Engineering of Graphene Layer Orientation to Attain High Rate Capability and Anisotropic Properties in Li‐Ion Battery Electrodes

Novel carbon films with different graphene layer orientations are investigated as electrode materials for Li-ion batteries. It is demonstrated that engineering the crystallographic orientation with graphene layers oriented perpendicular to the surface substantially alters stress evolution during Li insertion. With this crystallographic orientation the intercalating/de-intercalating Li-ions also have direct access to the graphene interlayer spaces, resulting in higher capacity at faster electrochemical cycling, compared to carbon films with graphene layers parallel to the film surface. Electrodes with perpendicular alignment are prepared by supramolecular synthesis using either spin coating or bar coating of chromonic liquid crystal precursors into precursor organic films followed by in situ carbonization. These materials are compared with in situ stress measurements during lithiation/delithiation cycles, and the bar-coated films exhibit a highly anisotropic stress which is consistent with long-range alignment of the graphene layers. In contrast, the in-plane stresses in the spin-coated films are isotropic, which is consistent with the presence of randomly oriented domains (still with graphene layers oriented perpendicular to the surface). Overall, the use of thin film graphitic materials with controlled crystallographic orientations provides a valuable platform for investigating the impact of graphene structure on the properties of Li-ion battery electrode materials.

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

[2]  Petr Novák,et al.  SEI film formation on highly crystalline graphitic materials in lithium-ion batteries , 2006 .

[3]  Ping Yu,et al.  Determination of the Lithium Ion Diffusion Coefficient in Graphite , 1999 .

[4]  A. K. Dutta.  Electrical Conductivity of Single Crystals of Graphite , 1953 .

[5]  Amartya Mukhopadhyay,et al.  Stress development due to surface processes in graphite electrodes for Li-ion batteries: A first report , 2012 .

[6]  M. Wakihara.  Recent developments in lithium ion batteries , 2001 .

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

[8]  M. Wakihara,et al.  Chemical Diffusion Coefficient of Lithium in Carbon Fiber , 1996 .

[9]  Xingcheng Xiao,et al.  Thickness effects on the lithiation of amorphous silicon thin films , 2011 .

[10]  Brian W. Sheldon,et al.  Monitoring Stress in Thin Films During Processing , 2003 .

[11]  Ying Wang,et al.  Developments in Nanostructured Cathode Materials for High‐Performance Lithium‐Ion Batteries , 2008 .

[12]  Doron Aurbach,et al.  Diffusion Coefficients of Lithium Ions during Intercalation into Graphite Derived from the Simultaneous Measurements and Modeling of Electrochemical Impedance and Potentiostatic Intermittent Titration Characteristics of Thin Graphite Electrodes , 1997 .

[13]  M. Morita,et al.  Charge/discharge cycling behavior of pitch-based carbon fiber in organic electrolyte solutions , 1993 .

[14]  Petr Novák,et al.  The complex electrochemistry of graphite electrodes in lithium-ion batteries , 2001 .

[15]  Yoyo Hinuma,et al.  Lithium Diffusion in Graphitic Carbon , 2010, 1108.0576.

[16]  Rachid Yazami,et al.  Surface chemistry and lithium storage capability of the graphite-lithium electrode , 1999 .

[17]  Diana Golodnitsky,et al.  Effect of carbon substrate on SEI composition and morphology , 2004 .

[18]  M. Verbrugge,et al.  Diffusion Mediated Lithiation Stresses in Si Thin Film Electrodes , 2012 .

[19]  Klaus Müllen,et al.  A bottom-up approach from molecular nanographenes to unconventional carbon materials , 2008 .

[20]  Irene M. Plitz,et al.  A comparative study of Li-ion battery, supercapacitor and nonaqueous asymmetric hybrid devices for automotive applications , 2003 .

[21]  L. Onsager.  THE EFFECTS OF SHAPE ON THE INTERACTION OF COLLOIDAL PARTICLES , 1949 .

[22]  J. Dahn,et al.  Li-insertion in hard carbon anode materials for Li-ion batteries , 1999 .

[23]  H. Marsh,et al.  Catalysis of graphitisation , 2007 .

[24]  Byoungwoo Kang,et al.  Battery materials for ultrafast charging and discharging , 2009, Nature.

[25]  R. Hurt,et al.  Vertically Aligned Graphene Layer Arrays from Chromonic Liquid Crystal Precursors , 2011, Advanced materials.

[26]  K. Müllen,et al.  Nanographene‐Constructed Hollow Carbon Spheres and Their Favorable Electroactivity with Respect to Lithium Storage , 2010, Advanced materials.

[27]  Kang Xu,et al.  Understanding Solid Electrolyte Interface Film Formation on Graphite Electrodes , 2001 .

[28]  Yue Qi,et al.  Threefold Increase in the Young’s Modulus of Graphite Negative Electrode during Lithium Intercalation , 2010 .

[29]  Amartya Mukhopadhyay,et al.  Thin film graphite electrodes with low stress generation during Li-intercalation , 2011 .

[30]  Denis Billaud,et al.  Synthesis and electrical resistivity of lithium-pyrographite intercalation compounds (stages I, II and III) , 1979 .

[31]  L. Zhi,et al.  Graphene-based electrode materials for rechargeable lithium batteries , 2009 .

[32]  W. Primak,et al.  Electrical Conductivities of Natural Graphite Crystals , 1953 .

[33]  J. Pereira‐Ramos,et al.  A kinetic study of lithium transport in a new Li intercalation material Al{sub 0.11}V{sub 2}O{sub 5.15} synthesized via a sol-gel process , 1996 .

[34]  Ying Shirley Meng,et al.  Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries , 2006, Science.

[35]  Tao Zheng,et al.  Mechanisms for Lithium Insertion in Carbonaceous Materials , 1995, Science.

[36]  R. Beresford,et al.  Competition between tensile and compressive stress mechanisms during Volmer-Weber growth of aluminum nitride films , 2005 .