Silicon nanopowder as active material for hybrid electrodes of lithium-ion batteries

Kuksenko, S. P.; Konovalenko, I. O.

doi:10.1134/s107042721107010x

Cited by 12 publications

(7 citation statements)

References 27 publications

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“…The assumption that the LiPF 6 concentration does not change significantly over the course of the experiments is supported by a detailed inspection of the NMR-spectra, revealing no additional peaks from salt decomposition products like PO 2 F 2 − . Additionally, no signals originating from SiF 2− 6 (typically observed product in the event of glass fiber separator decomposition by HF) 37 were observed in the 19 F-NMR experiments, proving that the glass fiber separator is stable under our experimental conditions.…”

Section: Resultsmentioning

confidence: 66%

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

Jung

Metzger

Haering

et al. 2016

J. Electrochem. Soc.

264

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: Resultsmentioning

confidence: 66%

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

Jung

Metzger

Haering

et al. 2016

J. Electrochem. Soc.

264

311

View full text Add to dashboard Cite

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“…Kuksenko and Konovalenko [223] stated that a reduction in the size of Si, with transition to the nanoscale, improves the structural strength of Si electrodes against cracking upon large changes in volume, due to lithiation and delithiation of Si anodes. Thus, they fabricated hybrid electrodes using two different synthetic graphites (KS6 and MAG) and Si nanopowder and three different binders.…”

Section: Si Nanopowder Anode Materialsmentioning

confidence: 99%

Metal-assisted chemical etching of silicon and the behavior of nanoscale silicon materials as Li-ion battery anodes

2015

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This review outlines the developments and recent progress in metal-assisted chemical etching of silicon, summarizing a variety of fundamental and innovative processes and etching methods that form a wide range of nanoscale silicon structures. The use of silicon as an anode for Li-ion batteries is also reviewed, where factors such as film thickness, doping, alloying, and their response to reversible lithiation processes are summarized and discussed with respect to battery cell performance. Recent advances in improving the performance of silicon-based anodes in Li-ion batteries are also discussed. The use of a variety of nanostructured silicon structures formed by many different methods as Li-ion battery anodes is outlined, focusing in particular on the influence of mass loading, core-shell structure, conductive additives, and other parameters. The influence of porosity, dopant type, and doping level on the electrochemical response and cell performance of the silicon anodes are detailed based on recent findings. Perspectives on the future of silicon and related materials, and their compositional and structural modifications for energy storage via several electrochemical mechanisms, are also provided.

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“…A set of studies of silicon-containing anodes was carried out by Kuksenko and co-authors at the Institute of Surface Chemistry, National Academy of Sciences of Ukraine [156][157][158][159][160][161][162][163]. The author of [156] demonstrated that grinding of components in a high-speed vibration ball mill can be used to obtain highly dispersed silicon-graphite composites with increased reversible specifi c capacity (445 mA h g -1 ) at a fi rst-cycle effi ciency of 92.6%.…”

Section: E MVmentioning

confidence: 99%

“…The electrode with carbon-coated silicon nanoparticles has a high reversible specifi c capacity of 2029 mA h g -1 , fi rst-cycle effi ciency of 81.3%, 90.8% preservation of the reversible capacity after 100 cycles at a low accumulated irreversible capacity. In [159][160][161][162], data on the behavior of mixtures of silicon nanopowders and graphite of various brands in anodes of lithium-ion batteries were partly reproduced and supplemented. To obtain anodes with high loading capacity, it is advisable to use electrodes with a ceramic skeleton-ordered nano-Si/SiO 2 /solid carbon composite, and complex LiPF 6based mixture as electrolyte [163].…”

Section: E MVmentioning

confidence: 99%

Lithium-silicon alloys: Phase diagram, electrochemical studies, thermodynamic properties, application in chemical power cells

Морачевский

Demidov

2015

Russ J Appl Chem

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Review summarizes and analyzes data on the phase diagram, electrochemical behavior in molten media, and thermodynamic properties of alloys in the lithium-silicon system in the solid and liquid states. The use of Li-Si alloys in medium-temperature chemical power cells and prospects for application of silicon and silicon-containing components as the anode material in lithium-ion batteries are discussed.Lithium is one of the most important metals presently determining the scientifi c-technological progress. The metal itself and its alloys and compounds fi nd use in various industries: light alloys, chemical power cells, nuclear technologies, and nonferrous metallurgy [1][2][3][4][5][6][7][8][9][10][11]. The world's production of lithium steadily grows, data on lithium resources, their geographical distribution, and application fi elds of lithium-containing products as of the year of 2006 can be found in [12]. Silicon is the most widely occurring semiconductor; its annual world's production constitutes thousands of tons and continues to grow. LITHIUM-SILICON ALLOYS in detail by nuclear magnetic resonance (NMR), Raman spectroscopy, and electrical measurements. Based on the results of [28,29], Okamoto included the compound LiSi into the phase diagram of the Li-Si system (Fig. 1) in an additional review [30].It should be noted that studies of the electrochemical behavior of a lithium-silicon electrode in molten media made a major contribution to analyses of the phase diagram of the Li-Si system, its modeling, and calculation of the thermodynamic properties of compounds of lithium with silicon.Lithium-silicon electrode. In [31], the discharge of an electrode of the following composition (wt %): 60Li and 40Si (86 at % Li and 14 at % Si) was studied in a molten LiCl-KCl eutectic mixture in the temperature range 360-440°C. The discharge curve at 40°C, presented in [31], demonstrates four clearly pronounced plateaus, which indicate, with the exception of the fi rst plateau corresponding to the potential of pure lithium, that there are double-phase regions and boundaries of these. According to [31], the following compounds are formed in the Li-Si system: The thermodynamic characteristics of these compounds were also evaluated (see below).Nearly simultaneously, charge and discharge curves were recorded in the above-mentioned study [19] for the lithium-silicon electrode, together with electromotive force measurements for circuit (1). In a slow discharge, the presence of double-phase regions was clearly indicated (407 and 487°C). The electrode behaves reversibly in the LiCl-KCl melt and the values obtained for the plateau potentials can be used for thermodynamic calculations. The same authors [32] carried out an extensive study of how electrodes fabricated from alloys of various compositions in the Li-Si system (Li 2 Si, Li 21 Si 8 , Li 15 Si 4 ) behave in measurements of chargedischarge curves in molten LiCl-KCl, LiF-LiCl-KCl, and LiF-LiCl-LiBr electrolytes in the temperature range 400-480°C. The current density was within the ...

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Silicon nanopowder as active material for hybrid electrodes of lithium-ion batteries

Cited by 12 publications

References 27 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

Metal-assisted chemical etching of silicon and the behavior of nanoscale silicon materials as Li-ion battery anodes

Lithium-silicon alloys: Phase diagram, electrochemical studies, thermodynamic properties, application in chemical power cells

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