Printed solid-state electrolytes for form factor-free Li-metal batteries

With the ever-growing interest in ubiquitous smart electronics and the Internet of Things, the demand for high-energy-density power sources with aesthetic versatility has increased tremendously. High energy density Li-metal batteries have attracted considerable attention for fulfilling the high energy density requirement of smart electronics. To obtain form factor-free Li-metal batteries with both design diversity and electrochemical reliability, printed solid-state electrolytes are required as a key component because of their viability for the printing/solidification-based fabrication process and electrode-customized chemical/physical properties. This review presents an overview of printed solid-state electrolytes for form factor-free Li-metal batteries with a focus on materials chemistry and fabrication requirements. In addition, their structural/physical/electrochemical properties were discussed in terms of compatibility with Li-metal batteries.     

Morphology-Dependent Stability of Complex Metal Hydrides and Their Intermediates Using First-Principles Calculations

Complex light metal hydrides are promising candidates for efficient, compact solid-state hydrogen storage. (De)hydrogenation of these materials often proceeds via multiple reaction intermediates, the energetics of which determine reversibility and kinetics. At the solid-state reaction front, molecular-level chemistry eventually drives the formation of bulk product phases. Therefore, a better understanding of realistic (de)hydrogenation behavior requires considering possible reaction products along all stages of morphological evolution, from molecular to bulk crystalline. Here, we use first-principles calculations to explore the interplay between intermediate morphology and reaction pathways. Employing representative complex metal hydride systems, we investigate the relative energetics of three distinct morphological stages that can be expressed by intermediates during solid-state reactions: i) dispersed molecules; ii) clustered molecular chains; and iii) condensed-phase crystals. Our results verify that the effective reaction energy landscape strongly depends on the morphological features and associated chemical environment, offering a possible explanation for observed discrepancies between X-ray diffraction and nuclear magnetic resonance measurements. Our theoretical understanding also provides physical and chemical insight into phase nucleation kinetics upon (de)hydrogenation of complex metal hydrides.     

In-Situ/Operando X-ray Characterization of Metal Hydrides

In this article, the capabilities of soft and hard X-ray techniques, including X-ray absorption (XAS), soft X-ray emission spectroscopy (XES), resonant inelastic soft X-ray scattering (RIXS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD), and their application to solid-state hydrogen storage materials are presented. These characterization tools are indispensable for interrogating hydrogen storage materials at the relevant length scales of fundamental interest, which range from the micron scale to nanometer dimensions. Since nanostructuring is now well established as an avenue to improve the thermodynamics and kinetics of hydrogen release and uptake, due to properties such as reduced mean free paths of transport and increased surface-to-volume ratio, it becomes of critical importance to explicitly identify structure-property relationships on the nanometer scale. X-ray diffraction and spectroscopy are effective tools for probing size-, shape-, and structure-dependent material properties at the nanoscale. This article also discusses the recent development of in-situ soft X-ray spectroscopy cells, which enable investigation of critical solid/liquid or solid/gas interfaces under more practical conditions. These unique tools are providing a window into the thermodynamics and kinetics of hydrogenation and dehydrogenation reactions and informing a quantitative understanding of the fundamental energetics of hydrogen storage processes at the microscopic level. In particular, in-situ soft X-ray spectroscopies can be utilized to probe the formation of intermediate species, byproducts, as well as the changes in morphology and effect of additives, which all can greatly affect the hydrogen storage capacity, kinetics, thermodynamics, and reversibility. A few examples using soft X-ray spectroscopies to study these materials are discussed to demonstrate how these powerful characterization tools could be helpful to further understand the hydrogen storage systems.     

A High-Pressure Praseodymium Fluoride Borate Linking Multiple Structural Features of Apatite-Type Compounds

Pr₅(BO₄)_3−x(BO₃)_x(F,OH)_2.67O_0.28 (x≈1.6), a boron-containing fluoride-oxoapatite-like compound, was obtained by the application of high-pressure/high-temperature synthesis. It exhibits a superstructure of the apatite type with a tripled c lattice parameter (space group P6₃/m) and shows complex anion disorder along the 6₃ screw axis and occupation of distorted octahedra, as well as almost trigonal planar sites, by oxygen and fluorine atoms. Furthermore, a distinct BO₄/(BO₃+F) group disorder is found; 46 % of the sites being occupied by BO₄ groups and 54 % by BO₃ groups, with a fluoride ion located near the missing oxygen atom. The rare earth cations in the 4f sites exhibit a specific distorted tricapped trigonal prismatic coordination with a mean metaprism twist angle of 21.3°. The crystal structure of Pr₅(BO₄)_3−x(BO₃)_x(F,OH)_2.67O_0.28 (x≈1.6) shows much “flexibility” resulting in split and off-site positions of all other rare earth cations. The title compound therefore combines many structural features of apatite-like compounds, for example biologically highly-important carbonated apatites, shedding more light onto the complex structural chemistry of apatites.     

Is the 31P chemical shift anisotropy of aluminophosphates a useful parameter for NMR crystallography?

The ³¹P chemical shift anisotropy (CSA) offers a potential source of new information to help determine the structures of aluminophosphate (AlPO) framework materials. We investigate how to measure the CSAs, which are small (span of ~20–30 ppm) for AlPOs, demonstrating the need for CSA-amplification experiments (often in conjunction with ²⁷Al and/or ¹H decoupling) at high magnetic field (20.0 T) to obtain accurate values. We show that the most shielded component of the chemical shift tensor, δ₃₃, is related to the length of the shortest P─O bond, whereas the more deshielded components, δ₁₁ and δ₂₂ can be related more readily to the mean P─O bond lengths and P─O─Al angles. Using the case of Mg-doped STA-2 as an example, the CSA is shown to be much larger for P(OAl)_4–n(OMg)_n environments, primarily owing to a much shorter P─O(Mg) bond affecting δ₃₃, however, because the mean P─O bond lengths and P─O─T (T = Al, Mg) bond angles do not change significantly between P(OAl)₄ and P(OAl)_4–n(OMg)_n sites, the isotropic chemical shifts for these species are similar, leading to overlapped spectral lines. When the CSA information is included, spectral assignment becomes unambiguous, therefore, although the specialist conditions required might preclude the routine measurement of ³¹P CSAs in AlPOs, in some cases (particularly doped materials), the experiments can still provide valuable additional information for spectral assignment.     

TensorView: A software tool for displaying NMR tensors

The representation of nuclear magnetic resonance (NMR) tensors as surfaces on three-dimensional molecular models is an information-rich presentation that highlights the geometric relationship between tensor principal components and the underlying molecular and electronic structure. Here, we describe a new computational tool, TensorView, for depicting NMR tensors on the molecular framework. This package makes use of the graphical interface and built-in molecular display functionality present within the Mathematica programming environment and is robust for displaying tensor properties from a broad range of commercial and user-specific computational chemistry packages. Two mathematical forms for representing tensor interaction surfaces are presented, the popular ellipsoidal construct and the more technically correct “ovaloid” form. Examples are provided for chemical shielding and shift tensors, dipole–dipole and quadrupolar couplings, and atomic anisotropic displacement parameters (thermal ellipsoids) derived from NMR crystallography.     

NMR crystallography of zeolites: How far can we go without diffraction data?

Nuclear magnetic resonance (NMR) crystallography—an approach to structure determination that seeks to integrate solid-state NMR spectroscopy, diffraction, and computation methods—has emerged as an effective strategy to determine structures of difficult-to-characterize materials, including zeolites and related network materials. This paper explores how far it is possible to go in determining the structure of a zeolite framework from a minimal amount of input information derived only from solid-state NMR spectroscopy. It is shown that the framework structure of the fluoride-containing and tetramethylammonium-templated octadecasil clathrasil material can be solved from the 1D ²⁹Si NMR spectrum and a single 2D ²⁹Si NMR correlation spectrum alone, without the space group and unit cell parameters normally obtained from diffraction data. The resulting NMR-solved structure is in excellent agreement with the structures determined previously by diffraction methods. It is anticipated that NMR crystallography strategies like this will be useful for structure determination of other materials, which cannot be solved from diffraction methods alone.     

激光二极管侧面抽运Nd∶YAG锁模激光器的研究

利用谐振腔的稳定条件对激光二极管侧面抽运的 Nd∶YAG锁模直腔的稳区特性和谐振腔内的光斑分布进行了分析。根据对腔参量的分析,选取合适的腔参量设计了一个简单的侧面抽运直腔,该谐振腔腔形简单,没有像散,振荡光模式好,有利于激光器的锁模运转。实验中采用国内自行研制的半导体可饱和吸收镜,实现了激光二极管侧面抽运半导体可饱和吸收镜锁模Nd∶YAG激光器的连续锁模运转,平均输出功率为 2 W,锁模脉冲宽度为10 ps,重复频率为100 MHz。结合实验结果进一步讨论了半导体可饱和吸收镜的一些参量如饱和恢复时间、调制深度等对实现稳定连续锁模的影响。     

An insight into the passivation of cupronickel alloys in chloride environment

Cupronickels offer enhanced corrosion protection in marine environments by the formation of passive films on the surface. Cyclic voltammetric studies were carried on cupronickels in chloride solutions at pH 6.3 to understand the role of chloride ions in passive film formation. Increase in nickel content of the alloy and of chloride ions in solution decreases film resistance. Chloride ions take part in reduction of the passive film to copper. A solid-state model for passive film formation involving chloride ions has been attempted.