scholarly journals Ordered Porous TiO2@C Layer as an Electrocatalyst Support for Improved Stability in PEMFCs

Nanomaterials ◽  
2021 ◽  
Vol 11 (12) ◽  
pp. 3462
Author(s):  
Gaoyang Liu ◽  
Zhaoyi Yang ◽  
Xindong Wang ◽  
Baizeng Fang

Proton exchange membrane fuel cells (PEMFCs) are the most promising clean energy source in the 21st century. In order to achieve a high power density, electrocatalytic performance, and electrochemical stability, an ordered array structure membrane electrode is highly desired. In this paper, a new porous Pt-TiO2@C ordered integrated electrode was prepared and applied to the cathode of a PEMFC. The utilization of the TiO2@C support can significantly decrease the loss of catalyst caused by the oxidation of the carbon from the conventional carbon layer due to the strong interaction of TiO2 and C. Furthermore, the thin carbon layer coated on TiO2 provides the rich active sites for the Pt growth, and the ordered support and catalyst structure reduces the mass transport resistance and improves the stability of the electrode. Due to its unique structural characteristics, the ordered porous Pt-TiO2@C array structure shows an excellent catalytic activity and improved Pt utilization. In addition, the as-developed porous ordered structure exhibits superior stability after 3000 cycles of accelerated durability test, which reveals an electrochemical surface area decay of less than 30%, considerably lower than that (i.e., 80%) observed for the commercial Pt/C.

Polymers ◽  
2019 ◽  
Vol 11 (8) ◽  
pp. 1368 ◽  
Author(s):  
Yen-Zen Wang ◽  
Wen-Yao Huang ◽  
Tar-Hwa Hsieh ◽  
Li-Cheng Jheng ◽  
Ko-Shan Ho ◽  
...  

Calcinated tris(ethylenediamine)iron(III) chloride was used as a non-precious metal catalyst (NPMCs) for a proton exchanged membrane fuel cell (PEMFC) under the protection of polyaniline (PANI), which behaves as both nitrogen source and carbon supporter. The optimal ratio of FeCl3/EDA was found to be close to 1/3 under the consideration of the electrocatalytic performance, such as better oxygen reduction reaction (ORR) and higher power density. Two-stage calcination, one at 900 °C in N2 and the other at 800 °C in mixed gases of N2 and NH3, result in an FeNxC catalyst (FeNC-900-800-A) with pretty high specific surface area of 1098 m2·g−1 covered with both micro- and mesopores. The ORR active sites focused mainly on Fe–Nx bonding made of various pyridinic, pyrrolic, and graphitic N-s after calcination. The max. power density reaches 140 mW·cm−2 for FeNC-900-800-A, which is superior to other FeNxC catalysts, experiencing only one-stage calcination in N2. The FeNxC demonstrates only 10 mV half-wave-voltage (HWV) loss at 1600 rpm after 1000 redox cycles, as compared to be 27 mV for commercial Pt/C catalyst in the durability test.


Author(s):  
R. Bajon ◽  
S. Balaji ◽  
S. M. Guo

Proton exchange membrane fuel cells (PEMFCs) are attractive power plants for use in many applications, including portable power sources, electric vehicles, and on-site combined power/heat plants, due to the inherently high efficiency and low emission. The membrane electrode assembly (MEA) is the key component of a PEMFC. A standard five layer MEA consists of a proton exchange membrane, two catalyst layers, and two gas diffusion layers. The most commonly used electrolyte material is proton conductive perfluorinated sulfonic acid membrane, such as Nafion. Hydrogen is oxidized at the anode/electrolyte interface, the so-called triple-phase-boundary (TPB) active sites. TPB region must be a good electron conductor, a good ion conductor, and a porous structure for fuel/air diffusion. Typical PEMFC TPB is a porous structure made with Nafion and catalyst particle mixture. In this paper, electrospinning is used to synthesize polymer/Nafion nanofibers. Electrospinning is a straightforward method that has been successfully used to prepare fibers or fiber mats from a broad range of organic polymers. In the electrospinning process, a polymer solution held by its surface tension at the end of a capillary tube is subjected to an electric field, and as the electric field strength increases, a solid fiber is generated as the electrified jet is continuously stretched because of the electrostatic repulsions between the surface charges and the evaporation of solvent. Uniform one-dimensional Nafion nanofibers have been fabricated using Nafion solution and solutions containing polyvinyl pyrrolidone, polyethylene oxide, and polyvinyl alcohol. The morphologies of polymer/Nafion nanofibers, fabricated under different electrospinning conditions and different polymer compositions, are presented.


Author(s):  
Michel Fialin ◽  
Guy Rémond

Oxygen-bearing minerals are generally strong insulators (e.g. silicates), or if not (e.g. transition metal oxides), they are included within a rock matrix which electrically isolates them from the sample holder contacts. In this respect, a thin carbon layer (150 Å in our laboratory) is evaporated on the sections in order to restore the conductivity. For silicates, overestimated oxygen concentrations are usually noted when transition metal oxides are used as standards. These trends corroborate the results of Bastin and Heijligers on MgO, Al2O3 and SiO2. According to our experiments, these errors are independent of the accelerating voltage used (fig.l).Owing to the low density of preexisting defects within the Al2O3 single-crystal, no significant charge buildup occurs under irradiation at low accelerating voltage (< 10keV). As a consequence, neither beam instabilities, due to electrical discharges within the excited volume, nor losses of energy for beam electrons before striking the sample, due to the presence of the electrostatic charge-induced potential, are noted : measurements from both coated and uncoated samples give comparable results which demonstrates that the carbon coating is not the cause of the observed errors.


Author(s):  
Xi Yin ◽  
Ling Lin ◽  
Hoon T. Chung ◽  
Ulises Martinez ◽  
Andrew M. Baker ◽  
...  

Finding a low-cost and stable electrocatalyst for hydrogen evolution reaction (HER) as a replacement for scarce and expensive precious metal catalysts has attracted significant interest from chemical and materials research communities. Here, we demonstrate an organic catalyst based on 2,2’-dipyridylamine (dpa) molecules adsorbed on carbon surface, which shows remarkable hydrogen evolution activity and performance durability in strongly acidic polymer electrolytes without involving any metal. The HER onset potential at dpa adsorbed on carbon has been found to be less than 50 mV in sulfuric acid and in a Nafion-based membrane electrode assembly (MEA). At the same time, this catalyst has shown no performance loss in a 60-hour durability test. The HER reaction mechanisms and the low onset overpotential in this system are revealed based on electrochemical study. Density functional theory (DFT) calculations suggest that the pyridyl-N functions as the active site for H adsorption with a free energy of -0.13 eV, in agreement with the unusually low onset overpotential for an organic molecular catalyst.<br>


2019 ◽  
Author(s):  
Xi Yin ◽  
Ling Lin ◽  
Hoon T. Chung ◽  
Ulises Martinez ◽  
Andrew M. Baker ◽  
...  

Finding a low-cost and stable electrocatalyst for hydrogen evolution reaction (HER) as a replacement for scarce and expensive precious metal catalysts has attracted significant interest from chemical and materials research communities. Here, we demonstrate an organic catalyst based on 2,2’-dipyridylamine (dpa) molecules adsorbed on carbon surface, which shows remarkable hydrogen evolution activity and performance durability in strongly acidic polymer electrolytes without involving any metal. The HER onset potential at dpa adsorbed on carbon has been found to be less than 50 mV in sulfuric acid and in a Nafion-based membrane electrode assembly (MEA). At the same time, this catalyst has shown no performance loss in a 60-hour durability test. The HER reaction mechanisms and the low onset overpotential in this system are revealed based on electrochemical study. Density functional theory (DFT) calculations suggest that the pyridyl-N functions as the active site for H adsorption with a free energy of -0.13 eV, in agreement with the unusually low onset overpotential for an organic molecular catalyst.<br>


Energies ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2975
Author(s):  
Zikhona Nondudule ◽  
Jessica Chamier ◽  
Mahabubur Chowdhury

To decrease the cost of fuel cell manufacturing, the amount of platinum (Pt) in the catalyst layer needs to be reduced. In this study, ionomer gradient membrane electrode assemblies (MEAs) were designed to reduce Pt loading without sacrificing performance and lifetime. A two-layer stratification of the cathode was achieved with varying ratios of 28 wt. % ionomer in the inner layer, on the membrane, and 24 wt. % on the outer layer, coated onto the inner layer. To study the MEA performance, the electrochemical surface area (ECSA), polarization curves, and electrochemical impedance spectroscopy (EIS) responses were evaluated under 20, 60, and 100% relative humidity (RH). The stratified MEA Pt loading was reduced by 12% while maintaining commercial equivalent performance. The optimal two-layer design was achieved when the Pt loading ratio between the layers was 1:6 (inner:outer layer). This MEA showed the highest ECSA and performance at 0.65 V with reduced mass transport losses. The integrity of stratified MEAs with lower Pt loading was evaluated with potential cycling and proved more durable than the monolayer MEA equivalent. The higher ionomer loading adjacent to the membrane and the bi-layer interface of the stratified catalyst layer (CL) increased moisture in the cathode CL, decreasing the degradation rate. Using ionomer stratification to decrease the Pt loading in an MEA yielded a better performance compared to the monolayer MEA design. This study, therefore, contributes to the development of more durable, cost-effective MEAs for low-temperature proton exchange membrane fuel cells.


Crystals ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 47
Author(s):  
Yiqiu Xiang ◽  
Ling Xin ◽  
Jiwei Hu ◽  
Caifang Li ◽  
Jimei Qi ◽  
...  

Extensive use of fossil fuels can lead to energy depletion and serious environmental pollution. Therefore, it is necessary to solve these problems by developing clean energy. Graphene materials own the advantages of high electrocatalytic activity, high conductivity, excellent mechanical strength, strong flexibility, large specific surface area and light weight, thus giving the potential to store electric charge, ions or hydrogen. Graphene-based nanocomposites have become new research hotspots in the field of energy storage and conversion, such as in fuel cells, lithium-ion batteries, solar cells and thermoelectric conversion. Graphene as a catalyst carrier of hydrogen fuel cells has been further modified to obtain higher and more uniform metal dispersion, hence improving the electrocatalyst activity. Moreover, it can complement the network of electroactive materials to buffer the change of electrode volume and prevent the breakage and aggregation of electrode materials, and graphene oxide is also used as a cheap and sustainable proton exchange membrane. In lithium-ion batteries, substituting heteroatoms for carbon atoms in graphene composite electrodes can produce defects on the graphitized surface which have a good reversible specific capacity and increased energy and power densities. In solar cells, the performance of the interface and junction is enhanced by using a few layers of graphene-based composites and more electron-hole pairs are collected; therefore, the conversion efficiency is increased. Graphene has a high Seebeck coefficient, and therefore, it is a potential thermoelectric material. In this paper, we review the latest progress in the synthesis, characterization, evaluation and properties of graphene-based composites and their practical applications in fuel cells, lithium-ion batteries, solar cells and thermoelectric conversion.


2021 ◽  
Author(s):  
Dongsheng Xia ◽  
Chenchen Yu ◽  
Yinghao Zhao ◽  
Yinping Wei ◽  
Haiyan Wu ◽  
...  

The severe degradation of Fe-N-C electrocatalysts during long-term oxygen reduction reaction (ORR) has become a major obstacle for application in proton-exchange membrane fuel cells. Understanding the degradation mechanism and regeneration...


Author(s):  
Britta Mayerhöfer ◽  
Konrad Ehelebe ◽  
Florian Dominik Speck ◽  
Markus Bierling ◽  
Johannes Bender ◽  
...  

Bipolar membrane|electrode interface water electrolyzers (BPEMWE) were found to outperform a proton exchange membrane (PEM) water electrolyzer reference in a similar membrane electrode assembly (MEA) design based on individual porous...


Membranes ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 355
Author(s):  
Tamar Zelovich ◽  
Mark E. Tuckerman

Fuel cell-based anion-exchange membranes (AEMs) and proton exchange membranes (PEMs) are considered to have great potential as cost-effective, clean energy conversion devices. However, a fundamental atomistic understanding of the hydroxide and hydronium diffusion mechanisms in the AEM and PEM environment is an ongoing challenge. In this work, we aim to identify the fundamental atomistic steps governing hydroxide and hydronium transport phenomena. The motivation of this work lies in the fact that elucidating the key design differences between the hydroxide and hydronium diffusion mechanisms will play an important role in the discovery and determination of key design principles for the synthesis of new membrane materials with high ion conductivity for use in emerging fuel cell technologies. To this end, ab initio molecular dynamics simulations are presented to explore hydroxide and hydronium ion solvation complexes and diffusion mechanisms in the model AEM and PEM systems at low hydration in confined environments. We find that hydroxide diffusion in AEMs is mostly vehicular, while hydronium diffusion in model PEMs is structural. Furthermore, we find that the region between each pair of cations in AEMs creates a bottleneck for hydroxide diffusion, leading to a suppression of diffusivity, while the anions in PEMs become active participants in the hydronium diffusion, suggesting that the presence of the anions in model PEMs could potentially promote hydronium diffusion.


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