Carbons and Hybrid Materials

Scientific objectives

 

  • Development of new synthesis pathways and innovative carbon and hybrid carbon materials (C/metal or C/ceramic nanocomposites) with perfectly controlled characteristics (texture, structure, morphology, functionalities)
  • Understanding the mechanisms occurring during the preparation of these materials
  • Understanding the interactions between the carbon (or hybrid carbon) materials and their environment (gas, liquid, solid) under different constraints (thermal, mechanical, chemical, electrochemical) occurring during their utilisation in different applications
  • Improving performances of carbon material in the field of energy and gas storage, catalysis and water/air depollution.

Members

 Luc DELMOTTE Research EngineerCV

 Bénédicte RETY EngineerCV

Joseph DENTZER Research EngineerCV

Dominique SCHWARTZ Assistant professor CV

Roger GADIOU ProfessorCV

Camélia GHIMBEU Research Scientist Co-leaderCV

Jean-Marc LE MEINS Assistant professorCV

Julien PARMENTIER 

Assistant professor Co-animateurCV

Research fields

The main research activities appear in the next figure :

Nanostructured carbon materials obtained by green synthesis concepts

J. Parmentier, C. Matei Ghimbeu, J.-M. Le Meins, L. Delmotte, C. Vix-Guterl

The simultaneous control of porosity, morphology, surface chemistry and structure of carbon materials are of prime importance in several application fields. The design of such materials requires a good control of classical synthesis routes but also, in some cases, the development of new and original synthesis pathways. In this case, the understanding of the formation mechanisms of these carbons is required to obtain materials with well-tailored physico-chemical features. These mechanisms concern the soft-template route, the thermal and laser pyrolysis, wood welding, graphitization assisted by catalysis, hydrothermal synthesis and shaping of carbon (or hybrid carbon) materials.

In this framework, we developed original environmentally-friendly synthesis approaches combining biosourced carbon precursors, soft-synthesis conditions (limited temperature and normal pressure), less corrosive reagents and reduced number of synthesis steps (“one-pot” synthesis)

 

Reprinted with permission from [Exceptionally highly performing Na-ion battery anode using SnO2 nanoparticles confined in mesoporous carbon, A Jahel, C Matei Ghimbeu, A Darwiche, L. Vidal, S. Hijjar-Garreau, C Vix-Guterl, L Monconduit, , J Mater Chem A, 3 (2015) 11960] © 2015 RSC publishing   DOI : 10.1039/C5TA01963J

Publications

S.Schlienger, A.L. Graff, A. Celzard, J. Parmentier Green Chem. 2012, 14, 313 DOI : 10.1039/C2GC16160E C.Matei Ghimbeu, L.Vidal, L. Delmotte, J.M. Le Meins, C. Vix-Guterl Green Chem. 2014, 16, 3079 DOI : 10.1039/C4GC00269E F. Braghiroli, V. Fierro, J. Parmentier, A. Pasc, A. Celzard, Green Chem. 2016 18, 3265.DOI : 10.1039/C5GC02788H A Maetz, L Delmotte, G Moussa, J Dentzer, S Knopf, C. Matei Ghimbeu, Green Chem. 2017, 19, 2266 DOI : 10.1039/C7GC00684E   F. L Braghiroli, V. Fierro, M. T. Izquierdo, J Parmentier, A Pizzi, A Celzard, Carbon 2012, 50, 5411–5420. DOI : 10.1016/j.carbon.2012.07.027

Understanding the performances of carbon materials used in adsorption and energy storage

 

C. Matei Ghimbeu, J. Dentzer, R. Gadiou, J.-M. Le Meins, J. Parmentier, B. Rety, C. Vix-Guterl

To understand the influence of each physico-chemical characteristic of carbon on their performances (adsorption/storage capacity, selectivity, stability during electrochemical cycling…), an original approach was developed consisting of a systematic variation of one characteristic of the material (texture, structure, functionalities) keeping, as far as possible, the others unchanged. This strategy, requiring deep knowledge of the formation/modification mechanisms of carbons, enabled correlations between carbon characteristics and their performances to be established. Indeed, we could demonstrate that the active surface area (ASA) is the key parameter influencing the irreversible capacity of Li and Na+ ion batteries as well as the capacitance of supercapacitors.

 

Reprinted with permission from [Insights on the Na+ ion storage mechanism in hard carbon: Discrimination between the porosity, surface functional groups and defects, C. Matei Ghimbeu, J Gorka, V Simone, L Simonin, S Martinet, C Vix-Guterl, NanoEnergy 2018, 44, 327 ] © 2018 Elsevier B.V.    DOI : 10.1016/j.nanoen.2017.12.013

Publications

C. Bousige, C.Ghimbeu, C. Vix-Guterl, A Pomerantz, A. Suleimenova, G. Vaughan, G. Garbarino, M. Feygenson, C. Wildgruber, F.J. Ulm, R.-M.  Pellenq, and B. Coasne, Nature Materials 2016, 15, 576 DOI :10.1038/nmat4541 Ph. Bernardo, J.-M. Le Meins, L.Vidal  J. Dentzer, R. Gadiou, W. Märkle, P. Novák, M.E. Spahr, C. Vix-Guterl,  Carbon 2015, 91, 458 DOI : 10.1016/j.carbon.2015.05.001 G. Moussa, C. Ghimbeu, P.L. Taberna, P. Simon, C. Vix-Guterl, Carbon 2016, 105, 628 DOI : 10.1016/j.carbon.2016.05.010 C. Decaux, C. Matei Ghimbeu, M. Dahbi, M. Anouti, D. Lemordant, F. Béguin, C.Vix-Guterl, E. Raymundo-Piñero, J Power Sources 2014, 263, 130-140 DOI : 10.1016/j.jpowsour.2014.04.024

 

Another important objective is to understand the interactions of carbon materials with their environment (gas, liquid, solid) in conditions similar to their application. For this purpose, specific characterization techniques were developed in our laboratory, such as TPD-MS (temperature programmed desorption coupled to mass spectrometry). This technique was able to identify and quantify the surface chemistry of carbon materials, study their affinity with certain molecules and even study the pyrolysis process of carbon precursors. Combined with other complementary techniques like XPS (X-ray photoelectron spectroscopy) and physisorption analysis (N2, CO2, H2O, COVs) led to an understanding of the nature of the interaction with their environment and  improved performances in applications such as pollutant removal from water (amoxicillin, chlorinated hydrocarbons, pesticides…) and from air (NOx, COVs),  gas storage and gas separation (H2, CO2 and CH4).

 

Reprinted with permission from [Microporous carbon adsorbents with high CO2 capacities for industrial applications, S Builes, T. Roussel,  C Matei GhimbeuJ Parmentier,  R Gadiou, C Vix-Guterl, L. F. Vega, Phys. Chem. Chem. Phys., 2011,13, 16063 ] © 2011 RSC publishing . DOI : 10.1039/C1CP21673B

Publications

J. Parmentier, F.O.M. Gaslain, O. Ersen, T.A. Centeno, L.A. Solovyov, Langmuir. 2014, 30, 297–307 DOI : 10.1021/la402762v  S Masson, C Vaulot, L Reiner, S Guittonneau, R Gadiou , L, Duclaux, Environ Sci Pollution Res, 2017, 24, 10005-10017 DOI : 10.1007/s11356-016-7614-0   B Wanassi, I Ben Hariz, C Matei Ghimbeu, C Vaulot, M Jeguirim, Energies 2017, 10, 1321 DOI : 10.3390/en10091321  C. Ducrot-Boisgontier, J. Parmentier, A. Faour, J. Patarin, G.D. Pirngruber, Energy Fuels. 2010, 24, 3595–3602 DOI : 10.1021/ef100011q  C. Matei Ghimbeu, R. Gadiou, J. Dentzer , D. Schwartz, C. Vix-Guterl, Langmuir 2010, 26, 18824–18833 DOI : 10.1021/la103405j

 

Development of hybrid carbon materials (C/M and C/MXn, X=C, N, O, S) via the confinement of metal- based nanoparticles (NPs) in carbon

C. Matei Ghimbeu, J. Parmentier, J.-M. Le Meins, C Vaulot, L Delmotte, C. Vix-Guterl

The addition of a second phase to the carbon framework enabled the introduction of new functionalities and therefore an extension of their application fields or an improvement of their performances. Hybrid materials, combining a carbon matrix (porous or not) and metal (M)-based nanoparticles (NPs) were developed. Depending on the synthesis conditions it is possible to control the carbon characteristics (mesoporosity, surface functionalities, structure…) but also those of NPs, such as :

  • Chemical nature (metal (Pd, Co), alloys (PdxM1-x), metal oxides and non-oxides (SnO2, GeO2 ,TiO2, CrN, WC, WS, LiFePO4)
  • Location (in the pores, in the wall or on the external surface of carbon)
  • Size and dispersion

The CHM team has most notably developed the “one-pot” soft-template approach with the in situ formation of NPs during the carbonization of a mixture of carbon precursor/surfactant/metallic salt. These NPs, confined in carbon matrix and/or in carbon mesoporosity, appear accessible to fluids/electrolytes via the opened porosity. This confinement leads to different behaviour and performances of the materials compared to those obtained by classical infiltration of NPs into the carbon matrix.

 

Reprinted with permission from [Controlled synthesis of NiCo nanoalloys embedded in ordered porous carbon by a novel soft-template strategy C. Matei Ghimbeu, J.-M. Le Meins, C. Z., L.Vidal, G. Schrodj, M. Latroche, C. Vix-Guterl; Carbon 2014 67 260-272] © 2016 Elsevier B.V. DOI : 10.1016/j.carbon.2013.09.089  and from [ One-pot laser-assisted synthesis of porous carbon with embedded magnetic cobalt nanoparticles  C.Matei Ghimbeu,   M. Sopronyi,  F.Sima,  L.Delmotte,  C. Vaulot,  C. Zlotea,  V. Paul-Boncour and  J.-M. Le Meins   Nanoscale  2015 7 10111] © 2015 RSC publishing    DOI :10.1039/C5NR01687H

Publications

C Matei Ghimbeu, M Sopronyi, F Sima, L Delmotte, C Vaulot, C Zlotea, V Paul-Boncour, J-M Le Meins, Nanoscale 2015, 7, 10111 DOI : 10.1039/C5NR01687H  A Martínez de Yuso, Y Oumellal, C Zlotea, L. Vidal, C Matei Ghimbeu, Nanostructures & Nano-Objects, 2017, 9, 1-12 DOI : 10.1016/j.nanoso.2016.11.001     C Peter, A Derible, J-M Becht, J Kiener ; CL Drian, J Parmentier, V Fierro, M Girleanu, O Ersen. J. Mater. Chem. A 2015 3, 12297-12306, DOI ; 10.1039/C4TA06478J

Nanoparticles (NPs) confinement in carbon for gas and energy storage applications

 C. Matei Ghimbeu, J-M Le Meins, J. Parmentier,  L. Vidal, C. Vix-Guterl

Hybrid carbon materials present supplementary functionalities due to the presence of nanoparticles (NPs) which act as an active phase for electrochemical, catalytic, magnetic or absorption applications. Interestingly, these biphasic materials exhibit specific behaviours due to the in situ growth of the NPs and specifically derived structure (good dispersion of NPs in the carbon walls or pores, crystalline growth directed by confinement, accessibility of NPs). The objective is to understand the synergy observed for these nanocomposites carbon/NPs to improve performances in applications such as hydrogen storage (metallic hydride formation) or electrochemical energy storage (Li and Na batteries, supercapacitors).

 

NPs size effects on the kinetic and thermodynamics of the thermal evolution of  metal hydride NPs (MgH2) confined in a microporous carbon matrix. The release temperature of hydrogen from MgH2 is significantly decreased for NPs confined compared to bulk MgH2 (~ 200°C).

 

Reprinted with permission from [Ultrasmall MgH2 Nanoparticles Embedded in an Ordered Microporous Carbon Exhibiting Rapid Hydrogen Sorption Kinetics, C Zlotea, Y Oumellal, S-J Hwang, C Matei Ghimbeu, PE de Jongh, M Latroche,  J. Phys. Chem. C, 2015, 119 (32), pp 18091–18098, DOI: 10.1021/acs.jpcc.5b05754] Copyright © 2015, American Chemical Society.

Positive effects of the confinement of SnO2 NPs in the mesoporosity of carbon-based electrodes on the cyclability in Li-ion batteries. The confinement limits nanoparticles growth during charge/discharge cycling and improves the stability of the electrochemical capacity of the material with time.

 

Reprinted with permission from [Confined Ultrasmall SnO2 Particles in Micro/Mesoporous Carbon as an Extremely Long Cycle-Life Anode Material for Li-Ion Batteries; A. Jahel, C. Matei Ghimbeu, L. Monconduit, C. Vix-Guterl Advanced Energy Materials 2014 4  1400025] © 2014 John Wiley and Sons   DOI : 10.1002/aenm.201400025

Publications

A. Jahel, C. Matei Ghimbeu, A.  Darwiche, L. Vidal, S. Hajjar-Garreau, C. Vix-Guterl, and L. Monconduit,  J Mater Chem A 2015,  3, 11960 DOI : 10.1039/C5TA01963J   C. Zlotea, C. Matei Ghimbeu, Y. Oumellal, J.C. Crivello, C. Vix-Guterl, M. Latroche Nanoscale 2015, 7, 15469 DOI : 0.1039/c5nr03143e

Specific facilities

Temperature-programmed desorption coupled with mass spectroscopy (TPD-MS)

Qualitative and quantitative analysis of desorbed molecules

Measurement of active sites content

Equipment developed by the CMH team

 

Temperature-programmed desorption coupled with mass spectroscopy (TPD-MS) with a cryogenic trap

Analysis of desorbed molecules using a cryogenic trap which allows separating and isolating gases

Equipment developed by the CMH team

Temperature-programmed desorption coupled with mass spectroscopy (TPD-MS) high temperature

Study of the surface functions stable at high temperature (>900°)

Equipment develop by the CMH team

Furnaces used for thermal treatments under gas flow

Carbonizations – Oxidations – Reductions – Activations – Nitridations – CVD (Chemical Vapor Deposition)

The furnaces and the computer program controlling the gas flows were developed by the CMH team

High temperature furnace (<1600°C) under gaz flow

Device model : Vecstar – Furnace with an electrical chamber

Very high temperature furnace (<2000°C)

Under gas flow or under vacuum coupled with TGA

Device model : Setaram – Four TG96

Microwave reactor

Open or closed vessel for material quick synthesis under pressure

Device model : CEM – Discover SP

Disk mill under controlled atmosphere

Materials milling and activations

Device model : Retsch – RS200

Ball miller under controlled atmosphere

Materials milling and activations – Mecanosynthesis

Device model : Fritsch – Pulverisette 6

Glove box

Materials storage and preparation under inert atmosphere

Device model : Jacomex – GPT2

Temperature controlled gas and vapor adsorption manometer

Measurement of gas/vapor adsorption capacity

Study of the interactions material-gas/vapor

Device model : Micromeritics – 3Flex

Gas pycnometer

Powder density measurement

Device model : Micromeritics – Accupyc 1340

Galvanostat-Potentiostat with a quartz balance

Cyclic voltametry – Galvanostatic cycling – Impedance Spectroscopy

Measurement of loss/gain of weight during electrochemical analysis

Device model : Bio Logic Science Instruments – SP200

Main collaborators

Institut de Chimie et des Matériaux de Paris Est (France)

Université de Strasbourg (France)

CIRIMAT  (France)

Collège de France (France)

Institut Charles Gerhart (France)

Institut Jean-Lamour (France)

Université Blaise Pascal (France)

Ecole des Mines d’Albi, France

ENS Paris (France)

MIT (Boston, USA)

Instituto Nacional del Carbon (Spain)

Université de Monastir et Ecole Nationale des Ingénieurs de Gabes (Tunisia)

National Institute for Laser (Romania)

Université d’Ostrava (Czech Republic)

Poznan University of Technology (Poland)

University of Tokyo (Japan)

SAFRAN

ONET

IS2M

Bâtiment CNRS
15, rue Jean Starcky - BP 2488
68057 Mulhouse cedex

Bâtiment IRJBD
3 bis, rue Alfred Werner
68093 Mulhouse cedex

tel: (+33)3 89 60 87 00
fax: (+33)3 89 60 87 99

Réseaux sociaux

 

  

IS2M

Bâtiment CNRS
15, rue Jean Starcky - BP 2488
68057 Mulhouse cedex

Bâtiment IRJBD
3 bis, rue Alfred Werner
68093 Mulhouse cedex

tel: (+33)3 89 60 87 00
fax: (+33)3 89 60 87 99

Réseaux sociaux

 

  

IS2M

Bâtiment CNRS
15, rue Jean Starcky - BP 2488
68057 Mulhouse cedex

Bâtiment IRJBD
3 bis, rue Alfred Werner
68093 Mulhouse cedex

tel: (+33)3 89 60 87 00
fax: (+33)3 89 60 87 99

Réseaux sociaux