Polysilane-Based Ceramics as Anodes in Lithium Ion Batteries

Abstract: Two different polysilanes, poly(methyl(phenyl)silane) (PMPS) and poly(methyl(phenyl)silane-co-methyl(vinyl)silane) (PMPS-co-PMVS), were synthesized as precursor polymers to ceramics as anodes in lithium ion batteries.Upon pyrolysis at 1000 o C, the polysilanes yielded ceramics with a Si content of 67−70%. The vinyl group containingPMPS-co-PMVS showed a higher ceramic yield than that containing PMPS due to the thermal crosslinking reactionsbetween the vinyl groups. The ceramic products were characterized using elemental analysis, Fourier transform-infraredspectroscopy, thermogravimetry, X-ray diffractometry, and atomic force microscopy. It was revealed that the ceramicsfrom PMPS-co-PMVS had a higher Si atomic content, had more Si-Si bonds, and a more crystalline structure than thosefrom PMPS. The discharge capacities of the ceramics were less than 200 mAh/g, but they showed excellent cycling per-formance, maintaining their capacities after 100 charge/discharge cycles. Keywords: lithium ion battery, polysilane, discharge capacity, pre-ceramic polymer

[1]  Robert H. Doremus,et al.  Pyrolysis chemistry of an organometallic precursor to silicon carbide , 1991 .

[2]  Ralf Riedel,et al.  Lithium insertion into dense and porous carbon-rich polymer-derived SiOC ceramics , 2012 .

[3]  Sophie Demoustier-Champagne,et al.  Synthesis and characterization of alpha,omega-dichloro-polymethylphenylsilane , 1996 .

[4]  Michael Holzapfel,et al.  A new type of nano-sized silicon/carbon composite electrode for reversible lithium insertion. , 2005, Chemical communications.

[5]  Zi-Feng Ma,et al.  Cu5Si–Si/C composites for lithium-ion battery anodes , 2006 .

[6]  T. Ohsaki,et al.  Rechargeable Lithium‐Ion Cells Using Graphitized Mesophase‐Pitch‐Based Carbon Fiber Anodes , 1995 .

[7]  B. Way,et al.  Nanodispersed silicon in pregraphitic carbons , 1995 .

[8]  X. B. Zhang,et al.  Lithium Insertion in Carbon‐Silicon Composite Materials Produced by Mechanical Milling , 1998 .

[9]  Ralf Riedel,et al.  Carbon-rich SiCN ceramics as high capacity/high stability anode material for lithium-ion batteries , 2013 .

[10]  Brian F. Yates,et al.  Pyrolysed pitch-polysilane blends for use as anode materials in lithium ion batteries II: the effect of oxygen , 1997 .

[11]  Kai Xie,et al.  Mechanism of lithium storage in SiOC composite anodes , 2011 .

[12]  Jung-Ho Ahn,et al.  Nanostructured Si–C composite anodes for lithium-ion batteries , 2004 .

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

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

[15]  W. Xing,et al.  Pyrolysed pitch-polysilane blends for use as anode materials in lithium ion batteries , 1997 .

[16]  Takeshi Okutani,et al.  Structure and morphology of phenylsilanes polymer films synthesized by the plasma polymerization method , 1998 .

[17]  Andrzej Nowak,et al.  Electrochemical study of lithium insertion into carbon-rich polymer-derived silicon carbonitride ceramics , 2010 .

[18]  Hajime Yasuda,et al.  Preparation of carbons from pitch containing polysilane and their anode properties for lithium-ion batteries , 2000 .

[19]  Noboru Masuko,et al.  Morphology and Structure of Oxide Films Formed on Magnesium by Exposure to Air and Water , 1995 .

[20]  Robert Kolb,et al.  SiCN/C-ceramic composite as anode material for lithium ion batteries , 2006 .

[21]  Andrew J. Steckl,et al.  SiC Silicon‐on‐Insulator Structures by Direct Carbonization Conversion and Postgrowth from Silacyclobutane , 1994 .

[22]  Ralf Riedel,et al.  Electrochemical studies of carbon-rich polymer-derived SiCN ceramics as anode materials for lithium-ion batteries , 2010 .

[23]  Martin Winter,et al.  Filming mechanism of lithium-carbon anodes in organic and inorganic electrolytes , 1995 .