SEI investigations on copper electrodes after lithium plating with Raman spectroscopy and mass spectrometry

Müller, Romek; Schmitz, René; Schreiner, Christian; Kunze, Miriam; Lex‐Balducci, Alexandra; Passerini, Stefano; Winter, Martin

doi:10.1016/j.jpowsour.2013.01.105

Cited by 64 publications

(68 citation statements)

References 20 publications

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“…Especially, at the power of 0.5 mW, the site under laser irradiation turns black, indicating the occurrence of laser‐induced processes. It is noteworthy that there exist two different insights in the literature works regarding the mechanism for the appearance of the 1846 cm −1 band: Lassègues et al suggested the appearance of 1846 cm −1 as a result of heat‐induced processes by laser, based on the investigation of Raman spectra of Li foils with different pretreatments; While Schmitz et al suggested that the band arises intrinsically because of the formation of SEI during Li deposition, based on combined investigations of surface Raman spectroscopy and mass spectroscopy of Li surface. In the present work, the 1846 cm −1 band can be observed at lower laser power (#2 of Fig.…”

Section: Resultsmentioning

confidence: 99%

An electrochemical surface‐enhanced Raman spectroscopic study on nanorod‐structured lithium prepared by electrodeposition

Tang

et al. 2016

J Raman Spectroscopy

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Lithium is an s‐electron metal which is expected to support surface‐enhanced Raman scattering (SERS) effect. But the experimental investigation of the SERS effect of Li was reported once under high vacuum condition because of its extremely active surface chemistry. However, such investigations become increasingly important with stimulation by the active researches in lithium‐based batteries. In this paper, we present an electrochemical Raman spectroscopic study of electrochemically prepared Li surface combined with a simulation on the enhancement factor. Electrochemical roughening of Li foil surface and electrodeposition of Li on copper substrates are employed to prepare Li nanostructures. Only the nanorod arrays prepared by the electrodeposition on Cu in the electrolyte of LiPF6–PC–H2O or LiPF6–EC–DMC–H2O appear to be effective for obtaining the SERS effect. The spectra show two broad yet dominant bands at 720 and 1020 cm−1, which are considered to arise mainly from combined contribution by LiOH and LiF (720 cm−1) and LiF and Li2CO3 (1020 cm−1) contained in the solid‐electrolyte interphase (SEI) layer on the nanorod‐structured Li surface. The enhancement factor is calculated for coupled nanorods of ca. 240 nm in diameter, which is about 30 and 7 times for 638 and 532‐nm excitations, respectively. Experimentally, the signals with 638‐nm laser excitation are two to three times stronger than those with 532‐nm laser excitation. The SERS effect of Li may provide a useful and convenient in‐situ method to follow the SEI evolution process in lithium‐based batteries without introducing extra SPR active metals that may have impact on the performance of the Li anode. Copyright © 2016 John Wiley & Sons, Ltd.

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Section: Resultsmentioning

confidence: 99%

An electrochemical surface‐enhanced Raman spectroscopic study on nanorod‐structured lithium prepared by electrodeposition

Tang

et al. 2016

J Raman Spectroscopy

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“…The rst band at 510 cm À1 has been reported to be Li 2 O, 42 and the second one at 910 cm À1 can be assigned to R-O-C and C-C bond stretching vibrations in semicarbonates. 43 The peak at 1846 cm À1 Fig. 8 (band not displayed in Fig.…”

Section: Ex Situ Shiners Studies On Lithium Metalmentioning

confidence: 98%

“…40 One of the major challenges of using Raman for investigation of the lithium SEI is the sensitivity of this metal to local laser heating decomposition. [41][42][43] Due to the Raman signal enhancement, SHINERS allows the measurement of the lithium surface layer with an improved signal-to-noise ratio at short exposure times and low laser powers (10 s, ca. 0.1 mW).…”

Section: Ex Situ Shiners Studies On Lithium Metalmentioning

confidence: 99%

“…9) is assigned to C^C stretching of the acetylene group of Li 2 C 2 species. [41][42][43][44] Naudin et al 42 reported that the presence of this compound on the metallic lithium surface is due to decomposition of Li 2 CO 3 induced by local laser heating. Therefore, even with SHINERS, the complete avoidance of laser decomposition seems unachievable.…”

Section: Ex Situ Shiners Studies On Lithium Metalmentioning

confidence: 99%

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Shell isolated nanoparticles for enhanced Raman spectroscopy studies in lithium–oxygen cells

et al. 2017

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A critical and detailed assessment of using Shell Isolated Nanoparticles for Enhanced Raman Spectroscopy (SHINERS) on different electrode substrates was carried out, providing relative enhancement factors, as well as an evaluation of the distribution of shell-isolated nanoparticles upon the electrode surfaces. The chemical makeup of surface layers formed upon lithium metal electrodes and the mechanism of the oxygen reduction reaction on carbon substrates relevant to lithium-oxygen cells are studied with the employment of the SHINERS technique. SHINERS enhanced the Raman signal at these surfaces showing a predominant LiO based layer on lithium metal in a variety of electrolytes. The formation of LiO and LiO, as well as degradation reactions forming LiCO, upon planar carbon electrode interfaces and upon composite carbon black electrodes were followed under potential control during the reduction of oxygen in a non-aqueous electrolyte based on dimethyl sulfoxide.

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“…Li 2 C 2 is no stranger to the field of LIBs, although no one has ever attempted to use it as an electrode material. Schmitz et al 16. claimed its presence in the solid electrolyte interphase (SEI) layer on a lithium‐plated copper electrode, although it has not been experimentally observed.…”

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confidence: 99%

Li₂C₂, a High‐Capacity Cathode Material for Lithium Ion Batteries

Tian

Gao

et al. 2015

Angewandte Chemie

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As a typical alkaline earth metal carbide, lithium carbide (Li2C2) has the highest theoretical specific capacity (1400 mA h g−1) among all the reported lithium‐containing cathode materials for lithium ion batteries. Herein, the feasibility of using Li2C2 as a cathode material was studied. The results show that at least half of the lithium can be extracted from Li2C2 and the reversible specific capacity reaches 700 mA h g−1. The CC bond tends to rotate to form C4 (CC⋅⋅⋅CC) chains during lithium extraction, as indicated with the first‐principles molecular dynamics (FPMD) simulation. The low electronic and ionic conductivity are believed to be responsible for the potential gap between charge and discharge, as is supported with density functional theory (DFT) calculations and Arrhenius fitting results. These findings illustrate the feasibility to use the alkali and alkaline earth metal carbides as high‐capacity electrode materials for secondary batteries.

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SEI investigations on copper electrodes after lithium plating with Raman spectroscopy and mass spectrometry

Cited by 64 publications

References 20 publications

An electrochemical surface‐enhanced Raman spectroscopic study on nanorod‐structured lithium prepared by electrodeposition

An electrochemical surface‐enhanced Raman spectroscopic study on nanorod‐structured lithium prepared by electrodeposition

Shell isolated nanoparticles for enhanced Raman spectroscopy studies in lithium–oxygen cells

Li₂C₂, a High‐Capacity Cathode Material for Lithium Ion Batteries

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SEI investigations on copper electrodes after lithium plating with Raman spectroscopy and mass spectrometry

Cited by 64 publications

References 20 publications

An electrochemical surface‐enhanced Raman spectroscopic study on nanorod‐structured lithium prepared by electrodeposition

An electrochemical surface‐enhanced Raman spectroscopic study on nanorod‐structured lithium prepared by electrodeposition

Shell isolated nanoparticles for enhanced Raman spectroscopy studies in lithium–oxygen cells

Li2C2, a High‐Capacity Cathode Material for Lithium Ion Batteries

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Product

Resources

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Li₂C₂, a High‐Capacity Cathode Material for Lithium Ion Batteries