the IB family is as active component, and wherein Pt and Ni account for 30% of total weight metal content at least.
3. according to the described catalyst of claim 2, it is characterized in that: also contain among Ru, Rh, Pd, Os, Ir, Au, Ag, Ti, Mo, W, Fe and the Re one or more in the described catalyst as active component.
4. according to the described catalyst of claim 2, it is characterized in that: also contain among Ru, Rh, Pd, Os, Ir, Au and the Ag one or more in the described catalyst as active component.
5. according to the described catalyst of claim 1, it is characterized in that: the weight content of described activity of such catalysts component is 30-60%.
6. according to the described catalyst of claim 1, it is characterized in that: the nitrate that described soluble metal active component predecessor is a respective metal, sulfate, acetate, halide, dinitroso two amine salt, acetylacetonate, encircle in complex compound porphyrin, phthalocyanine, porphyrin polymer, the phthalocyanine polymer one or more greatly;
Described electroconductive carbon carrier is one or more in graphitic carbon, carbon nano-tube, carbon fiber, carbosphere and the carbon aerogels;
Described solvent is water, C
2～C
8Monohydric alcohol, C
2～C
8Dihydroxylic alcohols and C
2～C
8In the trihydroxy alcohol one or more; Described dispersant is water, C
2～C
8Monohydric alcohol, C
2～C
8Dihydroxylic alcohols, C
2～C
8In the trihydroxy alcohol and the carboxylate of deriving by these alcohol one or more.
7. according to the described catalyst of claim 1, it is characterized in that: the frequency of oscillation of described microwave is 1～50 Gigahertz, and described microwave output power is 400～1000W.
8. according to the described catalyst of claim 1, it is characterized in that: the frequency of oscillation of described microwave is 2～20 Gigahertzs, and microwave output power is 500-800W.
9. according to the described catalyst of claim 1, it is characterized in that: the percentage by volume of reproducibility component is 0.5-10% in the described reproducibility air-flow.
10. according to the described catalyst of claim 1, it is characterized in that: the percentage by volume of reproducibility component is 1-5% in the described reproducibility air-flow.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100459899A CN100511789C (en) | 2005-03-09 | 2005-03-09 | Anode catalyst of high active PtNi base proton exchange film fuel cell |
| KR1020060016673A KR20060097590A (en) | 2005-03-09 | 2006-02-21 | Ptni based electrocatalyst for proton exchange membrane fuel cell with improved co tolerance |
| US11/371,080 US20060280997A1 (en) | 2005-03-09 | 2006-03-09 | PtNi based supported electrocatalyst for proton exchange membrane fuel cell having CO tolerance |
| JP2006064894A JP4758789B2 (en) | 2005-03-09 | 2006-03-09 | Electrode supported catalyst and production method thereof, electrode for proton exchange membrane fuel cell and proton exchange membrane fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100459899A CN100511789C (en) | 2005-03-09 | 2005-03-09 | Anode catalyst of high active PtNi base proton exchange film fuel cell |
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| CN1832233A CN1832233A (en) | 2006-09-13 |
| CN100511789C true CN100511789C (en) | 2009-07-08 |
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| CN (1) | CN100511789C (en) |
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| CN109616669A (en) * | 2018-11-30 | 2019-04-12 | 上海师范大学 | Nanometer cobalt/nitrogen-doped carbon nanometer pipe composite material preparation method and applications |
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| KR100766978B1 (en) * | 2006-05-10 | 2007-10-12 | 삼성에스디아이 주식회사 | Anode catalyst for fuel cell and membrane-electrode assembly for fuel cell comprising same and fuel cell system comprising same |
| JP5139002B2 (en) * | 2007-08-10 | 2013-02-06 | 株式会社東芝 | Fine particle carrying method and fine particle carrying device |
| CN103084582B (en) * | 2013-01-08 | 2016-04-27 | 江苏大学 | A kind of method preparing atomic scale noble metal nano particles stable colloid suspension |
| CN104707598B (en) * | 2013-12-15 | 2017-02-15 | 中国科学院大连化学物理研究所 | Proton exchange membrane fuel cell electrocatalyst and preparation method thereof |
| KR101575463B1 (en) * | 2014-03-26 | 2015-12-07 | 현대자동차주식회사 | A method for manufacturing alloy catalyst for a fuel cell |
| CN104096575A (en) * | 2014-06-26 | 2014-10-15 | 南京航空航天大学 | Method for preparing platinum-nickel nucleocapsid structure fuel cell catalyst through microwave reduction |
| CN105903492B (en) * | 2016-04-27 | 2018-07-10 | 扬州大学 | The preparation method of the liquefied ammonia system anode material of carbon fiber loaded Cr-MIL-101-M noble metal catalysts |
| KR101962265B1 (en) * | 2018-01-30 | 2019-03-26 | 연세대학교 산학협력단 | A method for manufacturing carbon nanofiber having excellent stability and durability |
| CN108550870A (en) * | 2018-04-18 | 2018-09-18 | 广东高明产业创新研究院 | A kind of porous graphene/ruthenium selenium composite catalyst and its preparation method and application |
| CN108598499A (en) * | 2018-05-28 | 2018-09-28 | 东莞众创新能源科技有限公司 | A kind of preparation method of hydrogen fuel cell catalyst |
| CN109126819B (en) * | 2018-08-21 | 2021-12-31 | 同济大学 | Preparation method of high-dispersity carbon-supported Pt-Ni catalyst |
| CN109713323B (en) * | 2018-11-27 | 2021-02-09 | 浙江大学 | Preparation method of PtNi/C alloy catalyst |
| KR102478160B1 (en) | 2019-10-30 | 2022-12-15 | 부산대학교 산학협력단 | Bimetallic nanoparticle-carbon hybrid catalyst for fuel cell, method for preparing the same and fuel cell comprising the same |
| CN113258090A (en) * | 2021-06-23 | 2021-08-13 | 南京大学 | Transition metal doped Pt/C fuel cell catalyst and preparation method thereof |
| CN113745555A (en) * | 2021-09-30 | 2021-12-03 | 深圳市燃电科技有限公司 | Device and method for preparing carbon-supported platinum nano catalyst by solid phase mixing |
| CN114284514A (en) * | 2021-12-27 | 2022-04-05 | 格林美股份有限公司 | Fuel cell electrocatalyst Pt3M-N/C and preparation method thereof |
| CN114628700A (en) * | 2022-04-06 | 2022-06-14 | 南京大学 | Preparation method of platinum-nickel-gold alloy nano catalyst |
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| CN1832233A (en) | 2006-09-13 |
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