In situ atomic-scale imaging of electrochemical lithiation in silicon

Liu, Xiao Hua; Wang, Jiangwei; Huang, Shan; Fan, Fenliang; Huang, Xu; Liu, Yang; Krylyuk, Sergiy; Yoo, Jinkyoung; Dayeh, Shadi A.; Davydov, Albert V.; Mao, Scott X.; Picraux, S. T.; Zhang, Sulin; Li, Ju; Zhu, Ting; Huang, Jian Yu

doi:10.1038/nnano.2012.170

Cited by 558 publications

(669 citation statements)

References 30 publications

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“…In recent years, the in situ TEM electrochemical testing technique has been used to probe structural variations of nanoscale electrode materials with high spatial resolution during discharge/charge 36, 37, 38, 39, 40, 41, 42, 43, 44, 45. We also constructed an electrochemical nanodevice using an Fe‐S@CNT as a working electrode for an in situ TEM experiment to examine its structural changes and to obtain direct insight into its Li‐storage mechanism.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Electrochemical Lithium Storage Behavior of Carbon Nanotubes Filled with Iron Sulfide Nanoparticles

Liu

Zhang

et al. 2016

Advanced Science

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Carbon nanotubes (CNTs) filled with iron sulfide nanoparticles (NPs) are prepared by inserting sulfur and ferrocene into the hollow core of CNTs followed by heat treatment. It is found that pyrrhotite‐11T iron sulfide (Fe‐S) NPs with an average size of ≈15 nm are encapsulated in the tubular cavity of the CNTs (Fe‐S@CNTs), and each particle is a single crystal. When used as the anode material of lithium‐ion batteries, the Fe‐S@CNT material exhibits excellent electrochemical lithium storage performance in terms of high reversible capacity, good cyclic stability, and desirable rate capability. In situ transmission electron microscopy studies show that the CNTs not only play an essential role in accommodating the volume expansion of the Fe‐S NPs but also provide a fast transport path for Li ions. The results demonstrate that CNTs act as a unique nanocontainer and reactor that permit the loading and formation of electrochemically active materials with desirable electrochemical lithium storage performance. CNTs with their superior structural stability and Li‐ion transfer kinetics are responsible for the improved rate capability and cycling performance of Fe‐S NPs in CNTs.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Electrochemical Lithium Storage Behavior of Carbon Nanotubes Filled with Iron Sulfide Nanoparticles

Liu

Zhang

et al. 2016

Advanced Science

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“…The lithiation process during electrochemical cycling for several electrode materials has been studied using this configuration. [56][57][58][59] Although intercalation materials were also studied, alloying and conversion anode materials have been more frequently studied because the large volume change that is associated with the charge/discharge can be readily detectable even under low magnifications. Liu et al 60 reported the direct observation of anisotropic swelling of Si nanowires during lithiation, and a following study further revealed electrochemical-induced fractures on the nanostructured Si that had different particle sizes.…”

Section: Open-cell Configurationmentioning

confidence: 99%

“…Liu et al 60 reported the direct observation of anisotropic swelling of Si nanowires during lithiation, and a following study further revealed electrochemical-induced fractures on the nanostructured Si that had different particle sizes. 56 The lithiation process was observed at the atomic scale, which led to the discovery of a layer-by-layer peeling mechanism for the lithiation on Si {111} facets, 57 and it explained the orientation-dependent Li mobility in Si. Wang et al 58 studied the lithiation mechanism of amorphous SnO 2 nanowires and observed a simultaneous partitioning and coarsening characteristic of Li x Sn as a result of Sn and Li diffusion.…”

Section: Open-cell Configurationmentioning

confidence: 99%

Advanced analytical electron microscopy for lithium-ion batteries

Qian

et al. 2015

NPG Asia Mater

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Lithium-ion batteries are a leading candidate for electric vehicle and smart grid applications. However, further optimizations of the energy/power density, coulombic efficiency and cycle life are still needed, and this requires a thorough understanding of the dynamic evolution of each component and their synergistic behaviors during battery operation. With the capability of resolving the structure and chemistry at an atomic resolution, advanced analytical transmission electron microscopy (AEM) is an ideal technique for this task. The present review paper focuses on recent contributions of this important technique to the fundamental understanding of the electrochemical processes of battery materials. A detailed review of both static (ex situ) and real-time (in situ) studies will be given, and issues that still need to be addressed will be discussed. NPG Asia Materials (2015) 7, e193; doi:10.1038/am.2015.50; published online 26 June 2015 INTRODUCTIONTo implement the commercialization of lithium-ion batteries in electric vehicles and smart grid systems, further improvements are required, especially with respect to the energy/power density, coulombic efficiency and cycle life. These parameters primarily depend on the diffusion of lithium-metal ions, electron transport, structure and chemical dynamics of the electrode/electrolyte materials, among others. During electrochemical cycling, significant changes in the material structure and elemental distributions occur, including ion relocation, lattice expansion/contraction, phase transition and structure/surface reconstruction. These changes could substantially influence ion and electron transport and affect the performance of the entire battery system. Understanding the structure-property relationships for each component and their synergistic behaviors during electrochemical processes is, therefore, essential for the design of new battery materials and the optimization of existing systems.Although many analysis techniques (for example, X-ray diffraction, X-ray absorption spectroscopy, neutron diffraction, nuclear magnetic resonance and so on) have been employed for such studies, most of them can acquire only spatially averaged information. Nevertheless, the structural and chemical evolution of battery materials upon electrochemical cycling can often be linked to specific nanofeatures, such as defects, interfaces and surfaces. As a result, techniques based on analytical transmission electron microscopy (AEM) are ideal tools to study these issues. The capability of AEM to precisely probe the structural/chemical evolutions at an ultrahigh spatial resolution frequently provides insight that cannot be obtained directly using macroscopic characterization methods.

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“…Furthermore, Lee et al [26] demonstrated anisotropic deformation of silicon nanopillars during lithitation. A number of first-principles calculations and experimental studies have shown that the lithiation reaction is anisotropic and fastest in the <110> direction [26][27][28][29]. If lithiation is controlled by this reaction mechanism as opposed to diffusion through the lithiated phase, anisotropic expansion may occur [29,30].…”

Section: Introductionmentioning

confidence: 99%

Microstructural evolution induced by micro-cracking during fast lithiation of single-crystalline silicon

Choi

Pharr

Kang

et al. 2014

Journal of Power Sources

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We report observations of microstructural changes in {100} and {110} oriented silicon wafers during initial lithiation under relatively high current densities. Evolution of the microstructure during lithiation was found to depend on the crystallographic orientation of the silicon wafers. In {110} silicon wafers, the phase boundary between silicon and Li x Si remained flat and parallel to the surface. In contrast, lithiation of the {100} oriented substrate resulted in a complex vein-like microstructure of Li x Si in a crystalline silicon matrix. A simple calculation demonstrates that the formation of such structures is energetically unfavorable in the 2 absence of defects due to the large hydrostatic stresses that develop. However, TEM observations revealed micro-cracks in the {100} silicon wafer, which can create fast diffusion paths for lithium and contribute to the formation of a complex vein-like Li x Si network. This defect-induced microstructure can significantly affect the subsequent delithiation and following cycles, resulting in degradation of the electrode.

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In situ atomic-scale imaging of electrochemical lithiation in silicon

Cited by 558 publications

References 30 publications

Synthesis and Electrochemical Lithium Storage Behavior of Carbon Nanotubes Filled with Iron Sulfide Nanoparticles

Synthesis and Electrochemical Lithium Storage Behavior of Carbon Nanotubes Filled with Iron Sulfide Nanoparticles

Advanced analytical electron microscopy for lithium-ion batteries

Microstructural evolution induced by micro-cracking during fast lithiation of single-crystalline silicon

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