[en] This work aims at shedding light on how the microporous texture of porous carbons influences their electrochemical behavior when used as anodes for Li-ion batteries. To this aim, a synthetic hard carbon (carbon xerogel, CX), prepared from a resorcinol-formaldehyde precursor gel, underwent several post-synthesis treatments in order to modulate its micropore to total pore volume ratio. The micropore volume was either expanded by physical activation or decreased using chemical vapor deposition (CVD) of a carbon layer.
Several variables other than the micropore texture of the obtained carbons, which could influence their behavior as anode active materials for Li-ion batteries, such as the particle size or the electrode characteristics, were carefully controlled. The thickness of electrode coatings and the pore texture of the active material-binder composite were analyzed. It was shown that CX-binder composites resulting from water-based slurries preserve the microporosity of the starting materials. Detailed electrochemical characterization of the electrodes prepared with carbon xerogels displaying various defined micropore textures was performed. A clear linear dependency could be evidenced between the Li+ insertion and de-insertion in half-cell configuration with the increase of the volume of supermicropores (0.7 – 2 nm), demonstrating the effect of micropore enlargement by activation on the storage capacity, provided the maximum charge potential value is set at 3.0 V vs. Li+/Li.
Disciplines :
Chemistry
Author, co-author :
Piedboeuf, Marie-Laure
Léonard, Alexandre ; Université de Liège - ULiège > Department of Chemical Engineering > Ingéniérie électrochimique
Reichenauer, Gudrun; Bavarian Center for Applied Energy Research > Division Energy Efficiency
Balzer, Christian; Bavarian Center for Applied Energy Research > Division Energy Efficiency
Job, Nathalie ; Université de Liège - ULiège > Department of Chemical Engineering > Ingéniérie électrochimique
Language :
English
Title :
How do the micropores of carbon xerogels influence their electrochemical behavior as anodes for lithium-ion batteries?
Nagaura, T., Tozaawa, K., Lithium Ion rechargeable battery. Prog. Batter. Sol. Cells. 9 (1990), 209–212.
Buiel, E., Dahn, J.R., Li-insertion in hard carbon anode materials for Li-ion batteries. Electrochim. Acta 45 (1999), 121–130 https://doi.org/10.1016/S0013-4686(99)00198-X.
Fujimoto, H., Tokumitsu, K., Mabuchi, A., Chinnasamy, N., Kasuh, T., The anode performance of the hard carbon for the lithium ion battery derived from the oxygen-containing aromatic precursors. J. Power Sources 195 (2010), 7452–7456, 10.1016/j.jpowsour.2010.05.041.
Ni, J., Huang, Y., Gao, L., A high-performance hard carbon for Li-ion batteries and supercapacitors application. J. Power Sources 223 (2013), 306–311 https://doi.org/10.1016/j.jpowsour.2012.09.047.
Piedboeuf, M.-L.C., Léonard, A.F., Deschamps, F.L., Job, N., Carbon xerogels as model materials: toward a relationship between pore texture and electrochemical behavior as anodes for lithium-ion batteries. J. Mater. Sci. 51 (2016), 4358–4370, 10.1007/s10853-016-9748-3.
Job, N., Pirard, R., Marien, J., Pirard, J.-P., Porous carbon xerogels with texture tailored by pH control during sol–gel process. Carbon N. Y. 42 (2004), 619–628 https://doi.org/10.1016/j.carbon.2003.12.072.
Rey-Raap, N., Piedboeuf, M.-L.C., Arenillas, A., Menéndez, J.A., Léonard, A.F., Job, N., Aqueous and organic inks of carbon xerogels as models for studying the role of porosity in lithium-ion battery electrodes. Mater. Des. 109 (2016), 282–288, 10.1016/j.matdes.2016.07.007.
Contreras, M.S., Páez, C.A., Zubizarreta, L., Léonard, A., Blacher, S., Olivera-Fuentes, C.G., et al. A comparison of physical activation of carbon xerogels with carbon dioxide with chemical activation using hydroxides. Carbon N. Y. 48 (2010), 3157–3168, 10.1016/j.carbon.2010.04.054.
Yang, Z., Xia, Y., Sun, X., Mokaya, R., Preparation and hydrogen storage properties of zeolite-templated carbon materials nanocast via chemical vapor deposition: effect of the zeolite template and nitrogen doping. J. Phys. Chem. B 110 (2006), 18424–18431, 10.1021/jp0639849.
Zhu, Y., Xiang, X., Liu, E., Wu, Y., Xie, H., Wu, Z., et al. An activated microporous carbon prepared from phenol-melamine-formaldehyde resin for lithium ion battery anode. Mater. Res. Bull. 47 (2012), 2045–2050 https://doi.org/10.1016/j.materresbull.2012.04.003.
Nian-Ping, S.J.L., Da-Yong, G., Dong, L., Xiao-Wei, Z., Ya-Jie, L., Effect of carbon aerogel activation on electrode lithium insertion performance. Acta Physico-Chemica Sin. 29 (2013), 966–972, 10.3866/PKU.WHXB201302281.
Liu, X., Li, S., Mei, J., Lau, W.-M., Mi, R., Li, Y., et al. From melamine-resorcinol-formaldehyde to nitrogen-doped carbon xerogels with micro- and meso-pores for lithium batteries. J. Mater. Chem. A. 2 (2014), 14429–14438, 10.1039/C4TA02928C.
Piedboeuf, M.-L.C., Léonard, A.F., Traina, K., Job, N., Influence of the textural parameters of resorcinol–formaldehyde dry polymers and carbon xerogels on particle sizes upon mechanical milling. Colloids Surfaces A Physicochem. Eng. Asp. 471 (2015), 124–132 https://doi.org/10.1016/j.colsurfa.2015.02.014.
Thommes, M., Kaneko, K., Neimark, A.V., Olivier, J.P., Rodriguez-Reinoso, F., Rouquerol, J., Sing, K.S.W., Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87 (2015), 1051–1069 https://doi.org/10.1515/pac-2014-1117.
Magee, R.W., Evaluation of the external surface area of carbon black by nitrogen adsorption. Rubber Chem. Technol. 68 (1995), 590–600 http://doi.org/10.5254/1.3538760.
Tarazona, P., A density functional theory of melting. Mol. Phys. 52 (1984), 81–96 http://doi.org/10.1080/00268978400101071.
Tarazona, P., Free-energy density functional for hard spheres. Phys. Rev. 31 (1985), 2672–2679 http://doi.org/10.1103/PhysRevA.31.2672.
Tarazona, P., Marconi, M.B., Evans, R., Phase equilibria of fluids interfaces and confined fluids: non-local versus local density functionals. Mol. Phys. 60 (1987), 573–595 http://doi.org/10.1080/00268978700100381.
Olivier, J.P., Modeling physical adsorption on porous and nonporous solids using density functional theory. J. Porous Mater. 2 (1995), 9–17 http://doi.org/10.1007/BF00486565.
Maddox, M.W., Olivier, J.P., Gubbins, K.E., Characterization of MCM-41 using molecular simulation: heterogeneity effects. Langmuir 13 (1997), 1737–1745 https://pubs.acs.org/doi/abs/10.1021/la961068o.
Balzer, C., Cimino, R.T., Gor, G.Y., Neimark, A.V., Reichenauer, G., Deformation of microporous carbons during N2, Ar, and CO2 adsorption: insight from the density functional theory. Langmuir 32 (2016), 8265–8274 http://pubs.acs.org/doi/10.1021/acs.langmuir.6b02036.
Washburn, E.W., Note on a method of determining the distribution of pore sizes in a porous material. Proc. Natl. Acad. Sci. Unit. States Am. 7 (1921), 115–116.
Antonio, G.F.M., Franco, F., Batalha, N., Pereira, M.M., Coupling CH4 pyrolysis with CO2 activation via reverse Boudouard reaction in the presence of O2 through a multifunctional catalyst Ni-V-Li/Al2O3. J. CO2 Util. 16 (2016), 458–465, 10.1016/j.jcou.2016.10.011.