All Publications


  • Transient Voltammetry with Ultramicroelectrodes Reveals the Electron Transfer Kinetics of Lithium Metal Anodes Adv. Energy Lett. Boyle, D., Kong, X., Pei, A., Rudnicki, P., Shi, F., Huang, W., Bao, Z., Qin, J., Cui, Y. 2020; 5: 701-709
  • Evolution of the Solid-Electrolyte Interphase on Carbonaceous Anodes Visualized by Atomic-Resolution Cryogenic Electron Microscopy. Nano letters Huang, W. n., Attia, P. M., Wang, H. n., Renfrew, S. E., Jin, N. n., Das, S. n., Zhang, Z. n., Boyle, D. T., Li, Y. n., Bazant, M. Z., McCloskey, B. D., Chueh, W. C., Cui, Y. n. 2019

    Abstract

    The stability of modern lithium-ion batteries depends critically on an effective solid-electrolyte interphase (SEI), a passivation layer that forms on the carbonaceous negative electrode as a result of electrolyte reduction. However, a nanoscopic understanding of how the SEI evolves with battery aging remains limited due to the difficulty in characterizing the structural and chemical properties of this sensitive interphase. In this work, we image the SEI on carbon black negative electrodes using cryogenic transmission electron microscopy (cryo-TEM) and track its evolution during cycling. We find that a thin, primarily amorphous SEI nucleates on the first cycle, which further evolves into one of two distinct SEI morphologies upon further cycling: (1) a compact SEI, with a high concentration of inorganic components that effectively passivates the negative electrode; and (2) an extended SEI spanning hundreds of nanometers. This extended SEI grows on particles that lack a compact SEI and consists primarily of alkyl carbonates. The diversity in observed SEI morphologies suggests that SEI growth is a highly heterogeneous process. The simultaneous emergence of these distinct SEI morphologies highlights the necessity of effective passivation by the SEI, as large-scale extended SEI growths negatively impact lithium-ion transport, contribute to capacity loss, and may accelerate battery failure.

    View details for DOI 10.1021/acs.nanolett.9b01515

    View details for PubMedID 31322896

  • Dynamic Structure and Chemistry of the Silicon Solid-Electrolyte Interphase Visualized by Cryogenic Electron Microscopy Matter Huang, W., Wang, J., Braun, M. R., Zhang, Z., Li, Y., Boyle, D. T., McIntyre, P. C., Cui, Y. 2019; 1 (5)
  • Nanostructural and Electrochemical Evolution of the Solid-Electrolyte Interphase on CuO Nanowires Revealed by Cryogenic-Electron Microscopy and Impedance Spectroscopy ACS NANO Huang, W., Boyle, D. T., Li, Y., Li, Y., Pei, A., Chen, H., Cui, Y. 2019; 13 (1): 737–44

    Abstract

    Battery performance is critically dependent on the nanostructure and electrochemical properties of the solid-electrolyte interphase (SEI) - a passivation film that exists on most lithium battery anodes. However, knowledge of how the SEI nanostructure forms and its impact on ionic transport remains limited due to its sensitivity to transmission electron microscopy and difficulty in accurately probing the SEI impedance. Here, we track the voltage-dependent, stepwise evolution of the nanostructure and impedance of the SEI on CuO nanowires using cryogenic-electron microscopy (cryo-EM) and electrochemical impedance spectroscopy (EIS). In carbonate electrolyte, the SEI forms at 1.0 V vs Li/Li+ as a 3 nm-thick amorphous SEI and grows to 4 nm at 0.5 V; as the potential approaches 0.0 V vs Li/Li+, the SEI on the CuO nanowires forms an 8 nm-thick inverted multilayered nanostructure in ethylene carbonate/diethyl carbonate (EC/DEC) electrolyte with 10 vol. % fluoroethylene carbonate (FEC) and a mosaic nanostructure in EC/DEC electrolyte. Upon Li deposition, the total SEI thickness grows to 16 nm and significant growth of the inner amorphous layer takes place in the inverted multilayered nanostructure, indicating electrolyte permeates the SEI. Using a refined EIS methodology, we isolate the SEI impedance on Cu and find that the SEI nanostructure directly correlates to macroscopic Li-ion transport through the SEI. The inverted layered nanostructure decreases the interfacial impedance upon formation, whereas the mosaic nanostructure continually increases the interfacial impedance during growth. These structural and electrochemical findings illustrate a more complete portrait of SEI formation and guide further improvements in engineered SEI.

    View details for DOI 10.1021/acsnano.8b08012

    View details for Web of Science ID 000456749900075

    View details for PubMedID 30589528

  • Correlating Structure and Function of Battery Interphases at Atomic Resolution Using Cryoelectron Microscopy JOULE Li, Y., Huang, W., Li, Y., Pei, A., Boyle, D., Cui, Y. 2018; 2 (10): 2167–77
  • Lithium metal stripping beneath the solid electrolyte interphase. Proceedings of the National Academy of Sciences of the United States of America Shi, F., Pei, A., Boyle, D. T., Xie, J., Yu, X., Zhang, X., Cui, Y. 2018

    Abstract

    Lithium stripping is a crucial process coupled with lithium deposition during the cycling of Li metal batteries. Lithium deposition has been widely studied, whereas stripping as a subsurface process has rarely been investigated. Here we reveal the fundamental mechanism of stripping on lithium by visualizing the interface between stripped lithium and the solid electrolyte interphase (SEI). We observed nanovoids formed between lithium and the SEI layer after stripping, which are attributed to the accumulation of lithium metal vacancies. High-rate dissolution of lithium causes vigorous growth and subsequent aggregation of voids, followed by the collapse of the SEI layer, i.e., pitting. We systematically measured the lithium polarization behavior during stripping and find that the lithium cation diffusion through the SEI layer is the rate-determining step. Nonuniform sites on typical lithium surfaces, such as grain boundaries and slip lines, greatly accelerated the local dissolution of lithium. The deeper understanding of this buried interface stripping process provides beneficial clues for future lithium anode and electrolyte design.

    View details for PubMedID 30082382

  • Low temperature exchange of hydrogen and deuterium between molecular ethanol and water on Au(111) Surface Science Deponte, M. C., Wilke, J. A., Boyle, D. T., Gillum, M. C., Schlosser, D. A., Lam, V. H., Kaleem, H., Maxwell, E. M., Baber, A. E. 2018; 680: 1-5
  • Elucidation of Active Sites for the Reaction of Ethanol on TiO2/Au(111) JOURNAL OF PHYSICAL CHEMISTRY C Boyle, D. T., Wilke, J. A., Palomino, R. M., Lam, V. H., Schlosser, D. A., Andahazy, W. J., Stopak, C. Z., Stacchiola, D. J., Rodriguez, J. A., Baber, A. E. 2017; 121 (14): 7794–7802