Browsing by Author "Chen, EY"

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    Gallium-doped Li7La3Zr2O12 garnet-type electrolytes with high lithium-ion conductivity
    (American Chemical Society, 2016-12-22) Wu, JF; Chen, EY; Yu, Y; Liu, L; Pang, WK; Peterson, VK; Guo, X
    Owing to their high conductivity, crystalline Li7–3xGaxLa3Zr2O12 garnets are promising electrolytes for all-solid-state lithium-ion batteries. Herein, the influence of Ga doping on the phase, lithium-ion distribution, and conductivity of Li7–3xGaxLa3Zr2O12 garnets is investigated, with the determined concentration and mobility of lithium ions shedding light on the origin of the high conductivity of Li7–3xGaxLa3Zr2O12. When the Ga concentration exceeds 0.20 Ga per formula unit, the garnet-type material is found to assume a cubic structure, but lower Ga concentrations result in the coexistence of cubic and tetragonal phases. Most lithium within Li7–3xGaxLa3Zr2O12 is found to reside at the octahedral 96h site, away from the central octahedral 48g site, while the remaining lithium resides at the tetrahedral 24d site. Such kind of lithium distribution leads to high lithium-ion mobility, which is the origin of the high conductivity; the highest lithium-ion conductivity of 1.46 mS/cm at 25 °C is found to be achieved for Li7–3xGaxLa3Zr2O12 at x = 0.25. Additionally, there are two lithium-ion migration pathways in the Li7–3xGaxLa3Zr2O12 garnets: 96h-96h and 24d-96h-24d, but the lithium ions transporting through the 96h-96h pathway determine the overall conductivity. © 2016 American Chemical Society
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    Role of oxygen vacancy ordering and channel formation in tuning intercalation pseudocapacitance in Mo single-ion-implanted CeO2–x nanoflakes
    (American Chemical Society, 2021-12-07) Zheng, XR; Mofarah, SS; Cen, A; Cazorla, C; Haque, E; Chen, EY; Atanacio, AJ; Manohar, M; Vutukuri, C; Abraham, JL; Koshy, P; Sorrell, CC
    Metal oxide pseudocapacitors are limited by low electrical and ionic conductivities. The present work integrates defect engineering and architectural design to exhibit, for the first time, intercalation pseudocapacitance in CeO2–x. An engineered chronoamperometric electrochemical deposition is used to synthesize 2D CeO2–x nanoflakes as thin as ∼12 nm. Through simultaneous regulation of intrinsic and extrinsic defect concentrations, charge transfer and charge–discharge kinetics with redox and intercalation capacitances together are optimized, where reduction increases the gravimetric capacitance by 77% to 583 F g–1, exceeding the theoretical capacitance (562 F g–1). Mo ion implantation and reduction processes increase the specific capacitance by 133%, while the capacitance retention increases from 89 to 95%. The role of ion-implanted Mo6+ is critical through its interstitial solid solubility, which is not to alter the energy band diagram but to facilitate the generation of electrons and to establish the midgap states for color centers, which facilitate electron transfer across the band gap, thus enhancing n-type semiconductivity. Critically, density functional theory simulations reveal, for the first time, that the reduction causes the formation of ordered oxygen vacancies that provide an atomic channel for ion intercalation. These channels enable intercalation pseudocapacitance but also increase electrical and ionic conductivities. In addition, the associated increased active site density enhances the redox such that the 10% of the Ce3+ available for redox (surface only) increases to 35% by oxygen vacancy channels. These findings are critical for any oxide system used for energy storage systems, as they offer both architectural design and structural engineering of materials to maximize the capacitance performance by achieving accumulative surface redox and intercalation-based redox reactions during the charge/discharge process. © 2021 American Chemical Society