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Title: Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes

Abstract

Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Here, our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [4];  [5];  [3];  [2]; ORCiD logo [6]; ORCiD logo [7];  [3];  [3];  [3];  [3];  [3]; ORCiD logo [8]
  1. Seoul National Univ. (Korea, Republic of). Research Inst. of Advanced Materials (RIAM)
  2. Seoul National Univ. (Korea, Republic of). Research Inst. of Advanced Materials (RIAM), and Center for Nanoparticle Research, Inst. for Basic Science (IBS)
  3. Seoul National Univ. (Korea, Republic of). Research Inst. of Advanced Materials (RIAM)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Institute for Materials and Energy Science (SIMES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. Seoul National Univ. (Korea, Republic of). National Center for Inter-Univ. Research Facilities
  6. Seoul National Univ. (Korea, Republic of). Research Inst. of Advanced Materials (RIAM); Samsung Advanced Institute of Technology (SAIT), Samsung Electronics, Suwon-si, Gyeonggi-do (Korea, Republic of). Next Generation Battery Lab, Material Research Center
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  8. Seoul National Univ. (Korea, Republic of). Research Inst. of Advanced Materials (RIAM), and Center for Nanoparticle Research, Inst. for Basic Science (IBS), and Inst. of Engineering Research
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; National Research Foundation of Korea (NRF)
OSTI Identifier:
1605377
Alternate Identifier(s):
OSTI ID: 1601221
Grant/Contract Number:  
[AC02-76SF00515; AC02-05CH11231; IBS-R006-A2; 2018R1A2A1A05079249]
Resource Type:
Accepted Manuscript
Journal Name:
Nature Materials
Additional Journal Information:
[ Journal Volume: 19; Journal Issue: 4]; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Country of Publication:
United States
Language:
English

Citation Formats

Eum, Donggun, Kim, Byunghoon, Kim, Sung Joo, Park, Hyeokjun, Wu, Jinpeng, Cho, Sung-Pyo, Yoon, Gabin, Lee, Myeong Hwan, Jung, Sung-Kyun, Yang, Wanli, Seong, Won Mo, Ku, Kyojin, Tamwattana, Orapa, Park, Sung Kwan, Hwang, Insang, and Kang, Kisuk. Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes. United States: N. p., 2020. Web. doi:10.1038/s41563-019-0572-4.
Eum, Donggun, Kim, Byunghoon, Kim, Sung Joo, Park, Hyeokjun, Wu, Jinpeng, Cho, Sung-Pyo, Yoon, Gabin, Lee, Myeong Hwan, Jung, Sung-Kyun, Yang, Wanli, Seong, Won Mo, Ku, Kyojin, Tamwattana, Orapa, Park, Sung Kwan, Hwang, Insang, & Kang, Kisuk. Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes. United States. doi:10.1038/s41563-019-0572-4.
Eum, Donggun, Kim, Byunghoon, Kim, Sung Joo, Park, Hyeokjun, Wu, Jinpeng, Cho, Sung-Pyo, Yoon, Gabin, Lee, Myeong Hwan, Jung, Sung-Kyun, Yang, Wanli, Seong, Won Mo, Ku, Kyojin, Tamwattana, Orapa, Park, Sung Kwan, Hwang, Insang, and Kang, Kisuk. Mon . "Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes". United States. doi:10.1038/s41563-019-0572-4.
@article{osti_1605377,
title = {Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes},
author = {Eum, Donggun and Kim, Byunghoon and Kim, Sung Joo and Park, Hyeokjun and Wu, Jinpeng and Cho, Sung-Pyo and Yoon, Gabin and Lee, Myeong Hwan and Jung, Sung-Kyun and Yang, Wanli and Seong, Won Mo and Ku, Kyojin and Tamwattana, Orapa and Park, Sung Kwan and Hwang, Insang and Kang, Kisuk},
abstractNote = {Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Here, our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.},
doi = {10.1038/s41563-019-0572-4},
journal = {Nature Materials},
number = [4],
volume = [19],
place = {United States},
year = {2020},
month = {1}
}

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