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

Title: Effect of composition on the structure of lithium- and manganese-rich transition metal oxides

Abstract

The choice of chemical composition of lithium- and manganese-rich transition metal oxides used as cathode materials in lithium-ion batteries can significantly impact their long-term viability as storage solutions for clean energy automotive applications. Their structure has been widely debated: conflicting conclusions drawn from individual studies often considering different compositions have made it challenging to reach a consensus and inform future research. In this, complementary electron microscopy techniques over a wide range of length scales reveal the effect of lithium-to-transition metal-ratio on the surface and bulk structure of these materials. We found that decreasing the lithium-to-transition metal-ratio resulted in a significant change in terms of order and atomic-level local composition in the bulk of these cathode materials. However, throughout the composition range studied, the materials consisted solely of a monoclinic phase, with lower lithium content materials showing more chemical ordering defects. In contrast, the spinel-structured surface present on specific crystallographic facets exhibited no noticeable structural change when varying the ratio of lithium to transition metal. The structural observations from this study warrant a reexamination of commonly assumed models linking poor electrochemical performance with bulk and surface structure.

Authors:
ORCiD logo [1];  [2];  [3];  [2];  [2];  [4];  [5];  [5];  [5]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Center for Electron Microscopy, The Molecular Foundry and Energy Storage and Distributed Resources Division; SuperSTEM, Daresbury (United Kingdom)
  2. SuperSTEM, Daresbury (United Kingdom)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Center for Electron Microscopy and Molecular Foundry
  4. Austrian Academy of Sciences, Leoben (Austria). Erich Schmid Inst. of Materials Science
  5. Envia Systems, Newark, NY (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); Engineering and Physical Science Research Council (EFRC)
OSTI Identifier:
1420189
Alternate Identifier(s):
OSTI ID: 1465456
Grant/Contract Number:  
AC02-05CH11231; EE0006443
Resource Type:
Journal Article: Published Article
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 11; Journal Issue: 4; Related Information: © 2018 The Royal Society of Chemistry.; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Shukla, Alpesh Khushalchand, Ramasse, Quentin M., Ophus, Colin, Kepaptsoglou, Despoina Maria, Hage, Fredrik S., Gammer, Christoph, Bowling, Charles, Gallegos, Pedro Alejandro Hernández, and Venkatachalam, Subramanian. Effect of composition on the structure of lithium- and manganese-rich transition metal oxides. United States: N. p., 2018. Web. doi:10.1039/c7ee02443f.
Shukla, Alpesh Khushalchand, Ramasse, Quentin M., Ophus, Colin, Kepaptsoglou, Despoina Maria, Hage, Fredrik S., Gammer, Christoph, Bowling, Charles, Gallegos, Pedro Alejandro Hernández, & Venkatachalam, Subramanian. Effect of composition on the structure of lithium- and manganese-rich transition metal oxides. United States. doi:10.1039/c7ee02443f.
Shukla, Alpesh Khushalchand, Ramasse, Quentin M., Ophus, Colin, Kepaptsoglou, Despoina Maria, Hage, Fredrik S., Gammer, Christoph, Bowling, Charles, Gallegos, Pedro Alejandro Hernández, and Venkatachalam, Subramanian. Wed . "Effect of composition on the structure of lithium- and manganese-rich transition metal oxides". United States. doi:10.1039/c7ee02443f.
@article{osti_1420189,
title = {Effect of composition on the structure of lithium- and manganese-rich transition metal oxides},
author = {Shukla, Alpesh Khushalchand and Ramasse, Quentin M. and Ophus, Colin and Kepaptsoglou, Despoina Maria and Hage, Fredrik S. and Gammer, Christoph and Bowling, Charles and Gallegos, Pedro Alejandro Hernández and Venkatachalam, Subramanian},
abstractNote = {The choice of chemical composition of lithium- and manganese-rich transition metal oxides used as cathode materials in lithium-ion batteries can significantly impact their long-term viability as storage solutions for clean energy automotive applications. Their structure has been widely debated: conflicting conclusions drawn from individual studies often considering different compositions have made it challenging to reach a consensus and inform future research. In this, complementary electron microscopy techniques over a wide range of length scales reveal the effect of lithium-to-transition metal-ratio on the surface and bulk structure of these materials. We found that decreasing the lithium-to-transition metal-ratio resulted in a significant change in terms of order and atomic-level local composition in the bulk of these cathode materials. However, throughout the composition range studied, the materials consisted solely of a monoclinic phase, with lower lithium content materials showing more chemical ordering defects. In contrast, the spinel-structured surface present on specific crystallographic facets exhibited no noticeable structural change when varying the ratio of lithium to transition metal. The structural observations from this study warrant a reexamination of commonly assumed models linking poor electrochemical performance with bulk and surface structure.},
doi = {10.1039/c7ee02443f},
journal = {Energy & Environmental Science},
issn = {1754-5692},
number = 4,
volume = 11,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/c7ee02443f

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Figures / Tables:

Table 1 Table 1: Composition of LMRTMOs studied as measured using ICP-OES

Save / Share:

Works referenced in this record:

The role of composition in the atomic structure, oxygen loss, and capacity of layered Li–Mn–Ni oxide cathodes
journal, January 2014

  • Jarvis, Karalee A.; Wang, Chih-Chieh; Manthiram, Arumugam
  • J. Mater. Chem. A, Vol. 2, Issue 5
  • DOI: 10.1039/C3TA12440A

Conflicting Roles of Nickel in Controlling Cathode Performance in Lithium Ion Batteries
journal, September 2012

  • Gu, Meng; Belharouak, Ilias; Genc, Arda
  • Nano Letters, Vol. 12, Issue 10
  • DOI: 10.1021/nl302249v

Solid-State Chemistry and Electrochemistry of LiCo[sub 1∕3]Ni[sub 1∕3]Mn[sub 1∕3]O[sub 2] for Advanced Lithium-Ion Batteries
journal, January 2005

  • Yabuuchi, Naoaki; Koyama, Yukinori; Nakayama, Noriaki
  • Journal of The Electrochemical Society, Vol. 152, Issue 7
  • DOI: 10.1149/1.1924227

Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance
journal, January 2017

  • Kuppan, Saravanan; Shukla, Alpesh Khushalchand; Membreno, Daniel
  • Advanced Energy Materials, Vol. 7, Issue 11
  • DOI: 10.1002/aenm.201602010

Structural studies of Li1.2Mn0.55Ni0.15Co0.1O2 electrode material
journal, September 2016


Cation Ordering in Layered O3 Li[Ni x Li 1/3 - 2 x /3 Mn 2/ 3 - x /3 ]O 2 (0 ≤ x1 / 2 ) Compounds
journal, May 2005

  • Meng, Y. S.; Ceder, G.; Grey, C. P.
  • Chemistry of Materials, Vol. 17, Issue 9
  • DOI: 10.1021/cm047779m

Facet-Dependent Disorder in Pristine High-Voltage Lithium–Manganese-Rich Cathode Material
journal, November 2014

  • Dixit, Hemant; Zhou, Wu; Idrobo, Juan-Carlos
  • ACS Nano, Vol. 8, Issue 12
  • DOI: 10.1021/nn505740v

Ni and Co Segregations on Selective Surface Facets and Rational Design of Layered Lithium Transition-Metal Oxide Cathodes
journal, February 2016

  • Yan, Pengfei; Zheng, Jianming; Zheng, Jiaxin
  • Advanced Energy Materials, Vol. 6, Issue 9
  • DOI: 10.1002/aenm.201502455

Reinvestigation of Li 2 MnO 3 Structure: Electron Diffraction and High Resolution TEM
journal, September 2009

  • Boulineau, A.; Croguennec, L.; Delmas, C.
  • Chemistry of Materials, Vol. 21, Issue 18
  • DOI: 10.1021/cm900998n

Study of Structure of Li- and Mn-rich Transition Metal Oxides Using 4D-STEM
journal, July 2016

  • Shukla, Alpesh Khushalchand; Ophus, Colin; Gammer, Christoph
  • Microscopy and Microanalysis, Vol. 22, Issue S3
  • DOI: 10.1017/S1431927616003329

Crystalline Grain Interior Configuration Affects Lithium Migration Kinetics in Li-Rich Layered Oxide
journal, April 2016


Comments on the structural complexity of lithium-rich Li1+xM1−xO2 electrodes (M=Mn, Ni, Co) for lithium batteries
journal, September 2006

  • Thackeray, M. M.; Kang, S.-H.; Johnson, C. S.
  • Electrochemistry Communications, Vol. 8, Issue 9, p. 1531-1538
  • DOI: 10.1016/j.elecom.2006.06.030

Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries
journal, January 2016

  • Liu, Hanshuo; Bugnet, Matthieu; Tessaro, Matteo Z.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 42
  • DOI: 10.1039/C6CP05262B

Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes
journal, August 2015

  • Devaraj, A.; Gu, M.; Colby, R.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9014

Effect of Synthesis Conditions on the First Charge and Reversible Capacities of Lithium-Rich Layered Oxide Cathodes
journal, July 2013

  • Wang, Chih-Chieh; Jarvis, Karalee A.; Ferreira, Paulo J.
  • Chemistry of Materials, Vol. 25, Issue 15
  • DOI: 10.1021/cm402181f

Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides
journal, October 2015

  • Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9711

Neutron Diffraction and Magnetic Susceptibility Studies on a High-Voltage Li 1.2 Mn 0.55 Ni 0.15 Co 0.10 O 2 Lithium Ion Battery Cathode: Insight into the Crystal Structure
journal, September 2013

  • Mohanty, Debasish; Huq, Ashfia; Payzant, E. Andrew
  • Chemistry of Materials, Vol. 25, Issue 20
  • DOI: 10.1021/cm402278q

Cation ordering in the layered Li1+x(Ni0.425Mn0.425Co0.15)1−xO2 materials (x=0 and 0.12)
journal, October 2007


Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling
journal, July 2014

  • Yang, Feifei; Liu, Yijin; Martha, Surendra K.
  • Nano Letters, Vol. 14, Issue 8
  • DOI: 10.1021/nl502090z

Synthetic optimization of Li[Ni1/3Co1/3Mn1/3]O2 via co-precipitation
journal, December 2004


Li2MnO3-based composite cathodes for lithium batteries: A novel synthesis approach and new structures
journal, October 2011

  • Croy, J. R.; Kang, S.-H.; Balasubramanian, M.
  • Electrochemistry Communications, Vol. 13, Issue 10, p. 1063-1066
  • DOI: 10.1016/j.elecom.2011.06.037

Atomic Structure of a Lithium-Rich Layered Oxide Material for Lithium-Ion Batteries: Evidence of a Solid Solution
journal, August 2011

  • Jarvis, Karalee A.; Deng, Zengqiang; Allard, Lawrence F.
  • Chemistry of Materials, Vol. 23, Issue 16
  • DOI: 10.1021/cm200831c

Recording and Using 4D-STEM Datasets in Materials Science
journal, August 2014

  • Ophus, Colin; Ercius, Peter; Sarahan, Michael
  • Microscopy and Microanalysis, Vol. 20, Issue S3
  • DOI: 10.1017/S1431927614002037

Diffraction contrast imaging using virtual apertures
journal, August 2015


Enhancing the rate capability of high capacity xLi2MnO3 · (1−x)LiMO2 (M=Mn, Ni, Co) electrodes by Li–Ni–PO4 treatment
journal, April 2009


Surface structure and equilibrium particle shape of the LiMn 2 O 4 spinel from first-principles calculations
journal, February 2013


Formation of Layered–Layered Composites in the Li–Co–Mn Oxide Pseudoternary System during Slow Cooling
journal, March 2013

  • McCalla, E.; Lowartz, C. M.; Brown, C. R.
  • Chemistry of Materials, Vol. 25, Issue 6
  • DOI: 10.1021/cm304002b