Bismuth vanadate (BiVO4) is a promising photoelectrode material for the oxidation of water, but fundamental studies of this material are lacking. To address this, we report electrical and photoelectrochemical (PEC) properties of BiVO4 single crystals (undoped, 0.6% Mo, and 0.3% W:BiVO4) grown using the floating zone technique. We demonstrate that a small polaron hopping conduction mechanism dominates from 250 to 400 K, undergoing a transition to a variable-range hopping mechanism at lower temperatures. An anisotropy ratio of ~3 was observed along the c axis, attributed to the layered structure of BiVO4. Measurements of the ac field Hall effect yielded an electron mobility of ~0.2 cm(2) V(-1) s(-1) for Mo and W:BiVO4 at 300 K. By application of the Gärtner model, a hole diffusion length of ~100 nm was estimated. As a result of low carrier mobility, attempts to measure the dc Hall effect were unsuccessful. Analyses of the Raman spectra showed that Mo and W substituted for V and acted as donor impurities. Mott-Schottky analysis of electrodes with the (001) face exposed yielded a flat band potential of 0.03-0.08 V versus the reversible H2 electrode, while incident photon conversion efficiency tests showed that the dark coloration of the doped single crystals did not result in additional photocurrent. Comparison of these intrinsic properties to those of other metal oxides for PEC applications gives valuable insight into this material as a photoanode.

Transition-metal oxides are a promising class of semiconductors for the oxidation of water, a process that underpins both photoelectrochemical water splitting and carbon dioxide reduction. However, these materials are limited by very slow charge transport. This is because, unlike conventional semiconductors, material aspects of metal oxides favor the formation of slow-moving, self-trapped charge carriers: small polarons. In this Perspective, we seek to highlight the salient features of small-polaron transport in metal oxides, offer guidelines for their experimental characterization, and examine recent transport studies of two prototypical oxide photoanodes: tungsten-doped monoclinic bismuth vanadate (W:BiVO4) and titanium-doped hematite (Ti:α-Fe2O3). Analysis shows that conduction in both materials is well-described by the adiabatic small-polaron model, with electron drift mobility (distinct from the Hall mobility) values on the order of 10(-4) and 10(-2) cm(2) V(-1) s(-1), respectively. Future directions to build a full picture of charge transport in this family of materials are discussed.

Porous, nanostructured BiVO4 films are incorporated with Mo and W by simultaneous evaporation of Bi, V, Mo, and W in vacuum followed by oxidation in air. Synthesis parameters such as the Bi : V : Mo : W atomic ratio and deposition angle are adjusted to optimize the films for photoelectrochemical (PEC) water oxidation. Films synthesized with a Bi : V : Mo : W atomic ratio of 46 : 46 : 6 : 2 (6% Mo, 2% W) demonstrate the best PEC performance with photocurrent densities 10 times higher than for pure BiVO4 and greater than previously reported for Mo and W containing BiVO4. The films consist of a directional, nanocolumnar layer beneath an irregular surface structure. Backside illumination utilizes light scattering off the irregular surface structure resulting in 30-45% higher photocurrent densities than for frontside illumination. To improve the kinetics for water oxidation Pt is photo-deposited onto the surface of the 6% Mo, 2% W BiVO4 films as an electrocatalyst. These films achieve quantum efficiencies of 37% at 1.1 V vs. RHE and 50% at 1.6 V vs. RHE for 450 nm light.

We report on the underlying mechanism that enables the SnTe−AgSbTe 2 system to exhibit superior thermoelectric figure of merit (ZT) compared to its parent compound SnTe. We show that AgSbTe 2 alloying has a profound impact on the band structure of SnTe by converging the energies of its light and heavy valence bands, leading to significantly enhanced Seebeck coefficients. We have also unraveled a significant connection between alloying and defect stability in this system, wherein the Sn vacancy concentration increases significantly when Ag and Sb are alloyed on the Sn site. The increased Sn vacancy concentration dramatically reduces the lattice thermal conductivity through both lattice softening and phonon−vacancy scattering to ∼0.4 W m −1 K −1 at 800 K. Consequently, a ZT value of 1.2 at 800 K for AgSn 5 SbTe 7 can be achieved by doping I on Te sites. This represents a 300% improvement over pristine SnTe, outperforming many reported SnTe-based thermoelectric materials.

Electrochemical impedance spectroscopy (EIS) is widely used to probe the physical and chemical processes in lithium (Li)-ion batteries (LiBs). The key parameters include state-of-charge, rate capacity or power fade, degradation and temperature dependence, which are needed to inform battery management systems as well as for quality assurance and monitoring. All-solid-state batteries using a solid-state electrolyte (SE), promise greater energy densities via a Li metal anode as well as enhanced safety, but their development is in its nascent stages and the EIS measurement, cell set-up and modelling approach can be vastly different for various SE chemistries and cell configurations. This review aims to condense the current knowledge of EIS in the context of state-of-the-art solid-state electrolytes and batteries, with a view to advancing their scale-up from the laboratory to commercial deployment. Experimental and modelling best practices are highlighted, as well as emerging impedance methods for conventional LiBs as a guide for opportunities in the solid-state.

The influence of micro/nanostructure on thermal conductivity is a topic of great scientific interest and of particular technological importance to thermoelectrics. The current understanding is that structural defects primarily decrease thermal conductivity through phonon scattering where the phonon dispersion and speed of sound are fixed when describing thermal transport, especially when chemical composition is unchanged. Experimental work on a PbTe model system is presented which shows that the speed of sound linearly decreases with increased internal-strain. This softening of the materials lattice completely accounts for the reduction in lattice thermal conductivity, without the introduction of additional phonon scattering mechanisms. Additionally, we show that a major contribution to the reduction in thermal conductivity, and the resulting improvement in thermoelectric figure of merit (zT > 2), in high efficiency Na-doped PbTe can be attributed to this internal-strain induced lattice softening effect. While inhomogeneous internal-strain fields are known to introduce phonon scattering centers, this study demonstrates that internal-strain can also soften a materials lattice on average, modifying the speeds of sound and phonon dispersion. This presents new avenues to control lattice thermal conductivity, beyond phonon scattering, with microstructural defects and internal-strain. In practice, many engineering materials will exhibit both softening and scattering effects, as is shown in silicon. This work shines new light on studies of thermal conductivity in fields of energy materials, microelectronics, and nano-scale heat transfer.

DC electrical conductivity, Seebeck and Hall coefficients are measured between 300 and 450 K on single crystals of monoclinic bismuth vanadate that are doped n-type with 0.3% tungsten donors (W:BiVO4). Strongly activated small-polaron hopping is implied by the activation energies of the Arrhenius conductivities (about 300 meV) greatly exceeding the energies characterizing the falls of the Seebeck coefficients' magnitudes with increasing temperature (about 50 meV). Small-polaron hopping is further evidenced by the measured Hall mobility in the ab-plane (10−1 cm2 V−1 s−1 at 300 K) being larger and much less strongly activated than the deduced drift mobility (about 5 × 10−5 cm2 V−1 s−1 at 300 K). The conductivity and n-type Seebeck coefficient is found to be anisotropic with the conductivity larger and the Seebeck coefficient's magnitude smaller and less temperature dependent for motion within the ab-plane than that in the c-direction. These anisotropies are addressed by considering highly anisotropic next-nearest-neighbor (≈5 Å) transfers in addition to the somewhat shorter (≈4 Å), nearly isotropic nearest-neighbor transfers.

BiSI (indirect band gap = 1.57 eV) is a recently discovered photoelectrode material possessing promising optical properties for use in alternative thin film solar cells. In this work, we study the effects of selenium doping on BiSI film properties and also demonstrate the incorporation of BiS1–x Se x I films into both electrochemical and solid state solar cells. Tuning the band gap of BiS1–x Se x I by substituting selenium for sulfur was accomplished by substituting various amounts of SeO2 for thiourea in the BiSI spray pyrolysis precursor solutions. This strategy was employed to reduce the direct band gap of BiS1–x Se x I films from 1.63 eV to as low as 1.48 eV, as measured by UV–vis–NIR diffuse reflectance spectroscopy for x = 0.4. Both electrochemical and solid state solar cell devices utilizing n-BiSI as the light absorbing material demonstrated open circuit voltages of nearly 0.4 V. The electrochemical devices showed much higher short circuit currents and power conversion efficiencies than the solid state devices. Power conversion efficiencies of up to 0.25 and 0.012% were measured for electrochemical and solid state devices, respectively, under AM1.5G illumination.