In Situ X-ray imaging of HT-PEMFC hot-pressing using contrast enhancement

A contrast enhancement agent is used to visualise phosphoric acid penetration and distribution in high-temperature polymer electrolyte membrane fuel cells. This new method is demonstrated in the investigation of hot-pressing parameters on phosphoric acid penetration and distribution. In situ radiography of the hot-press process showed acid plumes breaking through the catalyst layer, microporous layer (MPL) and gas diffusion layer (GDL). The phosphoric acid volume and distribution within the MPL and GDL are quantified, and their dependence on hot-press pressure, duration and compression control are analysed. Increasing hot-press pressure and duration was found to increase acid penetration and delamination of the membrane and catalyst layers. The absence of a compression control gasket also led to significant infiltration into the MPL and GDL. Penetration occurred first at the anode for all tests, which was attributed to a higher number of cracks and greater degree of crack connectivity. Phosphoric acid entered the MPL and GDL either through initial breakthrough of the catalyst layer, or from acid pooling on the GDL surface and being compressed into the fibres. This work provides a novel method to improve visualisation of phosphoric acid and highlights the acid loss mechanisms resulting from hot-press conditions

Electrochemical Impedance Spectroscopy for All-Solid-State Batteries: Theory, Methods and Future Outlook

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

Engineering Solution-Processed Non-Crystalline Solid Electrolytes for Li Metal Batteries

Non-crystalline Li-ion solid electrolytes (SEs), such as lithium phosphorus oxynitride, can uniquely enable high-rate solid-state battery operation over thousands of cycles in thin film form. However, they are typically produced by expensive and low throughput vacuum deposition, limiting their wide application and study. Here, we report non-crystalline SEs of composition Li-Al-P-O (LAPO) with ionic conductivities > 10-7 S cm-1 at room temperature made by spin coating from aqueous solutions and subsequent annealing in air. Homogenous, dense, flat layers can be synthesized with submicrometer thickness at temperatures as low as 230 °C. Control of the composition is shown to significantly affect the ionic conductivity, with increased Li and decreased P content being optimal, while higher annealing temperatures result in decreased ionic conductivity. Activation energy analysis reveals a Li-ion hopping barrier of ≈0.4 eV. Additionally, these SEs exhibit low room temperature electronic conductivity (< 10-11 S cm-1) and a moderate Young’s modulus of ≈54 GPa, which may be beneficial in preventing Li dendrite formation. In contact with Li metal, LAPO is found to form a stable but high impedance passivation layer comprised of Al metal, Li-P, and Li-O species. These findings should be of value when engineering non-crystalline SEs for Li-metal batteries with high energy and power densities

Quasi-Two-Dimensional Heterostructures (KM1 – xTe)(LaTe3) (M = Mn and Zn) with Charge Density Waves

Layered heterostructure materials with two different functional building blocks can teach us about emergent physical properties and phenomena arising from interactions between the layers. We report intergrowth compounds KLaM1 – xTe4 (M = Mn and Zn; x ≈ 0.35) featuring two chemically distinct alternating layers [LaTe3] and [KM1 – xTe]. Their crystal structures are incommensurate, determined by single X-ray diffraction for the Mn compound and a transmission electron microscope study for the Zn compound. KLaMn1 – xTe4 crystallizes in the orthorhombic superspace group Pmnm(01/2γ)s00 with lattice parameters a = 4.4815(3) Å, b = 21.6649(16) Å, and c = 4.5220(3) Å. It exhibits charge density wave order at room temperature with a modulation wave vector q = 1/2b* + 0.3478c* originating from electronic instability of Te-square nets in [LaTe3] layers. The Mn analog exhibits a cluster spin glass behavior with spin freezing temperature Tf ≈ 5 K attributed to disordered Mn vacancies and competing magnetic interactions in the [Mn1 – xTe] layers. The Zn analog also has charge density wave order at room temperature with a similar q-vector having the c* component ∼0.346 confirmed by selected-area electron diffraction. Electron transfer from [KM1 – xTe] to [LaTe3] layers exists in KLaM1 – xTe4, leading to an enhanced electronic specific heat coefficient. The resistivities of KLaM1 – xTe4 (M = Mn and Zn) exhibit metallic behavior at high temperatures and an upturn at low temperatures, suggesting partial localization of carriers in the [LaTe3] layers with some degree of disorder associated with the M atom vacancies in the [M1 – xTe] layers

The subchalcogenides Ir₂In₈Q (Q = S, Se, Te): Dirac semimetal candidates with re-entrant structural modulation

Subchalcogenides are uncommon compounds where the metal atoms are in unusually low formal oxidation states. They bridge the gap between intermetallics and semiconductors, and can have unexpected structures and properties because of the exotic nature of their chemical bonding, as they contain both metal-metal and metal-main group (e.g. halide, chalcogenide) interactions. Finding new members of this class of materials presents synthetic challenges, as attempts to make them often result in phase separation into binary compounds. We overcome this difficulty by utilizing indium as a metal flux to synthesize large (mm scale) single crystals of novel subchalcogenide materials. Herein, we report two new compounds Ir2In8Q (Q = Se, Te) and compare their structural and electrical properties to the previously reported Ir2In8S analogue. Ir2In8Se and Ir2In8Te crystallize in the P42/mnm space group and are isostructural to Ir2In8S but also have commensurately modulated (with q-vectors q = 1/6a* + 1/6b* and q= 1/10a* + 1/10b* for Ir2In8Se and Ir2In8Te, respectively) low temperature phase transitions, where the chalcogenide anions in the channels experience a distortion in the form of In-Q bond alternation along the ab plane. Both compounds display re-entrant structural behavior, where the supercells appear on cooling but revert to the original subcell below 100 K, suggesting competing structural and electronic interactions dictate the overall structure. Notably, these materials are topological semimetal candidates with symmetry-protected Dirac crossings near the Fermi level, and exhibit high electron mobilities (~1500 cm2 V-1 s-1 at 1.8 K) and moderate carrier concentrations (~1020 cm-3) from charge transport measurements. This work highlights metal flux as a powerful synthetic route to high quality single crystals of novel intermetallic subchalcogenides

A two-dimensional type I superionic conductor

Superionic conductors possess liquid-like ionic diffusivity in the solid state, finding wide applicability from electrolytes in energy storage to materials for thermoelectric energy conversion. Type I superionic conductors (for example, AgI, Ag2Se and so on) are defined by a first-order transition to the superionic state and have so far been found exclusively in three-dimensional crystal structures. Here, we reveal a two-dimensional type I superionic conductor, α-KAg3Se2, by scattering techniques and complementary simulations. Quasi-elastic neutron scattering and ab initio molecular dynamics simulations confirm that the superionic Ag+ ions are confined to subnanometre sheets, with the simulated local structure validated by experimental X-ray powder pair-distribution-function analysis. Finally, we demonstrate that the phase transition temperature can be controlled by chemical substitution of the alkali metal ions that compose the immobile charge-balancing layers. Our work thus extends the known classes of superionic conductors and will facilitate the design of new materials with tailored ionic conductivities and phase transitions

Towards optimised cell design of thin film silicon-based solid-state batteries via modelling and experimental characterisation

To realise the promise of solid-state batteries, negative electrode materials exhibiting large volumetric expansions, such as Li and Si, must be used. These volume changes can cause significant mechanical stresses and strains that affect cell performance and durability, however their role and nature in SSBs are poorly understood. Here, a 2D electro-chemo-mechanical model is constructed and experimentally validated using steady-state, transient and pulsed electrochemical methods. The model geometry is taken as a representative cross-section of a non-porous, thin-film solid-state battery with an amorphous Si (a-Si) negative electrode, lithium phosphorous oxynitride (LiPON) solid electrolyte and LiCoO2 (LCO) positive electrode. A viscoplastic model is used to predict the build-up of strains and plastic deformation of a-Si as a result of (de)lithiation during cycling. A suite of electrochemical tests, including electrochemical impedance spectroscopy, the galvanostatic intermittent titration technique and hybrid pulse power characterisation are carried out to establish key parameters for model validation. The validated model is used to explore the peak interfacial (a-Si∣LiPON) stress and strain as a function of the relative electrode thickness (up to a factor of 4), revealing a peak volumetric expansion from 69% to 104% during cycling at 1C. The validation of this electro-chemo-mechanical model under load and pulsed operating conditions will aid in the cell design and optimisation of solid-state battery technologies

Ultralow Thermal Conductivity, Multiband Electronic Structure and High Thermoelectric Figure of Merit in TlCuSe

The entanglement of lattice thermal conductivity, electrical conductivity, and Seebeck coefficient complicates the process of optimizing thermoelectric performance in most thermoelectric materials. Semiconductors with ultralow lattice thermal conductivities and high power factors at the same time are scarce but fundamentally interesting and practically important for energy conversion. Herein, an intrinsic p-type semiconductor TlCuSe that has an intrinsically ultralow thermal conductivity (0.25 W m−1 K−1), a high power factor (11.6 µW cm−1 K−2), and a high figure of merit, ZT (1.9) at 643 K is described. The weak chemical bonds, originating from the filled antibonding orbitals p-d* within the edge-sharing CuSe4 tetrahedra and long TlSe bonds in the PbClF-type structure, in conjunction with the large atomic mass of Tl lead to an ultralow sound velocity. Strong anharmonicity, coming from Tl+ lone-pair electrons, boosts phonon–phonon scattering rates and further suppresses lattice thermal conductivity. The multiband character of the valence band structure contributing to power factor enhancement benefits from the lone-pair electrons of Tl+ as well, which modify the orbital character of the valence bands, and pushes the valence band maximum off the Γ-point, increasing the band degeneracy. The results provide new insight on the rational design of thermoelectric materials

A New Three-Dimensional Subsulfide Ir₂In₈S with Dirac Semimetal Behavior

Dirac and Weyl semimetals host exotic quasiparticles with unconventional transport properties, such as high magnetoresistance and carrier mobility. Recent years have witnessed a huge number of newly predicted topological semimetals from existing databases; however, experimental verification often lags behind such predictions. Common reasons are synthetic difficulties or the stability of predicted phases. Here, we report the synthesis of the Type-II Dirac semimetal Ir2In8S, an air-stable compound with a new structure type. This material has two Dirac crossings in its electronic structure along the Γ-Z direction of the Brillouin zone. We further show that Ir2In8S has a high electron carrier mobility of ~10,000 cm2/Vs at 1.8 K, and a large, non-saturating transverse magnetoresistance of ~6000% at 3.34 K in a 14 T applied field. Shubnikov de-Haas oscillations reveal several small Fermi pockets and the possibility of a nontrivial Berry phase. With its facile crystal growth, novel structure type, and striking electronic structure, Ir2In8S introduces a new material system to study topological semimetals and enable advances in the field of topological materials

Phase transition systematics in BiVO4 by means of high-pressure-high-temperature Raman experiments

We report here high-pressure–high-temperature Raman experiments performed on BiVO 4 . We characterized the fergusonite and scheelite phases (powder and single crystal samples) and the zircon polymorph (nanopowder). The experimental results are supported by ab initio calculations, which, in addition, provide the vibrational patterns. The temperature and pressure behavior of the fergusonite lattice modes reflects the distortions associated with the ferroelastic instability. The linear coefficients of the zircon phase are in sharp contrast to the behavior observed in the fergusonite phase. The boundary of the fergusonite-to-scheelite second-order phase transition is given by T F − Sch ( K ) = − 166 ( 8 ) P ( GPa ) + 528 ( 5 ) . The zircon-to-scheelite, irreversible, first-order phase transition takes place at T Z − Sch ( K ) = − 107 ( 8 ) P ( GPa ) + 690 ( 10 ) . We found evidence of additional structural changes around 15.7 GPa, which in the downstroke were found to be not reversible. We analyzed the anharmonic contribution to the wave-number shift in fergusonite using an order parameter. The introduction of a critical temperature depending both on temperature and pressure allows for a description of the results of all the experiments in a unified way