No abstract

Colloidal iron pyrite nanocrystals (or FeS 2 NC inks) are desirable as active materials in lithium ion batteries and photovoltaics and are particularly suitable for large-scale, roll-to-roll deposition or inkjet printing. However, to date, FeS 2 NC inks have only been synthesized using the hot-injection technique, which requires air-free conditions and may not be desirable at an industrial scale. Here, we report the synthesis of monodisperse, colloidal, spherical, and phase-pure FeS 2 NCs of 5.5 ± 0.3 nm in diameter via a scalable solvothermal method using iron diethyldithiocarbamate as the precursor, combined with a postdigestive ripening process. The phase purity and crystallinity are determined using X-ray diffraction, transmission electron microscopy, farinfrared spectroscopy, and Raman spectroscopy techniques. Through this study, a hypothesis has been verified that solvothermal syntheses can also produce FeS 2 NC inks by incorporating three experimental conditions: high solubility of the precursor, efficient mass transport, and sufficient stabilizing ligands. The addition of ligands and stirring decrease the NC size and led to a narrow size distribution. Moreover, using density functional theory calculations, we have identified an acid-mediated decomposition of the precursor as the initial and critical step in the synthesis of FeS 2 from iron diethyldithiocarbamate.

Iron pyrite (p-FeS2) has been widely utilized as a commercial cathode material for lithium ion batteries (LIBs) for 30+ years, due to its high charge capacity, natural abundance, low cost, and non-toxicity. Industrialized versions include both non-rechargeable Li/FeS2 batteries at ambient temperatures (-40 – 60 °C) and rechargeable Li/FeS2 batteries at high temperatures (400 – 450 °C). However, FeS2 cathodes suffer from very poor cyclability at room temperature. Four specific reasons have been identified for this problem: 1) Volume fluctuations during cycling, resulting in pulverization of large particles and a subsequent loss of contact to the current collector; 2) poor electrical conductivity of the lithiation product, lithium sulfide; 3) detrimental reactions between the electrolyte solution and the active materials (FeS2and its subsequent derivatives); 4) the loss of materials due to the formation of soluble lithium polysulfides. In this presentation, we will outline our strategy to address all of the above challenges for FeS2 through the encapsulation of FeS2 nanoparticles in an elastic carbon (EC) matrix. Two carbon sources are explored to produce an ideal EC matrix, which is chemically and mechanically stable, elastic, and conductive. These unique properties allow accommodation of the volume fluctuation, enhance the charge transfer, and protect the FeS2 from damaging chemical reactions. The obtained FeS2@EC composites present significantly improved cyclability over bare FeS2 nanoparticles. Scanning electron microscopy, Raman spectroscopy, electrochemical impedance spectroscopy, and cyclability studies are utilized to confirm the structure-performance relationship.