Revealing the formation and electrochemical properties of bis(trifluoromethanesulfonyl) imide intercalated graphite with first-principles calculations

TL;DR

This study uses first-principles calculations to explore how TFSI anions intercalate into graphite, revealing stability, structural changes, and electrochemical properties relevant for dual ion batteries.

Contribution

It provides a detailed theoretical analysis of TFSI intercalation into graphite, including stability, structural evolution, and electrochemical performance, which was previously not fully understood.

Findings

TFSI-Cn compounds become more stable with increasing unit cell size.

Interlayer distance and volume expansion increase with TFSI concentration.

Electrode voltage ranges from 3.8 V to 3.0 V, matching experimental data.

Abstract

Graphite has been reported to have anion as well as cation intercalation capacities as both cathode and anode host materials for the dual ion battery. In this work, we study the intercalation of bis(trifluoromethanesulfonyl) imide (TFSI) anion from ionic liquid electrolyte into graphite with first-principles calculations. We build models for TFSI-C$_n$ compounds with systematically increasing unit cell sizes of graphene sheet and investigate their stabilities by calculating the formation energy, resulting in the linear decrease and arriving at the limit of stability. With identified unit cell sizes for stable compound formation, we reveal that the interlayer distance and relative volume expansion ratio of TFSI-C$_n$ increase as increasing the concentration of TFSI intercalate during the charge process. The electrode voltage is determined to be ranged from 3.8 V to 3.0 V at the specific capacity ranging from 30 mAh g$^{-1}$ to 54 mAh g$^{-1}$ in agreement with experiment. Moreover, a very low activation barrier of under 50 meV for TFSI migration and good electronic conductivity give a proof of using these compounds as a promising cathode. Through the analysis of charge transfer, we clarify the mechanism of TFSI-C$_n$ formation, and reveal new prospects for developing graphite based cathode.