Tailoring the surface properties of LiNi0.4Mn0.4Co0.2O₂ by titanium substitution for improved high voltage cycling performance

Wolff-Goodrich, Silas; Xin, Huolin L.; Lin, Feng; Markus, Isaac M.; Nordlund, Dennis; Asta, Mark; Doeff, Marca M.

doi:10.1039/C5CP03228H

Tailoring the surface properties of LiNi_0.4Mn_0.4Co_0.2O₂ by titanium substitution for improved high voltage cycling performance

Journal Article · Thu Jul 30 00:00:00 EDT 2015 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/C5CP03228H· OSTI ID:1214098

Wolff-Goodrich, Silas ^[1]; Xin, Huolin L. ^[2]; Lin, Feng ^[3]; Markus, Isaac M. ^[1]; Nordlund, Dennis ^[4]; Asta, Mark ^[1]; Doeff, Marca M. ^[3]

Univ. of California, Berkeley, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Collider-Accelerator Dept.
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

The present research aims to provide insights into the behavior of LiNi0.4Mn0.4Co0.2O2 (NMC442) and LiNi_0.4Mn_0.4Co_0.2O₂ (NMC442-Ti02) cathode materials under galvanostatic cycling to high potentials, in the context of previous work which predicted that Ti-substituted variants should deliver higher capacities and exhibit better cycling stability than the unsubstituted compounds. It is found that NMC cathodes containing Ti show equivalent capacity fading but greater specific capacity than those without Ti in the same potential range. When repeatedly charged to the same degree of delithiation, NMC cathodes containing Ti showed better capacity retention. Soft x-ray absorption spectroscopy (XAS) spectra for Mn and Co indicated increased reduction in these elements for NMC cathodes without Ti, indicating that the substitution of Ti for Co acts to suppress the formation of a high impedance rock salt phase at the surface of NMC cathode particles. The results of this study validate the adoption of a facile change to existing NMC chemistries to improve cathode capacity retention under high voltage cycling conditions.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1214098

Report Number(s):: BNL--108310-2015-JA; KC0403020

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 34 Vol. 17; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (17)

LixCoO2 (0 Mizushima, K.; Jones, P. C.; Wiseman, P. J. Materials Research Bulletin, Vol. 15, Issue 6 https://doi.org/10.1016/0025-5408(80)90012-4	journal	June 1980
LixCoO2 (0 Mizushima, K.; Jones, P.; Wiseman, P. Solid State Ionics, Vol. 3-4 https://doi.org/10.1016/0167-2738(81)90077-1	journal	August 1981
Performance of layered Li(Ni1/3Co1/3Mn1/3)O2 as cathode for Li-ion batteries Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R. Electrochimica Acta, Vol. 48, Issue 2 https://doi.org/10.1016/S0013-4686(02)00593-5	journal	November 2002
Novel lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for advanced lithium-ion batteries Yabuuchi, Naoaki; Ohzuku, Tsutomu Journal of Power Sources, Vol. 119-121 https://doi.org/10.1016/S0378-7753(03)00173-3	journal	June 2003
Direct synthesis of LiNi1/3Co1/3Mn1/3O2 from nitrate precursors Patoux, Sébastien; Doeff, Marca M. Electrochemistry Communications, Vol. 6, Issue 8 https://doi.org/10.1016/j.elecom.2004.05.024	journal	August 2004
Covalent Hybrid of Spinel Manganese–Cobalt Oxide and Graphene as Advanced Oxygen Reduction Electrocatalysts Liang, Yongye; Wang, Hailiang; Zhou, Jigang Journal of the American Chemical Society, Vol. 134, Issue 7 https://doi.org/10.1021/ja210924t	journal	February 2012
The Formation Mechanism of Fluorescent Metal Complexes at the Li _x Ni _0.5 Mn _1.5 O _4−δ /Carbonate Ester Electrolyte Interface Jarry, Angélique; Gottis, Sébastien; Yu, Young-Sang Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/ja5116698	journal	March 2015
Oxygen Contribution on Li-Ion Intercalation−Deintercalation in LiCoO ₂ Investigated by O K-Edge and Co L-Edge X-ray Absorption Spectroscopy Yoon, Won-Sub; Kim, Kwang-Bum; Kim, Min-Gyu The Journal of Physical Chemistry B, Vol. 106, Issue 10 https://doi.org/10.1021/jp013735e	journal	March 2002
Multiple Scattering Calculations of Bonding and X-ray Absorption Spectroscopy of Manganese Oxides Gilbert, B.; Frazer, B. H.; Belz, A. The Journal of Physical Chemistry A, Vol. 107, Issue 16 https://doi.org/10.1021/jp021493s	journal	April 2003
Soft X-ray Absorption Spectroscopic and Raman Studies on Li _1.2 Ni _0.2 Mn _0.6 O ₂ for Lithium-Ion Batteries Hy, Sunny; Su, Wei-Nien; Chen, Jing-Ming The Journal of Physical Chemistry C, Vol. 116, Issue 48 https://doi.org/10.1021/jp309313m	journal	November 2012
Computational and Experimental Investigation of Ti Substitution in Li ₁ (Ni _x Mn _x Co _{1–2 x – y} Ti _y )O ₂ for Lithium Ion Batteries Markus, Isaac M.; Lin, Feng; Kam, Kinson C. The Journal of Physical Chemistry Letters, Vol. 5, Issue 21 https://doi.org/10.1021/jz5017526	journal	October 2014
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
Profiling the nanoscale gradient in stoichiometric layered cathode particles for lithium-ion batteries Lin, Feng; Nordlund, Dennis; Markus, Isaac M. Energy & Environmental Science, Vol. 7, Issue 9 https://doi.org/10.1039/C4EE01400F	journal	January 2014
Aliovalent titanium substitution in layered mixed Li Ni–Mn–Co oxides for lithium battery applications Kam, Kinson C.; Doeff, Marca M. Journal of Materials Chemistry, Vol. 21, Issue 27 https://doi.org/10.1039/c0jm04193a	journal	January 2011
Layered Li[Ni[sub x]Co[sub 1−2x]Mn[sub x]]O[sub 2] Cathode Materials for Lithium-Ion Batteries Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R. Electrochemical and Solid-State Letters, Vol. 4, Issue 12 https://doi.org/10.1149/1.1413182	journal	January 2001
Electrochemical and Physical Properties of Ti-Substituted Layered Nickel Manganese Cobalt Oxide (NMC) Cathode Materials Kam, Kinson C.; Mehta, Apurva; Heron, John T. Journal of The Electrochemical Society, Vol. 159, Issue 8 https://doi.org/10.1149/2.060208jes	journal	January 2012
Layered Lithium Insertion Material of LiCo _1/3 Ni _1/3 Mn _1/3 O ₂ for Lithium-Ion Batteries Ohzuku, Tsutomu; Makimura, Yoshinari Chemistry Letters, Vol. 30, Issue 7 https://doi.org/10.1246/cl.2001.642	journal	July 2001

Cited By (6)

Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries Mohanty, Debasish; Dahlberg, Kevin; King, David M. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep26532	journal	May 2016
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
Electrospun Nb-doped LiNi _0.4 Co _0.2 Mn _0.4 O ₂ nanobelts for lithium-ion batteries Lv, Congjie; Peng, Yi; Yang, Jing Inorganic Chemistry Frontiers, Vol. 5, Issue 5 https://doi.org/10.1039/c7qi00811b	journal	January 2018
Empowering multicomponent cathode materials for sodium ion batteries by exploring three-dimensional compositional heterogeneities Rahman, Muhammad Mominur; Xu, Yahong; Cheng, Hao Energy & Environmental Science, Vol. 11, Issue 9 https://doi.org/10.1039/c8ee00309b	journal	January 2018
Chemomechanical behaviors of layered cathode materials in alkali metal ion batteries Xu, Zhengrui; Rahman, Muhammad Mominur; Mu, Linqin Journal of Materials Chemistry A, Vol. 6, Issue 44 https://doi.org/10.1039/c8ta06875e	journal	January 2018
Depth-Dependent Redox Behavior of LiNi _0.6 Mn _0.2 Co _0.2 O ₂ Tian, Chixia; Nordlund, Dennis; Xin, Huolin L. Journal of The Electrochemical Society, Vol. 165, Issue 3 https://doi.org/10.1149/2.1021803jes	journal	January 2018

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