Separating electronic and ionic conductivity in mix-conducting layered lithium transition-metal oxides

被引:143
作者
Wang, Shanyu [1 ]
Yan, Mengyu [1 ]
Li, Yun [1 ]
Vinado, Carolina [1 ]
Yang, Jihui [1 ]
机构
[1] Univ Washington, Mat Sci & Engn Dept, Seattle, WA 98195 USA
关键词
Li-ion batteries; Electronic conductivity; Ionic conductivity; Rate performance; Activation energy; CATHODE MATERIAL; ELECTROCHEMICAL PROPERTIES; DIFFERENT TEMPERATURES; DEFECT CHEMISTRY; RATE CAPABILITY; BATTERIES; LICOO2; LIXCOO2; PERSPECTIVE; DEPOSITION;
D O I
10.1016/j.jpowsour.2018.05.005
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Electronic and ionic conductivities of active materials are the fundamental properties in determining the dynamical behavior and rate performance of batteries, yet, they are typically hard to be distinguished due to the convolution of the two conduction processes, the complexity of the dynamic responses in composite electrodes, and other extrinsic factors such as porosity and interfacial effects. Herein, we report a simple and reliable method that combines the electrochemical impedance spectroscopy with direct-current polarization to accurately resolve the electronic and ionic conductivities of conventional layered cathode materials for Li-ion batteries, including LiCoO2 and LiNi1-x-yMnxCoyO2. A significant increase in the electronic conductivity was observed with the increasing Ni content, accompanied by a large decrease in the activation energy. Meanwhile, a similar variation trend in Li+ conductivity was observed, together with a large decrease in the Li+ hopping barrier. These can be attributed to the variations in electronic structure and defect chemistry, the apparent lattice expansion with incorporating Ni, especially along the c-axis, as well as a weakened Li+-transition metal interaction via decreasing the Mn4+ content.
引用
收藏
页码:75 / 82
页数:8
相关论文
共 38 条
[21]  
Moradabadi A., 2017, ARXIV170601709
[22]   An ac impedance spectroscopic study of Mg-doped LiCoO2 at different temperatures:: electronic and ionic transport properties [J].
Nobili, F ;
Dsoke, S ;
Croce, F ;
Marassi, R .
ELECTROCHIMICA ACTA, 2005, 50 (11) :2307-2313
[23]   An AC impedance spectroscopic study of LixCoO2 at different temperatures [J].
Nobili, F ;
Tossici, R ;
Marassi, R ;
Croce, F ;
Scrosati, B .
JOURNAL OF PHYSICAL CHEMISTRY B, 2002, 106 (15) :3909-3915
[24]   Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x=1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries [J].
Noh, Hyung-Joo ;
Youn, Sungjune ;
Yoon, Chong Seung ;
Sun, Yang-Kook .
JOURNAL OF POWER SOURCES, 2013, 233 :121-130
[25]   Effect of Al2O3 coating on electrochemical performance of LiCoO2 as cathode materials for secondary lithium batteries [J].
Oh, S ;
Lee, JK ;
Byun, D ;
Cho, WI ;
Cho, BW .
JOURNAL OF POWER SOURCES, 2004, 132 (1-2) :249-255
[26]   A review of conduction phenomena in Li-ion batteries [J].
Park, Myounggu ;
Zhang, Xiangchun ;
Chung, Myoungdo ;
Less, Gregory B. ;
Sastry, Ann Marie .
JOURNAL OF POWER SOURCES, 2010, 195 (24) :7904-7929
[27]   Electrochemical and electronic properties of LiCoO2 cathode investigated by galvanostatic cycling and EIS [J].
Qiu, Xiang-Yun ;
Zhuang, Quan-Chao ;
Zhang, Qian-Qian ;
Cao, Ru ;
Ying, Peng-Zhan ;
Qiang, Ying-Huai ;
Sun, Shi-Gang .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2012, 14 (08) :2617-2630
[28]   Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives [J].
Quartarone, Eliana ;
Mustarelli, Piercarlo .
CHEMICAL SOCIETY REVIEWS, 2011, 40 (05) :2525-2540
[29]   Determination of the chemical diffusion coefficient of Li+ in intercalation-type Li3V2(PO4)3 anode material [J].
Rui, X. H. ;
Yesibolati, N. ;
Li, S. R. ;
Yuan, C. C. ;
Chen, C. H. .
SOLID STATE IONICS, 2011, 187 (01) :58-63
[30]   Capacity Fading of Ni-Rich Li[NixCoyMn1-x-y]O2 (0.6 ≤ x ≤ 0.95) Cathodes for High-Energy-Density Lithium-Ion Batteries: Bulk or Surface Degradation? [J].
Ryu, Hoon-Hee ;
Park, Kang-Joon ;
Yoon, Chong S. ;
Sun, Yang-Kook .
CHEMISTRY OF MATERIALS, 2018, 30 (03) :1155-1163