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Abstract: LiCoO2 is the prototypical cathode in lithium-ion batteries. Its crystal structure consists of Li+ and CoO2– layers that alternate along the hexagonal ⟨0001⟩ axis. It is well established that the ionic and electronic conduction are anisotropic, but little is known regarding the heat transport. We analyze the phonon dispersion and lifetimes using anharmonic lattice dynamics based on quantum-chemical force constants. Around room temperature, the thermal conductivity in the hexagonal ab plane of the layered cathode is ∼6 times higher than that along the c axis. An upper limit to the average thermal conductivity at T = 300 K of 38.5 W m–1 K–1 is set by short phonon lifetimes associated with anharmonic interactions within the octahedral face-sharing CoO2– network. Observations of conductivity <10 W m–1 K–1 can be understood by additional scattering channels including grain boundaries in polycrystalline samples. The impact on thermal processes in lithium-ion batteries is discussed.

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Abstract: The concepts of oxidation state and atomic charge are entangled in modern materials science. We distinguish between these quantities and consider their fundamental limitations and utility for understanding material properties. We discuss the nature of bonding between atoms and the techniques that have been developed for partitioning electron density. While formal oxidation states help us count electrons (in ions, bonds, lone pairs), variously defined atomic charges are usefully employed in the description of physical processes including dielectric response and electronic spectroscopies. Such partial charges are introduced as quantitative measures in simple mechanistic models of a more complex reality, and therefore may not be comparable or transferable. In contrast, oxidation states are defined to be universal, with deviations constituting exciting challenges as evidenced in mixed-valence compounds, electrides and highly correlated systems. This Perspective covers how these concepts have evolved in recent years, our current understanding and their significance.

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Abstract: The source of n-type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In2O3,SnO2, and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In2O3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO2, the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n-type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In2O3, but also in SnO2 and ZnO.

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Abstract: We report on the synthesis, characterization, and optoelectronic properties of the novel trimethylsulfonium lead triiodide perovskite, (CH3)3SPbI3. At room temperature, the air-stable compound adopts a hexagonal crystal structure with a 1D network of face-sharing [PbI6] octahedra along the c axis. UV–vis reflectance spectroscopy on a pressed pellet revealed a band gap of 3.1 eV, in agreement with first-principles calculations, which show a small separation between direct and indirect band gaps. Electrical resistivity measurements on single crystals indicated that the compound behaves as a semiconductor. According to multi-temperature single-crystal X-ray diffraction, synchrotron powder X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry, two fully reversible structural phase transitions occur at −5 and ca. −100 °C with reduction of the unit cell symmetry to monoclinic as temperature decreases. The role of the trimethylsulfonium cation regarding the chemical stability and optoelectronic properties of the new compound is discussed in comparison with APbI3 (A = Cs, methylammonium, and formamidinium cation), which are most commonly used in perovskite solar cells.

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Abstract: Recently, there has been an explosive growth in research based on hybrid lead–halide perovskites for photovoltaics owing to rapid improvements in efficiency. The advent of these materials for solar applications has led to widespread interest in understanding the key enabling properties of these materials. This has resulted in renewed interest in related compounds and a search for materials that may replicate the defect-tolerant properties and long lifetimes of the hybrid lead-halide perovskites. Given the rapid pace of development of the field, the rises in efficiencies of these systems have outpaced the more basic understanding of these materials. Measuring or calculating the basic properties, such as crystal/electronic structure and composition, can be challenging because some of these materials have anisotropic structures, and/or are composed of both heavy metal cations and volatile, mobile, light elements. Some consequences are beam damage during characterization, composition change under vacuum, or compound effects, such as the alteration of the electronic structure through the influence of the substrate. These effects make it challenging to understand the basic properties integral to optoelectronic operation. Compounding these difficulties is the rapid pace with which the field progresses. This has created an ongoing need to continually evaluate best practices with respect to characterization and calculations, as well as to identify inconsistencies in reported values to determine if those inconsistencies are rooted in characterization methodology or materials synthesis. This article describes the difficulties in characterizing hybrid lead–halide perovskites and new materials and how these challenges may be overcome. The topic was discussed at a seminar at the 2015 Materials Research Society Fall Meeting & Exhibit. This article highlights the lessons learned from the seminar and the insights of some of the attendees, with reference to both recent literature and controlled experiments to illustrate the challenges discussed. The focus in this article is on crystallography, composition measurements, photoemission spectroscopy, and calculations on perovskites and new, related absorbers. We suggest how the reporting of the important artifacts could be streamlined between groups to ensure reproducibility as the field progresses.