In Situ XRD of Thin Film Tin Electrodes for Lithium Ion Batteries

Rhodes, Kevin; Meisner, Roberta Ann; Kirkham, Melanie J.; Dudney, Nancy J.; Daniel, Claus

doi:10.1149/2.077203jes

Cited by 76 publications

(81 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Upon charging, the Li 22 Sn 5 and Sn peaks vanish and then reappear, indicating delithiation and the formation of metallic Sn. These results are in agreement with previous in situ XRD studies showing that lithiation of Sn results in the formation of a Li 22 Sn 5 alloy upon full lithiation . Importantly, as observed by TEM, no evidence of significant Sn NP aggregation was found upon lithiation and delithiation of SiOC/Sn (see Figure b,c).…”

Section: Resultssupporting

confidence: 92%

Silicon Oxycarbide—Tin Nanocomposite as a High‐Power‐Density Anode for Li‐Ion Batteries

et al. 2019

View full text Add to dashboard Cite

Tin‐based materials are an emerging class of Li‐ion anodes with considerable potential for use in high‐energy‐density Li‐ion batteries. However, the long‐lasting electrochemical performance of Sn remains a formidable challenge due to the large volume changes occurring upon its lithiation. The prevailing approaches toward stabilization of such electrodes involve embedding Sn in the form of nanoparticles (NPs) in an active/inactive matrix. The matrix helps to buffer the volume changes of Sn, impart better electronic connectivity and prevent particle aggregation upon lithiation/delithiation. Herein, facile synthesis of Sn NPs embedded in a SiOC matrix via the pyrolysis of a preceramic polymer as a single‐source precursor is reported. This polymer contains Sn 2‐ethyl‐hexanoate (Sn(Oct)2) and poly(methylhydrosiloxane) as sources of Sn and Si, respectively. Upon functionalization with apolar divinyl benzene sidechains, the polymer is rendered compatible with Sn(Oct)2. This approach yields a homogeneous dispersion of Sn NPs in a SiOC matrix with sizes on the order of 5–30 nm. Anodes of the SiOC/Sn nanocomposite demonstrate high capacities of 644 and 553 mAh g−1 at current densities of 74.4 and 2232 mA g−1 (C/5 and 6C rates for graphite), respectively, and show superior rate capability with only 14% capacity decay at high currents.

show abstract

Section: Resultssupporting

confidence: 92%

Silicon Oxycarbide—Tin Nanocomposite as a High‐Power‐Density Anode for Li‐Ion Batteries

et al. 2019

View full text Add to dashboard Cite

show abstract

“…It is difficult to determine whether in addition to Li 7 Sn 3 , higher concentration Li phases such as Li 5 Sn 2 , Li 13 Sn 5 , Li 7 Sn 2 and Li 22 Sn 5 formed since (as shown later in Figure 4) the ambient temperature lithiation/delithiation voltage vs. Li concentration behavior for Li x Sn for x > 2.33 behaves as if the system was single-phase. [39][40][41] Clearly, not all of the intermetallic phases that appear on the equilibrium Li-Sn phase diagram are accessible by electrochemical lithiation at 300 K. Figure 3A shows linear sweep voltammetry (LSV) data as a function of sweep rate for planar Sn sheets lithiated to 400 mV. The waves in the polarization curves correspond to delithiation of Li-Sn phases initially present and those that may be evolving on the electrode surface during potential scanning.…”

Section: Morphology Evolutionmentioning

confidence: 99%

Dealloying at High Homologous Temperature: Morphology Diagrams

Geng

Sieradzki

2017

J. Electrochem. Soc.

View full text Add to dashboard Cite

Dealloying under conditions of high homologous temperature, T H , (or high intrinsic diffusivity of the more electrochemically reactive component) is considerably more complicated than at low T H since solid-state mass transport is available to support this process. At low T H the only mechanism available for dealloying a solid is percolation dissolution, which results in a bicontinuous solid-void morphology for which nanoporous gold serves as the prototypical example. At high T H , there is a rich set of morphologies that can evolve depending on alloy composition and the imposed electrochemical conditions, including negative or void dendrites, Kirkendall voids and bi-continuous porous structures. We report on a study of morphology evolution upon delithiation of Li-Sn alloys, produced by the electrochemical lithiation of Sn sheets. Electrochemical titration and time of flight measurements were performed in order to determine the intrinsic diffusivity of Li,D Li , as a function of alloy composition, which ranged from ∼5 × 10 −8 -4 × 10 −12 cm 2 s −1 . The activation energy forD Li was measured in the temperature range 30-140 • C and found to be 37.4, 37.9 and 22.5 kJ/mole, respectively for the phases Li 2 Sn 5 , LiSn and Li 7 Sn 3 . Morphology evolution was studied under conditions of fixed dealloying potential and fixed current density and our results are summarized by the introduction of dealloying morphology diagrams that reveal the electrochemical conditions for the evolution of the various morphologies. Today electrochemical dealloying processes are used to design nanostructures for a variety of functions encompassing electrocatalysis 1-3 and biosensors 4-7 with additional applications being explored such as actuation [8][9][10][11] and structural composites. 12-14 To date, the targeted nanoscale morphologies include bi-continuous structures such as nanoporous gold (NPG) formed by a percolation dissolution mechanism 15-18 and so-called skin or core-shell nanoparticle structures, formed by a passivation-like process.2 Several of these architectures are employed in the fabrication of Pt-based alloy nanoparticle electrocatalysts for fuel cell applications, 1,3,19 Since the solid-state transport processes available to support selective dissolution are temperature dependent one should expect the resulting morphologies to be similarly dependent on temperature. For example, in a noble metal alloy such as Ag-Au at 300 K (i.e., low homologous temperature) the diffusivity of each of the components is of order 10 −32 cm 2 s −120 which is about 20 orders of magnitude too low to contribute to dealloying processes over technologically relevant time scales. Consequently, percolation dissolution is the only mechanism available for dealloying resulting in the well-studied morphology of NPG. However, at higher homologous temperature, T H , we should expect additional sets of dealloying morphologies to evolve. Here our use of the term high T H is meant to designate that the solid-state mobility of the component that is selecti...

show abstract

“…Phase transitions of a Sn thin film has been studied using an in situ XRD technique systematically . This investigation provided useful data regarding various phases formed during lithiation and delithiation processes.…”

Section: X‐ray Techniquesmentioning

confidence: 99%

Advances in In Situ Techniques for Characterization of Failure Mechanisms of Li‐Ion Battery Anodes

Hapuarachchi

Sun

Chen

2018

Advanced Sustainable Systems

View full text Add to dashboard Cite

Li‐ion rechargeable battery, the prevailing market leader for energy storage applications throughout the past few decades, needs to be improved greatly in terms of capacity, cycling performance, and safety to cater future generation energy requirements. The failure of electrode materials, which leads to early capacity decay and safety issues in existing Li‐ion batteries, however, is still a technical challenge and deserves further investigation. In this review, recent advances in how in situ characterization techniques can be adopted to understand material failure mechanisms in Li‐ion battery are highlighted with a focus on failure and degradation of negative electrode materials. The information presented in this article is believed to be beneficial to application of advanced in situ characterization techniques in the development of next‐generation battery systems with improved electrochemical properties and structural integrity.

show abstract

In Situ XRD of Thin Film Tin Electrodes for Lithium Ion Batteries

Cited by 76 publications

References 22 publications

Silicon Oxycarbide—Tin Nanocomposite as a High‐Power‐Density Anode for Li‐Ion Batteries

Silicon Oxycarbide—Tin Nanocomposite as a High‐Power‐Density Anode for Li‐Ion Batteries

Dealloying at High Homologous Temperature: Morphology Diagrams

Advances in In Situ Techniques for Characterization of Failure Mechanisms of Li‐Ion Battery Anodes

Contact Info

Product

Resources

About