Facet-Dependent Ni Segregation in a Micron-Sized Single-Crystal Li1.2Ni0.2Mn0.6O2 Cathode

Zuo, Peng; Wang, Faxing; Chen, Guoying; Wang, Chongmin

doi:10.1021/acsami.4c02885

Facet-Dependent Ni Segregation in a Micron-Sized Single-Crystal Li_1.2Ni_0.2Mn_0.6O₂ Cathode

Journal Article · Tue Apr 23 00:00:00 EDT 2024 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.4c02885· OSTI ID:2447358

^[1]; Wang, Faxing ^[2]; ^[2]; ^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Elemental surface segregation in cathode materials is critical for determining the phase and interfacial reaction between electrode and electrolyte, which consequently affects the electrochemical properties. Single-crystal cathode of Li_1.2Ni_0.2Mn_0.6O₂ and Li_1.2Ni_0.2Mn_0.6O_1.95F_0.05 with an octahedral morphology of (102) and (003) dominated facets have been manifested to show enhanced electrochemical properties. However, the surface structural features of such single crystals have not been investigated. Herein, using scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, and electron energy loss spectroscopy, we probe the elemental surface segregation characteristics in these single-crystal cathode. We reveal that Ni surface segregation shows dependence on the crystal facet such that it occurs on crystal facets with a mix of cations and anions, but not on the facets with only cations or anions. Furthermore, facet-dependent surface reconstructions are observed, featuring a spinel-like structure at the Ni-rich facet but rock-salt structure at the facet without Ni segregation. The commonly known Mn reduction appears at the single crystal surfaces, more pronounced at the facet without Ni segregation. We further reveal that fluorination leads to the stabilization of surface oxygens. In conclusion, this study provides detailed structural and chemical information about the facet-dependent Ni surface segregation and the resulted phase formation in the rather less explored micron-sized octahedral Li_1.2Ni_0.2Mn_0.6O₂ and Li_1.2Ni_0.2Mn_0.6O_1.95F_0.05 single crystals, which is key to further exploration of electrochemical properties of cathode in the form of micro-sized single crystal.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2447358

Report Number(s):: PNNL-SA--195120

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 18 Vol. 16; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (42)

Fluorination‐Enhanced Surface Stability of Cation‐Disordered Rocksalt Cathodes for Li‐Ion Batteries Li, Linze; Lun, Zhengyan; Chen, Dongchang Advanced Functional Materials, Vol. 31, Issue 25 https://doi.org/10.1002/adfm.202101888	journal	April 2021
Direct Visualization of the Reversible O ²⁻ /O ⁻ Redox Process in Li-Rich Cathode Materials Li, Xiang; Qiao, Yu; Guo, Shaohua Advanced Materials, Vol. 30, Issue 14 https://doi.org/10.1002/adma.201705197	journal	February 2018
Fluorination‐Enhanced Surface Stability of Disordered Rocksalt Cathodes Li, Linze; Ahn, Juhyeon; Yue, Yuan Advanced Materials, Vol. 34, Issue 12 https://doi.org/10.1002/adma.202106256	journal	February 2022
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
Fluorination of Lithium-Excess Transition Metal Oxide Cathode Materials Richards, William D.; Dacek, Stephen T.; Kitchaev, Daniil A. Advanced Energy Materials, Vol. 8, Issue 5 https://doi.org/10.1002/aenm.201701533	journal	October 2017
Electron energy levels determining cathode electrolyte interphase formation Zhang, Zhengfeng; Qin, Changdong; Cheng, Xiaopeng Electron, Vol. 1, Issue 2 https://doi.org/10.1002/elt2.9	journal	October 2023
Single‐Crystal LiNi _x Mn _y Co ₁₋ _x ₋ _y O ₂ Cathodes for Extreme Fast Charging Lu, Yanying; Zhu, Tianyu; McShane, Eric Small, Vol. 18, Issue 12 https://doi.org/10.1002/smll.202105833	journal	January 2022
Synthesis and structural characterization of the normal spinel Li[Ni2]O4 Thomas, M. G. S. R.; David, W. I. F.; Goodenough, J. B. Materials Research Bulletin, Vol. 20, Issue 10 https://doi.org/10.1016/0025-5408(85)90087-X	journal	October 1985
Conditions and reasons for incoherent imaging in STEM Hartel, P.; Rose, H.; Dinges, C. Ultramicroscopy, Vol. 63, Issue 2 https://doi.org/10.1016/0304-3991(96)00020-4	journal	June 1996
The significance of the Li₂MnO₃ component in ‘composite’ xLi₂MnO₃·(1−x)LiMn_0.5Ni_0.5O₂ electrodes Johnson, C. S.; Kim, J-S.; Lefief, C. Electrochemistry Communications, Vol. 6, Issue 10, p. 1085-1091 https://doi.org/10.1016/j.elecom.2004.08.002	journal	October 2004
Single-crystal nickel-rich layered-oxide battery cathode materials: synthesis, electrochemistry, and intra-granular fracture Qian, Guannan; Zhang, Youtian; Li, Linsen Energy Storage Materials, Vol. 27 https://doi.org/10.1016/j.ensm.2020.01.027	journal	May 2020
Single crystal cathodes enabling high-performance all-solid-state lithium-ion batteries Wang, Changhong; Yu, Ruizhi; Hwang, Sooyeon Energy Storage Materials, Vol. 30 https://doi.org/10.1016/j.ensm.2020.05.007	journal	September 2020
Single-crystal Li-rich layered cathodes with suppressed voltage decay by double-layer interface engineering Zeng, Weihao; Liu, Fang; Yang, Jinlong Energy Storage Materials, Vol. 54 https://doi.org/10.1016/j.ensm.2022.11.016	journal	January 2023
NMR evidence of LiF coating rather than fluorine substitution in Li(Ni0.425Mn0.425Co0.15)O2 Ménétrier, M.; Bains, J.; Croguennec, L. Journal of Solid State Chemistry, Vol. 181, Issue 12 https://doi.org/10.1016/j.jssc.2008.09.002	journal	December 2008
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
High-Voltage “Single-Crystal” Cathode Materials for Lithium-Ion Batteries Wang, Yinzhong; Wang, Errui; Zhang, Xu Energy & Fuels, Vol. 35, Issue 3 https://doi.org/10.1021/acs.energyfuels.0c03608	journal	January 2021
Operando EPR for Simultaneous Monitoring of Anionic and Cationic Redox Processes in Li-Rich Metal Oxide Cathodes Tang, Mingxue; Dalzini, Annalisa; Li, Xiang The Journal of Physical Chemistry Letters, Vol. 8, Issue 17 https://doi.org/10.1021/acs.jpclett.7b01425	journal	August 2017
Hidden Subsurface Reconstruction and Its Atomic Origins in Layered Oxide Cathodes Li, Linze; Self, Ethan C.; Darbar, Devendrasinh Nano Letters, Vol. 20, Issue 4 https://doi.org/10.1021/acs.nanolett.0c00380	journal	March 2020
Facet-Dependent Thermal Instability in LiCoO ₂ Sharifi-Asl, Soroosh; Soto, Fernando A.; Nie, Anmin Nano Letters, Vol. 17, Issue 4 https://doi.org/10.1021/acs.nanolett.6b04502	journal	March 2017
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
Fluorination Induced the Surface Segregation of High Voltage Spinel on Lithium-Rich Layered Cathodes for Enhanced Rate Capability in Lithium Ion Batteries Jin, Yi-Chun; Duh, Jenq-Gong ACS Applied Materials & Interfaces, Vol. 8, Issue 6 https://doi.org/10.1021/acsami.5b10759	journal	February 2016
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
Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni_0.2Li_0.2Mn_0.6]O₂ Armstrong, A. Robert; Holzapfel, Michael; Novák, Petr Journal of the American Chemical Society, Vol. 128, Issue 26 https://doi.org/10.1021/ja062027+	journal	June 2006
Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li _0.2 Ni _0.2 Mn _0.6 ]O ₂ Luo, Kun; Roberts, Matthew R.; Guerrini, Niccoló Journal of the American Chemical Society, Vol. 138, Issue 35 https://doi.org/10.1021/jacs.6b05111	journal	August 2016
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
Mitigating Voltage Fade in Cathode Materials by Improving the Atomic Level Uniformity of Elemental Distribution Zheng, Jianming; Gu, Meng; Genc, Arda Nano Letters, Vol. 14, Issue 5 https://doi.org/10.1021/nl500486y	journal	April 2014
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
Facet-Dependent Disorder in Pristine High-Voltage Lithium–Manganese-Rich Cathode Material Dixit, Hemant; Zhou, Wu; Idrobo, Juan-Carlos ACS Nano, Vol. 8, Issue 12 https://doi.org/10.1021/nn505740v	journal	November 2014
Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9711	journal	October 2015
Eutectic salt-assisted planetary centrifugal deagglomeration for single-crystalline cathode synthesis Yoon, Moonsu; Dong, Yanhao; Huang, Yimeng Nature Energy, Vol. 8, Issue 5 https://doi.org/10.1038/s41560-023-01233-8	journal	March 2023
Single-crystal based studies for correlating the properties and high-voltage performance of Li[Ni _x Mn _y Co _1−x−y ]O ₂ cathodes Zhu, Jian; Chen, Guoying Journal of Materials Chemistry A, Vol. 7, Issue 10 https://doi.org/10.1039/C8TA10329A	journal	January 2019
Strain-driven surface reconstruction and cation segregation in layered Li(Ni _1−x−y Mn _x Co _y )O ₂ (NMC) cathode materials Garcia, Juan C.; Bareño, Javier; Chen, Guoying Physical Chemistry Chemical Physics, Vol. 22, Issue 42 https://doi.org/10.1039/D0CP03942J	journal	January 2020
Improving LiNiO₂ cathode performance through particle design and optimization Kim, Minkyung; Zou, Lianfeng; Son, Seoung-Bum Journal of Materials Chemistry A, Vol. 10, Issue 24 https://doi.org/10.1039/D2TA02492F	journal	January 2022
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode Bi, Yujing; Tao, Jinhui; Wu, Yuqin Science, Vol. 370, Issue 6522 https://doi.org/10.1126/science.abc3167	journal	December 2020
Preferred Orientation of Polycrystalline LiCoO[sub 2] Films Bates, J. B.; Dudney, N. J.; Neudecker, B. J. Journal of The Electrochemical Society, Vol. 147, Issue 1 https://doi.org/10.1149/1.1393157	journal	January 2000
Synthesis of “Li[sub 1.1](Ni[sub 0.425]Mn[sub 0.425]Co[sub 0.15])[sub 0.9]O[sub 1.8]F[sub 0.2]” Materials by Different Routes: Is There Fluorine Substitution for Oxygen? Croguennec, L.; Bains, J.; Ménétrier, M. Journal of The Electrochemical Society, Vol. 156, Issue 5 https://doi.org/10.1149/1.3080659	journal	January 2009
Synthesis of Single Crystal LiNi _0.5 Mn _0.3 Co _0.2 O ₂ for Lithium Ion Batteries Li, Jing; Li, Hongyang; Stone, Will Journal of The Electrochemical Society, Vol. 164, Issue 14 https://doi.org/10.1149/2.0401714jes	journal	January 2017
Comparison of Single Crystal and Polycrystalline LiNi _0.5 Mn _0.3 Co _0.2 O ₂ Positive Electrode Materials for High Voltage Li-Ion Cells Li, Jing; Cameron, Andrew R.; Li, Hongyang Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.0991707jes	journal	January 2017
Determination of manganese valence states in (Mn3+, Mn4+) minerals by electron energy-loss spectroscopy Zhang, S.; Livi, K. J. T.; Gaillot, A. -C. American Mineralogist, Vol. 95, Issue 11-12 https://doi.org/10.2138/am.2010.3468	journal	November 2010
A Critical Review of Single-Crystal LiNi _x Mn _y Co _{1- x - y} O ₂ Cathode Materials Liu, Wenbo; Li, Dongyang; Liu, Yongqiang Renewables, Vol. 2, Issue 1 https://doi.org/10.31635/renewables.024.202300044	journal	February 2024

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Facet-Dependent Ni Segregation in a Micron-Sized Single-Crystal Li1.2Ni0.2Mn0.6O2 Cathode

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Facet-Dependent Ni Segregation in a Micron-Sized Single-Crystal Li_1.2Ni_0.2Mn_0.6O₂ Cathode