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Title: Unraveling the Voltage Decay Phenomenon in Li‐Rich Layered Oxide Cathode of No Oxygen Activity

Abstract

Extensive efforts have been devoted to unraveling the true cause of voltage decay in Li, Mn-rich layered oxides. An initial consensus was reached on structural rearrangement, then leaned towards the newly discovered lattice oxygen activity. It is challenging to differentiate their explicit roles because these events typically co-exist during the electrochemical reaction of most Li-rich layered oxides. Here, we probe the voltage decay behavior in Li 1.2Ni 0.2Ru 0.6O 2, a structurally and electrochemically relevant compound to Li, Mn-rich layered oxide, but of no oxygen activity. Such intriguing characteristics allow us to explicitly decouple the contribution of transition metal migration and lattice oxygen activity to voltage decay in Li-rich layered oxides. Our results demonstrate that the microstructural evolution, mainly originating from transition metal migration, is a direct cause of voltage decay, and lattice oxygen activity likely accelerates the decay.

Authors:
 [1];  [2];  [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Div.
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1574426
Alternate Identifier(s):
OSTI ID: 1573283
Report Number(s):
BNL-212335-2019-JAAM
Journal ID: ISSN 1614-6832
Grant/Contract Number:  
SC0012704; DE‐AC02‐05CH11231; DE‐SC0012704; DE‐AC02‐76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Name: Advanced Energy Materials; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Li‐ion battery cathodes; Li‐rich layered oxide; oxygen activity; transition metal migration; voltage decay

Citation Formats

Li, Ning, Hwang, Sooyeon, Sun, Meiling, Fu, Yanbao, Battaglia, Vincent S., Su, Dong, and Tong, Wei. Unraveling the Voltage Decay Phenomenon in Li‐Rich Layered Oxide Cathode of No Oxygen Activity. United States: N. p., 2019. Web. doi:10.1002/aenm.201902258.
Li, Ning, Hwang, Sooyeon, Sun, Meiling, Fu, Yanbao, Battaglia, Vincent S., Su, Dong, & Tong, Wei. Unraveling the Voltage Decay Phenomenon in Li‐Rich Layered Oxide Cathode of No Oxygen Activity. United States. doi:10.1002/aenm.201902258.
Li, Ning, Hwang, Sooyeon, Sun, Meiling, Fu, Yanbao, Battaglia, Vincent S., Su, Dong, and Tong, Wei. Wed . "Unraveling the Voltage Decay Phenomenon in Li‐Rich Layered Oxide Cathode of No Oxygen Activity". United States. doi:10.1002/aenm.201902258.
@article{osti_1574426,
title = {Unraveling the Voltage Decay Phenomenon in Li‐Rich Layered Oxide Cathode of No Oxygen Activity},
author = {Li, Ning and Hwang, Sooyeon and Sun, Meiling and Fu, Yanbao and Battaglia, Vincent S. and Su, Dong and Tong, Wei},
abstractNote = {Extensive efforts have been devoted to unraveling the true cause of voltage decay in Li, Mn-rich layered oxides. An initial consensus was reached on structural rearrangement, then leaned towards the newly discovered lattice oxygen activity. It is challenging to differentiate their explicit roles because these events typically co-exist during the electrochemical reaction of most Li-rich layered oxides. Here, we probe the voltage decay behavior in Li1.2Ni0.2Ru0.6O2, a structurally and electrochemically relevant compound to Li, Mn-rich layered oxide, but of no oxygen activity. Such intriguing characteristics allow us to explicitly decouple the contribution of transition metal migration and lattice oxygen activity to voltage decay in Li-rich layered oxides. Our results demonstrate that the microstructural evolution, mainly originating from transition metal migration, is a direct cause of voltage decay, and lattice oxygen activity likely accelerates the decay.},
doi = {10.1002/aenm.201902258},
journal = {Advanced Energy Materials},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {11}
}

Journal Article:
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Works referenced in this record:

Electrochemical and Structural Properties of xLi2M‘O3 ·(1− x )LiMn0.5Ni0.5O2 Electrodes for Lithium Batteries (M‘ = Ti, Mn, Zr; 0 ≤ x ⩽ 0.3)
journal, May 2004

  • Kim, Jeom-Soo; Johnson, Christopher S.; Vaughey, John T.
  • Chemistry of Materials, Vol. 16, Issue 10, p. 1996-2006
  • DOI: 10.1021/cm0306461

Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries
journal, January 2001

  • Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 11
  • DOI: 10.1149/1.1407994

Synthesis, Structure, and Electrochemical Behavior of Li[Ni[sub x]Li[sub 1/3−2x/3]Mn[sub 2/3−x/3]]O[sub 2]
journal, January 2002

  • Lu, Zhonghua; Beaulieu, L. Y.; Donaberger, R. A.
  • Journal of The Electrochemical Society, Vol. 149, Issue 6
  • DOI: 10.1149/1.1471541

Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress and Perspectives
journal, October 2015

  • Manthiram, Arumugam; Knight, James C.; Myung, Seung-Taek
  • Advanced Energy Materials, Vol. 6, Issue 1
  • DOI: 10.1002/aenm.201501010

Review—Li-Rich Layered Oxide Cathodes for Next-Generation Li-Ion Batteries: Chances and Challenges
journal, January 2015

  • Rozier, Patrick; Tarascon, Jean Marie
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.0111514jes

Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries
journal, January 2016

  • Hy, Sunny; Liu, Haodong; Zhang, Minghao
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C5EE03573B

Review of the U.S. Department of Energy’s “Deep Dive” Effort to Understand Voltage Fade in Li- and Mn-Rich Cathodes
journal, October 2015

  • Croy, Jason R.; Balasubramanian, Mahalingam; Gallagher, Kevin G.
  • Accounts of Chemical Research, Vol. 48, Issue 11
  • DOI: 10.1021/acs.accounts.5b00277

Effect of interface modifications on voltage fade in 0.5Li2MnO3·0.5LiNi0.375Mn0.375Co0.25O2 cathode materials
journal, March 2014


Electrochemical characterization of voltage fade of Li1.2Ni0.2Mn0.6O2 cathode
journal, December 2014


Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes
journal, August 2013

  • Gallagher, Kevin G.; Croy, Jason R.; Balasubramanian, Mahalingam
  • Electrochemistry Communications, Vol. 33
  • DOI: 10.1016/j.elecom.2013.04.022

Correlation Between Oxygen Vacancy, Microstrain, and Cation Distribution in Lithium-Excess Layered Oxides During the First Electrochemical Cycle
journal, April 2013

  • Fell, Christopher R.; Qian, Danna; Carroll, Kyler J.
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm4000119

Mitigating Voltage Decay of Li-Rich Cathode Material via Increasing Ni Content for Lithium-Ion Batteries
journal, July 2016

  • Shi, Ji-Lei; Zhang, Jie-Nan; He, Min
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 31
  • DOI: 10.1021/acsami.6b06733

Effect of Morphology and Manganese Valence on the Voltage Fade and Capacity Retention of Li[Li 2/12 Ni 3/12 Mn 7/12 ]O 2
journal, October 2014

  • Verde, Michael G.; Liu, Haodong; Carroll, Kyler J.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 21
  • DOI: 10.1021/am504701s

Smart design of lithium-rich layered oxide cathode compositions with suppressed voltage decay
journal, January 2014

  • Lee, Eun-Sung; Manthiram, Arumugam
  • Journal of Materials Chemistry A, Vol. 2, Issue 11
  • DOI: 10.1039/c3ta14975g

Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li 2 MnO 3 −LiCo 1/3 Ni 1/3 Mn 1/3 O 2
journal, March 2011

  • Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek
  • Journal of the American Chemical Society, Vol. 133, Issue 12
  • DOI: 10.1021/ja108588y

Synthesis and Characterization of the Lithium-Rich Core–Shell Cathodes with Low Irreversible Capacity and Mitigated Voltage Fade
journal, April 2015


Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study
journal, January 2013

  • Mohanty, Debasish; Sefat, Athena S.; Li, Jianlin
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 44
  • DOI: 10.1039/c3cp53658k

Corrosion/Fragmentation of Layered Composite Cathode and Related Capacity/Voltage Fading during Cycling Process
journal, July 2013

  • Zheng, Jianming; Gu, Meng; Xiao, Jie
  • Nano Letters, Vol. 13, Issue 8
  • DOI: 10.1021/nl401849t

Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale
journal, January 2015

  • Wu, Yan; Ma, Cheng; Yang, Jihui
  • Journal of Materials Chemistry A, Vol. 3, Issue 10
  • DOI: 10.1039/C4TA06856D

Origin of voltage decay in high-capacity layered oxide electrodes
journal, December 2014

  • Sathiya, M.; Abakumov, A. M.; Foix, D.
  • Nature Materials, Vol. 14, Issue 2
  • DOI: 10.1038/nmat4137

Different oxygen redox participation for bulk and surface: A possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2
journal, August 2013


Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013

  • Sathiya, M.; Rousse, G.; Ramesha, K.
  • Nature Materials, Vol. 12, Issue 9
  • DOI: 10.1038/nmat3699

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries
journal, January 2016

  • Assat, Gaurav; Delacourt, Charles; Corte, Daniel Alves Dalla
  • Journal of The Electrochemical Society, Vol. 163, Issue 14
  • DOI: 10.1149/2.0531614jes

Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes
journal, December 2017


Oxygen release and oxygen redox
journal, July 2018


Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li 2 MnO 3 Content
journal, January 2018

  • Teufl, Tobias; Strehle, Benjamin; Müller, Philipp
  • Journal of The Electrochemical Society, Vol. 165, Issue 11
  • DOI: 10.1149/2.0691811jes

Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging
journal, July 2018


Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides
journal, December 2017


Understanding voltage decay in lithium-excess layered cathode materials through oxygen-centred structural arrangement
journal, August 2018


Elucidating anionic oxygen activity in lithium-rich layered oxides
journal, March 2018


Synthesis of Single Crystal LiNi 0.5 Mn 0.3 Co 0.2 O 2 for Lithium Ion Batteries
journal, January 2017

  • Li, Jing; Li, Hongyang; Stone, Will
  • Journal of The Electrochemical Society, Vol. 164, Issue 14
  • DOI: 10.1149/2.0401714jes

Voltage Fade of Layered Oxides: Its Measurement and Impact on Energy Density
journal, January 2013

  • Bettge, Martin; Li, Yan; Gallagher, Kevin
  • Journal of The Electrochemical Society, Vol. 160, Issue 11
  • DOI: 10.1149/2.034311jes

Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries
journal, March 2015

  • Liu, Wen; Oh, Pilgun; Liu, Xien
  • Angewandte Chemie International Edition, Vol. 54, Issue 15
  • DOI: 10.1002/anie.201409262

A review of Ni-based layered oxides for rechargeable Li-ion batteries
journal, January 2017

  • Xu, Jing; Lin, Feng; Doeff, Marca M.
  • Journal of Materials Chemistry A, Vol. 5, Issue 3
  • DOI: 10.1039/C6TA07991A

Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: x Li 2 MnO 3 ·(1 − x )LiMn 0.333 Ni 0.333 Co 0.333 O 2 (0 ≤ x ≤ 0.7)
journal, October 2008

  • Johnson, Christopher S.; Li, Naichao; Lefief, Christina
  • Chemistry of Materials, Vol. 20, Issue 19
  • DOI: 10.1021/cm801245r

A comparison of destabilization mechanisms of the layered NaxMO2 and LixMO2 compounds upon alkali de-intercalation
journal, January 2012

  • Kim, Sangtae; Ma, Xiaohua; Ong, Shyue Ping
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 44
  • DOI: 10.1039/c2cp43377j

Role of Electronic Structure in the Susceptibility of Metastable Transition-Metal Oxide Structures to Transformation
journal, October 2004

  • Reed, John; Ceder, Gerbrand
  • Chemical Reviews, Vol. 104, Issue 10
  • DOI: 10.1021/cr020733x

Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion
journal, October 2014

  • Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P.
  • Chemistry of Materials, Vol. 26, Issue 21
  • DOI: 10.1021/cm5031415

Re-entrant Lithium Local Environments and Defect Driven Electrochemistry of Li- and Mn-Rich Li-Ion Battery Cathodes
journal, February 2015

  • Dogan, Fulya; Long, Brandon R.; Croy, Jason R.
  • Journal of the American Chemical Society, Vol. 137, Issue 6
  • DOI: 10.1021/ja511299y

Role of the composition of lithium-rich layered oxide materials on the voltage decay
journal, April 2015


EXPGUI , a graphical user interface for GSAS
journal, April 2001