Phase transformation and ionic conductivity mechanism of a low-temperature sintering semiconductor Na2CaV4O12

Caige Liu; Shuangfeng Wu; Changzhi Yin; Jungu Xu; Ying Xiong; Laijun Liu; Jibran Khaliq; Chunchun Li

doi:10.1016/j.jallcom.2021.161259

Phase transformation and ionic conductivity mechanism of a low-temperature sintering semiconductor Na2CaV4O12

Caige Liu, Shuangfeng Wu, Changzhi Yin, Jungu Xu^*, Ying Xiong, Laijun Liu^*, Jibran Khaliq, Chunchun Li^*

^*Corresponding author for this work

Mechanical and Construction Engineering

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

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Abstract

Alkaline earth metal vanadates have drawn attention because of their potential applications in electrochemical devices. Here, Na2CaV4O12 was prepared at extremely low temperatures (350-550 oC) and showed a semiconductor behavior with a bandgap of 2.92 eV. A phase transition from P4/nbm to P
̅
b2 occurred at 510 oC was identified by an in-situ XRD upon heating, where the 16 n site for oxygen atoms in the P4/nbm phase evolves into two distinguishable 8i sites in the P
̅
b2 phase. Ionic conduction in Na2CaV4O12 at elevated temperatures was reported for the first time in the present work. A strong correlation between ionic conductivity and phase structure of Na2CaV4O12 is observed. The charged carriers are mainly sodium ions for the low-temperature P4/nbm phase, while mixed conduction contributed by sodium ions and oxide ions happened in the transformed phase. Bond valence-based energy landscape calculations disclosed a two-dimensional interstitial diffusion mechanism for Na+ ions in the Na2Ca-layers, as well as a two-dimensional diffusion mechanism for oxide ions in the V4O12-layers. The novel semiconductor ceramic would have potential applications in all-solid sodium ions batteries or solid oxide fuel cells as electrolytes.

Original language	English
Article number	161259
Number of pages	6
Journal	Journal of Alloys and Compounds
Volume	886
Early online date	21 Jul 2021
DOIs	https://doi.org/10.1016/j.jallcom.2021.161259
Publication status	Published - 15 Dec 2021

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10.1016/j.jallcom.2021.161259

1-s2.0-S0925838821026682-mainAccepted author manuscript, 1.02 MBLicence: CC BY-NC-ND

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@article{e55a0d45c11b448181da26a434a57c80,

title = "Phase transformation and ionic conductivity mechanism of a low-temperature sintering semiconductor Na2CaV4O12",

abstract = "Alkaline earth metal vanadates have drawn attention because of their potential applications in electrochemical devices. Here, Na2CaV4O12 was prepared at extremely low temperatures (350-550 oC) and showed a semiconductor behavior with a bandgap of 2.92 eV. A phase transition from P4/nbm to P̅b2 occurred at 510 oC was identified by an in-situ XRD upon heating, where the 16 n site for oxygen atoms in the P4/nbm phase evolves into two distinguishable 8i sites in the P̅b2 phase. Ionic conduction in Na2CaV4O12 at elevated temperatures was reported for the first time in the present work. A strong correlation between ionic conductivity and phase structure of Na2CaV4O12 is observed. The charged carriers are mainly sodium ions for the low-temperature P4/nbm phase, while mixed conduction contributed by sodium ions and oxide ions happened in the transformed phase. Bond valence-based energy landscape calculations disclosed a two-dimensional interstitial diffusion mechanism for Na+ ions in the Na2Ca-layers, as well as a two-dimensional diffusion mechanism for oxide ions in the V4O12-layers. The novel semiconductor ceramic would have potential applications in all-solid sodium ions batteries or solid oxide fuel cells as electrolytes.",

keywords = "Mixed-cation vanadate, Electrical conductivity, Dielectric properties, Ceramics",

author = "Caige Liu and Shuangfeng Wu and Changzhi Yin and Jungu Xu and Ying Xiong and Laijun Liu and Jibran Khaliq and Chunchun Li",

note = "Funding information: The authors gratefully acknowledge the financial support from the Natural Science Foundation of China (No. 62061011), Natural Science Foundation of Guangxi Zhuang Autonomous Region (No. 2018GXNSFAA281253, 2019GXNSFGA245006, 2019GXNSFBA245069, 2020GXNSFBA297029), the high-level innovation team and outstanding scholar program of Guangxi institutes, and Open Fund from Guangxi Key Laboratory of Optical and Electronic Materials and Devices (No. 20AA-4, 20AA-7).",

year = "2021",

month = dec,

day = "15",

doi = "10.1016/j.jallcom.2021.161259",

language = "English",

volume = "886",

journal = "Journal of Alloys and Compounds",

issn = "0925-8388",

publisher = "Elsevier",

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TY - JOUR

T1 - Phase transformation and ionic conductivity mechanism of a low-temperature sintering semiconductor Na2CaV4O12

AU - Liu, Caige

AU - Wu, Shuangfeng

AU - Yin, Changzhi

AU - Xu, Jungu

AU - Xiong, Ying

AU - Liu, Laijun

AU - Khaliq, Jibran

AU - Li, Chunchun

N1 - Funding information: The authors gratefully acknowledge the financial support from the Natural Science Foundation of China (No. 62061011), Natural Science Foundation of Guangxi Zhuang Autonomous Region (No. 2018GXNSFAA281253, 2019GXNSFGA245006, 2019GXNSFBA245069, 2020GXNSFBA297029), the high-level innovation team and outstanding scholar program of Guangxi institutes, and Open Fund from Guangxi Key Laboratory of Optical and Electronic Materials and Devices (No. 20AA-4, 20AA-7).

PY - 2021/12/15

Y1 - 2021/12/15

N2 - Alkaline earth metal vanadates have drawn attention because of their potential applications in electrochemical devices. Here, Na2CaV4O12 was prepared at extremely low temperatures (350-550 oC) and showed a semiconductor behavior with a bandgap of 2.92 eV. A phase transition from P4/nbm to P̅b2 occurred at 510 oC was identified by an in-situ XRD upon heating, where the 16 n site for oxygen atoms in the P4/nbm phase evolves into two distinguishable 8i sites in the P̅b2 phase. Ionic conduction in Na2CaV4O12 at elevated temperatures was reported for the first time in the present work. A strong correlation between ionic conductivity and phase structure of Na2CaV4O12 is observed. The charged carriers are mainly sodium ions for the low-temperature P4/nbm phase, while mixed conduction contributed by sodium ions and oxide ions happened in the transformed phase. Bond valence-based energy landscape calculations disclosed a two-dimensional interstitial diffusion mechanism for Na+ ions in the Na2Ca-layers, as well as a two-dimensional diffusion mechanism for oxide ions in the V4O12-layers. The novel semiconductor ceramic would have potential applications in all-solid sodium ions batteries or solid oxide fuel cells as electrolytes.

AB - Alkaline earth metal vanadates have drawn attention because of their potential applications in electrochemical devices. Here, Na2CaV4O12 was prepared at extremely low temperatures (350-550 oC) and showed a semiconductor behavior with a bandgap of 2.92 eV. A phase transition from P4/nbm to P̅b2 occurred at 510 oC was identified by an in-situ XRD upon heating, where the 16 n site for oxygen atoms in the P4/nbm phase evolves into two distinguishable 8i sites in the P̅b2 phase. Ionic conduction in Na2CaV4O12 at elevated temperatures was reported for the first time in the present work. A strong correlation between ionic conductivity and phase structure of Na2CaV4O12 is observed. The charged carriers are mainly sodium ions for the low-temperature P4/nbm phase, while mixed conduction contributed by sodium ions and oxide ions happened in the transformed phase. Bond valence-based energy landscape calculations disclosed a two-dimensional interstitial diffusion mechanism for Na+ ions in the Na2Ca-layers, as well as a two-dimensional diffusion mechanism for oxide ions in the V4O12-layers. The novel semiconductor ceramic would have potential applications in all-solid sodium ions batteries or solid oxide fuel cells as electrolytes.

KW - Mixed-cation vanadate

KW - Electrical conductivity

KW - Dielectric properties

KW - Ceramics

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U2 - 10.1016/j.jallcom.2021.161259

DO - 10.1016/j.jallcom.2021.161259

M3 - Article

SN - 0925-8388

VL - 886

JO - Journal of Alloys and Compounds

JF - Journal of Alloys and Compounds

M1 - 161259

ER -

Phase transformation and ionic conductivity mechanism of a low-temperature sintering semiconductor Na2CaV4O12

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