Unexpected discovery of magnesium-vanadium spinel oxide containing extractable Mg2+ as a high-capacity cathode material for magnesium ion batteries

Chunli Zuo; Wen Tang; Binxu Lan; Fangyu Xiong; Han Tang; Shijie Dong; Wenwei Zhang; Chen Tang; Jiantao Li; Yushan Ruan; Shibo Xi; Qinyou An; Ping Luo

doi:10.1016/j.cej.2020.127005

Unexpected discovery of magnesium-vanadium spinel oxide containing extractable Mg²⁺ as a high-capacity cathode material for magnesium ion batteries

Chunli Zuo, Wen Tang, Binxu Lan, Fangyu Xiong, Han Tang, Shijie Dong, Wenwei Zhang, Chen Tang, Jiantao Li, Yushan Ruan, Shibo Xi, Qinyou An^*, Ping Luo

^*Corresponding author for this work

Chemical and Biological Engineering

Research output: Contribution to journal › Article › peer-review

50 Scopus citations

Abstract

Magnesium ion batteries (MIBs) have attracted significant attention as a promising candidate for the next generation energy storage system owing to their large volumetric capacity and abundant resource. Currently, several researchers have focused on Mg-free materials to be used as cathode in MIBs; But the exploration of Mg-rich electrode materials will promote the development of magnesium batteries towards obtaining more flexible MIBs. Herein, a Mg(Mg_0.5V_1.5)O₄ is investigated as a potential cathode material, in which the Mg²⁺ can be extracted and the fast Mg²⁺ reaction kinetics. Benefited from the exceptional cathode, the Mg battery shows a high reversible specific capacity of 250 mA h g⁻¹ at 100 mA g⁻¹ and capacity retention of 100 mA h g⁻¹ after 500 cycles at high rate of 1 A g⁻¹. The excellent rate capability and desirable cycling performance obtained herein outperformed those of previously reported magnesium spinel oxides. It is also demonstrated that Mg²⁺ extraction/insertion mechanism of Mg(Mg_0.5V_1.5)O₄ is related to the coexistence of two-phase process and single-phase solid solution reaction through a series of systematic in situ/ex situ characterizations. X-ray absorption near edge structure (XANES) demonstrates that the valence state of vanadium changes and the octahedral symmetry of vanadium site varies due to the extraction of Mg²⁺ from spinel Mg(Mg_0.5V_1.5)O₄. Significantly, the cathode containing extractable Mg²⁺ can be coupled with Mg-free anode materials (Na₂Ti₃O₇) to assemble a full cell in Mg(TFSI)₂/acetonitrile electrolyte, displaying a discharge capacity of 102 mA h g⁻¹ after 100 cycles at 50 mA g⁻¹. The encouraging results show that the Mg(Mg_0.5V_1.5)O₄ is a promising electrode material, which paves ways for the development and further improvements of MIBs.

Original language	English (US)
Article number	127005
Journal	Chemical Engineering Journal
Volume	405
DOIs	https://doi.org/10.1016/j.cej.2020.127005
State	Published - Feb 1 2021

Funding

This work was supported by the National Natural Science Foundation of China ( 51771071 , 51972259 ), the International Science & Technology Cooperation Program of China (Grant No. 2016YFE0124300 ), and the open fund of Collaborative Innovation Center of Green Light-weight Materials and Processing and Hubei Provincial Key Laboratory of Green Materials for Light Industry (Grant No. 201710A05 and 201611A07 ), and the guidance project of scientific research program from Hubei provincial department of education (Grant No. B 2019046). The special funds for guiding local scientific and technological development by the central government of China (No. 2019ZYYD015). C.Z carried out the experiments including sample preparation and electrochemical performance measurement. W. T. measured the BET. B. L contributed to schematic. F. X. and H. T and analyzed the XRD. W. Z. and C. T. contributed to TEM characterization. Y. R. measured the SEM. S. X. and J. L. measured and analyzed the vanadium K-edge XANES. S. D. and Q. A. and P. L analyzed the experimental data systematically. C.Z wrote the manuscript with input from all authors. This work was supported by the National Natural Science Foundation of China (51771071, 51972259), the International Science & Technology Cooperation Program of China (Grant No. 2016YFE0124300), and the open fund of Collaborative Innovation Center of Green Light-weight Materials and Processing and Hubei Provincial Key Laboratory of Green Materials for Light Industry (Grant No. 201710A05 and 201611A07), and the guidance project of scientific research program from Hubei provincial department of education (Grant No. B 2019046). The special funds for guiding local scientific and technological development by the central government of China (No. 2019ZYYD015). C.Z carried out the experiments including sample preparation and electrochemical performance measurement. W. T. measured the BET. B. L contributed to schematic. F. X. and H. T and analyzed the XRD. W. Z. and C. T. contributed to TEM characterization. Y. R. measured the SEM. S. X. and J. L. measured and analyzed the vanadium K-edge XANES. S. D. and Q. A. and P. L analyzed the experimental data systematically. C.Z wrote the manuscript with input from all authors.

Keywords

Magnesium ion battery
Mg-rich material
Mg extraction/ insertion
Spinel oxide cathode

ASJC Scopus subject areas

General Chemistry
Environmental Chemistry
General Chemical Engineering
Industrial and Manufacturing Engineering

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.cej.2020.127005

Cite this

Zuo, C., Tang, W., Lan, B., Xiong, F., Tang, H., Dong, S., Zhang, W., Tang, C., Li, J., Ruan, Y., Xi, S., An, Q., & Luo, P. (2021). Unexpected discovery of magnesium-vanadium spinel oxide containing extractable Mg²⁺ as a high-capacity cathode material for magnesium ion batteries. Chemical Engineering Journal, 405, Article 127005. https://doi.org/10.1016/j.cej.2020.127005

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title = "Unexpected discovery of magnesium-vanadium spinel oxide containing extractable Mg2+ as a high-capacity cathode material for magnesium ion batteries",

abstract = "Magnesium ion batteries (MIBs) have attracted significant attention as a promising candidate for the next generation energy storage system owing to their large volumetric capacity and abundant resource. Currently, several researchers have focused on Mg-free materials to be used as cathode in MIBs; But the exploration of Mg-rich electrode materials will promote the development of magnesium batteries towards obtaining more flexible MIBs. Herein, a Mg(Mg0.5V1.5)O4 is investigated as a potential cathode material, in which the Mg2+ can be extracted and the fast Mg2+ reaction kinetics. Benefited from the exceptional cathode, the Mg battery shows a high reversible specific capacity of 250 mA h g−1 at 100 mA g−1 and capacity retention of 100 mA h g−1 after 500 cycles at high rate of 1 A g−1. The excellent rate capability and desirable cycling performance obtained herein outperformed those of previously reported magnesium spinel oxides. It is also demonstrated that Mg2+ extraction/insertion mechanism of Mg(Mg0.5V1.5)O4 is related to the coexistence of two-phase process and single-phase solid solution reaction through a series of systematic in situ/ex situ characterizations. X-ray absorption near edge structure (XANES) demonstrates that the valence state of vanadium changes and the octahedral symmetry of vanadium site varies due to the extraction of Mg2+ from spinel Mg(Mg0.5V1.5)O4. Significantly, the cathode containing extractable Mg2+ can be coupled with Mg-free anode materials (Na2Ti3O7) to assemble a full cell in Mg(TFSI)2/acetonitrile electrolyte, displaying a discharge capacity of 102 mA h g−1 after 100 cycles at 50 mA g−1. The encouraging results show that the Mg(Mg0.5V1.5)O4 is a promising electrode material, which paves ways for the development and further improvements of MIBs.",

keywords = "Magnesium ion battery, Mg-rich material, Mg extraction/ insertion, Spinel oxide cathode",

author = "Chunli Zuo and Wen Tang and Binxu Lan and Fangyu Xiong and Han Tang and Shijie Dong and Wenwei Zhang and Chen Tang and Jiantao Li and Yushan Ruan and Shibo Xi and Qinyou An and Ping Luo",

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AU - Zuo, Chunli

AU - Tang, Wen

AU - Lan, Binxu

AU - Xiong, Fangyu

AU - Tang, Han

AU - Dong, Shijie

AU - Zhang, Wenwei

AU - Tang, Chen

AU - Li, Jiantao

AU - Ruan, Yushan

AU - Xi, Shibo

AU - An, Qinyou

AU - Luo, Ping

PY - 2021/2/1

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N2 - Magnesium ion batteries (MIBs) have attracted significant attention as a promising candidate for the next generation energy storage system owing to their large volumetric capacity and abundant resource. Currently, several researchers have focused on Mg-free materials to be used as cathode in MIBs; But the exploration of Mg-rich electrode materials will promote the development of magnesium batteries towards obtaining more flexible MIBs. Herein, a Mg(Mg0.5V1.5)O4 is investigated as a potential cathode material, in which the Mg2+ can be extracted and the fast Mg2+ reaction kinetics. Benefited from the exceptional cathode, the Mg battery shows a high reversible specific capacity of 250 mA h g−1 at 100 mA g−1 and capacity retention of 100 mA h g−1 after 500 cycles at high rate of 1 A g−1. The excellent rate capability and desirable cycling performance obtained herein outperformed those of previously reported magnesium spinel oxides. It is also demonstrated that Mg2+ extraction/insertion mechanism of Mg(Mg0.5V1.5)O4 is related to the coexistence of two-phase process and single-phase solid solution reaction through a series of systematic in situ/ex situ characterizations. X-ray absorption near edge structure (XANES) demonstrates that the valence state of vanadium changes and the octahedral symmetry of vanadium site varies due to the extraction of Mg2+ from spinel Mg(Mg0.5V1.5)O4. Significantly, the cathode containing extractable Mg2+ can be coupled with Mg-free anode materials (Na2Ti3O7) to assemble a full cell in Mg(TFSI)2/acetonitrile electrolyte, displaying a discharge capacity of 102 mA h g−1 after 100 cycles at 50 mA g−1. The encouraging results show that the Mg(Mg0.5V1.5)O4 is a promising electrode material, which paves ways for the development and further improvements of MIBs.

AB - Magnesium ion batteries (MIBs) have attracted significant attention as a promising candidate for the next generation energy storage system owing to their large volumetric capacity and abundant resource. Currently, several researchers have focused on Mg-free materials to be used as cathode in MIBs; But the exploration of Mg-rich electrode materials will promote the development of magnesium batteries towards obtaining more flexible MIBs. Herein, a Mg(Mg0.5V1.5)O4 is investigated as a potential cathode material, in which the Mg2+ can be extracted and the fast Mg2+ reaction kinetics. Benefited from the exceptional cathode, the Mg battery shows a high reversible specific capacity of 250 mA h g−1 at 100 mA g−1 and capacity retention of 100 mA h g−1 after 500 cycles at high rate of 1 A g−1. The excellent rate capability and desirable cycling performance obtained herein outperformed those of previously reported magnesium spinel oxides. It is also demonstrated that Mg2+ extraction/insertion mechanism of Mg(Mg0.5V1.5)O4 is related to the coexistence of two-phase process and single-phase solid solution reaction through a series of systematic in situ/ex situ characterizations. X-ray absorption near edge structure (XANES) demonstrates that the valence state of vanadium changes and the octahedral symmetry of vanadium site varies due to the extraction of Mg2+ from spinel Mg(Mg0.5V1.5)O4. Significantly, the cathode containing extractable Mg2+ can be coupled with Mg-free anode materials (Na2Ti3O7) to assemble a full cell in Mg(TFSI)2/acetonitrile electrolyte, displaying a discharge capacity of 102 mA h g−1 after 100 cycles at 50 mA g−1. The encouraging results show that the Mg(Mg0.5V1.5)O4 is a promising electrode material, which paves ways for the development and further improvements of MIBs.

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KW - Spinel oxide cathode

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