Morphology of the Solid Electrolyte Interphase on Graphite in Dependency on the Formation Current

Märkle, Wolfgang; Lu, Chia-Ying; Novák, Petr

doi:10.1149/2.077112jes

Cited by 34 publications

(24 citation statements)

References 28 publications

(36 reference statements)

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“…The onset of gas generation during this process, according to online electrochemical mass spectrum, also occurred in a similar range (∼1.0 V), although this reaction lasted until the potential range where the bare Li + -intercalation occurred (<0.3 V). 546,579,580 This may indicate that the solvated Li + is actually unstable within the graphite interior because the solvating molecules become more reactive with EC as the potential of graphite drops. Lithiation processes carried out with less graphitized carbon also exhibited the distinct stage of cointercalation by solvated Li + at edge planes of the crystalline regions.…”

Section: Formation Mechanismmentioning

confidence: 99%

Electrolytes and Interphases in Li-Ion Batteries and Beyond

2014

Chem. Rev.

4,200

3,989

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Section: Formation Mechanismmentioning

confidence: 99%

Electrolytes and Interphases in Li-Ion Batteries and Beyond

2014

Chem. Rev.

4,200

3,989

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“…35 SEI formation is clearly affected by the electrode used. For example, solvent intercalation between graphite sheets 36 competes with electrolyte decomposition on graphite edges, 37 and Si-F covalent bonds in the SEI are unique to silicon anodes. 38 While these electrode-specific effects are undoubtedly present, the extent to which they are critical for SEI passivation has not been completely estabilished.…”

mentioning

confidence: 99%

Two-electron reduction of ethylene carbonate: A quantum chemistry re-examination of mechanisms

Leung

2013

Chemical Physics Letters

147

237

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Passivating solid-electrolyte interphase (SEI) films arising from electrolyte decomposition on low-voltage lithium ion battery anode surfaces are critical for battery operations. We review the recent theoretical literature on electrolyte decomposition and emphasize the modeling work on two-electron reduction of ethylene carbonate (EC, a key battery organic solvent). One of the two-electron pathways, which releases CO gas, is re-examined using simple quantum chemistry calculations. Excess electrons are shown to preferentially attack EC in the order (broken EC − ) > (intact EC − ) > EC. This confirms the viability of two electron processes and emphasizes that they need to be considered when interpreting SEI experiments. An estimate of the crossover between one-and two-electron regimes under a homogeneous reaction zone approximation is proposed. 1 arXiv:1307.3165v1 [physics.chem-ph] 11 Jul 2013 EC charge neutral ethylene carbonate c-EC − intact ethylene carbonate radical anion o-EC − ring-opened ethylene carbonate radical anion EDC ethylene dicarbonate BDC butylene dicarbonate k 1 bimolecular EC − recombination rate to form BDC k 2 unimolecular EC 2− decay rate k 3 unimolecular EC − ring-opening rate (C E -O E bond) k e rate of electron tunneling to EC k e rate of electron tunneling to EC − I. INTRODUCTION Solid electrolyte interphase (SEI) films on low voltage anode surfaces (e.g., graphite, Li metal, Si) are critical for lithium ion battery operations. 1-5 They arise from electrochemical reduction and subsequent breakdown of the organic solvent-based electrolyte which is metastable under battery charging voltage. Once formed, the SEI hinders electron tunneling from the anode and prevents further electrolyte decomposition while still permitting Li + ions to diffuse between the electrolyte and the anode. The electrolyte and electrode have to be matched to produce stable SEI films. For example, ethylene carbonate (EC) is essential for widely used graphitic anodes. Substantial experimental work has been performed to study the SEI structure and chemical composition, which is extremely complex and heterogeneous. The gases released during the first charging cycle, when the SEI is largely created, have also been analyzed. 5-21 Despite this, SEI formation mechanisms at the atomic lengthscale are difficult to elucidate by purely experimental means, and significant uncertainties remain. With some exceptions, proposed mechanisms have been indirectly inferred from SEI chemical composition and gas product distribution. Such analysis can be hampered by further reactions of initial electrolyte breakdown products 18 and even sample preparation procedures during ex-situ measurements. 17 Battery material surfaces are not clean or homogeneous, and differences in synthetic/experimental conditions likely contribute to SEI variations reported in different laboratories. For example, there are significant differences in the amount of CO gas 2reported. 5,[9][10][11][12][13]20 As will be discussed, CO release is the signature of a key SEI f...

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“…Of crucial importance for Lithium ion batteries is the formation of an organic/inorganic layer at the graphite anode/electrolyte interface, the so-called solid-electrolyte interface (SEI). [149][150][151][152][153] It prevents further electron injection into the electrolyte accompanied with electrolyte decomposition as well as exfoliation of the graphene layers whereas Lithium ions can ideally still diffuse through the SEI. The complex mechanism of SEI formation has not been completely understood and numerous experimental and theoretical work has been conducted (for an overview about recent work, we refer to Refs.…”

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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Morphology of the Solid Electrolyte Interphase on Graphite in Dependency on the Formation Current

Cited by 34 publications

References 28 publications

Electrolytes and Interphases in Li-Ion Batteries and Beyond

Electrolytes and Interphases in Li-Ion Batteries and Beyond

Two-electron reduction of ethylene carbonate: A quantum chemistry re-examination of mechanisms

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

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