Elucidating the Impact of LiInCl-Coated LiNiCoAlO on the Electro-Chemo-Mechanics of LiPSCl-Based Solid-State Batteries.

LiPSCl has attracted significant attention due to its high Li-ion conductivity and processability, facilitating large-scale solid-state battery applications. However, when paired with high-voltage cathodes, it experiences adverse side reactions. LiInCl (LIC), known for its higher stability at high voltages and moderate Li-ion conductivity, is considered a catholyte to address the limitations of LiPSCl.

Deflecting Dendrites by Introducing Compressive Stress in LiLaZrO Using Ion Implantation.

Lithium dendrites belong to the key challenges of solid-state battery research. They are unavoidable due to the imperfect nature of surfaces containing defects of a critical size that can be filled by lithium until fracturing the solid electrolyte. The penetration of Li metal occurs along the propagating crack until a short circuit takes place.

Li/H exchange of LiLaZrO single and polycrystals investigated by quantitative LIBS depth profiling.

LiLaZrO (LLZO) garnets are highly attractive to be used as solid electrolyte in solid-state Li batteries. However, LLZO suffers from chemical interaction with air and humidity, causing Li/H exchange with detrimental implication on its performance, processing and scalability. To better understand the kinetics of the detrimental Li/H exchange and its dependence on microstructural features, accelerated Li/H exchange experiments were performed on single crystalline and polycrystalline LLZO, exposed for 80 minutes to 80 °C hot water.

Water as a monomer: synthesis of an aliphatic polyethersulfone from divinyl sulfone and water.

Using water as a monomer in polymerization reactions presents a unique and exquisite strategy towards more sustainable chemistry. Herein, the feasibility thereof is demonstrated by the introduction of the oxa-Michael polyaddition of water and divinyl sulfone. Upon nucleophilic or base catalysis, the corresponding aliphatic polyethersulfone is obtained in an interfacial polymerization at room temperature in high yield (>97%) within an hour.

Blacklight sintering of ceramics.

For millennia, ceramics have been densified sintering in a furnace, a time-consuming and energy-intensive process. The need to minimize environmental impact calls for new physical concepts beyond large kilns relying on thermal radiation and insulation. Here, we realize ultrarapid heating with intense blue and UV-light.

Deep hydration of an LiLaZrMO solid-state electrolyte material: a case study on Al- and Ga-stabilized LLZO.

Single crystals of an Li-stuffed, Al- and Ga-stabilized garnet-type solid-state electrolyte material, LiLaZrO (LLZO), have been analysed using single-crystal X-ray diffraction to determine the pristine structural state immediately after synthesis via ceramic sintering techniques. Hydrothermal treatment at 150 °C for 28 d induces a phase transition in the Al-stabilized compound from the commonly observed cubic Ia-3d structure to the acentric I-43d subtype. Li ions at the interstitial octahedrally (4 + 2-fold) coordinated 48e site are most easily extracted and Al ions order onto the tetrahedral 12a site.

Investigating the electrochemical stability of LiLaZrO solid electrolytes using field stress experiments.

Cubic LiLaZrO (LLZO) garnets are among the most promising solid electrolytes for solid-state batteries with the potential to exceed conventional battery concepts in terms of energy density and safety. The electrochemical stability of LLZO is crucial for its application, however, controversial reports in the literature show that it is still an unsettled matter. Here, we investigate the electrochemical stability of LLZO single crystals by applying electric field stress macro- and microscopic ionically blocking Au electrodes in ambient air.

Wet-Environment-Induced Structural Alterations in Single- and Polycrystalline LLZTO Solid Electrolytes Studied by Diffraction Techniques.

LiLaZrO (LLZO) is one of the potential candidates for Li metal-based solid-state batteries owing to its high Li conductivity (≈10 S cm) at room temperature and large electrochemical stability window. However, LLZO undergoes protonation under the influence of moisture-forming LiCO layers, thereby affecting its structural and transport properties. Therefore, a detailed understanding on the impact of the exchange of H on Li sites on structural alteration and kinetics under the influence of wet environments is of great importance.

Highly Conductive Garnet-Type Electrolytes: Access to LiLaZrTaO Prepared by Molten Salt and Solid-State Methods.

Tantalum-doped garnet (LiLaZrTaO, LLZTO) is a promising candidate to act as a solid electrolyte in all-solid-state batteries owing to both its high Li conductivity and its relatively high robustness against the Li metal. Synthesizing LLZTO using conventional solid-state reaction (SSR) requires, however, high calcination temperature (>1000 °C) and long milling steps, thereby increasing the processing time. Here, we report on a facile synthesis route to prepare LLZTO using a molten salt method (MSS) at lower reaction temperatures and shorter durations (900 °C, 5 h).

Anomalies in Bulk Ion Transport in the Solid Solutions of LiLaMO (M = Hf, Sn) and LiLaTaO.

Cubic LiLaZrO(LLZO), stabilized by supervalent cations, is one of the most promising oxide electrolyte to realize inherently safe all-solid-state batteries. It is of great interest to evaluate the strategy of supervalent stabilization in similar compounds and to describe its effect on ionic bulk conductivity σ'. Here, we synthesized solid solutions of Li LaM Ta O with M = Hf, Sn over the full compositional range ( = 0, 0.

Lithium-Ion Transport in Nanocrystalline Spinel-Type Li[InLi]Br as Seen by Conductivity Spectroscopy and NMR.

Currently, a variety of solid Li conductors are being discussed that could potentially serve as electrolytes in all-solid-state Li-ion batteries and batteries using metallic Li as the anode. Besides oxides, sulfides and thioposphates, and also halogenides, such as LiYBr, belong to the group of such promising materials. Here, we report on the mechanosynthesis of ternary, nanocrystalline (defect-rich) Li[In Li ]Br, which crystallizes with a spinel structure.

Lithium ion dynamics in LiZr(PO) and LiCaZr(PO).

High ionic conductivity, electrochemical stability and small interfacial resistances against Li metal anodes are the main requirements to be fulfilled in powerful, next-generation all-solid-state batteries. Understanding ion transport in materials with sufficiently high chemical and electrochemical stability, such as rhombohedral LiZr2(PO4)3, is important to further improve their properties with respect to translational Li ion dynamics. Here, we used broadband impedance spectroscopy to analyze the electrical responses of LiZr2(PO4)3 and Ca-stabilized Li1.

Apparatus for operando x-ray diffraction of fuel electrodes in high temperature solid oxide electrochemical cells.

Characterizing electrochemical energy conversion devices during operation is an important strategy for correlating device performance with the properties of cell materials under real operating conditions. While operando characterization has been used extensively for low temperature electrochemical cells, these techniques remain challenging for solid oxide electrochemical cells due to the high temperatures and reactive gas atmospheres these cells require. Operando X-ray diffraction measurements of solid oxide electrochemical cells could detect changes in the crystal structure of the cell materials, which can be useful for understanding degradation process that limit device lifetimes, but the experimental capability to perform operando X-ray diffraction on the fuel electrodes of these cells has not been demonstrated.

Arrhenius Behavior of the Bulk Na-Ion Conductivity in NaSc(PO) Single Crystals Observed by Microcontact Impedance Spectroscopy.

NASICON-based solid electrolytes with exceptionally high Na-ion conductivities are considered to enable future all solid-state Na-ion battery technologies. Despite 40 years of research the interrelation between crystal structure and Na-ion conduction is still controversially discussed and far from being fully understood. In this study, microcontact impedance spectroscopy combined with single crystal X-ray diffraction, and differential scanning calorimetry is applied to tackle the question how bulk Na-ion conductivity σ of sub-mm-sized flux grown NaSc(PO) (NSP) single crystals is influenced by supposed phase changes (α, β, and γ phase) discussed in literature.

Interface Instability of Fe-Stabilized LiLaZrO versus Li Metal.

The interface stability versus Li represents a major challenge in the development of next-generation all-solid-state batteries (ASSB), which take advantage of the inherently safe ceramic electrolytes. Cubic LiLaZrO garnets represent the most promising electrolytes for this technology. The high interfacial impedance versus Li is, however, still a bottleneck toward future devices.

Synthesis, Crystal Structure, and Stability of Cubic LiLaZrBiO.

Li oxide garnets are among the most promising candidates for solid-state electrolytes in novel Li ion and Li metal based battery concepts. Cubic LiLaZrO stabilized by a partial substitution of Zr by Bi has not been the focus of research yet, despite the fact that Bi would be a cost-effective alternative to other stabilizing cations such as Nb and Ta. In this study, LiLaZrBiO (x = 0.

Fast Li-Ion-Conducting Garnet-Related Li Fe LaZrO with Uncommon 4̅3 Structure.

Fast Li-ion-conducting Li oxide garnets receive a great deal of attention as they are suitable candidates for solid-state Li electrolytes. It was recently shown that Ga-stabilized LiLaZrO crystallizes in the acentric cubic space group 4̅3. This structure can be derived by a symmetry reduction of the garnet-type 3̅ structure, which is the most commonly found space group of Li oxide garnets and garnets in general.

Purification of heavy metal loaded wastewater from electroplating industry under synthesis of delafossite (ABO2) by "Lt-delafossite process".

In this study we present a new, environmental friendly and economic method, called Lt-delafossite process to treat industrial wastewater (initial Cu(2+)-concentrations of 1-15.6 g/l) by subsequent synthesis of nano-crystalline (doped) delafossite (CuFeO2) solely by precipitation and ageing at temperatures between 50 °C and 90 °C. The reached water purification rates are exclusively ≥99.

Structural and Electrochemical Consequences of Al and Ga Cosubstitution in LiLaZrO Solid Electrolytes.

Several "Beyond Li-Ion Battery" concepts such as all solid-state batteries and hybrid liquid/solid systems envision the use of a solid electrolyte to protect Li-metal anodes. These configurations are very attractive due to the possibility of exceptionally high energy densities and high (dis)charge rates, but they are far from being realized practically due to a number of issues including high interfacial resistance and difficulties associated with fabrication. One of the most promising solid electrolyte systems for these applications is Al or Ga stabilized LiLaZrO (LLZO) based on high ionic conductivities and apparent stability against reduction by Li metal.

Crystal Structure of Garnet-Related Li-Ion Conductor Li Ga LaZrO: Fast Li-Ion Conduction Caused by a Different Cubic Modification?

Li-oxide garnets such as LiLaZrO (LLZO) are among the most promising candidates for solid-state electrolytes to be used in next-generation Li-ion batteries. The garnet-structured cubic modification of LLZO, showing space group -3, has to be stabilized with supervalent cations. LLZO stabilized with Ga shows superior properties compared to LLZO stabilized with similar cations; however, the reason for this behavior is still unknown.

Synthesis, Crystal Chemistry, and Electrochemical Properties of Li(7-2x)La3Zr(2-x)Mo(x)O12 (x = 0.1-0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr(4+) by Mo(6+).

Cubic Li7La3Zr2O12 (LLZO) garnets are exceptionally well suited to be used as solid electrolytes or protecting layers in "Beyond Li-ion Battery" concepts. Unfortunately, cubic LLZO is not stable at room temperature (RT) and has to be stabilized by supervalent dopants. In this study we demonstrate a new possibility to stabilize the cubic phase at RT via substitution of Zr(4+) by Mo(6+).

DFT Study of the Role of Al in the Fast Ion-Conductor Li Al LaZrO Garnet.

We investigate theoretically the site occupancy of Al in the fast-ion-conducting cubic-garnet Li Al LaZrO (-3 using density functional theory. By comparing calculated and measured Al NMR chemical shifts an analysis shows that Al prefers the tetrahedrally coordinated 24 site and a distorted 4-fold coordinated 96 site. The site energies for Al ions, which are slightly displaced from the exact crystallographic sites (i.

A synthesis and crystal chemical study of the fast ion conductor Li(7-3x)Ga(x)La3 Zr2O12 with x = 0.08 to 0.84.

Fast-conducting phase-pure cubic Ga-bearing Li7La3Zr2O12 was obtained using solid-state synthesis methods with 0.08 to 0.52 Ga(3+) pfu in the garnet.

Synthesis and crystal chemistry of the fast Li-ion conductor Li7La3Zr2O12 doped with Fe.

Nominal Li7La3Zr2O12 (LLZO) garnet, doped with (57)Fe2O3, was synthesized by sintering oxides and carbonates at T = 1100 °C in air. X-ray powder diffraction measurements show that Li(7-3x)Fe(3+)(x)La3Zr2O12 with x = 0.19 crystallizes in the cubic space group Ia-3d, with a0 = 12.