In this work, we examine the Mg-ion desolvation and intercalation process at the Chevrel phase Mo 6 S 8 cathode surface from first-principles. It is reported that in electrolytes based on chlorides in tetrahydrofuran (THF), Mg 2+ is strongly coordinated by the counterion Cl and can form singly charged MgCl + and Mg 2 Cl + 3 species in solution. During cell discharge, Mg intercalation into the Chevrel phase requires breaking the strong, ionic Mg-Cl bond. Our simulation results indicate that the stripping of Cl is facilitated by the existence of another cationic species, Mo on the Chevrel phase surface. Once Mg is intercalated, it leaves the counterion, Cl , on the surface, bound to Mo. It is found that the chlorinated surface presents higher activation barriers to further intercalate Mg. Instead, the chlorinated surface continues to interact with incoming MgCl + species and form various MgCl y surface adsorbates. With certain energy costs, the neutral MgCl 2 unit may be released from these surface adsorbates to reopen Mo sites on the surface and permit continuous Mg intercalation. Presuming compatibility of chloride electrolytes with the Mg metal anode, our work implies that finding a compatible cathode material will depend critically on its ability to catalyze Mg-Cl bond-breaking. This may explain the success of the Chevrel phase, with its open Mo sites, permitting intercalation of Mg from the halide solutions, whereas higher voltage transition metal oxides, which typically lack open metal sites, require more weakly coordinating anions in their electrolytes.

Li-S batteries have been extensively studied using rigid carbon as the host for sulfur encapsulation, but improving the properties with a reduced electrolyte amount remains a significant challenge. This is critical for achieving high energy density. Here, we developed a soft PEOLiTFSI polymer swellable gel as a nanoscale reservoir to trap the polysulfides under lean electrolyte conditions. The PEOLiTFSI gel immobilizes the electrolyte and confines polysulfides within the ion conducting phase. The Li-S cell with a much lower electrolyte to sulfur ratio (E/S) of 4 g/g (3.3 mL/g) could deliver a capacity of 1200 mA h/g, 4.6 mA h/cm, and good cycle life. The accumulation of polysulfide reduction products, such as LiS, on the cathode, is identified as the potential mechanism for capacity fading under lean electrolyte conditions.

Lithium-metal anodes can theoretically enable 10× higher gravimetric capacity than conventional graphite anodes. However, Li-metal anode cycling has proven difficult due to porous and dendritic morphologies, extensive parasitic solid electrolyte interphase reactions, and formation of dead Li. We systematically investigate the effects of applied interfacial pressure on Li-metal anode cycling performance and morphology in the recently developed and highly efficient 4 M lithium bis­(fluorosulfonyl)­imide in 1,2-dimethoxyethane electrolyte. We present cycling, morphology, and impedance data at a current density of 0.5 mA/cm2 and a capacity of 2 mAh/cm2 at applied interfacial pressures of 0, 0.01, 0.1, 1, and 10 MPa. Cryo-focused ion beam milling and cryo-scanning electron microscopy imaging in cross section reveal that increasing the applied pressure during Li deposition from 0 to 10 MPa leads to greater than a fivefold reduction in thickness (and therefore volume) of the deposited Li. This suggests that pressure during cycling can have a profound impact on the practical volumetric energy density for Li-metal anodes. A “goldilocks zone” of cell performance is observed at intermediate pressures of 0.1–1 MPa. Increasing pressure from 0 to 1 MPa generally improves cell-to-cell reproducibility, cycling stability, and Coulombic efficiency. However, the highest pressure (10 MPa) results in high cell overpotential and evidence of soft short circuits, which likely result from transport limitations associated with increased pressure causing local pore closure in the separator. All cells exhibit at least some signs of cycling instability after 50 cycles when cycled to 2 mAh/cm2 with thin 50 μm Li counter electrodes, though instability decreases with increasing pressure. In contrast, cells cycled to only 1 mAh/cm2 perform well for 50 cycles, indicating that capacity plays an important role in cycling stability.

To suppress dendrite formation in lithium metal batteries, high cation transference number electrolytes that reduce electrode polarization are highly desirable, but rarely available using conventional liquid electrolytes. Here, we show that liquid electrolytes increase their cation transference numbers (e.g., ∼0.2 to >0.70) when confined to a structurally rigid polymer host whose pores are on a similar length scale (0.5–2 nm) as the Debye screening length in the electrolyte, which results in a diffuse electrolyte double layer at the polymer–electrolyte interface that retains counterions and reject co-ions from the electrolyte due to their larger size. Lithium anodes coated with ∼1 μm thick overlayers of the polymer host exhibit both a low area-specific resistance and clear dendrite-suppressing character, as evident from their performance in Li–Li and Li–Cu cells as well as in post-mortem analysis of the anode’s morphology after cycling. High areal capacity Li–S cells (4.9 mg cm–2; 8.2 mAh cm–2) implementing these high transference number polymer-hosted liquid electrolytes were remarkably stable, considering ∼24 μm of lithium was electroreversibly deposited in each cycle at a C-rate of 0.2. We further identified a scalable manufacturing path for these polymer-coated lithium electrodes, which are drop-in components for lithium metal battery manufacturing.