Lithium, Ether, and Graphite: A Retrospective Trilogy of the Anode-Electrolyte Interface
Authors: Xia Dawei , Tao Lei , Lin Feng 
Published: December 2024

Ethers represent a family of solvents widely applied in various battery chemistries, except in the most successful battery—Li-ion batteries (LIBs). It is believed that ether electrolytes are incompatible with graphite anodes in LIBs due to detrimental solvent co-intercalation and exfoliation. Here, we demonstrate that ether electrolytes at standard salt concentration can enable outstanding reversibility and fast-charge capability of graphite anodes in LIBs. In short, for ether electrolytes, the anion and the solid-electrolyte interphase (SEI) govern the electrochemical behaviors of graphite anodes. Firstly, we point out that exfoliation and co-intercalation are not always the root causes of the documented cell failures using graphite anodes. Matching the reductive stability between solvents and salts is key to resolving the interphase problem. Reductively unstable lithium bis(fluorosulfonyl)imide (LiFSI) is the optimal salt paired with 1,3-dioxolane (DOL), enabling weakened Li-solvent interaction, preferential reduction of the FSI anion, and a homogeneous SEI enriched with inorganic species. Consequently, electrolyte reduction and Li-DOL co-intercalation are inhibited. Secondly, reductively stable LiBF4 paired with dimethoxyethane (DME) realizes improved cyclability of graphite based on a cointercalation mechanism. We conducted a holistic investigation into the nature, function, and formation of the heterogeneous SEI. Specifically, we revealed a self-terminating, heterogeneous interphase based on grainy LiF located on the catalytically active edge plane of natural graphite. Thirdly, we discovered a novel cointercalation mechanism, namely, in-situ synthesis of ternary graphite-intercalation compounds in a new electrolyte. We characterize the progressive cointercalation via operando synchrotron X-ray analyses, supporting reduced volume expansion and high structural integrity of the cointercalated graphite. The resulting t-GIC chemistry delivers unprecedented fast charging (1 minute) and ultralong lifetimes exceeding 10,000 cycles. The full cells based on cointercalated graphite display remarkable cycling stability upon a 15-minute charging and excellent rate capability even at -40°C. In these three case studies combined as a trilogy with strong correlation, we clarify a long-standing confusing issue in the LIBs community—that is, the compatibility between ether electrolytes and graphite anodes. This trilogy summarizes and reflects on past experiences with the anode/electrolyte interface (mostly failures of ether electrolytes when cycling graphite anodes) dating back to the 1970s. Learning from history, we exemplify different intercalation chemistries of graphite based on DOL, DME, and another common ether solvent, paired with 1M lithium salts, all showing approximately 99.9% Coulombic efficiency, high capacity retention, and rapid interphase kinetics. Our findings not only shed light on the enigmatic interphase formed by ether electrolytes but also offer critical insights into future electrolyte design for graphite anodes operated under extreme conditions.