CN109507240A - The method for assessing fuel-cell catalyst oxygen reduction activity under specified potential - Google Patents

The method for assessing fuel-cell catalyst oxygen reduction activity under specified potential Download PDF

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Publication number
CN109507240A
CN109507240A CN201811230728.8A CN201811230728A CN109507240A CN 109507240 A CN109507240 A CN 109507240A CN 201811230728 A CN201811230728 A CN 201811230728A CN 109507240 A CN109507240 A CN 109507240A
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fuel
fuel cell
oxygen reduction
reduction activity
activity under
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潘牧
饶妍
谭金婷
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid

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Abstract

The present invention devises a kind of method for assessing fuel-cell catalyst oxygen reduction activity under specified potential, including measurement fuel cell in the electrochemical impedance spectroscopy in different potential sections, obtains the charge transfer impedance value of cathode.The electrochemical impedance spectroscopy of fuel cell can be tested under different potentials, can use constant current mode or constant voltage mode.Cathode charge transfer impedance value is obtained by the electrochemical impedance spectroscopy of fuel cell, can be obtained using Equivalent Circuit Fitting method, or the analytic method acquisition of frequency dividing, programming can be used.Compared with traditional catalyst characterization method, the present invention is used as indicator using charge transfer impedance, not only it is applicable at high potential 0.9V, and activity of the catalyst under fuel cell real work potential can be assessed, can be filtered out for membrane electrode of fuel batter with proton exchange film high activated catalyst.

Description

The method for assessing fuel-cell catalyst oxygen reduction activity under specified potential
Technical field
The invention belongs to catalyst of fuel batter with proton exchange film assessment technology field more particularly to a kind of assessment fuel electricity The method of pond catalyst oxygen reduction activity under specified potential.
Background technique
Proton Exchange Membrane Fuel Cells is due to very high power density and clean and environmental protection, it has also become energy of greatest concern Source device.High cost is to hinder the significant bottleneck of Proton Exchange Membrane Fuel Cells commercialized development, and wherein Pt base catalyst It uses, greatly improves the cost of fuel cell.In order to which compared with internal combustion engine cost, Proton Exchange Membrane Fuel Cells is required 10g precious metals pt is used only on the automobile that a power is 80kW, i.e. every kilowatt of electricity only needs 0.125 gram of Pt dosage.Accordingly, U.S. DOE proposes 1W/cm2Membrane electrode performance indicator, corresponding Pt carrying capacity be 0.125mg/cm2.It is required that the Pt of membrane electrode Dosage 0.125g/kW, power density reach 1.4W/cm2Performance indicator, then corresponding Pt carrying capacity be 0.175mg/cm2.So Developing the low high performance membrane electrode of Pt carrying capacity is to promote the commercialized the only way which must be passed of Proton Exchange Membrane Fuel Cells.
With the reduction of cathode Pt carrying capacity, especially when Pt carrying capacity is down to 0.1mg/cm2When following, activation overpotential can be anxious Increase severely big, this depends on the activity of catalyst oxygen reduction reaction, so seeking to have higher active catalyst is one Important topic.U.S. DOE proposes that the performance indicator of the year two thousand twenty vehicle fuel battery catalyst will reach 0.44 A/ at 0.9V The quality specific activity of mg, 0.7mA/cm2Area specific activity.DOE annual work assessment report shows that Pt alloy is urged within 2016 The activity of agent is above Pt/C catalyst and has reached even more than this index.But it is made of Pt alloy catalyst Membrane electrode performance be lower than membrane electrode performance made of Pt/C catalyst instead in real work voltage range.PtCo, PtNi are closed Au catalyst can reach the catalyst index of DOE, but cannot reach the performance indicator of membrane electrode, therefore cannot be under 0.9V Performance of the oxygen reduction activity evaluation catalyst in membrane electrode.And the indicator of catalytic oxygen reduction activity, including DOE at present The index provided is applicable under high potential, and activity can not represent catalyst in fuel cell real work section The catalytic activity of (0.8V-0.6V), so we, which not only need to find, has higher active catalyst, with greater need in fuel electricity The specified potential section in pond has the catalyst of high catalytic activity, the characterizing method of Study of Catalyst catalytic activity under specified potential To screening, high performance fuel cell membrane electrode oxygen reduction catalyst is most important.
Summary of the invention
A kind of the technical problem to be solved by the invention is to provide assessment fuel-cell catalysts under specified potential oxygen is also Former active method can assess catalyst between High potential area, and the catalytic activity in specified potential section.
The technical solution adopted by the present invention to solve the technical problems is: providing a kind of assessment fuel-cell catalyst in volume Determine the method for oxygen reduction activity under potential, this approach includes the following steps, electrification of the measurement fuel cell in different potential sections Impedance spectrum is learned, the charge transfer impedance value of cathode is obtained.
Charge transfer impedance value is smaller, represents electrochemical reaction and is easier to occur, catalyst has higher catalytic activity.
Tafel slope can be obtained by charge transfer impedance Rct backstepping according to calculation formula, to obtain different potentials Under Tafel slope value, calculation formula is as follows:
Derivation process are as follows: under high overpotential, Butler-Volmer equation can simplify are as follows:
J=j0eαnFη/RT) (1)
Tafel equation is solved,
According to the definition of charge transfer impedance,
Simultaneous (2), (3) formula obtain:
Wherein, b is Tafel slope.
Rct(Charge-transfer resistance) is charge transfer impedance.
Wherein: η is activation overpotential；
J is current density；
R is ideal gas constant, numerical value 8.314J/mol；
F is Faraday constant, numerical value 96485C/mol；
T is thermodynamic temperature, unit K；
α is charge transmission coefficient, and for oxygen reduction reaction, numerical value is generally 0.5；
N is the electronics transfer number of oxygen reduction reaction rate controlling elementary reaction, it is considered that its numerical value is 2；
j0It is exchange current density.
According to the above technical scheme, measurement fuel cell has in the test condition of the electrochemical impedance time spectrum in different potential sections Body is that fuel battery negative pole side uses high-purity (oxygen concentration >=99.999%) oxygen, and gas flow >=1000mL/min, Gas excess coefficient ratio >=9.5/2 of cathode and anode.To guarantee that gaseous mass is transmitted to limitation bring influence to be dropped to most It is low.
According to the above technical scheme, the electrochemical impedance spectroscopy of fuel cell can be tested under different potentials.
According to the above technical scheme, the frequency of the electrochemical impedance spectroscopy test of fuel cell is 1000000Hz-0.01Hz, is disturbed Fatigue resistance is 5%-10% current strength.
According to the above technical scheme, the electrochemical impedance spectroscopy test of fuel cell uses constant current mode or constant voltage mould Formula.
According to the above technical scheme, cathode charge transfer impedance value is obtained by the electrochemical impedance spectroscopy of fuel cell, can adopted It is obtained with Equivalent Circuit Fitting method, or the analytic method acquisition of frequency dividing, programming can be used.
According to the above technical scheme, the frequency of the electrochemical impedance spectroscopy test of fuel cell is 10000Hz-0.1Hz, and disturbance is strong Degree is 10% current strength.
According to the above technical scheme, different test sections includes, can be in specified potential section, including end value；Or OCV (open-circuit voltage) is to the section 0.9V, including end value；It or does not include end value in the section 0.9V-0.8V；Or in 0.6V Following potential section is tested.Specified potential section refers to 0.6V-0.8V.
The beneficial effect comprise that: (1) charge transfer impedance be used as indicator, not only fits at high potential 0.9V With can more assess oxygen reduction activity of the catalyst under fuel cell real work potential.
(2) it uses charge transfer impedance as active indicator, high performance fuel cell membrane electrode can be filtered out and used Oxygen reduction catalyst.
(3) electrochemical impedance spectroscopy experiment is relatively easy, and can nondestructively obtain the bulk information of cell components.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples, in attached drawing:
Fig. 1 is obtained 40mA/cm in embodiment 12-400mA/cm2Under electrochemical impedance spectroscopy；
Fig. 2 is obtained 500mA/cm in embodiment 12-1100mA/cm2Under electrochemical impedance spectroscopy；
Fig. 3 is obtained 1200mA/cm in embodiment 12-1700mA/cm2Under electrochemical impedance spectroscopy；
Fig. 4 is change curve of the obtained Tafel slope extrapolated by charge transfer impedance of embodiment 1 with voltage；
Fig. 5 is the charge transfer impedance of embodiment 1 and embodiment 2 under different potentials；
Fig. 6 is the equivalent-circuit model in embodiment 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not For limiting the present invention.
Embodiment 1:
Fig. 1-Fig. 3 is the electrochemical impedance spectroscopy under different current densities, test condition are as follows: battery temperature be 75 DEG C, 100% Humidification, hydrogen-oxygen blowing model, firm discharge is respectively 1000mL/min and 2500mL/min, and anode and cathode applies 150kPa back pressure.Using constant current test pattern, 10% current disturbing intensity, test frequency range is 10,000Hz- 0.1Hz.Under this test condition, the semicircle then very little for the mass transport impedance that low frequency range represents in electrochemical impedance spectrogram, quilt It covers；Quickly due to hydroxide reaction rate, the charge transfer impedance of anode is generally negligible for anode；So can only be seen in Fig. 1 The semicircle big to one occupies leading position, and corresponding is the charge transfer impedance of cathode catalysis layer.It can see with being apparent, Half diameter of a circle reduces with the increase of current density, i.e., cathode charge transfer impedance subtracts with the increase of current density It is small.
Equivalent-circuit model is selected, as shown in fig. 6, obtaining the electricity of cathode to parse the electrochemical impedance spectroscopy that experiment measures Lotus transfer impedance value (Rct represents charge transfer impedance in model).
According to the formula (4) being derived by summary of the invention, we can be extrapolated accordingly by charge transfer impedance Rct Tafel slope.Fig. 4 is change curve of the Tafel slope with voltage by charge transfer impedance according to formula to calculating out, Cong Tuzhong Can clearly it see between High potential area, (> 0.8V), Tafel slope is substantially a definite value (80mV/dec. or so), At the lower section of potential (< 0.8V), Tafel slope can be gradually increased with the reduction of potential.With trend one reported in document It causes, it is seen then that it is reasonable that catalyst activity is assessed with charge transfer impedance.
Embodiment 2:
Fig. 5 is the charge transfer impedance value of the Pt/C catalyst and PtCo/C catalyst in 0.65V-0.95V potential section. Test condition are as follows: battery temperature is 75 DEG C, and 100% humidification, hydrogen-oxygen blowing model, firm discharge is respectively 1000mL/ Min and 2500mL/min, anode and cathode apply 150kPa back pressure.Using constant current test pattern, 10% current disturbing is strong Degree, test frequency range are 10,000Hz-0.1Hz.It is greater than PtCo/C in the charge transfer impedance of High potential area, Pt/C catalyst Catalyst, PtCo/C catalyst have more preferably catalytic performance；And in low potential area, the i.e. specified work of Proton Exchange Membrane Fuel Cells Make potential section, the charge transfer impedance of Pt/C catalyst is suitable with PtCo/C catalyst, and the two catalytic activity is very close, because This, catalytic activity of the PtCo/C alloy catalyst within the scope of fuel cell membrane electrode rated operational voltage and Pt/C are close, make The membrane electrode performance and Pt/C catalyst of its handy preparation are close.Due to the leaching etc. of catalyst layer structure design and alloy catalyst The influence of factor, in high current density region, the performance of alloy catalyst can be lower than Pt/C catalyst instead.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description, And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.

Claims (8)

1. a kind of method for assessing fuel-cell catalyst oxygen reduction activity under specified potential, which is characterized in that this method packet Following steps are included, fuel cell is measured in the electrochemical impedance spectroscopy in different potential sections, obtains the charge transfer impedance value of cathode.
2. the method for assessment fuel-cell catalyst oxygen reduction activity under specified potential according to claim 1, special Sign is, measures fuel cell in the test condition of the electrochemical impedance time spectrum in different potential sections specifically, fuel cell is negative Pole side uses high purity oxygen gas, and gas flow >=1000mL/min, gas excess coefficient ratio >=9.5/2 of cathode and anode.
3. the method for assessment fuel-cell catalyst oxygen reduction activity under specified potential according to claim 1 or 2, It is characterized in that, the electrochemical impedance spectroscopy of fuel cell can be tested under different potentials.
4. the method for assessment fuel-cell catalyst oxygen reduction activity under specified potential according to claim 1 or 2, It is characterized in that, the frequency of the electrochemical impedance spectroscopy test of fuel cell is 1000000Hz-0.01Hz, strength of turbulence 5%- 10% current strength.
5. the method for assessment fuel-cell catalyst oxygen reduction activity under specified potential according to claim 1 or 2, It is characterized in that, the electrochemical impedance spectroscopy test of fuel cell uses constant current mode or constant voltage mode.
6. the method for assessment fuel-cell catalyst oxygen reduction activity under specified potential according to claim 1 or 2, It is characterized in that, cathode charge transfer impedance value is obtained by the electrochemical impedance spectroscopy of fuel cell, Equivalent Circuit Fitting can be used Method obtains, or the analytic method acquisition of frequency dividing, programming can be used.
7. the method for assessment fuel-cell catalyst oxygen reduction activity under specified potential according to claim 4, special Sign is that the frequency of the electrochemical impedance spectroscopy test of fuel cell is 10000Hz-0.1Hz, and strength of turbulence is that 10% electric current is strong Degree.
8. the method for assessment fuel-cell catalyst oxygen reduction activity under specified potential according to claim 3, special Sign is, different test sections includes, can be in specified potential section, including end value；Or in OCV to the section 0.9V, packet Include end value；It or does not include end value in the section 0.9V-0.8V；Or it is tested in 0.6V or less potential section.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110530954A (en) * 2019-08-28 2019-12-03 上海交通大学 A kind of non-precious metal catalyst membrane electrode durability test method
CN111257385A (en) * 2020-01-20 2020-06-09 华侨大学 Oxygen reduction activity testing device and method based on gas diffusion electrode
CN115856038A (en) * 2022-12-27 2023-03-28 武汉理工大学 Method for evaluating oxidation resistance of Pt-based oxygen reduction catalyst through charge transfer resistance

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CN104409752B (en) * 2014-11-07 2016-09-21 清华大学 The equivalent circuit group of evaluation and test fuel battery anode catalyst superficial catalytic activation and evaluating method
JP2017018858A (en) * 2015-07-07 2017-01-26 昭和電工株式会社 Method for evaluating oxygen reduction catalyst, and selection method therefor
CN106450358A (en) * 2016-12-08 2017-02-22 湘潭大学 N-doped carbon nano-tube/carbon compound oxygen reduction catalyst and preparation method thereof

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CN104409752B (en) * 2014-11-07 2016-09-21 清华大学 The equivalent circuit group of evaluation and test fuel battery anode catalyst superficial catalytic activation and evaluating method
JP2017018858A (en) * 2015-07-07 2017-01-26 昭和電工株式会社 Method for evaluating oxygen reduction catalyst, and selection method therefor
CN106450358A (en) * 2016-12-08 2017-02-22 湘潭大学 N-doped carbon nano-tube/carbon compound oxygen reduction catalyst and preparation method thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110530954A (en) * 2019-08-28 2019-12-03 上海交通大学 A kind of non-precious metal catalyst membrane electrode durability test method
CN111257385A (en) * 2020-01-20 2020-06-09 华侨大学 Oxygen reduction activity testing device and method based on gas diffusion electrode
CN115856038A (en) * 2022-12-27 2023-03-28 武汉理工大学 Method for evaluating oxidation resistance of Pt-based oxygen reduction catalyst through charge transfer resistance
CN115856038B (en) * 2022-12-27 2024-07-30 武汉理工大学 Method for evaluating oxidation resistance of Pt-based oxygen reduction catalyst by charge transfer impedance

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