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With the increasing focus on decarbonisation of the transport sector, it is imperative to consider routes to electrify vehicles beyond those achievable using lithium-ion battery technology. These include heavy goods vehicles and aerospace applications that require propulsion systems that can provide gravimetric energy densities, which are more likely to be delivered by fuel cell systems. While the discussion of light-duty vehicles is abundant in the literature, heavy goods vehicles are under-represented. This paper presents an overview of the electrochemical degradation of a proton exchange membrane fuel cell integrated into a simulated Class 8 heavy goods range-extender fuel cell hybrid electric vehicle operating in urban driving conditions. Electrochemical degradation data such as polarisation curves, cyclic voltammetry values, linear sweep voltammetry values, and electrochemical impedance spectroscopy values were collected and analysed to understand the expected degradation modes in this application. In this application, the proton exchange membrane fuel cell stack power was designed to remain constant to fulfil the mission requirements, with dynamic and peak power demands managed by lithium-ion batteries, which were incorporated into the hybridised powertrain. A single fuel cell or battery cell can either be operated at maximum or nominal power demand, allowing four operational scenarios: maximum fuel cell maximum battery, maximum fuel cell nominal battery, nominal fuel cell maximum battery, and nominal fuel cell nominal battery. Operating scenarios with maximum fuel cell operating power experienced more severe degradation after endurance testing than nominal operating power. A comparison of electrochemical degradation between these operating scenarios was analysed and discussed. By exploring the degradation effects in proton exchange membrane fuel cells, this paper offers insights that will be useful in improving the long-term performance and durability of proton exchange membrane fuel cells in heavy-duty vehicle applications and the design of hybridised powertrains. [ABSTRACT FROM AUTHOR]

Crystals growing via nonclassical crystallisation pathways often lose the shape factor and the mechanisms involved are often anomalous. This makes it difficult to predict the crystal growth kinetics using the conventional crystal growth kinetic models. A new pseudo second order growth kinetic expression to predict the anomalous growth behaviour of curcumin crystals is introduced. This model also allows several important parameters relevant to the kinetics of the crystal growth, such as mass crystallised with respect to time, overall crystal growth kinetic constant, the maximum number of active sites involved in the crystal growth process and the initial crystal growth rate, to be obtained. According to the pseudo second order kinetics, the activation energy for the nonclassical crystal growth of curcumin was found to be ∼69 kJ mol−1, which seems to agree with the activation energy for the classical crystal growth of organic compounds reported in the literature. The total number of active sites involved in the crystal growth process was found to be ∼1022 per gram of the seeds. [ABSTRACT FROM AUTHOR]

The next generation of proton exchange membrane fuel cells (PEMFCs) require a substantial reduction or elimination of Pt-based electrocatalyst from the cathode, where O 2 reduction takes place. The most promising alternative to Pt is atomic Fe embedded in N-doped C (Fe–N–C). Successful incorporation of Fe–N–C in PEMFCs relies on a thorough understanding of the catalyst layer properties, both ex situ and in situ , with tailored electrode interface engineering. To help resolve this conundrum, we provide a quantitative protocol on the optimisation of I/C for Fe–N–Cs. It is demonstrated that a high pore volume (3.33 cm3 g−1 FeNC) Fe–N–C catalyst requires a sufficiently high ionomer to catalyst mass ratio (I/C, 2.8≤I/C ≤ 4.2) for optimum PEMFC activity under H 2 /O 2. Emerging electrochemical techniques (distribution of relaxation times and Fourier transformed alternating current voltammetry) were used to deconvolute for the first time the trade-off between proton and electron resistance and accessible FeN x active site density with increasing ionomer loading. These findings highlight the significant impact of tuning the I/C ratio based on the catalyst layer properties and feature the power of evolving electrochemical tools for optimising performance in PEMFCs and other electrochemical devices. [Display omitted] • In situ FTacV quantified Fe–N–C electrochemical active site density in fuel cell. • Fe–N–C active site density and current density correlated with ionomer loading. • DRT quantified resistance to proton transport and oxygen diffusion in fuel cell. • Fe–N–C to ionomer ratio optimised based on quantitative protocol. [ABSTRACT FROM AUTHOR]

A recycled solvent-based green synthesis strategy for 2D/3D zeolitic imidazolate frameworks (ZIFs) has been developed to produce functional nanoporous carbons (NPCs) with tuneable morphology, graphitization, N-doping and high porosity via direct pyrolysis. These tailored NPCs show superior supercapacitance performance over typical NPC derived from MOFs and chemical activation/template-directed methods. [Display omitted] • Two important aspects of green synthesis and improved supercapacitance are reported. • A green synthesis route for ZIF-8 via recycling mother liquors (RMLs) is developed. • Rod-/sheet-/polyhedral-like 2D/3D microstructures are produced with RMLs. • 2D/3D NPCs deliver excellent capacitance values and device-level performance. Carbonized metal–organic frameworks (MOFs)-based nanoporous carbon materials (NPCs) offer attractive activities in electrochemical energy conversion and storage (EECS) applications; however, there is the need for scalable MOFs production under reduced energy/environmental impact. This study reports a green synthesis route for model zeolitic imidazolate framework (ZIF-8) materials via recycling methanol-based mother liquors (ZIF-RML x) under room temperature stirring and their carbonized materials (CZC-RML x) for high-performance supercapacitors. Series of ZIF-RML x samples produced in four recycles offer rod-/sheet-/polyhedral-like 2D/3D microstructures with tuneable internal and external framework and morphological features. Accordingly, CZC-RML x , obtained by direct pyrolysis, with high microporosity and surface area of 1500 m2 g−1 deliver excellent capacitance values of 200–340 F g−1, compared to typical MOFs-derived or chemically activated/templated NPCs, produced via extended chemical processing. Structure-relevant and comparative performance analysis reveal insights for improved charge storage and carbonization-dependent graphitization, nitrogen-doping and microporosity-controlled capacitance characteristics in the CZC-RML x over typical NPCs in literature. The device-level performance with a long-term durability over 21,000 cycles is demonstrated. The practical potential of CZC-RML x is further evaluated by fabricating solid-state cells and their parallel and series circuit combinations result in overall capacitance and voltage boost to 450 F g−1 and 2.4 V, respectively. [ABSTRACT FROM AUTHOR]

The current work reports an unprecedented multifunctional material with optical activity and a modified magnetic response by a unique combination of doping with P and Fe into the spinel LiMn 2 O 4. Through inductively coupled plasma – optical emission spectroscopy, X-ray absorption near-edge spectroscopy, X-ray diffraction and scanning transmission electron microscopy, the chemical composition, oxidation state and the crystalline structure are determined. Solid-state UV-Vis spectroscopy, magnetic susceptibility and electronic conductivity reveal the critical importance of the interaction between iron and phosphorus when simultaneously doping the crystalline structure of LiMn 2 O 4. The presence of Fe and P considerably increases charge carrier concentration as a mechanism for enhancing electronic conductivity. Fe and P doping also creates Fe-Fe spin interactions that allow double electron optical excitations. This opens a pathway to create multifunctional materials for light-assisted charging lithium-ion batteries. P doping also induces the formation of magnetic clusters arising from the Fe-O-Fe, Fe-O-Mn and Mn-O-Mn spin exchange interactions. The magnetic response of the materials is strongly influenced by the relative amount of Fe in octahedral or tetrahedral sites of the spinel structure. Such ferrimagnetic behaviour has not been reported before LiMn 2 O 4 doped with Fe or P separately. The potential applicability of this newly identified magnetic feature was demonstrated by a significant capacity gain when a lithium-ion cell is exposed to a static external magnetic field. • Simultaneous P and Fe doping of the LiMn 2 O 4 spinel develops new ferro/ferrimagnetic properties in this material. • Phosphorous stabilizes iron-iron magnetic interactions, unseen in previous Fe doped LiMn 2 O 4. • Iron-iron magnetic interaction gives rise to double optical electron excitation and ferro/ferrimagnetic features. • Under magnetic field, ferromagnetic P and Fe doped LiMn 2 O 4 delivers higher capacity gains than other generic LIB materials. • Enhanced capacity gains occur due to an increased magnetohydrodynamic effect on the surface of the particles. [ABSTRACT FROM AUTHOR]