Enhanced room-temperature Na+ ionic conductivity in Na4.92Y0.92Zr0.08Si4O12
Aikai Yang,
Kai Yao,
Mareen Schaller,
Enkhtsetseg Dashjav,
Hang Li,
Shuo Zhao,
Qiu Zhang,
Martin Etter,
Xingchen Shen,
Huimin Song,
Qiongqiong Lu,
Ruijie Ye,
Igor Moudrakovski,
Quanquan Pang,
Sylvio Indris,
Xingchao Wang,
Qianli Ma,
Frank Tietz,
Jun Chen,
Olivier Guillon
Affiliations
Aikai Yang
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany; Institute of Mineral Engineering (GHI), RWTH Aachen University, Forckenbeckstraße 33, 52074 Aachen, Germany
Kai Yao
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany
Mareen Schaller
Institute for Applied Materials-Energy Storage Systems (IAM-ESS), Karlsruhe Institute of Technology (KIT), 76344 Eggenstein-Leopoldshafen, Germany
Enkhtsetseg Dashjav
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany
Hang Li
Institute for Applied Materials-Energy Storage Systems (IAM-ESS), Karlsruhe Institute of Technology (KIT), 76344 Eggenstein-Leopoldshafen, Germany
Shuo Zhao
Renewable Energy Conversion and Storage Center (RECAST), Haihe Laboratory of Sustainable Chemical Transformations, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China
Qiu Zhang
Renewable Energy Conversion and Storage Center (RECAST), Haihe Laboratory of Sustainable Chemical Transformations, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China
Laboratoire de Cristallographie et Sciences des Matériaux (CRISMAT), CNRS, ENSICAEN, 14000 Caen, France
Huimin Song
Beijing Key Laboratory of Theory and Technology for Advanced Batteries Materials, School of Materials Science and Engineering, Peking University, Beijing 100871, China
Qiongqiong Lu
Institute of Materials, Henan Academy of Sciences, Henan Key Laboratory of Advanced Conductor Materials, Zhengzhou 450046, China
Ruijie Ye
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany
Igor Moudrakovski
Max Planck Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart, Germany
Quanquan Pang
Beijing Key Laboratory of Theory and Technology for Advanced Batteries Materials, School of Materials Science and Engineering, Peking University, Beijing 100871, China
Sylvio Indris
Institute for Applied Materials-Energy Storage Systems (IAM-ESS), Karlsruhe Institute of Technology (KIT), 76344 Eggenstein-Leopoldshafen, Germany; Corresponding authors.
Xingchao Wang
State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, Key Laboratory of Advanced Functional Materials, Autonomous Region, Institute of Applied Chemistry, College of Chemistry, Xinjiang University, Urumqi, Xinjiang 830046, China; Corresponding authors.
Qianli Ma
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany; Corresponding authors.
Frank Tietz
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany; Forschungszentrum Jülich GmbH, Helmholtz Institute Münster (IEK-12), 52425 Jülich, Germany
Jun Chen
Renewable Energy Conversion and Storage Center (RECAST), Haihe Laboratory of Sustainable Chemical Transformations, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China; Corresponding authors.
Olivier Guillon
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany; Institute of Mineral Engineering (GHI), RWTH Aachen University, Forckenbeckstraße 33, 52074 Aachen, Germany; Forschungszentrum Jülich GmbH, Helmholtz Institute Münster (IEK-12), 52425 Jülich, Germany; Jülich Aachen Research Alliance, JARA-Energy, 52425 Jülich, Germany
Developing cost-effective and reliable solid-state sodium batteries with superior performance is crucial for stationary energy storage. A key component in facilitating their application is a solid-state electrolyte with high conductivity and stability. Herein, we employed aliovalent cation substitution to enhance ionic conductivity while preserving the crystal structure. Optimized substitution of Y3+ with Zr4+ in Na5YSi4O12 introduced Na+ ion vacancies, resulting in high bulk and total conductivities of up to 6.5 and 3.3 mS cm−1, respectively, at room temperature with the composition Na4.92Y0.92Zr0.08Si4O12 (NYZS). NYZS shows exceptional electrochemical stability (up to 10 V vs. Na+/Na), favorable interfacial compatibility with Na, and an excellent critical current density of 2.4 mA cm−2. The enhanced conductivity of Na+ ions in NYZS was elucidated using solid-state nuclear magnetic resonance techniques and theoretical simulations, revealing two migration routes facilitated by the synergistic effect of increased Na+ ion vacancies and improved chemical environment due to Zr4+ substitution. NYZS extends the list of suitable solid-state electrolytes and enables the facile synthesis of stable, low-cost Na+ ion silicate electrolytes.
