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Garnet-type lithium lanthanum zirconate (Li 7 La 3 Zr 2 O 12 , LLZO) shows great promise as a solid electrolyte for future solid-state lithium batteries as it possesses a uniquely beneficial combination of high ionic conductivity, electrochemical stability against metallic lithium, and generally low reactivity in ambient conditions. Conventionally synthesized by using solid-state reactions, LLZO powders have also been prepared by using variations of sol-gel or combustion synthesis with sacrificial organic templates or polymers containing metal nitrate precursors. Herein, a novel nonaqueous polymer (NAP) method using metalorganic precursors and poly(vinylpyrrolidone) is demonstrated to easily form LLZO nanopowders. Compared to similar techniques using aqueous solutions with metal nitrates, the NAP method confers greater control over synthesis conditions. Undoped cubic phase LLZO is obtained after calcination at 700-800 °C between 0 and 4 h, and the NAP process is easily extended to Ta-doped LLZO. To elucidate the general formation mechanism of nanosized LLZO in the NAP combustion synthesis, scanning transmission electron microscopy is used to perform energy dispersive X-ray and electron energy loss spectral imaging. The results show that in situ formation of a carbonaceous foam during combustion physically segregates pockets of reagents and is responsible for maintaining the small particle size of the as-synthesized material during combustion and crystallization. The room temperature ionic conductivity of nanosized Ta-doped LLZO synthesized by using the NAP method was studied under various sintering conditions, with ionic conductivities between 0.24 and 0.67 mS cm -1 , activation energies between 0.34 and 0.42 eV, and relative densities in excess of 90% obtained by sintering at 1100 °C for between 6 and 15 h.

Li 7 La 3 Zr 2 O 12 (LLZO) and related compounds are considered as promising candidates for future all-solid-state Li-ion battery applications. Still, the processing of those materials into thin membranes with the right stoichiometry and crystal structure is difficult and laborious. The sensitivity of the Li-ion conductive garnets against moisture and the associated Li + /H + cation exchange makes their processing even more difficult. Formulation of suitable polymer/ceramic hybrid solid state electrolytes could be a prosperous way to reach the future large scale production of solid state Li-ion batteries. In fact, solvent mediated and/or slurry based wet-processing of the LLZO, e.g., tape-casting, could result in irreversible Li-ion loss of the pristine material due to Li + /H + cation exchange. The concomitant structural changes and loss in functionality in terms of Li-ion conductivity are the results of the above process. Therefore, in the present work a systematic study on the chemical stability and structural retention of Al-substituted LLZO in different solvents is reported. It was found that Li + /H + exchange in LLZO occurs upon solvent immersion, and its magnitude is dependent on the availability of -OH functional groups of the solvent molecules. As a result, a larger degree of Li + /H + exchange causes higher increase of the lattice parameter of the LLZO, determined by synchrotron diffraction analyses. The expansion of the cubic unit cell was ascertained, when Li + was replaced by H + in the host lattice, by ab initio computational studies. The application of the most common solvent as dispersion medium, i.e., high purity water, causes the most significant Li + /H + exchange and, therefore, structural change, while acetonitrile was proven to be the best suitable solvent for wet postprocessing of LLZO. Finally, computational calculations suggested that the Li + /H + exchange could result in diminished ionic, i.e., mixed Li + -H + , conductivity due to the insertion of protons with lower mobility than that of Li-ions.

Complex hydrides have played important roles in energy storage area. Here a complex hydride made of Li 2 NH and LiBH 4 was synthesized, which has a structure tentatively indexed using an orthorhombic cell with a space group of Pna2 1 and lattice parameters of a=10.121, b=6.997, and c=11.457 Å. The Li 2 NH-LiBH 4 sample (in a molar ratio of 1:1) shows excellent hydrogenation kinetics, starting to absorb H 2 at 310 K, which is more than 100 K lower than that of pristine Li 2 NH. Furthermore, the Li + ion conductivity of the Li 2 NH-LiBH 4 sample is about 1.0×10 -5  S cm -1 at room temperature, and is higher than that of either Li 2 NH or LiBH 4 at 373 K. Those unique properties of the Li 2 NH-LiBH 4 complex render it a promising candidate for hydrogen storage and Li ion conduction., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Advanced techniques for overcoming problems encountered during in situ electron holography experiments in which a voltage is applied to an ionic conductor are reported. The three major problems encountered were 1) electric-field leakage from the specimen and its effect on phase images, 2) high electron conductivity of damage layers formed by the focused ion beam method, and 3) chemical reaction of the specimen with air. The first problem was overcome by comparing experimental phase distributions with simulated images in which three-dimensional leakage fields were taken into account, the second by removing the damage layers using a low-energy narrow Ar ion beam, and the third by developing an air-tight biasing specimen holder., (Copyright © 2017. Published by Elsevier B.V.)

Advanced techniques for overcoming problems encountered during in situ electron holography experiments in which a voltage is applied to an ionic conductor are reported. The three major problems encountered were 1) electric-field leakage from the specimen and its effect on phase images, 2) high electron conductivity of damage layers formed by the focused ion beam method, and 3) chemical reaction of the specimen with air. The first problem was overcome by comparing experimental phase distributions with simulated images in which three-dimensional leakage fields were taken into account, the second by removing the damage layers using a low-energy narrow Ar ion beam, and the third by developing an air-tight biasing specimen holder., (Copyright © 2016 Elsevier B.V. All rights reserved.)