Impact of Lithium Bis(oxalate)borate Electrolyte Additive on the Performance of High-Voltage Spinel/Graphite Li-Ion Batteries

被引:160
作者
Pieczonka, Nicholas P. W. [2 ]
Yang, Li [1 ]
Balogh, Michael P. [1 ]
Powell, Bob R. [1 ]
Chemelewski, Katharine [3 ]
Manthiram, Arumugam [3 ]
Krachkovskiy, Sergey A. [4 ]
Goward, Gillian R. [4 ]
Liu, Minghong [5 ]
Kim, Jung-Hyun [1 ]
机构
[1] Gen Motors Global R&D Ctr, Chem & Mat Syst Lab, Warren, MI 48090 USA
[2] Optimal CAE Inc, Plymouth, MI 48170 USA
[3] Univ Texas Austin, Mat Sci & Engn Program, Austin, TX 78712 USA
[4] McMaster Univ, Dept Chem, Hamilton, ON L8S 4L8, Canada
[5] MEDA Engn & Tech Serv, Southfield, MI 48075 USA
基金
加拿大自然科学与工程研究理事会;
关键词
THERMAL-STABILITY; CYCLING BEHAVIOR; SPINEL; LIBOB; LINI0.5MN1.5O4; SURFACE; INTERFACE; MECHANISM; LIPF6; TEMPERATURE;
D O I
10.1021/jp408717x
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
The impact of lithium bis(oxalate)borate (LiBOB) electrolyte additive on the performance of full lithium-ion cells pairing the high-voltage spinel cathode with the graphite anode was systematically investigated. Adding 1 wt % LiBOB to the electrolyte significantly improved the cycle life and Coulombic efficiency of the full-cells at 30 and 45 degrees C. As the LiBOB was preferentially oxidized and reduced compared with LiBOB-free electrolyte during cycling, their relative contributions to the improved capacity retention in full-cells was gauged by pairing fresh and LiBOB-treated electrodes with various combinations. The results indicated that a solid-electrolyte interphase (SEI) film on graphite produced by the reduction of the LiBOB additive is more robust and stable against Mn dissolution problem during cycling at 45 degrees C compared with the SEI formed by the reduction of the base (LiBOB-free) electrolyte. In addition, a 3 wt % LiBOB-added electrolyte showed reduced Mn dissolution compared with the base electrolyte after storing the fully charged Li1-xNi0.42Fe0.08Mn1.5O4 (LNFMO) electrodes at 60 degrees C for one month. It is believed that LiBOB aids in stabilizing the electrolyte by trapping the PF5, i.e., sequestering the radical which tends to oxidize EC and DEC electrolyte solvents. Thus, oxidation is suppressed on the carbon black particles in the positive electrode, as evidenced by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR) analyses. As a result, HF generation is suppressed, which in turn results in less Mn dissolution from the spinel cathode.
引用
收藏
页码:22603 / 22612
页数:10
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