Hollow core–shell structured porous Si–C nanocomposites for Li-ion battery anodes

Li, Xin; Meduri, Praveen; Chen, Xilin; Qi, Wen; Engelhard, Mark H.; Xu, Wu; Ding, Fei; Xiao, Jie; Wang, Wei; Wang, Chong M.; Zhang, Ji‐Guang; Liu, Jun

doi:10.1039/c2jm31286g

Cited by 286 publications

(204 citation statements)

References 38 publications

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“…Uncoated (bare) Si surface is evident from the X-ray photoelectron spectroscopy (XPS) analysis, in which the Si2p signal is still strong in the coated sample. 23 In addition, the cycling performance of the coated Si is not much different than that of bare SiNPs. Therefore, a conformal and homogeneous coating is crucial for good electrochemical performance of the yolk-shell structure.…”

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confidence: 98%

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

Liu¹,

Wu²,

McDowell³

et al. 2012

Nano Lett.

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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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mentioning

confidence: 98%

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

Liu¹,

Wu²,

McDowell³

et al. 2012

Nano Lett.

Self Cite

1,623

1,437

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“…However, insufficient emphasis has been placed on dealing with the third challenge-the large volumetric expansion of sulphur during lithiation coupled with polysulphide dissolution. This poses a critical problem because volume expansion of the sulphur core will cause the protective coating layer to crack and fracture, rendering the conventional core-shell morphology [32][33][34][35] ineffective in trapping polysulphides (Fig. 1b).…”

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confidence: 99%

Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries

et al. 2013

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Sulphur is an attractive cathode material with a high specific capacity of 1,673 mAh g À 1 , but its rapid capacity decay owing to polysulphide dissolution presents a significant technical challenge. Despite much efforts in encapsulating sulphur particles with conducting materials to limit polysulphide dissolution, relatively little emphasis has been placed on dealing with the volumetric expansion of sulphur during lithiation, which will lead to cracking and fracture of the protective shell. Here, we demonstrate the design of a sulphur-TiO 2 yolk-shell nanoarchitecture with internal void space to accommodate the volume expansion of sulphur, resulting in an intact TiO 2 shell to minimize polysulphide dissolution. An initial specific capacity of 1,030 mAh g À 1 at 0.5 C and Coulombic efficiency of 98.4% over 1,000 cycles are achieved. Most importantly, the capacity decay after 1,000 cycles is as small as 0.033% per cycle, which represents the best performance for long-cycle lithium-sulphur batteries so far.

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“…1 Silicon, with a much larger theoretical specific capacity of 4200 mAh·g −12 and superior safety characteristics 3,4 compared to the current graphite anode, has been regarded as the most promising next generation anode for lithium ions battery. 5 However, some inherent drawbacks of Si anode such as a low electronic conductivity (≈10 −4 S m −1 ) 6 and a large volumetric change 2,7,8 during charging and discharging processes, have limited the electrochemical performances and the practical application of Si anodes in lithium ions battery.…”

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confidence: 99%

One-Step Electrodeposition of Layer by Layer Architectural Si-Graphene Nanocomposite Anode of Lithium Ion Battery with Enhanced Cycle Performance

Shen¹,

Wang²,

Guo³

et al. 2018

J. Electrochem. Soc.

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One step electrodeposition is applied to prepare Si-Graphene (SiG) composites from Graphene(G)-SiCl 4 - [BMP]tf 2 N ionic liquid. The SiG composites have shown an alternate layer-structure of Si and graphene caused by alternate processes of Si reduction and graphene adsorption on the electrode, which is confirmed by the regular current pulsation in the chronoamperometric curves during the whole electrodeposition process. The SEM and TEM morphologies indicate that each layer is about 120 nm thickness for the SiG3 composites electrodeposited from the 0.1852 mol·l −1 Graphene(G)-SiCl 4 -[BMP]tf 2 N ionic liquid, in which Si particle size is about 80-110 nm closely stick on 4-5 layers of graphene with a molar ratio of Si and C of 4.57:1. SiG3 anode displays a specific capacity of 1378 mAh·g −1 at the initial cycle, and 1083 mAh·g −1 at the end of 400 cycle (retention of 78%) at 4 A·g −1 , as well as 988 mAh·g −1 at 8A·g −1 , showing a good cycle life and rate performance. The layer-structured SiG anode significantly improve the conductivity and electrochemical performances of Si anode. The research provides a feasibility for electrodeposition preparation of layer-structured materials, especially for semiconductor-based alloys, graphene-based alloys in large-scale. Lithium ions battery has attracted more and more attention as one of the most promising power sources in the electric vehicles and portable electronic devices.1 Silicon, with a much larger theoretical specific capacity of 4200 mAh·g −12 and superior safety characteristics 3,4 compared to the current graphite anode, has been regarded as the most promising next generation anode for lithium ions battery.5 However, some inherent drawbacks of Si anode such as a low electronic conductivity (≈10 −4 S m −1 ) 6 and a large volumetric change 2,7,8 during charging and discharging processes, have limited the electrochemical performances and the practical application of Si anodes in lithium ions battery.Extensive investigations show that nano-structured Si such as Si nanotubes 9-12 and nanowires [13][14][15][16][17] can improve the electrochemical performances of Si anodes. The Si nanotubes by reductive decomposition of silicon precursors in an alumina template followed by etching according to Cui 11 maintain 2878 mAh·g −1 at a 5C rate after 200 cycles. However, Si-based anodes are still needed to further enhance the cyclability and rate performances.Graphene (G), as reported, not only can increase the conductivity of Si anode 1,18,19 but also can accommodate the large volumetric change of Si anode during cycling 18,21 due to its excellent electrical conductivity and exceptionally large specific surface area.20 Yi and Ran 19 use H 2 to reduce SiO 2 and graphene oxide mixture at 950• C to prepare G/Si-C composite, and the capacity of this composite is about 1314 mAh·g −1 at a rate of 0.4 A·g −1 . And the charge transfer resistance of G/Si-C is reduced from 59.98 to 9.14 as the addition of graphene.Compared with the above methods, electrodeposition can simplify the produ...

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Hollow core–shell structured porous Si–C nanocomposites for Li-ion battery anodes

Cited by 286 publications

References 38 publications

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

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

Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries

One-Step Electrodeposition of Layer by Layer Architectural Si-Graphene Nanocomposite Anode of Lithium Ion Battery with Enhanced Cycle Performance

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