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The discovery of liquid battery electrolytes that facilitate the formation of stable solid electrolyte interphases (SEIs) to mitigate dendrite formation is imperative to enable lithium anodes in next‐generation energy‐dense batteries. Compared to traditional electrolyte solvents, tetrahydrofuran (THF)‐based electrolyte systems have demonstrated great success in enabling high‐stability lithium anodes by encouraging the decomposition of anions (instead of organic solvent) and thus generating inorganic‐rich SEIs. Herein, by employing a variety of different lithium salts (i.e., LiPF_6,LiTFSI, LiFSI, and LiDFOB), it is demonstrated that electrolyte anions modulate the inorganic composition and resulting properties of the SEI. Through novel analytical time‐of‐flight secondary‐ion mass spectrometry methods, such as hierarchical clustering of depth profiles and compositional analysis using integrated yields, the chemical composition and morphology of the SEIs generated from each electrolyte system are examined. Notably, the LiDFOB electrolyte provides an exceptionally stable system to enable lithium anodes, delivering >1500 cycles at a current density of 0.5 mAh g⁻¹and a capacity of 0.5 mAh g⁻¹in symmetrical cells. Furthermore, Li//LFP cells using this electrolyte demonstrate high‐rate, reversible lithium storage, supplying 139 mAh g_(LFP)⁻¹at C/2 (≈0.991 mAh cm⁻², @ 0.61 mA cm⁻²) with 87.5% capacity retention over 300 cycles (average Coulombic efficiency >99.86%).

 

The performance of the rechargeable Li metal battery anode is limited by the poor ionic conductivity and poor mechanical properties of its solid-electrolyte interphase (SEI) layer. To overcome this, a 3 : 1 v/v ethyl methyl carbonate (EMC) : fluoroethylene carbonate (FEC) containing 0.8 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 0.2 M lithium difluoro(oxalate)borate (LiDFOB) dual-salts with 0.05 M lithium hexafluorophosphate (LiPF 6 ) was tested to promote the formation of a multitude of SEI-beneficial species. The resulting SEI layer was rich in LiF, Li 2 CO 3 , oligomeric and glass borates, Li 3 N, and Li 2 S, which enhanced its role as a protective yet Li + conductive film, stabilizing the lithium metal anode and minimizing dead lithium build-up. With a stable SEI, a Li/Li[Ni 0.59 Co 0.2 Mn 0.2 Al 0.01 ]O 2 Li-metal battery (LMB) retains 75% of its 177 mA h g −1 specific discharge capacity for 500 hours at a coulombic efficiency of greater than 99.3% at the fast charge–discharge rate of 1.8 mA cm −2 . 

With more than 10 times the capacity of the graphite used in current commercial batteries, lithium metal is ideal for a high-capacity battery anode; however, lithium metal electrodes suffer from safety and efficiency problems that prevent their wide industrial adoption. Their intrinsic high reactivity towards most liquid organic electrolytes leads to lithium loss and dendrite growth, which result in poor efficiency and short circuiting. However, the multitude of factors that contribute to dendrite formation make determining a nucleation mechanism extremely difficult. Here, we study the intricate science of dendrite nucleation on metallic lithium by using an array of analytical techniques that provide simultaneous ultra-high spatial sensitivity and chemical selectivity. Our results reveal a 3D picture of the chemical make-up of the native Li surface and the resulting solid electrolyte interphase (SEI) with better than 200 nm resolution. We find that, contrary to the general understanding, the initial surface chemistry, not the topography, is the dominant factor leading to dendrite nucleation. Specifically, inhomogeneously distributed organic material in the native surface leads to inhomogeneously dispersed LiF-rich SEI regions where dendrite nucleation is favored. This has significant implications for battery research as it elucidates a mechanism for inhomogeneous SEI formation, something that is accepted, but not well understood, and highlights the importance of Li surface preparation for experimental studies, which is implicit in battery research, but not directly addressed in the literature. By homogenizing the initial lithium surface composition, and thus the SEI composition, we increase the number of dendrite nucleation sites and thereby decrease the dendrite size, which significantly increases the electrode lifetime.