Exceptional Electrochemical Performance of Si-Nanowires in 1,3-Dioxolane Solutions: A Surface Chemical Investigation

Etacheri, Vinodkumar; Geiger, Uzi; Gofer, Yosef; Roberts, G. A.; Stefan, Ionel C.; Fasching, Rainier; Aurbach, Doron

doi:10.1021/la300306v

Cited by 133 publications

(150 citation statements)

References 73 publications

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“…21,27,39 Furthermore, a pure DOL solution with LiNO 3 addition was investigated since high reversibility with SiNW was reported. 7 Fig. 1a displays the galvanostatic cycling performance of the porous silicon nanocomposite vs Li/Li + in all three electrolytes.…”

Section: Resultsmentioning

confidence: 99%

“…[7][8][9] This observation is mainly caused by the characteristics of the interfacial layer strongly related to the surface area of the electrode material which is especially high on nanostructures. The interfacial layer, commonly known as solid-electrolyte-interface (SEI), is a surface film typically formed in the initial cycles by decomposition of electrolyte components.…”

mentioning

confidence: 99%

“…7 It was majorly attributed to the DOL solution which is typically used as co-solvent in electrolytes for Li-S batteries. DOL plays a significant role in secondary lithium batteries since it was shown to stabilize lithium metal anodes due to its polymerization to form polydioxolanes.…”

mentioning

confidence: 99%

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Role of 1,3-Dioxolane and LiNO₃Addition on the Long Term Stability of Nanostructured Silicon/Carbon Anodes for Rechargeable Lithium Batteries

Jaumann

Balach

Klose

et al. 2016

J. Electrochem. Soc.

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In order to utilize silicon as alternative anode for unfavorable lithium metal in lithium -sulfur (Li-S) batteries, a profound understanding of the interfacial characteristics in ether-based electrolytes is required. Herein, the solid electrolyte interface (SEI) of a nanostructured silicon/carbon anode after long-term cycling in an ether-based electrolyte for Li-S batteries is investigated. The role of LiNO 3 and 1,3-dioxolane (DOL) in dimethoxy ethane (DME) solutions as typically used electrolyte components on the electrochemical performance and interfacial characteristics on silicon are evaluated. Because of the high surface area of our nanostructured electrode owing to the silicon particle size of around 5 nm and the porous carbon scaffold, the interfacial characteristics dominate the overall electrochemical reversibility opening a detailed analysis. We show that the use of DME/DOL solutions under ambient temperature causes higher degradation of electrolyte components compared to carbonate-based electrolytes used for Li-ion batteries (LIB). This behavior of DME/DOL mixtures is associated with different SEI component formation and it is demonstrated that LiNO 3 addition can significantly stabilize the cycle performance of nanostructured silicon/carbon anodes. A careful postmortem analysis and a discussion in context to carbonate-based electrolyte solutions helps to understand the degradation mechanism of silicon-based anodes in rechargeable lithium-based batteries. Silicon is a highly attractive anode material for rechargeable Liion batteries (LIB) and post LIB systems owing to its high capacity and comparable discharge potential to lithium metal. Considerable progress has been achieved in recent years to tackle the peculiarities of silicon during de-/lithiation.1-2 The enormous volume expansion which causes fracture of individual particles and a low reversibility could be addressed by hierarchically designed nano-sized and amorphous silicon structures.3-6 However, it was shown that among other parameters the electrochemical performance of particularly nanostructured silicon significantly depends on the chosen electrolyte. [7][8][9] This observation is mainly caused by the characteristics of the interfacial layer strongly related to the surface area of the electrode material which is especially high on nanostructures. The interfacial layer, commonly known as solid-electrolyte-interface (SEI), is a surface film typically formed in the initial cycles by decomposition of electrolyte components. Because of the large volume expansion of silicon during lithiation, the SEI likely cracks and is regenerated causing continuous electrolyte consumption and high degradation. In order to reduce degradation and apply silicon as high-performance anode in rechargeable Li-based batteries, a profound knowledge of the interfacial characteristics is necessary. The SEI on silicon is typically studied in carbonate-based electrolytes since silicon is majorly considered as alternative anode for graphite in LIB. [10][11][12][13] Howeve...

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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Role of 1,3-Dioxolane and LiNO₃Addition on the Long Term Stability of Nanostructured Silicon/Carbon Anodes for Rechargeable Lithium Batteries

Jaumann

Balach

Klose

et al. 2016

J. Electrochem. Soc.

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“…The liquid electrolyte was prepared by mixing 1,3-dioxolane (DOL, Sigma-Aldrich) and bis(trifluoromethane)sulfonimide Li salt (Sigma Aldrich) to make a 1 M solution. 31 Electrodes were separated using a porous polymer separator (Celgard). Electrochemical experiments were performed using a Solartron 1470 E potentiostat.…”

Section: Methodsmentioning

confidence: 99%

Kinetic Study of the Initial Lithiation of Amorphous Silicon Thin Film Anodes

Miao

Thompson

2018

J. Electrochem. Soc.

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The mechanisms and kinetics of lithiation and delithiation of amorphous silicon were investigated using potentiostatic techniques and thin films of different thickness, with a focus on the initial lithiation process that occurs in the first cycle. In potentiostatic tests, distinct kinks were observed in the current vs. time curves, and the time at which the kink occurred increased for thicker films. This behavior can be explained using a model in which a sharp interface between an amorphous Li x Si phase and Li-saturated amorphous Si propagates through the film. Using this model, the rate-limiting process was determined to be diffusion of Li in the Li x Si phase rather than reaction at the lithiation front. The Li diffusivity in the lithiated phase was determined to be in the 10 −13 cm 2 /s range, independent of film thickness above 135 nm. The thin-film potentiostatic technique used in this study should prove useful in investigation of the mechanisms and rate parameters for other phase transitions that occur during lithiation of silicon and for kinetic studies of other electrode materials. Li-ion rechargeable batteries have been the focus of much research and development over recent decades. They power products ranging from electric vehicles to miniaturized electronic and medical devices. Due to its largest known capacity (8375 Ah/cm 3 , 3579 Ah/kg), Si is viewed as a promising anode material for batteries with high energy and power densities. Its abundance and relatively low cost also make it a practically feasible anode material.1 However, Si anodes suffer from capacity fade due to the very large volume expansion (up to 400%) 2 that occurs during lithiation and the consequent mechanical degradation it causes.3 In storing lithium, silicon goes through a sequence of structural transitions that affect the rate at which mechanical stress develops. 4,5 This, in turn, affects the degree to which mechanical stresses can be accommodated through plastic deformation rather than fracture. 6 Hence, a detailed understanding of the nature and kinetics of structural transitions that occur during lithiation and delithiation of silicon should provide insight into means of mediating the effects of mechanical stress on the cyclability of Si anodes.Electrochemically driven reactions between Li and Si have been studied under a variety of conditions, including at elevated and room temperature. Equilibrium titration experiments at 415• C show that four crystalline lithium silicide (Li x Si) phases form (Li 12 Si 7 , Li 7 Si 3 , Li 13 Si 4 and Li 22 Si 5 ).7-9 At room temperature, however, it is found using X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) that the equilibrium crystalline Li-Si phases are absent and the crystalline Li 15 Si 4 phase is observed only at the highest levels of lithiation.10 At lower levels of lithiation, metastable amorphous phases are formed instead.11 This phenomenon is similar to chemically driven solid-state amorphization reactions, 12 which are thought to be assoc...

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“…Polydispersed commercial Ge nanopowder, along with the use of fluorinated ethylene carbonate (FEC)-based electrolyte, demonstrated a capacity near 700 mAh g -1 at 10C rate over 500 cycles. The significant improvement in cycling stability resulted from the highly stable SEI/Ge interface, as a consequence of the different surface films containing lithium fluoride, alkoxy, and polycarbonate species [50,51].…”

Section: Ge Npsmentioning

confidence: 99%

High Energy Density Germanium Anodes for Next Generation Lithium Ion Batteries

Ocon¹,

Lee²,

Lee³

2014

Applied Chemistry for Engineering

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Lithium ion batteries (LIBs) are the state-of-the-art technology among electrochemical energy storage and conversion cells, and are still considered the most attractive class of battery in the future due to their high specific energy density, high efficiency, and long cycle life. Rapid development of power-hungry commercial electronics and large-scale energy storage applications (e.g. off-peak electrical energy storage), however, requires novel anode materials that have higher energy densities to replace conventional graphite electrodes. Germanium (Ge) and silicon (Si) are thought to be ideal prospect candidates for next generation LIB anodes due to their extremely high theoretical energy capacities. For instance, Ge offers relatively lower volume change during cycling, better Li insertion/extraction kinetics, and higher electronic conductivity than Si. In this focused review, we briefly describe the basic concepts of LIBs and then look at the characteristics of ideal anode materials that can provide greatly improved electrochemical performance, including high capacity, better cycling behavior, and rate capability. We then discuss how, in the future, Ge anode materials (Ge and Ge oxides, Ge-carbon composites, and other Ge-based composites) could increase the capacity of today's Li batteries. In recent years, considerable efforts have been made to fulfill the requirements of excellent anode materials, especially using these materials at the nanoscale. This article shall serve as a handy reference, as well as starting point, for future research related to high capacity LIB anodes, especially based on semiconductor Ge and Si.

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Exceptional Electrochemical Performance of Si-Nanowires in 1,3-Dioxolane Solutions: A Surface Chemical Investigation

Cited by 133 publications

References 73 publications

Role of 1,3-Dioxolane and LiNO₃Addition on the Long Term Stability of Nanostructured Silicon/Carbon Anodes for Rechargeable Lithium Batteries

Role of 1,3-Dioxolane and LiNO₃Addition on the Long Term Stability of Nanostructured Silicon/Carbon Anodes for Rechargeable Lithium Batteries

Kinetic Study of the Initial Lithiation of Amorphous Silicon Thin Film Anodes

High Energy Density Germanium Anodes for Next Generation Lithium Ion Batteries

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Exceptional Electrochemical Performance of Si-Nanowires in 1,3-Dioxolane Solutions: A Surface Chemical Investigation

Cited by 133 publications

References 73 publications

Role of 1,3-Dioxolane and LiNO3Addition on the Long Term Stability of Nanostructured Silicon/Carbon Anodes for Rechargeable Lithium Batteries

Role of 1,3-Dioxolane and LiNO3Addition on the Long Term Stability of Nanostructured Silicon/Carbon Anodes for Rechargeable Lithium Batteries

Kinetic Study of the Initial Lithiation of Amorphous Silicon Thin Film Anodes

High Energy Density Germanium Anodes for Next Generation Lithium Ion Batteries

Contact Info

Product

Resources

About

Role of 1,3-Dioxolane and LiNO₃Addition on the Long Term Stability of Nanostructured Silicon/Carbon Anodes for Rechargeable Lithium Batteries

Role of 1,3-Dioxolane and LiNO₃Addition on the Long Term Stability of Nanostructured Silicon/Carbon Anodes for Rechargeable Lithium Batteries