Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 2. Radiolytically Induced Polymerization of Ethylene Carbonate

Shkrob, Ilya A.; Zhu, Ye; Marin, Timothy W.; Abraham, Daniel P.

doi:10.1021/jp406273p

Cited by 83 publications

(130 citation statements)

References 39 publications

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“…Previous studies [1,3] have suggested two reasons for this. Low-molecular-weight electrolyte additives such as maleimides [9][10][11][12][13], vinylene carbonate (VC) [6,7], or sulfones [8] can be electrochemically polymerized; thereby causing C-H bonding of the polymer on the anode surface. In this study, the VC was used to the additive in the electrolyte.…”

Section: Analysis Of Eis Characteristicsmentioning

confidence: 99%

“…Electrolyte additives, which are low-molecular-weight monomers that exhibit high reduction potentials, are used for reinforcing SEI formation and preventing the polarization of the electrochemical reaction. Chemical compounds based on vinylene carbonates [6,7], sulfones [8], maleimides [9][10][11][12][13], and phosphates [14,15] were previously developed for generating an SEI that prevented the exfoliation effects on carbon when PC was used as the solvent: using this process, a 3D electrochemically active surface area was formed and frame-retardant applications were improved. However, large-scale solubility and electrochemical stability of the additives in electrolytes cannot be readily maintained.…”

Section: Introductionmentioning

confidence: 99%

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Forward and reverse differential-pulse effects applied in the formation of a solid electrolyte interface to enhance the performance of lithium batteries

Wang

Rick

2014

Electrochimica Acta

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Section: Analysis Of Eis Characteristicsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Forward and reverse differential-pulse effects applied in the formation of a solid electrolyte interface to enhance the performance of lithium batteries

Wang

Rick

2014

Electrochimica Acta

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“…Redistribution subject to ECS terms of use (see 18.236.120. 13 Downloaded on 2018-05-11 to IP passivated and VC-passivated spectra to contain similar peaks. Therefore, we propose that the similarities in formation charge for neat and FEC-containing electrolyte, coupled with the significant differences in impedance responses of ferrocene, can be partially attributed to the presence of these peaks in neat electrolyte observed at high frequencies in the IR response.…”

mentioning

confidence: 95%

“…[10][11][12] Shkrob et al used beam radiolysis to polymerize ethylene carbonate (EC) with masses of up to 2 kDa. 13 * Electrochemical Society Student Member. * * Electrochemical Society Fellow.…”

mentioning

confidence: 99%

Investigating the Solid Electrolyte Interphase Formed by Additive Reduction Using Physics-Based Modeling

Jaini

Setzler

Star

et al. 2016

J. Electrochem. Soc.

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In lithium-ion batteries, chemical additives are used as co-solvents to primary electrolytes to improve capacity and power retention. These additives facilitate the formation of a passivation layer, the solid electrolyte interphase (SEI), on the electrode surface. In this work, SEIs are formed in neat electrolyte and in electrolyte containing fluoroethylene carbonate and vinylene carbonate. The formed SEIs are then compared using a redox couple to probe their physical properties. For passivated samples, the impedance response of the redox couple shows the presence of multiple time constants, with processes at longer time scales corresponding to redox couple transport in the porous layer of the SEI. Samples passivated with additive-containing electrolyte versus neat electrolyte exhibit less redox-couple kinetic and mass-transport impedance. Simulations of the electrode-electrolyte interface indicate that compact and porous layer growth lead to slowed redox kinetics and mass transport. Model results suggest that SEI thicknesses are found to be at least an order of magnitude larger than expected compared to graphite electrodes. SEM cross sections of SEIs formed by neat and additive-containing electrolyte support the model findings. Experimentally measured formation charges, coupled with FTIR measurements of SEI composition, suggest that polymerization reactions are causing the unexpected film growth. In lithium-ion batteries, formation and growth of the solid electrolyte interphase (SEI) is a well-established mode of capacity and power fade. 1,2 Cell characteristics, including electrode chemistry and primary electrolyte composition, influence the chemical and physical properties of SEIs formed. 3 In addition to the primary electrolyte, chemical additives have been incorporated as co-solvents to address SEI formation and growth. When included as co-solvents, both fluoroethylene carbonate (FEC) and vinylene carbonate (VC) electrolyte additives preferentially react with the electrode during the SEI formation process instead of the primary electrolyte. Improved capacity retention, calendar life, and thermal stability are observed with additive inclusion in the electrolyte mixture. Additives such as FEC and VC have been prescribed as co-solvents to primary electrolytes for a variety of electrode chemistries. [4][5][6][7][8] Several groups have investigated the efficacy of these co-solvents to enhance cell performance. In these studies, the additives are limited to less than or equal to ten weight percent of the total electrolyte. For example, Ryou et al. found improved capacity retention at 60 • C with the addition of FEC, for a graphite negative electrode and LiMn 2 O 4 positive electrode full cell. 7 Bordes et al. found that, for a silicon-graphene composite negative electrode, FEC enhanced electrochemical performance by forming a less resistive SEI with smaller thickness using impedance spectroscopy and electron microscopy. 9 Aurbach et al. observed improved capacity with the addition of VC to a graphite negative ele...

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“…The decomposition products will form a solid electrolyte interface (SEI) layer on the surface of graphite anode. This process occurs mainly (but not exclusively) at the beginning of the initial cycle [1][2][3]. The formed SEI film can separate the graphite anode from the organic electrolyte and thereby prevents the organic electrolyte from further intercalating into the graphite electrode [4].…”

Section: Introductionmentioning

confidence: 99%

Study of SEI forming process with Li BOB-DMS/SL electrolyte in first cycle

Li¹,

Wang²,

Li³

et al. 2017

AIP Conference Proceedings

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Abstract. Lithium bis (oxalate) borate (Li BOB) has attracted much attention as a lithium salt or an additive in no aqueous electrolyte for lithium-ion battery. In this work, the formation of a solid electrolyte interphase (SEI) film of sulfolane (SL) with Li BOB was studied by employment of dimethyl sulfite (DMS) as mixed solvents. When used in Li/ MCMB (mesosphere carbon micro beads) cells, cell with 0.7M Li BOB-zSL/DMS (1:1) electrolyte at high temperature shows lower impedance than that at room temperature. The scanning electron microscope (SEM) results find that 0.7M Li BOB-SL/DMS (1:1) electrolyte at high temperature shows excellent film-forming characteristics than that at room temperature. The Li2SO3, ROSO2Li, Li2S, Li2CO3 substances are found in SEI film by X-ray photoelectron spectroscopy (XPS). It suggests that Li BOB-SL/DMS electrolyte has an excellent solid electrolyte interphase formation capacity.

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Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 2. Radiolytically Induced Polymerization of Ethylene Carbonate

Cited by 83 publications

References 39 publications

Forward and reverse differential-pulse effects applied in the formation of a solid electrolyte interface to enhance the performance of lithium batteries

Forward and reverse differential-pulse effects applied in the formation of a solid electrolyte interface to enhance the performance of lithium batteries

Investigating the Solid Electrolyte Interphase Formed by Additive Reduction Using Physics-Based Modeling

Study of SEI forming process with Li BOB-DMS/SL electrolyte in first cycle

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