(Best Student Presentation) Is Solid-Electrolyte Interphase Formation Affected by Electrode Conductivity?
Authors: Rakov Dmitrii 
Published: September 2023

Accurate analysis of the mechanism of interphase formation and its composition is imperative for the development of stable and efficient lithium/sodium-ion batteries. One of the most practically scalable ways to optimize interphase chemistry and morphology for reversible charge transport is electrolyte engineering and the application of formation protocol with specific current/voltage conditions. In this sense, the analysis of structure and dynamics within the electrode/electrolyte interface, i.e., the so-called electric-double layer, is essential to predicting the possible chemistry and mechanism of interphase formation.

The latest was recently advanced by understanding the effect of electrolyte chemistry, e.g., the chemical structure of solvent and salt, their ratio, the presence of additives etc.1–4 Although, the role of electrode material is often neglected which creates an impression that both metallic and semiconductive electrodes form an identical electric-double layer within the same electrolyte, therefore, the mechanism of interphase formation should be very similar regardless of the chemical nature of the electrode.

Here, we used examples of sodium-salt-containing ionic liquids and carbonate electrolytes to demonstrate that structural changes at the electrified interface are greatly affected by the dielectric nature of electrode material. The key observation is attributed to the different abilities of electrified electrodes to form van der Waals interactions with the electrolyte species. This affects the concentration of metal-anion complexes in relation to organic solvent near the electrode, therefore, different interphase chemistry will be formed (inorganic-rich vs. organic-rich), and different formation protocols must be used. For example, Fig. 1 shows the summary of this phenomenon for ionic liquid electrolytes with 50 mol% sodium bis(fluorosulfonyl)imide. Besides, metallic and semiconductive electrodes demonstrated different affinity toward polar organic solvent, i.e., ethylene carbonate, in 1.0 M NaPF6 in EC:DMC (1:1 by volume) electrolyte. This presentation will discuss the details of these fundings and introduce future applications.

Fig. 1 | Schematic relationships between solid-electrolyte interphase (SEI) composition, applied current of preconditioning cycling, and dielectric nature of anode material.

References

Zheng, X. et al. Toward High Temperature Sodium Metal Batteries via Regulating the Electrolyte/Electrode Interfacial Chemistries. ACS Energy Lett.
7, 2032–2042 (2022).

Rakov, D. A. et al. Engineering high-energy-density sodium battery anodes for improved cycling with superconcentrated ionic-liquid electrolytes. Nat. Mater.
19, 1096–1101 (2020).

Rakov, D. A. et al. Polar Organic Cations at Electrified Metal with Superconcentrated Ionic Liquid Electrolyte and Implications for Sodium Metal Batteries. ACS Mater. Lett.
4, 1984–1990 (2022).

Rakov, D. et al. Stable and Efficient Lithium Metal Anode Cycling through Understanding the Effects of Electrolyte Composition and Electrode Preconditioning. Chem. Mater. (2021). doi:10.1021/acs.chemmater.1c02981

Figure 1