Search

*Akpınar, Işıl ( Aksaray, Yazar ), Hydrogen is one of the most attractive renewables for future energy application, therefore it is vital to develop cost-effective and highly-efficient electrocatalysts for the hydrogen evolution reaction (HER) to promote the generation of hydrogen from mild methods. In this work, Co–Mo phosphide nanosheets with the adjustable ratio of Co and Mo were fabricated on carbon cloth by a facile hydrothermal-annealing method. Owing to the unique nanostructures, abundant active surfaces and small resistance were achieved. Excellent electrocatalytic performances are obtained, such as the small overpotential of ∼67.3 mV to realize a current density of 10 mA cm−2 and a Tafel slope of 69.9 mV dec−1. Rapid recovery of the current response under multistep chronoamperometry is realized and excellent stability retained after the CV test for 2000 cycles. The change of electronic states of different elements was carefully studied which suggested the optimal electrochemical performance can be realized by tuning phosphorous and metal interactions.

Redox flow batteries represent a remarkable alternative for grid-scale energy storage. They commonly employ carbon felts or carbon papers, which suffer from low activity towards the redox reactions involved, leading to poor performance. Here we propose the use of electrospun freestanding carbon materials derived from lignin as alternative sustainable electrodes for all-vanadium flow batteries. The lignin-derived carbon electrospun mats exhibited a higher activity towards the VO2+/VO2+ reaction than commercial carbon papers when tested in a three-electrode electrochemical cell (or half-cell), which we attribute to the higher surface area and higher amount of oxygen functional groups at the surface. The electrospun carbon electrodes also showed performance comparable to commercial carbon papers, when tested in a full cell configuration. The modification of the surface chemistry with the addition of phosphorous produced different effect in both samples, which needs further investigation. This work demonstrates for the first time the application of sustainably produced electrospun lignin-derived carbon electrodes in a redox flow cell, with comparable performance to commercial materials and establishes the great potential of biomass-derived carbons in energy devices.

The porous transport layer (PTL) in polymer electrolyte membrane water electrolysers (PEMWEs) has the multiple roles of delivering water to the electro-catalyst, removal of product gas, and acts as a conduit for electronic and thermal transport. They are, thus, a critical component for optimized performance, especially at high current density operation. This study examines the relationship between the microstructure and corresponding electrochemical performance of commonly used titanium sinter PTLs. Four PTLs, with mean pore diameter (MPD) ranging from 16 μm to 90 μm, were characterized ex-situ using scanning electron microscopy and X-ray computed micro-tomography to determine key structural properties. The performance of these PTLs was studied operando using polarization and electrochemical impedance spectroscopy. Results showed that an increase in mean pore size of the PTLs correlates to an increase in the spread and multimodality of the pore size distribution and a reduction in homogeneity of porosity distribution. Electrochemical measurements reveal a strong correlation of mean pore size of the PTLs with performance. Smaller pore PTLs showed lower Ohmic resistance but higher mass transport resistance at high current density of 3.0 A cm−2. A non-monotonic trend of mass transport resistance was observed for different PTLs, which suggests an optimal pore size beyond which the advantageous influence of macroporosity for mass transport is diminished. The results indicate that maximizing contact points between the PTL and the catalyst layer is the overriding factor in determining the overall performance. These results guide PTL design and fabrication of PEMWEs.

This work considers the relationship between the morphology of porous carbon materials used for supercapacitors and the electrochemical impedance spectroscopy (EIS) response. EIS is a powerful tool that can be used to study the porous 3-dimensional electrode behavior in different electrochemical systems. Porous carbons prepared by treatment of cellulose with different compositions of potassium hydroxide (KOH) were used as model systems to investigate the form vs. electrochemical function relationship. A simple equivalent circuit that represents the electrochemical impedance behavior over a wide range of frequencies was designed. The associated impedances with the bulk electrolyte, Faradaic electrode processes and different pore size ranges were investigated using a truncated version of the standard transmission line model. The analysis considers the requirements of porous materials as electrodes in supercapacitor applications, reasons for their non-ideal performance and the concept of ‘best capacitance’ behavior in different frequency ranges. Graphical Abstract: The electrolyte ions penetrate the macropores, into the mesopores and finally reach the micropores. The capacitance measured by impedance spectroscopy is a function of frequency and porous structure.

Redox flow batteries offer a potential solution to an increase in renewable energy generation on the grid by offering long-term, large-scale storage and regulation of power. However, they are currently underutilised due to cost and performance issues, many of which are linked to the microstructure of the porous carbon electrodes used. Here, for the first time, we offer a detailed study of the in situ effects of compression on a commercially available carbon felt electrode. Visualisation of electrode structure using X-ray computed tomography shows the non-linear way that these materials compress and various metrics are used to elucidate the changes in porosity, pore size distribution and tortuosity factor under compressions from 0%–90%.

In-depth understanding of the dynamics of water formation, accumulation and removal is important for flow-field design optimization to ensure robust performance and durability of polymer electrolyte fuel cells (PEFCs). Here, in-operando neutron radiography is used to display and quantify liquid water distribution across the entire active area of single-, double- and quad-channel serpentine flow-fields. The results revealed that the water management and performance of PEFCs is strongly affected by the number of serpentine channels in the cathode flow-field. The single-channel serpentine-based PEFC exhibits both a better cell performance and uniformity in the local water distribution. The quad-channel based PEFC exhibits the largest voltage fluctuations caused by severe water flooding in the gas channels. However, the single-channel design leads to significantly larger pressure drop than the multiple-channel counterparts, which requires much higher parasitic power to pressurize and recirculate the reactants. Three different regimes of operation can be defined based on the current density: gradually increasing hydration ( > 600 mA cm−2). The reduced overall quantity of water in the channels with an increase in current density can be attributed to faster gas velocity and higher cell temperature.

The solid polymer electrolyte (SPE) alkaline anion exchange membrane (AAEM) fuel cell exhibits facile oxygen reduction reaction (ORR) kinetics and has the ability to utilise non-precious metal electrocatalysts. However, the AAEM is reported to suffer from increased instability within the alkaline media (degradation) via a number of routes, including nucleophilic elimination when operated at temperatures above 60 °C, somewhat eliminating the kinetic advantage of operating at higher temperatures. Nonetheless, modelling studies have indicated that the membrane hydration could show improved resistance to alkaline instability and subsequent degradation when operated at elevated temperatures. This investigation uses the quartz crystal microbalance (QCM) to examine the thermal stability of a commercial AAEM as a function of humidity. The results show that hydration improves ionomer resistance to degradation, as the ions within the system (namely the OH− nucleophile and cationic headgroups) become less reactive. In-line mass spectrometry data confirms that the ionomer degrades during the elevated temperature excursions used in this study.

Many electrochemical studies exist using the acidic ionomer Nafion as a binder in the ink formulation when operating in high pH systems. However, Nafion acts as an ionic insulator for OH−, and for reactions such as the hydrogen oxidation reaction, the transport of OH− to the catalyst surface is of utmost importance when elucidating the performance of a catalyst. This work demonstrates that when using an alkaline polymer binder in the ink, the apparent activity of a commercially synthesized Pt/C catalyst is increased due to a lower diffusion resistance for the reaction. In order to obtain accurate values for kinetic data in alkaline media, the use of the acidic binder should be avoided.

The need to understand the effects of degradation in polymer electrolyte fuel cells (PEFCs) has led to the development of in-situ and operando imaging studies of failure mechanisms occurring in their constituent materials, but studies using X-ray computed tomography (X-ray CT) for imaging have focussed primarily on a single region of the PEFC flow channel. Whilst studies have shown local variation in degradation rates using electrochemical techniques, this work employs identical-location X-ray CT imaging to elucidate the local degradation of a membrane electrode assembly (MEA) at various locations along-the-channel of a serpentine flow field. Using a carbon corrosion specific accelerated stress test (AST), in-depth analyses of the catalyst layers (CLs) and crack network allow for quantification of the material’s degradation at the inlet, middle and outlet regions of the flow channel on the cathode side. Imaging of the regions was done after 0, 2000 and 5000 cycles and results show significant regional variation in the extent of degradation of the cathode CL. The order of degradation was found to be outlet > middle > inlet, with the outlet CL found to be thinner than the middle and inlet regions, with a greater extent of cracking. Furthermore, additional land and channel degradation effects were probed, with the land regions found to be less degraded than channel regions. This work further highlights the need to understand and develop ASTs that can promote a more uniform degradation rate across an MEA.

Water uptake, sorption mechanics and swelling characteristics of thin-film Nafion and a commercially available Tokuyama alkaline anion exchange membrane ionomer from the vapour phase is explored using a quartz crystal microbalance (QCM). The water uptake measures the number of water molecules adsorbed by the ionomer per functional group and is determined in-situ using the QCM frequency responses allowing for comparison with nanogram precision. Crystal admittance spectroscopy, along with equivalent circuit fitting, is applied to both thin films for the first time and is used to investigate the ionomer's viscoelastic changes during hydration; to elucidate the mechanisms at play during low, medium and high relative humidities.

Flow-field plates are essential components for polymer electrolyte fuel cells (PEFCs), the most common types incorporating parallel or serpentine channels. A novel flow-field, the ‘through-plane array’ (TPA), is presented which provides significantly improved performance at higher current density with the advantage of lower backpressure. The concept modifies a conventional flow-field operating in dead-ended mode and incorporates an array of holes (

This paper describes the use of an in situ analytical technique based on simultaneous displacement and resistance measurement of gas diffusion layers (GDLs) used in polymer electrolyte fuel cells (PEFCs), when exposed to varying compaction pressure. In terms of the losses within fuel cells, the ohmic loss makes up a significant portion. Of this loss, the contact resistance between the GDL and the bipolar plate (BPP) is an important constituent. By analysing the change in thickness and ohmic resistance of GDLs under compression, important mechanical and electrical properties are obtained. Derived parameters such as the ‘displacement factor’ are used to characterise a representative range of commercial GDLs. Increasing compaction pressure leads to a non-linear decrease in resistance for all GDLs. For Toray paper, compaction becomes more irreversible with pressure with no elastic region observed. Different GDLs have different intrinsic resistance; however, all GDLs of the same class share a common compaction profile (change in resistance with pressure). Cyclic compression of Toray GDL leads to progressive improvement in resistance and reduction in thickness that stabilises after ∼10 cycles.

A combined X-ray diffraction and thermal imaging technique is described to investigate the effect of thermal gradients on high-temperature composite materials., A new technique combining in situ X-ray diffraction using synchrotron radiation and infrared thermal imaging is reported. The technique enables the application, generation and measurement of significant thermal gradients, and furthermore allows the direct spatial correlation of thermal and crystallographic measurements. The design and implementation of a novel furnace enabling the simultaneous thermal and X-ray measurements is described. The technique is expected to have wide applicability in material science and engineering; here it has been applied to the study of solid oxide fuel cells at high temperature.