<i>In Situ</i> Transmission Electron Microscopy Study of Electrochemical Lithiation and Delithiation Cycling of the Conversion Anode RuO<sub>2</sub>

Gregorczyk, Keith; Liu, Yang; Sullivan, John P.; Rubloff, Gary W.

doi:10.1021/nn402451s

Cited by 78 publications

(100 citation statements)

References 37 publications

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“…This shape, corresponding to the processes already observed through CV in Figure , is reversed during charging into a tilted line that extends from 0.01 to 2 V with a capacity of about 200 mAh g −1 , and a plateau above 2 V at the end of which the capacity approaches 400 mAh g −1 . Hence, the first cycle is characterized by a low coulombic efficiency (Figure b), which is ascribed to both the irreversible formation of the SEI layer and the nature of the conversion process involving changes of the electrode structure, likely leading to a partial loss or insulation of the active material . The second cycle (not reported) and the steady‐state cycles at 0.1 C (Figure a) were characterized by a different, more sloped profile during discharge compared with the first one, whereas similar charge profiles were observed with a remarkably stable capacity of about 540 mAh g −1 (80 % of the theoretical capacity) and a coulombic efficiency approaching 100 % (Figure b).…”

Section: Resultsmentioning

confidence: 63%

X‐ray Nano‐computed Tomography of Electrochemical Conversion in Lithium‐ion Battery

et al. 2019

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Section: Resultsmentioning

confidence: 63%

X‐ray Nano‐computed Tomography of Electrochemical Conversion in Lithium‐ion Battery

et al. 2019

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“…This may also partially be the result of the low diffusivity of Mo atoms, similar to Fe in the case of FeF 2 lithiation recently reported. [ 30 ] The formation of conductive paths by metal nanoparticles after lithiation has also been reported in RuO 2 , [ 31 ] FeF 2 , [ 30 ] and NiO. [ 32 ] An in situ optical transmittance measurement was also made during lithiation of MoS 2 using with the microbattery setup, as illustrated in Figure 4 a. wileyonlinelibrary.com potentials of 2.8, 0.9, and 0.05 V (vs Li + /Li).…”

Section: Doi: 101002/aenm201401742mentioning

confidence: 63%

In Situ Investigations of Li‐MoS₂ with Planar Batteries

Wan

Bao

Liu

et al. 2014

Advanced Energy Materials

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109

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We have designed a planar microbattery that allows in situ electrical transport measurement during electrochemical charge and discharge in micron-sized individual crystallites of 2D-layered nanosheets, as well as optical studies (transmittance, Raman spectroscopy), which can give information about the electronic structure of the active material. To demonstrate the utility of our microbattery platform, we study the lithiation of MoS 2 crystallites. We observe that the electrical conductivity of the 2D MoS 2 crystallites is highly dependent on thickness and the rate of lithiation in the fi rst cycle. We use in situ TEM to confi rm that upon rapid fi rst-cycle lithiation the formation of a Mo conductive network imbedded in the Li 2 S matrix leads to an enhanced electrical conductivity compared to the pristine MoS 2 . We applied the results in Li-MoS 2 coin cells with composite electrodes, demonstrating that batteries with fast lithiation on the fi rst cycle showed signifi cantly higher specifi c capacity than batteries lithiated slowly. The microbattery platform can be generally applied to other energy storage materials and a wide range of characterization techniques, and is thus a powerful tool to uncover the properties of nanoscale materials undergoing electrochemical modifi cation. As in the example demonstrated here, we expect this platform will lead to new insights into the operation of battery materials at the nanoscale, leading to new strategies in improving the cell performance.A schematic crystal structure of 2H-MoS 2 is illustrated in Figure 1 a, with the lattice parameters a = 3.16 Å and c = 12.29 Å. Our microbattery platform developed for the in situ measurement of the optical transmittance and electrical transport of 2D nanomaterials is illustrated in Figure 1 b. A MoS 2 crystal and lithium metal are deposited on top of the Cu transport electrodes and current collector, respectively. The MoS 2 fl ake can be charged/discharged by connecting transport electrodes and current collector to an electrochemical workstation. Coupling the microbattery with a transmission optical microscope/probe station, we can then carry out in situ optical transmittance and electrical transport measurements on the same MoS 2 crystal. Optical images of uniform-thickness mechanically exfoliated MoS 2 crystals are shown in Figure 1 c,d, with dimensions as large as 100 µm × 100 µm. We used atomic force microscopy (AFM) to determine the morphology and thickness of exfoliated MoS 2 , in Figure 1 e,f. A photograph of the complete microbattery device is shown in Figure 1 g. The region of the transport electrodes is expanded in Figure 1 h, showing a large uniform area of MoS 2 crystal spanning the electrodes.To understand the intrinsic resistance change during lithiation, an in situ electrical transport measurement was carried out using our microbattery setup. Figure 2 a shows the simultaneously measured resistance and electrochemical potential at a small constant lithiation current at 0.5 µA for a single MoS 2 crystal of thickness 35 n...

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“…This result resolves the previous misconception about the morphology of transition metal nanostructures that were exclusively identified as discrete nanoparticles 20,24,49,50 , amorphous domains 51 or localized interconnected nanoparticles 7 . Furthermore, the nanoporous framework creates an electron diffusion network to enable high-rate capability for conversion reactions 55 . Thirdly, heterogeneous phase conversion was found to prevail in conversion reactions, which is likely caused in part by the preferential nucleation at grain boundaries.…”

Section: Discussionmentioning

confidence: 99%

Phase evolution for conversion reaction electrodes in lithium-ion batteries

et al. 2014

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The performance of battery materials is largely governed by structural and chemical evolutions during electrochemical reactions. Therefore, resolving spatially dependent reaction pathways could enlighten mechanistic understanding, and enable rational design for rechargeable battery materials. Here, we present a phase evolution panorama via spectroscopic and three-dimensional imaging at multiple states of charge for an anode material (that is, nickel oxide nanosheets) in lithium-ion batteries. We reconstruct the threedimensional lithiation/delithiation fronts and find that, in a fully electrolyte immersion environment, phase conversion can nucleate from spatially distant locations on the same slab of material. In addition, the architecture of a lithiated nickel oxide is a bent porous metallic framework. Furthermore, anode-electrolyte interphase is found to be dynamically evolving upon charging and discharging. The present study has implications for resolving the inhomogeneity of the general electrochemically driven phase transition (for example, intercalation reactions) and for the origin of inhomogeneous charge distribution in large-format battery electrodes.

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In Situ Transmission Electron Microscopy Study of Electrochemical Lithiation and Delithiation Cycling of the Conversion Anode RuO₂

Cited by 78 publications

References 37 publications

X‐ray Nano‐computed Tomography of Electrochemical Conversion in Lithium‐ion Battery

X‐ray Nano‐computed Tomography of Electrochemical Conversion in Lithium‐ion Battery

In Situ Investigations of Li‐MoS₂ with Planar Batteries

Phase evolution for conversion reaction electrodes in lithium-ion batteries

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In Situ Transmission Electron Microscopy Study of Electrochemical Lithiation and Delithiation Cycling of the Conversion Anode RuO2

Cited by 78 publications

References 37 publications

X‐ray Nano‐computed Tomography of Electrochemical Conversion in Lithium‐ion Battery

X‐ray Nano‐computed Tomography of Electrochemical Conversion in Lithium‐ion Battery

In Situ Investigations of Li‐MoS2 with Planar Batteries

Phase evolution for conversion reaction electrodes in lithium-ion batteries

Contact Info

Product

Resources

About

In Situ Transmission Electron Microscopy Study of Electrochemical Lithiation and Delithiation Cycling of the Conversion Anode RuO₂

In Situ Investigations of Li‐MoS₂ with Planar Batteries