Distinct Solid‐Electrolyte‐Interphases on Sn (100) and (001) Electrodes Studied by Soft X‐Ray Spectroscopy

Qiao, Ruimin; Lucas, Ivan T.; Karim, Altaf; Syzdek, Jarosław; Liu, Xiaosong; Chen, Wei; Persson, Kristin A.; Kostecki, Robert; Yang, Wanli

doi:10.1002/admi.201300115

Cited by 100 publications

(109 citation statements)

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“…During electrochemical cycling, valence states as well as the local geometric environment undergo changes due to the diffusion of lithium and other elements in the material. Based on this theoretical prediction, lithium secondary batteries have been intensively studied with the use of XAFS to find out what happens during the process, including electrochemical reaction, formation of interfaces between electrodes and electrolytes . In this section, the study of electrochemical reactions as well as degradation mechanisms of lithium secondary batteries will be introduced and summarized with a focus on the application of XAFS.…”

Section: X‐ray Absorption Fine Structure and Applicationsmentioning

confidence: 99%

Synchrotron‐Based X‐ray Absorption Fine Structures, X‐ray Diffraction, and X‐ray Microscopy Techniques Applied in the Study of Lithium Secondary Batteries

et al. 2018

Small Methods

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Owing to the recent advance of third‐generation synchrotron radiation (SR) sources, SR‐based X‐ray techniques have been widely applied to study lithium‐ion batteries, lithium–sulfur batteries, and lithium–oxygen batteries to solve material challenges. SR‐based techniques provide high chemical and physical sensitivity and a comprehensive picture of material structure and reaction mechanisms. An in‐depth understanding of batteries is imperative for the development of future energy storage devices with enhanced electrochemical performance to meet societies' growing need for devices with high energy density. Here, recent progress in the application of SR techniques for lithium secondary batteries with a focus on several techniques, including X‐ray absorption fine structure, synchrotron X‐ray diffraction, and synchrotron X‐ray microscopy techniques is reviewed. The working principle for all characterization techniques is introduced to provide context for how the technique is used in the field of energy storage. Through discussing the utilization of SR techniques in different directions of batteries, including electrodes, electrolytes, and interfaces, the practical application strategies of techniques in batteries are clarified. By summarizing and discussing the application of SR techniques in batteries, the aim is to highlight the crucial role of SR characterization in the development of advanced energy materials.

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Section: X‐ray Absorption Fine Structure and Applicationsmentioning

confidence: 99%

Synchrotron‐Based X‐ray Absorption Fine Structures, X‐ray Diffraction, and X‐ray Microscopy Techniques Applied in the Study of Lithium Secondary Batteries

et al. 2018

Small Methods

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“…[19][20][21] Interestingly, recent model studies on Sn single crystal electrodes in organic carbonate electrolytes revealed a strong correlation between the crystal surface orientation and the SEI composition. 22,23 A similar study of the composition of the SEI on a silicon monocrystal electrode showed strong effects of different SEI formation protocols, presence/absence of intrinsic SiO 2 , electrolyte composition and impurities e.g., HF. [24][25][26] Also graphite exhibits different SEI layer compositions on plane and edge sites.…”

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confidence: 99%

The Mechanism of SEI Formation on a Single Crystal Si(100) Electrode

Vogl

Lux

Crumlin

et al. 2015

J. Electrochem. Soc.

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A fundamental study of interfacial phenomena on a Si(100) single crystal electrode in organic carbonate-based electrolytes was carried out. The SEI formation on the Si(100) single crystal electrode was investigated as a function of the electrolyte composition, electrode potential and Li x Si lithiation degree. Fourier transform infrared spectroscopy (FTIR) and X-ray photon spectroscopy (XPS) studies of the SEI layer during early stages of SEI formation indicate a strong dependence of the SEI composition on the electrolyte composition. However, the influence of the electrolyte composition becomes negligible at low potentials, when lithium alloys with Si and forms amorphous Li Currently, graphite is the most common negative electrode material in commercial lithium ion batteries for portable electronics. [1][2][3] However, lithium ion batteries for large-scale transportation applications require new inexpensive electrode materials with higher specific capacity. For decades, silicon has been considered as a promising negative electrode material, mainly because of its high specific capacity of ca. 3500 mAh/g 4 and its abundance in the earth crust. [4][5][6] The key problems that prevent its widespread use are large, up to ∼300 % volumetric changes during lithiation/delithiation processes and interfacial instability of lithium silicides in organic solvent based electrolytes. 6-12The resultant poor electrochemical cycling performance and large irreversible capacities during formation and operation of the Si negative electrode contribute to rapid degradation and failure of the battery. 6,7,13 The solid electrolyte interphase (SEI) layer, which forms at the electrode/electrolyte interface during the initial charge/discharge cycles, is the key component that determines the long-term stability and cycling behavior of carbonaceous and intermetallic negative Li-ion battery electrodes.14-16 Electrolyte reduction and SEI layer formation on a Si electrode usually take place at potentials below 1.8 V vs. Li/Li + and accompany the formation of Li-Si phases, the so-called "Si-Li alloying" process at E <0.4 V vs. Li/Li + . 17 The exact mechanism of the SEI formation processes on Si, the SEI composition and the effect on the Si electrode electrochemical cycling performance is not well understood. 18 On the other hand, SEI-forming electrolyte additives such as vinylene carbonate (VC) and fluoroethylene carbonate (FEC) are known to alter the composition and properties of the SEI on Si and improve the electrode electrochemical performance. [19][20][21] Interestingly, recent model studies on Sn single crystal electrodes in organic carbonate electrolytes revealed a strong correlation between the crystal surface orientation and the SEI composition.22,23 A similar study of the composition of the SEI on a silicon monocrystal electrode showed strong effects of different SEI formation protocols, presence/absence of intrinsic SiO 2 , electrolyte composition and impurities e.g., HF. [24][25][26] Also graphite exhibits different SEI layer compos...

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“…sXAS spectra are sensitive to the unoccupied electronic states in the vicinity of the Fermi energy EF. They provide a powerful tool to study the oxidation states, chemical bonds, spin properties and orbital characteristics of the transition-metals involved in battery electrodes [14][15] . Moreover, sXAS is a unique tool that can provide information about both the surface (probe depth of about 10 nm) and the bulk (probe depth of about 100 nm) through the total electron yield (TEY) and total fluorescence yield (TFY), respectively.…”

Section: Introductionmentioning

confidence: 99%

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi_0.5Mn_1.5O₄ Electrodes

et al. 2015

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KEYWORDS: high voltage spinel, LiNi0.5Mn1.5O4, Ni(III), soft x-ray spectroscopy.2 ABSTRACT LiNi0.5Mn1.5O4 spinel is an appealing cathode material for next generation rechargeable Li-ion batteries due to its high operating voltage of ~4.7 V (vs. Li/Li + ). Although it is widely believed that the full range electrochemical cycling involves the redox of Ni(II)/(IV), it has not been experimentally clarified whether Ni(III) exists as the intermediate state, or a double-electron transfer takes place. Here, combined with theoretical calculations, we show unambiguous spectroscopic evidence of the Ni(III) state when the LiNi0.5Mn1.5O4 electrode is half charged.This provides a direct verification of single-electron-transfer reactions in LiNi0.5Mn1.5O4 upon cycling, namely, from Ni(II) to Ni(III), then to Ni(IV). Additionally, by virtue of its surface sensitivity, soft x-ray absorption spectroscopy also reveals the electrochemically inactive Ni 2+and Mn 2+ phases on the electrode surface. Our work provides the long-awaited clarification of the single-electron transfer mechanism in LiNi0.5Mn1.5O4 electrodes. Furthermore, the experimental results serve as a benchmark for further spectroscopic characterizations of Nibased battery electrodes.3

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Distinct Solid‐Electrolyte‐Interphases on Sn (100) and (001) Electrodes Studied by Soft X‐Ray Spectroscopy

Cited by 100 publications

References 49 publications

Synchrotron‐Based X‐ray Absorption Fine Structures, X‐ray Diffraction, and X‐ray Microscopy Techniques Applied in the Study of Lithium Secondary Batteries

Synchrotron‐Based X‐ray Absorption Fine Structures, X‐ray Diffraction, and X‐ray Microscopy Techniques Applied in the Study of Lithium Secondary Batteries

The Mechanism of SEI Formation on a Single Crystal Si(100) Electrode

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi_0.5Mn_1.5O₄ Electrodes

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Distinct Solid‐Electrolyte‐Interphases on Sn (100) and (001) Electrodes Studied by Soft X‐Ray Spectroscopy

Cited by 100 publications

References 49 publications

Synchrotron‐Based X‐ray Absorption Fine Structures, X‐ray Diffraction, and X‐ray Microscopy Techniques Applied in the Study of Lithium Secondary Batteries

Synchrotron‐Based X‐ray Absorption Fine Structures, X‐ray Diffraction, and X‐ray Microscopy Techniques Applied in the Study of Lithium Secondary Batteries

The Mechanism of SEI Formation on a Single Crystal Si(100) Electrode

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi0.5Mn1.5O4 Electrodes

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Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi_0.5Mn_1.5O₄ Electrodes