Catalyst-free soft-template synthesis of ordered mesoporous carbon tailored using phloroglucinol/ glyoxylic acid environmentally friendly precursors

International audienceCarbon porous materials with a periodically ordered pore structure, controlled pore size and geometry and high thermal stability are synthesized using self-assembly of environmentally friendly phloroglucinol/ glyoxylic acid precursors with an amphiphilic triblock copolymer template. Glyoxylic acid, a plant-derived compound, is used for the first time as a substituent of carcinogen formaldehyde usually employed in such a synthesis. Thanks to the double functionality, i.e., aldehyde and carboxylic acid, glyoxylic acid plays not only the role of a cross-linker for the formation of the resin but also the role of a catalyst by creation of H-bonding or specific reactions between the precursors. Hence, no extra catalyst such as strong acids (HCl) or bases (NaOH) is any longer required. Carbon films and powders were successfully prepared with high surface areas (up to 800 m2 g−1), high porous volume (up to 1 cm3 g−1), tunable pore size (0.6 nm to 7 nm) and various pore architectures (hexagonal, cubic, and ink-bottle) by tuning the precursor ratio and by applying different manufacturing engineering strategies. Insights on the synthesis mechanism of the phenolic resin and carbon mesostructures were obtained using several analysis techniques, i.e., nuclear magnetic resonance (13C NMR) and FTIR spectroscopy, temperature programmed desorption coupled with mass spectrometry (TPD-MS) and thermo-gravimetric analysis (TGA)

Eco-friendly synthesis of SiO2 nanoparticles confined in hard carbon: A promising material with unexpected mechanism for Li-ion batteries

Times Cited: 3Nita, Cristina Fullenwarth, Julien Monconduit, Laure Le Meins, Jean-Marc Fioux, Philippe Parmentier, Julien Ghimbeu, Camelia MateiGhimbeu, Camelia/N-7855-2015Ghimbeu, Camelia/0000-0003-3600-587731873-3891A fast, simple and environmentally friendly one-pot route to obtain carbon/SiO2 hybrid materials is reported in this work. This consists in simple mixture of carbon and silica precursors, followed by thermal annealing at different temperatures. An interpenetrating hybrid network composed of hard carbon and amorphous SiO2 nanoparticles (2–5 nm) homogeneously distributed was achieved. Increasing the annealing temperature from 600 °C up to 1200 °C, the material porosity and oxygen functional groups are gradually removed, while the amorphous nature of SiO2 is conserved. This allows to diminish the irreversible capacity during the first charge-discharge cycle and to increase the reversible capacity. An excellent cycling capability, with a reversible capacity up to 535 mA h/g at C/5 constant current rate was obtained for C/SiO2 materials used as anodes for Li-ion batteries. An atypical increase of the capacity during the first 50 cycles followed by a stable plateau up to 250 cycles was observed and related to electrolyte wettability limitation through the materials, particularly for those annealed at high temperatures which are more hydrophobic, less porous and the SiO2 nanoparticles less accessible. The SiO2 lithiation mechanism was evaluated by XRD, TEM and XPS post-mortem analyses and revealed the formation of reversible lithium silicate phases

Alkaline hydrogel electrolyte from biosourced chitosan to enhance the rate capability and energy density of carbon-based supercapacitors

International audienceThis paper reports the development of a safe carbon-based supercapacitor, which is based on a green biodegradable hydrogel electrolyte that is prepared from chitosan biopolymer and KOH as the electrolyte source. The impact of electrolyte solution ageing time on electrolyte gel formation is investigated. A critical time of 2 days is necessary to obtain gel electrolytes mechanically exploitable. This is associated with the gel structural modification, as observed by FTIR and 1H/13C NMR. Between 2 and 4 days, the capacitance increases from 76 to 95 F g−1 and remains stable up to 21 days. Good rate handling is achieved (62%) with a capacitance of 59 F g−1 at 10 A g−1. Remarkably, the developed gel exhibits good stability when the cell voltage is increased from 0.8 V to 1.3 V. The voltage window extension allows to obtain for the C–C device, a high energy density (5.1 W h kg−1) at a power density of 32.5 W kg−1, which is almost 3 times higher than that delivered by liquid 2 M KOH at 0.8 V. The gel electrolyte could be used with pseudocapacitive materials, C/Co3O4 and voltage window extension is achieved along with significant increase in energy density from 1.66 to 6.31 W h kg−1. Better capacitance retention is obtained by the chitosan–KOH gel electrolyte than by liquid KOH. Advantageously, the gel electrolyte prevents the electrode degradation and positive current collector from undergoing corrosion

Is There a Ready-Recipe for Hard Carbon-Electrode Engineering to Enhance Na-Ion Battery Performance?

International audienceHard carbon (HC) materials are commonly used as anode materials in Na-ion batteries. In most of the cases, their electrochemical performance is correlated only to their physicochemical properties, and the impact of the electrode additives (binders–conductive agent) and electrolyte is often neglected. In this work, a systematic study is performed to understand the role of electrode/electrolyte engineering on HC initial Coulombic efficiency (iCE), specific capacity, and cycle stability. Four HCs obtained by pyrolysis of several biopolymers, i.e., cellulose (HC-Cell), chitosan (HC-Chs), chitin (HC-Cht), and lignin (HC-Lig), are used. The binder was found to have an important impact on the electrochemical performance, with PVDF resulting in better performance than CMC. The carbon black additive had no significant impact on CMC-based electrochemical performance while it boosted the electrochemical performance of PVDF-based electrodes. For an optimized formulation (PVDF/carbon black), the best HC performance in NaPF6 in 1 EC:DEC was delivered by HC-Cell (83% iCE, 332 mAh g–1 at C/10, and 97% retention). This was attributed to its large graphene interlayer space, high purity, and low surface area. HC-Cht and HC-Chs exhibited similar good electrochemical performance (∼280 mAh g–1) whereas the use of HC-Lig resulted in low iCE and capacity fading overcycling due to the high level of impurities in its structure. This could be overcome by changing the electrolyte salt, by using NaClO4 (76% retention) instead of NaPF6 (52% retention). Based on the obtained results, the electrochemical performance could be correlated with the HC physicochemical properties and binder/conductive additive. It could be demonstrated that careful electrode engineering combined with proper electrolyte selection and tuned HC properties allowed all investigated materials achieving reasonable iCE (up to 83%), high specific capacity (∼280 to 332 mAh g–1), and high-capacity retention (72–97% after 50 cycles)

Is There a Ready Recipe for Hard Carbon Electrode Engineering to Enhance Na-Ion Battery Performance?

International audienceHard carbon (HC) materials are commonly used as anode materials in Na-ion batteries. In most of the cases, their electrochemical performance is correlated only to their physicochemical properties, and the impact of the electrode additives (binders–conductive agent) and electrolyte is often neglected. In this work, a systematic study is performed to understand the role of electrode/electrolyte engineering on HC initial Coulombic efficiency (iCE), specific capacity, and cycle stability. Four HCs obtained by pyrolysis of several biopolymers, i.e., cellulose (HC-Cell), chitosan (HC-Chs), chitin (HC-Cht), and lignin (HC-Lig), are used. The binder was found to have an important impact on the electrochemical performance, with PVDF resulting in better performance than CMC. The carbon black additive had no significant impact on CMC-based electrochemical performance while it boosted the electrochemical performance of PVDF-based electrodes. For an optimized formulation (PVDF/carbon black), the best HC performance in NaPF6 in 1 EC:DEC was delivered by HC-Cell (83% iCE, 332 mAh g–1 at C/10, and 97% retention). This was attributed to its large graphene interlayer space, high purity, and low surface area. HC-Cht and HC-Chs exhibited similar good electrochemical performance (∼280 mAh g–1) whereas the use of HC-Lig resulted in low iCE and capacity fading overcycling due to the high level of impurities in its structure. This could be overcome by changing the electrolyte salt, by using NaClO4 (76% retention) instead of NaPF6 (52% retention). Based on the obtained results, the electrochemical performance could be correlated with the HC physicochemical properties and binder/conductive additive. It could be demonstrated that careful electrode engineering combined with proper electrolyte selection and tuned HC properties allowed all investigated materials achieving reasonable iCE (up to 83%), high specific capacity (∼280 to 332 mAh g–1), and high-capacity retention (72–97% after 50 cycles)

Synthesis and stability of Pd–Rh nanoalloys with fully tunable particle size and composition

International audienc

Is There a Ready-Recipe for Hard Carbon-Electrode Engineering to Enhance Na-Ion Battery Performance?

International audienceHard carbon (HC) materials are commonly used as anode materials in Na-ion batteries. In most of the cases, their electrochemical performance is correlated only to their physicochemical properties, and the impact of the electrode additives (binders–conductive agent) and electrolyte is often neglected. In this work, a systematic study is performed to understand the role of electrode/electrolyte engineering on HC initial Coulombic efficiency (iCE), specific capacity, and cycle stability. Four HCs obtained by pyrolysis of several biopolymers, i.e., cellulose (HC-Cell), chitosan (HC-Chs), chitin (HC-Cht), and lignin (HC-Lig), are used. The binder was found to have an important impact on the electrochemical performance, with PVDF resulting in better performance than CMC. The carbon black additive had no significant impact on CMC-based electrochemical performance while it boosted the electrochemical performance of PVDF-based electrodes. For an optimized formulation (PVDF/carbon black), the best HC performance in NaPF6 in 1 EC:DEC was delivered by HC-Cell (83% iCE, 332 mAh g–1 at C/10, and 97% retention). This was attributed to its large graphene interlayer space, high purity, and low surface area. HC-Cht and HC-Chs exhibited similar good electrochemical performance (∼280 mAh g–1) whereas the use of HC-Lig resulted in low iCE and capacity fading overcycling due to the high level of impurities in its structure. This could be overcome by changing the electrolyte salt, by using NaClO4 (76% retention) instead of NaPF6 (52% retention). Based on the obtained results, the electrochemical performance could be correlated with the HC physicochemical properties and binder/conductive additive. It could be demonstrated that careful electrode engineering combined with proper electrolyte selection and tuned HC properties allowed all investigated materials achieving reasonable iCE (up to 83%), high specific capacity (∼280 to 332 mAh g–1), and high-capacity retention (72–97% after 50 cycles)

Is There a Ready-Recipe for Hard Carbon-Electrode Engineering to Enhance Na-Ion Battery Performance?

International audienceHard carbon (HC) materials are commonly used as anode materials in Na-ion batteries. In most of the cases, their electrochemical performance is correlated only to their physicochemical properties, and the impact of the electrode additives (binders–conductive agent) and electrolyte is often neglected. In this work, a systematic study is performed to understand the role of electrode/electrolyte engineering on HC initial Coulombic efficiency (iCE), specific capacity, and cycle stability. Four HCs obtained by pyrolysis of several biopolymers, i.e., cellulose (HC-Cell), chitosan (HC-Chs), chitin (HC-Cht), and lignin (HC-Lig), are used. The binder was found to have an important impact on the electrochemical performance, with PVDF resulting in better performance than CMC. The carbon black additive had no significant impact on CMC-based electrochemical performance while it boosted the electrochemical performance of PVDF-based electrodes. For an optimized formulation (PVDF/carbon black), the best HC performance in NaPF6 in 1 EC:DEC was delivered by HC-Cell (83% iCE, 332 mAh g–1 at C/10, and 97% retention). This was attributed to its large graphene interlayer space, high purity, and low surface area. HC-Cht and HC-Chs exhibited similar good electrochemical performance (∼280 mAh g–1) whereas the use of HC-Lig resulted in low iCE and capacity fading overcycling due to the high level of impurities in its structure. This could be overcome by changing the electrolyte salt, by using NaClO4 (76% retention) instead of NaPF6 (52% retention). Based on the obtained results, the electrochemical performance could be correlated with the HC physicochemical properties and binder/conductive additive. It could be demonstrated that careful electrode engineering combined with proper electrolyte selection and tuned HC properties allowed all investigated materials achieving reasonable iCE (up to 83%), high specific capacity (∼280 to 332 mAh g–1), and high-capacity retention (72–97% after 50 cycles)

Co3O4 Nanoparticles Embedded in Mesoporous Carbon for Supercapacitor Applications

International audienceMetal oxides are of great interest for supercapacitor application; however, they suffer from capacity fading during cycling and limited cycle life. In this work, a one-pot bottom-up approach is proposed to design cobalt oxide (Co 3 O 4) nanoparticles confined in a mesoporous carbon. This involved the coassembly of a phenolic resin, a surfactant, and a cobalt salt followed by a high temperature pyrolysis (600−800°C) and a subsequent low temperature oxidation (190−240°C) step. Very small Co 3 O 4 particle size (2.3−7.4 nm) could be achieved for high loadings of Co 3 O 4 (up to 59%) in the carbon network. Both the pyrolysis and oxidation temperature increase led to an increase of nanoparticle size, porosity and electronic conductivity. At low temperatures, i.e., 600 and 650°C , and despite the low particle size, the performances are poor and limited by the carbon low electronic conductivity. At high temperature (800°C), the conductivity is improved translating in a higher capacitance, but the larger and more aggregated nanoparticles induced low rate capability. The best compromise to maintain high capacitance and rate capability was observed at 700 and 750°C and thus for composite materials combining simultaneously dispersed nanoparticles, high porosity, and good electronic conductivity. In particular, the material treated at 750°C presents, in a 2 electrode system using 2 M KOH, a capacitance of 54 F g −1 at 0.1 A g −1 , a very high rate capability of 48.7% at 10 A g −1 , and a superior rate performance of 82% after 10000 cycles

Large and Giant Unilamellar Vesicle(s) Obtained by Self-Assembly of Poly(dimethylsiloxane)-b-poly(ethylene oxide) Diblock Copolymers, Membrane Properties and Preliminary Investigation of their Ability to Form Hybrid Polymer/Lipid Vesicles

In the emerging field of hybrid polymer/lipid vesicles, relatively few copolymers have been evaluated regarding their ability to form these structures and the resulting membrane properties have been scarcely studied. Here, we present the synthesis and self-assembly in solution of poly(dimethylsiloxane)-block-poly(ethylene oxide) diblock copolymers (PDMS-b-PEO). A library of different PDMS-b-PEO diblock copolymers was synthesized using ring-opening polymerization of hexamethylcyclotrisiloxane (D3) and further coupling with PEO chains via click chemistry. Self-assembly of the copolymers in water was studied using Dynamic Light Scattering (DLS), Static Light Scattering (SLS), Small Angle Neutron Scattering (SANS), and Cryo-Transmission Electron Microscopy (Cryo-TEM). Giant polymersomes obtained by electroformation present high toughness compared to those obtained from triblock copolymer in previous studies, for similar membrane thickness. Interestingly, these copolymers can be associated to phospholipids to form Giant Hybrid Unilamellar Vesicles (GHUV); preliminary investigations of their mechanical properties show that tough hybrid vesicles can be obtained