Dynamic in situ fourier transform infrared measurements of chemical bonds of electrolyte solvents during the initial charging process in a Li ion battery

Hongyou, Kenichi; Hattori, Takashi; Nagai, Youko; Tanaka, Toshihiro; Nii, Hiroyuki; Shoda, Kaoru

doi:10.1016/j.jpowsour.2013.05.192

Cited by 44 publications

(39 citation statements)

References 20 publications

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“…Similarly, Hongyou et al. showed, using in situ FTIR (attenuated total reflectance, ATR, mode), the possible bands of organic solvents, with and without LiPF 6 , to be in good agreement with our results …”

Section: Resultssupporting

confidence: 92%

“…Table presents a comparison of band positions for C−H, C=O, and C−O stretching modes ( ν C−H, ν C=O, and ν C−O) of free EC and with different electrode materials, namely, MCMB, stainless steel, and metal oxides. The band positions of EC over stainless steel and those over the two metal‐oxide electrodes are similar, wherein the ν C−H and ν C=O signals show a redshift and the C−O stretching vibration ( ν C−O) shows a blueshift compared to free EC and that over MCMB.…”

Section: Resultsmentioning

confidence: 99%

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In Situ DRIFTS Analysis of Solid‐Electrolyte Interphase Formation on Li‐Rich Li_1.2Ni_0.2Mn_0.6O₂ and LiCoO₂ Cathodes during Oxidative Electrolyte Decomposition

et al. 2015

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In situ diffuse reflectance infrared Fourier‐transformed spectroscopy (DRIFTS) investigations have been made to examine solid‐electrolyte interphase (SEI) formation on lithium‐rich Li1.2Ni0.2Mn0.6O2 (LLNMO) and LiCoO2 cathodes during first‐ and second‐cycle charging and discharging. This DRIFTS technique allows us to clarify SEI formation with different charging voltages. Both cathodes revealed the formation of the same surface species during first‐cycle charging, initially including ethylene carbonate (EC) adsorption, and SEI species, for example, ROCOF, RCOOR, Li2CO3, ROCO2Li, and PFx, are formed above the onset potential, namely 4.0 and 4.5 V for LiCoO2 and LLNMO, respectively. The onset potentials correspond to the upper limit of the reversible redox potential range for transition‐metal couples (e.g. Co3+/Co4+ in LiCoO2 and Ni2+/Ni4+ in LLNMO), which account for the intrinsic instability of these cathode materials. Such results suggest the participation of intermediate reactive oxygen species in SEI formation. SEI species continue to form during the discharge process when the potential is scanned cathodically below 3.6 and 4.0 V for LiCoO2 and LLNMO, respectively. Similar SEI species are also observed during the second cycle charge–discharge over LLNMO, where additional oxidized species such as carboxylate (−COO−) and CO2 are also found during charging. With the exception of PFx, all of the observed SEI species can be attributed to the oxidative decomposition of the organic solvent, EC. Finally, possible reaction mechanisms related to the oxidative decomposition of EC are discussed.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

In Situ DRIFTS Analysis of Solid‐Electrolyte Interphase Formation on Li‐Rich Li_1.2Ni_0.2Mn_0.6O₂ and LiCoO₂ Cathodes during Oxidative Electrolyte Decomposition

et al. 2015

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“…Several window materials, that are transparent to infra-red light and allow the beam to reach the working electrode, have been applied. Examples are KBr [69], CaF 2 [70] and diamond [71]. Most experimental setups do not have a conventional half-cell, sandwich-like, structure but have a more open structure with the counter electrode positioned aside the working electrode.…”

Section: Fourier Transform Infrared Spectroscopymentioning

confidence: 99%

“…Positioning the IR-window as close as possible to the working electrode is critical to limit the light absorption by the electrolyte between the window and electrode. However, it should be taken into consideration that as the liquid electrolyte film becomes too thin, the diffusion of electrolyte species to/from the electrode may become a limiting factor [71].…”

Section: Fourier Transform Infrared Spectroscopymentioning

confidence: 99%

In situ methods for Li-ion battery research: A review of recent developments

Harks

Mulder

Notten

2015

Journal of Power Sources

329

244

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“…151 It is thus important to understand the formation and influence of the SEI, which, however, requires the application of a surface-sensitive method such as certain variants of vibrational spectroscopy. 154,155,159,160 A combination of in situ Raman/FT-IR spectroscopy has recently been applied by Novák et al for the characterization of Lithium ion containing electrolytes and their behaviour at glassy carbon electrodes with EC and DMC as solvents. 154 In order to be able to interpret features in measured IR spectra, it is helpful to differentiate the contributions of the various ingredients.…”

Section: Example Applications: Ec and Dmcmentioning

confidence: 99%

Local electric dipole moments for periodic systems via density functional theory embedding

Luber

2014

The Journal of Chemical Physics

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We describe a novel approach for the calculation of local electric dipole moments for periodic systems. Since the position operator is ill-defined in periodic systems, maximally localized Wannier functions based on the Berry-phase approach are usually employed for the evaluation of local contributions to the total electric dipole moment of the system. We propose an alternative approach: within a subsystemdensity functional theory based embedding scheme, subset electric dipole moments are derived without any additional localization procedure, both for hybrid and non-hybrid exchange-correlation functionals. This opens the way to a computationally efficient evaluation of local electric dipole moments in (molecular) periodic systems as well as their rigorous splitting into atomic electric dipole moments. As examples, Infrared spectra of liquid ethylene carbonate and dimethyl carbonate are presented, which are commonly employed as solvents in Lithium ion batteries. We describe a novel approach for the calculation of local electric dipole moments for periodic systems. Since the position operator is ill-defined in periodic systems, maximally localized Wannier functions based on the Berry-phase approach are usually employed for the evaluation of local contributions to the total electric dipole moment of the system. We propose an alternative approach: within a subsystem-density functional theory based embedding scheme, subset electric dipole moments are derived without any additional localization procedure, both for hybrid and non-hybrid exchangecorrelation functionals. This opens the way to a computationally efficient evaluation of local electric dipole moments in (molecular) periodic systems as well as their rigorous splitting into atomic electric dipole moments. As examples, Infrared spectra of liquid ethylene carbonate and dimethyl carbonate are presented, which are commonly employed as solvents in Lithium ion batteries. © 2014 AIP Publishing LLC. [http://dx

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Dynamic in situ fourier transform infrared measurements of chemical bonds of electrolyte solvents during the initial charging process in a Li ion battery

Cited by 44 publications

References 20 publications

In Situ DRIFTS Analysis of Solid‐Electrolyte Interphase Formation on Li‐Rich Li_1.2Ni_0.2Mn_0.6O₂ and LiCoO₂ Cathodes during Oxidative Electrolyte Decomposition

In Situ DRIFTS Analysis of Solid‐Electrolyte Interphase Formation on Li‐Rich Li_1.2Ni_0.2Mn_0.6O₂ and LiCoO₂ Cathodes during Oxidative Electrolyte Decomposition

In situ methods for Li-ion battery research: A review of recent developments

Local electric dipole moments for periodic systems via density functional theory embedding

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Dynamic in situ fourier transform infrared measurements of chemical bonds of electrolyte solvents during the initial charging process in a Li ion battery

Cited by 44 publications

References 20 publications

In Situ DRIFTS Analysis of Solid‐Electrolyte Interphase Formation on Li‐Rich Li1.2Ni0.2Mn0.6O2 and LiCoO2 Cathodes during Oxidative Electrolyte Decomposition

In Situ DRIFTS Analysis of Solid‐Electrolyte Interphase Formation on Li‐Rich Li1.2Ni0.2Mn0.6O2 and LiCoO2 Cathodes during Oxidative Electrolyte Decomposition

In situ methods for Li-ion battery research: A review of recent developments

Local electric dipole moments for periodic systems via density functional theory embedding

Contact Info

Product

Resources

About

In Situ DRIFTS Analysis of Solid‐Electrolyte Interphase Formation on Li‐Rich Li_1.2Ni_0.2Mn_0.6O₂ and LiCoO₂ Cathodes during Oxidative Electrolyte Decomposition

In Situ DRIFTS Analysis of Solid‐Electrolyte Interphase Formation on Li‐Rich Li_1.2Ni_0.2Mn_0.6O₂ and LiCoO₂ Cathodes during Oxidative Electrolyte Decomposition