High performance silicon nanoparticle anode in fluoroethylene carbonate-based electrolyte for Li-ion batteries

Lin, Yong‐Mao; Klavetter, Kyle C.; Abel, Paul R.; Davy, Nicholas C.; Snider, Jonathan L.; Heller, Adam; Mullins, C. Buddie

doi:10.1039/c2cc31712e

Cited by 277 publications

(235 citation statements)

References 16 publications

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“…7). We believe that this is the explanation for frequently reported long cycle life of cells with silicon anodes and FEC co-solvent if tested in coin cells (>hundreds of cycles), 25,46 while to our knowledge this has never been reported for actual batteries, in which the amount of electrolyte in terms of μL/cm 2 is much smaller.…”

Section: Cellmentioning

confidence: 88%

“…This is consistent with the literature, which shows that the use of FEC as co-solvent (typically ≥10% wt FEC) strongly stabilizes the cycle-life of silicon anodes. 22,25,46 The cycle number of the Si-Li cells at which the rapid capacity drop occurs is depicted by the black symbols in Fig. 7 (data from Figs.…”

Section: Cellmentioning

confidence: 99%

“…[22][23][24][25] In this study, we examine the effect and in particular the consumption of FEC on silicon-carbon composite electrodes. The continuous consumption of FEC is shown by 19 F-NMR spectroscopy and an observed sudden cell failure which is detected as a rapid drop in capacity is analyzed and related to the total consumption of FEC.…”

mentioning

confidence: 99%

“…23 Due to the significant improvement caused by FEC, it is nowadays established as a standard additive for silicon electrodes, even though the exact working principle and decomposition mechanism are not fully understood yet. [22][23][24][25] In this study, we examine the effect and in particular the consumption of FEC on silicon-carbon composite electrodes. The continuous consumption of FEC is shown by 19 F-NMR spectroscopy and an observed sudden cell failure which is detected as a rapid drop in capacity is analyzed and related to the total consumption of FEC.…”

mentioning

confidence: 99%

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Consumption of Fluoroethylene Carbonate (FEC) on Si-C Composite Electrodes for Li-Ion Batteries

Jung

Metzger

Haering

et al. 2016

J. Electrochem. Soc.

262

311

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The electrolyte additive fluoroethylene carbonate (FEC) is known to significantly improve the lifetime of Li-ion batteries with silicon anodes. In this work, we show that FEC can indeed improve the lifetime of silicon-carbon composite anodes but is continuously consumed during electrochemical cycling. By the use of 19 F-NMR spectroscopy and charge/discharge cycling we demonstrate that FEC is only capable to stabilize the cell performance as long as FEC is still remaining in the cell. Its total consumption causes a significant increase of the cell polarization leading to a rapid capacity drop. We show with On-line Electrochemical Mass Spectrometry (OEMS) that the presence of FEC in the electrolyte prohibits the reduction of other electrolyte components almost entirely. Consequently, the cumulative irreversible capacity until the rapid capacity drop correlates linearly with the specific amount of FEC (in units of μmol FEC /mg electrode ) in the cell. The latter quantity therefore determines the lifetime of silicon anodes rather than the concentration of FEC in the electrolyte. By correlating the cumulative irreversible capacity and the specific amount of FEC in the cell, we present an easy tool to predict how much cumulative irreversible capacity can be tolerated until all FEC will be consumed in either half-cells or full-cells. We further demonstrate that four electrons are consumed for the reduction of one FEC molecule and that one carbon dioxide molecule is released for every FEC molecule that is reduced. Using all information from this study and combining it with previous reports in literature, a new reductive decomposition mechanism for FEC is proposed yielding CO 2 , LiF, In the emerging market of electric vehicles (EVs), the development of batteries with higher energy density and improved cycle-life is essential.1 However, their penetration of the mass market significantly depends on cost and the available driving range.2 The US Advanced Battery Consortium (USABC) defined the target value of 235 Wh/kg (at a C/3 rate) on a battery level until 2020.3 As outlined in the recent review by Andre et al., 4 reaching this goal requires an increase of the energy density of today's batteries by a factor of roughly 2 to 2.5 and can only be achieved by the development and integration of novel anode and cathode active materials. A critical element to reach this goal is the implementation of anode active materials with much higher specific capacity than currently used graphite anodes (372 mAh/g 1,5,6 ), with silicon being considered as the most likely next generation anode material due to its high natural abundance and very high theoretical specific capacity of roughly 3600 mAh/g (corresponding to the Li 15 Si 4 phase 7 ). The alloying of silicon with lithium is accompanied by large structural changes, resulting in a volume increase by 310% upon full lithiation.5,7-11 These huge volumetric changes upon lithium insertion and extraction are responsible for the generally shorter cycle-life of silicon electrode materials comp...

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Section: Cellmentioning

confidence: 88%

Section: Cellmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Consumption of Fluoroethylene Carbonate (FEC) on Si-C Composite Electrodes for Li-Ion Batteries

Jung

Metzger

Haering

et al. 2016

J. Electrochem. Soc.

262

311

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“…However, the Si is well known to suffer from severe volume change during reaction with lithium 3 followed by electrochemical and mechanical particle disintegration 2,4 leading to a poor cycling ability. Recent reports have shown that the use of amorphous 5 or nanostructured Si, 6 and carboncoating 7,8 or carbon composite, [9][10][11] and the use of advanced elastic binder [12][13][14] and electrolyte composition 15,16 yields enhancement of cycling ability. It still however remains a great challenge to develop new approaches for obtaining a reliable performance of lithium-ion batteries employing Si-based anodes.…”

mentioning

confidence: 99%

Self-organized Artificial SEI for Improving the Cycling Ability of Silicon-based Battery Anode Materials

Min¹,

Bae²,

Kim³

et al. 2013

Bulletin of the Korean Chemical Society

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Silicon (Si)-based materials are considered as potential alternative anode materials to graphite for a use in the lithium-ion batteries for electric vehicles and energy storage systems because of superior theoretical capacity of 3759 mAhg −1 at room temperature 1,2 and appropriate operation voltages of a few hundreds milivolts above lithium. However, the Si is well known to suffer from severe volume change during reaction with lithium 3 followed by electrochemical and mechanical particle disintegration 2,4 leading to a poor cycling ability. Recent reports have shown that the use of amorphous 5 or nanostructured Si, 6 and carboncoating 7,8 or carbon composite, 9-11 and the use of advanced elastic binder 12-14 and electrolyte composition 15,16 yields enhancement of cycling ability. It still however remains a great challenge to develop new approaches for obtaining a reliable performance of lithium-ion batteries employing Si-based anodes.Our earlier work showed that the interfacial reaction between LiPF 6 of commercial electrolyte and the Li x Si deleteriously affects cycling performance.17-20 The interfacial reaction did not provide the formation of a stable solid electrolyte interphase (SEI) layer at the Si surface but deactivates the Si gradually with cycling by surface coverage with PF-containing species together with LiF salt, while accelerating irreversible particle disintegration and a consequent and dynamic change in the active surface area. We have proposed that interfacial control is a promising approach for improving the cycling ability of Si-based anodes, which was determined based on a basic understanding of electrode-electrolyte interfacial reactions and its impacts on structural degradation and performance fade via electrochemical and interfacial studies of film model electrodes. Surface protection of Si was necessary both to prevent the attack by LiPF 6 -derived species and to form a stable SEI layer. 17-20In the present work, we demonstrate that the cycling ability of Si nanoparticle anode is improved via a new approach of interfacial control. In order to suppress direct interfacial contact between Si and electrolyte while protecting the Si surface, we build up siloxane network as an artificial SEI at the surface of bulk Si active material, utilizing self-organized condensation reaction between alkoxy groups of silane molecules and hydroixde or oxygen groups of Si surface. The Si nanoparticles and composite with graphite decorated with an artificial SEI show significantly improved cycling stability.Building up of an artificial SEI with siloxane network is simply made first by dispersing commercial Si nanoparticles in the solution of tris(2-methoxyethoxy)vinylsilane (hereafter TMVS) using ultrasonication. The presence of a trace of water in the electrolyte assists the hydrolysis and polycondensation of silanes forming the siloxane network at the Si surface.

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Nanostructured Silicon Anodes for High‐Performance Lithium‐Ion Batteries

Rahman

Song

Bhatt

et al. 2015

Adv Funct Materials

297

167

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Despite the high theoretical capacity of Si anodes, the electrochemical performance of Si anodes is hampered by severe volume changes during lithiation and delithiation, leading to poor cyclability and eventual electrode failure. Nanostructured silicon and its nanocomposite electrodes could overcome this problem holding back the deployment of Si anodes in lithium‐ion batteries (LIBs) by providing facile strain relaxation, short lithium diffusion distances, enhanced mass transport, and effective electrical contact. Here, the recent progress in nanostructured Si‐based anode materials such as nanoparticles, nanotubes, nanowires, porous Si, and their respective composite materials and fabrication processes in the application of LIBs have been reviewed. The ability of nanostructured Si materials in addressing the above mentioned challenges have been highlighted. Future research directions in the field of nanostructured Si anode materials for LIBs are summarized.

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High performance silicon nanoparticle anode in fluoroethylene carbonate-based electrolyte for Li-ion batteries

Cited by 277 publications

References 16 publications

Consumption of Fluoroethylene Carbonate (FEC) on Si-C Composite Electrodes for Li-Ion Batteries

Consumption of Fluoroethylene Carbonate (FEC) on Si-C Composite Electrodes for Li-Ion Batteries

Self-organized Artificial SEI for Improving the Cycling Ability of Silicon-based Battery Anode Materials

Nanostructured Silicon Anodes for High‐Performance Lithium‐Ion Batteries

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