New materials

The initial work of the team focused on finding new electrode materials instead of activated carbon for use in aqueous or organic media. The research strategies consist in synthesizing pseudocapacitive materials (transition metal nitrides, manganese and iron oxides, etc.) whose capacities exceed by two or three times that of the current carbons. Three projects illustrate this approach: the ANR projects ABHYS (STOCK-E 2007), Advanced NiBaCa (STOCK-E 2008) and the thesis initiated in October 2013 under the RS2E network on mixed oxides.

Theme: Manganese oxides for supercapacitors

This theme, initiated by a close collaboration with Professor Daniel Bélanger (Université du Québec à Montréal), has given rise to many of the most frequently cited publications in the field. The ANR ABHYS project (AAP STOCK-E 2007) brought together leading French academic laboratories (ICGM, CIRIMAT, CRMD and IMN) with an industrialist in the field (BatScap) for the integration and evaluation of MnO2 in asymmetric storage devices. The project, completed in 2011, has resulted in numerous communications and publications (www.abhys.fr) and is currently continuing with the design of flexible supercapacitors that can be integrated into clothing or other devices (FLEXCAP project).

Theme: Transition metal nitrides for supercapacitor electrodes

The project concerns the study of the electrochemical properties of transition metal nitrides and elements of groups IIIA, IVA and VA as electrode materials for supercapacitors and lithium-ion accumulators. For the supercapacitor application, the important requirements concern the power and energy density as well as the lifetime over a very large number of cycles. The first axis of this project is therefore dedicated to the evaluation and selection of various performing nitrides first studied in the form of thin films and then, for the best, in the form of powders as composite electrodes of supercapacitors. It is also necessary to understand the mechanism for storing charges at the electrolyte-electrode interface and to study the consequences thereof over the lifetime of the supercapacitor. The great variability of the structures allowed by the group of nitrides is an important parameter that will be exploited. The choice of producing deposits of thin films of nitride compounds is well suited to obtaining intrinsic data, and therefore particularly rich in information on the materials in question. The synthesis methods used, sputtering, all-solid reactions and soft chemistry allow access to a wide range of compounds prepared in the form of films and powders of metal nitrides and oxynitrides of stoichiometry, morphologies and modular structures. The expertise of two partners specializing in the chemistry and synthesis of metal nitrides (SCR, IJL) combined with that of two others strongly involved in the electrochemistry of electrode materials for supercapacitors and Li-ion batteries (IMN, GESMAT ) Has made significant progress.

Theme: mixed oxides for supercapacitor electrodes

The vast majority of industrial supercapacitors are limited to a certain volume and not to a maximum mass as can the batteries. In this perspective, a thesis studies dense oxide materials. This thesis is carried out within the framework of a project of the RS2E network with the University of Nantes.

Capacité Volumique (en Wh/L) en fonction de la densité des matériaux.

Références

Toupin, M., Brousse, T., Bélanger, D., Influence of microstucture on the charge storage properties of chemically synthesized manganese dioxide, (2002) Chemistry of Materials, 14 (9), pp. 3946-3952.

Brousse, T., Bélanger, D., A hybrid Fe3O4-MnO2 capacitor in mild aqueous electrolyte, (2003) Electrochemical and Solid-State Letters, 6 (11), pp. A244-A248.

Brousse, T., Toupin, M., Bélanger, D., A Hybrid Activated Carbon-Manganese Dioxide Capacitor using a Mild Aqueous Electrolyte (2004) Journal of the Electrochemical Society, 151 (4), pp. A614-A622.

Toupin, M., Brousse, T., Bélanger, D., Charge storage mechanism of MnO2 electrode used in aqueous electrochemical capacitor (2004) Chemistry of Materials, 16 (16), pp. 3184-3190.

Brousse, T., Toupin, M., Dugas, R., Athouël, L., Crosnier, O., Bélanger, D., Crystalline MnO2 as possible alternatives to amorphous compounds in electrochemical supercapacitors (2006) Journal of the Electrochemical Society, 153 (12), art. no. 010612JES, pp. A2171-A2180.

Brousse, T., Taberna, P.-L., Crosnier, O., Dugas, R., Guillemet, P., Scudeller, Y., Zhou, Y., Favier, F., Bélanger, D., Simon, P., Long-term cycling behavior of asymmetric activated carbon/MnO2 aqueous electrochemical supercapacitor (2007) Journal of Power Sources, 173 (1), pp. 633-641.

Athouël, L., Moser, F., Dugas, R., Crosnier, O., Bélanger, D., Brousse, T., Variation of the MnO2 birnessite structure upon charge/discharge in an electrochemical supercapacitor electrode in aqueous Na2SO4 electrolyte (2008) J. Phys Chem C, 112, pp. 7270-7277.

Moser, F., Athouël, L., Crosnier, O., Favier, F., Bélanger, D., Brousse, T., Transparent electrochemical capacitor based on electrodeposited MnO2 thin film electrodes and gel-type electrolyte (2009) Electrochemistry Communication, 11 (6), pp.1259-1251.

Mosqueda, H.A., Crosnier, O., Athouël, L., Dandeville, Y., Scudeller, Y., Guillemet, P., Schleich, D.M., Brousse, T., Electrolytes for hybrid carbon-MnO2 electrochemical capacitors (2010) Electrochimica Acta, 55 (25), pp. 7479-7483.

Santos-Peña, J., Crosnier, O., Brousse, T., Nanosized α-LiFeO2 as electrochemical supercapacitor electrode in neutral sulfate electrolytes (2010) Electrochimica Acta, 55 (25), pp. 7511-7515.

Nakayama, M., Suzuki, K., Okamura, K., Inoue, R., Athouël, L., Crosnier, O., Brousse, T., Doping of cobalt into multilayered manganese oxide for improved pseudocapacitive properties (2010) Journal of the Electrochemical Society, 157 (10), pp. A1067-A1072.

Long, J.W., Bélanger, D., Brousse, T., Sugimoto, W., Sassin, M.B., Crosnier, O., Asymmetric electrochemical capacitors-Stretching the limits of aqueous electrolytes (2011) MRS Bulletin, 36 (7), pp. 513-522.

Athouël, L., Arcidiacono, P., Ramirez-Castro, C., Crosnier, O., Hamel, C., Dandeville, Y., Guillemet, P., Scudeller, Y., Guay, D., Bélanger, D., Brousse, T., Investigation of cavity microelectrode technique for electrochemical study with manganese dioxides (2012) Electrochimica Acta, 86, pp. 268-276.

Porto, R.L., Frappier, R., Ducros, J.B., Aucher, C., Mosqueda, H., Chenu, S., Chavillon, B., Tessier, F., Cheviré, F., Brousse, T., Titanium and vanadium oxynitride powders as pseudo-capacitive materials for electrochemical capacitors (2012) Electrochimica Acta, 82, pp. 257-262.

Boisset, A., Athouël, L., Jacquemin, J., Porion, P., Brousse, T., Anouti, M., Comparative performances of birnessite and cryptomelane MnO2 as electrode material in neutral aqueous lithium salt for supercapacitor application (2013) Journal of Physical Chemistry C, 117 (15), pp. 7408-7422.

Mendoza-Sánchez, B., Brousse, T., Ramirez-Castro, C., Nicolosi, V., S. Grant, P., An investigation of nanostructured thin film α-MoO3 based supercapacitor electrodes in an aqueous electrolyte (2013) Electrochimica Acta, 91, pp. 253-260.

Eustache, E., Frappier, R., Porto, R.L., Bouhtiyya, S., Pierson, J.-F., Brousse, T., Asymmetric electrochemical capacitor microdevice designed with vanadium nitride and nickel oxide thin film electrodes (2013) Electrochemistry Communications, 28, pp. 104-106.

Bouhtiyya, S., Lucio Porto, R., Laïk, B., Boulet, P., Capon, F., Pereira-Ramos, J.P., Brousse, T., Pierson, J.F., Application of sputtered ruthenium nitride thin films as electrode material for energy-storage devices (2013) Scripta Materialia, 68 (9), pp. 659-662.