High-Potential Redox Shuttle for Use in Lithium-Ion Batteries

Redox shuttle additives can be used in lithium-ion cells to protect against overcharging and for cell balancing in multicell packs. Most previously reported redox shuttles have been either unstable as shuttles, resulting in a short duration of overcharge protection, or have redox potentials that make them suitable only for cells containing lower potential positive electrode materials, such as LiFePO 4 . A new molecule, l,4-di-t-butyl-2,5-bis(2,2,2-trifluoroethoxy)benzene, is shown here to be a stable redox shuttle with a redox potential of 4.25 V and provides overcharge protection in full Li-ion cells, implying adequate reductive stability. Experiments using Li/LiCoO 2 and Li/Li[Ni 1/3 Mn 1/3 Co 1/3 ]O 2 cells show that this molecule can work with high-energy-density positive electrodes as well as in full cells containing LiFePO 4 positive electrodes and Li, mesocarbon microbead, or Li 4 Ti 5 O 12 negative electrodes.

[1]  T. Richardson,et al.  Overcharge Protection for Rechargeable Lithium Polymer Electrolyte Batteries , 1996 .

[2]  Subbarao Surampudi,et al.  Analysis of Redox Additive‐Based Overcharge Protection for Rechargeable Lithium Batteries , 1991 .

[3]  Simon S. Woo,et al.  Applications of Metallocenes in Rechargeable Lithium Batteries for Overcharge Protection , 1992 .

[4]  J. Dahn,et al.  Calculations of Oxidation Potentials of Redox Shuttle Additives for Li-Ion Cells , 2006 .

[5]  Momoe Adachi,et al.  Aromatic Compounds as Redox Shuttle Additives for 4 V Class Secondary Lithium Batteries , 1999 .

[6]  M. Taggougui,et al.  2,5-Difluoro-1,4-dimethoxybenzene for overcharge protection of secondary lithium batteries , 2007 .

[7]  J. Dahn,et al.  A Combined Computational/Experimental Study on Tertbutyl- and Methoxy-Substituted Benzene Derivatives as Redox Shuttles for Lithium-Ion Cells , 2008 .

[8]  J. Dahn,et al.  Spectroelectrochemical Studies of Redox Shuttle Overcharge Additive for LiFePO4-Based Li-Ion Batteries , 2005 .

[9]  J. Dahn,et al.  Computational Estimates of Stability of Redox Shuttle Additives for Li-Ion Cells , 2006 .

[10]  J. Dahn,et al.  High-Rate Overcharge Protection of LiFePO4-Based Li-Ion Cells Using the Redox Shuttle Additive 2,5-Ditertbutyl-1,4-dimethoxybenzene , 2005 .

[11]  K. Abraham,et al.  n‐Butylferrocene for Overcharge Protection of Secondary Lithium Batteries , 1990 .

[12]  J. Dahn,et al.  Chemical Overcharge and Overdischarge Protection for Lithium-Ion Batteries , 2005 .

[13]  Zonghai Chen,et al.  Understanding the Stability of Aromatic Redox Shuttles for Overcharge Protection of Lithium-Ion Cells , 2006 .

[14]  Jeff Dahn,et al.  Studies of aromatic redox shuttle additives for LiFePO4-based Li-ion cells , 2005 .