Designing New Electrolytes for Lithium Ion Batteries Using Superhalogen Anions

TL;DR

This study explores the potential of superhalogen and hyperhalogen anions to create safer, non-toxic electrolytes for lithium-ion batteries, demonstrating promising candidates with lower dissociation energies through computational analysis.

Contribution

The paper introduces a new class of electrolyte salts based on superhalogen and hyperhalogen anions, expanding beyond traditional halogen-based salts for LIBs.

Findings

LiB4H13 and LiB5H16 are promising electrolyte candidates.

Li-salts of superhalogen anions are non-toxic and halogen-free.

Dissociation energy inversely correlates with VDE of anions.

Abstract

The electrolytes used in Lithium Ion Batteries (LIBs) such as LiBF4, LiPF6 etc. are Li-salts of some complex anions, BF4-, PF6- etc. The investigation shows that the vertical detachment energy (VDE) of these anions exceeds to that of halogen, and therefore they behave as superhalogen anions. Consequently, it might be possible to design new electrolytic salts using other superhalogen anions. We have explored this possibility using Li-salts of various superhalogen anions such as BO2-, AlH4-, TiH5- and VH6- as well as hyperhalogen anions, BH4-y(BH4)y-(y = 1 to 4). Our density functional calculations show that Li-salts of these complex anions possess similar characteristics as those of electrolytic salts in LIBs. Note that they all are halogen free and hence, non-toxic and safer than LiBF4, LiPF6 etc. In particular, LiB4H13 and LiB5H16 are two potential candidates for electrolytic salt due to their smaller Li-dissociation energy ({\Delta}E) than those of LiBF4, LiPF6 etc. We have also noticed that {\Delta}E of LiBH4-y(BH4)y varies inversely with the VDE of BH4-y(BH4)y- anions, which increases with the increase in y. These findings may guide experimentalists and future researchers to design and synthesize more efficient and environment friendly electrolytic salts for LIBs.