Carbon xerogels as model materials: toward a relationship between pore texture and electrochemical behavior as anodes for lithium-ion batteries

The mechanisms of Li+ insertion in porous hard carbons used as anodes for Li-ion batteries are still a matter of debate, especially considering the divergence of electrochemical performances observed in the literature. Since these materials usually exhibit several levels of porosity, the pore texture versus electrochemical behavior relationship is difficult to establish. In this paper, we propose to use carbon xerogels, prepared from aqueous resorcinol–formaldehyde mixtures, as model materials for Li-ion battery anodes to study the influence of the pore texture on the overall electrochemical behavior. Indeed, carbon xerogels are described as microporous nodules linked together to form meso- or macroporous voids inside a 3D gel structure; the size of these voids can be tuned by changing the synthesis conditions without affecting other parameters such as the micropore volume. The materials are chosen so as to obtain identical average particle sizes, homogeneous coatings with similar thicknesses, and a comparable surface chemistry. The electrochemical behaviors of carbon xerogels as Li-ion anodes are correlated with the surface accessible to the electrolyte and are not dependent on the total specific surface area calculated by the BET method from nitrogen adsorption isotherms. The key parameter proposed to understand their behavior is the external surface area of the nodules, which corresponds to the surface of the meso/macropores.

[1]  Justin C. Lytle,et al.  Synthesis and Rate Performance of Monolithic Macroporous Carbon Electrodes for Lithium‐Ion Secondary Batteries , 2005 .

[2]  N. Job,et al.  Influence of the textural parameters of resorcinol–formaldehyde dry polymers and carbon xerogels on particle sizes upon mechanical milling , 2015 .

[3]  S. J. Gregg,et al.  Adsorption Surface Area and Porosity , 1967 .

[4]  Zi-Feng Ma,et al.  Preparation and characterization of carbon xerogel (CX) and CX-SiO composite as anode material for lithium-ion battery , 2007 .

[5]  Youyuan Huang,et al.  A high-performance hard carbon for Li-ion batteries and supercapacitors application , 2013 .

[6]  D. Do,et al.  The Dubinin-Radushkevich equation and the underlying microscopic adsorption description , 2001 .

[7]  V. Presser,et al.  Carbons and Electrolytes for Advanced Supercapacitors , 2014, Advanced materials.

[8]  J. Lee,et al.  Preparation and Characterization of Carbon Nanospheres as Anode Materials in Lithium-Ion Secondary Batteries , 2008 .

[9]  J. A. Menéndez,et al.  RF xerogels with tailored porosity over the entire nanoscale , 2014 .

[10]  M. Chi,et al.  Soft‐Templated Mesoporous Carbon‐Carbon Nanotube Composites for High Performance Lithium‐ion Batteries , 2011, Advanced materials.

[11]  Yoji Shirato,et al.  Preparation of carbon gel microspheres containing silicon powder for lithium ion battery anodes , 2004 .

[12]  F. Béguin,et al.  Electrochemical storage of energy in carbon nanotubes and nanostructured carbons , 2002 .

[13]  A. Lecloux Texture of Catalysts , 1982 .

[14]  Kai-Xue Wang,et al.  Surface and Interface Engineering of Electrode Materials for Lithium‐Ion Batteries , 2015, Advanced materials.

[15]  P. Biensan,et al.  A 7Li NMR study of a hard carbon for lithium–ion rechargeable batteries , 2000 .

[16]  Yinchuan Li,et al.  From melamine–resorcinol–formaldehyde to nitrogen-doped carbon xerogels with micro- and meso-pores for lithium batteries , 2014 .

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

[18]  Chandra Shekhar Sharma,et al.  Synthesis of carbon xerogel nanoparticles by inverse emulsion polymerization of resorcinol–formaldehyde and their use as anode materials for lithium-ion battery , 2015 .

[19]  Hao-qing Wu,et al.  Structural and electrochemical properties of disordered carbon prepared by the pyrolysis of poly(p-phenylene) below 1000°C for the anode of a lithium-ion battery , 1999 .

[20]  H. Sakaebe,et al.  Analysis of hard carbon for lithium-ion batteries by hard X-ray photoelectron spectroscopy , 2013 .

[21]  P. Notten,et al.  Electrochemical storage of energy in single wall carbon nanotubes , 2004 .

[22]  J. Dahn,et al.  Dramatic Effect of Oxidation on Lithium Insertion in Carbons Made from Epoxy Resins , 1995 .

[23]  David Linden,et al.  Linden's Handbook of Batteries , 2010 .

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

[25]  John B. Goodenough,et al.  Electrochemical energy storage in a sustainable modern society , 2014 .

[26]  Haijiao Zhang,et al.  Synthesis of morphology-controlled carbon hollow particles by carbonization of resorcinol–formaldehyde precursor microspheres and applications in lithium-ion batteries , 2012 .

[27]  Nathalie Job,et al.  Porous carbon xerogels with texture tailored by pH control during sol–gel process , 2004 .

[28]  R. Kanno,et al.  Structure Characterization and Lithiation Mechanism of Nongraphitized Carbon for Lithium Secondary Batteries , 2006 .

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

[30]  H. Fujimoto,et al.  7Li nuclear magnetic resonance studies of hard carbon and graphite/hard carbon hybrid anode for Li i , 2011 .

[31]  J. Rouzaud,et al.  Carbon aerogels, cryogels and xerogels: Influence of the drying method on the textural properties of porous carbon materials , 2005 .

[32]  T. Ohsaki,et al.  Lithium insertion and extraction for high-capacity disordered carbons with large hysteresis , 1997 .

[33]  E. W. Washburn Note on a Method of Determining the Distribution of Pore Sizes in a Porous Material. , 1921, Proceedings of the National Academy of Sciences of the United States of America.

[34]  Xiao-Guang Sun,et al.  In Situ Observation of Solid Electrolyte Interphase Formation in Ordered Mesoporous Hard Carbon by Small-Angle Neutron Scattering , 2012 .

[35]  A. Puente,et al.  RF xerogels with tailored porosity over the entire nanoscale , 2014 .

[36]  E. Liu,et al.  An activated microporous carbon prepared from phenol-melamine-formaldehyde resin for lithium ion battery anode , 2012 .

[37]  Liu Dong,et al.  Effect of Carbon Aerogel Activation on Electrode Lithium Insertion Performance , 2013 .