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Research Article

Nano self-assembly of fluorophosphate cathode induced by surface energy evolution towards high-rate and stable sodium-ion batteries

Zhen-Yi Gu1,§, Yong-Li Heng1,§, Jin-Zhi Guo1, Jun-Ming Cao1, Xiao-Tong Wang1, Xin-Xin Zhao2, Zhong-Hui Sun3, Shuo-Hang Zheng1, Hao-Jie Liang1, Bo Li4( ), Xing-Long Wu1,2 ( )
MOE Key Laboratory for UV Light-Emitting Materials and Technology, Northeast Normal University, Changchun 130024, China
Department of Chemistry, Northeast Normal University, Changchun 130024, China
Center for Advanced Analytical Science, School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China
Key Laboratory of Hazardous Chemicals Safety and Control Technology, School of Chemical and Environmental Engineering, North China Institute of Science and Technology, Langfang 065201, China

§ Zhen-Yi Gu and Yong-Li Heng contributed equally to this work.

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Graphical Abstract

Through the regulation of active vanadium sites with moderate Mn2+ substitution, a self-assembly two-dimensional (2D) nanosheet-like Na3.1V1.9Mn0.1(PO4)2F3 (NVPF-NS) is obtained due to surface energy evolution and preferential orientation growth. Consequently, the prepared NVPF-NS cathode can achieve the improved sodium storage behaviors with superior rate capability, cycling stability, and low-temperature performance for advanced sodium-ion batteries.

Abstract

In the field of materials science and engineering, controlling over shape and crystal orientation remains a tremendous challenge. Herein, we realize a nano self-assembly morphology adjustment of Na3V2(PO4)2F3 (NVPF) material, based on surface energy evolution by partially replacing V3+ with aliovalent Mn2+. Crystal growth direction and surface energy evolution, main factors in inducing the nano self-assembly of NVPF with different shapes and sizes, are revealed by high-resolution transmission electron microscope combined with density functional theory. Furthermore, NVPF with a two-dimensional nanosheet structure (NVPF-NS) exhibits the best rate capability with 68 mAh·g−1 of specific capacity at an ultrahigh rate of 20 C and cycle stability with 80.7% of capacity retention over 1,000 cycles at 1 C. More significantly, when matched with Se@reduced graphene oxide (rGO) anode, NVPF-NS//Se@rGO sodium-ion full cells display a remarkable long-term stability with a high capacity retention of 93.8% after 500 cycles at 0.5 C and −25 °C. Consequently, experimental and theoretical calculation results manifest that NVPF-NS demonstrates such superior performances, which can be mainly due to its inherent crystal structure and preferential orientation growth of {001} facets. This work will promise insights into developing novel architectural design strategies for high-performance cathode materials in advanced sodium-ion batteries.

Keywords

nano self-assemblysodium-ion batteriescathodefluorophosphate

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Nano Research
Volume 16 Issue 1,
January 2023
Pages 439-448
DOI: 10.1007/s12274-022-4687-6
Cite this article:
Gu Z-Y, Heng Y-L, Guo J-Z, et al. Nano self-assembly of fluorophosphate cathode induced by surface energy evolution towards high-rate and stable sodium-ion batteries. Nano Research, 2023, 16(1): 439-448. https://doi.org/10.1007/s12274-022-4687-6
Topics:
Energy storageIon batteriesSecondary batteries

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Received: 09 April 2022
Revised: 11 June 2022
Accepted: 21 June 2022
Published: 31 August 2022
© Tsinghua University Press 2022
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