Stabilizing high-Ni cathodes with gradient surface Ti-enrichment

Zhu, Wenchang; Zhu, Xiaotian; Qi, Jizhen; Yao, Junyi; Shen, Yanbin; Cheng, Guanjian; Huang, Xue; Yang, Shiqi; Zhang, Hao; Chiang, Chao-Lung; Lin, Yan-Gu; Bai, Jianming; Yin, Wanjian; Gao, Lijun; Chen, Liwei; Wang, Feng; Zhao, Jianqing

doi:10.1016/j.cej.2024.151208

Title: Stabilizing high-Ni cathodes with gradient surface Ti-enrichment

Journal Article · 15 April 2024 · Chemical Engineering Journal

DOI: https://doi.org/10.1016/j.cej.2024.151208 · OSTI ID:2440593

Zhu, Wenchang ^[1]; Zhu, Xiaotian ^[1]; Qi, Jizhen ^[2];

^[1]; Shen, Yanbin ^[2]; Cheng, Guanjian ^[1]; Huang, Xue ^[1]; Yang, Shiqi ^[1]; Zhang, Hao ^[3]; Chiang, Chao-Lung ^[4];

^[4];

^[5]; Yin, Wanjian ^[1]; Gao, Lijun ^[1];

^[6]; Wang, Feng ^[3];

^[1]

Soochow University, Suzhou (China)
Chinese Academy of Sciences (CAS), Suzhou (China). Suzhou Institute of Nano-Tech and Nano-Bionics (SINANO)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Chinese Academy of Sciences (CAS), Suzhou (China). Suzhou Institute of Nano-Tech and Nano-Bionics (SINANO); Shanghai Jiao Tong Univ. (China)

High-Ni cathodes are being intensely pursued worldwide for electric vehicles and other energy-dense applications due to their high capacity and low cost. However, structural instabilities during electrochemical cycling and when subjected to thermal treatment have been the major issues hindering their practical deployment. We here report a rational design of coating-integrated-into-synthesis protocol for fabricating surface Ti-enriched LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811#Ti) material. The coating to intermediates is crucial to obtain high structural ordering, both in the bulk and surface of high-Ni cathodes, and the Ti substitute has a unique tri-valence (Ti³⁺) in a gradient surface distribution. Further, the simulations of projected density of states in the atomistic understanding further certify significantly enhanced stability of lattice oxygen for the NMC811 through such a Ti³⁺-based structure reinforcement. Consequently, the NMC811#Ti cathode delivers a high capacity up to 200mAhg^-1 at 0.1 C, along with superior stabilities during air-storage and thermal treatment (up to 297°C at the fully charged state under differential scanning calorimetric measurements). The corresponding NMC811#Ti||graphite full cell exhibits a desired 83.6% capacity retention after 1000 cycles at 0.5 C in a voltage range of 2.8–4.3V. This work demonstrates a delicate surface reinforcement to stabilize high-Ni cathodes for long-life and safe lithium-ion batteries.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 2440593

Report Number(s):: BNL--226046-2024-JAAM

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Vol. 489; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

Simultaneously Dual Modification of Ni‐Rich Layered Oxide Cathode for High‐Energy Lithium‐Ion Batteries Yang, Huiping; Wu, Hong‐Hui; Ge, Mingyuan Advanced Functional Materials, Vol. 29, Issue 13 https://doi.org/10.1002/adfm.201808825	journal	February 2019
Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes Wang, Dawei; Kou, Ronghui; Ren, Yang Advanced Materials, Vol. 29, Issue 39 https://doi.org/10.1002/adma.201606715	journal	August 2017
Regulating Surface Oxygen Activity by Perovskite‐Coating‐Stabilized Ultrahigh‐Nickel Layered Oxide Cathodes Wang, Lifan; Liu, Guicheng; Wang, Rui Advanced Materials, Vol. 35, Issue 11 https://doi.org/10.1002/adma.202209483	journal	January 2023
In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes Zhao, Jianqing; Zhang, Wei; Huq, Ashfia Advanced Energy Materials, Vol. 7, Issue 3 https://doi.org/10.1002/aenm.201601266	journal	October 2016
Prospect and Reality of Ni-Rich Cathode for Commercialization Kim, Junhyeok; Lee, Hyomyung; Cha, Hyungyeon Advanced Energy Materials, Vol. 8, Issue 6 https://doi.org/10.1002/aenm.201702028	journal	November 2017
Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides Zhang, Ming‐Jian; Hu, Xiaobing; Li, Maofan Advanced Energy Materials, Vol. 9, Issue 43 https://doi.org/10.1002/aenm.201901915	journal	October 2019
Rational Design of Coating Ions via Advantageous Surface Reconstruction in High‐Nickel Layered Oxide Cathodes for Lithium‐Ion Batteries Kim, Youngjin; Park, Hyoju; Shin, Kihyun Advanced Energy Materials, Vol. 11, Issue 38 https://doi.org/10.1002/aenm.202101112	journal	August 2021
Competitive Doping Chemistry for Nickel‐Rich Layered Oxide Cathode Materials Guo, Yu‐Jie; Zhang, Chao‐Hui; Xin, Sen Angewandte Chemie, Vol. 134, Issue 21 https://doi.org/10.1002/ange.202116865	journal	March 2022
A New Insight into the Capacity Decay Mechanism of Ni‐Rich Layered Oxide Cathode for Lithium‐Ion Batteries Wu, Shumeng; Zhang, Xiaodong; Ma, Su Small, Vol. 18, Issue 47 https://doi.org/10.1002/smll.202204613	journal	October 2022
Fabrication and electrochemical investigation of Li0.5TiO2 as anode materials for lithium ion batteries Kuang, Yan; Chen, Yuxi; Xia, Xiaohong Ionics, Vol. 23, Issue 12 https://doi.org/10.1007/s11581-017-2148-0	journal	June 2017
Nonstoichiometric Titanium Oxides via Pulsed Laser Ablation in Water Huang, Chang-Ning; Bow, Jong-Shing; Zheng, Yuyuan Nanoscale Research Letters, Vol. 5, Issue 6 https://doi.org/10.1007/s11671-010-9591-4	journal	April 2010
A universal multifunctional rare earth oxide coating to stabilize high-voltage lithium layered oxide cathodes Shen, Yabin; Zhang, Xiuyun; Wang, Licheng Energy Storage Materials, Vol. 56 https://doi.org/10.1016/j.ensm.2023.01.015	journal	February 2023
Washing effects on electrochemical performance and storage characteristics of LiNi0.8Co0.1Mn0.1O2 as cathode material for lithium-ion batteries Xiong, Xunhui; Wang, Zhixing; Yue, Peng Journal of Power Sources, Vol. 222 https://doi.org/10.1016/j.jpowsour.2012.08.029	journal	January 2013
Interfacial and cycle stability of sulfide all-solid-state batteries with Ni-rich layered oxide cathodes Wang, Jiacheng; Zhang, Zhenyu; Han, Jiufang Nano Energy, Vol. 100 https://doi.org/10.1016/j.nanoen.2022.107528	journal	September 2022
A comparative study of LiNi0.8Co0.2O2 cathode materials modified by lattice-doping and surface-coating Liu, H. Solid State Ionics, Vol. 166, Issue 3-4 https://doi.org/10.1016/j.ssi.2003.11.010	journal	January 2004
Long-Life, Ultrahigh-Nickel Cathodes with Excellent Air Storage Stability for High-Energy Density Lithium-Based Batteries Xie, Qiang; Manthiram, Arumugam Chemistry of Materials, Vol. 32, Issue 17 https://doi.org/10.1021/acs.chemmater.0c02374	journal	August 2020
Oxygen Loss in Layered Oxide Cathodes for Li-Ion Batteries: Mechanisms, Effects, and Mitigation Zhang, Hanlei; Liu, Hao; Piper, Louis F. J. Chemical Reviews, Vol. 122, Issue 6 https://doi.org/10.1021/acs.chemrev.1c00327	journal	January 2022
Simultaneous Enhancement of Interfacial Stability and Kinetics of Single-Crystal LiNi _0.6 Mn _0.2 Co _0.2 O ₂ through Optimized Surface Coating and Doping Bao, Wenda; Qian, Guannan; Zhao, Lianqi Nano Letters, Vol. 20, Issue 12 https://doi.org/10.1021/acs.nanolett.0c03778	journal	November 2020
In Situ Tuning Residual Lithium Compounds and Constructing TiO₂ Coating for Surface Modification of a Nickel-Rich Cathode toward High-Energy Lithium-Ion Batteries Wang, Wenzhi; Wu, Langyuan; Li, Zhiwei ACS Applied Energy Materials, Vol. 3, Issue 12 https://doi.org/10.1021/acsaem.0c02406	journal	December 2020
Modifying the Surface of a High-Voltage Lithium-Ion Cathode Gao, Han; Zeng, Xiaoqiao; Hu, Yixin ACS Applied Energy Materials, Vol. 1, Issue 5 https://doi.org/10.1021/acsaem.8b00323	journal	April 2018
Li–Nb–O Coating/Substitution Enhances the Electrochemical Performance of the LiNi _0.8 Mn _0.1 Co _0.1 O ₂ (NMC 811) Cathode Xin, Fengxia; Zhou, Hui; Chen, Xiaobo ACS Applied Materials & Interfaces, Vol. 11, Issue 38 https://doi.org/10.1021/acsami.9b09696	journal	June 2019
Targeted Surface Doping with Reversible Local Environment Improves Oxygen Stability at the Electrochemical Interfaces of Nickel-Rich Cathode Materials Steiner, James D.; Cheng, Hao; Walsh, Julia ACS Applied Materials & Interfaces, Vol. 11, Issue 41 https://doi.org/10.1021/acsami.9b14729	journal	October 2019
What is the Role of Nb in Nickel-Rich Layered Oxide Cathodes for Lithium-Ion Batteries? Xin, Fengxia; Zhou, Hui; Zong, Yanxu ACS Energy Letters https://doi.org/10.1021/acsenergylett.1c00190	journal	March 2021
Isotropic Microstrain Relaxation in Ni-Rich Cathodes for Long Cycling Lithium Ion Batteries Wang, Zhihong; Wei, Wu; Han, Qiang ACS Nano, Vol. 17, Issue 17 https://doi.org/10.1021/acsnano.3c04773	journal	August 2023
Nanoscale Coating of LiMO ₂ (M = Ni, Co, Mn) Nanobelts with Li ⁺ -Conductive Li ₂ TiO ₃ : Toward Better Rate Capabilities for Li-Ion Batteries Lu, Jun; Peng, Qing; Wang, Weiyang Journal of the American Chemical Society, Vol. 135, Issue 5 https://doi.org/10.1021/ja308717z	journal	January 2013
Cationic Ordering Coupled to Reconstruction of Basic Building Units during Synthesis of High-Ni Layered Oxides Zhang, Ming-Jian; Teng, Gaofeng; Chen-Wiegart, Yu-chen Karen Journal of the American Chemical Society, Vol. 140, Issue 39 https://doi.org/10.1021/jacs.8b06150	journal	August 2018
High-throughput computational design of cathode coatings for Li-ion batteries Aykol, Muratahan; Kim, Soo; Hegde, Vinay I. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13779	journal	December 2016
Unlocking the passivation nature of the cathode–air interfacial reactions in lithium ion batteries Zou, Lianfeng; He, Yang; Liu, Zhenyu Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17050-6	journal	June 2020
Surface enrichment and diffusion enabling gradient-doping and coating of Ni-rich cathode toward Li-ion batteries Yu, Haifeng; Cao, Yueqiang; Chen, Long Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-24893-0	journal	July 2021
In situ inorganic conductive network formation in high-voltage single-crystal Ni-rich cathodes Fan, Xinming; Ou, Xing; Zhao, Wengao Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-25611-6	journal	September 2021
Epitaxial growth of an atom-thin layer on a LiNi0.5Mn1.5O4 cathode for stable Li-ion battery cycling Zhu, Xiaobo; Schülli, Tobias U.; Yang, Xiaowei Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-28963-9	journal	March 2022
In situ multiscale probing of the synthesis of a Ni-rich layered oxide cathode reveals reaction heterogeneity driven by competing kinetic pathways Park, Hyeokjun; Park, Hayoung; Song, Kyung Nature Chemistry, Vol. 14, Issue 6 https://doi.org/10.1038/s41557-022-00915-2	journal	April 2022
Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries Yan, Pengfei; Zheng, Jianming; Liu, Jian Nature Energy, Vol. 3, Issue 7 https://doi.org/10.1038/s41560-018-0191-3	journal	June 2018
High-nickel layered oxide cathodes for lithium-based automotive batteries Li, Wangda; Erickson, Evan M.; Manthiram, Arumugam Nature Energy, Vol. 5, Issue 1 https://doi.org/10.1038/s41560-019-0513-0	journal	January 2020
Heuristic solution for achieving long-term cycle stability for Ni-rich layered cathodes at full depth of discharge Kim, Un-Hyuck; Park, Geon-Tae; Son, Byoung-Ki Nature Energy, Vol. 5, Issue 11 https://doi.org/10.1038/s41560-020-00693-6	journal	September 2020
Reactive boride infusion stabilizes Ni-rich cathodes for lithium-ion batteries Yoon, Moonsu; Dong, Yanhao; Hwang, Jaeseong Nature Energy, Vol. 6, Issue 4 https://doi.org/10.1038/s41560-021-00782-0	journal	March 2021
Introducing high-valence elements into cobalt-free layered cathodes for practical lithium-ion batteries Park, Geon-Tae; Namkoong, Been; Kim, Su-Bin Nature Energy, Vol. 7, Issue 10 https://doi.org/10.1038/s41560-022-01106-6	journal	September 2022
Bulk fatigue induced by surface reconstruction in layered Ni-rich cathodes for Li-ion batteries Xu, Chao; Märker, Katharina; Lee, Juhan Nature Materials, Vol. 20, Issue 1 https://doi.org/10.1038/s41563-020-0767-8	journal	August 2020
Facile synthesis and performances of nanosized Li₂TiO₃-based shell encapsulated LiMn_1/3Ni_1/3Co_1/3O₂ microspheres Yang, Xiukang; Yu, Ruizhi; Ge, Long J. Mater. Chem. A, Vol. 2, Issue 22 https://doi.org/10.1039/C4TA00888J	journal	January 2014
Highly enhanced lithium storage capability of LiNi _0.5 Mn _1.5 O ₄ by coating with Li ₂ TiO ₃ for Li-ion batteries Deng, Haifu; Nie, Ping; Luo, Haifeng J. Mater. Chem. A, Vol. 2, Issue 43 https://doi.org/10.1039/C4TA03802A	journal	January 2014
Enhanced high-voltage cycling stability of Ni-rich cathode materials via the self-assembly of Mn-rich shells Dong, Xinyu; Yao, Junyi; Zhu, Wenchang Journal of Materials Chemistry A, Vol. 7, Issue 35 https://doi.org/10.1039/C9TA07147D	journal	January 2019
Suppressing structural degradation of Ni-rich cathode materials towards improved cycling stability enabled by a Li₂MnO₃ coating Huang, Xue; Zhu, Wenchang; Yao, Junyi Journal of Materials Chemistry A, Vol. 8, Issue 34 https://doi.org/10.1039/D0TA00924E	journal	January 2020
Facile and scalable dry surface doping technique to enhance the electrochemical performance of LiNi _0.64 Mn _0.2 Co _0.16 O ₂ cathode materials Shi, Yang; Kim, Kitae; Xing, Yingjie Journal of Materials Chemistry A, Vol. 8, Issue 38 https://doi.org/10.1039/D0TA07779H	journal	January 2020
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
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

Similar Records

Conditioning the Surface and Bulk of High-Nickel Cathodes with a Nb Coating: An In Situ X-ray Study

Journal Article · 2021 · Journal of Physical Chemistry Letters · OSTI ID:1823630

Xin, Fengxia; Zhou, Hui; Bai, Jianming; +2 more

In Situ Ion‐Exchange Metathesis Induced Conformal LiF Surface Films on Cathode (NMC811) as a Cathode Electrolyte Interphase

Journal Article · 2023 · Advanced Functional Materials · OSTI ID:1997741

Thapaliya, Bishnu P.; Wang, Tao; Borisevich, Albina Y.; +5 more

Unveiling the Role of Al₂O₃ in Preventing Surface Reconstruction During High-Voltage Cycling of Lithium-Ion Batteries

Journal Article · 2019 · ACS Applied Energy Materials · OSTI ID:1784207

David, Lamuel; Dahlberg, Kevin; Mohanty, Debasish; +8 more

Related Subjects

36 MATERIALS SCIENCE
Cycling stability
Lithium-ion battery
Surface Ti-enrichment
Thermal stability
high-Ni cathode

Title: Stabilizing high-Ni cathodes with gradient surface Ti-enrichment

Citation Formats

References (45)

Similar Records

Related Subjects