journal article·2023-06-13

Synergistic Ion Diffusion in Lithium Titanium Phosphate Conductors: A Tale from Solo to Ensemble

Xinyu Zhang, Denys Butenko, Lei Gao, Xinyan Ye, Bolong Hong, Songbai Han, Wei Xia, Shaofei Wang, Yang Sun, Yusheng Zhao, Jinlong Zhu

Chemistry of Materials· Volume 35· Issue 11
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Abstract

The rational design of solid electrolytes for the next-generation batteries entails an accurate understanding of ionic transport mechanisms. To elucidate the detailed ion hopping processes in different coordinate environments, two solid electrolytes, LiTi 2 (PO 4 ) 3 and Li 3 Ti 2 (PO 4 ) 3, with the same NASICON-type framework but different sites for accommodating mobile ions, were synthesized and investigated by in situ neutron diffraction and theoretical calculations. The temperature-dependent anisotropic thermal vibrational ellipsoids and migration paths from the maximum entropy method (MEM) indicated that Li ions move faster at higher coordinate architectures, exhibiting three-dimensional (3D) diffusion pathways. In this rhombohedral structure, “one” node (M1 site) out of “three” interconnected transition sites was found to be the lithium configuration of NASICON. Li ions located at the nodes along the 3D pathway in LiTi 2 (PO 4 ) 3 can only drive out another Li-ion species at the node site, while Li ions located at transition sites between two nodes in Li 3 Ti 2 (PO 4 ) 3 have repulsive force from their five surrounding Li ions. These different configurations lead to distinct overall transport modes. In LiTi 2 (PO 4 ) 3, concerted Li ions transport along a separated chain, while in Li 3 Ti 2 (PO 4 ) 3, concerted motion occurs along multiple cooperating chains in the 3D channels. Theoretical calculations further indicated that a larger diffusion bottleneck size of Li 3 Ti 2 (PO 4 ) 3 enables lower hopping energy compared to LiTi 2 (PO 4 ) 3 . This study clarifies the detailed ionic hopping processes and the underlying structure–conductivity relationships. Overall, these results elucidate the synergistic events in Li-ion hopping from thermodynamic and kinetic points of view, which will greatly benefit the rational design of solid electrolytes for next-generation batteries.
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Research context

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Advanced NMR Techniques and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Shenzhen Key Laboratory of Solid State Batteries, Southern University of Science and Technology, Shenzhen 518055, China

Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, Shenzhen 518055, China

School of Materials Science and Engineering, Peking University, Beijing 100871, China

Eastern Institute for Advanced Study, Ningbo, Zhejiang 315200, China

Australian Centre for Neuron Scattering (ACNS), Australian Nuclear Science and Technology Organization (ANSTO), Locked Bag 2001, Kirrawee DC, New South Wales 2232, Australia

School of Materials, Sun Yat-sen University, Shenzhen 518107, China

Department of Physics, Southern University of Science and Technology, Shenzhen 518055, China

Guangdong Provincial Key Laboratory of Energy Materials for Electric Power, Southern University of Science and Technology, Shenzhen 518055, China

Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices, Southern University of Science and Technology, Shenzhen 518055, China

Funding

Science, Technology and Innovation Commission of Shenzhen Municipality · National Natural Science Foundation of China · Shenzhen Key Laboratory of Solid State Batteries · Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices · Laboratory of Electro chemical Energy Storage Technologies, Academy for Advanced Interdisciplinary Studies · Guangdong Provincial Key Laboratory of Energy Materials for Electric Power · Ministry of Education Key Laboratory of Energy Conversion and Storage Technologies, Southern University of Science and Technology

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