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

Journal Article · · Energy & Environmental Science
DOI:https://doi.org/10.1039/C7EE02443F· OSTI ID:1420189
ORCiD logo [1];  [2];  [3];  [2];  [2];  [4];  [5];  [5];  [5]
  1. Energy Storage and Distributed Resources Division; Lawrence Berkeley National Laboratory; Berkeley; USA; SuperSTEM
  2. SuperSTEM; Daresbury; UK
  3. National Center for Electron Microscopy; Molecular Foundry; Lawrence Berkeley National Laboratory; Berkeley; USA
  4. Erich Schmid Institute of Materials Science; Austrian Academy of Sciences; Leoben; Austria
  5. Envia Systems; Newark; USA
+ Show Author Affiliations

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); Engineering and Physical Science Research Council (EFRC)
Grant/Contract Number:
EE0006443; AC02-05CH11231
OSTI ID:
1420189
Alternate ID(s):
OSTI ID: 1465456
Journal Information:
Energy & Environmental Science, Journal Name: Energy & Environmental Science Vol. 11 Journal Issue: 4; ISSN 1754-5692
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science

References (32)

The role of composition in the atomic structure, oxygen loss, and capacity of layered Li–Mn–Ni oxide cathodes journal January 2014
Conflicting Roles of Nickel in Controlling Cathode Performance in Lithium Ion Batteries journal September 2012
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
Understanding the Anomalous Capacity of Li / Li [ NixLi ( 1 / 3 − 2x / 3 ) Mn ( 2 / 3 − x / 3 ) ]  O2 Cells Using In Situ X-Ray Diffraction and Electrochemical Studies journal January 2002
Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance journal January 2017
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 ≤ x ≤ 1 / 2 ) Compounds journal May 2005
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal March 2014
Facet-Dependent Disorder in Pristine High-Voltage Lithium–Manganese-Rich Cathode Material journal November 2014
Ni and Co Segregations on Selective Surface Facets and Rational Design of Layered Lithium Transition-Metal Oxide Cathodes journal February 2016
Advanced Computing in Electron Microscopy book January 2010
Reinvestigation of Li 2 MnO 3 Structure: Electron Diffraction and High Resolution TEM journal September 2009
Study of Structure of Li- and Mn-rich Transition Metal Oxides Using 4D-STEM journal July 2016
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
Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries journal January 2016
Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes journal August 2015
Evolution of Lattice Structure and Chemical Composition of the Surface Reconstruction Layer in Li 1.2 Ni 0.2 Mn 0.6 O 2 Cathode Material for Lithium Ion Batteries journal December 2014
Effect of Synthesis Conditions on the First Charge and Reversible Capacities of Lithium-Rich Layered Oxide Cathodes journal July 2013
Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides journal October 2015
Understanding the Role of Lithium Content on the Structure and Capacity of Lithium-Rich Layered Oxides by Aberration-Corrected STEM, D-STEM, and EDS journal July 2012
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
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
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
Atomic Structure of a Lithium-Rich Layered Oxide Material for Lithium-Ion Batteries: Evidence of a Solid Solution journal August 2011
Recording and Using 4D-STEM Datasets in Materials Science journal August 2014
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

Figures / Tables (10)

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