journal article·2021-03-24

Insight into Ion Diffusion Dynamics/Mechanisms and Electronic Structure of Highly Conductive Sodium-Rich Na3+xLaxZr2–xSi2PO12 (0 ≤ x ≤ 0.5) Solid-State Electrolytes

Fei Sun, Yuxuan Xiang, Qian Sun, Guiming Zhong, Mohammad Norouzi Banis, Weihan Li, Yulong Liu, Jing Luo, Ruying Li, Riqiang Fu, Tsun-Kong Sham, Yong Yang, Xuhui Sun, Xueliang Sun

ACS Applied Materials & Interfaces· Volume 13· Issue 11
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Abstract

Solid-state electrolytes (SSEs) have attracted considerable attention as an alternative for liquid electrolytes to improve safety and durability. Sodium Super Ionic CONductor (NASICON)-type SSEs, typically Na3Zr2Si2PO12, have shown great promise because of their high ionic conductivity and low thermal expansivity. Doping La into the NASICON structure can further elevate the ionic conductivity by an order of magnitude to several mS/cm. However, the underlying mechanism of ionic transportation enhancement has not yet been fully disclosed. Herein, we fabricate a series of Na3+xLaxZr2–xSi2PO12 (0 ≤ x ≤ 0.5) SSEs. The electronic and local structures of constituent elements are studied via synchrotron-based X-ray absorption spectroscopy, and the ionic dynamics and Na-ion conduction mechanism are investigated by solid-state nuclear magnetic resonance spectroscopy. The results prove that La3+ ions exist in the form of phosphate impurities such as Na3La(PO4)2 instead of occupying the Zr4+ site. As a result, the increased Si/P ratio in the NASICON phase, accompanied by an increase in the sodium ion occupancy, makes a major contribution to the enhancement of ionic conductivity. The spin–lattice relaxation time study confirms the accelerated Na+ motions in the altered NASICON phase. Modifications on the Si/P composition can be a promising strategy to enhance the ionic conductivity of NASICON.
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Research context

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Thermal Expansion and Ionic Conductivity

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

Affiliations

Soochow University−Western University Center for Synchrotron Radiation Research, Institute of Functional Nano and Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, China

Department of Mechanical and Materials Engineering, University of Western Ontario, London, Ontario N6A 5B9, Canada

State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

Xiamen Institute of Rare Earth Materials, Chinese Academy of Sciences, Xiamen 361021, China

National High Magnetic Field Laboratory, 1800 E. Paul Dirac Drive, Tallahassee, Florida 32310, United States

Department of Chemistry, University of Western Ontario, London, Ontario N6A 5B7, Canada

Funding

National High Magnetic Field Laboratory · Collaborative Innovation Center of Suzhou Nano Science and Technology · Ministry of Science and Technology of the People's Republic of China · Canada Foundation for Innovation · Western University · Canada Research Chairs · Natural Sciences and Engineering Research Council of Canada · National Natural Science Foundation of China · Priority Academic Program Development of Jiangsu Higher Education Institutions · Division of Materials Research

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