Strain-driven surface reconstruction and cation segregation in layered Li(Ni1–x–yMnxCoy)O2 (NMC) cathode materials

Garcia, Juan C.; Bareño, Javier; Chen, Guoying; Croy, Jason R.; Iddir, Hakim

doi:10.1039/d0cp03942j

Strain-driven surface reconstruction and cation segregation in layered Li(Ni_1–x–yMn_xCo_y)O₂ (NMC) cathode materials

Journal Article · Wed Oct 14 00:00:00 EDT 2020 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d0cp03942j· OSTI ID:1775102

Garcia, Juan C. ^[1]; Bareño, Javier ^[1]; ^[2]; Croy, Jason R. ^[1]; ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The composition, structure and phase transformations occurring on cathode surfaces greatly affect the performance of Li-ion batteries. Li-Ion diffusion and surface–electrolyte interaction are two major phenomena that impact the capacity and cell impedance. The effects of surface reconstruction (SR) of cathode materials on the performance of Li-ion batteries are of current interest. However, the origin and evolution of the SR are still not well understood. In this work, density functional theory (DFT) calculations are used to investigate the processes taking place during surface segregation and reconstruction. Facet dependent segregation was found in Li(Ni_1–x–yMn_xCo_y)O₂ (NMC) cathodes. Specifically, Co tends to segregate to the (104) surface of the primary particles within the transition metal layer, while Ni ions tend to segregate to the (012) surface in the Li layer, forming a SR. Experimental evidence shows the SR to be epitaxial with the bulk of the as-synthesized material, and the new SR phase is pinned to the NMC unit cell leading to a strained SR. Here, we demonstrate that strain can stabilize a spinel structure of the SR layers. Understanding the effects of surface strain opens a new avenue for the design of cathode materials with enhanced surface properties.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Laboratory Computing Resource Center (LCRC); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1775102

Alternate ID(s):: OSTI ID: 1682363

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 42 Vol. 22; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Understanding the Degradation Mechanisms of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ Cathode Material in Lithium Ion Batteries Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun Advanced Energy Materials, Vol. 4, Issue 1 https://doi.org/10.1002/aenm.201300787	journal	August 2013
Ni and Co Segregations on Selective Surface Facets and Rational Design of Layered Lithium Transition-Metal Oxide Cathodes Yan, Pengfei; Zheng, Jianming; Zheng, Jiaxin Advanced Energy Materials, Vol. 6, Issue 9 https://doi.org/10.1002/aenm.201502455	journal	February 2016
Theory of surface enrichment in disordered monophasic binary alloys. Numerical computations for Ag-Au alloys Vansanten, R. Journal of Catalysis, Vol. 34, Issue 1 https://doi.org/10.1016/0021-9517(74)90004-9	journal	July 1974
Entropy of segregation of isovalent impurity cations at the surface of an ionic crystal: MgO(100)Ca2+ Masri, P.; Tasker, P. W.; Hoare, J. P. Surface Science, Vol. 173, Issue 2-3 https://doi.org/10.1016/0039-6028(86)90201-3	journal	August 1986
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Surface element segregation and electrical conductivity of lithium layered transition-metal oxide cathode materials Li, Guohua; Li, Qi; Li, Liping Applied Surface Science, Vol. 427 https://doi.org/10.1016/j.apsusc.2017.07.275	journal	January 2018
Surface segregation in Cr-Mn-Fe-Co-Ni high entropy alloys Ferrari, Alberto; Körmann, Fritz Applied Surface Science, Vol. 533 https://doi.org/10.1016/j.apsusc.2020.147471	journal	December 2020
Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration Croy, Jason R.; Garcia, Juan C.; Iddir, Hakim Journal of Power Sources, Vol. 471 https://doi.org/10.1016/j.jpowsour.2020.228335	journal	September 2020
Insight into the origin of lithium/nickel ions exchange in layered Li(NixMnyCoz)O2 cathode materials Xiao, Yinguo; Liu, Tongchao; Liu, Jiajie Nano Energy, Vol. 49 https://doi.org/10.1016/j.nanoen.2018.04.020	journal	July 2018
A new insight into continuous performance decay mechanism of Ni-rich layered oxide cathode for high energy lithium ion batteries Lin, Qingyun; Guan, Wenhao; Meng, Jie Nano Energy, Vol. 54 https://doi.org/10.1016/j.nanoen.2018.09.066	journal	December 2018
Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds Tornheim, Adam; Sharifi-Asl, Soroosh; Garcia, Juan C. Nano Energy, Vol. 55 https://doi.org/10.1016/j.nanoen.2018.10.065	journal	January 2019
On the evolution of stresses due to lattice misfit at a Ni-superalloy and YSZ interface Bhattacharyya, Abir; Maurice, David Surfaces and Interfaces, Vol. 12 https://doi.org/10.1016/j.surfin.2018.05.007	journal	September 2018
Atomic-Resolution Visualization of Distinctive Chemical Mixing Behavior of Ni, Co, and Mn with Li in Layered Lithium Transition-Metal Oxide Cathode Materials Yan, Pengfei; Zheng, Jianming; Lv, Dongping Chemistry of Materials, Vol. 27, Issue 15 https://doi.org/10.1021/acs.chemmater.5b02016	journal	July 2015
Surface Reconstruction in Li-Rich Layered Oxides of Li-Ion Batteries Jarvis, Karalee; Wang, Chih-Chieh; Varela, Maria Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b00120	journal	September 2017
First-Principles Simulation of the (Li–Ni–Vacancy)O Phase Diagram and Its Relevance for the Surface Phases in Ni-Rich Li-Ion Cathode Materials Das, Hena; Urban, Alexander; Huang, Wenxuan Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b02546	journal	September 2017
Facet-Dependent Rock-Salt Reconstruction on the Surface of Layered Oxide Cathodes Zhang, Hanlei; May, Brian M.; Serrano-Sevillano, Jon Chemistry of Materials, Vol. 30, Issue 3 https://doi.org/10.1021/acs.chemmater.7b03901	journal	January 2018
Electronic Structure and Comparative Properties of LiNi _x Mn _y Co _z O ₂ Cathode Materials Sun, Hong; Zhao, Kejie The Journal of Physical Chemistry C, Vol. 121, Issue 11 https://doi.org/10.1021/acs.jpcc.7b00810	journal	March 2017
Surface Structure, Morphology, and Stability of Li(Ni _1/3 Mn _1/3 Co _1/3 )O ₂ Cathode Material Garcia, Juan C.; Bareño, Javier; Yan, Jianhua The Journal of Physical Chemistry C, Vol. 121, Issue 15 https://doi.org/10.1021/acs.jpcc.7b00896	journal	April 2017
Chemical “Pickling” of Phosphite Additives Mitigates Impedance Rise in Li Ion Batteries Peebles, Cameron; Garcia, Juan; Tornheim, Adam P. The Journal of Physical Chemistry C, Vol. 122, Issue 18 https://doi.org/10.1021/acs.jpcc.8b02056	journal	April 2018
Atomic-Level Understanding of Surface Reconstruction Based on Li[Ni _x Mn _y Co _{1– x – y} ]O ₂ Single-Crystal Studies Zhu, Jian; Sharifi-Asl, Soroosh; Garcia, Juan C. ACS Applied Energy Materials, Vol. 3, Issue 5 https://doi.org/10.1021/acsaem.0c00411	journal	April 2020
Strain-Driven Mn-Reorganization in Overlithiated Li _x Mn ₂ O ₄ Epitaxial Thin-Film Electrodes Chen, Xiao; Vörös, Márton; Garcia, Juan C. ACS Applied Energy Materials, Vol. 1, Issue 6 https://doi.org/10.1021/acsaem.8b00270	journal	May 2018
From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes Han, Binghong; Key, Baris; Lapidus, Saul H. ACS Applied Materials & Interfaces, Vol. 9, Issue 47 https://doi.org/10.1021/acsami.7b13597	journal	November 2017
Nanoscale Phase Separation, Cation Ordering, and Surface Chemistry in Pristine Li _1.2 Ni _0.2 Mn _0.6 O ₂ for Li-Ion Batteries Gu, Meng; Genc, Arda; Belharouak, Ilias Chemistry of Materials, Vol. 25, Issue 11 https://doi.org/10.1021/cm4009392	journal	May 2013
Electronic Spin Transition in Nanosize Stoichiometric Lithium Cobalt Oxide Qian, Danna; Hinuma, Yoyo; Chen, Hailong Journal of the American Chemical Society, Vol. 134, Issue 14 https://doi.org/10.1021/ja300868e	journal	March 2012
Conflicting Roles of Nickel in Controlling Cathode Performance in Lithium Ion Batteries Gu, Meng; Belharouak, Ilias; Genc, Arda Nano Letters, Vol. 12, Issue 10 https://doi.org/10.1021/nl302249v	journal	September 2012
First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries Boulineau, Adrien; Simonin, Loïc; Colin, Jean-François Nano Letters, Vol. 13, Issue 8 https://doi.org/10.1021/nl4019275	journal	July 2013
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 Yan, Pengfei; Nie, Anmin; Zheng, Jianming Nano Letters, Vol. 15, Issue 1 https://doi.org/10.1021/nl5038598	journal	December 2014
Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries Gu, Meng; Belharouak, Ilias; Zheng, Jianming ACS Nano, Vol. 7, Issue 1 https://doi.org/10.1021/nn305065u	journal	December 2012
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries Lin, Feng; Markus, Isaac M.; Nordlund, Dennis Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4529	journal	March 2014
Elucidation of the surface characteristics and electrochemistry of high-performance LiNiO ₂ Xu, Jing; Lin, Feng; Nordlund, Dennis Chemical Communications, Vol. 52, Issue 22 https://doi.org/10.1039/C5CC09434H	journal	January 2016
Lithium transport through lithium-ion battery cathode coatings Xu, Shenzhen; Jacobs, Ryan M.; Nguyen, Ha M. Journal of Materials Chemistry A, Vol. 3, Issue 33 https://doi.org/10.1039/C5TA01664A	journal	January 2015
A review of Ni-based layered oxides for rechargeable Li-ion batteries Xu, Jing; Lin, Feng; Doeff, Marca M. Journal of Materials Chemistry A, Vol. 5, Issue 3 https://doi.org/10.1039/C6TA07991A	journal	January 2017
Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study Xu, Bo; Fell, Christopher R.; Chi, Miaofang Energy & Environmental Science, Vol. 4, Issue 6 https://doi.org/10.1039/c1ee01131f	journal	January 2011
Influence of the exchange screening parameter on the performance of screened hybrid functionals Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F. The Journal of Chemical Physics, Vol. 125, Issue 22 https://doi.org/10.1063/1.2404663	journal	December 2006
The stability of ionic crystal surfaces Tasker, P. W. Journal of Physics C: Solid State Physics, Vol. 12, Issue 22 https://doi.org/10.1088/0022-3719/12/22/036	journal	November 1979
The Theory of Defect Concentration in Crystals Vineyard, G. H.; Dienes, G. J. Physical Review, Vol. 93, Issue 2 https://doi.org/10.1103/PhysRev.93.265	journal	January 1954
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds Chevrier, V. L.; Ong, S. P.; Armiento, R. Physical Review B, Vol. 82, Issue 7 https://doi.org/10.1103/PhysRevB.82.075122	journal	August 2010
Energy barriers for point-defect reactions in 3 C -SiC Zheng, Ming-Jie; Swaminathan, Narasimhan; Morgan, Dane Physical Review B, Vol. 88, Issue 5 https://doi.org/10.1103/PhysRevB.88.054105	journal	August 2013
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries Kang, Kisuk; Shirley Meng, Ying; Breger, Julien Science, Vol. 311, Issue 5763, p. 977-980 https://doi.org/10.1126/science.1122152	journal	February 2006
Electrochemical Properties and Thermal Stability of Li[sub a]Ni[sub 1−x]CO[sub x]O[sub 2] Cathode Materials Cho, Jaephil; Jung, HyunSook; Park, YoungChul Journal of The Electrochemical Society, Vol. 147, Issue 1 https://doi.org/10.1149/1.1393137	journal	January 2000
Decomposition of Phosphorus-Containing Additives at a Charged NMC Surface through Potentiostatic Holds Tornheim, Adam; Garcia, Juan C.; Sahore, Ritu Journal of The Electrochemical Society, Vol. 166, Issue 4 https://doi.org/10.1149/2.0951902jes	journal	January 2019

Similar Records

Single-crystal based studies for correlating the properties and high-voltage performance of Li[Ni_xMn_yCo_1₋x₋y]O₂ cathodes

Journal Article · Sun Feb 03 19:00:00 EST 2019 · Journal of Materials Chemistry. A · OSTI ID:1515780

Surface Structure, Morphology, and Stability of Li(Ni_1/3Mn_1/3Co1/3)O₂ Cathode Material

Journal Article · Mon Mar 27 20:00:00 EDT 2017 · Journal of Physical Chemistry. C · OSTI ID:1352891

Degradation in Ni-Rich LiNi_1–x–yMn_xCo_yO₂/Graphite Batteries: Impact of Charge Voltage and Ni Content

Journal Article · Wed Apr 05 20:00:00 EDT 2023 · Journal of Physical Chemistry. C · OSTI ID:1984421

Related Subjects

25 ENERGY STORAGE

Strain-driven surface reconstruction and cation segregation in layered Li(Ni1–x–yMnxCoy)O2 (NMC) cathode materials

Citation Formats

References (44)

Similar Records

Related Subjects

Strain-driven surface reconstruction and cation segregation in layered Li(Ni_1–x–yMn_xCo_y)O₂ (NMC) cathode materials