LG2A

Laboratoire de Glycochimie, des Antimicrobiens
et des Agroressources UMR 7378 CNRS

UMR 7378 CNRS

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  • Tutelle du CNRS
  • Tutelle UPJV

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Franck DOLHEM

Maître de Conférences

Mail :

Tel : 03 22 82 79 39

Fax : 03 22 82 75 60

Axe de recherche : Chimie pour le Développement Durable

Description des travaux de recherche


Nos travaux de recherche ont pour base commune l’utilisation de ressources renouvelables pour la préparation de nouveaux composés et de nouveaux matériaux.

Notre principal axe de recherche consiste en la synthèse et l’étude électrochimique de matériaux organiques capables de remplacer les électrodes inorganiques  dans les batteries Li-Ion. Actuellement les batteries Li-Ion commerciales ont des électrodes basées sur des matériaux d’insertion non renouvelables. Les avantages de notre démarche sont un cout intéressant, une démarche éco-compatible en réduisant l’empreinte écologique du matériau d’électrode. Ces recherches sont menées en partenariat avec l’UMR 6007 d’Amiens, et en particulier P. Poizot.

Mots clés : N.C.

Sélection de publications


Tuning the Chemistry of Organonitrogen Compounds for Promoting All-Organic Anionic Rechargeable Batteries
Jouhara, A.; Quarez, E.; Dolhem, F.; Armand, M.; Dupré, N.; Poizot, P.
Angewandte Chemie International Edition 2019, 0.
Abstract The ever-increasing demand for rechargeable batteries induces significant pressure on the worldwide metal supply, depleting resources and increasing costs and environmental concerns. In this context, developing the chemistry of anion-inserting electrode organic materials could promote the fabrication of molecular (metal-free) rechargeable batteries. However, few examples have been reported because little effort has been made to develop such anionic-ion batteries. Here we show the design of two anionic host electrode materials based on the N-substituted salts of azaaromatics (zwitterions). A combination of NMR, EDS, FTIR spectroscopies coupled with thermal analyses and single-crystal XRD allowed a thorough structural and chemical characterization of the compounds. Thanks to a reversible electrochemical activity located at an average potential of 2.2 V vs. Li+/Li, the coupling with dilithium 2,5-(dianilino)terephthalate (Li2DAnT) as the positive electrode enabled the fabrication of the first all-organic anionic rechargeable batteries based on crystallized host electrode materials capable of delivering a specific capacity of ≈27 mAh/gelectrodes with a stable cycling over dozens of cycles (≈24 Wh/kgelectrodes).
https://dx.doi.org/10.1002/anie.201908475


Raising the redox potential in carboxyphenolate-based positive organic materials via cation substitution
Jouhara, A.; Dupre, N.; Gaillot, A. C.; Guyomard, D.; Dolhem, F.; Poizot, P.
Nat Commun 2018, 9, 4401.
Meeting the ever-growing demand for electrical storage devices requires both superior and "greener" battery technologies. Nearly 40 years after the discovery of conductive polymers, long cycling stability in lithium organic batteries has now been achieved. However, the synthesis of high-voltage lithiated organic cathode materials is rather challenging, so very few examples of all-organic lithium-ion cells currently exist. Herein, we present an inventive chemical approach leading to a significant increase of the redox potential of lithiated organic electrode materials. This is achieved by tuning the electronic effects in the redox-active organic skeleton thanks to the permanent presence of a spectator cation in the host structure exhibiting a high ionic potential (or electronegativity). Thus, substituting magnesium (2,5-dilithium-oxy)-terephthalate for lithium (2,5-dilithium-oxy)-terephthalate enables a voltage gain of nearly +800 mV. This compound being also able to act as negative electrode via the carboxylate functional groups, an all-organic symmetric lithium-ion cell exhibiting an output voltage of 2.5 V is demonstrated.
http://dx.doi.org/10.1038/s41467-018-06708-x


An air-stable lithiated cathode material based on a 1,4-benzenedisulfonate backbone for organic Li-ion batteries
Lakraychi, A. E.; Deunf, E.; Fahsi, K.; Jimenez, P.; Bonnet, J. P.; Djedaini-Pilard, F.; Bécuwe, M.; Poizot, P.; Dolhem, F.
Journal of Materials Chemistry A 2018.
To meet current market demands as well as emerging environmental concerns there is a need to develop less polluting battery technologies. Organic electrode materials could offer the possibility of preparing electrode materials from naturally more abundant elements and eco-friendly processes coupled with simplified recycling management. However, the potential use of organic electrode materials for energy storage is still challenging and a lot of developments remain to be achieved. For instance, promoting high-energy Li-ion organic batteries inevitably requires the development of lithiated organic electrode materials which are able to be charged (delithiated) at a high enough potential (>3 V vs. Li+/Li0) – a challenging point rarely discussed in the literature. Here, we evaluate tetralithium 2,5-dihydroxy-1,4-benzenedisulfonate as an air-stable lithiated cathode material for the first time and its reversible Li+ electrochemical extraction. Quite interestingly, in comparison with the dicarboxylate counterpart, it was observed that the theoretical two-electron reaction is readily reached with this organic structure and at an average operating potential of 650 mV higher.
http://dx.doi.org/10.1039/c8ta07097k


Carboxylic and sulfonic N-substituted naphthalene diimide salts as highly stable non-polymeric organic electrodes for lithium batteries
Lakraychi, A. E.; Fahsi, K.; Aymard, L.; Poizot, P.; Dolhem, F.; Bonnet, J. P.
Electrochem. Commun. 2017, 76, 47-50.
Two N-substituted naphthalene tetracarboxylic diimide (NTCDI) ionic compounds, carboxylic and sulfonic sodium salts, were prepared and used as positive electrode active materials in lithium-half cells. The aim of this investigation was to assess the solubility-suppressing effect of two different negatively charged substituent groups on a redox-active organic backbone using a carbonate-based liquid electrolyte. NTCDI derivatives were obtained in high yields from reaction of naphthalene tetracarboxylic dianhydride with neutralized glycine or with neutralized taurine. They were mixed with carbon black and cycled in galvanostatic mode against lithium metal using 1 M LiPF6 EC/DMC liquid electrolyte. These two NTCDI derivatives exhibit a quite stable electrochemical activity upon cycling at an average potential of 2.3 V vs. Li+/Li0 giving rise to specific capacity values of 147 mAh·g− 1 and 113 mAh·g− 1 for the dicarboxylate and the disulfonate derivative, respectively. This study clearly supports the useful effect of such grafted permanent charges as a general rule on the electrochemical stability of crystallized organic materials based on the assembly of small redox-active units.
http://dx.doi.org/10.1016/j.elecom.2017.01.019


Decreasing redox voltage of terephthalate-based electrode material for Li-ion battery using substituent effect
Lakraychi, A. E.; Dolhem, F.; Djedaïni-Pilard, F.; Thiam, A.; Frayret, C.; Becuwe, M.
J. Power Sources 2017, 359, 198-204.
The preparation and assessment versus lithium of a functionalized terephthalate-based as a potential new negative electrode material for Li-ion battery is presented. Inspired from molecular modelling, a decrease in redox potential is achieved through the symmetrical adjunction of electron-donating fragments (–CH3) on the aromatic ring. While the electrochemical activity of this organic material was maximized when used as nanocomposite and without any binder, the potential is furthermore lowered by 110 mV upon functionalization, consistently with predicted value gained from DFT calculations.
http://dx.doi.org/https://doi.org/10.1016/j.jpowsour.2017.05.046


Reversible anion intercalation in a layered aromatic amine: a high-voltage host structure for organic batteries
Deunf, E.; Moreau, P.; Quarez, E.; Guyomard, D.; Dolhem, F.; Poizot, P.
J. Mater. Chem. A 2016, 4, 6131-6139.
Cation insertion reactions in inorg. host frameworks are well-established phenomena. Over the last 40 years, a myriad of examples have been documented, which have given rise to key applications such as for electrochem. storage devices. By contrast, materials able to reversibly insert anions into their host lattice are rare, and consist essentially of graphite intercalation compds. (GICs), thus limiting their potential use. Org. materials, conversely, if properly designed, could pave the way for future developments in anionic insertion electrochem., by virtue of the rational incorporation of p-type redox-active org. moieties. Here, we report the discovery of a p-type org. host lattice based on a simple crystd. arom. diamine. The reversible anion insertion process relies on the electrochem. activity of neutral secondary amino groups incorporated into a robust terephthalate backbone. XRD, TEM and EELS studies reveal the attainment of a unique lamellar structure conducive to the oxidative insertion of anions (including the bulky TFSI-). In a dual-ion cell configuration using lithium as the neg. electrode, this org. structure can react reversibly at high operating potential (〈E〉 ≈ 3.22 V vs. Li+/Li) with good cycling performance even without carbon addn., hence generating further avenues for the development of org. batteries and more generally, the field of intercalation chem.
http://dx.doi.org/10.1039/C6TA02356H


Chapter 6 - Perspectives in Lithium Batteries A2 - Chagnes, Alexandre
Poizot, P.; Dolhem, F.; Gaubicher, J.; Renault, S.
Lithium Process Chemistry 2015, 191-232.
Abstract Li-ion batteries still fall short of fulfilling the ever-increasing storage needs while keeping their environmental footprint as low as possible. In this chapter, without being exhaustive we tackle what next promising Li-based battery technologies could be; through the implementation of alternative (electro)chemistries including the use of more abundant components and/or less-polluting processing solutions. Li-chalcogen (O2 and S) batteries are presented herein as quite promising systems especially for the market of electrically powered vehicles thanks to particularly high (expected) energy density values. Li-aqueous batteries, beyond the obvious environmental benefit in using water-based electrolytes, offer also some attractive perspectives to promote low-cost electrical storage solutions, potentially interesting for stationary applications. Finally, electroactive organic compounds could play an important role in the forthcoming battery technologies, since they exhibit several assets such as the possibility of being prepared from renewable resources and eco-friendly processes coupled with a simplified recycling management.
http://dx.doi.org/10.1016/B978-0-12-801417-2.00006-2


A rechargeable lithium/quinone battery using a commercial polymer electrolyte
Lecuyer, M.; Gaubicher, J.; Barres, A.-L.; Dolhem, F.; Deschamps, M.; Guyomard, D.; Poizot, P.
Electrochem. Commun. 2015, 55, 22-25.
The present study reports superior electrochem. performance with capacity doubled for org. pos. electrodes based on a small redox-active mol. when using the Lithium Metal Polymer (LMP) technol. Particularly, the simple use of the regular solid polymer electrolyte currently employed in com. LMP cells allows obtaining for the first time an efficient two-electron cycling of tetramethoxy-p-benzoquinone with high-rate capability at temps. as high as 100 °C. With no optimization, the restored capacity represents 80% of the theor. value (190 mAh/g) after 20 cycles operated at a C rate. On the contrary, when cycled in conventional carbonate-based electrolytes, this quinone compd. exhibits quite poor electrochem. features such as a very limited depth of discharge (∼ 50% of the theor. capacity in the first cycle) followed by rapid capacity decay. After cycling, preliminary post-mortem characterizations did not evidence any obvious degrdn. in the cell. Although the adverse effect of the diffusion of the active material is not fully inhibited, the coulombic efficiency is close to 100% while the Li/electrolyte interface appears stable.
http://dx.doi.org/10.1016/j.elecom.2015.03.010


Pyrolysis reaction of squaric acid: A one-step method for producing expanded foam of mesoporous carbon
Leclere, M.; Lejeune, M.; Dupont, L.; Barres, A.-L.; Renault, S.; Dolhem, F.; Poizot, P.
Mater. Lett. 2014, 137, 233-236.
A template-free approach is described for the synthesis of expanded foams of mesoporous carbon exhibiting high surface areas ranging from 550 to 1100 m2.g-1. The procedure is based on the exceptional carbonization reaction that occurs with squaric acid (H2C4O4), a strained four-membered carbocycle belonging to the oxocarbon acids. Indeed the pyrolysis reaction proceeds just above 300 °C through an amazing one-step and sharp exothermic phenomenon coupled with a wt. loss of 90%, thereby promoting a porous structure. This massive gas release behaves also as a "fluid" template during the carbon prodn., which explains the formation of expanded foams. This particular thermal behavior seems related to the phase transition that occurs in H2C4O4 crystals at Tc=121 °C. Below Tc the planar squaric acid mols. exhibit a fully ordered structure in a monoclinic system whereas for T>Tc the structure undergoes a disordered tetragonal structure where all C-O bonds of squaric acid become statistically equiv. in a perfect square, making a discrete thermal decompn. reaction possible.
http://dx.doi.org/10.1016/j.matlet.2014.08.148


Voltage Gain in Lithiated Enolate-Based Organic Cathode Materials by Isomeric Effect
Gottis, S.; Barres, A.-L.; Dolhem, F.; Poizot, P.
ACS Appl. Mater. Interfaces 2014, 6, 10870-10876.
Li-ion batteries (LIBs) appear nowadays as flagship technol. able to power an increasing range of applications starting from small portable electronic devices to advanced elec. vehicles. Over the past 2 decades, the discoveries of new metal-based host structures, together with substantial tech. developments, have considerably improved their electrochem. performance, particularly in terms of energy d. To further promote electrochem. storage systems while limiting the demand on metal-based raw materials, a possible parallel research to inorg.-based batteries consists in developing efficient and low-polluting org. electrode materials. For a long time, this class of redox-active materials was disregarded mainly due to stability issues but, in recent years, progress was made demonstrating that orgs. undeniably exhibit considerable assets. From the ongoing research aiming at elaborating lithiated org. cathode materials, the authors report herein on a chem. approach that takes advantage of the pos. potential shift when switching from para to ortho-position in the dihydroxyterephthaloyl system. In practice, dilithium (2,3-dilithium-oxy)-terephthalate compd. (Li4C8H2O6) was 1st produced through an eco-friendly synthesis scheme based on CO2 sequestration, then characterized, and finally tested electrochem. as lithiated cathode material vs. Li. This new org. salt shows promising electrochem. performance, notably fast kinetics, good cycling stability and above all an av. operating potential of 2.85 V vs. Li+/Li0 (i.e., +300 mV in comparison with its para-regioisomer), verifying the relevance of the followed strategy.
http://dx.doi.org/10.1021/am405470p