Max Planck Institute for Dynamics of Complex Technical Systems assisted in meeting the publication costs of this article.

1. Material preparation
<ol>
	<li>Cut and perforate two rectangular pieces of Teflon of the same size as the end plates by using a cutting press; take care and ensure that the holes are in the exact position where the bolts should be placed.</li>
	<li>Using the same procedure cut Teflon gaskets considering the outer and inner dimensions of the flow field, and the position of the holes where the screws should be placed.</li>
	<li>Cut the gas diffusion layers using a metal frame fitting the size of the gaskets.</li>
	<li>Cut the excess Nafion from the catalyst coated membrane (CCM) in order to adjust it to the size of the bipolar plates. Make holes in the membrane at the positions where the screws should go through with the help of the metal frame used previously. Take care to center the frame before making the holes.</li>
</ol>
2. Fuel cell assembly
<ol>
	<li>Place the cathode bipolar plate on a smooth and sturdy surface with the flow field side up.</li>
	<li>Place the gasket on top. Make sure it aligns with the screw holes.</li>
	<li>Place the cathode GDL in the middle of the gasket and put the CCM on top. Make sure the CCM is aligned with the screw holes.</li>
	<li>Place the anode GDL and gasket on top. Make sure the gasket aligns with the screw holes and the GDL is placed in the middle.</li>
	<li>Place the anode bipolar plate on top (flow field side down) and use screws to clamp the parts together. 
	NOTE: The bipolar plates must not be strongly tightened. The purpose of the screws is just to keep aligned the different parts.</li>
	<li>Place the cathode stainless steel end plate on a smooth and sturdy surface.</li>
	<li>Place the rectangular Teflon piece and the copper current collector on top. Make sure they align with the bolt holes.</li>
	<li>Slot the cathode side of the cell unit assembled in step 2.1 on the cathode current collector taking into account the notches in the flow fields.</li>
	<li>Slot the anode side of the unit on the anode current collector, position the Teflon gaskets and finish with the anode stainless steel end plate on top.</li>
	<li>Place the insulating sleeves, the O-ring and the bolts in the holes of the anode end plates; insert the bolts in the holes.</li>
	<li>Position the insulation sleeves and the O-ring; finish by placing the nuts on the bolts on the cathode side.</li>
	<li>Tighten the bolts crosswise using a torque-wrench until you reach the recommended torque value of 5 N&#183;m. 5 crosswise cycles are suggested; start by low torque value (1 N&#183;m) and increase by 1 N&#183;m in each subsequent cycle.</li>
</ol>
3. Integration of a fuel cell with the periphery
<ol>
	<li>Place the fuel cell in the heating box and connect the inlets and outlets to the periphery. Use snoop liquid to check for leakages.</li>
	<li>Insert the thermocouple in the cathode end plate.</li>
	<li>Interface the fuel cell with the potentiostat; choose 2 electrode-configuration. Connect the cables marked as RE and CE to the anode side and the ones marked as WE and SE to the cathode side.</li>
	<li>Start the software used to control the cell periphery; a scheme of the experimental setup is visualized (see schematic in Figure 1). Choose the values of the anode and cathode inlet gas flow rates and open the valves. In the experiments shown in this protocol, flow rates of 850, 300 and 300 mL/min were used for hydrogen (anode side), nitrogen and oxygen (cathode side) respectively.</li>
	<li>Choose the temperature of the inlet gases and turn on the heating tapes. Wait until the set point temperature is reached. In all experiments in this protocol, the set point temperature of the inlet gases at the anode and cathode side was 68 &#176;C.</li>
	<li>Set the temperatures of the thermostats to define the desired dew point temperature of the inlet gases; turn the thermostats on.</li>
	<li>Set the chosen temperature of the fuel cell on the control panel of the heating box. Then, turn the heating on. In the experiments described in this protocol a fuel cell temperature of 80 &#176;C was set.</li>
	<li>Wait until the set point temperature of the fuel cell is reached; check the humidification state of the inlet gases; check the fuel cell open circuit cell potential. The open circuit cell potential value on the display of the potentiostat should be between 1 and 1.2 V.</li>
</ol>
4. Fuel cell start up procedure
NOTE: The procedure described in the following section uses a specific software program and potentiostat (Autolab N104, NOVA 2.0 software). However, it can be also performed using other software and potentiostats without changing the main outcomes. The start-up procedure must be performed if a new CCM is used.
<ol>
	<li>Start the Autolab NOVA 2.0 software.
	<ol>
		<li>Select New Procedure in the Action section of the software; the procedure editing page opens.</li>
		<li>In Command, click on the Autolab Control icon ; drag the Autolab Control icon to the workspace section. Then, in Properties, select Mode On Potentiostatic. 
		NOTE: The Autolab NOVA 2.0 software does not differentiate between the terms potentiostatic and voltastatic.</li>
		<li>In Command, select the Cell icon and place it next to the Autolab Control icon. Then, in Properties choose Cell On. Add the Apply icon and in Properties set 0.9 V as Cell Potential with respect to the reference electrode.</li>
		<li>Add the Wait command and set Duration to 1800 s.</li>
		<li>Add the LSV Staircase command from Measurement Cyclic and Linear Sweep Voltammetry. Set the Start Potential to 0.9 V, the Stop Potential to 0.6 V, the Scan Rate to 0.4 mV/s and Step to 0.244 mV.</li>
		<li>Add the Wait command and set Duration to 1800 s.</li>
		<li>Add the LSV Staircase command from Measurement Cyclic and Linear Sweep Voltammetry. Set the Start Potential to 0.6 V, the Stop Potential to 0.9 V, the Scan Rate to 0.4 mV/s and the Step to 0.244 mV.</li>
		<li>Add the Repeat command. In the workspace select the commands from step 4.1.4 (the first Wait command) to step 4.1.7 (the last LSV Staircase command); drag and drop the icons into the Repeat box. In Properties asset the number of repetitions to 20.</li>
	</ol>
	</li>
	<li>Start the cell start up procedure by clicking the Play button.</li>
	<li>After 2 h, if the current is stable at 0.6 V stop the program by pressing on the Stop button. If the current is still changing, let the program run until it terminates.</li>
</ol>
5. Galvanostatic electrochemical impedance spectroscopy experiment
<ol>
	<li>Start the Autolab NOVA 2.0 software.
	<ol>
		<li>Select New Procedure in the Action section of the software; the procedure editing page opens.</li>
		<li>In Command click on the Autolab Control icon ; drag and drop the Autolab Control icon to the workspace section. Then, in Properties select Mode On Galvanostatic.</li>
		<li>Add the Cell On command.</li>
		<li>Add the LSV Staircase command. In Properties set the Start Current to 0 A, the chosen steady state current to Stop Current, the Scan Rate to 0.005 A/s and Step to 0.01 A.</li>
		<li>Insert the Record Signal command; in Properties set the Duration to 7200 s and the Interval Sampling Time to 0.1 s.</li>
		<li>Insert the FRA measurement command window. In Properties set the First applied frequency to 1000 Hz, the Last applied frequency to 0.01 Hz and the Number of frequencies per decade to 5. Set the Amplitude to 5% of the steady state current.</li>
		<li>Add the Cell Off command.</li>
	</ol>
	</li>
	<li>Start the cell galvanostatic EIS program by pressing the Play button.</li>
	<li>Wait until the cell potential value stabilizes by observing the change in the recording window. Then click on the Forward button to start the EIS experiment.</li>
	<li>Check the stability of the system during the experiment and wait until the program is terminated.</li>
</ol>
6. Concentration-alternating frequency response experiment
NOTE: The following instructions describe the procedure for performing cFRA experiments under galvanostatic conditions. However, the procedure would not differ if performing cFRA experiments under voltastatic conditions, apart from setting the galvanostatic to potentiostatic control in the software and fixing a certain cell potential as a steady state instead of current.
<ol>
	<li>Set up the Pyro fiber oxygen sensor for fast dynamic measurements.
	<ol>
		<li>Push gently down on the plunger in the upper part of the Pyro fiber oxygen sensor in order to remove the sensitive part of the fiber from the protective needle and place it in the center of the tubing at the cell inlet.</li>
		<li>Open the Pyro software.</li>
		<li>Click on Options | Advance and choose Enable Fast Sampling.</li>
		<li>Set the Sampling Interval to 0.15 s.</li>
	</ol>
	</li>
	<li>Edit the cFRA procedure by using Autolab NOVA 2.0 software.
	<ol>
		<li>Open the NOVA software and select New Procedure in the Action section ; the software editing page opens.</li>
		<li>In Commands select the Control icon and insert it in the workspace. In Properties select Mode On Galvanostatic. Then select the Cell On command and place it next to the Control icon.</li>
		<li>Add the LSV Staircase command from the Measurement Cyclic and Linear Sweep Voltammetry. In Properties set the Start Current to 0.0 A; set as Stop current the steady state current value at which the cFRA experiment should be performed. Then use 0.005 A/s as the Scan Rate and 0.01 A as the Step.</li>
		<li>Insert two Record Signal commands; in Properties set Duration to 7200 s and Interval Sampling Time to 0.05 s. Repeat the same step 20 times by adding a Repetition command. The number of repetitions must be equivalent to the number of signal frequencies that need to be measured. 
		NOTE: Two recording signal windows are convenient for the following reasons: one recording window is used to monitor the transient part of the periodic output signal, while the second one is used to register the steady state part of the periodic output signal. The steady state part of the signal is used for transfer function determinations.</li>
	</ol>
	</li>
	<li>Press the Play button to start the cFRA program.</li>
	<li>In the first set of repetitions, check if the cell potential reaches the steady state value by observing the recording window.</li>
	<li>Open the additional oxygen valve and set the mass flow controller to 5% of the value of the total flow rate of the main feed in order to ensure a linear response (example: set 30 mL/min with 600 mL/min of total flow rate). Then set the switching time of the valve to an initial value of 0.5 s. Press the switching control Start button.</li>
	<li>Monitor the recording window and wait until the cell potential achieves a periodic steady state; then click on the Next button.</li>
	<li>Register the periodic steady state signal in the new recording window for 60 s. Then, click again on the Next button.</li>
	<li>Simultaneously with the previous step 6.7, register the periodic oxygen input. Select the Start button in the sensor software, insert a name which recalls the frequency input (example: 1 Hz), and click on OK. Register the signal for 60 s as in the current output case and press the Stop button.</li>
	<li>Repeat the previous steps 6.6-6.8 at increasing switching time values in order to measure periodic input/output correlations for a frequency range from 8-1000 mHz by taking 8 frequency points per decade. For experiments at a frequency higher than 100 mHz, register input and output for 60 s. At lower frequencies, sample the signals for a range of time equivalent to 5 periods.</li>
</ol>
7. Analysis of cFRA data
<ol>
	<li>Export measured cell potential responses from the Autolab NOVA 2.0 software.
	<ol>
		<li>In the recording window click on the diagram with the measured periodic steady state cell potential output.</li>
		<li>Click on the Show Data | Key | Export buttons. Insert a file name which recalls the frequency of the input (Example: 1 Hz) and click on Save.</li>
		<li>Repeat steps 7.1.1-7.1.2 for each measured cell potential output at each frequency.</li>
	</ol>
	</li>
	<li>Open the Matlab scripts FFT_input.mat and FFT_output.mat. In the Address Folder section insert the specifications of the location of the folder where the measured oxygen pressure and current data files are stored. 
	NOTE: The script was written with the aim of performing the windowing of the collected inputs in order to have an integer number of periodic cycles to analyze, and calculate their Fourier transforms accurately and quickly. Any other procedure which performs the same task does not change the results.</li>
	<li>Run the FFT_PO2.mat and FFT_Pot.mat scripts; check in the plotted diagrams if the computed algorithm works properly (in the time domain, an integer number of input and output cycles should be extracted from the original input and output samples). 
	CAUTION: A Fourier transform based on a non-integer number of periodic cycles could result in misleading analysis of the inputs and outputs resulting in inaccurate cFRA spectra.</li>
	<li>Open the Matlab script cFRA_spectra.mat and run it. Magnitude, phase angle and Nyquist spectra of the cFRA transfer function under galvanostatic conditions are plotted. 
	NOTE: The script calculates the cFRA transfer function by using the Fourier transform values at the fundamental frequency of the oxygen pressure (inputs) and cell potential (outputs) signal using the following equation. 
<img src="/files/ftp_upload/60129/60129eq1.jpg" /></li>
</ol>

<ol>
	<li>Yuan, X., Wang, H., Sun, J. C., Zhang, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=AC+impedance+technique+in+PEM+fuel+cell+diagnosis+-+a+review.">AC impedance technique in PEM fuel cell diagnosis - a review.</a> International Journal of Hydrogen Energy. 32 (7), 4365-4380 (2007).</li><li>Niya, S. M. R., Hoorfar, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Study+of+proton+exchange+membrane+fuel+cells+using+electrochemical+impedance+spectroscopy+technique+-+a+review.">Study of proton exchange membrane fuel cells using electrochemical impedance spectroscopy technique - a review.</a> Journal of Power Sources. 240 (8), 281-293 (2013).</li><li>Niroumand, A. M., Merida, W., Eikerling, M., Safi, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Pressure+voltage+oscillations+as+diagnostic+tool+for+PEFC+cathode.">Pressure voltage oscillations as diagnostic tool for PEFC cathode.</a> Electrochemistry Communications. 12 (1), 122-124 (2010).</li><li>Engebretsen, E., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electro-thermal+impedance+spectroscopy+applied+to+an+open-cathode+polymer+electrolyte+fuel+cell.">Electro-thermal impedance spectroscopy applied to an open-cathode polymer electrolyte fuel cell.</a> Journal of Power Sources. 302, 210-214 (2014).</li><li>Engebretsen, E., Mason, T. J., Shearing, P. R., Hinds, G., Brett, D. J. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrochemical+pressure+impedance+spectroscopy+applied+to+the+study+of+polymer+electrolyte+fuel+cells.">Electrochemical pressure impedance spectroscopy applied to the study of polymer electrolyte fuel cells.</a> Electrochemistry Communications. 75, 60-63 (2016).</li><li>Sorrentino, A., Vidakovi&#263;-Koch, T., Hanke-Rauschenbach, R., Sundmacher, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Concentration+frequency+response+analysis:+A+new+method+for+studying+polymer+electrolyte+membrane+fuel+cell+dynamics.">Concentration frequency response analysis: A new method for studying polymer electrolyte membrane fuel cell dynamics.</a> Electrochimica Acta. 243, 53-64 (2017).</li><li>Sorrentino, A., Vidakovi&#263;-Koch, T., Sundmacher, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Studying+mass+transport+dynamics+in+polymer+electrolyte+membrane+fuel+cells+using+concentration-alternating+frequency+response+analysis.">Studying mass transport dynamics in polymer electrolyte membrane fuel cells using concentration-alternating frequency response analysis.</a> Journal of Power Sources. 412, 331-335 (2019).</li><li>Pivac, I., Barbir, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Inductive+phenomena+at+low+frequencies+in+impedance+spectra+of+proton+exchange+membrane+fuel+cells-A+review.">Inductive phenomena at low frequencies in impedance spectra of proton exchange membrane fuel cells-A review.</a> Journal of Power Sources. 326, 112-119 (2016).</li><li>Benziger, J., Chia, J. E., Kimbal, E., Kevrekidis, I. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Reaction+Dynamics+in+a+Parallel+Flow+Channel+PEM+Fuel+Cell.">Reaction Dynamics in a Parallel Flow Channel PEM Fuel Cell.</a> Journal of Electrochemical Society. 154, B835-B844 (2007).</li><li>Rannow, M. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Achieving+Efficient+Control+of+Hydraulic+Systems+Using+On/Off+Valves.">Achieving Efficient Control of Hydraulic Systems Using On/Off Valves.</a> Doctoral Dissertation. , (2016).</li></ol>

The authors have nothing to disclose.

In contrast to classical EIS, cFRA is a diagnostic tool focused on the characterization of dynamics related to the different mass transport phenomena occurring in the fuel cell. It is not able to detect any transients having a time constant below the oxygen diffusion in the electrode, as for example the charging/discharging of the double layer6. Therefore, unlike EIS where several phenomena are coupled, cFRA can help to identify patterns related to specific dynamics more clearly. This would decrea...

Characterizing the dynamic behavior of a PEM fuel cell is important in order to understand which mechanisms dominate the transient operational states lowering the performance of the cell. Electrochemical impedance spectroscopy (EIS) is the most commonly used methodology for studying PEM fuel cell dynamics, due to its ability to separate different process contributions to the overall dynamic performance1,2. However, transient processes with similar time constants are often coupled in the EIS spectra, making it difficult to interpret them. For this reason, in the past transient diagnostic tools based on the application of non-electrical inputs with the aim of detecting the impact of a few or individual dynamics have been developed and proposed3,4,5,6,7.
A novel frequency response technique based on concentration perturbation input and electrical outputs named concentration-alternating frequency response analysis (cFRA) has been developed in our group. The potential of cFRA as a selective diagnostic tool has been investigated theoretically and experimentally6,7. It was found that cFRA can separate different kinds of mass transport phenomena and discriminate between the different states of operation of the cell. In this protocol, we focus on the step-by-step description of the procedure for performing cFRA experiments. The assembling of the cell, its conditioning and the experimental setup for creating a feed with periodic concentration perturbation, as well as the data analysis will be shown and discussed in detail. Finally, the most critical points of the procedure will be highlighted and several strategies for improving the quality and selectivity of cFRA spectra will be pinpointed.

<table><tbody><tr><td>Membrane Electrode Assemby N115 25,8 cm2</td><td>QuinTech</td><td>EC-NM-115</td><td>cathode/anode loding: 1mg Pt/cm2</td></tr><tr><td>Potentiostat</td><td>Metrhohm</td><td>PGSTAT302N</td><td></td></tr><tr><td>Booster</td><td>Metrohm</td><td>BOOSTER20A</td><td></td></tr><tr><td>Retractable fiber oxygen sensor</td><td>Pyro Science</td><td>OXR430-UHS</td><td></td></tr><tr><td>Dew Point and Temperature Meter</td><td>VAISALA</td><td>DMT340</td><td></td></tr><tr><td>Software process control system</td><td>Siemens</td><td>Simatic PCS 7</td><td></td></tr><tr><td>Software MATLAB2012a</td><td>Mathworks</td><td></td><td></td></tr><tr><td>Hydrogen</td><td>Linde</td><td>Hydrogen 6.0</td><td></td></tr><tr><td>Nitrogen</td><td>Linde</td><td>Nitrogen 5.0</td><td></td></tr><tr><td>Oxygen</td><td>Linde</td><td>Oxygen 5.0</td><td></td></tr></tbody></table>

a guide to concentration alternating frequency response analysis of fuel cells

An experimental setup capable of generating a periodic concentration input perturbation of oxygen was used to perform concentration-alternating frequency response analysis (cFRA) on proton-exchange membrane (PEM) fuel cells. During cFRA experiments, the modulated concentration feed was sent to the cathode of the cell at different frequencies. The electric response, which can be cell potential or current depending on the control applied on the cell, was registered in order to formulate a frequency response transfer function. Unlike traditional electrochemical impedance spectroscopy (EIS), the novel cFRA methodology makes it possible to separate the contribution of different mass transport phenomena from the kinetic charge transfer processes in the frequency response spectra of the cell. Moreover, cFRA is able to differentiate between varying humidification states of the cathode. In this protocol, the focus is on the detailed description of the procedure to perform cFRA experiments. The most critical steps of the measurements and future improvements to the technique are discussed.

The preliminary analysis of the fuel cell dynamics based on EIS spectra is shown in Figure 2. EIS magnitude (Figure 2A) and phase Bode plots (Figure 2B) spectra are measured at three different steady state current densities under galvanostatic control. As expected, all main transient processes are observed: the double layer charging/discharging in the high frequency ...

Watch this Scientific Journal Video about A Guide to Concentration Alternating Frequency Response Analysis of Fuel Cells at JoVE.com

A Guide to Concentration Alternating Frequency Response Analysis of Fuel Cells

We present a protocol for concentration alternating frequency response analysis of fuel cells, a promising new method of studying fuel cell dynamics.

An experimental setup capable of generating a periodic concentration input perturbation of oxygen was used to perform concentration-alternating frequency ...

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Frequency Response

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6.6K Views.  Max Planck Institute for Dynamics of Complex Technical Systems. We present a protocol for concentration alternating frequency response analysis of fuel cells, a promising new method of studying fuel cell dynamics.

Video: A Guide to Concentration Alternating Frequency Response Analysis of Fuel Cells

Probing and Mapping Electrode Surfaces in Solid Oxide Fuel Cells

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen 1-7. The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion2. Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation8-12. It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition8, 10, 13, 14 ("coking") and sulfur poisoning11, 15 and the manner in which surface modifications stave off this degradation16. The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM, other properties such as local electronic states, ion diffusion coefficient and surface potential can also be investigated17-22. In this work, electrochemical measurements, Raman spectroscopy, and SPM were used in conjunction with a novel test electrode platform that consists of a Ni mesh electrode embedded in an yttria-stabilized zirconia (YSZ) electrolyte. Cell performance testing and impedance spectroscopy under fuel containing H2S was characterized, and Raman mapping was used to further elucidate the nature of sulfur poisoning. In situ Raman monitoring was used to investigate coking behavior. Finally, atomic force microscopy (AFM) and electrostatic force microscopy (EFM) were used to further visualize carbon deposition on the nanoscale. From this research, we desire to produce a more complete picture of the SOFC anode.

We present a unique platform for characterizing electrode surfaces in solid oxide fuel cells (SOFCs) that allows simultaneous performance of multiple characterization techniques (e.g. in situ Raman spectroscopy and scanning probe microscopy alongside electrochemical measurements). Complementary information from these analyses may help to advance toward a more profound understanding of electrode reaction and degradation mechanisms, providing insights into rational design of better materials for SOFCs.

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen ...

Engineering

On the Preparation and Testing of Fuel Cell Catalysts Using the Thin Film Rotating Disk Electrode Method

We present a step-by-step tutorial to prepare proton exchange membrane fuel cell (PEMFC) catalysts, consisting of Pt nanoparticles (NPs) supported on a high surface area carbon, and to test their performance in thin film rotating disk electrode (TF-RDE) measurements. The TF-RDE methodology is widely used for catalyst screening; nevertheless, the measured performance sometimes considerably differs among research groups. These uncertainties impede the advancement of new catalyst materials and, consequently, several authors discussed possible best practice methods and the importance of benchmarking.
The visual tutorial highlights possible pitfalls in the TF-RDE testing of Pt/C catalysts. A synthesis and testing protocol to assess standard Pt/C catalysts is introduced that can be used together with polycrystalline Pt disks as benchmark catalysts. In particular, this study highlights how the properties of the catalyst film on the glassy carbon (GC) electrode influence the measured performance in TF-RDE testing. To obtain thin, homogeneous catalyst films, not only the catalyst preparation, but also the ink deposition and drying procedures are essential. It is demonstrated that an adjustment of the ink&#39;s pH might be necessary, and how simple control measurements can be used to check film quality. Once reproducible TF-RDE measurements are obtained, determining the Pt loading on the catalyst support (expressed as Pt wt%) and the electrochemical surface area is necessary to normalize the determined reaction rates to either surface area or Pt mass. For the surface area determination, so-called CO stripping, or the determination of the hydrogen underpotential deposition (Hupd) charge, are standard. For the determination of the Pt loading, a straightforward and cheap procedure using digestion in aqua regia with subsequent conversion of Pt(IV) to Pt(II) and UV-vis measurements is introduced.

Preparing and testing Pt/C fuel cell catalysts is subject to continuous discussion in the scientific community with respect to reproducibility and best practice. With the presented work, we intend to present a step-by-step tutorial to make and test Pt/C catalysts, which can serve as benchmark for novel catalyst systems.

We present a step-by-step tutorial to prepare proton exchange membrane fuel cell (PEMFC) catalysts, consisting of Pt nanoparticles (NPs) supported on a ...

Original Experimental Approach for Assessing Transport Fuel Stability

The study of fuel oxidation stability is an important issue for the development of future fuels. Diesel and kerosene fuel systems have undergone several technological changes to fulfill environmental and economic requirements. These developments have resulted in increasingly severe operating conditions whose suitability for conventional and alternative fuels needs to be addressed. For example, fatty acid methyl esters (FAMEs) introduced as biodiesel are more prone to oxidation and may lead to deposit formation. Although several methods exist to evaluate fuel stability (induction period, peroxides, acids, and insolubles), no technique allows one to monitor the real-time oxidation mechanism and to measure the formation of oxidation intermediates that may lead to deposit formation. In this article, we developed an advanced oxidation procedure (AOP) based on two existing reactors. This procedure allows the simulation of different oxidation conditions and the monitoring of the oxidation progress by the means of macroscopic parameters, such as total acid number (TAN) and advanced analytical methods like gas chromatography coupled to mass spectrometry (GC-MS) and Fourier Transform Infrared - Attenuated Total Reflection (FTIR-ATR). We successfully applied AOP to gain an in-depth understanding of the oxidation kinetics of a model molecule (methyl oleate) and commercial diesel and biodiesel fuels. These developments represent a key strategy for fuel quality monitoring during logistics and on-board utilization.

Oxidation stability of transport fuels has become a concern for future fuel development. This work presents an original methodology developed by IFP Energies Nouvelles for assessing fuel stability using two different reactors. This methodology was successfully applied to gain an in-depth understanding of the oxidation kinetics and pathways of model molecules and commercial fuels.

The study of fuel oxidation stability is an important issue for the development of future fuels. Diesel and kerosene fuel systems have undergone several ...

Chemistry

Combustion Characterization and Model Fuel Development for Micro-tubular Flame-assisted Fuel Cells

Combustion based power generation has been accomplished for many years through a number of heat engine systems. Recently, a move towards small scale power generation and micro combustion as well as development in fuel cell research has created new means of power generation that combine solid oxide fuel cells with open flames and combustion exhaust. Instead of relying upon the heat of combustion, these solid oxide fuel cell systems rely on reforming of the fuel via combustion to generate syngas for electrochemical power generation. Procedures were developed to assess the combustion by-products under a wide range of conditions. While theoretical and computational procedures have been developed for assessing fuel-rich combustion exhaust in these applications, experimental techniques have also emerged. The experimental procedures often rely upon a gas chromatograph or mass spectrometer analysis of the flame and exhaust to assess the combustion process as a fuel reformer and means of heat generation. The experimental techniques developed in these areas have been applied anew for the development of the micro-tubular flame-assisted fuel cell. The protocol discussed in this work builds on past techniques to specify a procedure for characterizing fuel-rich combustion exhaust and developing a model fuel-rich combustion exhaust for use in flame-assisted fuel cell testing. The development of the procedure and its applications and limitations are discussed.

A protocol for creating a model fuel-rich combustion exhaust is developed through combustion characterization and is applied for micro-tubular flame-assisted fuel cell testing and research.

Combustion based power generation has been accomplished for many years through a number of heat engine systems. Recently, a move towards small scale power ...

A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery

Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, non-aqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of non-aqueous electrolytes. However, significant technical hurdles exist currently limiting non-aqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we recently reported a non-aqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox material exhibits an ambipolar electrochemical property, and therefore can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry. Moreover, we demonstrated that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC), as cross-validated by electron spin resonance (ESR) measurements. Herein we present a video protocol for the electrochemical evaluation and SOC diagnosis of the PTIO symmetric flow battery. With a detailed description, we experimentally demonstrated the route to achieve such purposes. This protocol aims to spark more interests and insights on the safety and reliability in the field of non-aqueous redox flow batteries.

We present the protocols for electrochemically evaluating a symmetric non-aqueous organic redox flow battery and for diagnosing its state of charge using FTIR.

Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid ...

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity in aqueous CO2 reduction. Different from traditional metal nanocrystals, the synthesis of metal single atoms involves a matrix material that can confine those single atoms and prevent them from aggregation. We report an electrospinning and thermal annealing method to prepare Ni single atoms dispersed and coordinated in a graphene shell, as active centers for CO2 reduction to CO. During the synthesis, N dopants play a critical role in generating graphene vacancies to trap Ni atoms. Aberration-corrected scanning transmission electron microscopy and three-dimensional atom probe tomography were employed to identify the single Ni atomic sites in graphene vacancies. Detailed setup of electrochemical CO2 reduction apparatus coupled with an on-line gas chromatography is also demonstrated. Compared to metallic Ni, Ni single atom catalyst exhibit dramatically improved CO2 reduction and suppressed H2 evolution side reaction.

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Here, we present a protocol for the synthesis and electrochemical testing of transition metal single atoms coordinated in graphene vacancies as active centers for selective carbon dioxide reduction to carbon monoxide in aqueous solutions.

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity ...

Three-electrode Coin Cell Preparation and Electrodeposition Analytics for Lithium-ion Batteries

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and subsequent safety issues becomes increasingly important. In a Li-ion cell setup, the voltage measurement across the positive and negative terminals inherently includes the effect of the cathode and anode which are coupled and sum to the total cell performance. Accordingly, the ability to monitor the degradation aspects associated with a specific electrode is extremely difficult because the electrodes are fundamentally coupled. A three-electrode setup can overcome this problem. By introducing a third (reference) electrode, the influence of each electrode can be decoupled, and the electrochemical properties can be measured independently. The reference electrode (RE) must have a stable potential that can then be calibrated against a known reference, for example, lithium metal. The three-electrode cell can be used to run electrochemical tests such as cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). Three-electrode cell EIS measurements can elucidate the contribution of individual electrode impedance to the full cell. In addition, monitoring the anode potential allows the detection of electrodeposition due to lithium plating, which can cause safety concerns. This is especially important for the fast charging of Li-ion batteries in electric vehicles. In order to monitor and characterize the safety and degradation aspects of an electrochemical cell, a three-electrode setup can prove invaluable. This paper aims to provide a guide to constructing a three-electrode coin cell setup using the 2032-coin cell architecture, which is easy to produce, reliable, and cost-effective.

Three-electrode cells are useful in studying the electrochemistry of lithium-ion batteries. Such an electrochemical setup allows the phenomena associated with the cathode and anode to be decoupled and examined independently. Here, we present a guide for construction and use of a three-electrode coin cell with emphasis on lithium plating analytics.

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and ...

Development and Validation of Chromium Getters for Solid Oxide Fuel Cell Power Systems

Degradation of cathode in solid oxide fuel cells (SOFC) remains a major concern for the long-term performance stability and operational reliability. The presence of gas phase chromium species in air has demonstrated significant cathode performance degradation during long-term exposure due to unwanted compound formation at the cathode and electrolyte interface which retards the oxygen reduction reaction (ORR). We have demonstrated a novel method to mitigate the cathode degradation using chromium getters which capture the gas phase chromium species before it is ingested in the cathode chamber. Low-cost getter materials, synthesized from alkaline earth and transition metal oxides, are coated on the cordierite honeycomb substrate for application in the SOFC power systems. As-fabricated getters have been screened by chromium transpiration tests for 500 h in humidified air atmosphere in presence of chromium vapor. Selected getters have been further validated utilizing electrochemical tests. Typically, electrochemical performance of SOFCs (lanthanum strontium manganite (LSM) &#449; yttria stabilized zirconia (YSZ) &#449; Pt) was measured at 850 &#176;C in the presence and absence of Cr getter. For the 100 h cell tests containing getters, stable electrochemical performance was maintained, whereas the cell performance in the absence of Cr getters rapidly decreased in 10 h. Analyses of Nyquist plots indicated significant increase in the polarization resistance within the first 10 h of the cell operation. Characterization results from posttest SOFCs and getters have demonstrated the high efficiency of chromium capture for the mitigation of cell degradation.

Cathode poisoning from airborne contaminants in trace levels remains a major concern for long-term stability of high-temperature electrochemical systems. We provide a novel method to mitigate the cathode degradations using getters, which capture airborne contaminants at high temperature before entering electrochemically active stack area.

Degradation of cathode in solid oxide fuel cells (SOFC) remains a major concern for the long-term performance stability and operational reliability. The ...

Exploring Innovative 3D Electrodes for Hydrogen Peroxide Fuel Cells

Membraneless Hydrogen Peroxide Fuel Cells as a Promising Clean Energy Source

In an in-depth investigation of membraneless hydrogen peroxide-based fuel cells (H2O2 FCs), hydrogen peroxide (H2O2), a carbon-neutral compound, is demonstrated to undergo electrochemical decomposition to produce H2O, O2, and electrical energy. The unique redox properties of H2O2 position it as a viable candidate for sustainable energy applications. The proposed membraneless design addresses the limitations of conventional fuel cells, including fabrication complexities and design challenges. A novel three-dimensional electrode, synthesized via electroplating techniques, is introduced. Constructed from Au-electroplated carbon fiber cloth combined with Ni-foam, this electrode showcases enhanced electrochemical reaction kinetics, leading to an increased power density for H2O2 FCs. The performance of fuel cells is intricately linked to the pH levels of the electrolyte solution. Beyond FC applications, such electrodes hold potential in portable energy systems and as high surface area catalysts. This study emphasizes the significance of electrode engineering in optimizing the potential of H2O2 as an environmentally friendly energy source.

Author Spotlight: Design and Evaluation of Au-Electroplated Carbon Fiber Cloth Electrodes for Hydrogen Peroxide Fuel Cells 

This protocol introduces the design and evaluation of innovative three-dimensional electrodes for hydrogen peroxide fuel cells, utilizing Au-electroplated carbon fiber cloth and Ni-foam electrodes. The research findings highlight hydrogen peroxide's potential as a promising candidate for sustainable energy technologies.

In an in-depth investigation of membraneless hydrogen peroxide-based fuel cells (H2O2 FCs), hydrogen peroxide (H2O2), a carbon-neutral compound, is ...

Proton Exchange Membrane Fuel Cells

Source: Laboratories of Margaret Workman and Kimberly Frye - Depaul University
The United States consumes a large amount of energy &#8211; the current rate is around 97.5 quadrillion BTUs annually. The vast majority (90%) of this energy comes from non-renewable fuel sources. This energy is used for electricity (39%), transportation (28%), industry (22%), and residential/commercial use (11%). As the world has a limited supply of these non-renewable sources, the United States (among others) is expanding the use of renewable energy sources to meet future energy needs. One of these sources is hydrogen.
Hydrogen is considered a potential renewable fuel source, because it meets many important criteria: it&#8217;s available domestically, it has few harmful pollutants, it&#8217;s energy efficient, and it&#8217;s easy to harness. While hydrogen is the most abundant element in the universe, it is only found in compound form on Earth. For example, it is combined with oxygen in water as H2O. To be useful as a fuel, it needs to be in the form of H2 gas. Therefore, if hydrogen is to be used as a fuel for cars or other electronics, H2 needs to be made first. Thusly, hydrogen is often called an &#8220;energy carrier&#8221; rather than a &#8220;fuel.&#8221;
Currently, the most popular way to make H2 gas is from fossil fuels, through steam reforming of hydrocarbons or coal gasification. This does not reduce dependence on fossil fuels and is energy intensive. A less-used method is by electrolysis of water. This also requires an energy source, but it can be a renewable source, like wind or solar power. In electrolysis, water (H2O) is split into its component parts, hydrogen gas (H2) and oxygen gas (O2), through an electrochemical reaction. The hydrogen gas made through the process of electrolysis can then be used in a Proton Exchange Membrane (PEM) fuel cell, generating an electric current. This electric current can be used to power motors, lights, and other electrical devices.

Source: Laboratories of Margaret Workman and Kimberly Frye - Depaul University
The United States consumes a large amount of energy &#8211; the current ...