Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries

被引:827
|
作者
Gu, Meng [1 ]
Belharouak, Ilias [4 ]
Zheng, Jianming [3 ]
Wu, Huiming [4 ]
Xiao, Jie [3 ]
Genc, Arda [5 ]
Amine, Khalil [4 ]
Thevuthasan, Suntharampillai [1 ]
Baer, Donald R. [1 ]
Zhang, Ji-Guang [3 ]
Browning, Nigel D. [2 ]
Liu, Jun [2 ]
Wang, Chongmin [1 ]
机构
[1] Pacific NW Natl Lab, Environm Mol Sci Lab, Richland, WA 99352 USA
[2] Pacific NW Natl Lab, Fundamental & Computat Sci Directorate, Richland, WA 99352 USA
[3] Pacific NW Natl Lab, Energy & Environm Directorate, Richland, WA 99352 USA
[4] Argonne Natl Lab, Chem Sci & Engn Div, Argonne, IL 60439 USA
[5] FEI Co, Hillsboro, OR 97124 USA
关键词
lithium ion battery; layered structure; spinel formation; phase transformation; ELECTROCHEMICAL PERFORMANCE; ANOMALOUS CAPACITY; OXYGEN LOSS; LITHIUM; ELECTRODE; STABILITY; OXIDES;
D O I
10.1021/nn305065u
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Pristine Li-rich layered cathodes, such as Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.1Mn0.525- Co0.175O2, were identified to exist in two different structures: LiMO2 R (3) over barm and LI2MO3 C2/m phases. Upon 300 cycles of charge/discharge, both phases gradually transform to the spinel structure. The transition from LiMO2 R (3) over barm to spinel is accomplished through the migration of transition metal ions to the Li site without breaking down the lattice, leading to the formation of mosaic structured spinel grains within the parent particle. In contrast, transition from Li2MO3 C2/m to spinel involves removal of Li+ and O2-, which produces large lattice strain and leads to the breakdown of the parent lattice. The newly formed spinel grains show random orientation within the same particle. Cracks and pores were also noticed within some layered nanoparticles after cycling, which is believed to be the consequence of the lattice breakdown and vacancy condensation upon removal of lithium ions. The AlF3-coating can partially relieve the spinel formation In the layered structure during cycling, resulting in a slower capacity decay. However, the AlF3-coating on the layered structure cannot ultimately stop the spinel formation. The observation of structure transition characteristics discussed in this paper provides direct explanation for the observed gradual capacity loss and poor rate performance of the layered composite. It also provides clues about how to improve the materials structure in order to Improve electrochemical performance.
引用
收藏
页码:760 / 767
页数:8
相关论文
共 50 条
  • [21] Layered/Spinel Heterostructured and Hierarchical Micro/Nanostructured Li-Rich Cathode Materials with Enhanced Electrochemical Properties for Li-Ion Batteries
    Deng, Ya-Ping
    Yin, Zu-Wei
    Wu, Zhen-Guo
    Zhang, Shao-Jian
    Fu, Fang
    Zhang, Tao
    Li, Jun-Tao
    Huang, Ling
    Sun, Shi-Gang
    ACS APPLIED MATERIALS & INTERFACES, 2017, 9 (25) : 21065 - 21070
  • [22] Structural and Electrochemical Characterization of Composite Layered-Spinel Electrodes Containing Ni and Mn for Li-Ion Batteries
    Cabana, Jordi
    Kang, Sun-Ho
    Johnson, Christopher S.
    Thackeray, Michael M.
    Grey, Clare P.
    JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2009, 156 (09) : A730 - A736
  • [23] Dual active material composite cathode structures for Li-ion batteries
    Whitacre, J. F.
    Zaghib, K.
    West, W. C.
    Ratnakumar, B. V.
    JOURNAL OF POWER SOURCES, 2008, 177 (02) : 528 - 536
  • [24] Advances in Co-free layered cathode materials for Li-ion batteries
    Ge, Jian-hua
    Xie, Min-yan
    Zhao, Qun-fang
    Zhang, Shu-qiong
    Sun, Hao
    INTERNATIONAL JOURNAL OF ELECTROCHEMICAL SCIENCE, 2023, 18 (10):
  • [25] High-entropy Li-rich layered oxide cathode for Li-ion batteries
    Kim, Jaemin
    Yang, Songge
    Zhong, Yu
    Tompsett, Geoffrey
    Jeong, Seonghun
    Mun, Junyoung
    Sunariwal, Neelam
    Cabana, Jordi
    Yang, Zhenzhen
    Wang, Yan
    JOURNAL OF POWER SOURCES, 2025, 628
  • [26] Recent progress in Li-rich layered oxides as cathode materials for Li-ion batteries
    Yan, Jianhua
    Liu, Xingbo
    Li, Bingyun
    RSC ADVANCES, 2014, 4 (108) : 63268 - 63284
  • [27] Template-engaged synthesis of spinel-layered Li1.5MnTiO4+δ nanorods as a cathode material for Li-ion batteries
    Ngoc Hung Vu
    Unithrattil, Sanjith
    Van Hien Hoang
    Chun, Sangeun
    Im, Won Bin
    JOURNAL OF POWER SOURCES, 2017, 355 : 134 - 139
  • [28] Spinel-Layered Core-Shell Cathode Materials for Li-Ion Batteries (vol 1, pg 821, 2011)
    Cho, Yonghyun
    Lee, Sanghan
    Lee, Yongseok
    Hong, Taeeun
    Cho, Jaephil
    ADVANCED ENERGY MATERIALS, 2011, 1 (06) : 986 - 986
  • [29] Advances in cathode technology for Li-ion batteries
    Chua, D
    Choblet, A
    Manivanna, V
    Lin, HW
    Wolfenstine, J
    SIXTEENTH ANNUAL BATTERY CONFERENCE ON APPLICATIONS AND ADVANCES, 2001, : 275 - 275
  • [30] C/Li2MnSiO4 as a Composite Cathode Material for Li-ion Batteries
    Swietoslawski, M.
    Molenda, M.
    Zaitz, M. M.
    Dziembaj, R.
    RECHARGEABLE LITHIUM AND LITHIUM ION BATTERIES, 2012, 41 (41): : 129 - 137