Novel Ordered Rocksalt-Type Lithium-Rich Li2Ru1-xNixO3-δ (0.3 ≤ x ≤ 0.5) Cathode Material with Tunable Anionic Redox Potential

Shiyao Zheng; Feng Zheng; Haodong Liu; Guiming Zhong; Jue Wu; Min Feng; Qihui Wu; Wenhua Zuo; Chaoyu Hong; Yan Chen; Ke An; Ping Liu; Shunqing Wu; Yong Yang

doi:10.1021/acsaem.9b01051

Novel Ordered Rocksalt-Type Lithium-Rich Li₂Ru_1-xNi_xO_3-δ (0.3 ≤ x ≤ 0.5) Cathode Material with Tunable Anionic Redox Potential

Shiyao Zheng, Feng Zheng, Haodong Liu, Guiming Zhong, Jue Wu, Min Feng, Qihui Wu, Wenhua Zuo, Chaoyu Hong, Yan Chen, Ke An, Ping Liu, Shunqing Wu, Yong Yang

Materials Engineering

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

23 Scopus citations

Abstract

In this work, a series of ordered rocksalt (OR) type Li-rich Li₂Ru_1-xNi_xO_3-δ (LRN_xO, 0.3 ≤ x ≤ 0.5) are successfully synthesized and investigated for the first time. X-ray diffraction and neutron powder diffraction patterns exhibit an obvious phase transition from layered to an OR structure as the Ni content gradually increases from x = 0 to x = 0.5, which leads to different electrochemical behaviors. In the case of OR-LRN_0.4O, an ?350 mV decrease of the oxygen oxidation potential compared with Li₂RuO₃ (LRO) is observed from around 4.2 to 3.85 V, which is confirmed by both X-ray photelectron O 1s spectra and dQ/dV results. The role of Ni substitution on the oxygen redox reaction is studied by first-principles calculations, and it is concluded that the formation of the OR structure caused by Ni substitution is the main reason for lowering the oxygen oxidation potential. In addition, the average discharge voltage of OR-LRN_0.4O is also enhanced compared with LRO. This work provides a novel innovative strategy to modulate and control the oxygen anion redox reaction for high-energy-density Li-rich materials, which shed light on the fundamental understanding and optimizing of the anion redox process in Li-rich materials.

Original language	English
Pages (from-to)	5933-5944
Number of pages	12
Journal	ACS Applied Energy Materials
Volume	2
Issue number	8
DOIs	https://doi.org/10.1021/acsaem.9b01051
State	Published - Aug 26 2019

Funding

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 21761132030, 21428303, and 21621091) and the National Key Research and Development Program of China (Grant Nos. 2018YFB0905400 and 2016YFB0901500). This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Neutron diffraction work was carried out at the Spallation Neutron Source (SNS), which is the U.S. Department of Energy (DOE) user facility at the Oak Ridge National Laboratory, sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences. We thank Mr. M. J. Frost at SNS for the technique support. We also thank SSRF (Shanghai Synchrotron Radiation Facility), beamlines BL14B1 and BL14W1, for providing beam time. This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 21761132030, 21428303, and 21621091) and the National Key Research and Development Program of China (Grant Nos. 2018YFB0905400 and 2016YFB0901500). This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). Neutron diffraction work was carried out at the Spallation Neutron Source (SNS), which is the U.S. Department of Energy (DOE) user facility at the Oak Ridge National Laboratory, sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences. We thank Mr. M. J. Frost at SNS for the technique support. We also thank SSRF (Shanghai Synchrotron Radiation Facility), beamlines BL14B1 and BL14W1, for providing beam time.

Keywords

Li-rich materials
Ru-based materials
anionic redox
cathode materials
ordered rocksalt

UN SDGs

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

Access to Document

10.1021/acsaem.9b01051

Cite this

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title = "Novel Ordered Rocksalt-Type Lithium-Rich Li2Ru1-xNixO3-δ (0.3 ≤ x ≤ 0.5) Cathode Material with Tunable Anionic Redox Potential",

abstract = "In this work, a series of ordered rocksalt (OR) type Li-rich Li2Ru1-xNixO3-δ (LRNxO, 0.3 ≤ x ≤ 0.5) are successfully synthesized and investigated for the first time. X-ray diffraction and neutron powder diffraction patterns exhibit an obvious phase transition from layered to an OR structure as the Ni content gradually increases from x = 0 to x = 0.5, which leads to different electrochemical behaviors. In the case of OR-LRN0.4O, an ?350 mV decrease of the oxygen oxidation potential compared with Li2RuO3 (LRO) is observed from around 4.2 to 3.85 V, which is confirmed by both X-ray photelectron O 1s spectra and dQ/dV results. The role of Ni substitution on the oxygen redox reaction is studied by first-principles calculations, and it is concluded that the formation of the OR structure caused by Ni substitution is the main reason for lowering the oxygen oxidation potential. In addition, the average discharge voltage of OR-LRN0.4O is also enhanced compared with LRO. This work provides a novel innovative strategy to modulate and control the oxygen anion redox reaction for high-energy-density Li-rich materials, which shed light on the fundamental understanding and optimizing of the anion redox process in Li-rich materials.",

keywords = "Li-rich materials, Ru-based materials, anionic redox, cathode materials, ordered rocksalt",

author = "Shiyao Zheng and Feng Zheng and Haodong Liu and Guiming Zhong and Jue Wu and Min Feng and Qihui Wu and Wenhua Zuo and Chaoyu Hong and Yan Chen and Ke An and Ping Liu and Shunqing Wu and Yong Yang",

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T1 - Novel Ordered Rocksalt-Type Lithium-Rich Li2Ru1-xNixO3-δ (0.3 ≤ x ≤ 0.5) Cathode Material with Tunable Anionic Redox Potential

AU - Zheng, Shiyao

AU - Zheng, Feng

AU - Liu, Haodong

AU - Zhong, Guiming

AU - Wu, Jue

AU - Feng, Min

AU - Wu, Qihui

AU - Zuo, Wenhua

AU - Hong, Chaoyu

AU - Chen, Yan

AU - An, Ke

AU - Liu, Ping

AU - Wu, Shunqing

AU - Yang, Yong

PY - 2019/8/26

Y1 - 2019/8/26

N2 - In this work, a series of ordered rocksalt (OR) type Li-rich Li2Ru1-xNixO3-δ (LRNxO, 0.3 ≤ x ≤ 0.5) are successfully synthesized and investigated for the first time. X-ray diffraction and neutron powder diffraction patterns exhibit an obvious phase transition from layered to an OR structure as the Ni content gradually increases from x = 0 to x = 0.5, which leads to different electrochemical behaviors. In the case of OR-LRN0.4O, an ?350 mV decrease of the oxygen oxidation potential compared with Li2RuO3 (LRO) is observed from around 4.2 to 3.85 V, which is confirmed by both X-ray photelectron O 1s spectra and dQ/dV results. The role of Ni substitution on the oxygen redox reaction is studied by first-principles calculations, and it is concluded that the formation of the OR structure caused by Ni substitution is the main reason for lowering the oxygen oxidation potential. In addition, the average discharge voltage of OR-LRN0.4O is also enhanced compared with LRO. This work provides a novel innovative strategy to modulate and control the oxygen anion redox reaction for high-energy-density Li-rich materials, which shed light on the fundamental understanding and optimizing of the anion redox process in Li-rich materials.

AB - In this work, a series of ordered rocksalt (OR) type Li-rich Li2Ru1-xNixO3-δ (LRNxO, 0.3 ≤ x ≤ 0.5) are successfully synthesized and investigated for the first time. X-ray diffraction and neutron powder diffraction patterns exhibit an obvious phase transition from layered to an OR structure as the Ni content gradually increases from x = 0 to x = 0.5, which leads to different electrochemical behaviors. In the case of OR-LRN0.4O, an ?350 mV decrease of the oxygen oxidation potential compared with Li2RuO3 (LRO) is observed from around 4.2 to 3.85 V, which is confirmed by both X-ray photelectron O 1s spectra and dQ/dV results. The role of Ni substitution on the oxygen redox reaction is studied by first-principles calculations, and it is concluded that the formation of the OR structure caused by Ni substitution is the main reason for lowering the oxygen oxidation potential. In addition, the average discharge voltage of OR-LRN0.4O is also enhanced compared with LRO. This work provides a novel innovative strategy to modulate and control the oxygen anion redox reaction for high-energy-density Li-rich materials, which shed light on the fundamental understanding and optimizing of the anion redox process in Li-rich materials.

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