Covalent vs. non-covalent redox functionalization of C-LiFePO4 based electrodes

During high rate utilization of porous Li battery, Li+ refuelling from the electrolyte limits the discharge kinetics of positive electrodes. In the case of thick electrodes a strategy to buffer the resulting sharp drop of Li+ concentration gradient would be to functionalize the electrode with anionic based redox molecules (RMR) that would be therefore able to relay intercalation process. The occurrence of these RMR in the electrode should not however, induce adverse effect on Li intercalation processes. In this respect, this work studies the effect of functionalizing LFPC based electrodes by either covalent or non-covalent chemistry, on Li intercalation kinetics. To do so, model molecules containing a nitro group were introduced at the surface of both carbon conducting additives and active material (C-LiFePO4). It is shown that presumably due to formation of sp(3) defects, covalent anchoring using diazonium chemistry inhibits the intercalation kinetics in C-FePO4. On the contrary, if molecules such as pyrene derivatives are immobilized by pi-staking interactions, Li intercalation is not impeded. Therefore non-covalent functionalization of pyrene based RMR appears as a promising route to relay Li intercalation reaction during high power demand. The framework for future development of this strategy is discussed. (C) 2013 Elsevier B.V. All rights reserved

Interest of Redox Molecular Grafting for Energy Storage Applications

International audienc

New Concept to Boost Energy and Power Peformance of Practical Electrochemical Devices

International audienc

Optimization of Electronic Transport at the Nanoscale through the Formation of Molecular Junctions within Composite Electrodes for Li-battery

National audienc

In situ redox functionalization of composite electrodes for high power-high energy electrochemical storage systems via a non-covalent approach

The growing demand for new global resources of clean and sustainable energy emerges as the greatest challenge in today\u27s society. For numerous applications such as hybrid vehicles, electrochemical storage systems simultaneously require high energy and high power. For this reason, intensive researches focus on proposing alternative devices to conventional Li battery and supercapacitors. Here, we report a proof of concept based on non-covalent redox functionalization of composite electrodes that may occur either during the calendar life or during the device functioning. The active material, a multi-redox pyrene derivative, is initially contained in the electrolyte. No additional benchmarking step is therefore required, and it can, in principle, be readily applied to any type of composite electrode (supercapacitors, battery, semi-solid flow cell etc.). Accordingly, a practical carbon fiber electrode that is 10 mg cm(-2) loaded can deliver up to 130 kW kg(electrode)(-1) and 130 Wh kg(electrode)(-1) with negligible capacity loss over the first 60 000 charge/discharge cycles

New concept and electrochemistry of in situ non-covalent immobilization of redox molecules for energy storage applications

International audienc

Lithium n-Doped Polyaniline as a High-Performance Electroactive Material for Rechargeable Batteries

The discovery of conducting lithium-doped polyaniline with reversible redox chemistry allows simultaneous unprecedented capacity and stability in a non-aqueous Li battery. This compound (lithium emeraldinate) was synthesized by lithium–proton exchange on the emeraldine base in an anhydrous lithium-based electrolyte. A combination of UV/Vis-NIR spectroelectrochemistry, XPS, FTIR, and EQCM characterization allowed a unified description of the chemical and electrochemical behavior, showing facile charge delocalization of the doped states and the reversibility of the redox processes in this form of polyaniline. From a practical point of view, lithium emeraldinate behaves as a high-capacity organic active material (230 mAh g−1) that enables preparation of relatively thick composite electrodes with a low amount of carbon additives and high energy density (460 Wh kg−1). Concomitantly, at 1C rate, 400 cycles were achieved without significant capacity loss, while the coulombic efficiency is greater than 99 %