skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Mesoscale Chemomechanical Interplay of the LiNi0.8Co0.15Al0.05O2 Cathode in Solid-State Polymer Batteries

Abstract

Complex chemomechanical interplay exists over a wide range of length scales within the hierarchically structured lithium-ion battery. At the mesoscale, the interdependent structural complexity and chemical heterogeneity collectively govern the local chemistry and, as a result, critically influence the cell level performance. Here in this paper we investigate the morphology and state of charge (SOC) inhomogeneity within secondary NCA particles that were cycled in solid polymer batteries. We observe substantial inhomogeneity in the nickel oxidation state (a proxy for SOC) and loss of structural integrity within secondary particles after only 20 cycles due to significant intergranular cracking. The formation of mesoscale cracks causes loss of ionic and electrical contact within cathode particles, triggering increases in local impedance and rearrangement of transport pathways for charge carriers. This can eventually lead to deactivation of subparticle level domains in solid-state lithium-ion batteries. Our findings highlight the importance of proper mesoscale strain and defect management in polymer lithium-ion batteries.

Authors:
 [1];  [2]; ORCiD logo [3];  [4]; ORCiD logo [3];  [5];  [6];  [3];  [3]; ORCiD logo [7]; ORCiD logo [2]
  1. Robert Bosch LLC, Sunnyvale, CA (United States). Research and Technology Center; Karlsruhe Inst. of Technology (KIT) (Germany). Dept. of Mechanical Engineering
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  3. Robert Bosch LLC, Sunnyvale, CA (United States). Research and Technology Center
  4. Seeo Inc., Hayward, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Center of Electron Microscopy, Molecular Foundry
  6. Karlsruhe Inst. of Technology (KIT) (Germany). Dept. of Mechanical Engineering; Aalen Univ., Aalen (Germany). Materials Research Inst.
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area; Univ. of California, Berkeley, CA (United States)
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)
OSTI Identifier:
1503545
Alternate Identifier(s):
OSTI ID: 1637289
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 2; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE

Citation Formats

Besli, Münir M., Xia, Sihao, Kuppan, Saravanan, Huang, Yiqing, Metzger, Michael, Shukla, Alpesh Khushalchand, Schneider, Gerhard, Hellstrom, Sondra, Christensen, Jake, Doeff, Marca M., and Liu, Yijin. Mesoscale Chemomechanical Interplay of the LiNi0.8Co0.15Al0.05O2 Cathode in Solid-State Polymer Batteries. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.chemmater.8b04418.
Besli, Münir M., Xia, Sihao, Kuppan, Saravanan, Huang, Yiqing, Metzger, Michael, Shukla, Alpesh Khushalchand, Schneider, Gerhard, Hellstrom, Sondra, Christensen, Jake, Doeff, Marca M., & Liu, Yijin. Mesoscale Chemomechanical Interplay of the LiNi0.8Co0.15Al0.05O2 Cathode in Solid-State Polymer Batteries. United States. https://doi.org/10.1021/acs.chemmater.8b04418
Besli, Münir M., Xia, Sihao, Kuppan, Saravanan, Huang, Yiqing, Metzger, Michael, Shukla, Alpesh Khushalchand, Schneider, Gerhard, Hellstrom, Sondra, Christensen, Jake, Doeff, Marca M., and Liu, Yijin. Wed . "Mesoscale Chemomechanical Interplay of the LiNi0.8Co0.15Al0.05O2 Cathode in Solid-State Polymer Batteries". United States. https://doi.org/10.1021/acs.chemmater.8b04418. https://www.osti.gov/servlets/purl/1503545.
@article{osti_1503545,
title = {Mesoscale Chemomechanical Interplay of the LiNi0.8Co0.15Al0.05O2 Cathode in Solid-State Polymer Batteries},
author = {Besli, Münir M. and Xia, Sihao and Kuppan, Saravanan and Huang, Yiqing and Metzger, Michael and Shukla, Alpesh Khushalchand and Schneider, Gerhard and Hellstrom, Sondra and Christensen, Jake and Doeff, Marca M. and Liu, Yijin},
abstractNote = {Complex chemomechanical interplay exists over a wide range of length scales within the hierarchically structured lithium-ion battery. At the mesoscale, the interdependent structural complexity and chemical heterogeneity collectively govern the local chemistry and, as a result, critically influence the cell level performance. Here in this paper we investigate the morphology and state of charge (SOC) inhomogeneity within secondary NCA particles that were cycled in solid polymer batteries. We observe substantial inhomogeneity in the nickel oxidation state (a proxy for SOC) and loss of structural integrity within secondary particles after only 20 cycles due to significant intergranular cracking. The formation of mesoscale cracks causes loss of ionic and electrical contact within cathode particles, triggering increases in local impedance and rearrangement of transport pathways for charge carriers. This can eventually lead to deactivation of subparticle level domains in solid-state lithium-ion batteries. Our findings highlight the importance of proper mesoscale strain and defect management in polymer lithium-ion batteries.},
doi = {10.1021/acs.chemmater.8b04418},
journal = {Chemistry of Materials},
number = 2,
volume = 31,
place = {United States},
year = {2018},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Aging Mechanisms of Electrode Materials in Lithium-Ion Batteries for Electric Vehicles
journal, January 2015


Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011


Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li 7 La 3 Zr 2 O 12
journal, September 2017


Atomic Layer Deposition of the Solid Electrolyte Garnet Li 7 La 3 Zr 2 O 12
journal, April 2017


Are All-Solid-State Lithium-Ion Batteries Really Safe?–Verification by Differential Scanning Calorimetry with an All-Inclusive Microcell
journal, January 2017

  • Inoue, Takao; Mukai, Kazuhiko
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 2
  • DOI: 10.1021/acsami.6b13224

Recent progress in solid oxide and lithium ion conducting electrolytes research
journal, April 2006


Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries
journal, January 2017


Deformation and stress in electrode materials for Li-ion batteries
journal, June 2014


Microstructural Observation of LiNi 0.8 Co 0.15 Al 0.05 O 2 after Charge and Discharge by Scanning Transmission Electron Microscopy
journal, January 2012

  • Makimura, Yoshinari; Zheng, Shijian; Ikuhara, Yuichi
  • Journal of The Electrochemical Society, Vol. 159, Issue 7
  • DOI: 10.1149/2.073207jes

Intrinsic Origins of Crack Generation in Ni-rich LiNi0.8Co0.1Mn0.1O2 Layered Oxide Cathode Material
journal, January 2017

  • Lim, Jin-Myoung; Hwang, Taesoon; Kim, Duho
  • Scientific Reports, Vol. 7, Issue 1
  • DOI: 10.1038/srep39669

Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi 0.8 Co 0.15 Al 0.05 O 2
journal, June 2017


Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials
journal, March 2018


Probing electrical degradation of cathode materials for lithium-ion batteries with nanoscale resolution
journal, July 2018


STEM characterization for lithium-ion battery cathode materials
journal, February 2012


Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials
journal, April 2018


Modeling Diffusion-Induced Stress in Li-Ion Cells with Porous Electrodes
journal, January 2010

  • Christensen, Jake
  • Journal of The Electrochemical Society, Vol. 157, Issue 3, p. A366-A380
  • DOI: 10.1149/1.3269995

Stress generation and fracture in lithium insertion materials
journal, March 2006


Evolution of stress within a spherical insertion electrode particle under potentiostatic and galvanostatic operation
journal, May 2009


“Electrochemical Shock” of Intercalation Electrodes: A Fracture Mechanics Analysis
journal, January 2010

  • Woodford, William H.; Chiang, Yet-Ming; Carter, W. Craig
  • Journal of The Electrochemical Society, Vol. 157, Issue 10
  • DOI: 10.1149/1.3464773

Failure mechanism analysis of LiNi 0.88 Co 0.09 Mn 0.03 O 2 cathodes in Li-ion full cells
journal, August 2017


Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries
journal, January 2017

  • Yan, Pengfei; Zheng, Jianming; Gu, Meng
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14101

Suppressed oxygen extraction and degradation of LiNi x Mn y Co z O2 cathodes at high charge cut-off voltages
journal, September 2017


Post mortem analysis of fatigue mechanisms in LiNi0.8Co0.15Al0.05O2 – LiNi0.5Co0.2Mn0.3O2 – LiMn2O4/graphite lithium ion batteries
journal, September 2016


Chemomechanical interplay of layered cathode materials undergoing fast charging in lithium batteries
journal, November 2018


High-Energy Ni-Rich Li[Ni x Co y Mn 1 –x–y ]O 2 Cathodes via Compositional Partitioning for Next-Generation Electric Vehicles
journal, November 2017


Capacity fading behavior of Ni-rich layered cathode materials in Li-ion full cells
journal, December 2016


Structural Origin of Overcharge-Induced Thermal Instability of Ni-Containing Layered-Cathodes for High-Energy-Density Lithium Batteries
journal, September 2011

  • Wu, Lijun; Nam, Kyung-Wan; Wang, Xiaojian
  • Chemistry of Materials, Vol. 23, Issue 17
  • DOI: 10.1021/cm201452q

Correlating Structural Changes and Gas Evolution during the Thermal Decomposition of Charged Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials
journal, January 2013

  • Bak, Seong-Min; Nam, Kyung-Wan; Chang, Wonyoung
  • Chemistry of Materials, Vol. 25, Issue 3
  • DOI: 10.1021/cm303096e

Mechanism of anodic cleavage of benzyl ethers
journal, May 1980

  • Boyd, Jean W.; Schmalzl, Paul W.; Miller, Larry L.
  • Journal of the American Chemical Society, Vol. 102, Issue 11
  • DOI: 10.1021/ja00531a030

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries
journal, February 2017


In Situ X-Ray Absorption Studies of a High-Rate LiNi[sub 0.85]Co[sub 0.15]O[sub 2] Cathode Material
journal, January 2000

  • Balasubramanian, M.; Sun, X.; Yang, X. Q.
  • Journal of The Electrochemical Society, Vol. 147, Issue 8
  • DOI: 10.1149/1.1393624

A study of room-temperature LixMn1.5Ni0.5O4 solid solutions
journal, January 2015

  • Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08027

Controlling side reactions and self-discharge in high-voltage spinel cathodes: the critical role of surface crystallographic facets
journal, January 2015

  • Kuppan, Saravanan; Duncan, Hugues; Chen, Guoying
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 39
  • DOI: 10.1039/C5CP04899K

Profiling the nanoscale gradient in stoichiometric layered cathode particles for lithium-ion batteries
journal, January 2014

  • Lin, Feng; Nordlund, Dennis; Markus, Isaac M.
  • Energy & Environmental Science, Vol. 7, Issue 9
  • DOI: 10.1039/C4EE01400F

Investigation of Changes in the Surface Structure of Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials Induced by the Initial Charge
journal, December 2013

  • Hwang, Sooyeon; Chang, Wonyoung; Kim, Seung Min
  • Chemistry of Materials, Vol. 26, Issue 2
  • DOI: 10.1021/cm403332s

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014

  • Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4529

High performance PEO-based polymer electrolytes and their application in rechargeable lithium polymer batteries
journal, August 2007


Mesoscale Battery Science: The Behavior of Electrode Particles Caught on a Multispectral X-ray Camera
journal, June 2018


TXM-Wizard : a program for advanced data collection and evaluation in full-field transmission X-ray microscopy
journal, January 2012

  • Liu, Yijin; Meirer, Florian; Williams, Phillip A.
  • Journal of Synchrotron Radiation, Vol. 19, Issue 2
  • DOI: 10.1107/S0909049511049144

Three-dimensional imaging of chemical phase transformations at the nanoscale with full-field transmission X-ray microscopy
journal, July 2011

  • Meirer, Florian; Cabana, Jordi; Liu, Yijin
  • Journal of Synchrotron Radiation, Vol. 18, Issue 5
  • DOI: 10.1107/S0909049511019364

Nanoscale elemental sensitivity study of Nd 2 Fe 14 B using absorption correlation tomography : Nanoscale Elemental Sensitivity Study of N
journal, August 2013

  • Kao, Thomas L.; Shi, Crystal Y.; Wang, Junyue
  • Microscopy Research and Technique, Vol. 76, Issue 11
  • DOI: 10.1002/jemt.22273

Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy
journal, February 2017

  • Kuppan, Saravanan; Xu, Yahong; Liu, Yijin
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14309

Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries
journal, January 2018

  • Tsai, Ping-Chun; Wen, Bohua; Wolfman, Mark
  • Energy & Environmental Science, Vol. 11, Issue 4
  • DOI: 10.1039/C8EE00001H

Formation of an Anti-Core–Shell Structure in Layered Oxide Cathodes for Li-Ion Batteries
journal, October 2017


Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li 1 - x Co 1/3 Ni 1/3 Mn 1/3 O 2 Electrode System by Combination of Soft and Hard X-ray Absorption Spectroscopy
journal, December 2005

  • Yoon, Won-Sub; Balasubramanian, Mahalingam; Chung, Kyung Yoon
  • Journal of the American Chemical Society, Vol. 127, Issue 49
  • DOI: 10.1021/ja0530568

Structural and Electrochemical Investigation of Li(Ni[sub 0.4]Co[sub 0.15]Al[sub 0.05]Mn[sub 0.4])O[sub 2] Cathode Material
journal, January 2010

  • Rumble, C.; Conry, T. E.; Doeff, Marca
  • Journal of The Electrochemical Society, Vol. 157, Issue 12
  • DOI: 10.1149/1.3494211

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

Single-Crystalline Particles: An Effective Way to Ameliorate the Intragranular Cracking, Thermal Stability, and Capacity Fading of the LiNi 0.6 Co 0.2 Mn 0.2 O 2 Electrodes
journal, January 2018

  • Liu, Guilong; Li, Minglu; Wu, Naiteng
  • Journal of The Electrochemical Society, Vol. 165, Issue 13
  • DOI: 10.1149/2.0491813jes

Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries
journal, May 2016

  • Mohanty, Debasish; Dahlberg, Kevin; King, David M.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep26532

Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes
journal, July 2009

  • Panday, Ashoutosh; Mullin, Scott; Gomez, Enrique D.
  • Macromolecules, Vol. 42, Issue 13
  • DOI: 10.1021/ma900451e

Simultaneous Electronic and Ionic Conduction in a Block Copolymer: Application in Lithium Battery Electrodes
journal, September 2011

  • Javier, Anna E.; Patel, Shrayesh N.; Hallinan, Daniel T.
  • Angewandte Chemie International Edition, Vol. 50, Issue 42
  • DOI: 10.1002/anie.201102953

Discharge Characteristics of Lithium Battery Electrodes with a Semiconducting Polymer Studied by Continuum Modeling and Experiment
journal, January 2014

  • Wu, Shao-Ling; Javier, Anna E.; Devaux, Didier
  • Journal of The Electrochemical Society, Vol. 161, Issue 12
  • DOI: 10.1149/2.0261412jes

Phase retrieval using polychromatic illumination for transmission X-ray microscopy
journal, January 2011

  • Liu, Yijin; Andrews, Joy C.; Wang, Junyue
  • Optics Express, Vol. 19, Issue 2
  • DOI: 10.1364/OE.19.000540

    Works referencing / citing this record:

    Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies
    journal, December 2019

    • Liang, Longwei; Zhang, Wenheng; Zhao, Fei
    • Advanced Materials Interfaces, Vol. 7, Issue 3
    • DOI: 10.1002/admi.201901749

    Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials
    journal, January 2020


    Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries
    journal, January 2020

    • Teichert, Philipp; Eshetu, Gebrekidan Gebresilassie; Jahnke, Hannes
    • Batteries, Vol. 6, Issue 1
    • DOI: 10.3390/batteries6010008

    Long-term chemothermal stability of delithiated NCA in polymer solid-state batteries
    journal, January 2019

    • Besli, Münir M.; Usubelli, Camille; Metzger, Michael
    • Journal of Materials Chemistry A, Vol. 7, Issue 47
    • DOI: 10.1039/c9ta11103d