CN104716341B - One kind improves the anti-SO of fuel-cell catalyst2The auxiliary agent and adding method of poisoning performance - Google Patents

One kind improves the anti-SO of fuel-cell catalyst2The auxiliary agent and adding method of poisoning performance Download PDF

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CN104716341B
CN104716341B CN201310691086.2A CN201310691086A CN104716341B CN 104716341 B CN104716341 B CN 104716341B CN 201310691086 A CN201310691086 A CN 201310691086A CN 104716341 B CN104716341 B CN 104716341B
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ruo
catalyst
fuel
auxiliary agent
cell
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CN104716341A (en
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邵志刚
谢峰
秦晓平
张耕
衣宝廉
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

The anti-SO of fuel-cell catalyst is improved the invention provides one kind2The auxiliary agent and adding method of poisoning performance.The composition of auxiliary agent is RuO2, adding method is a certain amount of RuO2It is mixed in PEMFC catalyst in alcohol solution, slurry is formed after agitated, ultrasonic disperse, then this is pulp centrifuged, wash, drying obtains target mixture catalyst.The catalyst is as the cathod catalyst of fuel cell in use, with good anti-SO2Poisoning performance.The anti-SO of fuel-cell catalyst is improved the invention provides one kind2The auxiliary agent and adding method of poisoning performance, it is, simple to operate with raw material sources extensively, the advantages of energy-conserving and environment-protective.

Description

One kind improves the anti-SO of fuel-cell catalyst2The auxiliary agent and adding method of poisoning performance
Technical field
It is specifically a kind of to improve the anti-SO of fuel-cell catalyst the present invention relates to low-temperature fuel cell field2Poisoning The auxiliary agent and adding method of performance.
Background technology
With the increasingly depleted of fossil energy, and environmental pollution and climate change is increasingly serious, and clean energy resource is Cause the great attention of countries in the world.Proton Exchange Membrane Fuel Cells has cleaning, efficient, power density height and low temperature fast The advantages of speed starts, has a wide range of applications in the field such as vehicle power and distributed power generation.But, pem fuel electricity SO in the problem of large-scale application in pond is faced with ambient impurities adaptability, especially air2Battery performance can be produced tight The influence of irreversible recovery while weight.
SO in air2Influence to fuel battery performance, is mainly reflected in its influence to catalyst performance.SO2Very Characteristic Adsorption easily is produced on the catalyst metals nano particle Pt of fuel cell, the active sites on Pt surfaces are occupied, this side Face hinders O2Hydrogen reduction process on Pt surfaces, another aspect SO2Chemisorbed on Pt surfaces, changes Pt surface electricity Lotus is distributed, so that part changes the path of hydrogen reduction, hydrogen reduction is changed into 2 electronic processes by 4 electronic processes, so as to produce big The H of amount2O2, the performance of the film of fuel cell is decayed rapidly.
The current fuel cell that solves is easily by SO in air2The strategy of influence, mainly external purifying and interior purification.External purifying bag Include an additional SO2Adsorbent equipment, makes the SO in air2First it is adsorbed before battery is entered.External purifying has the following disadvantages： One is the increase in the complexity and cost of system, and two be that often purification capacity is limited or purification is not complete enough for external purifying, this Result in the need for frequently changing external purifying device, so that becoming more troublesome using fuel cell.Interior purification is mainly included in combustion Expect that inside battery increases an adsorption element or uses anti-SO2Fouled catalyst.Internally increase an adsorption element, it lacks Point is the same with external purifying, and adsorption capacity is limited, and absorption is incomplete, and it is more complicated to change the operation of adsorption layer.So, using anti- SO2Fouled catalyst is as the method that can be purified, with the complexity for not increasing system, environmental protection convenient and simple for operation etc. Advantage, is the target that people pursue.
However, current both at home and abroad without the excessively anti-SO of document report2Fouled catalyst, this aspect is because ambient impurities SO in adaptability, particularly air ambient2Foreign gas adaptability problem is just proposed in recent years, is a brand-new class Topic；On the other hand, due to SO2It is particularly easy to produce characteristic suction in most of metal, particularly metal nanoparticle surface It is attached, it is necessary to be modified to avoid this Characteristic Adsorption by the surface of metal nanoparticle, this fundamental research and it is actual should Also compare shortage in.Garsany et al.（Journal of The Electrochemical Society,2007,154 (7), B670-B675）It has studied SO2In Pt/C and Pt3The absorption situation on Co/C surfaces, it is believed that Pt3Co is easier by SO than Pt2 Influence, but Pt3Co is aoxidized more easily by high potential and is made the SO of absorption2Desorption.Fu Jie et al.（One kind is in proton exchange The method of purification cathode reaction gas, Chinese Patent Application No. inside membrane cell：200810229122.2）Use highly conductive oil Vulcan XC-72 carbon blacks in burnt matter activated carbon replacing fuel cell cathode microporous layers, using activated carbon high-specific surface area and Abundant active sites, the foreign gas molecule such as SO to entering battery2Deng being adsorbed, make the SO of the actual contact of Catalytic Layer2Concentration Less than 1ppm, the protection to fuel-cell catalyst is realized to a certain extent, adds the anti-SO of battery2Poisoning performance.
Using RuO2Auxiliary agent improves the anti-SO2 poisoning performances of fuel-cell catalyst, it is to avoid common inside purifying method is inhaled The problem of attached finite capacity, adsorption layer are difficult to regeneration, while additional components and increase system needed for avoiding external purifying method The problem of burden, and, it is simple to operate, the advantages of energy-conserving and environment-protective. with raw material sources extensively.
The content of the invention
It is an object of the invention to propose a kind of anti-SO of raising fuel-cell catalyst2The auxiliary agent of poisoning performance and addition side Method.The composition of auxiliary agent is RuO2, its particle size is in 1~50nm, by RuO2It is added in fuel-cell catalyst, RuO2With combustion The mass ratio for expecting cell catalyst is 1:10~10:1.RuO2It is added to by physical method in fuel-cell catalyst, specifically Comprise the following steps：
1）By fuel-cell catalyst and RuO2As solids, 1 is pressed with alcohol solution：8~150 mass ratio mixing, Slurry, wherein fuel-cell catalyst and RuO are made by stirring, ultrasonic disperse2Mass ratio be 1：10~10:1, alcohol is water-soluble The mass ratio of liquid reclaimed water and alcohol is 1：100~100:1, alcohol is more than one or both of ethanol, normal propyl alcohol, isopropanol.
2）By above-mentioned pulp centrifuged separation, washing is placed in handling in vacuum drying chamber, treatment temperature is 60~100 DEG C, Processing time is 0.5~24 hour.Obtained product is purpose catalyst.
Brief description of the drawings
The Pt_RuO that Fig. 1 is prepared for the TEM photos (a) and embodiment one of commercialized Pt/C catalyst2/ C catalyst The comparison diagram of TEM photos (b), wherein Pt and RuO2Particle diameter in 3~8nm or so, and be uniformly dispersed.
Fig. 2 is electrochemical surface area and the curve of the relation of poisoning time in embodiment two.
Fig. 3 is hydrogen reduction and the curve of poisoning time relationship in embodiment two.
Fig. 4 is oxygen reduction activity and the relation of residual activity area in embodiment two
Embodiment
Embodiment 1
40mg Johnson Matthey (JM) 40wt.%Pt/C catalyst is weighed, 15 mg RuO are charged with2 (prepared by Adams methods, particle diameter about 7nm), adding 1ml deionized waters infiltrates solid, then is charged with absolute ethyl alcohol 4ml, stirs Mix 30 minutes, ultrasonic disperse 90 minutes, wherein the power of ultrasound is 200W, ultrasonic frequency is 53kHz.Afterwards by gained slurry Centrifugation, washing, and in vacuum drying chamber 80 DEG C dry 10 hours, obtain Pt_RuO2/ C catalyst.
The TEM photographs of catalyst obtained by the present embodiment are shown in Fig. 1.As seen from Figure 1, RuO is mixed2Grain on carrier afterwards Sub- density is significantly increased, while particle distribution is homogeneous, and granular size is between 2~10 nm.
Embodiment 2
5mg JM40%Pt/C catalyst and 1mg RuO are weighed respectively2, adding 0.2ml deionized waters infiltrates solid, then Absolute ethyl alcohol 1ml is charged with, simultaneously ultrasonic disperse 60 minutes, afterwards that gained is pulp centrifuged, washing is shaken up, and do in vacuum Dried 10 hours for 80 DEG C in dry case, obtain Pt_RuO2/ C catalyst.Using the catalyst and undoped with RuO2The Pt/C of auxiliary agent is urged Agent is compared, and contrasts the anti-SO of the two2Poisoning performance.The Nafion that 50 μ l5wt% are added into mixture catalyzer is different Propyl alcohol mixed solution, then it is charged with 1ml isopropanol, 60 minutes obtained slurries of ultrasonic disperse.The 3 μ l slurries are taken to be coated in rotation Turn disk electrode（RDE）Go up and dry.The electrode is first swept into CV activation in three-electrode system（Three-electrode system：Using RDE as work Make electrode, saturated calomel electrode（SCE）For reference electrode, 0.5M H2SO4For electrolyte, potential range is 0.05V-1.2V- 0.05V vs.RHE, it is 50mV/s to sweep speed）To CV curve co-insides.The poisoning experiment of catalyst is carried out on this basis, to verify RuO2The anti-SO of raising fuel cell of auxiliary agent2The effect of poisoning performance.In above-mentioned three-electrode system, electrolyte be changed to containing 0.2mM Na2SO30.5M H2SO4Solution, by the electrode activated respectively in 0.65V（vs.RHE）Lower constant potential 0.5 minute, 1 minute, 2 minutes, 5 minutes.The electrode is taken out, with about 100ml deionized water rinsing electrode surfaces, makes the SO of non-chemisorbed2 It is rinsed.Then the electrode after being poisoned is placed in above-mentioned three-electrode system, electrolyte changes 0.5M H into2SO4Solution, first In 0.05V（vs.RHE）Lower constant potential 10 minutes, then carries out CV scannings, and scanning range is 0.05V to 1.4V（vs.RHE）, Take the integral area of the curve in 0.05V to 0.4V in first lap (vs.RHE) to be calculated, after being poisoned and absorption SO2 0 valency S remaining ECA is reduced into, this ECA and initial p t ECA are divided by, normalized remaining ECA, is designated as after being poisoned The coverage of hydrogen（θH）, by θHTo the mapping of poisoning time, curve obtained is as shown in Figure 2.Figure it is seen that poisoning same time When, Pt_RuO2/ C θHIt is higher than Pt/C, illustrate Pt_RuO2/ C is avoiding avtive spot by SO2Covering, i.e., in anti-SO2In Performance in terms of poison is better than pure Pt/C.
Handled by identical, Pt/C and Pt_RuO are prepared respectively2/ C's is not poisoned and SO2Electrode after poisoning（Not By low potential reduction treatment）.This electrode is placed in progress ORR tests in three-electrode system, electrolyte is full of O20.5M H2SO4Solution, potential scan scope is 1.0V to 0.2V, and sweep speed is 5mV/s, and rotary rpm is 1600rpm.After being poisoned Obtained dynamics electric current Ik（0.9V vs.RHE）With the I not being poisonedkIt is divided by, obtains normalized dynamics electric current Iknorm.Will This oxygen reduction activity value is mapped to the poisoning time, as a result as shown in Figure 3.As seen from Figure 3, it is poisoned and operates by identical, Pt_RuO2/ C has the oxygen reduction activity higher than pure Pt/C, illustrates Pt_RuO2/ C has higher anti-SO2Poisoning capability.
Above-mentioned IknormTo θHMapping, as a result as shown in Figure 4.From fig. 4, it can be seen that identical θHUnder the conditions of IknormValue, Pt_RuO2/ C's is higher than Pt/C, illustrates RuO2Presence, it is possible to change the charge distribution state on Pt surfaces so that Even if making it adsorb same amount of SO2When, its ORR activity is also higher than pure Pt/C, illustrates Pt_RuO2/ C has higher anti-SO2 The ability of poisoning.

Claims (4)

1. one kind improves the anti-SO of fuel battery cathod catalyst2The auxiliary agent of poisoning performance, it is characterised in that：The composition of auxiliary agent is RuO2, the active component of the catalyst is Pt；RuO2Granular size is in 1~50nm；
Fuel battery cathod catalyst and RuO2Mass ratio be 1:10~10:1.
2. it is a kind of toward addition auxiliary agent RuO in fuel battery cathod catalyst2Method, it is characterised in that：Comprise the following steps that：
1) by fuel battery cathod catalyst and RuO2As solids, 1 is pressed with alcohol solution：8~150 mass ratio mixing, leads to Cross stirring, ultrasonic disperse and slurry, wherein fuel cell cathode cell catalyst and RuO is made2Mass ratio be 1：10~10:1, alcohol water The mass ratio of solution reclaimed water and alcohol is 1：100~100:1；
2) by step 1) in prepare slurries filtration, washing, and under vacuum conditions 60~100 DEG C handle 0.5~24 hour, obtain To RuO2The fuel battery cathod catalyst of modification.
3. the method according to claims 2, it is characterised in that：Fuel battery cathod catalyst and RuO2In nanoscale water It is uniformly dispersed on flat.
4. the method according to claims 2, it is characterised in that：Alcohol is one kind or two in ethanol, normal propyl alcohol, isopropanol More than kind.
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