In situ X-ray diffraction studies of (de)lithiation mechanism in silicon nanowire anodes.

Silicon is a promising anode material for Li-ion batteries due to its high theoretical specific capacity. From previous work, silicon nanowires (SiNWs) are known to undergo amorphorization during lithiation, and no crystalline Li-Si product has been observed. In this work, we use an X-ray transparent battery cell to perform in situ synchrotron X-ray diffraction on SiNWs in real time during electrochemical cycling. At deep lithiation voltages the known metastable Li(15)Si(4) phase forms, and we show that avoiding the formation of this phase, by modifying the SiNW growth temperature, improves the cycling performance of SiNW anodes. Our results provide insight on the (de)lithiation mechanism and a correlation between phase evolution and electrochemical performance for SiNW anodes.

[1]  Michael F Toney,et al.  In Operando X-ray diffraction and transmission X-ray microscopy of lithium sulfur batteries. , 2012, Journal of the American Chemical Society.

[2]  Chongwu Zhou,et al.  Bulk synthesis of crystalline and crystalline core/amorphous shell silicon nanowires and their application for energy storage. , 2011, ACS nano.

[3]  Yi Cui,et al.  Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life. , 2011, Nano letters.

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

[5]  Yi Cui,et al.  Inorganic Glue Enabling High Performance of Silicon Particles as Lithium Ion Battery Anode , 2011 .

[6]  H.-S. Philip Wong,et al.  In situ transmission electron microscopy observation of nanostructural changes in phase-change memory. , 2011, ACS nano.

[7]  J. Tarascon,et al.  Pair distribution function analysis and solid state NMR studies of silicon electrodes for lithium ion batteries: understanding the (de)lithiation mechanisms. , 2011, Journal of the American Chemical Society.

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

[9]  Vincent Chevrier,et al.  First principles study of Li–Si crystalline phases: Charge transfer, electronic structure, and lattice vibrations , 2010 .

[10]  J. Rogers,et al.  Arrays of sealed silicon nanotubes as anodes for lithium ion batteries. , 2010, Nano letters.

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

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

[13]  J. Goodenough,et al.  Challenges for Rechargeable Li Batteries , 2010 .

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

[15]  Yi Cui,et al.  Carbon-silicon core-shell nanowires as high capacity electrode for lithium ion batteries. , 2009, Nano letters.

[16]  Rangeet Bhattacharyya,et al.  Real-time NMR investigations of structural changes in silicon electrodes for lithium-ion batteries. , 2009, Journal of the American Chemical Society.

[17]  Candace K. Chan,et al.  Crystalline-amorphous core-shell silicon nanowires for high capacity and high current battery electrodes. , 2009, Nano letters.

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

[19]  M. Shikano,et al.  Gold model anodes for Li-ion batteries: Single crystalline systems studied by in situ X-ray diffraction , 2008 .

[20]  Wenjun Zhang,et al.  Silicon nanowires for rechargeable lithium-ion battery anodes , 2008 .

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

[22]  Wei Lu,et al.  Si/a-Si core/shell nanowires as nonvolatile crossbar switches. , 2008, Nano letters.

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

[24]  Jing Li,et al.  An In Situ X-Ray Diffraction Study of the Reaction of Li with Crystalline Si , 2007 .

[25]  K. Möller,et al.  Monitoring dynamics of electrode reactions in Li-ion batteries by in situ ESEM , 2006 .

[26]  M. Whittingham,et al.  Lithium batteries and cathode materials. , 2004, Chemical reviews.

[27]  T. D. Hatchard,et al.  In Situ XRD and Electrochemical Study of the Reaction of Lithium with Amorphous Silicon , 2004 .

[28]  F. E. Little,et al.  Electrochemical performance of lithium ion battery, nano-silicon-based, disordered carbon composite anodes with different microstructures , 2004 .

[29]  T. D. Hatchard,et al.  Reaction of Li with Alloy Thin Films Studied by In Situ AFM , 2003 .

[30]  G. Taillades,et al.  Metal-based very thin film anodes for lithium ion microbatteries , 2002 .

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

[32]  T. Roisnel,et al.  WinPLOTR: A Windows Tool for Powder Diffraction Pattern Analysis , 2001 .

[33]  Kevin W. Eberman,et al.  Colossal Reversible Volume Changes in Lithium Alloys , 2001 .

[34]  Margret Wohlfahrt-Mehrens,et al.  A room temperature study of the binary lithium–silicon and the ternary lithium–chromium–silicon system for use in rechargeable lithium batteries , 1999 .

[35]  Martin Winter,et al.  Will advanced lithium-alloy anodes have a chance in lithium-ion batteries? , 1997 .

[36]  Juan Rodriguez-Carvaj,et al.  Recent advances in magnetic structure determination neutron powder diffraction , 1993 .

[37]  R. Nesper.  Structure and chemical bonding in zintl-phases containing lithium , 1990 .

[38]  Reinhard Nesper,et al.  Li21Si5, a Zintl phase as well as a Hume-Rothery phase , 1987 .

[39]  R. Nesper,et al.  Li12Si7, eine Verbindung mit trigonal‐planaren Si4‐Clustern und isometrischen Si5‐Ringen , 1986 .

[40]  Robert A. Huggins,et al.  All‐Solid Lithium Electrodes with Mixed‐Conductor Matrix , 1981 .

[41]  R. Nesper,et al.  Li12Si7, a Compound Having a Trigonal Planar Si4 Cluster and Planar Si5 Rings , 1980 .

[42]  W. Klemm,et al.  Notiz über die Verbindungen zwischen Lithium und Silicium , 1955 .