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

Shi, Feifei; Zhao, Hui; Liu, Gao; Ross, Philip N.; Somorjai, Gábor A.; Komvopoulos, K.

doi:10.1021/jp500558x

Cited by 36 publications

(48 citation statements)

References 34 publications

(87 reference statements)

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“…These bands were also found in the 1 st delithiation cycle when approaching OCP and they can be attributed to polyethylene carbonate. Similarly, Shi et al 48 showed the formation of this species using EC-based electrolyte over Ni-electrodes. This suggests that SEI film formation in the absence of FEC is somewhat potential-dependent.…”

Section: Resultsmentioning

confidence: 81%

In Situ DRIFTS Analysis of Solid Electrolyte Interphase of Si-Based Anode with and without Fluoroethylene Carbonate Additive

Yohannes

Lin

2017

J. Electrochem. Soc.

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The effect of fluoroethylene carbonate (FEC) additive has been studied in the formation of solid electrolyte interphase (SEI) over Si-based anode using in-situ DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy). SEI species were observed in the first lithiation cycle at an onset potential of 1.4 V in electrolyte containing 2 wt% vinylene carbonate (VC) + 10 wt% FEC and at 1.1 V in electrolyte without FEC additive. With blended VC and FEC, high carbon containing species including poly (FEC), poly (VC), and polycarbonates were identified, while poly (VC) and polycarbonates formed in the absence of FEC. The FEC additive also led to a higher content of organic phosphorous fluorides as compared to the electrolyte containing no FEC. Electrochemical analyses indicated that the combination of 2 wt% VC and 10 wt% FEC resulted in lower impedances and improved the stability of the Si-electrode through cycling as compared to that without FEC. DRIFTS provided evidence that similar SEI species formed after the initiation in the first cycle, and this formation was recorded for five cycles. With the increasing demand for battery systems with high energy density and high power for applications such as hybrid and electric vehicles, the development of Li-ion batteries has attracted much attention in recent years.1,2 This self-supporting energy storage system 3 works based on the principle of redox reactions that can reversibly convert chemical energy into electrical energy. In Li-ion battery operation, the negative electrodes function at low potentials close to the potential of metallic lithium, where electrolytes are not stable thermodynamically. As a result, the reduction of solvents and salts of the electrolyte will result in the formation of a surface film on the electrode. Typically, this surface film is composed of organic reduction products (closer to the electrolyte) and inorganic species (closer to the electrode). 4 This film, called the solid electrolyte interphase (SEI), is known to be an important feature of graphite anodes that can allow for reversible cycling and long-term stability due to surface passivation. 5,6 Numerous replacements for the graphite anode have been investigated, with silicon 7,8 being one of the most attractive for its high theoretical specific capacity of 4200 mAhg −1 , which is more than ten times larger than that of graphite (372 mAhg −1 ). 9 However, Si undergoes large volume changes during lithiation and delithiation cycling, which cause capacity fading.10 Many studies have tried to improve the capacity retention of Si anodes by using nano-structured silicon, [11][12][13] silicon composite electrodes, 14,15 carbon coated silicon, 16 thin film silicon, [17][18][19] and new binders. [20][21][22] The formation of a stable surface layer for Si-based anodes would have an impact on achieving a long cycle life. One way to address this issue is to use a new electrolyte and/or to add a small amount (< 10 wt%) of electrolyte additives. Different types of electrolyte additives, such as...

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Section: Resultsmentioning

confidence: 81%

In Situ DRIFTS Analysis of Solid Electrolyte Interphase of Si-Based Anode with and without Fluoroethylene Carbonate Additive

Yohannes

Lin

2017

J. Electrochem. Soc.

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“…Indeed, reduction products of linear carbonates are known to be responsible for changes in electrolyte composition over time; [1][2][3][4][5][6][7][8] the generated alkoxide can trigger the chemical formation of soluble oligomers through consumption of linear and cyclic carbonates, which can explain the decay in battery performance. Indeed, reduction products of linear carbonates are known to be responsible for changes in electrolyte composition over time; [1][2][3][4][5][6][7][8] the generated alkoxide can trigger the chemical formation of soluble oligomers through consumption of linear and cyclic carbonates, which can explain the decay in battery performance.…”

Section: Resultsmentioning

confidence: 99%

Hindered Glymes for Graphite‐Compatible Electrolytes

et al. 2015

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Organic carbonate mixtures are used almost exclusively as lithium battery electrolyte solvents. The linear compounds (dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate) act mainly as thinner for the more viscous and high-melting ethylene carbonate but are the least stable component and have low flash points; these are serious handicaps for lifetime and safety. Polyethers (glymes) are useful co-solvents, but all formerly known representatives solvate Li(+) strongly enough to co-intercalate in the graphite negative electrode and exfoliate it. We have put forward a new electrolyte composition comprising a polyether to which a bulky tert-butyl group is attached ("hindered glyme"), thus completely preventing co-intercalation while maintaining good conductivity. This alkyl-carbonate-free electrolyte shows remarkable cycle efficiency of the graphite electrode, not only at room temperature, but also at 50 and 70 °C in the presence of lithium bis(fluorosulfonimide). The two-ethylene-bridge hindered glyme has a high boiling point and a flash point of 80 °C, a considerable advantage for safety.

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“…1,2,3 The electrolytes used for LIBs are normally composed of highly polar solvents such as carbonate derivatives 4,5,6 or poly(ethylene oxide) (PEO) and lithium salts such as LiPF 6 (LiTFSI), 7 Li[N(SO 2 C 2 F 5 ) 2 ] (LiBETI) 8 etc. Lithium bis(trifluoromethane) sulfonamide (LiTFSI) was first brought to the application of lithium ion electrolytes by Armand.…”

Section: Introductionmentioning

confidence: 99%

Plasticized Polymer Composite Single-Ion Conductors for Lithium Batteries

Zhao

Asfour

et al. 2015

ACS Appl. Mater. Interfaces

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Lithium bis(trifluoromethane) sulfonamide (TFSI) is a promising electrolyte salt in lithium batteries, due to its good conductivity and high dissociation between the lithium cation and its anion. By tethering N-pentane triflouromethane sulfonamide (C5NHTf), a TFSI analogue molecule, onto the surface of silica nanoparticle as a monolayer coverage should increase the Li + transference number to unity since anions bound to particles have reduced mobilities. Silica polymer composite has better mechanical property than that of the pure PEO. Analogously trifluoromethane sulfonic aminoethylmethacrylate (TfMA), a TFSI analogue vinyl monomer was polymerized on silica nanoparticle surface as a multilayer coverage. Anchored polyelectrolytes to particle surfaces offer multiple sites for anions, and in principle, the carrier concentration would increase arbitrarily and approach the carrier concentration of the bulk polyelectrolyte. Monolayer grafted nanoparticle have a lithium content of 1.2*10 -3 g Li/g and multilayer grafted nanoparticle have a lithium content over an order higher at 2*10 -2 g Li/g. Electrolytes made from monolayer grafted particles exhibit a weak conductivity dependence on temperature, exhibiting an ionic conductivity in the range of 10 -6 S/cm when temperatures increase to 80 °C. While electrolytes made from multilayer grafted particles show a steep increase in conductivity with temperature with an ionic conductivity increase to 3*10 -5 S/cm at 80 °C, with a O/Li ratio of 32.

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

Cited by 36 publications

References 34 publications

In Situ DRIFTS Analysis of Solid Electrolyte Interphase of Si-Based Anode with and without Fluoroethylene Carbonate Additive

In Situ DRIFTS Analysis of Solid Electrolyte Interphase of Si-Based Anode with and without Fluoroethylene Carbonate Additive

Hindered Glymes for Graphite‐Compatible Electrolytes

Plasticized Polymer Composite Single-Ion Conductors for Lithium Batteries

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