Electrochemical characterization of carbon coated bundle-type silicon nanorod for anode material in lithium ion secondary batteries

Halim, Martin; Kim, Jung Sub; Choi, Jeong-Gil; Lee, Joong Kee

doi:10.1016/j.apsusc.2014.08.085

Cited by 11 publications

(4 citation statements)

References 42 publications

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“…Compressive stress arising from capping layers in contact with the silicon can similarly disfavor formation of the c -Li 3.75 Si phase in silicon films or silicon in sheet-like geometries. , TiN also seems effective at preventing c -Li 3.75 Si formation in silicon nanowires . Capping layers of Al 2 O 3 , − C, TiO 2 , ,, and TiN , have been shown to also alleviate continuous growth of SEI and improve Coulombic efficiency (CE) of the silicon electrode. Thus, the role of capping layers in improving the capacity retention of silicon electrodes is convoluted.…”

Section: Introductionmentioning

confidence: 99%

“…22,29 TiN also seems effective at preventing c-Li 3.75 Si formation in silicon nanowires. 30 Capping layers of Al 2 O 3 , 31−33 C, 34 TiO 2 , 33,35,36 and TiN 30,33 have been shown to also alleviate continuous growth of SEI and improve Coulombic efficiency (CE) of the silicon electrode. Thus, the role of capping layers in improving the capacity retention of silicon electrodes is convoluted.…”

Section: ■ Introductionmentioning

confidence: 99%

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Adhesion and Surface Layers on Silicon Anodes Suppress Formation of c-Li_3.75Si and Solid-Electrolyte Interphase

Xie

Sayed

Kalisvaart

et al. 2020

ACS Appl. Energy Mater.

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The formation of c-Li3.75Si is known to be detrimental to silicon anodes in lithium-ion batteries. To suppress the formation of this crystalline phase and improve the electrochemical performance of Si-based anodes, three approaches were amalgamated: addition of a nickel adhesion sublayer, alloying of the silicon with titanium, and addition of either carbon or TiO2 as a capping layer. The silicon-based films were analyzed by a suite of methods, including scanning electron microscopy (SEM) and a variety of electrochemical techniques, as well as X-ray photoelectron spectroscopy (XPS) to provide insights into the composition of the resulting solid-electrolyte interphase (SEI). A nickel adhesion layer decreased the extent of delamination of the silicon from the underlying copper substrate, compared to Si deposited directly on Cu, which resulted in less capacity loss. Alloying of silicon with titanium (85% silicon, 15% titanium) further increased the stability. Finally, capping these multilayer electrodes with either a thin 10 nm layer of carbon or TiO2 resulted in the best electrode behavior and lowest cumulative relative irreversible capacity. TiO2 is slightly more effective in enhancing the capacity retention, most likely due to differences in the resulting solid-electrolyte interphase (SEI). The combination of an adhesion layer, alloying, and surface coatings shows a cumulative suppression of the formation of c-Li3.75Si and SEI, resulting in the greatest improvement of capacity retention when all three are incorporated together. However, these strategies appear to only delay the onset of the c-Li3.75Si phase; eventually, the c-Li3.75Si phase will form, and at that point, the capacity degradation rate of all the electrodes becomes similar.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Adhesion and Surface Layers on Silicon Anodes Suppress Formation of c-Li_3.75Si and Solid-Electrolyte Interphase

Xie

Sayed

Kalisvaart

et al. 2020

ACS Appl. Energy Mater.

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“…The stress–voltage coupling effect has been effectively harnessed to suppress the c -Li 15 Si 4 phase through the application of adhesive layers on thin films and capping layers on a variety of silicon morphologies, ,,,,, as well as alloying silicon with inactive transition metals. ,,− The hypothesis that alloying induces stress, thereby improving capacity retention by suppressing c -Li 15 Si 4 , has been applied to nano- and micron-sized silicon particle electrodes as well as thin films. ,, However, most, if not all previous studies that find a correlation between the suppression of c -Li 15 Si 4 formation and capacity retention, achieve this suppression through material changes that are convoluted with other beneficial effects. For instance, a capping layer on top of a Si film can induce clamping, thereby preventing c -Li 15 Si 4 by aforementioned stress–voltage coupling, while also minimizing reactivity with the electrolyte. ,− Prolonged ball-milling of Si with Mo and W, for instance, increases the proportion of silicide intermetallic and allegedly induces stress, but this processing also reduces the grain size of Si, , rendering its distribution more homogeneous. Rather than suppressing c -Li 15 Si 4 formation by changing the electrode material, a test of the intrinsic effects of c -Li 15 Si 4 on capacity retention would, ideally, involve inducing or preventing its formation by adjusting only the experimental conditions while keeping the electrode material constant.…”

Section: Introductionmentioning

confidence: 99%

Beyond Thin Films: Clarifying the Impact of c-Li₁₅Si₄ Formation in Thin Film, Nanoparticle, and Porous Si Electrodes

Woodard

Kalisvaart

Sayed

et al. 2021

ACS Appl. Mater. Interfaces

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The formation of the c-Li15Si4 phase has well-established detrimental effects on the capacity retention of thin film silicon electrodes. However, the role of this crystalline phase with respect to the loss of capacity is somewhat ambiguous in nanoscale morphologies. In this work, three silicon-based morphologies are examined, including planar films, porous planar films, and silicon nanoparticle composite powder electrodes. The cycling conditions are used as the lever to induce, or not induce, the formation of c-Li15Si4 through application of constant-current (CC) or constant-current constant-voltage (CCCV) steps. In this manner, the role of this phase on capacity retention and Coulombic efficiency can be determined with few other convoluting factors such as alteration of the composition or morphology of the silicon electrodes themselves. The results here confirm that the c-Li15Si4 phase increases the rate of capacity decay in planar films but has no major effect on capacity retention in half-cells based on porous silicon films or silicon nanoparticle composite powder electrodes, although this conclusion is nuanced. Besides using a constant-voltage step, formation of the c-Li15Si4 phase is influenced by the dimensions of the Si material and the lithiation cutoff voltage. Porous Si films, which, in this work, comprise primary Si particle sizes that are smaller than those in the preformed Si nanoparticle slurries, do not undergo the formation of c-Li15Si4 at 50 mV, whereas Si nanoparticle slurries are accompanied by the formation of c-Li15Si4 up to 80 mV. The solid-electrolyte interphase (SEI) formed from reaction of the c-Li15Si4 with the carbonate-based electrolyte causes polarization in both nanoparticle and porous film silicon electrodes and lowers the average Coulombic efficiency. A comparison of the cumulative irreversibilities due to SEI formation between different lithiation cutoff voltages in silicon nanoparticle slurry electrodes confirmed the connection between higher SEI buildup and formation of the c-Li15Si4 phase. This work indicates that concerns about the c-Li15Si4 phase in silicon nanoparticles and porous silicon electrodes should mainly focus on the stability of the SEI and a reduction of irreversible electrolyte reactions.

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“…Finding new anode materials with high energy density has become a new research hot spot. Due to the highest theoretical specific capacity (4200 mAh g -1 ) [7,8] reported so far, lower delithiation potential (<0.5 V vs Li/Li + ) [9], and abundant reserves, silicon is gradually becoming the preferred choice for the anode material [10][11][12][13][14][15][16]. It is currently one of the most promising next generation anode materials of lithium ion batteries.…”

Section: Introductionmentioning

confidence: 99%

Multifunctional imidazolium-based ionic liquid as additive for silicon/carbon lithium ion batteries

Cai

Solms

et al. 2020

Electrochimica Acta

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Electrochemical characterization of carbon coated bundle-type silicon nanorod for anode material in lithium ion secondary batteries

Cited by 11 publications

References 42 publications

Adhesion and Surface Layers on Silicon Anodes Suppress Formation of c-Li_3.75Si and Solid-Electrolyte Interphase

Adhesion and Surface Layers on Silicon Anodes Suppress Formation of c-Li_3.75Si and Solid-Electrolyte Interphase

Beyond Thin Films: Clarifying the Impact of c-Li₁₅Si₄ Formation in Thin Film, Nanoparticle, and Porous Si Electrodes

Multifunctional imidazolium-based ionic liquid as additive for silicon/carbon lithium ion batteries

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Electrochemical characterization of carbon coated bundle-type silicon nanorod for anode material in lithium ion secondary batteries

Cited by 11 publications

References 42 publications

Adhesion and Surface Layers on Silicon Anodes Suppress Formation of c-Li3.75Si and Solid-Electrolyte Interphase

Adhesion and Surface Layers on Silicon Anodes Suppress Formation of c-Li3.75Si and Solid-Electrolyte Interphase

Beyond Thin Films: Clarifying the Impact of c-Li15Si4 Formation in Thin Film, Nanoparticle, and Porous Si Electrodes

Multifunctional imidazolium-based ionic liquid as additive for silicon/carbon lithium ion batteries

Contact Info

Product

Resources

About

Adhesion and Surface Layers on Silicon Anodes Suppress Formation of c-Li_3.75Si and Solid-Electrolyte Interphase

Adhesion and Surface Layers on Silicon Anodes Suppress Formation of c-Li_3.75Si and Solid-Electrolyte Interphase

Beyond Thin Films: Clarifying the Impact of c-Li₁₅Si₄ Formation in Thin Film, Nanoparticle, and Porous Si Electrodes