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Structural and Electrochemical Consequences of Al and Ga Cosubstitution in Li7La3Zr2O12 Solid Electrolytes

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      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 Li 7La 3Zr 2O 12 (LLZO) based on high ionic conductivities and apparent stability against reduction by Li metal. Nevertheless, the fabrication of dense LLZO membranes with high ionic conductivity and low interfacial resistances remains challenging; it definitely requires a better understanding of the structural and electrochemical properties. In this study, the phase transition from garnet ( Iad, No. 230) to “non-garnet” ( I4̅3 d, No. 220) space group as a function of composition and the different sintering behavior of Ga and Al stabilized LLZO are identified as important factors in determining the electrochemical properties. The phase transition was located at an Al:Ga substitution ratio of 0.05:0.15 and is accompanied by a significant lowering of the activation energy for Li-ion transport to 0.26 eV. The phase transition combined with microstructural changes concomitant with an increase of the Ga/Al ratio continuously improves the Li-ion conductivity from 2.6 × 10 –4 S cm –1 to 1.2 × 10 –3 S cm –1, which is close to the calculated maximum for garnet-type materials. The increase in Ga content is also associated with better densification and smaller grains and is accompanied by a change in the area specific resistance (ASR) from 78 to 24 Ω cm 2, the lowest reported value for LLZO so far. These results illustrate that understanding the structure–properties relationships in this class of materials allows practical obstacles to its utilization to be readily overcome.

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      Most cited references 40

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        A short history of SHELX.

        An account is given of the development of the SHELX system of computer programs from SHELX-76 to the present day. In addition to identifying useful innovations that have come into general use through their implementation in SHELX, a critical analysis is presented of the less-successful features, missed opportunities and desirable improvements for future releases of the software. An attempt is made to understand how a program originally designed for photographic intensity data, punched cards and computers over 10000 times slower than an average modern personal computer has managed to survive for so long. SHELXL is the most widely used program for small-molecule refinement and SHELXS and SHELXD are often employed for structure solution despite the availability of objectively superior programs. SHELXL also finds a niche for the refinement of macromolecules against high-resolution or twinned data; SHELXPRO acts as an interface for macromolecular applications. SHELXC, SHELXD and SHELXE are proving useful for the experimental phasing of macromolecules, especially because they are fast and robust and so are often employed in pipelines for high-throughput phasing. This paper could serve as a general literature citation when one or more of the open-source SHELX programs (and the Bruker AXS version SHELXTL) are employed in the course of a crystal-structure determination.
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          Rationale for mixing exact exchange with density functional approximations


            Author and article information

            [§ ]Department of Chemistry and Physics of Materials, University of Salzburg , 5020, Salzburg, Austria
            [# ]Christian Doppler Laboratory for Lithium Batteries, Institute for Chemistry and Technology of Materials, DFG Research Unit 1277 molife, Graz University of Technology (NAWI Graz) , 8010, Graz, Austria
            []Lawrence Berkeley National Laboratory, Energy Storage and Distributed Resources Division, University of California , Berkeley, California 94720, United States
            []Department of Materials Science and Engineering, University of California , Berkeley, 94720, United States
            []Samsung Advanced Institute of Technology , 255 Main Street, Cambridge, Massachusetts 02140, United States
            []Institute for Chemical Technologies and Analytics, Vienna University of Technology , 1060 Vienna, Austria
            []Diffraction group, Institute Laue-Langevin (ILL) , 71 avenue des Martyrs, 38000 Grenoble, France
            Author notes
            Chem Mater
            Chem Mater
            Chemistry of Materials
            American Chemical Society
            04 March 2016
            12 April 2016
            : 28
            : 7
            : 2384-2392
            27110064 4836877 10.1021/acs.chemmater.6b00579
            Copyright © 2016 American Chemical Society

            This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

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