Nonstoichiometry and Li-ion transport in lithium zirconate: The role of oxygen vacancies

Xiaowen Zhan; Yang Tse Cheng; Mona Shirpour

doi:10.1111/jace.15583

Nonstoichiometry and Li-ion transport in lithium zirconate: The role of oxygen vacancies

Xiaowen Zhan, Yang Tse Cheng, Mona Shirpour

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

29 Scopus citations

Abstract

Understanding Li-ion migration mechanisms and enhancing Li-ion transport in Li₂ZrO₃ (LZO) is important to its role as solid absorbent for reversible CO₂ capture at elevated temperatures, as ceramic breeder in nuclear reactors, and as electrode coating in high-voltage lithium-ion batteries (LIBs). Although defect engineering is an effective way to tune the properties of ceramics, the defect structure of LZO is largely unknown. This study reports the defect structure and electrical properties of undoped LZO and a series of cation-doped LZOs: (i) depending on their charge states, cation dopants can control the oxygen vacancy concentration in doped LZOs; (ii) the doped LZOs with higher oxygen vacancy concentrations exhibit better Li⁺ conductivity, and consequently faster high-temperature CO₂ absorption. In fact, the Fe (II)-doped LZO shows the highest Li-ion conductivity reported for LZOs, reaching 3.3 mS/cm at ~300°C that is more than 1 order of magnitude higher than that of the undoped LZO.

Original language	English
Pages (from-to)	4053-4065
Number of pages	13
Journal	Journal of the American Ceramic Society
Volume	101
Issue number	9
DOIs	https://doi.org/10.1111/jace.15583
State	Published - Sep 2018

Bibliographical note

Publisher Copyright:
© 2018 The American Ceramic Society

Funding

Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The authors would like to acknowledge the support from US National Science Foundation Award 1355438 (Powering the Kentucky Bioeconomy for a Sustainable Future). Xiaowen Zhan and Mona Shirpour thank the Department of Chemical and Materials Engineering at the University of Kentucky for its financial support of this work. The authors also thank Long Zhang and Shuang Gao at the University of Kentucky for assisting with XPS and SEM experiments.

Funders	Funder number
Department of Chemical and Materials Engineering at the University of Kentucky
Powering the Kentucky Bioeconomy
Powering the Kentucky Bioeconomy
University of Kentucky
US National Science Foundation
U.S. Department of Energy Oak Ridge National Laboratory U.S. Department of Energy National Science Foundation National Energy Research Scientific Computing Center
Argonne National Laboratory
Department of Chemical and Materials Engineering
National Science Foundation Office of International Science and Engineering
U.S. Department of Energy Chinese Academy of Sciences Guangzhou Municipal Science and Technology Project Oak Ridge National Laboratory Extreme Science and Engineering Discovery Environment National Science Foundation National Energy Research Scientific Computing Center National Natural Science Foundation of China	1355438
Office of Basic Energy Sciences	DE-AC02-06CH11357
DOE Basic Energy Sciences	DE-AC02-06CH11357

Keywords

dopants/doping
electrical properties
lithium-ion transport
nonstoichiometry
oxygen vacancies

ASJC Scopus subject areas

Ceramics and Composites
Materials Chemistry

UN SDGs

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

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10.1111/jace.15583

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title = "Nonstoichiometry and Li-ion transport in lithium zirconate: The role of oxygen vacancies",

abstract = "Understanding Li-ion migration mechanisms and enhancing Li-ion transport in Li2ZrO3 (LZO) is important to its role as solid absorbent for reversible CO2 capture at elevated temperatures, as ceramic breeder in nuclear reactors, and as electrode coating in high-voltage lithium-ion batteries (LIBs). Although defect engineering is an effective way to tune the properties of ceramics, the defect structure of LZO is largely unknown. This study reports the defect structure and electrical properties of undoped LZO and a series of cation-doped LZOs: (i) depending on their charge states, cation dopants can control the oxygen vacancy concentration in doped LZOs; (ii) the doped LZOs with higher oxygen vacancy concentrations exhibit better Li+ conductivity, and consequently faster high-temperature CO2 absorption. In fact, the Fe (II)-doped LZO shows the highest Li-ion conductivity reported for LZOs, reaching 3.3 mS/cm at \textasciitilde{}300°C that is more than 1 order of magnitude higher than that of the undoped LZO.",

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author = "Xiaowen Zhan and Cheng, \{Yang Tse\} and Mona Shirpour",

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doi = "10.1111/jace.15583",

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volume = "101",

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N2 - Understanding Li-ion migration mechanisms and enhancing Li-ion transport in Li2ZrO3 (LZO) is important to its role as solid absorbent for reversible CO2 capture at elevated temperatures, as ceramic breeder in nuclear reactors, and as electrode coating in high-voltage lithium-ion batteries (LIBs). Although defect engineering is an effective way to tune the properties of ceramics, the defect structure of LZO is largely unknown. This study reports the defect structure and electrical properties of undoped LZO and a series of cation-doped LZOs: (i) depending on their charge states, cation dopants can control the oxygen vacancy concentration in doped LZOs; (ii) the doped LZOs with higher oxygen vacancy concentrations exhibit better Li+ conductivity, and consequently faster high-temperature CO2 absorption. In fact, the Fe (II)-doped LZO shows the highest Li-ion conductivity reported for LZOs, reaching 3.3 mS/cm at ~300°C that is more than 1 order of magnitude higher than that of the undoped LZO.

AB - Understanding Li-ion migration mechanisms and enhancing Li-ion transport in Li2ZrO3 (LZO) is important to its role as solid absorbent for reversible CO2 capture at elevated temperatures, as ceramic breeder in nuclear reactors, and as electrode coating in high-voltage lithium-ion batteries (LIBs). Although defect engineering is an effective way to tune the properties of ceramics, the defect structure of LZO is largely unknown. This study reports the defect structure and electrical properties of undoped LZO and a series of cation-doped LZOs: (i) depending on their charge states, cation dopants can control the oxygen vacancy concentration in doped LZOs; (ii) the doped LZOs with higher oxygen vacancy concentrations exhibit better Li+ conductivity, and consequently faster high-temperature CO2 absorption. In fact, the Fe (II)-doped LZO shows the highest Li-ion conductivity reported for LZOs, reaching 3.3 mS/cm at ~300°C that is more than 1 order of magnitude higher than that of the undoped LZO.

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Nonstoichiometry and Li-ion transport in lithium zirconate: The role of oxygen vacancies

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

Access to Document

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