The Study of Surface Film Formation on Noble-Metal Electrodes in Alkyl Carbonates/Li Salt Solutions, Using Simultaneous in Situ AFM, EQCM, FTIR, and EIS

Aurbach, Doron; Moshkovich, M.; Cohen, Yair; Schechter, Alex

doi:10.1021/la981275j

Cited by 141 publications

(154 citation statements)

References 22 publications

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“…19,30,[36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51] The electrochemical reduction of five organic carbonates -EC, PC, DEC, DMC and VCwere studied with the use of cyclic voltammetry at a gold electrode in THF/LiClO 4 supporting electrolyte. 52 The reduction potentials of all the carbonates were above 1 V (vs. Li/Li + ), with E VC being the most positive. In Ref.…”

Section: Chemical Composition and Properties Of The Sei On Inert Subsmentioning

confidence: 89%

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Review—SEI: Past, Present and Future

Peled

Menkin

2017

J. Electrochem. Soc.

1,546

1,474

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The Solid-Electrolyte-Interphase (SEI) model for non-aqueous alkali-metal batteries constitutes a paradigm change in the understanding of lithium batteries and has thus enabled the development of safer, durable, higher-power and lower-cost lithium batteries for portable and EV applications. Prior to the publication of the SEI model (1979), researchers used the Butler-Volmer equation, in which a direct electron transfer from the electrode to lithium cations in the solution is assumed. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the solution in a lithium battery, must be prevented, since it will result in fast self-discharge of the active materials and poor battery performance. This model provides [E. Peled, in "Lithium Batteries," J.P. Gabano (ed), Academic Press, (1983), E. Peled, J. Electrochem. Soc., 126, 2047Soc., 126, (1979.] new equations for: electrode kinetics (i o and b), anode corrosion, SEI resistivity and growth rate and irreversible capacity loss of lithium-ion batteries. This model became a cornerstone in the science and technology of lithium batteries. This paper reviews the past, present and the future of SEI batteries. The PastPrior to the publication of the SEI model (1979), 1,4 researchers used the Butler-Volmer equation, in which direct electron transfer from the electrode to lithium cations in the solution is assumed. It was generally assumed that the rate-determining step (RDS) is the transfer of electrons from the metal to the cations in the solution. Researchers found that the lithium anode is covered by a passivating layer which interferes with the deposition/dissolution process of the anode. Brummer and Newman 2,3 concluded that a passivating anode can offer only a limited cycle life and in order to obtain a deep-discharge high-cycle-life secondary battery, the lithium anode must be free of a passivating layer and kinetically stable with respect to the electrolyte. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the solution in a lithium battery, except when forming a SEI, must be prevented. The Present, Lithium-Metal and Lithium-Ion BatteriesIntroduction.-It is now generally accepted that the solidelectrolyte interphase (SEI) is essentially for the existence and successful operation of lithium-and sodium-battery systems, as primary and secondary power sources. 4 In 1979, it was proposed by Peled,

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Section: Chemical Composition and Properties Of The Sei On Inert Subsmentioning

confidence: 89%

“…In Ref. 52 it was shown that the preferential reduction of vinylene carbonate appears to favor SEI formation.…”

Section: Chemical Composition and Properties Of The Sei On Inert Subsmentioning

confidence: 99%

Review—SEI: Past, Present and Future

Peled

Menkin

2017

J. Electrochem. Soc.

1,546

1,474

View full text Add to dashboard Cite

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“…26,21,27 The spectra of organic compound would be especially affected by the presence of solvents and ions of the battery's electrolyte, collectively referred to as solvation effects. Thus, DEDOHC and poly-EC were introduced into the electrolyte, and FTIR spectra were acquired under the same condition as in in-situ and ex-situ experiments.…”

Section: Analysis Of LI Ion Solvation Effect On Dedohc and Poly-ec Irmentioning

confidence: 99%

Identification of Diethyl 2,5-Dioxahexane Dicarboxylate and Polyethylene Carbonate as Decomposition Products of Ethylene Carbonate Based Electrolytes by Fourier Transform Infrared Spectroscopy

et al. 2014

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The formation of passive films on electrode by electrolyte decomposition plays a crucial role in maintaining the reversibility of Li ion batteries (LIBs); however the understanding of the electrolyte decomposition process is still lacking. In this study, we investigated the decomposition of an electrolyte based on ethylene carbonate (EC) solvent, and identified the decomposition products on Sn and Ni surface by matching the IR spectra to that of synthesized reference compounds. The reference compounds diethyl 2,5-dioxahexane dicarboxylate (DEDOHC) and polyethylene carbonate (poly-EC) were synthesized and the chemical structures were characterized by nuclear magnetic resonance (NMR) andFourier transform infrared (FTIR) spectroscopy. Peak assignments were made based on quantum chemical (Hartree-Fock) calculations. By introducing the synthesized product compounds into the electrolyte, we studied the effect of Li-ion solvation on the IR spectra and were able to match the spectra of the decomposition products on Sn and Ni electrode surfaces to those of DEDOHC and poly-EC for the first time. This study clearly demonstrated the importance to include solvation effects in the IR spectra of reference compounds in identification of electrolyte decomposition products in LIBs.2

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“…5a-a', the C-Si surface shows strong IR features below 900 cm , related to the reduction of organic carbonate solvents. 16,17,[22][23][24]31,32,[40][41][42] With 1-(trimethylsilyloxy)-1,3-butadiene, Fig. 5b-b', the CSi surface also shows strong IR features below 900 cm .…”

Section: Resultsmentioning

confidence: 96%

Control of Surface Chemistry and Electrochemical Performance of Carbon-coated Silicon Anode Using Silane-based Self-Assembly for Rechargeable Lithium Batteries

Choi¹,

Nguyen²,

Song³

2010

Bulletin of the Korean Chemical Society

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Silane-based self-assembly was employed for the surface modification of carbon-coated Si electrodes and their surface chemistry and electrochemical performance in battery electrolyte depending on the molecular structure of silanes was studied. IR spectroscopic analyses revealed that siloxane formed from silane-based self-assembly possessed Si-O-Si network on the electrode surface and high surface coverage siloxane induced the formation of a stable solid-electrolyte interphase (SEI) layer that was mainly composed of organic compounds with alkyl and carboxylate metal salt functionalities, and PF-containing inorganic species. Scanning electron microscopy imaging showed that particle cracking were effectively reduced on the carbon-coated Si when having high coverage siloxane and thickened SEI layer, delivering > 1480 mAh/g over 200 cycles with enhanced capacity retention 74% of the maximum discharge capacity, in contrast to a rapid capacity fade with low coverage siloxane.

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The Study of Surface Film Formation on Noble-Metal Electrodes in Alkyl Carbonates/Li Salt Solutions, Using Simultaneous in Situ AFM, EQCM, FTIR, and EIS

Cited by 141 publications

References 22 publications

Review—SEI: Past, Present and Future

Review—SEI: Past, Present and Future

Identification of Diethyl 2,5-Dioxahexane Dicarboxylate and Polyethylene Carbonate as Decomposition Products of Ethylene Carbonate Based Electrolytes by Fourier Transform Infrared Spectroscopy

Control of Surface Chemistry and Electrochemical Performance of Carbon-coated Silicon Anode Using Silane-based Self-Assembly for Rechargeable Lithium Batteries

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