Explore the Effects of Microstructural Defects on Voltage Fade of Li- and Mn-Rich Cathodes

Enyuan Hu; Yingchun Lyu; Huolin L. Xin; Jue Liu; Lili Han; Seong Min Bak; Jianming Bai; Xiqian Yu; Hong Li; Xiao Qing Yang

doi:10.1021/acs.nanolett.6b01609

Explore the Effects of Microstructural Defects on Voltage Fade of Li- and Mn-Rich Cathodes

Enyuan Hu, Yingchun Lyu, Huolin L. Xin, Jue Liu, Lili Han, Seong Min Bak, Jianming Bai, Xiqian Yu, Hong Li, Xiao Qing Yang

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

81 Scopus citations

Abstract

Li- and Mn-rich (LMR) cathode materials have been considered as promising candidates for energy storage applications due to high energy density. However, these materials suffer from a serious problem of voltage fade. Oxygen loss and the layered-to-spinel phase transition are two major contributors of such voltage fade. In this paper, using a combination of X-ray diffraction (XRD), pair distribution function (PDF), X-ray absorption (XAS) techniques, and aberration-corrected scanning transmission electron microscopy (STEM), we studied the effects of micro structural defects, especially the grain boundaries, on the oxygen loss and layered-to-spinel phase transition through prelithiation of a model compound Li₂Ru_0.5Mn_0.5O₃. It is found that the nanosized micro structural defects, especially the large amount of grain boundaries created by the prelithiation can greatly accelerate the oxygen loss and voltage fade. Defects (such as nanosized grain boundaries) and oxygen release form a positive feedback loop, promote each other during cycling, and accelerate the two major voltage fade contributors: the transition metal reduction and layered-to-spinel phase transition. These results clearly demonstrate the important relationships among the oxygen loss, microstructural defects and voltage fade. The importance of maintaining good crystallinity and protecting the surface of LMR material are also suggested.

Original language	English
Pages (from-to)	5999-6007
Number of pages	9
Journal	Nano Letters
Volume	16
Issue number	10
DOIs	https://doi.org/10.1021/acs.nanolett.6b01609
State	Published - Oct 12 2016
Externally published	Yes

Funding

The work at Brookhaven National Laboratory was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies under Contract No. DE-SC0012704. Use of the beamline (28ID) at National Synchrotron Light Source II (NSLS-II) and STEM at Center for Functional Nanomaterials of Brookhaven National Laboratory were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contracts No. DE-SC0012704. Y.L. is supported by the Shanghai Municipal Science and Technology Commission (No. 14DZ2261200). H.L. is supported by National Science Foundation of China (51325206, 51421002), "Strategic Priority Research Program" of the Chinese Academy of Sciences (XDA09010000) and National project 973 (2012CB932900). We acknowledge technical support from the scientists at beamline 12-BM-B and 17-BMB of APS (ANL), supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. Part of this research was conducted at the BL2-2 of Stanford Synchrotron Radiation Lightsource. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.

Funders	Funder number
National project 973	2012CB932900
U.S. Department of Energy	DE-AC02-06CH11357, DE-AC02-76SF00515
Office of Science
Office of Energy Efficiency and Renewable Energy
Basic Energy Sciences
Vehicle Technologies Office	DE-SC0012704
National Natural Science Foundation of China	51421002, 51325206
Chinese Academy of Sciences	XDA09010000
Science and Technology Commission of Shanghai Municipality	14DZ2261200

Keywords

lithium-ion battery
microstructural defect
prelithiation
voltage fade

UN SDGs

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

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10.1021/acs.nanolett.6b01609

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title = "Explore the Effects of Microstructural Defects on Voltage Fade of Li- and Mn-Rich Cathodes",

abstract = "Li- and Mn-rich (LMR) cathode materials have been considered as promising candidates for energy storage applications due to high energy density. However, these materials suffer from a serious problem of voltage fade. Oxygen loss and the layered-to-spinel phase transition are two major contributors of such voltage fade. In this paper, using a combination of X-ray diffraction (XRD), pair distribution function (PDF), X-ray absorption (XAS) techniques, and aberration-corrected scanning transmission electron microscopy (STEM), we studied the effects of micro structural defects, especially the grain boundaries, on the oxygen loss and layered-to-spinel phase transition through prelithiation of a model compound Li2Ru0.5Mn0.5O3. It is found that the nanosized micro structural defects, especially the large amount of grain boundaries created by the prelithiation can greatly accelerate the oxygen loss and voltage fade. Defects (such as nanosized grain boundaries) and oxygen release form a positive feedback loop, promote each other during cycling, and accelerate the two major voltage fade contributors: the transition metal reduction and layered-to-spinel phase transition. These results clearly demonstrate the important relationships among the oxygen loss, microstructural defects and voltage fade. The importance of maintaining good crystallinity and protecting the surface of LMR material are also suggested.",

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AU - Xin, Huolin L.

AU - Liu, Jue

AU - Han, Lili

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AB - Li- and Mn-rich (LMR) cathode materials have been considered as promising candidates for energy storage applications due to high energy density. However, these materials suffer from a serious problem of voltage fade. Oxygen loss and the layered-to-spinel phase transition are two major contributors of such voltage fade. In this paper, using a combination of X-ray diffraction (XRD), pair distribution function (PDF), X-ray absorption (XAS) techniques, and aberration-corrected scanning transmission electron microscopy (STEM), we studied the effects of micro structural defects, especially the grain boundaries, on the oxygen loss and layered-to-spinel phase transition through prelithiation of a model compound Li2Ru0.5Mn0.5O3. It is found that the nanosized micro structural defects, especially the large amount of grain boundaries created by the prelithiation can greatly accelerate the oxygen loss and voltage fade. Defects (such as nanosized grain boundaries) and oxygen release form a positive feedback loop, promote each other during cycling, and accelerate the two major voltage fade contributors: the transition metal reduction and layered-to-spinel phase transition. These results clearly demonstrate the important relationships among the oxygen loss, microstructural defects and voltage fade. The importance of maintaining good crystallinity and protecting the surface of LMR material are also suggested.

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Explore the Effects of Microstructural Defects on Voltage Fade of Li- and Mn-Rich Cathodes

Abstract

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Keywords

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