Real-Time Measurement of Stress and Damage Evolution during Initial Lithiation of Crystalline Silicon

Chon, Michael J.; Sethuraman, Vijay A.; McCormick, A.W.; Srinivasan, Venkat; Guduru, Pradeep R.

doi:10.1103/physrevlett.107.045503

Cited by 349 publications

(370 citation statements)

References 21 publications

(37 reference statements)

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“…2b). It should be noted that the average measured thickness of the Li x Si layer is significantly smaller than the calculated value (4.8 µm) based on the total applied current density [25].…”

Section: Methodsmentioning

confidence: 77%

“…Obrovac et al [5] suggested that the lithiation of crystalline silicon is a two-phase reaction in which a reaction front separates the growing amorphous lithiated phase from pristine crystalline silicon. Chon et al [25] showed clear images of a crystalline-to-amorphous phase transformation that occurs during initial lithiation of a {100} silicon wafer. Furthermore, Lee et al [26] demonstrated anisotropic deformation of silicon nanopillars during lithitation.…”

Section: Introductionmentioning

confidence: 99%

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Microstructural evolution induced by micro-cracking during fast lithiation of single-crystalline silicon

Choi

Pharr

Kang

et al. 2014

Journal of Power Sources

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We report observations of microstructural changes in {100} and {110} oriented silicon wafers during initial lithiation under relatively high current densities. Evolution of the microstructure during lithiation was found to depend on the crystallographic orientation of the silicon wafers. In {110} silicon wafers, the phase boundary between silicon and Li x Si remained flat and parallel to the surface. In contrast, lithiation of the {100} oriented substrate resulted in a complex vein-like microstructure of Li x Si in a crystalline silicon matrix. A simple calculation demonstrates that the formation of such structures is energetically unfavorable in the 2 absence of defects due to the large hydrostatic stresses that develop. However, TEM observations revealed micro-cracks in the {100} silicon wafer, which can create fast diffusion paths for lithium and contribute to the formation of a complex vein-like Li x Si network. This defect-induced microstructure can significantly affect the subsequent delithiation and following cycles, resulting in degradation of the electrode.

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Section: Methodsmentioning

confidence: 77%

Section: Introductionmentioning

confidence: 99%

Microstructural evolution induced by micro-cracking during fast lithiation of single-crystalline silicon

Choi

Pharr

Kang

et al. 2014

Journal of Power Sources

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“…Second, it is clear that the carbon coating remains intact after Si expansion even though the expansion causes the Si particles to impinge upon the carbon coating. This could be attributed to (i) the plastic flow of lithiated Si so that it expands into the void space away from the carbon shell 35 and (ii) to the fact that there is enough void space to accommodate the full expansion of each Si particle. Because the overall shape of the yolk-shell structure does not change appreciably upon lithiation, it is expected that a battery electrode made of this Si@void@C structure will undergo minimal microstructural damage upon cycling, in contrast to an electrode made of bare SiNPs.…”

mentioning

confidence: 99%

A Yolk-Shell Design for Stabilized and Scalable Li-Ion Battery Alloy Anodes

Liu¹,

Wu²,

McDowell³

et al. 2012

Nano Lett.

1,623

1,437

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Silicon is regarded as one of the most promising anode materials for next generation lithium-ion batteries. For use in practical applications, a Si electrode must have high capacity, long cycle life, high efficiency, and the fabrication must be industrially scalable. Here, we design and fabricate a yolk-shell structure to meet all these needs. The fabrication is carried out without special equipment and mostly at room temperature. Commercially available Si nanoparticles are completely sealed inside conformal, thin, self-supporting carbon shells, with rationally designed void space in between the particles and the shell. The well-defined void space allows the Si particles to expand freely without breaking the outer carbon shell, therefore stabilizing the solid-electrolyte interphase on the shell surface. High capacity (∼2800 mAh/g at C/10), long cycle life (1000 cycles with 74% capacity retention), and high Coulombic efficiency (99.84%) have been realized in this yolk-shell structured Si electrode. KEYWORDS: Silicon nanoparticle, Li-ion battery, anode, yolk-shell, solid-electrolyte interphase, in situ TEM E lectrochemical energy storage has become a critical technology for a variety of applications, including grid storage, electric vehicles, and portable electronic devices. The lithium-ion battery (LIB) is an attractive energy storage device because of its relatively high energy density and good rate capability. To further increase the energy density for more demanding applications, however, new electrode materials with higher specific and volumetric capacity are required. Since the initial commercialization of the LIB two decades ago, there has been little progress in commercializing new electrode materials with significantly higher capacity. 1 To meet the increasing demand for energy storage capability, novel electrode materials with higher capacity, low cost, and the ability to be produced at large scale are of great interest.Alloy-type anodes (Si, Ge, Sn, Al, Sb, etc.) have much higher Li storage capacity than the intercalation-type graphite anode that is currently used in Li-ion batteries. 2 Among all the alloy anodes, silicon has the highest specific capacity: Experiments have demonstrated an initial specific capacity of >3500 mAh/g, which is 10 times the capacity of graphite. 3 In addition, silicon is the second most abundant element in the earth's crust (28% by mass), indicating its potential to be utilized in large quantities at low cost. 4 A further benefit is that mass production of elemental silicon is already a mature technology in the semiconductor industry. Despite these advantages, graphite anodes still dominate the marketplace due to the fact that alloy anodes have two major challenges that have prevented their widespread use. First, alloy anodes undergo significant volume expansion and contraction during Li insertion/extraction. 2 This volume change (∼300% for Si) can result in pulverization of the initial particle morphology and causes the loss of electrical contact between active mat...

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“…Amongst anode candidates, [1][2][3][4][5][6] silicon is especially attractive owing to its high specific capacity (3579 mAh/g for lithiation to the amorphous phase limit of Li 15 Si 4 vs. 372 mAh/g for graphite to composition LiC 6 ) and high natural abundance. 2,4,[7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] However, silicon electrodes suffer from accelerated capacity fade compared to established intercalation electrodes, which is attributed to losses originating from fracture and fragmentation induced by the nearly 300% particle volume expansion upon lithiation. 4,25 The general trend toward nanoscaling of silicon has been motivated almost entirely by these considerations.…”

mentioning

confidence: 99%

Electrochemical Charge Transfer Reaction Kinetics at the Silicon-Liquid Electrolyte Interface

Swamy¹,

Chiang²

2015

J. Electrochem. Soc.

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Since the gravimetric lithiation capacity of silicon is roughly ten times that of graphite, while their mass densities are comparable, for the same particle size the current density required to cycle a silicon electrode at a given C-rate is about ten times greater than that of graphite. Depending on the magnitude of the corresponding Butler-Volmer exchange current density, jo, such high current densities may cause the charge transfer kinetics at the silicon-electrolyte interface to become rate limiting. Previously reported values of jo for Si differ by about 10 orders of magnitude. Here we report jo measurements using electrochemical impedance spectroscopy (EIS) for single crystal electronically conductive silicon wafers with well-defined (100) and (111) orientations and active surface areas. The electrochemical cycling regime was designed to avoid artifacts due to stress-induced surface cracking of Si upon lithiation. The exchange current density of the silicon-electrolyte interface is found to be 0.1 ± 0.01 mA/cm2 when using electrolyte consisting of 1 M LiPF6 in EC/DMC (1/1 by wt) + FEC (10 wt%) + VC (2 wt%). These results are then used to illustrate the dependence of kinetic overpotential on particle size and C-rate for silicon compared to lower volumetric capacity compounds such as graphite.

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Real-Time Measurement of Stress and Damage Evolution during Initial Lithiation of Crystalline Silicon

Cited by 349 publications

References 21 publications

Microstructural evolution induced by micro-cracking during fast lithiation of single-crystalline silicon

Microstructural evolution induced by micro-cracking during fast lithiation of single-crystalline silicon

A Yolk-Shell Design for Stabilized and Scalable Li-Ion Battery Alloy Anodes

Electrochemical Charge Transfer Reaction Kinetics at the Silicon-Liquid Electrolyte Interface

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