Mellitic Triimides Showing Three One-Electron Redox Reactions with Increased Redox Potential as New Electrode Materials for Li-ion Batteries.

The mellitic triimide (MTI) bearing three imide groups on a benzene core with C3 symmetry is proposed as a new building block for organic electrode materials in lithium-ion batteries. MTI was anticipated to deliver a higher theoretical specific capacity of up to 282 mAh g(-1) with increased reduction potentials compared with the well-known pyromellitic diimide building block bearing two imide groups because the additional imide group can accept one more electron and provide an electron-withdrawing effect. A model compound, ethyl-substituted mellitic triimide (ETTI), shows three well distinguished and reversible one-electron redox reactions at -0.97, -1.62, and -2.34 V versus Ag/Ag+ in 0.1 m tetrabutylammonium hexafluorophosphate electrolyte, but the redox potentials were increased in 2 m lithium bis(trifluoromethanesulfonyl)imide electrolyte: -0.60 V, -0.86 V, and -1.42 V vs. Ag/Ag+. The DFT calculations revealed that the unique C3 symmetric structural design leads to the higher reduction potential of MTI in the Li-based electrolyte by formation of a stable 7-membered ring with a Li ion and the two carbonyl oxygen atoms from the adjacent imide groups. In a Li-ion coin cell, the ETTI electrode delivered a specific capacity of 176 mAh g(-1), corresponding to 81 % of capacity utilization, with three clear voltage plateaus. The higher average discharge voltage (2.41 V vs. Li/Li+) of ETTI allows it to deliver one of the highest specific energies (421 Wh kg(-1)) among reported diimide-based electrode materials. Finally, its redox mechanism was investigated by ex situ FTIR measurements and DFT calculations.