Measuring Spatially Resolved Collective Ionic Transport on Lithium Battery Cathodes Using Atomic Force Microscopy

Mascaro, Aaron; Wang, Zi; Hovington, Pierre; Miyahara, Yoichi; Paolella, Andrea; Gariépy, Vincent; Feng, Zimin; Enright, Tyler; Aiken, Connor; Zaghib, Karim; Bevan, Kirk H.; Grütter, Peter

doi:10.1021/acs.nanolett.7b01857

Cited by 31 publications

(54 citation statements)

References 41 publications

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“…Complement with other methods to measure the local structure and compositional analysis, they obtain the activation energies for ionic transport along the [010] direction. The results have good agreement with the DFT calculations . Chen et al.…”

Section: Positive Electrode Materials In Libssupporting

confidence: 76%

Advances in Understanding Materials for Rechargeable Lithium Batteries by Atomic Force Microscopy

Wang

Liu

Zhao

et al. 2018

Energy & Environ Materials

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The development of advanced lithium batteries represents a major technological challenge for the new century. Understanding the fundamental electrode degradation mechanisms is important for battery performance improvements. The complex electrochemical processes inside a working battery are being explored to a limited extent. Various advanced material characterization techniques have been used to monitor dynamic conditions for optimizing battery materials. State‐of‐the‐art atomic force microscopy methods have been applied to energy storage systems, specifically lithium‐ion batteries. Atomic force microscopy is an ideal tool to provide localized morphological, chemical, and physical information at nanoscale for the in‐depth understanding of the electrochemical processes, reaction mechanisms, and degradation of battery materials. Here, we review recent progress in the development and application of atomic force microscopy for high‐performance lithium‐ion batteries. We discuss atomic force microscopy as an analytical tool to help researchers understand graphite, silicon, layered metal oxides, and other representative electrode materials. We summarize the importance of atomic force microscopy technique in studying the next‐generation Li–S and Li–O2 batteries. We also highlight some of the remaining challenges and possible solutions for future development.

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Section: Positive Electrode Materials In Libssupporting

confidence: 76%

Advances in Understanding Materials for Rechargeable Lithium Batteries by Atomic Force Microscopy

Wang

Liu

Zhao

et al. 2018

Energy & Environ Materials

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“…The change in the spectrum's knee with increasing light intensity is in qualitative agreement with the light-dependent R s used to explain the Fig. 1 iments the response of ions to a step-change in tip voltage is tracked in real time through a shift in cantilever frequency [37][38][39][40][41][42]. EFM has been used to follow the time evolution of photocapacitance in response to illumination [43][44][45][46].…”

Section: Introductionsupporting

confidence: 70%

Lagrangian and Impedance-Spectroscopy Treatments of Electric Force Microscopy

2019

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Scanning probe microscopy is often extended beyond simple topographic imaging to study electrical forces and sample properties, with the most widely used experiment being frequency-modulated Kelvin probe force microscopy. The equations commonly used to interpret this frequency-modulated experiment, however, rely on two hidden assumptions. The first assumption is that the tip charge oscillates in phase with the cantilever motion to keep the tip voltage constant. The second assumption is that any changes in the tip-sample interaction happen slowly. Starting from an electro-mechanical model of the cantilever-sample interaction, we use Lagrangian mechanics to derive coupled equations of motion for the cantilever position and charge. We solve these equations analytically using perturbation theory, and, for verification, numerically. This general approach rigorously describes scanned probe experiments even in the case when the usual assumptions of fast tip charging and slowly changing samples properties are violated. We develop a Magnus-expansion approximation to illustrate how abrupt changes in the tip-sample interaction cause abrupt changes in the cantilever amplitude and phase. We show that feedback-free time-resolved electric force microscopy cannot uniquely determine sub-cycle photocapacitance dynamics. We then use first-order perturbation theory to relate cantilever frequency shift and dissipation to the sample impedance even when the tip charge oscillates out of phase with the cantilever motion. Analogous to the treatment of impedance spectroscopy in electrochemistry, we apply this approximation to determine the cantilever frequency shift and dissipation for an arbitrary sample impedance in both local dielectric spectroscopy and broadband local dielectric spectroscopy experiments. The general approaches we develop provide a path forward for rigorously modeling the coupled motion of the cantilever position and charge in the wide range of electrical scanned probe microscopy experiments where the hidden assumptions of the conventional equations are violated or inapplicable. arXiv:1807.01219v2 [cond-mat.mes-hall]

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“…Time‐domain electrostatic force spectroscopy (TD‐EFS) has been used to characterize the dynamics of ion transport beneath the surface of battery materials . In this measurement, frequency shift caused by the electrostatic force between ions and the biased tip is recorded as a function of time, which directly reflects the dynamic ionic conduction behavior.…”

Section: Energy Storage Devicesmentioning

confidence: 99%

“…In addition to conduction in nanocrystalline phase, ionic conduction paths at the glass–crystal interface have been observed . Grutter and co‐workers have also measured the local ionic transport behaviors on LiFePO 4 by this TD‐EFS technique and obtained values of the collective activation energy for ionic transport together with the single‐ion bulk hopping barrier …”

Section: Energy Storage Devicesmentioning

confidence: 99%

Functional Scanning Force Microscopy for Energy Nanodevices

et al. 2018

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Energy nanodevices, including energy conversion and energy storage devices, have become a major cross-disciplinary field in recent years. These devices feature long-range electron and ion transport coupled with chemical transformation, which call for novel characterization tools to understand device operation mechanisms. In this context, recent developments in functional scanning force microscopy techniques and their application in thin-film photovoltaic devices and lithium batteries are reviewed. The advantages of scanning force microscopy, such as high spatial resolution, multimodal imaging, and the possibility of in situ and in operando imaging, are emphasized. The survey indicates that functional scanning force microscopy is making significant contributions in understanding materials and interfaces in energy nanodevices.

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Measuring Spatially Resolved Collective Ionic Transport on Lithium Battery Cathodes Using Atomic Force Microscopy

Cited by 31 publications

References 41 publications

Advances in Understanding Materials for Rechargeable Lithium Batteries by Atomic Force Microscopy

Advances in Understanding Materials for Rechargeable Lithium Batteries by Atomic Force Microscopy

Lagrangian and Impedance-Spectroscopy Treatments of Electric Force Microscopy

Functional Scanning Force Microscopy for Energy Nanodevices

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