Adaptable silicon-carbon nanocables sandwiched between reduced graphene oxide sheets as lithium ion battery anodes.

Silicon has been touted as one of the most promising anode materials for next generation lithium ion batteries. Yet, how to build energetic silicon-based electrode architectures by addressing the structural and interfacial stability issues facing silicon anodes still remains a big challenge. Here, we develop a novel kind of self-supporting binder-free silicon-based anodes via the encapsulation of silicon nanowires (SiNWs) with dual adaptable apparels (overlapped graphene (G) sheaths and reduced graphene oxide (RGO) overcoats). In the resulted architecture (namely, SiNW@G@RGO), the overlapped graphene sheets, as adaptable but sealed sheaths, prevent the direct exposure of encapsulated silicon to the electrolyte and enable the structural and interfacial stabilization of silicon nanowires. Meanwhile, the flexible and conductive RGO overcoats accommodate the volume change of embedded SiNW@G nanocables and thus maintain the structural and electrical integrity of the SiNW@G@RGO. As a result, the SiNW@G@RGO electrodes exhibit high reversible specific capacity of 1600 mAh g⁻¹ at 2.1 A g⁻¹, 80% capacity retention after 100 cycles, and superior rate capability (500 mAh g⁻¹ at 8.4 A g⁻¹) on the basis of the total electrode weight.

[1]  A.K. Geim.  Random walk to graphene (Nobel lecture). , 2011, Angewandte Chemie.

[2]  J. Dahn,et al.  Study of Irreversible Capacities for Li Insertion in Hard and Graphitic Carbons , 1997 .

[3]  Jaephil Cho,et al.  A critical size of silicon nano-anodes for lithium rechargeable batteries. , 2010, Angewandte Chemie.

[4]  Jeff Dahn,et al.  Studies of Lithium Intercalation into Carbons Using Nonaqueous Electrochemical Cells , 1990 .

[5]  Zhen Zhou,et al.  Core double-shell Si@SiO2@C nanocomposites as anode materials for Li-ion batteries. , 2010, Chemical communications.

[6]  Harold H. Kung,et al.  Silicon nanoparticles-graphene paper composites for Li ion battery anodes. , 2010, Chemical communications.

[7]  Song Jin,et al.  Nanostructured silicon for high capacity lithium battery anodes , 2011 .

[8]  Yi Cui,et al.  Silicon–Carbon Nanotube Coaxial Sponge as Li‐Ion Anodes with High Areal Capacity , 2011 .

[9]  Jaephil Cho,et al.  Superior lithium electroactive mesoporous Si@carbon core-shell nanowires for lithium battery anode material. , 2008, Nano letters.

[10]  Hui Wu,et al.  A yolk-shell design for stabilized and scalable li-ion battery alloy anodes. , 2012, Nano letters.

[11]  K. Novoselov,et al.  Macroscopic graphene membranes and their extraordinary stiffness. , 2008, Nano letters.

[12]  E. Kaxiras,et al.  Concurrent Reaction and Plasticity during Initial Lithiation of Crystalline Silicon in Lithium-Ion Batteries , 2012 .

[13]  S. T. Picraux,et al.  Carbon Nanotube‐Enhanced Growth of Silicon Nanowires as an Anode for High‐Performance Lithium‐Ion Batteries , 2012 .

[14]  Yang Liu,et al.  Anisotropic swelling and fracture of silicon nanowires during lithiation. , 2011, Nano letters.

[15]  Jaephil Cho,et al.  Nitrogen-Doped Graphitic Layers Deposited on Silicon Nanowires for Efficient Lithium-Ion Battery Anodes , 2011 .

[16]  R. Schlögl,et al.  Superior storage performance of a Si@SiOx/C nanocomposite as anode material for lithium-ion batteries. , 2008, Angewandte Chemie.

[17]  Yi Cui,et al.  Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control. , 2012, Nature nanotechnology.

[18]  Jing Zhu,et al.  Carbon-coated silicon nanowire array films for high-performance lithium-ion battery anodes , 2009 .

[19]  W. S. Hummers,et al.  Preparation of Graphitic Oxide , 1958 .

[20]  Candace K. Chan,et al.  Stepwise nanopore evolution in one-dimensional nanostructures. , 2010, Nano letters.

[21]  Shadi A. Dayeh,et al.  Silicon and germanium nanowires: Growth, properties, and integration , 2010 .

[22]  Candace K. Chan,et al.  High-performance lithium battery anodes using silicon nanowires. , 2008, Nature nanotechnology.

[23]  Meng Gu,et al.  In situ TEM study of lithiation behavior of silicon nanoparticles attached to and embedded in a carbon matrix. , 2012, ACS nano.

[24]  Zheng Jia,et al.  Lithium-assisted electrochemical welding in silicon nanowire battery electrodes. , 2012, Nano letters.

[25]  John P. Sullivan,et al.  Ultrafast electrochemical lithiation of individual Si nanowire anodes. , 2011, Nano letters.

[26]  Jean-Marie Tarascon,et al.  Towards systems materials engineering. , 2012, Nature materials.

[27]  Yi Cui,et al.  Studying the Kinetics of Crystalline Silicon Nanoparticle Lithiation with In Situ Transmission Electron Microscopy , 2012, Advanced materials.

[28]  Li-Jun Wan,et al.  Cu‐Si Nanocable Arrays as High‐Rate Anode Materials for Lithium‐Ion Batteries , 2011, Advanced materials.

[29]  Jaephil Cho,et al.  Three-dimensional porous silicon particles for use in high-performance lithium secondary batteries. , 2008, Angewandte Chemie.

[30]  Yi Cui,et al.  Improving the cycling stability of silicon nanowire anodes with conducting polymer coatings , 2012 .

[31]  C. C. Ahn,et al.  Highly Reversible Lithium Storage in Nanostructured Silicon , 2003 .

[32]  Min Gyu Kim,et al.  Silicon nanotube battery anodes. , 2009, Nano letters.

[33]  Jian Yu Huang,et al.  Size-dependent fracture of silicon nanoparticles during lithiation. , 2011, ACS nano.

[34]  Chao Zhong,et al.  Flexible free-standing graphene-silicon composite film for lithium-ion batteries , 2010 .

[35]  Yi Cui,et al.  Prelithiated silicon nanowires as an anode for lithium ion batteries. , 2011, ACS nano.

[36]  Yong Min Lee,et al.  Electrospun core-shell fibers for robust silicon nanoparticle-based lithium ion battery anodes. , 2012, Nano letters.

[37]  Hui Wu,et al.  Engineering empty space between Si nanoparticles for lithium-ion battery anodes. , 2012, Nano letters.

[38]  David Wexler,et al.  Highly reversible lithium storage in spheroidal carbon-coated silicon nanocomposites as anodes for lithium-ion batteries. , 2006, Angewandte Chemie.

[39]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[40]  Qiang Zhang,et al.  A Three‐Dimensional Carbon Nanotube/Graphene Sandwich and Its Application as Electrode in Supercapacitors , 2010, Advanced materials.

[41]  G. Yushin,et al.  Deformations in Si-Li anodes upon electrochemical alloying in nano-confined space. , 2010, Journal of the American Chemical Society.

[42]  G. Yushin,et al.  A Major Constituent of Brown Algae for Use in High-Capacity Li-Ion Batteries , 2011, Science.

[43]  Young Hee Lee,et al.  Graphene/Substrate Charge Transfer Characterized by Inverse Photoelectron Spectroscopy , 2010 .

[44]  Prashant N. Kumta,et al.  Nanostructured hybrid silicon/carbon nanotube heterostructures: reversible high-capacity lithium-ion anodes. , 2010, ACS nano.

[45]  M. Armand,et al.  Building better batteries , 2008, Nature.

[46]  Chunsheng Wang,et al.  Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells , 2007 .

[47]  G. Yushin,et al.  High-performance lithium-ion anodes using a hierarchical bottom-up approach. , 2010, Nature materials.