Spatial Gaussian Markov Random Fields: Modelling, Applications and Efficient Computations

A powerful modelling tool for spatial data is the framework of Gaussian Markov random fields (GMRFs), which are discrete domain Gaussian random fields equipped with a Markov property. GMRFs allow us to combine the analytical results for the Gaussian distribution as well as Markov properties, thus allow for the development of computationally efficient algorithms. Here we briefly review popular spatial GMRFs, show how to construct them, and outline their recent developments and possible future work

Origins of Large Voltage Hysteresis in High Energy-Density Metal Fluoride Lithium-Ion Battery Conversion Electrodes

Metal fluoride and oxides can store multiple lithium-ions through conversion chemistry to enable high energy-density lithium-ion batteries. However, their practical applications have been hindered by an unusually large voltage hysteresis between charge and discharge voltage-profiles and the consequent low energy efficiency (< 80%). The physical origins of such hysteresis are rarely studied and poorly understood. Here we employ in situ X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), density-functional-theory (DFT) calculations, and galvanostatic intermittent titration technique (GITT) to first correlate the voltage profile of iron fluoride ($FeF_3$), a representative conversion electrode material, with evolution and spatial distribution of intermediate phases in the electrode. The results reveal that, contrary to conventional belief, the phase evolution in the electrode is symmetrical during discharge and charge. However, the spatial evolution of the electrochemically active phases, which is controlled by reaction kinetics, is different. We further propose that the voltage hysteresis in the $FeF_3$ electrode is kinetic in nature. It is the result of Ohmic voltage drop, reaction overpotential, and different spatial distributions of electrochemically-active phases (i.e. compositional inhomogeneity). Therefore, the large hysteresis can be expected to be mitigated by rational design and optimization of material microstructure and electrode architecture to improve the energy efficiency of lithium-ion batteries based on conversion chemistry

Structure-Function Relationship of Highly Reactive CuOx Clusters on Co3O4 for Selective Formaldehyde Sensing at Low Temperatures

Designing reactive surface clusters at the nanoscale on metal-oxide supports enables selective molecular interactions in low-temperature catalysis and chemical sensing. Yet, finding effective material combinations and identifying the reactive site remains challenging and an obstacle for rational catalyst/sensor design. Here, the low-temperature oxidation of formaldehyde with CuOx clusters on Co3 O4 nanoparticles is demonstrated yielding an excellent sensor for this critical air pollutant. When fabricated by flame-aerosol technology, such CuOx clusters are finely dispersed, while some Cu ions are incorporated into the Co3 O4 lattice enhancing thermal stability. Importantly, infrared spectroscopy of adsorbed CO, near edge X-ray absorption fine structure spectroscopy and temperature-programmed reduction in H2 identified Cu+ and Cu2+ species in these clusters as active sites. Remarkably, the Cu+ surface concentration correlated with the apparent activation energy of formaldehyde oxidation (Spearman's coefficient ρ = 0.89) and sensor response (0.96), rendering it a performance descriptor. At optimal composition, such sensors detected even the lowest formaldehyde levels of 3 parts-per-billion (ppb) at 75°C, superior to state-of-the-art sensors. Also, selectivity to other aldehydes, ketones, alcohols, and inorganic compounds, robustness to humidity and stable performance over 4 weeks are achieved, rendering such sensors promising as gas detectors in health monitoring, air and food quality control

Mn-oxide cathode material for aqueous Zn-ion battery: structure, mechanism, and performance

The wide-scale expansion of renewable energy sources has triggered the demand for advanced energy storage technologies. Aqueous zinc ion batteries (AZIBs) have been widely noticed in recent years because of their intrinsic safety, abundant raw materials, and environmental friendliness. Among the reported cathode materials for ZIBs, Mn-oxide materials stand out as one of the most promising candidates with their diverse structures, high capacity, and cost-effectiveness. However, the complex energy storage mechanism and unstable electrochemical properties persistently obstruct the practical application of this technology. It has been realized that these disturbances are related to the structural evolution of Mn-oxide materials during the charge/discharge process, and considerable relevant research was carried out. In this review, we present an up-to-date review of the most recent advancements and challenges concerning Mn-oxide cathode materials for aqueous zinc ion batteries. Firstly, we offer a concise summary and categorization of several widely recognized energy storage mechanisms and crystal structures. Then, we focused on sorting out the structural evolution path of Mn-oxide materials, and explored the relevant influencing factors and the relationship between phase evolution and property fluctuations. Finally, we distill key optimization strategies and provide a forward-looking perspective on future research

Enabling intercalation-type TiNb24O62 anode for sodium- and potassium-ion batteries via a synergetic strategy of oxygen vacancy and carbon incorporation

The key to develop earth-abundant energy storage technologies sodium- and potassium-ion batteries (SIBs and PIBs) is to identify low-cost electrode materials that allow fast and reversible Na+/K+ intercalation. Here, we report an intercalation-type material TiNb24O62 as a versatile anode for SIBs and PIBs, via a synergistic strategy of oxygen vacancy and carbon incorporation to enhance ion and electron diffusion. The TiNb24O62−x/reduced graphene oxide (rGO) composite anode delivers high reversible capacities (130 mA h g−1 for SIBs and 178 mA h g−1 for PIBs), great rate performance (54 mA h g−1 for SIBs and 37 mA h g−1 for PIBs at 1 A g−1), and superior cycle stability (73.7% after 500 cycles for SIBs and 84% after 300 cycles for PIBs). The performance is among the best results of intercalation-type metal oxide anodes for SIBs and PIBs. The better performance of TiNb24O62−x/rGO in SIBs than PIBs is due to the better reaction kinetics of the former. Moreover, mechanistic study confirms that the redox activity of Nb4+/5+ is responsible for the reversible intercalation of Na+/K+. Our results suggest that TiNb24O62−x/rGO is a promising anode for SIBs and PIBs and may stimulate further research on intercalation-type compounds as candidate anodes for large ion batteries

Robust Biomass-Derived Carbon Frameworks as High-Performance Anodes in Potassium-Ion Batteries

Potassium-ion batteries (PIBs) have become one of the promising candidates for electrochemical energy storage that can provide low-cost and high-performance advantages. The poor cyclability and rate capability of PIBs are due to the intensive structural change of electrode materials during battery operation. Carbon-based materials as anodes have been successfully commercialized in lithium- and sodium-ion batteries but is still struggling in potassium-ion battery field. This work conducts structural engineering strategy to induce anionic defects within the carbon structures to boost the kinetics of PIBs anodes. The carbon framework provides a strong and stable structure to accommodate the volume variation of materials during cycling, and the further phosphorus doping modification is shown to enhance the rate capability. This is found due to the change of the pore size distribution, electronic structures, and hence charge storage mechanism. The optimized electrode in this work shows a high capacity of 175 mAh g^{-1} at a current density of 0.2 A g^{-1} and the enhancement of rate performance as the PIB anode (60% capacity retention with the current density increase of 50 times). This work, therefore provides a rational design for guiding future research on carbon-based anodes for PIBs

Improving the ORR Performance by Enhancing the Pt Oxidation Resistance

Proton exchange membrane fuel cells require oxygen reduction catalysts with high activity and stability. Pt based alloy materials are most widely applied ORR catalyst due to its high intrinsic activity, but usually suffer from rapid deactivation as a result of particle agglomeration, detachment, Ostwald ripening and/or Pt dissolution. Here we investigate the degradation of the PdPt alloys via in situ X-ray absorption fine structure, Δμ analysis, identical location-electron microscopy and DFT calculations. We conclude that the origin of high activity and stability of the PdPt catalyst stems from the oxidation resistance of metallic Pt, forming mainly surface adsorbed O species at high potentials. Two stage degradation process are observed, showing an evolution of dynamic surface dependent ORR performance along with the deactivation process. The careful design of Pt alloy structure leads to controlled surface oxygen behaviours. This opens a new way to increase the lifespan of fuel cells and improve the Pt utilization efficiency

Advances and Challenges in Electrolyte Development for Magnesium-Sulfur Batteries: A Comprehensive Review.

Magnesium-sulfur batteries are an emerging technology. With their elevated theoretical energy density, enhanced safety, and cost-efficiency, they have the ability to transform the energy storage market. This review investigates the obstacles and progress made in the field of electrolytes which are especially designed for magnesium-sulfur batteries. The primary focus of the review lies in identifying electrolytes that can facilitate the reversible electroplating and stripping of Mg2+ ions whilst maintaining compatibility with sulfur cathodes and other battery components. The review also addresses the critical issue of managing the shuttle effect on soluble magnesium polysulfide by looking at the innovative engineering methods used at the sulfur cathode's interface and in the microstructure design, both of which can enhance the reaction kinetics and overall battery efficiency. This review emphasizes the significance of reaction mechanism analysis from the recent studies on magnesium-sulfur batteries. Through analysis of the insights proposed in the latest literature, this review identifies the gaps in the current research and suggests future directions which can enhance the electrochemical performance of Mg-S batteries. Our analysis highlights the importance of innovative electrolyte solutions and provides a deeper understanding of the reaction mechanisms in order to overcome the existing barriers and pave the way for the practical application of Mg-S battery technology