An improved electrolyte for the LiFePO4 cathode working in a wide temperature range

Abstract A LiBF4–LiBOB (lithium bis(oxalato)borate) salt mixture was used to formulate an electrolyte for the operation of a LiFePO4 cathode over a wide temperature range (−50 to 80 °C) by employing a solvent mixture of 1:1:3 (wt.) propylene carbonate (PC)/ethylene carbonate (EC)/ethylmethyl carbonate (EMC). In comparison with the ionic conductivity of a single salt electrolyte, LiBF4 electrolyte has a higher conductivity below −10 °C while the LiBOB electrolyte is higher above −10 °C. For cell performance, LiBF4 cell has a better low temperature performance and a higher power capability, but it cannot survive above 60 °C. In contrast, the LiBOB cell performs very well at high temperature even up to 90 °C, but it fails to perform below −40 °C. We found that the temperature performance of Li/LiFePO4 cells could be optimized by using a LiBF4–LiBOB salt mixture. At 1C and at −50 °C, for example, a Li/LiFePO4 cell using 90:10 (in mole) LiBF4–LiBOB salt mixture could provide up to ∼30% of capacity at ∼3.0 V and it still could be cycled at 90 °C. In addition, we observed and explained an opposite correlation between the ionic conductivity of the electrolyte and the power capability of the cell. That is, the LiBF4 cell at 20 °C discharges at a higher plateau voltage than the LiBOB cell, whereas the LiBF4 electrolyte has a lower ionic conductivity.

[1]  Kang Xu,et al.  LiBOB: Is it an alternative salt for lithium ion chemistry? , 2005 .

[2]  T. Jow,et al.  Liquid/Solid Phase Diagrams of Binary Carbonates for Lithium Batteries Part II , 2001 .

[3]  Kang Xu,et al.  LiBOB as Salt for Lithium-Ion Batteries:A Possible Solution for High Temperature Operation , 2002 .

[4]  Yet-Ming Chiang,et al.  Electronically conductive phospho-olivines as lithium storage electrodes , 2002, Nature materials.

[5]  Kang Xu,et al.  A new approach toward improved low temperature performance of Li-ion battery , 2002 .

[6]  Jeff Dahn,et al.  Comparison of the Thermal Stability of Lithiated Graphite in LiBOB EC/DEC and in LiPF6 EC/DEC , 2003 .

[7]  Siqi Shi,et al.  Enhancement of electronic conductivity of LiFePO4 by cr doping and its identification by first-principles calculations , 2003 .

[8]  Kang Xu,et al.  Conductivity and Viscosity of PC-DEC and PC-EC Solutions of LiBOB , 2003 .

[9]  K. Amine,et al.  High-temperature storage and cycling of C-LiFePO4/graphite Li-ion cells , 2005 .

[10]  Kang Xu,et al.  Optimization of reaction condition for solid-state synthesis of LiFePO4-C composite cathodes , 2005 .

[11]  Linda F. Nazar,et al.  Approaching Theoretical Capacity of LiFePO4 at Room Temperature at High Rates , 2001 .

[12]  Junwei Jiang,et al.  ARC studies of the reaction between Li0FePO4 and LiPF6 or LiBOB EC/DEC electrolytes , 2004 .

[13]  John O. Thomas,et al.  Thermal stability of LiFePO4-based cathodes , 1999 .

[14]  John O. Thomas,et al.  The source of first-cycle capacity loss in LiFePO4 , 2001 .

[15]  Kang Xu,et al.  Effect of propylene carbonate on the low temperature performance of Li-ion cells , 2002 .

[16]  J. Dahn,et al.  Reducing Carbon in LiFePO4 / C Composite Electrodes to Maximize Specific Energy, Volumetric Energy, and Tap Density , 2002 .

[17]  Kang Xu,et al.  Lithium Bis(oxalato)borate Stabilizes Graphite Anode in Propylene Carbonate , 2002 .

[18]  Kang Xu,et al.  Study of LiBF4 as an electrolyte salt for a Li-ion battery , 2002 .

[19]  Kang Xu,et al.  Low-temperature performance of Li-ion cells with a LiBF4-based electrolyte , 2003 .

[20]  John B. Goodenough,et al.  Effect of Structure on the Fe3 + / Fe2 + Redox Couple in Iron Phosphates , 1997 .