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    Revealing the Various Electrochemical Behaviors of Sn4P3 Binary Alloy Anodes in Alkali Metal Ion Batteries
    (Weinheim : Wiley-VCH, 2021) Zhou, Junhua; Lian, Xueyu; You, Yizhou; Shi, Qitao; Liu, Yu; Yang, Xiaoqin; Liu, Lijun; Wang, Dan; Choi, Jin-Ho; Sun, Jingyu; Yang, Ruizhi; Rummeli, Mark H.
    Sn4P3 binary alloy anode has attracted much attention, not only because of the synergistic effect of P and Sn, but also its universal popularity in alkali metal ion batteries (AIBs), including lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (PIBs). However, the alkali metal ion (A+) storage and capacity attenuation mechanism of Sn4P3 anodes in AIBs are not well understood. Herein, a combination of ex situ X-ray diffraction, transmission electron microscopy, and density functional theory calculations reveals that the Sn4P3 anode undergoes segregation of Sn and P, followed by the intercalation of A+ in P and then in Sn. In addition, differential electrochemical curves and ex situ XPS results demonstrate that the deep insertion of A+ in P and Sn, especially in P, contributes to the reduction in capacity of AIBs. Serious sodium metal dendrite growth causes further reduction in the capacity of SIBs, while in PIBs it is the unstable solid electrolyte interphase and sluggish dynamics that lead to capacity decay. Not only the failure mechanism, including structural deterioration, unstable SEI, dendrite growth, and sluggish kinetics, but also the modification strategy and systematic analysis method provide theoretical guidance for the development of other alloy-based anode materials. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
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    On the Catalytic Activity of Sn Monomers and Dimers at Graphene Edges and the Synchronized Edge Dependence of Diffusing Atoms in Sn Dimers
    (Weinheim : Wiley-VCH, 2021) Yang, Xiaoqin; Ta, Huy Q.; Hu, Huimin; Liu, Shuyuan; Liu, Yu; Bachmatiuk, Alicja; Luo, Jinping; Liu, Lijun; Choi, Jin-Ho; Rummeli, Mark H.
    In this study, in situ transmission electron microscopy is performed to study the interaction between single (monomer) and paired (dimer) Sn atoms at graphene edges. The results reveal that a single Sn atom can catalyze both the growth and etching of graphene by the addition and removal of C atoms respectively. Additionally, the frequencies of the energetically favorable configurations of an Sn atom at a graphene edge, calculated using density functional theory calculations, are compared with experimental observations and are found to be in good agreement. The remarkable dynamic processes of binary atoms (dimers) are also investigated and is the first such study to the best of the knowledge. Dimer diffusion along the graphene edges depends on the graphene edge termination. Atom pairs (dimers) involving an armchair configuration tend to diffuse with a synchronized shuffling (step-wise shift) action, while dimer diffusion at zigzag edge terminations show a strong propensity to collapse the dimer with each atom diffusing in opposite directions (monomer formation). Moreover, the data reveals the role of C feedstock availability on the choice a single Sn atom makes in terms of graphene growth or etching. This study advances the understanding single atom catalytic activity at graphene edges. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
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    High-performance electronics and optoelectronics of monolayer tungsten diselenide full film from pre-seeding strategy
    (Weinheim : Wiley, 2021) Zhang, Shu; Pang, Jinbo; Cheng, Qilin; Yang, Feng; Chen, Yu; Liu, Yu; Li, Yufen; Gemming, Thomas; Liu, Xiaoyan; Ibarlucea, Bergoi; Yang, Jiali; Liu, Hong; Zhou, Weijia; Cuniberti, Gianaurelio; Rümmeli, Mark H.
    Tungsten diselenide (WSe2) possesses extraordinary electronic properties for applications in electronics, optoelectronics, and emerging exciton physics. The synthesis of monolayer WSe2 film is of topmost for device arrays and integrated circuits. The monolayer WSe2 film has yet been reported by thermal chemical vapor deposition (CVD) approach, and the nucleation mechanism remains unclear. Here, we report a pre-seeding strategy for finely regulating the nuclei density at an early stage and achieving a fully covered film after chemical vapor deposition growth. The underlying mechanism is heterogeneous nucleation from the pre-seeding tungsten oxide nanoparticles. At first, we optimized the precursor concentration for pre-seeding. Besides, we confirmed the superiority of the pre-seeding method, compared with three types of substrate pretreatments, including nontreatment, sonication in an organic solvent, and oxygen plasma. Eventually, the high-quality synthetic WSe2 monolayer film exhibits excellent device performance in field-effect transistors and photodetectors. We extracted thermodynamic activation energy from the nucleation and growth data. Our results may shed light on the wafer-scale production of homogeneous monolayer films of WSe2, other 2D materials, and their van der Waals heterostructures.
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    Dual‐Salt Electrolyte Additives Enabled Stable Lithium Metal Anode/Lithium–Manganese‐Rich Cathode Batteries
    (Weinheim : Wiley-VCH, 2021) Zhou, Junhua; Lian, Xueyu; Shi, Qitao; Liu, Yu; Yang, Xiaoqin; Bachmatiuk, Alicja; Liu, Lijun; Sun, Jingyu; Yang, Ruizhi; Choi, Jin-Ho; Rummeli, Mark H.
    Although lithium (Li) metal anode/lithium–manganese-rich (LMR) cathode batteries have an ultrahigh energy density, the highly active Li metal and structural deterioration of LMR can make the usage of these batteries difficult. Herein, a multifunctional electrolyte containing LiBF4 and LiFSI dual-salt additives is designed, which enables the superior cyclability of Li/LMR cells with capacity retentions of ≈83.4%, 80.4%, and 76.6% after 400 cycles at 0.5, 1, and 2 C, respectively. The dual-salt electrolyte can form a thin, uniform, and inorganic species-rich solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI). In addition, it alleviates the bulk Li corrosion and enhances the structural sustainability of LMR cathode. Moreover, the electrolyte design strategy provides insights to develop other high-voltage lithium metal batteries (HVLMBs) to enhance the cycle stability.