New strategies for interrogation of redox flow batteries via Synchrotron radiation

Operando and in situ characterisation studies with the assistance of high energy light produced by synchrotrons are becoming increasingly attractive in the energy storage area, allowing for nondestructive investigations of material properties and device behaviour in realistic working environments, and with high temporal resolution afforded by the latest generation of high-flux beamlines. Many operando synchrotron techniques are well suited to redox flow batteries, which undergo redox changes of the active species in their electrolytes when flowed through porous electrodes. There is a large variety of redox flow battery designs and chemistries, spanning transition metal solutions, hybrid gas-liquid devices, plating and stripping mechanisms and organic redox species. This review presents an overview of recent progress and preponderance of synchrotron techniques in investigating the current issues of redox flow batteries. For each synchrotron X-ray analytical approach, practical examples and breakthrough findings are outlined and the potential applications on the newly developed redox flow batteries are discussed

A Review of Polymer Electrolyte Fuel Cells Fault Diagnosis: Progress and Perspectives

Polymer electrolyte fuel cells (PEFCs) are regarded as a substitution for the combustion engine with high energy conversion efficiency and zero CO2 emissions. Stable system operation requires control within a relatively narrow range of operating conditions to achieve the optimal output, leading to faults that can easily cause accelerated degradation when operating conditions deviate from the control targets. Performance recovery of the system can be realized through early fault diagnosis; therefore, accurate and effective diagnostic characterisation is vital for long-term serving. A review of off-line and on-line techniques applied to the fault diagnosis of fuel cells is presented in this work. Off-line approaches include electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), galvanostatic charge (GSC), visualisation-based and image-based techniques; the on-line methods can be divided into model-based, data-driven, signal-based and hybrid methods. Since each methodology has advantages and drawbacks, its effectiveness is analysed, and limitations are highlighted

Influence of NH4Cl additive in a VO2+/VO2+ - AQDS/AQDS2− solar redox flow battery

Solar redox flow batteries are a relatively new type of redox flow battery technology that uses solar energy to directly store chemical energy. Here we present a solar redox flow battery that uses a MoS2@TiO2 thin film with a Nafion protection layer supported on FTO glass substrate as photoanode, employing VO2+/VO2+ and AQDS/AQDS2− as redox active species. When the solar radiation strikes the photoelectrode, the photogenerated holes oxidize VO2+ to VO2+, while the photogenerated electrons reduce AQDS to AQDS2− at the counter electrode. The oxidized form of V5+ and reduced form of AQDS2− thus retain the chemical energy and can release the stored charged via the reverse electrochemical reaction. The addition of NH4Cl to the electrolyte was found to have a positive impact on the electrochemical performance of the redox flow cell. This effect was more evident for the VOSO4 electrolyte, leading to an enhancement of the voltaic and energy efficiencies of more than 17.5%. The results suggest that NH4Cl promotes both mass transport of the vanadium redox species and charge transfer of the AQDS in the electrolyte. The solar-to-output energy conversion efficiency (SOEE) of the solar redox flow battery using 1.6 g L−1 NH4Cl in both anolyte and catholyte reached 9.73%, and an energy density of 87.45% after 10 consecutive one-hour photocharging cycles. Additionally, the use of Nafion to protect the MoS2@TiO2 photoanode from photocorrosion was explored. The Nafion layer ensured an increased stability of MoS2@TiO2 against the strong acidic environment while maintaining effective light response, which translated into enhanced photon and mass transport. An energy storage capacity of ∼60 mAh L−1 after 1-hour photocharging was observed

Developments in Dilatometry for Characterisation of Electrochemical Devices

Since the 1970s, electrochemical dilatometry (ECD) has been used to investigate the dilation of layered host materials due to the intercalation of guest ions, atoms or molecules, and has recently gained traction in application to various electrochemical devices, such as lithium-ion batteries (LiBs), which have electrodes that undergo volume changes during cycling, resulting in particle cracking and electrode degradation. With resolution capabilities spanning tens of microns down to a few nanometres, dilatometry is a valuable tool in understanding how commonly used electrodes dilate and degrade and can therefore be of critical value in improving their performance. In recent years, there has been a plethora of studies using dilatometry as a monitoring tool for understanding operating performance in various electrochemical devices; however, to our knowledge, there has been no in-depth review of this body of research to date. This paper seeks to address this by reviewing how dilatometry works and how it has been used for the characterisation of electrochemical energy storage devices

Observation of Zn Dendrite Growth via Operando Digital Microscopy and Time-Lapse Tomography

The zinc-ion battery is one of the promising candidates for next-generation energy storage devices beyond lithium technology due to the earth’s abundance of Zn materials and their high volumetric energy density (5855 mA h cm–3). To date, the formation of Zn dendrites during charge–discharge cycling still hinders the practical application of zinc-ion batteries. It is, therefore, crucial to understand the formation mechanism of the zinc dendritic structure before effectively suppressing its growth. Here, the application of operando digital optical microscopy and in situ lab-based X-ray computed tomography (X-ray CT) is demonstrated to probe and quantify the morphologies of zinc electrodeposition/dissolution under multiple galvanostatic plating/stripping conditions in symmetric Zn||Zn cells. With the combined microscopy approaches, we directly observed the dynamic nucleation and subsequent growth of Zn deposits, the heterogeneous transportation of charged clusters/particles, and the evolution of ‘dead’ Zn particles via partial dissolution. Zn electrodeposition at the early stage is mainly attributed to activation, while the subsequent dendrite growth is driven by diffusion. The high current not only facilitates the formation of sharp dendrites with a larger mean curvature at their tips but also leads to dendritic tip splitting and the creation of a hyper-branching morphology. This approach offers a direct opportunity to characterize dendrite formation in batteries with a metal anode in the laboratory

Fault diagnosis of PEMFC based on the AC voltage response and 1D convolutional neural network

Real-time diagnosis is required to ensure the safety, reliability, and durability of the polymer electrolyte membrane fuel cell (PEMFC) system. Two categories of methods are (1) intrusive, time consuming, or require alterations to the cell architecture but provide detailed information about the system or (2) rapid and benign but low-information-yielding. A strategy based on alternating current (AC) voltage response and one-dimensional (1D) convolutional neural network (CNN) is proposed as a methodology for detailed and rapid fuel cell diagnosis. AC voltage response signals contain within them the convoluted information that is also available via electrochemical impedance spectroscopy (EIS), such as capacitive, inductive, and diffusion processes, and direct use of time-domain signals can avoid time-frequency conversion. It also overcomes the disadvantage that EIS can only be measured under steady-state conditions. The utilization of multi-frequency excitation can make the proposed approach an ideal real-time diagnostic/characterization tool for fuel cells and other electrochemical power systems

Up in smoke: Considerations for lithium-ion batteries in disposable e-cigarettes

In recent years, the use of disposable electric (e)-cigarettes containing lithium-ion batteries in the UK has led to remarkable wastage, the full environmental impact of which is yet to be realized. This study investigates the suitability for reuse and safety aspects of cells found in disposable e-cigarettes. Through electrochemical and safety characterization techniques, the cells’ performance and hazards were evaluated. Rate capability and long-term cycling experiments showed that cells sold as disposable were capable of completing 474 cycles at 1C charge/discharge before reaching 80% capacity fade. A nail penetration test revealed significant gas expulsion and a maximum temperature of 495°C. However, the cell format prevented significant material ejection. This work outlines the potential health hazards and highlights the possibility for second-life use of disposable e-cigarette cells, shedding light on the environmental impact and safety considerations

Nonuniform compensation of current density distribution in polymer electrolyte fuel cells by local heating

A homogeneous current density distribution improves a fuel cell’s performance and prolongs its service life. Effective cell structure designs and uniform compression during assembly could support this goal by ensuring a homogeneous reaction rate across the activation area. Due to the coupling of hydro-electro-thermal relationships, for instance, the concentration of reactants along the flow field decreases continuously as the electrochemical reaction proceeds, and the subsequent accumulation of liquid water leads to a low current density at the outlet. The effect of operating conditions, such as local heating, on the current density distribution requires further investigation. This paper studies the impact of local heating on polymer electrolyte fuel cell (PEFC) performance and analyses the effects on voltage by mapping the current density distribution across the active area. Local heating was supplied to the three regions of the electrode, namely, fuel inlet, central and outlet regions, with the latter exhibiting the best performance (in the activation, Ohmic and mass transport controlled region, the output voltage increases compared to no local heating corresponding to 1.28%, 2.17% and 2.46%, respectively). Here, we show that in all local heating cases, outlet heating can compensate for the lowest current density region with the largest current density increased by 91.10 mA cm−2 and achieves a more homogeneous current distribution, while inlet heating aggravates heterogeneity. This study provides practical guidance for optimal thermal management system development whereby the cooling channel design should be locally optimised for more uniform distributions of current density and temperature compared to heating the cell uniformly

Effects of an easy-to-implement water management strategy on performance and degradation of polymer electrolyte fuel cells

Intermittent switching between wet and dry reactant gases during operation in a polymer electrolyte fuel cell (PEFC) can improve performance stability, alleviating the effects of flooding by controlling the water content within the system. However, lifetime durability may be affected due to membrane electrode assembly (MEA) boundary delamination and membrane damage. Two relative humidity (RH) control strategies were investigated, using electrochemical performance and MEA degradation as critical indicators. It was found that intermittent switching between wet and dry gases does not accelerate fuel cell degradation if the duration of the dry gas period is set reasonably (dry gases stops before the voltage reaches the apex of the hump). Additionally, current and temperature distribution mapping was utilised to capture the dynamic response between these transitional stages. The switching of dry gases first makes the current density distribution homogeneous, and the maximum current density is reduced subsequently. Then, the current density near the inlet keeps decreasing. Intermittent switching between wet and dry reactant gases is easy to implement and overcomes limitations in mass transfer at medium and high current densities