Insights into Reversible Sodium Intercalation in a Novel Sodium-Deficient NASICON-Type Structure:Na3.40 □0.60 Co0.5 Fe0.5 V(PO4 )3

Jingrong Hou; Mohammed Hadouchi; Lijun Sui; Jie Liu; Mingxue Tang; Zhiwei Hu; Hong-Ji Lin; Chang-Yang Kuo; Chien-Te Chen; Chih-Wen Pao; Yunhui Huang; Jiwei Ma

doi:10.1002/smll.202302726

Insights into Reversible Sodium Intercalation in a Novel Sodium-Deficient NASICON-Type Structure:Na_3.40 □_0.60 Co_0.5 Fe_0.5 V(PO₄ )₃

Small. 2023 Nov;19(46):e2302726. doi: 10.1002/smll.202302726. Epub 2023 Jul 21.

Authors

Jingrong Hou¹, Mohammed Hadouchi^{1

2}, Lijun Sui¹, Jie Liu³, Mingxue Tang³, Zhiwei Hu⁴, Hong-Ji Lin⁵, Chang-Yang Kuo^{5

6}, Chien-Te Chen⁵, Chih-Wen Pao⁵, Yunhui Huang⁷, Jiwei Ma¹

Affiliations

¹ Shanghai Key Laboratory for R&D and Application of Metallic Functional Materials, Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai, 201804, China.
² Laboratoire de Chimie Appliquée des Matériaux, Centre des Sciences des Matériaux, Faculty of Science, Mohammed V University in Rabat, Avenue Ibn Battouta, Rabat, BP 1014, Morocco.
³ Center for High Pressure Science & Technology Advanced Research, Beijing, 100094, China.
⁴ Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Strasse 40, 01187, Dresden, Germany.
⁵ National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu, 30076, Taiwan.
⁶ Department of Electrophysics, National Yang Ming Chiao Tung University, Hsinchu, 30076, Taiwan.
⁷ Key Laboratory of Material Processing and Die & Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, China.

PMID: 37480195
DOI: 10.1002/smll.202302726

Abstract

The rational design of novel high-performance cathode materials for sodium-ion batteries is a challenge for the development of the renewable energy sector. Here, a new sodium-deficient NASICON phosphate, namely Na_3.40 □_0.60 Co_0.5 Fe_0.5 V(PO₄ )₃ , demonstrating the excellent electrochemical performance is reported. The presence of Co allows a third Na⁺ to participate in the reaction thus exhibiting a high reversible capacity of ≈155 mAh g^-1 in the voltage range of 2.0-4.0 V versus Na⁺ /Na with a reversible single-phase mechanism and a small volume shrinkage of ≈5.97% at 4.0 V. ²³ Na solid-state nuclear magnetic resonance (NMR) combined with ex situ X-ray diffraction (XRD) refinements provide evidence for a preferential Na⁺ insertion within the Na2 site. Furthermore, the enhanced sodium kinetics ascribed to Co-substitution is also confirmed in combination with electrochemical impedance spectroscopy (EIS), galvanostatic intermittent titration technique (GITT), and theoretical calculation.

Keywords: NASICON-type structures; operando X-ray diffraction; single-phase reaction mechanism; sodium intercalation; sodium-deficient.

Abstract

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