A Single-Ion Conducting Borate Network Polymer as a Viable Quasi-Solid Electrolyte for Lithium Metal Batteries.

Lithium-ion batteries have remained a state-of-the-art electrochemical energy storage technology for decades now, but their energy densities are limited by electrode materials and conventional liquid electrolytes can pose significant safety concerns. Lithium metal batteries featuring Li metal anodes, solid polymer electrolytes, and high-voltage cathodes represent promising candidates for next-generation devices exhibiting improved power and safety, but such solid polymer electrolytes generally do not exhibit the required excellent electrochemical properties and thermal stability in tandem. Here, an interpenetrating network polymer with weakly coordinating anion nodes that functions as a high-performing single-ion conducting electrolyte in the presence of minimal plasticizer, with a wide electrochemical stability window, a high room-temperature conductivity of 1.5 × 10-4 S cm-1 , and exceptional selectivity for Li-ion conduction (tLi+ = 0.95) is reported. Importantly, this material is also flame retardant and highly stable in contact with lithium metal. Significantly, a lithium metal battery prototype containing this quasi-solid electrolyte is shown to outperform a conventional battery featuring a polymer electrolyte.

Detection of the Order-to-Disorder Transition in Block Copolymer Electrolytes Using Quadrupolar 7Li NMR Splitting.

The order-to-disorder transition temperature (TODT) in a series of mixtures of polystyrene-b-poly(ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt is identified by the disappearance of a quadrupolar 7Li NMR triplet peak splitting above a critical temperature, where a singlet is observed. The macroscopic alignment of ordered domains required to produce a quadrupolar splitting occurs due to exposure to the NMR magnetic field. Alignment is confirmed using small-angle X-ray scattering (SAXS). The TODT determined by NMR is consistent with that determined using SAXS.

Anomalous Self-Assembly and Ion Transport in Nanostructured Organic-Inorganic Solid Electrolytes.

Nanostructured solid electrolytes containing ion-conducting domains and rigid nonconducting domains are obtained by block copolymer self-assembly. Here, we report on the synthesis and characteristics of mixtures of a hybrid diblock copolymer with an organic and inorganic block: poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) and a lithium salt. In the neat state, PEO-POSS exhibits a classical order-to-disorder transition upon heating. Dilute electrolytes exhibit a dramatic reversal; a disorder-to-order transition upon heating is obtained, indicating that the addition of salt fundamentally changes interactions between the organic and inorganic chains. At higher salt concentrations, the electrolytes primarily form a lamellar phase. Coexisting lamellae and cylinders are found at intermediate salt concentrations and high temperatures. The conductivity and shear modulus of PEO-POSS are significantly higher than that of an all-organic block copolymer electrolyte with similar molecular weight and morphology, demonstrating that organic-inorganic block copolymers provide a promising route for developing the next generation of solid electrolytes for lithium batteries.