Improvement in the Energy Density of Na3V2(PO4)3 by Mg Substitution

Atsushi Inoishi; Yuto Yoshioka; Liwei Zhao; Ayuko Kitajou; Shigeto Okada

doi:10.1002/celc.201700540

Improvement in the Energy Density of Na₃V₂(PO₄)₃ by Mg Substitution

Atsushi Inoishi, Yuto Yoshioka, Liwei Zhao, Ayuko Kitajou, Shigeto Okada

Department of Advanced Device Materials

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

15 Citations (Scopus)

Abstract

Na₃V₂(PO₄)₃, with a NASICON-type structure, is a promising cathode material for use in sodium-ion batteries based on a two-electron reaction and operating at 3.4 V. Herein, we report the synthesis of Na_3+xV_2-xMg_x(PO₄)₃ (x=0.1 to 0.7) for use as a cathode material in sodium-ion batteries. In this work, Na_3.2V_1.8Mg_0.2(PO₄)₃ was found to exhibit a larger reversible capacity than the theoretical capacity of undoped Na₃V₂(PO₄)₃, as a result of the larger number of Na⁺ in the initial composition, as well as access to the V⁴⁺/V⁵⁺ redox couple. In contrast, although Mg-rich samples such as Na_3.5V_1.5Mg_0.5(PO₄)₃ showed a relatively clear plateau for the V⁴⁺/V⁵⁺ redox couple, the total discharge capacities were lower than that of the undoped Na₃V₂(PO₄)₃ because of the irreversibility in the V⁴⁺/V⁵⁺ redox region. ICP data clearly indicated that Mg²⁺ are stable within the NASICON structure during redox cycling and that Na⁺ is the charge carriers in this cathode.

Original language	English
Pages (from-to)	2755-2759
Number of pages	5
Journal	ChemElectroChem
Volume	4
Issue number	11
DOIs	https://doi.org/10.1002/celc.201700540
Publication status	Published - Nov 1 2017

All Science Journal Classification (ASJC) codes

Catalysis
Electrochemistry

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title = "Improvement in the Energy Density of Na3V2(PO4)3 by Mg Substitution",

abstract = "Na3V2(PO4)3, with a NASICON-type structure, is a promising cathode material for use in sodium-ion batteries based on a two-electron reaction and operating at 3.4 V. Herein, we report the synthesis of Na3+xV2-xMgx(PO4)3 (x=0.1 to 0.7) for use as a cathode material in sodium-ion batteries. In this work, Na3.2V1.8Mg0.2(PO4)3 was found to exhibit a larger reversible capacity than the theoretical capacity of undoped Na3V2(PO4)3, as a result of the larger number of Na+ in the initial composition, as well as access to the V4+/V5+ redox couple. In contrast, although Mg-rich samples such as Na3.5V1.5Mg0.5(PO4)3 showed a relatively clear plateau for the V4+/V5+ redox couple, the total discharge capacities were lower than that of the undoped Na3V2(PO4)3 because of the irreversibility in the V4+/V5+ redox region. ICP data clearly indicated that Mg2+ are stable within the NASICON structure during redox cycling and that Na+ is the charge carriers in this cathode.",

author = "Atsushi Inoishi and Yuto Yoshioka and Liwei Zhao and Ayuko Kitajou and Shigeto Okada",

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T1 - Improvement in the Energy Density of Na3V2(PO4)3 by Mg Substitution

AU - Inoishi, Atsushi

AU - Yoshioka, Yuto

AU - Zhao, Liwei

AU - Kitajou, Ayuko

AU - Okada, Shigeto

PY - 2017/11/1

Y1 - 2017/11/1

N2 - Na3V2(PO4)3, with a NASICON-type structure, is a promising cathode material for use in sodium-ion batteries based on a two-electron reaction and operating at 3.4 V. Herein, we report the synthesis of Na3+xV2-xMgx(PO4)3 (x=0.1 to 0.7) for use as a cathode material in sodium-ion batteries. In this work, Na3.2V1.8Mg0.2(PO4)3 was found to exhibit a larger reversible capacity than the theoretical capacity of undoped Na3V2(PO4)3, as a result of the larger number of Na+ in the initial composition, as well as access to the V4+/V5+ redox couple. In contrast, although Mg-rich samples such as Na3.5V1.5Mg0.5(PO4)3 showed a relatively clear plateau for the V4+/V5+ redox couple, the total discharge capacities were lower than that of the undoped Na3V2(PO4)3 because of the irreversibility in the V4+/V5+ redox region. ICP data clearly indicated that Mg2+ are stable within the NASICON structure during redox cycling and that Na+ is the charge carriers in this cathode.

AB - Na3V2(PO4)3, with a NASICON-type structure, is a promising cathode material for use in sodium-ion batteries based on a two-electron reaction and operating at 3.4 V. Herein, we report the synthesis of Na3+xV2-xMgx(PO4)3 (x=0.1 to 0.7) for use as a cathode material in sodium-ion batteries. In this work, Na3.2V1.8Mg0.2(PO4)3 was found to exhibit a larger reversible capacity than the theoretical capacity of undoped Na3V2(PO4)3, as a result of the larger number of Na+ in the initial composition, as well as access to the V4+/V5+ redox couple. In contrast, although Mg-rich samples such as Na3.5V1.5Mg0.5(PO4)3 showed a relatively clear plateau for the V4+/V5+ redox couple, the total discharge capacities were lower than that of the undoped Na3V2(PO4)3 because of the irreversibility in the V4+/V5+ redox region. ICP data clearly indicated that Mg2+ are stable within the NASICON structure during redox cycling and that Na+ is the charge carriers in this cathode.

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