Promising catalytic activity from molybdenum disulfide (MoS2) in the hydrogen evolution reaction (HER) is attributed to active sites located along the edges of its two-dimensional layered crystal structure, but its performance is currently limited by the density and reactivity of active sites, poor electrical transport, and inefficient electrical contact to the catalyst. Here we report dramatically enhanced HER catalysis (an electrocatalytic current density of 10 mA/cm(2) at a low overpotential of -187 mV vs RHE and a Tafel slope of 43 mV/decade) from metallic nanosheets of 1T-MoS2 chemically exfoliated via lithium intercalation from semiconducting 2H-MoS2 nanostructures grown directly on graphite. Structural characterization and electrochemical studies confirmed that the nanosheets of the metallic MoS2 polymorph exhibit facile electrode kinetics and low-loss electrical transport and possess a proliferated density of catalytic active sites. These distinct and previously unexploited features of 1T-MoS2 make these metallic nanosheets a highly competitive earth-abundant HER catalyst.

We report the controlled synthesis of NiCo layered double hydroxide (LDH) nanoplates using a newly developed high temperature high pressure hydrothermal continuous flow reactor (HCFR), which enables direct growth onto conductive substrates in high yield and, most importantly, better control of the precursor supersaturation and, thus, nanostructure morphology and size. The solution coordination chemistry of metal-ammonia complexes was utilized to synthesize well-defined NiCo LDH nanoplates directly in a single step without topochemical oxidation. The as-grown NiCo LDH nanoplates exhibit a high catalytic activity toward the oxygen evolution reaction (OER). By chemically exfoliating LDH nanoplates to thinner nanosheets, the catalytic activity can be further enhanced to yield an electrocatalytic current density of 10 mA cm(-2) at an overpotential of 367 mV and a Tafel slope of 40 mV dec(-1). Such enhancement could be due to the increased surface area and more exposed active sites. X-ray photoelectron spectroscopy (XPS) suggests the exfoliation also caused some changes in electronic structure. This work presents general strategies to controllably grow nanostructures of LDH and ternary oxide/hydroxides in general and to enhance the electrocatalytic performance of layered nanostructures by exfoliation.

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The increasing demands from large-scale energy applications call for the development of lithium-ion battery (LIB) electrode materials with high energy density. Earth abundant conversion cathode material iron trifluoride (FeF(3)) has a high theoretical capacity (712 mAh g(-1)) and the potential to double the energy density of the current cathode material based on lithium cobalt oxide. Such promise has not been fulfilled due to the nonoptimal material properties and poor kinetics of the electrochemical conversion reactions. Here, we report for the first time a high-capacity LIB cathode that is based on networks of FeF(3) nanowires (NWs) made via an inexpensive and scalable synthesis. The FeF(3) NW cathode yielded a discharge capacity as high as 543 mAh g(-1) at the first cycle and retained a capacity of 223 mAh g(-1) after 50 cycles at room temperature under the current of 50 mA g(-1). Moreover, high-resolution transmission electron microscopy revealed the existence of continuous networks of Fe in the lithiated FeF(3) NWs after discharging, which is likely an important factor for the observed improved electrochemical performance. The loss of active material (FeF(3)) caused by the increasingly ineffective reconversion process during charging was found to be a major factor responsible for the capacity loss upon cycling. With the advantages of low cost, large quantity, and ease of processing, these FeF(3) NWs are not only promising battery cathode materials but also provide a convenient platform for fundamental studies and further improving conversion cathodes in general.

Metal fluorides 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, transmission electron microscopy, density functional theory calculations, and galvanostatic intermittent titration technique to first correlate the voltage profile of iron fluoride (FeF3), 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 FeF3 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.