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  1. Abstract

    The instability of Nickel (Ni)‐rich cathodes at high voltage is a critical bottleneck toward developing superior lithium‐ion batteries. This instability is driven by cathode‐electrolyte side reactions, causing rapid degradation, and compromising the overall cycle life. In this study, a protective coating using dispersed “magnetite (FeO.Fe2O3)” nanoparticles is used to uniformly decorate the surface of LiNi0.8Co0.1Mn0.1O2(NMC 811) microparticles. The modified cathode delivers significant improvement in electrochemical performance at high voltage (≈4.6 V) by suppressing deleterious electrode–electrolyte interactions. A notably higher cycle stability, rate performance, and overall energy density is realized for the coated cathode in a conventional liquid electrolyte battery. When deployed in pellet‐stacked solid‐state cells with Li6PS5Cl as the electrolyte, the magnetite‐coated NMC 811 showed strikingly superior cycling stability than its uncoated counterpart, proving the versatility of the chemistry. The facile surfactant‐assisted coating process developed in this work, in conjunction with the affordability, abundance, and nontoxic nature of magnetite makes this a promising approach to realize commercially viable high voltage Ni‐rich cathodes that exhibit stable performance in liquid as well as solid‐state lithium‐ion batteries.

     
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  2. Looming concerns regarding scarcity, high prices, and safety threaten the long-term use of lithium in energy storage devices. Calcium has been explored in batteries because of its abundance and low cost, but the larger size and higher charge density of calcium ions relative to lithium impairs diffusion kinetics and cyclic stability. In this work, an aqueous calcium–ion battery is demonstrated using orthorhombic, trigonal, and tetragonal polymorphs of molybdenum vanadium oxide (MoVO) as a host for calcium ions. Orthorhombic and trigonal MoVOs outperform the tetragonal structure because large hexagonal and heptagonal tunnels are ubiquitous in such crystals, providing facile pathways for calcium–ion diffusion. For trigonal MoVO, a specific capacity of ∼203 mAh g −1 was obtained at 0.2C and at a 100 times faster rate of 20C, an ∼60 mAh g −1 capacity was achieved. The open-tunnel trigonal and orthorhombic polymorphs also promoted cyclic stability and reversibility. A review of the literature indicates that MoVO provides one of the best performances reported to date for the storage of calcium ions. 
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  3. null (Ed.)
  4. The use of potassium (K) metal anodes could result in high-performance K-ion batteries that offer a sustainable and low-cost alternative to lithium (Li)-ion technology. However, formation of dendrites on such K-metal surfaces is inevitable, which prevents their utilization. Here, we report that K dendrites can be healed in situ in a K-metal battery. The healing is triggered by current-controlled, self-heating at the electrolyte/dendrite interface, which causes migration of surface atoms away from the dendrite tips, thereby smoothening the dendritic surface. We discover that this process is strikingly more efficient for K as compared to Li metal. We show that the reason for this is the far greater mobility of surface atoms in K relative to Li metal, which enables dendrite healing to take place at an order-of-magnitude lower current density. We demonstrate that the K-metal anode can be coupled with a potassium cobalt oxide cathode to achieve dendrite healing in a practical full-cell device.

     
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  5. Abstract

    Organic–inorganic halide perovskites are intrinsically unstable when exposed to moisture and/or light. Additionally, the presence of lead in many perovskites raises toxicity concerns. Herein, a thin film of barium zirconium sulfide (BaZrS3), a lead‐free chalcogenide perovskite, is reported. Photoluminescence and X‐ray diffraction measurements show that BaZrS3is far more stable than methylammonium lead iodide (MAPbI3) in moist environments. Moisture‐ and light‐induced degradations in BaZrS3and MAPbI3are compared by using simulations and calculations based on density functional theory. The simulations reveal drastically slower degradation in BaZrS3due to two factors—weak interaction with water and very low rates of ion migration. BaZrS3photodetecting devices with photoresponsivity of ≈46.5 mA W−1are also reported. The devices retain ≈60% of their initial photoresponse after 4 weeks under ambient conditions. Similar MAPbI3devices degrade rapidly and show a ≈95% decrease in photoresponsivity in just 4 days. The findings establish the superior stability of BaZrS3and strengthen the case for its use in optoelectronics. New possibilities for thermoelectric energy conversion using these materials are also demonstrated.

     
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