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Title: Unravelling the impact of reaction paths on mechanical degradation of intercalation cathodes for lithium-ion batteries

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.5b06178· OSTI ID:1246774
 [1];  [2];  [3];  [4];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. General Motors Research and Development Center, Warren, MI (United States); Univ. of Kentucky, Lexington, KY (United States)
  3. General Motors Research and Development Center, Warren, MI (United States)
  4. Univ. of Kentucky, Lexington, KY (United States)
+ Show Author Affiliations

The intercalation compounds are generally considered as ideal electrode materials for lithium-ion batteries thanks to their minimum volume expansion and fast lithium ion diffusion. However, cracking still occurs in those compounds and has been identified as one of the critical issues responsible for their capacity decay and short cycle life, although the diffusion-induced stress and volume expansion are much smaller than those in alloying-type electrodes. Here, we designed a thin-film model system that enables us to tailor the cation ordering in LiNi0.5Mn1.5O4 spinels and correlate the stress patterns, phase evolution, and cycle performances. Surprisingly, we found that distinct reaction paths cause negligible difference in the overall stress patterns but significantly different cracking behaviors and cycling performances: 95% capacity retention for disordered LiNi0.5Mn1.5O4 and 48% capacity retention for ordered LiNi0.5Mn1.5O4 after 2000 cycles. We were able to pinpoint that the extended solid-solution region with suppressed phase transformation attributed to the superior electrochemical performance of disordered spinel. Furthermore, this work envisions a strategy for rationally designing stable cathodes for lithium-ion batteries through engineering the atomic structure that extends the solid-solution region and suppresses phase transformation.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1246774
Journal Information:
Journal of the American Chemical Society, Vol. 137, Issue 43; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 53 works
Citation information provided by
Web of Science

References (40)

Stable cycling of double-walled silicon nanotube battery anodes through solid–electrolyte interphase control journal March 2012
Interconnected Silicon Hollow Nanospheres for Lithium-Ion Battery Anodes with Long Cycle Life journal July 2011
Regulated Breathing Effect of Silicon Negative Electrode for Dramatically Enhanced Performance of Li-Ion Battery journal January 2015
LiNi0.5Mn1.5O4 Hollow Structures as High-Performance Cathodes for Lithium-Ion Batteries journal November 2011
Fracture of electrodes in lithium-ion batteries caused by fast charging journal October 2010
Reversible Cycling of Crystalline Silicon Powder journal January 2007
A Major Constituent of Brown Algae for Use in High-Capacity Li-Ion Batteries journal September 2011
Toward an Ideal Polymer Binder Design for High-Capacity Battery Anodes journal July 2013
A Nanonet-Enabled Li Ion Battery Cathode Material with High Power Rate, High Capacity, and Long Cycle Lifetime journal December 2011
Improved Electrode Performance of Porous LiFePO4 Using RuO2 as an Oxidic Nanoscale Interconnect journal August 2007
Formation of Fe 2 O 3 Microboxes with Hierarchical Shell Structures from Metal–Organic Frameworks and Their Lithium Storage Properties journal October 2012
Design criteria for electrochemical shock resistant battery electrodes journal January 2012
Recent Achievements on Inorganic Electrode Materials for Lithium-Ion Batteries journal February 2015
TEM Study of Electrochemical Cycling-Induced Damage and Disorder in LiCoO[sub 2] Cathodes for Rechargeable Lithium Batteries journal January 1999
In Situ Observation of LiNiO[sub 2] Single-Particle Fracture during Li-Ion Extraction and Insertion journal January 1999
Structural fatigue in spinel electrodes in Li/Lix[Mn2]O4 cells journal September 1999
Strain Accommodation during Phase Transformations in Olivine-Based Cathodes as a Materials Selection Criterion for High-Power Rechargeable Batteries journal March 2007
Accelerated discovery of cathode materials with prolonged cycle life for lithium-ion battery journal August 2014
Safe and fast-charging Li-ion battery with long shelf life for power applications journal April 2011
Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries journal November 2013
A Guide to Li-Ion Coin-Cell Electrode Making for Academic Researchers journal January 2011
Electrochemical behavior and passivation of current collectors in lithium-ion batteries journal January 2011
Effects of cell positive cans and separators on the performance of high-voltage Li-ion batteries journal September 2012
A comparative study of Fd-3m and P4332 “LiNi0.5Mn1.5O4” journal June 2011
Nano-LiNi0.5Mn1.5O4 spinel: a high power electrode for Li-ion batteries journal January 2008
Three-volt Lithium-ion Battery Consisting of Li[Ni1/2Mn3/2]O4 and Li[Li1/3Ti5/3]O4: Improvement of Positive-electrode Material for Long-life Medium-power Applications journal January 2008
Solid Electrolyte: the Key for High-Voltage Lithium Batteries journal October 2014
Comparative Study of LiNi 0.5 Mn 1.5 O 4 - δ and LiNi 0.5 Mn 1.5 O 4 Cathodes Having Two Crystallographic Structures:  Fd 3̄ m and P 4 3 32 journal March 2004
A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries journal January 2014
Strategies to Avert Electrochemical Shock and Their Demonstration in Spinels journal January 2014
Recent progress in high-voltage lithium ion batteries journal September 2013
Topotactic Two-Phase Reactions of Li[Ni[sub 1/2]Mn[sub 3/2]]O[sub 4] (P4[sub 3]32) in Nonaqueous Lithium Cells journal January 2004
Revealing the coupled cation interactions behind the electrochemical profile of LixNi0.5Mn1.5O4 journal January 2012
Solid-Solution Li Intercalation as a Function of Cation Order/Disorder in the High-Voltage Li x Ni 0.5 Mn 1.5 O 4 Spinel journal July 2013
In situ measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation journal August 2010
Thin film graphite electrodes with low stress generation during Li-intercalation journal July 2011
Phase transition kinetics of LiNi0.5Mn1.5O4 electrodes studied by in situ X-ray absorption near-edge structure and X-ray diffraction analysis journal January 2013
Two-phase transition of Li-intercalation compounds in Li-ion batteries journal November 2014
Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes journal June 2014
Direct Evidence of Concurrent Solid-Solution and Two-Phase Reactions and the Nonequilibrium Structural Evolution of LiFePO 4 journal April 2012

Cited By (6)

High-Performance Cathode Material of FeF3·0.33H2O Modified with Carbon Nanotubes and Graphene for Lithium-Ion Batteries journal March 2019
Site-dependent multicomponent doping strategy for Ni-rich LiNi 1−2y Co y Mn y O 2 ( y = 1/12) cathode materials for Li-ion batteries journal January 2017
Realization of Ti Doping by Electrostatic Assembly to Improve the Stability of LiCoO 2 Cycled to 4.5 V journal January 2019
Decoration by dual-phase Li 2 ZrO 3 islands with core–shell structures enhances the electrochemical performance of high-voltage LiNi 0.5 Mn 1.5 O 4 journal January 2020
Trace molybdenum doped Li 2 RuO 3 as a cathode material with enhanced performance for lithium ion batteries journal January 2019
Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy journal February 2017

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
25 ENERGY STORAGE
lithium ion batteries
cathodes
stress
cycling life