The Li-ion battery design relies on quite a few components, mainly including anode, cathode, and electrolyte. The electrolyte is composed by lithium salt and additives. In the current work, we investigate if closo-boranes and their analogues could serve as effectively electrolyte anion part. Ligand engineering and size effects are carefully examined via first-principles calculations based on hybrid functional approach. The thermal stability, lithium ion mobility, and electrochemical stability effects are evaluated to screen the potential clusters. The solvation effects of different organic solvents have been considered as well. The work, performed by Ms. Xiao Li in our group and collaborated with Prof. Tao Yang, has just appeared on https://pubs.rsc.org/en/content/articlehtml/2022/cp/d1cp05230f.