Real-time measurement of stress and damage evolution during initial lithiation of crystalline silicon.

Crystalline to amorphous phase transformation during initial lithiation in (100) Si wafers is studied in an electrochemical cell with Li metal as the counter and reference electrode. During initial lithiation, a moving phase boundary advances into the wafer starting from the surface facing the lithium electrode, transforming crystalline Si into amorphous Li(x)Si. The resulting biaxial compressive stress in the amorphous layer is measured in situ, and it was observed to be ca. 0.5 GPa. High-resolution TEM images reveal a very sharp crystalline-amorphous phase boundary, with a thickness of ∼1  nm. Upon delithiation, the stress rapidly reverses and becomes tensile, and the amorphous layer begins to deform plastically at around 0.5 GPa. With continued delithiation, the yield stress increases in magnitude, culminating in a sudden fracture of the amorphous layer into microfragments, and the cracks extend into the underlying crystalline Si.

[1]  Ali Reza Kamali,et al.  Review on Carbon and Silicon Based Materials as Anode Materials for Lithium Ion Batteries , 2010 .

[2]  Mark N. Obrovac,et al.  Structural changes in silicon anodes during lithium insertion/extraction , 2004 .

[3]  Mark N. Obrovac,et al.  Reversible Cycling of Crystalline Silicon Powder , 2007 .

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

[5]  Christoph Stangl,et al.  High capacity graphite-silicon composite anode material for lithium-ion batteries , 2011 .

[6]  Young-Il Jang,et al.  Electrochemically-driven solid-state amorphization in lithium-silicon alloys and implications for lithium storage , 2003 .

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

[8]  S. Komaba,et al.  Polyacrylate as Functional Binder for Silicon and Graphite Composite Electrode in Lithium-Ion Batteries , 2011 .

[9]  Yung-Eun Sung,et al.  Failure Modes of Silicon Powder Negative Electrode in Lithium Secondary Batteries , 2004 .

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

[11]  Zhaoyin Wen,et al.  A novel nanosized silicon-based composite as anode material for high performance lithium ion batteries , 2011 .

[12]  Allan F. Bower,et al.  A finite strain model of stress, diffusion, plastic flow, and electrochemical reactions in a lithium-ion half-cell , 2011 .

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

[14]  F. Spaepen.  A survey of energies in materials science , 2005 .

[15]  Venkat Srinivasan,et al.  In Situ Measurements of Stress-Potential Coupling in Lithiated Silicon , 2010 .

[16]  Pradeep R. Guduru,et al.  In situ measurement of biaxial modulus of Si anode for Li-ion batteries , 2010 .

[17]  Claus Daniel,et al.  Understanding the Degradation of Silicon Electrodes for Lithium-Ion Batteries Using Acoustic Emission , 2010 .

[18]  Zhigang Suo,et al.  Inelastic hosts as electrodes for high-capacity lithium-ion batteries , 2011 .

[19]  Venkat Srinivasan,et al.  In situ measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation , 2010, 1108.0647.

[20]  Prashant N. Kumta,et al.  Interfacial Properties of the a-Si ∕ Cu :Active–Inactive Thin-Film Anode System for Lithium-Ion Batteries , 2006 .

[21]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

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

[23]  G. Stoney.  The Tension of Metallic Films Deposited by Electrolysis , 1909 .