Enhanced thermal stability of a lithiated nano-silicon electrode by fluoroethylene carbonate and vinylene carbonate

Profatilova, I. A.; Stöck, Christoph; Schmitz, Änne; Passerini, Stefano; Winter, Martin

doi:10.1016/j.jpowsour.2012.08.066

Cited by 232 publications

(223 citation statements)

References 89 publications

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“…The strong band observed at 838 cm −1 is attributed to ν P-F stretching of LiPF 6 . The FTIR spectra features associated with each electrolyte component are in good agreement with Haregewoin et al 46 and Profatilova et al 47 The presence of 10% FEC seemed to cause decreased peak broadening at ∼1150, ∼1300 and ∼1700 cm −1 .…”

Section: Resultssupporting

confidence: 87%

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: Resultssupporting

confidence: 87%

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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“…[41][42][43] This concept has also been expanded to a thermal SEI repair mechanism, recently. 32,44 On the Si(100) electrode, VC and FEC additives do not influence the formation of the "new" SEI on the lithiated/amorphous Li x Si as there is barely a difference visible in the SEI composition at 0.01 V. However, VC and FEC additives have a dramatic effect on the SEI layer behavior on Si(110) and Si(111), which will be subject of the upcoming part II of this study.…”

Section: Resultsmentioning

confidence: 89%

“…The triplet at 1775 cm −1 corresponds to the ν (C=O) stretch modes of DEC and EC decomposition products. 32 The asymmetric stretching mode ν (C=O) at 1484 cm −1 can be attributed to decomposition products of EC whereas the symmetric mode ν (C=O) at 1300 cm −1 originates from products of DEC reduction. The two peaks at 1200 and 1086 cm −1 are characteristic for carbonate ring stretching modes ν (C-O) of EC decomposition products.…”

Section: Resultsmentioning

confidence: 98%

The Mechanism of SEI Formation on a Single Crystal Si(100) Electrode

Vogl

Lux

Crumlin

et al. 2015

J. Electrochem. Soc.

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A fundamental study of interfacial phenomena on a Si(100) single crystal electrode in organic carbonate-based electrolytes was carried out. The SEI formation on the Si(100) single crystal electrode was investigated as a function of the electrolyte composition, electrode potential and Li x Si lithiation degree. Fourier transform infrared spectroscopy (FTIR) and X-ray photon spectroscopy (XPS) studies of the SEI layer during early stages of SEI formation indicate a strong dependence of the SEI composition on the electrolyte composition. However, the influence of the electrolyte composition becomes negligible at low potentials, when lithium alloys with Si and forms amorphous Li Currently, graphite is the most common negative electrode material in commercial lithium ion batteries for portable electronics. [1][2][3] However, lithium ion batteries for large-scale transportation applications require new inexpensive electrode materials with higher specific capacity. For decades, silicon has been considered as a promising negative electrode material, mainly because of its high specific capacity of ca. 3500 mAh/g 4 and its abundance in the earth crust. [4][5][6] The key problems that prevent its widespread use are large, up to ∼300 % volumetric changes during lithiation/delithiation processes and interfacial instability of lithium silicides in organic solvent based electrolytes. 6-12The resultant poor electrochemical cycling performance and large irreversible capacities during formation and operation of the Si negative electrode contribute to rapid degradation and failure of the battery. 6,7,13 The solid electrolyte interphase (SEI) layer, which forms at the electrode/electrolyte interface during the initial charge/discharge cycles, is the key component that determines the long-term stability and cycling behavior of carbonaceous and intermetallic negative Li-ion battery electrodes.14-16 Electrolyte reduction and SEI layer formation on a Si electrode usually take place at potentials below 1.8 V vs. Li/Li + and accompany the formation of Li-Si phases, the so-called "Si-Li alloying" process at E <0.4 V vs. Li/Li + . 17 The exact mechanism of the SEI formation processes on Si, the SEI composition and the effect on the Si electrode electrochemical cycling performance is not well understood. 18 On the other hand, SEI-forming electrolyte additives such as vinylene carbonate (VC) and fluoroethylene carbonate (FEC) are known to alter the composition and properties of the SEI on Si and improve the electrode electrochemical performance. [19][20][21] Interestingly, recent model studies on Sn single crystal electrodes in organic carbonate electrolytes revealed a strong correlation between the crystal surface orientation and the SEI composition.22,23 A similar study of the composition of the SEI on a silicon monocrystal electrode showed strong effects of different SEI formation protocols, presence/absence of intrinsic SiO 2 , electrolyte composition and impurities e.g., HF. [24][25][26] Also graphite exhibits different SEI layer compos...

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“…These results indicate that a VC-derived stable surface film forms on the Ge 0.1 Si 0.9 electrode in VC-containing electrolyte, and a VC-derived surface film has been shown to be effective on graphite and Si electrodes. 5,7,14,15 A Ge 0.1 Si 0.9 /LaSi 2 composite electrode also exhibited better cycle performance in VC-free electrolyte solution compared to a Ge 0.1 Si 0.9 electrode. The discharge capacity and capacity retention of the composite electrode were 332 mA h g ¹1 and 32% at the 400th cycle, respectively.…”

mentioning

confidence: 92%

Improved Electrochemical Performance of a Ge_xSi₁₋_xAlloy Negative Electrode for Lithium-Ion Batteries

Domi¹,

Usui²,

Takemoto³

et al. 2016

Chem. Lett.

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A Ge x Si 1¹x alloy electrode is useful for addressing the shortcomings of a Si negative electrode for lithium-ion batteries. To further improve the electrochemical performance of a Ge x Si 1¹x negative electrode, a film-forming additive and the formation of a composite with LaSi 2 were applied. A Ge 0.1 Si 0.9 electrode exhibited better cyclability in the additive-containing electrolyte with a discharge capacity of 1240 mA h g ¹1 at the 400th cycle. In addition, a Ge 0.1 Si 0.9 /LaSi 2 composite electrode showed better cycle performance than a Ge 0.1 Si 0.9 electrode.

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Enhanced thermal stability of a lithiated nano-silicon electrode by fluoroethylene carbonate and vinylene carbonate

Cited by 232 publications

References 89 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

The Mechanism of SEI Formation on a Single Crystal Si(100) Electrode

Improved Electrochemical Performance of a Ge_xSi₁₋_xAlloy Negative Electrode for Lithium-Ion Batteries

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Enhanced thermal stability of a lithiated nano-silicon electrode by fluoroethylene carbonate and vinylene carbonate

Cited by 232 publications

References 89 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

The Mechanism of SEI Formation on a Single Crystal Si(100) Electrode

Improved Electrochemical Performance of a GexSi1−xAlloy Negative Electrode for Lithium-Ion Batteries

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Improved Electrochemical Performance of a Ge_xSi₁₋_xAlloy Negative Electrode for Lithium-Ion Batteries