Ultrahigh Surface Area Three-Dimensional Porous Graphitic Carbon from Conjugated Polymeric Molecular Framework

Porous graphitic carbon is essential for many applications such as energy storage devices, catalysts, and sorbents. However, current graphitic carbons are limited by low conductivity, low surface area, and ineffective pore structure. Here we report a scalable synthesis of porous graphitic carbons using a conjugated polymeric molecular framework as precursor. The multivalent cross-linker and rigid conjugated framework help to maintain micro- and mesoporous structures, while promoting graphitization during carbonization and chemical activation. The above unique design results in a class of highly graphitic carbons at temperature as low as 800 ??C with record-high surface area (4073 m2 g-1), large pore volume (2.26 cm-3), and hierarchical pore architecture. Such carbons simultaneously exhibit electrical conductivity >3 times more than activated carbons, very high electrochemical activity at high mass loading, and high stability, as demonstrated by supercapacitors and lithium-sulfur batteries with excellent performance. Moreover, the synthesis can be readily tuned to make a broad range of graphitic carbons with desired structures and compositions for many applications.clos

A robust binary supramolecular organic framework (SOF) with high CO2 adsorption and selectivity

A robust binary hydrogen-bonded supramolecular organic framework (SOF-7) has been synthesized by solvothermal reaction of 1,4-bis-(4-(3,5-dicyano-2,6 dipyridyl)dihydropyridyl)benzene (1) and 5,5’-bis-(azanediyl)-oxalyl-diisophthalic acid (2). Single crystal X-ray diffraction analysis shows that SOF-7 comprises 2 and 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)benzene (3), the latter formed in situ from the oxidative dehydrogenation of 1. SOF-7 shows a three-dimensional four-fold interpenetrat-ed structure with complementary O−H···N hydrogen bonds to form channels that are decorated with cyano- and amide-groups. SOF-7 exhibits excellent thermal stability and sol-vent and moisture durability, as well as permanent porosity. The activated desolvated material SOF-7a shows high CO2 sorption capacity and selectivity compared with other po-rous organic materials assembled solely through hydrogen bonding

Direct observation of ion dynamics in supercapacitor electrodes using in situ diffusion NMR spectroscopy

Ionic transport inside porous carbon electrodes underpins the storage of energy in supercapacitors and the rate at which they can charge and discharge, yet few studies have elucidated the materials properties that influence ion dynamics. Here we use in situ pulsed field gradient NMR spectroscopy to measure ionic diffusion in supercapacitors directly. We find that confinement in the nanoporous electrode structures decreases the effective self-diffusion coefficients of ions by over two orders of magnitude compared with neat electrolyte, and in-pore diffusion is modulated by changes in ion populations at the electrode/electrolyte interface during charging. Electrolyte concentration and carbon pore size distributions also affect in-pore diffusion and the movement of ions in and out of the nanopores. In light of our findings we propose that controlling the charging mechanism may allow the tuning of the energy and power performances of supercapacitors for a range of different applications

Nanotexturation de TiO2 sur nanotubes de carbone pour pseudosupercondensateurs dans des électrolytes organiques

International audienceTitanium oxides have been considered potential electrode materials for pseudocapacitors because of their exceptional properties, such as high thermal and chemical stabilities, ready availability and low cost. However, they are not ideal for practical applications due to their poor ionic and electrical conductivity. The electrochemical performance of TiO 2 can be greatly improved if the material is nanotextured by reducing the particle size in optimizing the synthesis pathway. Actually, for metallic oxides, the electrochemical performance significantly depends on the particle size/morphology. At relatively low current densities the higher capacity values are exhibited by noncrystalline TiO 2 having 2 nm particle size, with values reaching 704 C g −1 . However, only thin electrodes are able to operate at a high charge density, limiting the energy density of the final device. Here, we propose a solution to circumvent such a drawback by further nanotexturing TiO 2 over multiwalled carbon nanotubes (CNTs). For that purpose, CNTs were introduced during oxide preparation. The synthesis protocol has been optimized for obtaining a uniform coverage of small TiO 2 particles on the surface of the CNTs. At low current densities, high mass loading TiO 2 /CNT composites electrodes are able to deliver capacitances as high as 480 F g −1 and the presence of CNTs allows keeping 70% of the capacitance at high current densities while only 27% is retained when using a regular conductivity agent as carbon black. The results demonstrate that uniform nanotexturation of TiO 2 over CNTs allows good rate capabilities to be obtained for thick electrodes having sufficient active material loading to achieve high specific energy and power densities

On the origin of the high capacitance of nitrogen-containing carbon nanotubes in acidic and alkaline electrolytes

The synthesis of nitrogenated carbon nanotubes (N-CNTs) with up to 6.1 wt% N, via the use of pyridine as the nitrogen containing carbon precursor, can provide a facile route to significantly enhance the low intrinsic specific capacitance of carbon nanotubes. The nitrogen functionalities determine this, at least, five-fold increase of the specific capacitance

Polyaniline/porous carbon electrodes by chemical polymerisation: effect of carbon surface chemistry

Polyaniline/porous carbon composite electrodes were prepared by chemical polymerisation and characterized in terms of porosity and performance as electrochemical capacitors. To obtain the composite electrodes two methods were used. The first method consisted of mixing, directly, the activated carbon with chemically polymerised polyaniline. The second one consisted of mixing the activated carbon with aniline and subsequent chemical polymerisation. Additionally, the second process was carried out with the porous carbon previously thermally treated in N2 up to 900 °C in order to remove surface oxygen groups. Changes in porosity with the polyaniline addition were analysed. It has been proved that the method used strongly affects the porous structure. Dealing with the electrochemical performance, polyaniline and carbon mechanically mixed seem to work independently, being the composite behaviour a combination of the corresponding performance of both materials separately. The composites prepared by the second method (polymerisation over carbon) reveal the key role of surface chemistry in polyaniline coating. Aniline reacts with the oxygen complexes and their positive effect in capacitance is not observed. The second method (polymerisation over carbon) using a thermally treated carbon seems to be the best one since a more porous (or thinner) polyaniline film is produced.The authors thank MEC for financial support (Project PPQ2003-03884 andMAT 2004-01479)