Toward Silicon Anodes for Next-Generation Lithium Ion Batteries: A Comparative Performance Study of Various Polymer Binders and Silicon Nanopowders

Erk, Christoph; Brezesinski, Torsten; Sommer, Heino; Schneider, Reinhard; Janek, Jürgen

doi:10.1021/am401642c

Cited by 197 publications

(196 citation statements)

References 47 publications

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“…>50 μL cm −2 instead of 5 μL cm −2 in commercial cells) 11 make it difficult to evaluate the degradation phenomena occurring at the silicon-based electrode, including the loss of active lithium and depletion of the electrolyte. [28][29][30] In this study, we present a comprehensive approach to understand the degradation mechanisms in silicon-graphite electrodes. Hence, we prepare silicon-graphite electrodes with practical areal capacities between 1.8 and 2.3 mAh cm −2 , composed of physical mixtures of different silicon/graphite active material ratios, with silicon contents between 20-60 wt%.…”

mentioning

confidence: 99%

Differentiating the Degradation Phenomena in Silicon-Graphite Electrodes for Lithium-Ion Batteries

Wetjen

Pritzl

Jung

et al. 2017

J. Electrochem. Soc.

143

173

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Silicon-graphite electrodes usually experience an increase in cycling performance by the addition of graphite, however, the relation of the silicon/graphite ratio and the aging mechanisms of the individual electrode and electrolyte compounds still requires a more fundamental understanding. In this study, we present a comprehensive approach to understand and quantify the degradation phenomena in silicon-graphite electrodes with silicon contents between 20-60 wt%. By evaluating the cycling performance and total irreversible capacity of silicon-graphite electrodes vs. capacitively oversized LiFePO 4 electrodes in presence of a fluoroethylene carbonate (FEC)-containing electrolyte, we demonstrate that the aging of silicon-based electrodes can be distinguished into two distinct phenomena, which we describe as silicon particle degradation and electrode degradation. Cross-sectional scanning electron microscopy (SEM) images and a detailed analysis of the electrode polarization upon cycling complement our discussion. Further, we deploy post-mortem 19 F-NMR spectroscopy to (i) quantify to loss of moles of FEC in the electrolyte and correlate this with the amount of charge that was exchanged by the silicon-graphite electrodes, (ii) estimate the pore volume of the silicon-graphite electrodes that is occupied by FEC decomposition products, and (iii) Silicon-based electrodes are very promising candidates to enable the next generation of Li-ion batteries with energy densities on the cell level beyond 350 Wh kg −1 . 1,2 In contrast to conventional intercalation anode materials, such as graphite (LiC 6 , 372 mAh g −1 , 890 Ah L −1 ), the specific capacity of silicon alloy electrodes is significantly higher (Li 15 Si 4 , 3579 mAh g −1 , 2194 Ah L −1 ). 3 Nonetheless, commercialization of silicon-based electrodes is still hampered because of two major challenges: 4 (i) Large volume expansions up to 280% upon repeated (de-)lithiation of silicon particles deteriorate the electrode integrity, thus causing isolation of active material. [5][6][7] The formerly reported pulverization of micron-sized silicon particles due to mechanical stress upon repeated volume expansion has been partially solved by using nanometer-sized particles. However, reduction of the silicon particle size also leads to inferior electronic conduction due to more numerous interparticle contacts, and higher solid-electrolyte-interphase (SEI) losses due to the larger relative surface area. [8][9][10] (ii) Continuous side reactions at the silicon/electrolyte interface caused by repeated volume expansion and contraction result in ongoing electrolyte decomposition and in a gradual loss of active lithium. 8In the course of this, SEI-forming additives in the electrolyte, e.g., FEC, are depleted, which was shown to result in a significant increase in cell polarization and a concomitant rapid capacity drop. 8,11 Various strategies have been proposed to overcome the detrimental effects associated with the volume expansion during (de-)lithiation of silicon and to reduce conc...

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mentioning

confidence: 99%

Differentiating the Degradation Phenomena in Silicon-Graphite Electrodes for Lithium-Ion Batteries

Wetjen

Pritzl

Jung

et al. 2017

J. Electrochem. Soc.

143

173

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confidence: 99%

“…polyvinylidene fluoride (PVDF). 6,8,10 Direct incorporation and mixing of silicon particles into standard graphite slurries also provides a means of incrementally improving electrode capacity, while retaining the higher durability of graphite electrodes. [11][12][13] In addition to variations in the electrode constitution, alternative electrolytes are being studied to improve cell cycling stability by tuning the electrochemical interfaces.…”

mentioning

confidence: 99%

Layered Oxide, Graphite and Silicon-Graphite Electrodes for Lithium-Ion Cells: Effect of Electrolyte Composition and Cycling Windows

Klett

Gilbert

Pupek

et al. 2016

J. Electrochem. Soc.

102

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The electrochemical performance of cells with a Li 1.03 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.97 O 2 (NCM523) positive electrode and a blended silicongraphite (Si-Gr) negative electrode are investigated using various electrolyte compositions and voltage cycling windows. Voltage profiles of the blended Si-Gr electrode show a superposition of graphite potential plateaus on a sloped Si profile with a large potential hysteresis. The effect of this hysteresis is seen in the cell impedance versus voltage data, which are distinctly different for the charge and discharge cycles. We confirm that the addition of compounds, such as vinylene carbonate (VC) and fluoroethylene carbonate (FEC) to the baseline 1.2 M LiPF 6 in ethylene carbonate (EC): ethyl methyl carbonate (EMC) (3:7 w/w) electrolyte, improves cell capacity retention with higher retention seen at higher additive contents. We show that reducing the lower cutoff voltage (LCV) of full cells to 2.5 V increases the Si-Gr electrode potential to 1.12 V vs. Li/Li + ; this relatively-high delithiation potential correlates with the lower capacity retention displayed by the cell. Furthermore, we show that raising the upper cutoff voltage (UCV) can increase cell energy density without significantly altering capacity retention over 100 charge-discharge cycles. The development of new high-energy electrochemical couples is important to reducing the overall cost and weight per kWh of Li-ion batteries. Silicon and silicon-containing blended electrodes have been a focus of much recent research as an alternative to the commercial graphite-based negative electrode because of the substantially higher theoretical capacity of silicon (3579 mAh g −1 , Li 15 Si 4 ) compared to that of graphite (372 mAh g −1 , LiC 6 ); the higher capacity enables reduction of the negative electrode weight thereby increasing energy density of the cell. However, concerns including electrode integrity and durability related to the substantial volume expansion/contraction (∼300%) of silicon during lithiation/delithiation reactions have hampered the use of silicon as a direct substitute for graphite.Several strategies to overcome the durability problems target design of the composite electrode and its components. For example, purposely-designed silicon particle morphologies 1-3 and the use of graphene 4,5 are reported to improve the cycle life of electrodes in cells with a Li-metal counter electrode (half-cells). The choice of binders also greatly influences electrode coherence; 6-10 for example lithiated polyacrylic acid (LiPAA) has been shown to increase cycle life compared to e.g. polyvinylidene fluoride (PVDF). 6,8,10 Direct incorporation and mixing of silicon particles into standard graphite slurries also provides a means of incrementally improving electrode capacity, while retaining the higher durability of graphite electrodes. 11-13In addition to variations in the electrode constitution, alternative electrolytes are being studied to improve cell cycling stability by tuning the electrochemical interfaces. The use ...

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“…The size of silicon particle plays an important role in the cycling stability of anodes. [22][23][24][28][29][30][31] In order to investigate the size effect of silicon, two types of silicon, micro-sized and nano-sized, are fabricated into electrodes for electrochemical study. To simplify the electrode design, only CMC is used as the binder.…”

Section: Coin Cell Fabrication and Testingmentioning

confidence: 99%

“…Therefore, it will be beneficial to develop binders that can be processed with less toxic, or even non-toxic solvents. Recently, it was reported that water-based binder such as styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) effectively improves the cycling stability of silicon electrode [15][16][17][18][19][20][21][22][23][24][25][26] . According to a previous report by Hochgatterer et al [21] , the formation of a covalent chemical bond between the CMC and silicon particle plays an important role in the effective binding and improved performance.…”

Section: Introductionmentioning

confidence: 99%

Organic Solvent Free Process to Fabricate High Performance Silicon and Graphite Composite Anode

Xiao¹,

Zheng²,

Liu³

2018

Preprint

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Abstract:Cycling reliability is crucial for Si-based materials due to severe volume change during cycles that results in the fast capacity fading. Though the binder only occupies a very low amount of the total mass of anodes, it is proved to perform a key parameter to improve the cycle performance of Si-based anodes. Because they are eco-friendly and cost saving, water-based binders styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) are regarded as the better binder to substitute Poly (vinylidene difluoride) (PVDF) as the binder for Si-based anode. In this study, the anodes are fabricated by simply mixing the active materials (naso Si, graphite and conductive additive) together and using the mixture of SBR and CMC as a binder. The results showed that the retention capacities of the anodes are more than 440 mAh/g after 400 cycles. It indicates that it is an easy and simple way to make high performance anodes.

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Toward Silicon Anodes for Next-Generation Lithium Ion Batteries: A Comparative Performance Study of Various Polymer Binders and Silicon Nanopowders

Cited by 197 publications

References 47 publications

Differentiating the Degradation Phenomena in Silicon-Graphite Electrodes for Lithium-Ion Batteries

Differentiating the Degradation Phenomena in Silicon-Graphite Electrodes for Lithium-Ion Batteries

Layered Oxide, Graphite and Silicon-Graphite Electrodes for Lithium-Ion Cells: Effect of Electrolyte Composition and Cycling Windows

Organic Solvent Free Process to Fabricate High Performance Silicon and Graphite Composite Anode

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