scholarly journals Polydopamine Coated CeO2 as Radical Scavenger Filler for Aquivion Membranes with High Proton Conductivity

Materials ◽  
2021 ◽  
Vol 14 (18) ◽  
pp. 5280
Author(s):  
Roberto D’Amato ◽  
Anna Donnadio ◽  
Chiara Battocchio ◽  
Paola Sassi ◽  
Monica Pica ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Open Circuit ◽  
Proton Exchange ◽  
Chemical Degradation ◽  
Ex Situ ◽  
Radical Scavenger ◽  
Stress Tests ◽  
Fenton Reagent ◽  
X Ray ◽  
Fluoride Emission

CeO2 nanoparticles were coated with polydopamine (PDA) by dopamine polymerization in water dispersions of CeO2 and characterized by Infrared and Near Edge X-ray Absorption Fine Structure spectroscopy, Transmission Electron Microscopy, Thermogravimetric analysis and X-ray diffraction. The resulting materials (PDAx@CeO2, with x = PDA wt% = 10, 25, 50) were employed as fillers of composite proton exchange membranes with Aquivion 830 as ionomer, to reduce the ionomer chemical degradation due to hydroxyl and hydroperoxyl radicals. Membranes, loaded with 3 and 5 wt% PDAx@CeO2, were prepared by solution casting and characterized by conductivity measurements at 80 and 110 °C, with relative humidity ranging from 50 to 90%, by accelerated ex situ degradation tests with the Fenton reagent, as well as by in situ open circuit voltage stress tests. In comparison with bare CeO2, the PDA coated filler mitigates the conductivity drop occurring at increasing CeO2 loading especially at 110 °C and 50% relative humidity but does not alter the radical scavenger efficiency of bare CeO2 for loadings up to 4 wt%. Fluoride emission rate data arising from the composite membrane degradation are in agreement with the corresponding changes in membrane mass and conductivity.

Mitigation of PtCo/C Cathode Catalyst Degradation via Control of Relative Humidity

2021 ◽  
Author(s):  
Nagappan Ramaswamy ◽  
Swami Kumaraguru ◽  
Ratandeep Singh Kukreja ◽  
Daniel Groom ◽  
Karalee Jarvis ◽  
...  
Keyword(s):  
Relative Humidity ◽  
High Performance ◽  
Proton Exchange Membrane ◽  
Stress Test ◽  
Catalyst Layer ◽  
Reduction Reaction ◽  
Proton Exchange ◽  
Ex Situ ◽  
Primary Power ◽  
Ptco Alloy

Abstract Maintaining the high performance of proton-exchange membrane fuel cells (PEMFC) over the course of its lifetime is a key enabling factor for its successful commercialization as a primary power source in zero-emission transportation applications. In this context, it is important to mitigate the degradation of PtCo-alloy based cathode catalysts used for oxygen reduction reaction (ORR). PtCo-alloy catalysts exhibit high activity at beginning-of-life (BOL) which tends to decrease during operation due to loss of electrochemical surface area (ECSA) and dissolution-contamination related effects of the Co-alloying component. Here, we demonstrate the use of relative humidity (RH) of the inlet gases as a controllable parameter to mitigate the degradation of PtCo-alloy catalyst degradation. We employ a catalyst-specific voltage cycling accelerated stress test (AST) durability protocol as a function of inlet RH to degrade PtCo catalysts. A series of in situ electrochemical diagnostics and ex situ characterizations have been carried out to investigate the catalyst layer characteristics at end-of-test (EOT). Our results show that at sub-saturated conditions of durability protocol operation, PtCo catalyst sustains higher EOT H2/air performance due to better retention of ECSA and smaller impact of Co2+ dissolution/contamination.

scholarly journals The Impact of Chemical-Mechanical Ex Situ Aging on PFSA Membranes for Fuel Cells

Membranes ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 366
Author(s):  
Mylène Robert ◽  
Assma El Kaddouri ◽  
Jean-Christophe Perrin ◽  
Kévin Mozet ◽  
Jérôme Dillet ◽  
...  
Keyword(s):  
Fuel Cell ◽  
Large Scale ◽  
Proton Exchange Membrane ◽  
Proton Exchange ◽  
Mitigation Strategies ◽  
Ex Situ ◽  
Polyelectrolyte Membrane ◽  
Fluoride Emission ◽  
Exchange Membrane ◽  
The Impact

A proton-exchange membrane fuel cell (PEMFC) constitutes today one of the preferred technologies to promote hydrogen-based alternative energies. However, the large-scale deployment of PEMFCs is still hampered by insufficient durability and reliability. In particular, the degradation of the polyelectrolyte membrane, caused by harsh mechanical and chemical stresses experienced during fuel cell operation, has been identified as one of the main factors restricting the PEMFC lifetime. An innovative chemical-mechanical ex situ aging device was developed to simultaneously expose the membrane to mechanical fatigue and an oxidizing environment (i.e., free radicals) in order to reproduce conditions close to those encountered in fuel cell systems. A cyclic compressive stress of 5 or 10 MPa was applied during several hours while a degrading solution (H2O2 or a Fenton solution) was circulated in contact with the membrane. The results demonstrated that both composite Nafion™ XL and non-reinforced Nafion™ NR211 membranes are significantly degraded by the conjoint mechanical and chemical stress exposure. The fluoride emission rate (FER) was generally slightly lower with XL than with NR211, which could be attributed to the degradation mitigation strategies developed for composite XL, except when the pressure level or the aging duration were increased, suggesting a limitation of the improved durability of XL.

In Situ and Ex Situ Studies on the Degradation of Pd/C Catalyst for Proton Exchange Membrane Fuel Cells

2014 ◽  
Vol 11 (5) ◽  
Author(s):  
Yongfu Tang ◽  
Shichun Mu ◽  
Shengxue Yu ◽  
Yufeng Zhao ◽  
Hongchao Wang ◽  
...  
Keyword(s):  
Single Cell ◽  
Electrochemical Impedance ◽  
Degradation Mechanism ◽  
Single Cells ◽  
Gas Diffusion ◽  
Proton Exchange ◽  
Ex Situ ◽  
Constant Current ◽  
Stress Tests

To investigate the degradation mechanism of the as-prepared Pd/C catalyst, in situ and ex situ accelerated stress tests were carried out via potential cycling. Durability tests of the single cells with Pd/C catalysts were performed through an interval constant current density mode. Electrochemical impedance spectroscopy (EIS) was applied to measure the impedance of the single cell during degradation tests. Results indicate that the degradation of Pd/C catalyst may be attributed to the phase transition of absorbed α-phase PdH to β-phase PdH, the dissolution of Pd metal, and the size increase of Pd nanoparticles. Moreover, the degradation of single cell may be predominantly ascribed to the degradation of catalyst, the deterioration of contact between electronic/ionic conductors, as well as the flooding of gas diffusion channels.

scholarly journals An Examination of the Catalyst Layer Contribution to the Disparity between the Nernst Potential and Open Circuit Potential in Proton Exchange Membrane Fuel Cells

Catalysts ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 965
Author(s):  
Peter Mardle ◽  
Isotta Cerri ◽  
Toshiyuki Suzuki ◽  
Ahmad El-kharouf
Keyword(s):  
Proton Exchange Membrane ◽  
Open Circuit Potential ◽  
Catalyst Layer ◽  
Catalyst Particle ◽  
Gas Diffusion ◽  
Open Circuit ◽  
Proton Exchange ◽  
Ex Situ ◽  
Nernst Potential ◽  
Exchange Membrane

The dependency of the Nernst potential in an operating proton exchange membrane fuel cell (PEMFC) on the temperature, inlet pressure and relative humidity (RH) is examined, highlighting the synergistic dependence of measured open circuit potential (OCP) on all three parameters. An alternative model of the Nernst equation is derived to more appropriately represent the PEMFC system where reactant concentration is instead considered as the activity. Ex situ gas diffusion electrode (GDE) measurements are used to examine the dependency of temperature, electrolyte concentration, catalyst surface area and composition on the measured OCP in the absence of H2 crossover. This is supported by single-cell OCP measurements, wherein RH was also investigated. This contribution provides clarity on the parameters that affect the practically measured OCP as well as highlighting further studies into the effects of catalyst particle surrounding environment on OCP as a promising way of improving PEMFC performance in the low current density regime.

Interfacial properties of GaSb/InAs superlattices

1993 ◽  
Vol 51 ◽  
pp. 826-827
Author(s):  
M. E. Twigg ◽  
B. R. Bennett ◽  
J. R. Waterman ◽  
J. L. Davis ◽  
B. V. Shanabrook ◽  
...  
Keyword(s):  
Gaas Substrate ◽  
Molecular Beam ◽  
Infrared Detector ◽  
Interfacial Properties ◽  
Ex Situ ◽  
X Ray Diffraction ◽  
Absorption Coefficients ◽  
X Ray ◽  
Short Period ◽  
High Optical Absorption

Recently, the GaSb/InAs superlattice system has received renewed attention. The interest stems from a model demonstrating that short period Ga1-xInxSb/InAs superlattices will have both a band gap less than 100 meV and high optical absorption coefficients, principal requirements for infrared detector applications. Because this superlattice system contains two species of cations and anions, it is possible to prepare either InSb-like or GaAs-like interfaces. As such, the system presents a unique opportunity to examine interfacial properties.We used molecular beam epitaxy (MBE) to prepare an extensive set of GaSb/InAs superlattices grown on an GaSb buffer, which, in turn had been grown on a (100) GaAs substrate. Through appropriate shutter sequences, the interfaces were directed to assume either an InSb-like or GaAs-like character. These superlattices were then studied with a variety of ex-situ probes such as x-ray diffraction and Raman spectroscopy. These probes confirmed that, indeed, predominantly InSb-like and GaAs-like interfaces had been achieved.

CO2 Reduction to Propanol by Copper Foams: A Pre- and Post-Catalysis Study

2020 ◽  
Author(s):  
Jennifer A. Rudd ◽  
Ewa Kazimierska ◽  
Louise B. Hamdy ◽  
Odin Bain ◽  
Sunyhik Ahn ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Photoelectron Spectroscopy ◽  
Carbon Capture ◽  
Surface Composition ◽  
Co2 Reduction ◽  
Structural Rearrangement ◽  
Copper Electrode ◽  
Ex Situ ◽  
X Ray ◽  
Copper Electrodes

The utilization of carbon dioxide is a major incentive for the growing field of carbon capture. Carbon dioxide could be an abundant building block to generate higher value products. Herein, we describe the use of porous copper electrodes to catalyze the reduction of carbon dioxide into higher value products such as ethylene, ethanol and, notably, propanol. For <i>n</i>-propanol production, faradaic efficiencies reach 4.93% at -0.83 V <i>vs</i> RHE, with a geometric partial current density of -1.85 mA/cm<sup>2</sup>. We have documented the performance of the catalyst in both pristine and urea-modified foams pre- and post-electrolysis. Before electrolysis, the copper electrode consisted of a mixture of cuboctahedra and dendrites. After 35-minute electrolysis, the cuboctahedra and dendrites have undergone structural rearrangement. Changes in the interaction of urea with the catalyst surface have also been observed. These transformations were characterized <i>ex-situ</i> using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. We found that alterations in the morphology, crystallinity, and surface composition of the catalyst led to the deactivation of the copper foams.

Atomic Layer Deposition of LiF and Lithium Ion Conducting (AlF3)(LiF)x Alloys Using Trimethylaluminum, Lithium Hexamethyldisilazide and Hydrogen Fluoride

2017 ◽  
Author(s):  
Younghee Lee ◽  
Daniela M. Piper ◽  
Andrew S. Cavanagh ◽  
Matthias J. Young ◽  
Se-Hee Lee ◽  
...  
Keyword(s):  
Lithium Ion ◽  
Atomic Layer ◽  
Mass Gain ◽  
Alloy Film ◽  
Ex Situ ◽  
X Ray ◽  
Layer Deposition ◽  
Ion Conducting ◽  
Good Agreement

<div>Atomic layer deposition (ALD) of LiF and lithium ion conducting (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloys was developed using trimethylaluminum, lithium hexamethyldisilazide (LiHMDS) and hydrogen fluoride derived from HF-pyridine solution. ALD of LiF was studied using in situ quartz crystal microbalance (QCM) and in situ quadrupole mass spectrometer (QMS) at reaction temperatures between 125°C and 250°C. A mass gain per cycle of 12 ng/(cm<sup>2</sup> cycle) was obtained from QCM measurements at 150°C and decreased at higher temperatures. QMS detected FSi(CH<sub>3</sub>)<sub>3</sub> as a reaction byproduct instead of HMDS at 150°C. LiF ALD showed self-limiting behavior. Ex situ measurements using X-ray reflectivity (XRR) and spectroscopic ellipsometry (SE) showed a growth rate of 0.5-0.6 Å/cycle, in good agreement with the in situ QCM measurements.</div><div>ALD of lithium ion conducting (AlF3)(LiF)x alloys was also demonstrated using in situ QCM and in situ QMS at reaction temperatures at 150°C A mass gain per sequence of 22 ng/(cm<sup>2</sup> cycle) was obtained from QCM measurements at 150°C. Ex situ measurements using XRR and SE showed a linear growth rate of 0.9 Å/sequence, in good agreement with the in situ QCM measurements. Stoichiometry between AlF<sub>3</sub> and LiF by QCM experiment was calculated to 1:2.8. XPS showed LiF film consist of lithium and fluorine. XPS also showed (AlF<sub>3</sub>)(LiF)x alloy consists of aluminum, lithium and fluorine. Carbon, oxygen, and nitrogen impurities were both below the detection limit of XPS. Grazing incidence X-ray diffraction (GIXRD) observed that LiF and (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloy film have crystalline structures. Inductively coupled plasma mass spectrometry (ICP-MS) and ionic chromatography revealed atomic ratio of Li:F=1:1.1 and Al:Li:F=1:2.7: 5.4 for (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloy film. These atomic ratios were consistent with the calculation from QCM experiments. Finally, lithium ion conductivity (AlF<sub>3</sub>)(LiF)<sub>x</sub> alloy film was measured as σ = 7.5 × 10<sup>-6</sup> S/cm.</div>

scholarly journals Electrochemical study on nickel aluminum layered double hydroxides as high-performance electrode material for lithium-ion batteries based on sodium alginate binder

2021 ◽  
Author(s):  
Xinyue Li ◽  
Marco Fortunato ◽  
Anna Maria Cardinale ◽  
Angelina Sarapulova ◽  
Christian Njel ◽  
...  
Keyword(s):  
Lithium Ion Batteries ◽  
Electrode Material ◽  
Photoelectron Spectroscopy ◽  
Negative Electrode ◽  
Lithium Ion ◽  
Electrochemical Study ◽  
Ex Situ ◽  
Potential Range ◽  
X Ray ◽  
Storage Mechanism

AbstractNickel aluminum layered double hydroxide (NiAl LDH) with nitrate in its interlayer is investigated as a negative electrode material for lithium-ion batteries (LIBs). The effect of the potential range (i.e., 0.01–3.0 V and 0.4–3.0 V vs. Li+/Li) and of the binder on the performance of the material is investigated in 1 M LiPF6 in EC/DMC vs. Li. The NiAl LDH electrode based on sodium alginate (SA) binder shows a high initial discharge specific capacity of 2586 mAh g−1 at 0.05 A g−1 and good stability in the potential range of 0.01–3.0 V vs. Li+/Li, which is better than what obtained with a polyvinylidene difluoride (PVDF)-based electrode. The NiAl LDH electrode with SA binder shows, after 400 cycles at 0.5 A g−1, a cycling retention of 42.2% with a capacity of 697 mAh g−1 and at a high current density of 1.0 A g−1 shows a retention of 27.6% with a capacity of 388 mAh g−1 over 1400 cycles. In the same conditions, the PVDF-based electrode retains only 15.6% with a capacity of 182 mAh g−1 and 8.5% with a capacity of 121 mAh g−1, respectively. Ex situ X-ray photoelectron spectroscopy (XPS) and ex situ X-ray absorption spectroscopy (XAS) reveal a conversion reaction mechanism during Li+ insertion into the NiAl LDH material. X-ray diffraction (XRD) and XPS have been combined with the electrochemical study to understand the effect of different cutoff potentials on the Li-ion storage mechanism. Graphical abstract The as-prepared NiAl-NO3−-LDH with the rhombohedral R-3 m space group is investigated as a negative electrode material for lithium-ion batteries (LIBs). The effect of the potential range (i.e., 0.01–3.0 V and 0.4–3.0 V vs. Li+/Li) and of the binder on the material’s performance is investigated in 1 M LiPF6 in EC/DMC vs. Li. Ex situ X-ray photoelectron spectroscopy (XPS) and ex situ X-ray absorption spectroscopy (XAS) reveal a conversion reaction mechanism during Li+ insertion into the NiAl LDH material. X-ray diffraction (XRD) and XPS have been combined with the electrochemical study to understand the effect of different cutoff potentials on the Li-ion storage mechanism. This work highlights the possibility of the direct application of NiAl LDH materials as negative electrodes for LIBs.

In Situ X-Ray Diffraction Investigations during Diffusion Anneals of Ni-Cu Thin Film Diffusion Couples

2010 ◽  
Vol 89-91 ◽  
pp. 503-508 ◽  
Author(s):  
J. Sheng ◽  
U. Welzel ◽  
Eric J. Mittemeijer
Keyword(s):  
Thermal Stresses ◽  
Stress Generation ◽  
Ex Situ ◽  
Diffusion Annealing ◽  
X Ray Diffraction ◽  
Individual Layer ◽  
X Ray ◽  
Bilayer System ◽  
Stress Changes

The stress evolution during diffusion annealing of Ni-Cu bilayers (individual layer thicknesses of 50 nm) was investigated employing ex-situ and in-situ X-ray diffraction measurements. Annealing at relatively low homologous temperatures (about 0.3 - 0.4 Tm) for durations up to about 100 hours results in considerable diffusional intermixing, as demonstrated by Auger-electron spectroscopy investigations (in combination with sputter-depth profiling). In addition to thermal stresses due to differences of the coefficients of thermal expansion of layers and substrate, tensile stress con-tributions in the sublayers arise during the diffusion anneals. The obtained stress data have been discussed in terms of possible mechanisms of stress generation. The influence of diffusion on stress development in the sublayers of the diffusion couple during heating and isothermal annealing was investigated by comparing stress changes in the bilayer system with corresponding results obtained under identical conditions for single layers of the components in the bilayer system. The specific residual stresses that emerge due to diffusion between the (sub)layers in the bilayer could thereby be identified.

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