CN104993155B - The preparation method of fuel battery cathode with proton exchange film oxygen reduction electro-catalyst - Google Patents

The preparation method of fuel battery cathode with proton exchange film oxygen reduction electro-catalyst Download PDF

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CN104993155B
CN104993155B CN201510282221.7A CN201510282221A CN104993155B CN 104993155 B CN104993155 B CN 104993155B CN 201510282221 A CN201510282221 A CN 201510282221A CN 104993155 B CN104993155 B CN 104993155B
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carbon
based material
preparation
reducing agent
catalyst
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CN104993155A (en
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苏海斌
李文
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Tianneng Battery Group Co Ltd
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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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a kind of preparation method of fuel battery cathode with proton exchange film oxygen reduction electro-catalyst, comprise the following steps：Carbon-based material is immersed in reducing agent aqueous solution, immerses aqueous metal salt after taking-up again, after the completion of taking out reaction, washing, vacuum drying, finished product.Metallic atom by the method for in-situ reducing is deposited on carbon-based material surface by the present invention, needs not move through calcining, and the metal nanoparticle in catalyst is non-lattice structure, reducing activity height, and technological process is simple, and manufacturing cost is low.

Description

The preparation method of fuel battery cathode with proton exchange film oxygen reduction electro-catalyst
Technical field
The present invention relates to field of fuel cell technology, more particularly to fuel battery cathode with proton exchange film hydrogen reduction electro-catalysis The preparation method of agent.
Background technology
PEM (PEM) fuel cell (FC) battery is using the oxygen in hydrogen and air as fuel, and water is anti- The exclusive product answered.Its basic functional principle is that hydrogen molecule occurs on the electrocatalyst materials (being usually Pt-C) in negative pole Oxidation reaction is broken down into an electronics and Hydrogen Proton, and wherein electronics flows into positive pole by outside line and forms electric current, and hydrogen matter Son flows into positive pole by PEM, and reduction reaction generation occurs in anode electrocatalyst (being usually Pt-C) with the oxygen molecule of positive pole Hydrone.Due to high-energy-density, high efficiency, the features such as pollution to environment, PEM (PEM) fuel cell (FCs) widely studied all the time.Including the international big motor corporation such as Toyota, GM, Ford all in research and development PEM-FC Fuel cell car, wherein Toyota will have issued the commercialization of its " Mirai " PEM-FC automobile with the end of the year 2014.
Both positive and negative polarity elctro-catalyst the most frequently used at present is Pt-C composites.Occur on anode electrocatalyst surface Reaction is referred to as oxygen reduction reaction (ORR).ORR is the key chemical reaction for restricting PEM fuel cell performance and cost.Due to big Amount uses precious metals pt, and ORR elctro-catalysts account for significant proportion in whole PEM-FC cost.So exploitation is cheap high performance Commercialization of the OOR elctro-catalysts for PEM-FC technologies plays the role of important.
The content of the invention
The invention provides a kind of fuel battery cathode with proton exchange film oxygen reduction electro-catalyst, to solve existing catalyst The problem of material metal particle agglomeration forms lattice structure, and activity is low.
A kind of preparation method of fuel battery cathode with proton exchange film oxygen reduction electro-catalyst, comprises the following steps：By carbon Sill is immersed in reducing agent aqueous solution, immerses aqueous metal salt after taking-up again, and after the completion of taking out reaction, washing, vacuum are done It is dry, finished product.
Reducing agent can be that hydrazine, ortho phosphorous acid are received, oxalic acid, boration potassium, boration receives or ethanol, it is preferred that reduction Agent is that hydrazine or ortho phosphorous acid are received.
Metal salt can be niobium salt, ruthenium salt, silver salt, palladium salt, platinum salt, gold salt, manganese salt, cobalt salt or nickel salt, it is preferred that metal Salt is platinum salt.
Preferably, the concentration of the reducing agent aqueous solution is 0.1-1mol/L.
Preferably, the concentration of the aqueous metal salt is 1-10mmol/L.
Preferably, dip time of the carbon-based material in reductant solution and metal salt solution is no more than 30s, long Dip time can cause feed blocking hole, reduce the catalytic activity of material.
Preferably, the carbon-based material is activated carbon, graphite, graphene, CNT or carbon cloth, more preferably activity Charcoal.
Preferably, vacuum dried processing before the aqueous solution of the carbon-based material immersion reducing agent.
Preferably, the carbon-based material stands 0.5-2 hours in air again after reductant solution taking-up, enters back into metal Salting liquid.Reductant solution can be allowed to be fully infiltrated into the space of carbon-based material, can by carbon-based material exposure air for a period of time To allow material to be fully infiltrated into material hole, increase the specific surface area of metal nano.
Metallic atom is deposited on carbon-based material surface by the present invention by the method for in-situ reducing, is needed not move through calcining, is urged Metal nanoparticle in agent is non-lattice structure, and reducing activity is high, and technological process is simple, and manufacturing cost is low.
Embodiment
Embodiment one
From commercially available activated carbon (Fluka), PdCl2(Aldrich, 99.999%), NaH2PO2·H2O (Aldrich, >= 99%).Alternative commercially available 2.0wt% Pt-C, 2.0wt% Pd-C samples are as control.
(1) 30mg activated carbon is taken, is dried 2 hours at 100 DEG C in a vacuum.
(2) 2.12 grams of NaH are weighed2PO2·H2O, it is dissolved in 100ml deionized waters (DI-H2O 0.2M NaH are configured in)2PO2 The aqueous solution (solution A).
(3) 35.5mg PdCl are weighed2, it is dissolved in 100ml deionized waters (DI-H2O) it is configured to 2mM PdCl2The aqueous solution is (molten Liquid B).
(4) after dried 30mg activated carbons are impregnated 10 seconds in 2ml solution As, 1 hour is stood in atmosphere.
(5) after and then being impregnated 10 seconds in 1.7ml solution Bs again, 1 hour is stood in atmosphere.
(6) under vacuum conditions, after material being washed with deionized into 2 times, 2 hours in standing, continue in a vacuum 80 DEG C are handled 2 hours.
Dried sample marker is Pd-P samples.
Hydrogen reduction electro-catalysis work is carried out to the above-mentioned sample of same sample weight using rotating disk electrode (r.d.e) device (RRED) Property measure.The experiment be using RRED devices by linear sweep voltammetry in oxygen-saturated KOH solution (0.1M) to above-mentioned What oxygen reduction catalyst was evaluated, as a result as shown in table 1.
Table 1
Sample Half wave potential (V) Activity (mA/cm2) Mass activity (mA/ μ g2)
Pd-C 0.75 0.48 0.07
Pt-C 0.86 1.59 0.19
Pd-P(3) 0.81 2.3 1.78
Pd-P(9) 0.84 5.15 2.19
Pd-P(18) 0.89 6.86 3.21
As it can be seen from table 1 result of the test shows that commercially available Pt-C and Pd-C hydrogen reduction electro catalytic activity are more stable.Its Middle Pt-C activity is significantly higher than Pd-C's.And the present invention Pd-P electro catalytic activities apparently higher than commercial samples, while its live Property increase in the starting stage with the increase of cycle-index, reach 18 times circulation after gradually settle out.The Pd-P of the present invention The activity and mass activity of oxygen reduction electro-catalyst reach as high as 6.86mA/cm2With 3.21mA/ μ g2., it is commercially available Pt-C oxygen respectively Reduce 4 times and 17 times of elctro-catalyst, and 14 times and 46 times of commercially available Pd-C oxygen reduction electro-catalysts.
Embodiment two
From commercially available activated carbon (Fluka), PdCl2(Aldrich, 99.999%), N2H4·H2O (Sigma-Aldrich, 64-65%, regent grade, 98%).The Pd-C samples for selecting commercially available 2.0wt% Pt-C, 2.0wt% else compare.
(1) 30mg activated carbon is taken, is dried 2 hours under 100C in a vacuum.
(2) 1.6ml N are weighed2H4·H2O, it is dissolved in 100ml deionized waters (DI-H2O 0.2M N are configured in)2H4The aqueous solution (solution A).
(3) 35.5mg PdCl are weighed2, it is dissolved in 100ml deionized waters (DI-H2O) it is configured to 2mM PdCl2The aqueous solution is (molten Liquid B).
(4) after dried 30mg activated carbon is impregnated 10 seconds in 2ml solution As, 1 hour is stood in atmosphere.
(5) after and then being impregnated 10 seconds in 1.7ml solution Bs again, 1 hour is stood in atmosphere.
(6) under vacuum conditions, after material being washed with deionized into 2 times, 2 hours in standing, continue in a vacuum 80 DEG C are handled 2 hours.
Dried sample marker is Pd-N2H4Sample.
Hydrogen reduction electro-catalysis work is carried out to the above-mentioned sample of same sample weight using rotating disk electrode (r.d.e) device (RRED) Property measure.The experiment be using RRED devices by linear sweep voltammetry in oxygen-saturated KOH solution (0.1M) to above-mentioned What oxygen reduction catalyst was evaluated, as a result as shown in table 2.
Table 2
Sample Half wave potential (V) Activity (mA/cm2) Mass activity (mA/ μ g2)
Pd-C 0.75 0.48 0.07
Pt-C 0.86 1.59 0.19
Pd-N2H4(3) 0.77 2.15 1.1
Pd-N2H4(9) 0.82 2.85 1.31
Pd-N2H4(18) 0.83 3.52 1.44
From table 2 it can be seen that the Pd-N of the present invention2H4Electro catalytic activity is apparently higher than commercial samples, while its activity is first Stage beginning increases with the increase of cycle-index, is gradually settled out after reaching 18 circulations.The Pd-N of the present invention2H4Oxygen is also The activity and mass activity of former elctro-catalyst reach as high as 3.52mA/cm2With 1.44mA/ μ g2.Although than the Pd-P of embodiment one Sample is low, but is also respectively 2 times and 8 times of commercially available Pt-C oxygen reduction electro-catalysts, and commercially available Pd-C hydrogen reduction electro-catalysis 7 times of agent and 21 times.

Claims (4)

1. a kind of preparation method of fuel battery cathode with proton exchange film oxygen reduction electro-catalyst, it is characterised in that including following Step：Carbon-based material is immersed in reducing agent aqueous solution, immerses aqueous metal salt after taking-up again, after the completion of taking out reaction, is washed Wash, be dried in vacuo, finished product；
Reducing agent is that hydrazine or ortho phosphorous acid are received；
Metal salt is platinum salt or palladium salt；
Dip time of the carbon-based material in reducing agent aqueous solution and aqueous metal salt is no more than 30s；
The carbon-based material stands 0.5-2 hours in atmosphere after reducing agent aqueous solution taking-up, then immerses aqueous metal salt；
The carbon-based material immerses vacuum dried processing before reducing agent aqueous solution.
2. preparation method as claimed in claim 1, it is characterised in that the concentration of the reducing agent aqueous solution is 0.1-1mol/ L。
3. preparation method as claimed in claim 1, it is characterised in that the concentration of the aqueous metal salt is 1-10mmol/ L。
4. preparation method as claimed in claim 1, it is characterised in that the carbon-based material be activated carbon, graphite, graphene, CNT or carbon cloth.
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Address after: 313100 Coal Mountain Industrial Park, Changxing County, Huzhou City, Zhejiang Province

Patentee after: TIANNENG BATTERY GROUP Co.,Ltd.

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Denomination of invention: Preparation method of cathode oxygen reduction electrocatalyst for proton exchange membrane fuel cell

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Record date: 20220810