Poly(ionic liquid)s (PILs) have attracted a considerable attention as innovative single-ion solid... more Poly(ionic liquid)s (PILs) have attracted a considerable attention as innovative single-ion solid polyelectrolytes (SPEs) in substitution to the more conventional electrolytes for a variety of electrochemical devices. Imidazolium-based PILs are amongst the most investigated, because they are easy to synthesize and some of them have shown a good combination between high ionic conductivity, wide chemical and electrochemical stability, and good mechanical properties. Herein, we report the precise synthesis, characterization, and use as single-ion SPE of a novel double PIL-based amphiphilic diblock copolymer (BCP), i.e. where all monomer units are of N-vinyl-imidazolium-type, with triethylene glycol pendant groups in the first block, and a statistical distribution of N-vinyl-3-ethyl- and N-vinyl-3-perfluorooctyl-imidazolium bromides in the second block. BCP synthesis is achieved directly in water by a one-pot process, following the principle of the cobalt-mediated radical polymerization-induced self-assembly (CMR-PISA). A subsequent anion exchange reaction substituting bis(trifluoromethylsulfonyl)imide (Tf2N-) for bromide (Br-) counter-anions leads to the targeted PIL BCPs with two different lengths of the first block. They demonstrate ionic conductivity σDC = 1-3 10-7 S cm-1, as determined by broadband dielectric spectroscopy at 30 °C (under anhydrous conditions), and form free standing films with mechanical properties suited for SPE applications with Young’s modulus of 3.8 MPa and elongation at break of 250 % as determined by stress/strain experiments
Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in man... more Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in many fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecules, and provide novel attractive functions. Recently, the precision design of novel PILs by controlled/living polymerization (CLP) techniques was intensively searched for developing emerging applications. This talk will first discuss recent routes for the precision synthesis of all vinyl-imidazolium based (co)polymers in water or in organic media under non-demanding experimental conditions. We will then describe the preparation of innovative redox and surface active PILs, and show the potential of these PILs in battery applications and for multifunctional coatings. More specifically, we will show how macromolecular engineering can be exploited for designing innovative polymer cathodes for ultra-high performance Li storage with unprecedented performances (high capacities and ultra-long life-span over more than 3000 cycles at an extreme current-rate). This innovative and effective molecular design for polymer cathodes opens up new horizons in developing an economical and environmentally benign platform for large-scalable fabrication of high performance batteries
A CO2-sourced self-standing solid electrolyte membrane is prepared and evaluated for room tempera... more A CO2-sourced self-standing solid electrolyte membrane is prepared and evaluated for room temperature operating lithium batteries.
Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by hi... more Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by higher discharge potentials than para-quinones, the latter being extensively used as organic cathode materials for lithium ion batteries (LIBs). Here, this study demonstrates that the rational molecular design of copolymers bearing catechol- and Li+ ion-conducting anionic pendants endow redox-active polymers (RAPs) with ultrarobust electrochemical energy storage features when combined to carbon nanotubes as a flexible, binder-, and metal current collector-free buckypaper electrode. The importance of the structure and functionality of the RAPs on the battery performances in LIBs is discussed. The structure-optimized RAPs can store high-capacities of 360 mA h g-1 at 5C and 320 mA h g-1 at 30C in LIBs. The high ion and electron mobilities within the buckypaper also enable to register 96 mA h g-1 (24% capacity retention) at an extreme C-rate of 600C (6 s for total discharge). Moreover, excellent cyclability is noted with a capacity retention of 98% over 3400 cycles at 30C. The high capacity, superior active-material utilization, ultralong cyclability, and excellent rate performances of RAPs-based electrode clearly rival most of the state-of-the-art Li+ ion organic cathodes, and opens up new horizons for large-scalable fabrication of electrode materials for ultrarobust Li storage.
We describe the construction, characteristics and interaction with proteins of stimuli-responsive... more We describe the construction, characteristics and interaction with proteins of stimuli-responsive nanostructured films prepared by layer-by-layer assembly of PAA-b-PNIPAM and PAH.
In aqueous solutions at room temperature, poly( N-methyl-2-vinyl pyridinium iodide)- block-poly(e... more In aqueous solutions at room temperature, poly( N-methyl-2-vinyl pyridinium iodide)- block-poly(ethylene oxide), P2MVP 38- b-PEO 211 and poly(acrylic acid)- block-poly(isopropyl acrylamide), PAA 55- b-PNIPAAm 88 spontaneously coassemble into micelles, consisting of a mixed P2MVP/PAA polyelectrolyte core and a PEO/PNIPAAm corona. These so-called complex coacervate core micelles (C3Ms), also known as polyion complex (PIC) micelles, block ionomer complexes (BIC), and interpolyelectrolyte complexes (IPEC), respond to changes in solution pH and ionic strength as their micellization is electrostatically driven. Furthermore, the PNIPAAm segments ensure temperature responsiveness as they exhibit lower critical solution temperature (LCST) behavior. Light scattering, two-dimensional 1H NMR nuclear Overhauser effect spectrometry, and cryogenic transmission electron microscopy experiments were carried out to investigate micellar structure and solution behavior at 1 mM NaNO 3, T = 25, and 60 degrees C, that is, below and above the LCST of approximately 32 degrees C. At T = 25 degrees C, C3Ms were observed for 7 < pH < 12 and NaNO 3 concentrations below approximately 105 mM. The PEO and PNIPAAm chains appear to be (randomly) mixed within the micellar corona. At T = 60 degrees C, onion-like complexes are formed, consisting of a PNIPAAm inner core, a mixed P2MVP/PAA complex coacervate shell, and a PEO corona.
Poly(ionic liquid)s (PILs) have attracted a considerable attention as innovative single-ion solid... more Poly(ionic liquid)s (PILs) have attracted a considerable attention as innovative single-ion solid polyelectrolytes (SPEs) in substitution to the more conventional electrolytes for a variety of electrochemical devices. Imidazolium-based PILs are amongst the most investigated, because they are easy to synthesize and some of them have shown a good combination between high ionic conductivity, wide chemical and electrochemical stability, and good mechanical properties. Herein, we report the precise synthesis, characterization, and use as single-ion SPE of a novel double PIL-based amphiphilic diblock copolymer (BCP), i.e. where all monomer units are of N-vinyl-imidazolium-type, with triethylene glycol pendant groups in the first block, and a statistical distribution of N-vinyl-3-ethyl- and N-vinyl-3-perfluorooctyl-imidazolium bromides in the second block. BCP synthesis is achieved directly in water by a one-pot process, following the principle of the cobalt-mediated radical polymerization-induced self-assembly (CMR-PISA). A subsequent anion exchange reaction substituting bis(trifluoromethylsulfonyl)imide (Tf2N-) for bromide (Br-) counter-anions leads to the targeted PIL BCPs with two different lengths of the first block. They demonstrate ionic conductivity σDC = 1-3 10-7 S cm-1, as determined by broadband dielectric spectroscopy at 30 °C (under anhydrous conditions), and form free standing films with mechanical properties suited for SPE applications with Young’s modulus of 3.8 MPa and elongation at break of 250 % as determined by stress/strain experiments
Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in man... more Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in many fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecules, and provide novel attractive functions. Recently, the precision design of novel PILs by controlled/living polymerization (CLP) techniques was intensively searched for developing emerging applications. This talk will first discuss recent routes for the precision synthesis of all vinyl-imidazolium based (co)polymers in water or in organic media under non-demanding experimental conditions. We will then describe the preparation of innovative redox and surface active PILs, and show the potential of these PILs in battery applications and for multifunctional coatings. More specifically, we will show how macromolecular engineering can be exploited for designing innovative polymer cathodes for ultra-high performance Li storage with unprecedented performances (high capacities and ultra-long life-span over more than 3000 cycles at an extreme current-rate). This innovative and effective molecular design for polymer cathodes opens up new horizons in developing an economical and environmentally benign platform for large-scalable fabrication of high performance batteries
A CO2-sourced self-standing solid electrolyte membrane is prepared and evaluated for room tempera... more A CO2-sourced self-standing solid electrolyte membrane is prepared and evaluated for room temperature operating lithium batteries.
Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by hi... more Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by higher discharge potentials than para-quinones, the latter being extensively used as organic cathode materials for lithium ion batteries (LIBs). Here, this study demonstrates that the rational molecular design of copolymers bearing catechol- and Li+ ion-conducting anionic pendants endow redox-active polymers (RAPs) with ultrarobust electrochemical energy storage features when combined to carbon nanotubes as a flexible, binder-, and metal current collector-free buckypaper electrode. The importance of the structure and functionality of the RAPs on the battery performances in LIBs is discussed. The structure-optimized RAPs can store high-capacities of 360 mA h g-1 at 5C and 320 mA h g-1 at 30C in LIBs. The high ion and electron mobilities within the buckypaper also enable to register 96 mA h g-1 (24% capacity retention) at an extreme C-rate of 600C (6 s for total discharge). Moreover, excellent cyclability is noted with a capacity retention of 98% over 3400 cycles at 30C. The high capacity, superior active-material utilization, ultralong cyclability, and excellent rate performances of RAPs-based electrode clearly rival most of the state-of-the-art Li+ ion organic cathodes, and opens up new horizons for large-scalable fabrication of electrode materials for ultrarobust Li storage.
We describe the construction, characteristics and interaction with proteins of stimuli-responsive... more We describe the construction, characteristics and interaction with proteins of stimuli-responsive nanostructured films prepared by layer-by-layer assembly of PAA-b-PNIPAM and PAH.
In aqueous solutions at room temperature, poly( N-methyl-2-vinyl pyridinium iodide)- block-poly(e... more In aqueous solutions at room temperature, poly( N-methyl-2-vinyl pyridinium iodide)- block-poly(ethylene oxide), P2MVP 38- b-PEO 211 and poly(acrylic acid)- block-poly(isopropyl acrylamide), PAA 55- b-PNIPAAm 88 spontaneously coassemble into micelles, consisting of a mixed P2MVP/PAA polyelectrolyte core and a PEO/PNIPAAm corona. These so-called complex coacervate core micelles (C3Ms), also known as polyion complex (PIC) micelles, block ionomer complexes (BIC), and interpolyelectrolyte complexes (IPEC), respond to changes in solution pH and ionic strength as their micellization is electrostatically driven. Furthermore, the PNIPAAm segments ensure temperature responsiveness as they exhibit lower critical solution temperature (LCST) behavior. Light scattering, two-dimensional 1H NMR nuclear Overhauser effect spectrometry, and cryogenic transmission electron microscopy experiments were carried out to investigate micellar structure and solution behavior at 1 mM NaNO 3, T = 25, and 60 degrees C, that is, below and above the LCST of approximately 32 degrees C. At T = 25 degrees C, C3Ms were observed for 7 < pH < 12 and NaNO 3 concentrations below approximately 105 mM. The PEO and PNIPAAm chains appear to be (randomly) mixed within the micellar corona. At T = 60 degrees C, onion-like complexes are formed, consisting of a PNIPAAm inner core, a mixed P2MVP/PAA complex coacervate shell, and a PEO corona.
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Papers by Christine Jérôme