Unconventional irreversible structural changes in a high-voltage Li-Mn-rich oxide for lithium-ion battery cathodes

Debasish Mohanty; Athena S. Sefat; E. Andrew Payzant; Jianlin Li; David L. Wood; Claus Daniel

doi:10.1016/j.jpowsour.2015.02.087

Unconventional irreversible structural changes in a high-voltage Li-Mn-rich oxide for lithium-ion battery cathodes

Debasish Mohanty, Athena S. Sefat, E. Andrew Payzant, Jianlin Li, David L. Wood, Claus Daniel

Materials Engineering

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

20 Scopus citations

Abstract

Making all-electric vehicles (EVs) commonplace in transportation applications will require affordable high-power and high-energy-density lithium-ion batteries (LIBs). The quest for suitable cathode materials to meet this end has currently plateaued with the discovery of high-voltage (≥4.7 V vs. Li⁺), high capacity (∼250 mAh/g) lithium-manganese-rich (LMR) layered composite oxides. Despite the promise of LMR oxides in high-energy-density LIBs, an irreversible structural change has been identified in this work that is governed by the formation of a 'permanent' spin-glass type magnetically frustrated phase indicating a dominant AB₂O₄ (A = Li, B = Mn) type spinel after a short-term lithium deintercalation (charging) and intercalation (discharging) process. Furthermore, reduction of transition metal (Mn) ions from the 4+ state (pristine LMR) to 3+ (cycled LMR), which alters the intercalation redox chemistry and suggests the presence of 'unfilled' lithium vacancies and/or oxygen vacancies in the lattice after cycling, has presented a major stumbling block. These situations result in both loss of capacity and fading of the voltage profile, and these combined effects significantly reduce the high energy density over even short-term cycling.

Original language	English
Article number	20715
Pages (from-to)	423-428
Number of pages	6
Journal	Journal of Power Sources
Volume	283
DOIs	https://doi.org/10.1016/j.jpowsour.2015.02.087
State	Published - Jun 1 2015

Funding

This research at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) under contract DE-AC05-00OR22725, was sponsored by the DOE Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO), Applied Battery Research (ABR) Program (Program Managers: Peter Faguy and David Howell). Part of this research was supported by the DOE Basic Energy Sciences (BES), Materials Sciences and Engineering Division . A portion of this research was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. The LMR oxide was obtained from Argonne National Laboratory, in collaboration with Andrew Jansen and Bryant Polzin. The electrodes and cell fabrication and pouch cell testing were carried out at the DOE Battery Manufacturing R&D Facility at Oak Ridge National Laboratory (BMF), which is supported by VTO's ABR Program . We specially thank Dr. Daniel P. Abraham from Argonne National Laboratory for his invaluable help to design the electrochemical experiments for this study.

Keywords

High-energy-density lithium-ion batteries
Lithium rich
Magnetic frustration
Spinel
Structural transformation

UN SDGs

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

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10.1016/j.jpowsour.2015.02.087

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title = "Unconventional irreversible structural changes in a high-voltage Li-Mn-rich oxide for lithium-ion battery cathodes",

abstract = "Making all-electric vehicles (EVs) commonplace in transportation applications will require affordable high-power and high-energy-density lithium-ion batteries (LIBs). The quest for suitable cathode materials to meet this end has currently plateaued with the discovery of high-voltage (≥4.7 V vs. Li+), high capacity (∼250 mAh/g) lithium-manganese-rich (LMR) layered composite oxides. Despite the promise of LMR oxides in high-energy-density LIBs, an irreversible structural change has been identified in this work that is governed by the formation of a 'permanent' spin-glass type magnetically frustrated phase indicating a dominant AB2O4 (A = Li, B = Mn) type spinel after a short-term lithium deintercalation (charging) and intercalation (discharging) process. Furthermore, reduction of transition metal (Mn) ions from the 4+ state (pristine LMR) to 3+ (cycled LMR), which alters the intercalation redox chemistry and suggests the presence of 'unfilled' lithium vacancies and/or oxygen vacancies in the lattice after cycling, has presented a major stumbling block. These situations result in both loss of capacity and fading of the voltage profile, and these combined effects significantly reduce the high energy density over even short-term cycling.",

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Unconventional irreversible structural changes in a high-voltage Li-Mn-rich oxide for lithium-ion battery cathodes

Abstract

Funding

Keywords

UN SDGs

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