On the electrochemical performance of anthracite-based graphite materials as anodes in lithium-ion batteries

Abstract The electrochemical performance as potential negative electrode in lithium-ion batteries of graphite materials that were prepared from two Spanish anthracites of different characteristics by heat treatment in the temperature interval 2400–2800 °C are investigated by galvanostatic cycling. The interlayer spacing, d002, and crystallite sizes along the c axis, Lc, and the a axis, La, calculated from X-ray diffractometry (XRD) as well as the relative intensity of the Raman D-band, ID/It, are used to assess the degree of structural order of the graphite materials. The galvanostatic cycling are carried out in the 2.1–0.003 V potential range at a constant current and C/10 rate during 50 cycles versus Li/Li+. Larger reversible lithium storage capacities are obtained from those anthracite-based graphite materials with higher structural order and crystal orientation. Reasonably good linear correlations were attained between the electrode reversible charge and the materials XRD and Raman crystal parameters. The graphite materials prepared show excellent cyclability as well as low irreversible charge; the reversible capacity being up to ∼250 mA h g−1. From this study, the utilization of anthracite-based graphite materials as negative electrode in lithium-ion batteries appears feasible. Nevertheless, additional work should be done to improve the structural order of the graphite materials prepared and therefore, the reversible capacity.

[1]  Kunio Nishimura,et al.  Recent development of carbon materials for Li ion batteries , 2000 .

[2]  Qinmin Pan,et al.  Novel modified graphite as anode material for lithium ion batteries , 2002 .

[3]  J. Dahn,et al.  Carbons prepared from coals for anodes of lithium-ion cells , 1996 .

[4]  P. Biensan,et al.  Effect of Graphite Crystal Structure on Lithium Electrochemical Intercalation , 1999 .

[5]  P. Novák,et al.  The role of graphite surface group chemistry on graphite exfoliation during electrochemical lithium insertion , 2003 .

[6]  A. Ishitani,et al.  Raman spectra of graphite edge planes , 1988 .

[7]  J. Rouzaud,et al.  Correlation of the irreversible lithium capacity with the active surface area of modified carbons , 2005 .

[8]  V. E. Strelnitsky,et al.  Direct observation of laser-induced crystallization of a-C:H films , 1994 .

[9]  P. Novák,et al.  The importance of the active surface area of graphite materials in the first lithium intercalation , 2007 .

[10]  Huaihe Song,et al.  Electrochemical performance of expanded mesocarbon microbeads as anode material for lithium-ion batteries , 2006 .

[11]  B. Way,et al.  Dependence of the electrochemical intercalation of lithium in carbons on the crystal structure of the carbon , 1993 .

[12]  Yue Min,et al.  A modified graphite anode with high initial efficiency and excellent cycle life expectation , 2005 .

[13]  H. Lee,et al.  Electrochemical performance of modified synthetic graphite for lithium ion batteries , 2005 .

[14]  Zhan-hong Yang,et al.  An investigation of lithium intercalation into the carbon nanotubes by a.c. impedance , 2005 .

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

[16]  Yuping Wu,et al.  A green method for the preparation of anodematerials for lithium ion batteries , 2001 .

[17]  S. Dou,et al.  Electrochemical studies of graphitized mesocarbon microbeads as an anode in lithium-ion cells , 2003 .

[18]  A. Oberlin,et al.  Graphitization studies of anthracites by high resolution electron microscopy , 1975 .

[19]  V. Suryanarayanan,et al.  Role of carbon host lattices in Li-ion intercalation/de-intercalation processes , 2002 .

[20]  J. Besenhard,et al.  Modified carbons for improved anodes in lithium ion cells , 2001 .

[21]  A. García,et al.  Structural study of graphite materials prepared by HTT of unburned carbon concentrates from coal combustion fly ashes , 2008 .

[22]  J. Rouzaud,et al.  Structural and electrochemical characterisation of nitrogen enriched carbons produced by the co-pyrolysis of coal-tar pitch with polyacrylonitrile , 2004 .

[23]  Influence of carbon black and binder on Li-ion batteries , 2001 .

[24]  P. Novák,et al.  Graphites for lithium-ion cells : The correlation of the first-cycle charge loss with the Brunauer-Emmett-Teller surface area , 1998 .

[25]  Seong-Ho Yoon,et al.  Anthracite as a candidate for lithium ion battery anode , 2003 .

[26]  P. Delhaès Graphite and Precursors , 2000 .

[27]  A. García,et al.  Influence of Inherent Coal Mineral Matter on the Structural Characteristics of Graphite Materials Prepared from Anthracites , 2005 .

[28]  J. Laureyns,et al.  Raman microprobe studies on carbon materials , 1994 .

[29]  B. Scrosati,et al.  Structural and electrochemical studies of a hexaphenylbenzene pyrolysed soft carbon as anode material in lithium batteries , 2006 .

[30]  Jean-Noël Rouzaud,et al.  Characterization of carbonaceous materials by correlated electron and optical microscopy and Raman microspectroscopy , 1985 .

[31]  N. Balasooriya,et al.  Lithium electrochemical intercalation into mechanically and chemically treated Sri Lanka natural graphite , 2006 .

[32]  V. Khomenko,et al.  Characterization of silicon-and carbon-based composite anodes for lithium-ion batteries , 2007 .

[33]  H. Schobert,et al.  Structural ordering of Pennsylvania anthracites on heat treatment to 2000-2900 °C , 2002 .

[34]  E. L. Evans,et al.  Direct electron microscopic studies of graphitic regions in heat-treated coals and coal extracts , 1972 .

[35]  R. Franklin The structure of graphitic carbons , 1951 .

[36]  J. Laureyns,et al.  Comparative performance of X-ray diffraction and Raman microprobe techniques for the study of carbon materials , 1998 .

[37]  M. Dresselhaus,et al.  Lithium storage behavior for various kinds of carbon anodes in Li ion secondary battery , 1996 .

[38]  B. Warren,et al.  An X‐Ray Study of Carbon Black , 1942 .

[39]  P. Bruce,et al.  Nanomaterials for rechargeable lithium batteries. , 2008, Angewandte Chemie.

[40]  I. Barsukov,et al.  Lithium-ion batteries based on carbon-silicon-graphite composite anodes , 2007 .

[41]  G. Fey,et al.  Lithium intercalation in graphites precipitated from pig iron melts , 2003 .

[42]  J. Rouzaud,et al.  Natural graphitization of anthracite: Experimental considerations , 1995 .

[43]  A. García,et al.  Structural Characterization of Graphite Materials Prepared from Anthracites of Different Characteristics: A Comparative Analysis , 2004 .

[44]  J. Rouzaud,et al.  Effects of post-treatments on the performance of hard carbons in lithium cells , 2001 .

[45]  F. Tuinstra,et al.  Raman Spectrum of Graphite , 1970 .

[46]  Sung-Man Lee,et al.  Spherical silicon/graphite/carbon composites as anode material for lithium-ion batteries , 2008 .

[47]  R. Menéndez,et al.  Iron–carbon composites as electrode materials in lithium batteries , 2006 .

[48]  R. Young,et al.  Raman spectroscopy study of HM carbon fibres: effect of plasma treatment on the interfacial properties of single fibre/epoxy composites , 2002 .