title: Ultrafine Iron Pyrite (FeS₂) Nanocrystals Improve Sodium-Sulfur and Lithium-Sulfur Conversion Reactions for Efficient Batteries.
abstract: Nanocrystals with quantum-confined length scales are often considered impractical for metal-ion battery electrodes due to the dominance of solid-electrolyte interphase (SEI) layer effects on the measured storage properties. Here we demonstrate that ultrafine sizes (∼4.5 nm, average) of iron pyrite, or FeS2, nanoparticles are advantageous to sustain reversible conversion reactions in sodium ion and lithium ion batteries. This is attributed to a nanoparticle size comparable to or smaller than the diffusion length of Fe during cation exchange, yielding thermodynamically reversible nanodomains of converted Fe metal and NaxS or LixS conversion products. This is compared to bulk-like electrode materials, where kinetic and thermodynamic limitations of surface-nucleated conversion products inhibit successive conversion cycles. Reversible capacities over 500 and 600 mAh/g for sodium and lithium storage are observed for ultrafine nanoparticles, with improved cycling and rate capability. Unlike alloying or intercalation processes, where SEI effects limit the performance of ultrafine nanoparticles, our work highlights the benefit of quantum dot length-scale nanocrystal electrodes for nanoscale metal sulfide compounds that store energy through chemical conversion reactions.
authors.forename: Anna
authors.initials: A
authors.lastname: Douglas
authors.forename: Rachel
authors.initials: R
authors.lastname: Carter
authors.forename: Landon
authors.initials: L
authors.lastname: Oakes
authors.forename: Keith
authors.initials: K
authors.lastname: Share
authors.forename: Adam P
authors.initials: AP
authors.lastname: Cohn
authors.affiliation: Vanderbilt Institute of Nanoscale Science and Engineering , Nashville, Tennessee 37235, United States.
authors.forename: Cary L
authors.initials: CL
authors.lastname: Pint
keywords: FeS2 nanoparticles; batteries; chemical transformations; iron pyrite; lithium sulfur; quantum dots; sodium sulfur