An Organophosphine Oxide Redox Shuttle Additive that Delivers Long-term Overcharge Protection for 4 V Lithium-ion Batteries

Organophosphine oxide groups not only can provide suitable steric protection of the generated radical cation, but also can increase the redox potential to 4.5 V, which is suitable for overcharge protection of LiMn2O4 cathode material

Scientific Achievement

  • A novel redox shuttle molecule, BPDB, was developed through replacing the tert-butyl group in DDB by bulky organophosphine oxide group
  • BPDB can provide overcharge protection for LiMn2O4/MCMB with 25 overcharge protection cycles of 100% overcharge per cycle
  • With the addition of LiBOB as a supporting additive to suppress the reductive decomposition of BPDB on the anode surface, the overcharge protection was increased from 25 cycles to more than 95 cycles

Significance and Impact

  • Our study shows a rare example striking the balance between the high redox potential and the electrochemical stability
  • The study also suggests that the improvement strategy for the redox shuttles should be advanced in the full awareness of the detrimental side reactions on the anode side

Research Details

  • Extensive characterizations including CV and coin cells were conducted to evaluate the new material for overcharge protection
  • The chemical reduction, the differential capacity profiles, and scanning electron microscopy (SEM) images were carried out to confirm the reductive decomposition

Work performed at Argonne National Laboratory (JCESR managing partner) by J. Huang, N, Azimi, L. Cheng, I. A. Shkrob, X. Xue, J. Zhang, N. R. Dietz Rago, L. A. Curtiss, K. Amine, Z. Zhang and L. Zhang, J. Mater. Chem. A 2015.

DOI: 10.1039/C5TA01326G

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