Solvation

Electrode

Diluent

Organic chemistry

Lithium metal

Endocrinology

Engineering

Physical chemistry

Inorganic chemistry

Chemistry

Salt (chemistry)

Metallurgy

Materials science

Solvent

Lithium (medication)

Cathode

Metal

Electrolyte

Chemical engineering

Medicine

Advanced Energy Materials

Electrolytes play a critical role in stabilizing highly reactive lithium‐metal anodes (LMAs) and high‐voltage cathodes for rechargeable lithium‐metal batteries (LMBs). Localized high concentration electrolytes (LHCEs) have achieved remarkable success in the context of LMBs. However, the state‐of‐the‐art LHCEs are based on LiFSI salt, which is prohibitively expensive. Here, the utility of low‐cost LiPF 6 salt in localized saturated electrolytes (LSEs) with a series of solvents and diluents in LMBs with cobalt‐free LiNiO 2 cathode is systematically explored. Experimental and theoretical analyses reveal that the unique solvation structure formed not only changes the distribution of solvents and anions but also alters the atom–atom distances within them, leading to different reduction and oxidation stabilities compared to low‐concentration electrolytes. In addition, LSEs help form LiF‐rich interphase layers on the LMA and LiNiO 2 cathode, protecting the electrodes from degradation during cycling. Different LSEs also lead to differences in lithium plating morphology and impedance buildup during cycling, impacting the performance of LMBs. The solvent and diluent must be carefully selected for compatibility with a lithium salt when developing LHCEs and LSEs for LMBs.

Uncovering the Solvation Structure of LiPF<sub>6</sub>‐Based Localized Saturated Electrolytes and Their Effect on LiNiO<sub>2</sub>‐Based Lithium‐Metal Batteries

Uncovering the Solvation Structure of LiPF6‐Based Localized Saturated Electrolytes and Their Effect on LiNiO2‐Based Lithium‐Metal Batteries

Uncovering the Solvation Structure of LiPF₆‐Based Localized Saturated Electrolytes and Their Effect on LiNiO₂‐Based Lithium‐Metal Batteries