N-Substituted Phenothiazine Derivatives: How the Stability of the Neutral and Radical Cation Forms Affects Overcharge Performance in Lithium-Ion Batteries

作者：Narayana Kishore Anand; Casselman Matthew D; Elliott Corrine F; Ergun Selin; Parkin Sean R; Risko Chad^*; Odom Susan A

来源：ChemPhysChem, 2015, 16(6): 1179-1189.

DOI：10.1002/cphc.201402674

• overcharge protection
• phenothiazine
• radical cations
• redox shuttles
• substituent effects

Phenothiazine and five N-substituted derivatives were evaluated as electrolyte additives for overcharge protection in LiFePO4/synthetic graphite lithium-ion batteries. We report on the stability and reactivity of both the neutral and radical-cation forms of these six compounds. While three of the compounds show extensive overcharge protection, the remaining three last for only one to a few cycles. UV/Vis studies of redox shuttle stability in the radical cation form are consistent with the overcharge performance: redox shuttles with spectra that show little change over time exhibit extensive overcharge performance, whereas those with changing spectra have limited overcharge protection. In one case, we determined that a CN bond cleaves upon oxidation, forming the phenothiazine radical cation and leading to premature overcharge protection failure; in another case, poor solubility appears to limit protection.

• 出版日期2015-4-27