Electrochemical and ab initio investigations to design a new phenothiazine based organic redox polymeric material for metal-ion battery cathodes
| Autor: | Thibault Godet-Bar, J.-C. Leprêtre, Alain Deronzier, Alain Pasturel, O. Le Bacq, Jean-Yves Sanchez |
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| Přispěvatelé: | Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI ), Institut de Chimie du CNRS (INC)-Institut National Polytechnique de Grenoble (INPG)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Université Joseph Fourier - Grenoble 1 (UJF)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Science et Ingénierie des Matériaux et Procédés (SIMaP), Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut de Chimie du CNRS (INC)-Institut National Polytechnique de Grenoble (INPG), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE), Département de Chimie Moléculaire (DCM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Joseph Fourier - Grenoble 1 (UJF) |
| Rok vydání: | 2015 |
| Předmět: |
chemistry.chemical_classification
Ab initio Substituent General Physics and Astronomy chemistry.chemical_element [CHIM.MATE]Chemical Sciences/Material chemistry Electrochemistry 7. Clean energy Combinatorial chemistry chemistry.chemical_compound chemistry Ab initio quantum chemistry methods Phenothiazine [CHIM]Chemical Sciences Organic chemistry Moiety Lithium Physical and Theoretical Chemistry Alkyl |
| Zdroj: | Physical Chemistry Chemical Physics Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2015, 17 (38), pp.25283-25296. ⟨10.1039/c5cp01495f⟩ Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2015, 17 (38), pp.25283-25296. ⟨10.1039/C5CP01495F⟩ |
| ISSN: | 1463-9084 1463-9076 |
| DOI: | 10.1039/c5cp01495f |
| Popis: | International audience; Different N-substituted phenothiazines have been synthesized and their electrochemical behavior has been investigated in CH3CN in order to design the best polyphenothiazine based cathodic material candidate for lithium batteries. These compounds exhibit two successive reversible one-electron oxidation processes. Ab initio calculations demonstrate that the potential of the first process is a result of both the hybridization effects between the substituent and the phenothiazine unit as well as the change of conformation of the phenothiazine heterocycle during the oxidation process. More specifically, we show that an asymmetric molecular orbital spreading throughout an external cycle of the phenothiazine unit and the alkyl fragment is formed only if the alkyl fragment is long enough (from the methyl moiety onwards) and is at the origin of the bent conformation for N-substituted phenothiazines during oxidation. Electrochemical investigations supported by ab initio calculations allow the selection of a phenothiazinyl unit which is then polymerized by a Suzuki coupling strategy to avoid the common solubilization issue in carbonate-based liquid electrolytes of lithium cells. The first electrochemical measurements performed show that phenothiazine derivatives pave the way for a promising family of redox polymers intended to be used as organic positives for lithium batteries. |
| Databáze: | OpenAIRE |
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