Title

A new class of lithium ion conductors with tunable structures and compositions: Quaternary diamond-like thiogermanates

Citation for published article

Brant, J. A., Devlin, K. P., Bischoff, C., Watson, D., Martin, S. W., Gross, M. D., & Aitken, J. A. (2015). A new class of lithium ion conductors with tunable structures and compositions: Quaternary diamond-like thiogermanates. Solid State Ionics, 278, 268–274. https://doi.org/10.1016/j.ssi.2015.05.019

DOI

10.1016/j.ssi.2015.05.019

Peer Reviewed

1

Audio/Visual Resources

Brant, J. A., Devlin, K. P., Bischoff, C., Watson, D., Martin, S. W., Gross, M. D., & Aitken, J. A. (2015). A new class of lithium ion conductors with tunable structures and compositions: Quaternary diamond-like thiogermanates. Solid State Ionics, 278, 268–274. https://doi.org/10.1016/j.ssi.2015.05.019

Document Type

Journal Article

School

Bayer School of Natural and Environmental Sciences

Primary Author Department

Chemistry and Biochemistry

Abstract

The new Li2CoGeS4 compound crystallizes in the Pn space group with the wurtz-kesterite structure, according to single crystal X-ray diffraction. The structure of Li2CoGeS4 and the high degree of phase-purity in which it is prepared are supported by high-resolution synchrotron X-ray powder diffraction. Varying the divalent ion in Li2-II-GeS4 materials yields three different structure types, all of which are derived from hexagonal diamond. These structural variations give rise to Li+-encompassing [II-GeS4]2- nets with different topologies that offer diversity in lithium ion diffusion pathways. In the first systematic study of the lithium ion conductivity in quaternary diamond-like materials, wurtz-kesterite-type Li2CoGeS4 and Li2FeGeS4 (Pn), lithium cobalt(II) silicate-type Li2MnGeS4 (Pna21), and wurtz-stannite-type Li2CdGeS4 (Pmn21) are presented as environmentally stable lithium ion conductors. These materials are comprised of cubic diamond-like [CoGeS4]2- and [FeGeS4]2- anionic frameworks, ABW-like [MnGeS4]2-, and square lattice-like [CdGeS4]2-. As assessed using impedance spectroscopy, Li2FeGeS4 exhibits the most promising Li+ ion conductivity of 1.8(3) × 10-4 S/cm at 100°C, while Li2CdGeS4 shows the lowest activation energy for lithium ion conduction, EA = 0.74(2) eV.

Rights

© 2015 Elsevier B.V. All rights reserved.

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