CN104218250A - PtM/C electrocatalyst for fuel cell and preparation method of PtM/C electrocatalyst for fuel cell - Google Patents
PtM/C electrocatalyst for fuel cell and preparation method of PtM/C electrocatalyst for fuel cell Download PDFInfo
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- CN104218250A CN104218250A CN201410475946.3A CN201410475946A CN104218250A CN 104218250 A CN104218250 A CN 104218250A CN 201410475946 A CN201410475946 A CN 201410475946A CN 104218250 A CN104218250 A CN 104218250A
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a PtM/C electrocatalyst for a fuel cell. The PtM/C electrocatalyst comprises the following components by mass percent: 18.16-36.52% of active components, 1.74-3.68% of auxiliary agents and the balance being a conductive carrier. The PtM/C electrocatalyst is prepared by the steps of feeding precursors of the active components and precursors of the auxiliary agents into a mixed suspension liquid of the conductive carrier and a reducing agent in one step; loading metal Pt and M onto the conductive carrier by adopting a pulse microwave-assisted chemical reduction method; and after that, precipitating, filtering, washing and carrying out vacuum drying to obtain the PtM/C electrocatalyst. Compared with the prior art, the preparation method is simple; the prepared PtM/C electrocatalyst is uniform in particle distribution, small in size and high in catalytic activity of oxygen reduction reaction, and can be used in the field of the fuel cell.
Description
Technical field
The invention belongs to fuel cell technology field, relate to a kind of Catalysts and its preparation method, especially relate to PtM/C eelctro-catalyst and preparation method thereof for a kind of fuel cell.
Background technology
Due to Proton Exchange Membrane Fuel Cells (PEMFC), to have energy conversion efficiency high, easily start, the features such as environmental pollution is little, it can be as power source, distributed power station and the Portable movable power supply of motor vehicle, be subject in recent years the extensive concern of countries in the world, its key technology is also developed rapidly.
As everyone knows, catalyst is the critical material of PEMFC, researchs and develops active catalyst high, good stability and plays a part very important to improving the performance of fuel cell.And produce in enormous quantities in order to be applicable to commercialization, the preparation method of PtM/C catalyst haves much room for improvement, and prepare PtM/C catalyst to adopt infusion process, liquid phase reduction and colloid method to be prepared, yet this several method all exists technological deficiency in various degree more in the past.For example, liquid phase reduction generally, by reducing agent reducing catalyst active component at a certain temperature, then makes it be supported on carbon carrier, and the method adopts traditional Convective Heating conventionally, has the shortcomings such as the inhomogeneous and reaction rate of heating is slow; Catalyst particle size prepared by infusion process is large, and particle size distribution homogeneity is poor, and a loading of metal can not be too high, need repeatedly flood; And colloid method manufacturing cycle is long, and process is wayward.
In order to improve the utilance of noble metal, often by noble-metal-supported on some carrier, to improve its dispersiveness.Catalyst carrier not only can play and support and peptizaiton catalyst activity component, meanwhile, the mass transfer of catalyst, heat transfer and chemical stability and thermal stability etc. is all had to important function.Conductive carbon black-materials are that the desirable carrier of fuel-cell catalyst is selected, because it possesses following condition: the specific area that (1) is higher, can effectively disperse noble metal active component; (2) high-graphitized, there is good electronic conduction ability; (3) suitable pore structure, to reduce the transmission migration resistance of reactant, intermediate and product.
Summary of the invention
Object of the present invention is exactly to provide a kind of particle size fuel cell PtM/C eelctro-catalyst little, that have higher catalytic activity in order to overcome the defect of above-mentioned prior art existence.
Object of the present invention can be achieved through the following technical solutions:
A fuel cell PtM/C eelctro-catalyst, this PtM/C eelctro-catalyst comprises the composition of following mass percent: active component 18.16～36.52%, auxiliary agent M1.74～3.68%, all the other are conductive carrier.
Described active component is Pt metal, and described auxiliary agent M comprises one or more simple substance in Fe, Co, Ni.
Described conductive carrier comprises that Vulcan XC-72, acetylene black, Ketjen are black, one or more in carbon nano-tube, carbon nanohorn, carbon nano molecular sieve, gnf, graphene oxide and Graphene.
The preparation method of PtM/C eelctro-catalyst for a kind of fuel cell, the method is that active component presoma and auxiliary agent presoma one step are joined in the mixing suspension of conductive carrier and reducing agent, adopt pulse microwave assistant chemical reducing process that Pt metal and M are reduced from presoma, and load in conductive carrier, again through precipitation, filtration, washing, vacuumize, make PtM/C eelctro-catalyst, specifically comprise the following steps:
(1) by the mass ratio of conductive carrier and reducing agent, be 1: (100～600), conductive carrier is joined in reductant solution, ultrasonic agitation is even, makes suspending liquid A;
(2) by the mol ratio of Pt in M in auxiliary agent presoma and active component presoma, it is 1: 3, active component presoma is joined together with auxiliary agent presoma in the suspending liquid A that step (1) makes, ultrasonic agitation is even, and regulator solution pH value is 8～12, makes suspension B;
(3) suspension B step (2) being made is placed in microwave reactor, adopt pulse microwave assistant chemical reducing process to react, after reaction finishes, treat that solution temperature is down to room temperature, through precipitation, filtration, washing, vacuumize, make PtM/C eelctro-catalyst.
The mass ratio of the conductive carrier that the active component presoma that step (2) is described and step (1) are described is 1: (1.5～2).
Described active component presoma comprises chloroplatinic acid or platinum nitrate.
Described auxiliary agent presoma comprises solubility organic salt or the soluble inorganic salt of M, soluble inorganic salt preferably nitrate, sulfate or the chloride of described M, the preferred acetate of solubility organic salt of described M.
Described reducing agent comprises one or more in formaldehyde, acetaldehyde, ethylene glycol, glycerol and sodium borohydride.
The operating condition of the employing pulse microwave assistant chemical reducing process that step (3) is described is: in microwave reactor, pass into inert protective gas; the operating time of microwave reactor is 5～50s; relaxation time is 50～300s; microwave power is 0.5～3kW, and microwave repeat function number of times is 5～30 times.
The described vacuum drying temperature of step (3) is 60～120 ℃, and vacuum degree is-0.09～-0.1MPa, and be 6～12h drying time.
Compared with prior art, the present invention has following characteristics:
(1) adopt pulse microwave assistant chemical reducing process to be prepared, method of operation is simple, and reaction condition is gentle, and reaction rate is fast, can realize active component and auxiliary agent are once carried in conductive carrier simultaneously;
(2) prepare the PtM/C electrocatalyst particles size of gained little, even particle size distribution, Heat stability is good, has good in oxygen reduction reaction catalytic performance.
Accompanying drawing explanation
Fig. 1 is the prepared PtM/C eelctro-catalyst linear sweep voltammetry test spectrogram of embodiment 1;
Fig. 2 is transmission electron microscope (TEM) spectrogram of the prepared PtM/C eelctro-catalyst of embodiment 1;
Fig. 3 is the prepared PtM/C eelctro-catalyst linear sweep voltammetry test spectrogram of embodiment 2;
Fig. 4 is transmission electron microscope (TEM) spectrogram of the prepared PtM/C eelctro-catalyst of embodiment 2;
Fig. 5 is cyclic voltammetric (CV) spectrogram of the prepared PtM/C eelctro-catalyst of embodiment 3;
Fig. 6 is the prepared PtM/C eelctro-catalyst linear sweep voltammetry test spectrogram of embodiment 3;
Fig. 7 is the prepared PtM/C eelctro-catalyst linear sweep voltammetry test spectrogram of embodiment 4;
Fig. 8 is the X-ray diffraction spectrogram (XRD) of the prepared PtM/C eelctro-catalyst of embodiment 4.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
The present embodiment, adopts pulse microwave assistant chemical reduction method for preparing Pt
3ni/XC-72 eelctro-catalyst (Pt and Ni mol ratio 3: 1, Pt
3the percentage that Ni accounts for catalyst gross mass is 20%, Pt to account for the percentage of catalyst gross mass be that the percentage that 18.18%, Ni accounts for catalyst gross mass is 1.82%), concrete preparation method is as follows:
(1) by Vulcan XC-72 carbon black (U.S. Cabot company), be 1: 200 with the mass ratio of ethylene glycol, Vulcan XC-72 is joined in ethylene glycol, ultrasonic agitation is even, makes suspending liquid A;
(2) by the mol ratio of Pt in Ni in nickel nitrate and chloroplatinic acid, it is 1: 3, chloroplatinic acid is joined together with nickel nitrate in the suspending liquid A that step (1) makes, wherein, it is 1: 1.66 that the mass ratio of chloroplatinic acid and Vulcan XC-72 is controlled, ultrasonic agitation is even, regulator solution pH value is 10, makes suspension B;
(3) suspension B step (2) being made is placed in microwave reactor, pass into inert nitrogen gas, drain air, the operating time that microwave reactor is set is 20s, relaxation time is 100s, and microwave power is 1kW, and microwave repeat function number of times is 15 times, start microwave reactor, carry out reduction reaction; After question response finishes, solution temperature is down to room temperature, take out solution through precipitation, filter, washing, obtain sample, and at 80 ℃, vacuum degree, be-0.1MPa that vacuumize 8h, prepares Pt by sample
3ni/XC-72 eelctro-catalyst.
The Pt that prepared by the present embodiment to gained
3ni/XC-72 eelctro-catalyst carries out linear sweep voltammetry test, test condition: sweep limits is 0.05～1.2V (vs.RHE), and sweep speed is 5mVs
-1, electrode rotating speed is 1600rpm, solution is the 0.1molL that oxygen is saturated
-1hClO
4solution, test result as shown in Figure 1.
As seen from Figure 1, the Pt for preparing gained
3the current density of Ni/XC-72 eelctro-catalyst under 0.9V voltage reaches 1.1mA/cm
2, have good in hydrogen reduction catalytic performance.
Figure 2 shows that the present embodiment prepares gained Pt
3the TEM spectrogram of Ni/XC-72 eelctro-catalyst, as seen from Figure 2, prepares the Pt of gained
3the even particle size of Ni/XC-72 eelctro-catalyst, good dispersion, unity phenomenon not substantially, the average grain diameter of particle is about 2.5nm.
Embodiment 2:
The present embodiment, adopts pulse microwave assistant chemical reduction method for preparing Pt
3ni/ acetylene black eelctro-catalyst (Pt and Ni mol ratio 3: 1, Pt
3the percentage that Ni accounts for catalyst gross mass is 20%, Pt to account for the percentage of catalyst gross mass be that the percentage that 18.18%, Ni accounts for catalyst gross mass is 1.82%), concrete preparation method is as follows:
(1) by acetylene black (U.S. Alfa company), be 1: 200 with the mass ratio of ethylene glycol, acetylene black is joined in ethylene glycol, ultrasonic agitation is even, makes suspending liquid A;
(2) by the mol ratio of Pt in Ni in nickel nitrate and chloroplatinic acid, it is 1: 3, chloroplatinic acid is joined together with nickel nitrate in the suspending liquid A that step (1) makes, wherein, it is 1: 1.66 that the mass ratio of chloroplatinic acid and acetylene black is controlled, ultrasonic agitation is even, regulator solution pH value is 10, makes suspension B;
(3) suspension B step (4) being made is placed in microwave reactor, pass into inert nitrogen gas and drain air, the operating time that microwave reactor is set is 30s, relaxation time is 200s, microwave power is 2kW, microwave repeat function number of times is 20 times, starts microwave reactor, carries out reduction reaction; After question response finishes, solution temperature is down to room temperature, take out solution through precipitation, filter, washing, obtain sample, and at 60 ℃, vacuum degree, be-0.10MPa that vacuumize 10h, prepares Pt by sample
3ni/ acetylene black eelctro-catalyst.
The Pt that prepared by the present embodiment to gained
3ni/ acetylene black eelctro-catalyst carries out linear sweep voltammetry test, test condition: sweep limits is 0.05～1.2V (vs.RHE), and sweep speed is 5mVs
-1, electrode rotating speed is 1600rpm, solution is the 0.1molL that oxygen is saturated
-1hClO
4solution, test result as shown in Figure 3, Pt
3ni/ acetylene black eelctro-catalyst has good in hydrogen reduction catalytic performance.
Figure 4 shows that the present embodiment prepares gained Pt
3the TEM spectrogram of Ni/ acetylene black eelctro-catalyst, as seen from Figure 4, prepares the Pt of gained
3the even particle size of Ni/ acetylene black eelctro-catalyst, good dispersion, unity phenomenon not substantially, the average grain diameter of particle is about 2.3nm.
Embodiment 3:
The present embodiment, adopts pulse microwave assistant chemical reduction method for preparing Pt
3fe/XC-72 eelctro-catalyst (Pt and Fe mol ratio 3: 1, Pt
3the percentage that Fe accounts for catalyst gross mass is 20%, Pt to account for the percentage of catalyst gross mass be that the percentage that 18.26%, Fe accounts for catalyst gross mass is 1.74%), concrete preparation method is as follows:
(1) by the mass ratio of Vulcan XC-72 and ethylene glycol, be 1: 300, Vulcan XC-72 is joined in ethylene glycol, ultrasonic agitation is even, makes suspending liquid A;
(2) by the mol ratio of Pt in Fe in ferric nitrate and chloroplatinic acid, it is 1: 3, chloroplatinic acid is joined together with ferric nitrate in the suspending liquid A that step (1) makes, wherein, it is 1: 1.66 that the mass ratio of chloroplatinic acid and Vulcan XC-72 is controlled, ultrasonic agitation is even, regulator solution pH value is 10, makes suspension B;
(3) suspension B step (2) being made is placed in microwave reactor, pass into inert nitrogen gas and drain air, the operating time that microwave reactor is set is 20s, relaxation time is 100s, microwave power is 1kW, microwave repeat function number of times is 15 times, starts microwave reactor, carries out reduction reaction; After question response finishes, solution temperature is down to room temperature, take out solution through precipitation, filter, washing, obtain sample, and at 80 ℃, vacuum degree, be-0.10MPa that vacuumize 8h, prepares Pt by sample
3fe/XC-72 eelctro-catalyst.
The Pt that prepared by this enforcement to gained
3fe/XC-72 eelctro-catalyst carries out cyclic voltammetry, test condition: sweep limits is 0.05～1.15V (vs.RHE), and sweep speed is 50mVs
-1, test curve as shown in Figure 5.
By Fig. 5, can calculate and learn, prepare the Pt of gained
3the electrochemical surface area of Fe/XC-72 eelctro-catalyst reaches 83m
2/ g, has larger active area.
The Pt that prepared by the present embodiment to gained
3fe/XC-72 eelctro-catalyst carries out linear sweep voltammetry test, test condition: sweep limits is 0.05～1.2V (vs.RHE), and sweep speed is 5mVs
-1, electrode rotating speed is 1600rpm, solution is the 0.1molL that oxygen is saturated
-1hClO
4solution, test result as shown in Figure 6, can be found out, prepare the Pt of gained
3the current density of Fe/XC-72 eelctro-catalyst under 0.9V voltage reaches 1.2mA/cm
2, have good in hydrogen reduction catalytic performance.
Embodiment 4:
The present embodiment, adopts pulse microwave assistant chemical reduction method for preparing Pt
3ni/GO eelctro-catalyst (Pt and Ni mol ratio 3: 1, Pt
3the percentage that Ni accounts for catalyst gross mass is 20%, to account for the percentage of catalyst gross mass be 18.18% to Pt, the percentage that Ni accounts for catalyst gross mass is 1.82%), wherein GO is graphene oxide (Nanjing Xian Feng nano material scientific & technical corporation), concrete preparation method is as follows:
(1) by the mass ratio of graphene oxide and glycerol, be 1: 200, graphene oxide is joined in glycerol, ultrasonic agitation is even, makes suspending liquid A;
(2) by the mol ratio of Pt in Ni in nickel nitrate and chloroplatinic acid, it is 1: 3, chloroplatinic acid is joined together with nickel nitrate in the suspending liquid A that step (1) makes, wherein, it is 1: 1.66 that the mass ratio of chloroplatinic acid and graphene oxide is controlled, ultrasonic agitation is even, regulator solution pH value is 10, makes suspension B;
(3) suspension B step (2) being made is placed in microwave reactor, pass into inert nitrogen gas and drain air, the operating time that microwave reactor is set is 20s, relaxation time is 100s, microwave power is 1kW, microwave repeat function number of times is 15 times, starts microwave reactor, carries out reduction reaction; After question response finishes, solution temperature is down to room temperature, take out solution through precipitation, filter, washing, obtain sample, and at 80 ℃, vacuum degree, be-0.10MPa that vacuumize 8h, prepares Pt by sample
3ni/GO eelctro-catalyst.
The Pt that prepared by the present embodiment to gained
3ni/GO eelctro-catalyst carries out linear sweep voltammetry test, test condition: sweep limits is 0.05-1.2V (vs.RHE), and sweep speed is 5mVs
-1, electrode rotating speed is 1600rpm, solution is the 0.1molL that oxygen is saturated
-1hClO
4solution, test result as shown in Figure 7, can be found out, prepare the Pt of gained
3the current density of Ni/GO eelctro-catalyst under 0.9V voltage reaches 1.0mA/cm
2, have good in hydrogen reduction catalytic performance.
Fig. 8 prepares gained Pt for this enforcement
3the XRD test spectrogram of Ni/GO eelctro-catalyst, test condition: operating pressure is 40kV, sweep limits is 20 °-90 °, sweep speed is 6 °/min.
In Fig. 8, first peak appears at 20=25 ° for C (002), Pt (111), Pt (200), Pt (220), Pt (311) respectively 2 θ angle values of correspondence are 40 °, 46 °, 68 °, 81 °, wherein the peak of Pt (111) is the strongest, and the Pt making is described
3in Ni/GO eelctro-catalyst, Pt particle is mainly face-centered cubic crystal formation.
Embodiment 5:
The present embodiment, adopts pulse microwave assistant chemical reduction method for preparing Pt
3fe/ carbon nano-tube (the organic institute in Chinese Academy of Sciences Chengdu) eelctro-catalyst (Pt and Fe mol ratio 3: 1, Pt
3the percentage that Fe accounts for catalyst gross mass is 40%, Pt to account for the percentage of catalyst gross mass be that the percentage that 36.52%, Fe accounts for catalyst gross mass is 3.48%), concrete preparation method is as follows:
(1) by the mass ratio of carbon nano-tube and ethylene glycol, be 1: 600, carbon nano-tube is joined in ethylene glycol, ultrasonic agitation is even, makes suspending liquid A;
(2) by the mol ratio of Pt in Fe in ferric nitrate and platinum nitrate, it is 1: 3, platinum nitrate is joined together with ferric nitrate in the suspending liquid A that step (1) makes, wherein, it is 1: 1.5 that the mass ratio of platinum nitrate and carbon nano-tube is controlled, ultrasonic agitation is even, regulator solution pH value is 8, makes suspension B;
(3) suspension B step (2) being made is placed in microwave reactor, pass into inert nitrogen gas and drain air, the operating time that microwave reactor is set is 50s, relaxation time is 300s, microwave power is 0.5kW, microwave repeat function number of times is 5 times, starts microwave reactor, carries out reduction reaction; After question response finishes, solution temperature is down to room temperature, take out solution through precipitation, filter, washing, obtain sample, and at 120 ℃, vacuum degree, be-0.09MPa that vacuumize 6h, prepares Pt by sample
3the agent of Fe/ carbon nanotube electrocatalytic.
Embodiment 6:
The present embodiment, adopts pulse microwave assistant chemical reduction method for preparing Pt
3co/ acetylene black eelctro-catalyst (Pt and Co mol ratio 3: 1, Pt
3the percentage that Co accounts for catalyst gross mass is 20%, Pt to account for the percentage of catalyst gross mass be that the percentage that 18.16%, Co accounts for catalyst gross mass is 1.84%), concrete preparation method is as follows:
(1) by the mass ratio of acetylene black and ethylene glycol, be 1: 300, acetylene black is joined in ethylene glycol, ultrasonic agitation is even, makes suspending liquid A;
(2) by the mol ratio of Pt in Co in cobalt nitrate and platinum nitrate, be 1: 3, platinum nitrate joined together with cobalt nitrate in the suspending liquid A that step (1) makes, wherein, it is 1 that the mass ratio of platinum nitrate and acetylene black is controlled
:1.8, ultrasonic agitation is even, and regulator solution pH value is 10, makes suspension B;
(3) suspension B step (2) being made is placed in microwave reactor, pass into inert nitrogen gas and drain air, the operating time that microwave reactor is set is 5s, relaxation time is 50s, microwave power is 3kW, microwave repeat function number of times is 30 times, starts microwave reactor, carries out reduction reaction; After question response finishes, solution temperature is down to room temperature, take out solution through precipitation, filter, washing, obtain sample, and at 60 ℃, vacuum degree, be-0.10MPa that vacuumize 12h, prepares Pt by sample
3co/ acetylene black eelctro-catalyst.
Embodiment 7:
The present embodiment, adopts pulse microwave assistant chemical reduction method for preparing Pt
3the agent of Co/ carbon nanotube electrocatalytic (Pt and Co mol ratio 3: 1, Pt
3the percentage that Co accounts for catalyst gross mass is 40%, Pt to account for the percentage of catalyst gross mass be that the percentage that 36.32%, Co accounts for catalyst gross mass is 3.68%), concrete preparation method is as follows:
(1) by the mass ratio of carbon nano-tube and ethylene glycol, be 1: 100, carbon nano-tube is joined in ethylene glycol, ultrasonic agitation is even, makes suspending liquid A;
(2) by the mol ratio of Pt in Co in cobalt nitrate and platinum nitrate, it is 1: 3, platinum nitrate is joined together with cobalt nitrate in the suspending liquid A that step (1) makes, wherein, it is 1: 2 that the mass ratio of platinum nitrate and carbon nano-tube is controlled, ultrasonic agitation is even, regulator solution pH value is 12, makes suspension B;
(3) suspension B step (2) being made is placed in microwave reactor, pass into inert nitrogen gas and drain air, the operating time that microwave reactor is set is 25s, relaxation time is 150s, microwave power is 1.5kW, microwave repeat function number of times is 30 times, starts microwave reactor, carries out reduction reaction; After question response finishes, solution temperature is down to room temperature, take out solution through precipitation, filter, washing, obtain sample, and at 100 ℃, vacuum degree, be-0.09MPa that vacuumize 10h, prepares Pt by sample
3the agent of Co/ carbon nanotube electrocatalytic.
Claims (10)
1. a fuel cell PtM/C eelctro-catalyst, is characterized in that, this PtM/C eelctro-catalyst comprises the composition of following mass percent: active component 18.16～36.52%, auxiliary agent M1.74～3.68%, all the other are conductive carrier.
2. a kind of fuel cell PtM/C eelctro-catalyst according to claim 1, is characterized in that, described active component is Pt metal, and described auxiliary agent M comprises one or more simple substance in Fe, Co, Ni.
3. a kind of fuel cell PtM/C eelctro-catalyst according to claim 1, it is characterized in that, described conductive carrier comprises that Vulcan XC-72, acetylene black, Ketjen are black, one or more in carbon nano-tube, carbon nanohorn, carbon nano molecular sieve, gnf, graphene oxide and Graphene.
4. the preparation method of PtM/C eelctro-catalyst for a fuel cell as claimed in claim 1, it is characterized in that, the method is that active component presoma and auxiliary agent presoma one step are joined in the mixing suspension of conductive carrier and reducing agent, adopt pulse microwave assistant chemical reducing process that Pt metal and M are reduced from presoma, and load in conductive carrier, through precipitation, filtration, washing, vacuumize, make PtM/C eelctro-catalyst again, specifically comprise the following steps:
(1) by the mass ratio of conductive carrier and reducing agent, be 1: (100～600), conductive carrier is joined in reductant solution, ultrasonic agitation is even, makes suspending liquid A;
(2) by the mol ratio of Pt in M in auxiliary agent presoma and active component presoma, it is 1: 3, active component presoma is joined together with auxiliary agent presoma in the suspending liquid A that step (1) makes, ultrasonic agitation is even, and regulator solution pH value is 8～12, makes suspension B;
(3) suspension B step (2) being made is placed in microwave reactor, adopt pulse microwave assistant chemical reducing process to react, after reaction finishes, treat that solution temperature is down to room temperature, through precipitation, filtration, washing, vacuumize, make PtM/C eelctro-catalyst.
5. the preparation method of PtM/C eelctro-catalyst for a kind of fuel cell according to claim 4, it is characterized in that, the mass ratio of the conductive carrier that the active component presoma that step (2) is described and step (1) are described is 1: (1.5～2).
6. the preparation method of PtM/C eelctro-catalyst for a kind of fuel cell according to claim 4, is characterized in that, described active component presoma comprises chloroplatinic acid or platinum nitrate.
7. according to a kind of fuel cell described in claim 3 or 4, use the preparation method of PtM/C eelctro-catalyst, it is characterized in that, described auxiliary agent presoma comprises solubility organic salt or the soluble inorganic salt of M, the soluble inorganic salt of described M comprises nitrate, sulfate or chloride, and the solubility organic salt of described M comprises acetate.
8. the preparation method of PtM/C eelctro-catalyst for a kind of fuel cell according to claim 4, is characterized in that, described reducing agent comprises one or more in formaldehyde, acetaldehyde, ethylene glycol, glycerol and sodium borohydride.
9. the preparation method of PtM/C eelctro-catalyst for a kind of fuel cell according to claim 4; it is characterized in that; the operating condition of the employing pulse microwave assistant chemical reducing process that step (3) is described is: in microwave reactor, pass into inert protective gas; the operating time of microwave reactor is 5～50s; relaxation time is 50～300s; microwave power is 0.5～3kW, and microwave repeat function number of times is 5～30 times.
10. the preparation method of PtM/C eelctro-catalyst for a kind of fuel cell according to claim 4, is characterized in that, the described vacuum drying temperature of step (3) is 60～120 ℃, and vacuum degree is-0.09～-0.1MPa, and be 6～12h drying time.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058275A (en) * | 2016-06-28 | 2016-10-26 | 中国科学院上海高等研究院 | Preparation method of carbon-supported PtCo intermetallic compound catalyst for proton-exchange membrane fuel cell and application thereof |
| CN107342426A (en) * | 2017-09-06 | 2017-11-10 | 厦门大学 | The preparation method of platinum cobalt alloy nanocatalyst and the application in oxygen reduction reaction |
| CN108899558A (en) * | 2018-06-07 | 2018-11-27 | 同济大学 | A kind of PtCo/C elctro-catalyst and preparation method thereof |
| CN108963284A (en) * | 2018-07-25 | 2018-12-07 | 南京大学 | A kind of preparation method of high activity platinum nickel C catalyst |
| CN109126819A (en) * | 2018-08-21 | 2019-01-04 | 同济大学 | A kind of polymolecularity carbon carries the preparation method of Pt-Ni catalyst |
| CN109216716A (en) * | 2018-08-06 | 2019-01-15 | 浙江高成绿能科技有限公司 | A kind of preparation method of the fuel cell Pt/C catalyst of high Pt carrying capacity |
| CN110227514A (en) * | 2019-06-28 | 2019-09-13 | 江西理工大学 | It is a kind of to grow the method for metal phosphide and its product of preparation and application on the surface of graphene using microwave method |
| CN111916764A (en) * | 2020-06-30 | 2020-11-10 | 南京大学 | Preparation method of platinum-cobalt alloy nano electro-catalyst |
| CN111933955A (en) * | 2020-06-30 | 2020-11-13 | 南京大学 | Preparation method of surface carbon-supported platinum-cobalt alloy electrocatalyst with high electrochemical activity |
| CN112259752A (en) * | 2020-10-19 | 2021-01-22 | 西安凯立新材料股份有限公司 | Catalyst for proton exchange membrane fuel cell and preparation method thereof |
| WO2021104106A1 (en) * | 2019-11-28 | 2021-06-03 | 深圳先进技术研究院 | Graphene-supported platinum-based alloy nanoparticle catalyst and preparation method therefor |
| CN115863669A (en) * | 2023-02-09 | 2023-03-28 | 江苏皇冠新材料科技有限公司 | Method for preparing nano particle catalyst by liquid phase deposition and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106058275A (en) * | 2016-06-28 | 2016-10-26 | 中国科学院上海高等研究院 | Preparation method of carbon-supported PtCo intermetallic compound catalyst for proton-exchange membrane fuel cell and application thereof |
| CN106058275B (en) * | 2016-06-28 | 2018-12-14 | 中国科学院上海高等研究院 | A kind of used in proton exchange membrane fuel cell carbon carries the preparation method and applications of PtCo intermetallic compound catalyst |
| CN107342426A (en) * | 2017-09-06 | 2017-11-10 | 厦门大学 | The preparation method of platinum cobalt alloy nanocatalyst and the application in oxygen reduction reaction |
| CN108899558A (en) * | 2018-06-07 | 2018-11-27 | 同济大学 | A kind of PtCo/C elctro-catalyst and preparation method thereof |
| CN108899558B (en) * | 2018-06-07 | 2022-07-12 | 同济大学 | PtCo/C electrocatalyst and preparation method thereof |
| CN108963284A (en) * | 2018-07-25 | 2018-12-07 | 南京大学 | A kind of preparation method of high activity platinum nickel C catalyst |
| CN109216716A (en) * | 2018-08-06 | 2019-01-15 | 浙江高成绿能科技有限公司 | A kind of preparation method of the fuel cell Pt/C catalyst of high Pt carrying capacity |
| CN109216716B (en) * | 2018-08-06 | 2023-09-05 | 浙江高成绿能科技有限公司 | Preparation method of Pt/C catalyst for fuel cell with high Pt loading |
| CN109126819A (en) * | 2018-08-21 | 2019-01-04 | 同济大学 | A kind of polymolecularity carbon carries the preparation method of Pt-Ni catalyst |
| CN109126819B (en) * | 2018-08-21 | 2021-12-31 | 同济大学 | Preparation method of high-dispersity carbon-supported Pt-Ni catalyst |
| CN110227514A (en) * | 2019-06-28 | 2019-09-13 | 江西理工大学 | It is a kind of to grow the method for metal phosphide and its product of preparation and application on the surface of graphene using microwave method |
| CN110227514B (en) * | 2019-06-28 | 2021-12-10 | 江西理工大学 | Method for growing metal phosphide on surface of graphene by microwave method, product prepared by method and application of product |
| WO2021104106A1 (en) * | 2019-11-28 | 2021-06-03 | 深圳先进技术研究院 | Graphene-supported platinum-based alloy nanoparticle catalyst and preparation method therefor |
| CN111916764A (en) * | 2020-06-30 | 2020-11-10 | 南京大学 | Preparation method of platinum-cobalt alloy nano electro-catalyst |
| CN111933955A (en) * | 2020-06-30 | 2020-11-13 | 南京大学 | Preparation method of surface carbon-supported platinum-cobalt alloy electrocatalyst with high electrochemical activity |
| CN112259752B (en) * | 2020-10-19 | 2021-11-12 | 西安凯立新材料股份有限公司 | Catalyst for proton exchange membrane fuel cell and preparation method thereof |
| CN112259752A (en) * | 2020-10-19 | 2021-01-22 | 西安凯立新材料股份有限公司 | Catalyst for proton exchange membrane fuel cell and preparation method thereof |
| CN115863669A (en) * | 2023-02-09 | 2023-03-28 | 江苏皇冠新材料科技有限公司 | Method for preparing nano particle catalyst by liquid phase deposition and application thereof |
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