DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials

Abstract

Nanoscale full-field (FF) transmission X-ray microscopy (TXM) and ensemble-averaged soft X-ray absorption spectroscopy (soft XAS) were used to investigate state-of-charge (SOC) heterogeneities in electrochemically charged or discharged and chemically oxidized samples of LiNi0.6Mn0.2Co0.2O2 cathode materials. We observed considerable and similar non-uniformities in terms of Ni oxidation states (and, by proxy, lithium distributions) for all the samples in the bulk. Therefore, the chemically delithiated samples are similar to the electrochemically charged samples in terms of mesoscale charge heterogeneity in large polycrystalline particle ensembles. However, the gradient oxidation states of transition metals on the surface, which is partly responsible for the electrode degradation mechanism known as surface reconstruction, is much less apparent in chemically delithiated samples. Chemical delithiation is extensively used in preparation of charged cathodes free of inactive components for fundamental battery studies. The surface chemistry and bulk lithium distribution of chemically delithiated samples may not accurately represent the electrochemically charged materials in a real battery. In our work, bulk and surface-sensitive characterization techniques were used to investigate the differences between chemically and electrochemically delithiated layered cathode materials. The two types of materials show similar bulk lithium distributions but distinctly different surface chemistries. The present study not only strongly implies thatmore » the electrolytic solution is an active participant in the reactions that lead to the surface reconstruction to a rock salt structure observed in layered oxide cathode materials, but also develops a chemical basis for understanding and improving charge homogeneity across the length scale of secondary particles. Both chemical and electrochemical delithiation methods lead to state-of-charge non-uniformity in the bulk of layered transition metal oxide cathode particles. Less surface reconstruction to rock salt is observed for chemically delithiated samples compared with electrochemically delithiated ones. This indicates that electrolytic solution plays a significant role in the surface reconstruction phenomenon.« less

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1548833
Alternate Identifier(s):
OSTI ID: 1601173
Grant/Contract Number:  
AC02-05CH11231; AC02-76SF00515
Resource Type:
Published Article
Journal Name:
Joule
Additional Journal Information:
Journal Name: Joule Journal Volume: 2 Journal Issue: 3; Journal ID: ISSN 2542-4351
Publisher:
Elsevier - Cell Press
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; lithium-ion battery; NMC cathode; transmission X-ray microscopy; TXM; soft X-ray absorption spectroscopy; XAS

Citation Formats

Tian, Chixia, Xu, Yahong, Nordlund, Dennis, Lin, Feng, Liu, Jin, Sun, Zhihong, Liu, Yijin, and Doeff, Marca. Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials. United States: N. p., 2018. Web. doi:10.1016/j.joule.2017.12.008.
Tian, Chixia, Xu, Yahong, Nordlund, Dennis, Lin, Feng, Liu, Jin, Sun, Zhihong, Liu, Yijin, & Doeff, Marca. Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials. United States. https://doi.org/10.1016/j.joule.2017.12.008
Tian, Chixia, Xu, Yahong, Nordlund, Dennis, Lin, Feng, Liu, Jin, Sun, Zhihong, Liu, Yijin, and Doeff, Marca. Thu . "Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials". United States. https://doi.org/10.1016/j.joule.2017.12.008.
@article{osti_1548833,
title = {Charge Heterogeneity and Surface Chemistry in Polycrystalline Cathode Materials},
author = {Tian, Chixia and Xu, Yahong and Nordlund, Dennis and Lin, Feng and Liu, Jin and Sun, Zhihong and Liu, Yijin and Doeff, Marca},
abstractNote = {Nanoscale full-field (FF) transmission X-ray microscopy (TXM) and ensemble-averaged soft X-ray absorption spectroscopy (soft XAS) were used to investigate state-of-charge (SOC) heterogeneities in electrochemically charged or discharged and chemically oxidized samples of LiNi0.6Mn0.2Co0.2O2 cathode materials. We observed considerable and similar non-uniformities in terms of Ni oxidation states (and, by proxy, lithium distributions) for all the samples in the bulk. Therefore, the chemically delithiated samples are similar to the electrochemically charged samples in terms of mesoscale charge heterogeneity in large polycrystalline particle ensembles. However, the gradient oxidation states of transition metals on the surface, which is partly responsible for the electrode degradation mechanism known as surface reconstruction, is much less apparent in chemically delithiated samples. Chemical delithiation is extensively used in preparation of charged cathodes free of inactive components for fundamental battery studies. The surface chemistry and bulk lithium distribution of chemically delithiated samples may not accurately represent the electrochemically charged materials in a real battery. In our work, bulk and surface-sensitive characterization techniques were used to investigate the differences between chemically and electrochemically delithiated layered cathode materials. The two types of materials show similar bulk lithium distributions but distinctly different surface chemistries. The present study not only strongly implies that the electrolytic solution is an active participant in the reactions that lead to the surface reconstruction to a rock salt structure observed in layered oxide cathode materials, but also develops a chemical basis for understanding and improving charge homogeneity across the length scale of secondary particles. Both chemical and electrochemical delithiation methods lead to state-of-charge non-uniformity in the bulk of layered transition metal oxide cathode particles. Less surface reconstruction to rock salt is observed for chemically delithiated samples compared with electrochemically delithiated ones. This indicates that electrolytic solution plays a significant role in the surface reconstruction phenomenon.},
doi = {10.1016/j.joule.2017.12.008},
journal = {Joule},
number = 3,
volume = 2,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.joule.2017.12.008

Citation Metrics:
Cited by: 41 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

In Situ X-Ray Absorption Study of a Layered Manganese-Chromium Oxide-Based Cathode Material
journal, January 2002

  • Balasubramanian, M.; McBreen, J.; Davidson, I. J.
  • Journal of The Electrochemical Society, Vol. 149, Issue 2
  • DOI: 10.1149/1.1431962

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Local State-of-Charge Mapping of Lithium-Ion Battery Electrodes
journal, July 2011

  • Nanda, Jagjit; Remillard, Jeffrey; O'Neill, Ann
  • Advanced Functional Materials, Vol. 21, Issue 17
  • DOI: 10.1002/adfm.201100157

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

Development of Microstrain in Aged Lithium Transition Metal Oxides
journal, June 2014

  • Lee, Eung-Ju; Chen, Zonghai; Noh, Hyung-Ju
  • Nano Letters, Vol. 14, Issue 8
  • DOI: 10.1021/nl5022859

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

High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries
journal, August 2016

  • Zhou, Yong-Ning; Yue, Ji-Li; Hu, Enyuan
  • Advanced Energy Materials, Vol. 6, Issue 21
  • DOI: 10.1002/aenm.201600597

Investigation of the Local Structure of the LiNi[sub 0.5]Mn[sub 0.5]O[sub 2] Cathode Material during Electrochemical Cycling by X-Ray Absorption and NMR Spectroscopy
journal, January 2002

  • Yoon, Won-Sub; Paik, Younkee; Yang, Xiao-Qing
  • Electrochemical and Solid-State Letters, Vol. 5, Issue 11
  • DOI: 10.1149/1.1513001

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

Reprint of “Studies of local degradation phenomena in composite cathodes for lithium-ion batteries”
journal, December 2007


Direct Observation of a Metastable Crystal Phase of Li x FePO 4 under Electrochemical Phase Transition
journal, April 2013

  • Orikasa, Yuki; Maeda, Takehiro; Koyama, Yukinori
  • Journal of the American Chemical Society, Vol. 135, Issue 15
  • DOI: 10.1021/ja312527x

Evaluation of the effective reaction zone in a composite cathode for lithium ion batteries
journal, September 2014


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

Visualization of Charge Distribution in a Lithium Battery Electrode
journal, June 2010

  • Liu, Jun; Kunz, Martin; Chen, Kai
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 14
  • DOI: 10.1021/jz100634n

Elucidation of the surface characteristics and electrochemistry of high-performance LiNiO 2
journal, January 2016

  • Xu, Jing; Lin, Feng; Nordlund, Dennis
  • Chemical Communications, Vol. 52, Issue 22
  • DOI: 10.1039/C5CC09434H

Direct in situ measurements of Li transport in Li-ion battery negative electrodes
journal, January 2010


Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles
journal, August 2016


Three Dimensional Simulation of Galvanostatic Discharge of LiCoO 2 Cathode Based on X-ray Nano-CT Images
journal, January 2012

  • Yan, Bo; Lim, Cheolwoong; Yin, Leilei
  • Journal of The Electrochemical Society, Vol. 159, Issue 10
  • DOI: 10.1149/2.024210jes

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

Spectroscopic X-ray Diffraction for Microfocus Inspection of Li-Ion Batteries
journal, August 2014

  • Murayama, Haruno; Kitada, Koji; Fukuda, Katsutoshi
  • The Journal of Physical Chemistry C, Vol. 118, Issue 36
  • DOI: 10.1021/jp5029273

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

Applications of Hard X‐ray Full‐Field Transmission X‐ray Microscopy at SSRL
conference, January 2011

  • Liu, Y.; Andrews, J. C.; Meirer, F.
  • THE 10TH INTERNATIONAL CONFERENCE ON X‐RAY MICROSCOPY, AIP Conference Proceedings
  • DOI: 10.1063/1.3625377

Intercalation Pathway in Many-Particle LiFePO 4 Electrode Revealed by Nanoscale State-of-Charge Mapping
journal, February 2013

  • Chueh, William C.; El Gabaly, Farid; Sugar, Joshua D.
  • Nano Letters, Vol. 13, Issue 3
  • DOI: 10.1021/nl3031899

Soft x-ray spectroscopy for probing electronic and chemical states of battery materials
journal, January 2016


Persistent State-of-Charge Heterogeneity in Relaxed, Partially Charged Li 1− x Ni 1/3 Co 1/3 Mn 1/3 O 2 Secondary Particles
journal, May 2016

  • Gent, William E.; Li, Yiyang; Ahn, Sungjin
  • Advanced Materials, Vol. 28, Issue 31
  • DOI: 10.1002/adma.201601273

In situ x-ray absorption spectroscopic study of the Li[Ni1∕3Co1∕3Mn1∕3]O2 cathode material
journal, June 2005

  • Deb, Aniruddha; Bergmann, Uwe; Cramer, Stephen P.
  • Journal of Applied Physics, Vol. 97, Issue 11
  • DOI: 10.1063/1.1921328

Proton Insertion into Oxide Cathodes during Chemical Delithiation
journal, January 2006

  • Choi, J.; Alvarez, E.; Arunkumar, T. A.
  • Electrochemical and Solid-State Letters, Vol. 9, Issue 5
  • DOI: 10.1149/1.2184495

Differences between L3 and L2 X-ray absorption spectra
journal, March 1995


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

Study of the LiFePO 4 /FePO 4 Two-Phase System by High-Resolution Electron Energy Loss Spectroscopy
journal, November 2006

  • Laffont, L.; Delacourt, C.; Gibot, P.
  • Chemistry of Materials, Vol. 18, Issue 23
  • DOI: 10.1021/cm0617182

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

A method for normalization of X-ray absorption spectra
journal, June 2005

  • Weng, Tsu-Chien; Waldo, Geoffrey S.; Penner-Hahn, James E.
  • Journal of Synchrotron Radiation, Vol. 12, Issue 4
  • DOI: 10.1107/S0909049504034193

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

Key electronic states in lithium battery materials probed by soft X-ray spectroscopy
journal, October 2013

  • Yang, Wanli; Liu, Xiaosong; Qiao, Ruimin
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 190
  • DOI: 10.1016/j.elspec.2013.03.008

Colorimetric Determination of Lithium Content in Electrodes of Lithium-Ion Batteries
journal, January 2008

  • Maire, Pascal; Evans, Anna; Kaiser, Hermann
  • Journal of The Electrochemical Society, Vol. 155, Issue 11
  • DOI: 10.1149/1.2979696

Visualization of Inhomogeneous Reaction Distribution in the Model LiCoO 2 Composite Electrode of Lithium Ion Batteries
journal, January 2017

  • Nakamura, Takashi; Watanabe, Toshiki; Kimura, Yuta
  • The Journal of Physical Chemistry C, Vol. 121, Issue 4
  • DOI: 10.1021/acs.jpcc.6b12133

Continuity and performance in composite electrodes
journal, August 2010


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


Visualization of the State-of-Charge Distribution in a LiCoO 2 Cathode by In Situ Raman Imaging
journal, January 2013

  • Nishi, Toshio; Nakai, Hideki; Kita, Akinori
  • Journal of The Electrochemical Society, Vol. 160, Issue 10
  • DOI: 10.1149/2.061310jes

Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes
journal, September 2014

  • Li, Yiyang; El Gabaly, Farid; Ferguson, Todd R.
  • Nature Materials, Vol. 13, Issue 12
  • DOI: 10.1038/nmat4084

A Combined Computational/Experimental Study on LiNi 1/3 Co 1/3 Mn 1/3 O 2
journal, September 2003

  • Hwang, B. J.; Tsai, Y. W.; Carlier, D.
  • Chemistry of Materials, Vol. 15, Issue 19
  • DOI: 10.1021/cm030299v

Works referencing / citing this record:

Revealing the Atomic Origin of Heterogeneous Li‐Ion Diffusion by Probing Na
journal, May 2019


Ameliorating the Interfacial Problems of Cathode and Solid‐State Electrolytes by Interface Modification of Functional Polymers
journal, July 2018

  • Wang, Li‐Ping; Zhang, Xu‐Dong; Wang, Tai‐Shan
  • Advanced Energy Materials, Vol. 8, Issue 24
  • DOI: 10.1002/aenm.201801528

Quantification of Heterogeneous Degradation in Li‐Ion Batteries
journal, May 2019


Operando Observation of Formation and Annihilation of Inhomogeneous Reaction Distribution in a Composite Electrode for Lithium‐Ion Batteries
journal, April 2019

  • Nakamura, Takashi; Chiba, Kazuki; Fakkao, Mahunnop
  • Batteries & Supercaps, Vol. 2, Issue 8
  • DOI: 10.1002/batt.201900018

Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials
journal, July 2018


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


Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes
journal, January 2020


Chemomechanical behaviors of layered cathode materials in alkali metal ion batteries
journal, January 2018

  • Xu, Zhengrui; Rahman, Muhammad Mominur; Mu, Linqin
  • Journal of Materials Chemistry A, Vol. 6, Issue 44
  • DOI: 10.1039/c8ta06875e

Thermally driven mesoscale chemomechanical interplay in Li 0.5 Ni 0.6 Mn 0.2 Co 0.2 O 2 cathode materials
journal, January 2018

  • Wei, Chenxi; Zhang, Yan; Lee, Sang-Jun
  • Journal of Materials Chemistry A, Vol. 6, Issue 45
  • DOI: 10.1039/c8ta08973f

Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles
journal, January 2019

  • Besli, Münir M.; Shukla, Alpesh Khushalchand; Wei, Chenxi
  • Journal of Materials Chemistry A, Vol. 7, Issue 20
  • DOI: 10.1039/c9ta01720h

Probing and quantifying cathode charge heterogeneity in Li ion batteries
journal, January 2019

  • Zhang, Yuxin; Yang, Zhijie; Tian, Chixia
  • Journal of Materials Chemistry A, Vol. 7, Issue 41
  • DOI: 10.1039/c9ta06977a

Laboratory-Based X-ray Absorption Spectroscopy on a Working Pouch Cell Battery at Industrially-Relevant Charging Rates
journal, January 2019

  • Jahrman, Evan P.; Pellerin, Lisa A.; Ditter, Alexander S.
  • Journal of The Electrochemical Society, Vol. 166, Issue 12
  • DOI: 10.1149/2.0721912jes

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