High-voltage liquid electrolytes for Li batteries: progress and perspectives

Since the advent of the Li ion batteries (LIBs), the energy density has been tripled, mainly attributed to the increase of the electrode capacities. Now, the capacity of transition metal oxide cathodes is approaching the limit due to the stability limitation of the electrolytes. To further promote the energy density of LIBs, the most promising strategies are to enhance the cut-off voltage of the prevailing cathodes or explore novel high-capacity and high-voltage cathode materials, and also replacing the graphite anode with Si/Si-C or Li metal. However, the commercial ethylene carbonate (EC)-based electrolytes with relatively low anodic stability of ∼4.3 V vs. Li⁺/Li cannot sustain high-voltage cathodes. The bottleneck restricting the electrochemical performance in Li batteries has veered towards new electrolyte compositions catering for aggressive next-generation cathodes and Si/Si-C or Li metal anodes, since the oxidation-resistance of the electrolytes and the in situ formed cathode electrolyte interphase (CEI) layers at the high-voltage cathodes and solid electrolyte interphase (SEI) layers on anodes critically control the electrochemical performance of these high-voltage Li batteries. In this review, we present a comprehensive and in-depth overview on the recent advances, fundamental mechanisms, scientific challenges, and design strategies for the novel high-voltage electrolyte systems, especially focused on stability issues of the electrolytes, the compatibility and interactions between the electrolytes and the electrodes, and reaction mechanisms. Finally, novel insights, promising directions and potential solutions for high voltage electrolytes associated with effective SEI/CEI layers are proposed to motivate revolutionary next-generation high-voltage Li battery chemistries.