Martin Oschatz

Sulfur‐Infiltrated Micro‐ and Mesoporous Silicon Carbide‐Derived Carbon Cathode for High‐Performance Lithium Sulfur Batteries

Novel nanostructured sulfur (S)-carbide derived carbon (CDC) composites with ordered mesopores and high S content are successfully prepared for lithium sulfur batteries. The tunable pore-size distribution and high pore volume of CDC allow for an excellent electrochemical performance of the composites at high current densities. A higher electrolyte molarity is found to enhance the capacity utilization dramatically and reduce S dissolution in S-CDC composite cathodes during cycling.

Hierarchical Micro- and Mesoporous Carbide-Derived Carbon as a High-Performance Electrode Material in Supercapacitors

Ordered mesoporous carbide-derived carbon (OM-CDC) materials produced by nanocasting of ordered mesoporous silica templates are characterized by a bimodal pore size distribution with a high ratio of micropores. The micropores result in outstanding adsorption capacities and the well-defined mesopores facilitate enhanced kinetics in adsorption processes. Here, for the first time, a systematic study is presented, in which the effects of synthesis temperature on the electrochemical performance of these materials in supercapacitors based on a 1 M aqueous solution of sulfuric acid and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid are reported. Cyclic voltammetry shows the specific capacitance of the OM-CDC materials exceeds 200 F g(-1) in the aqueous electrolyte and 185 F g(-1) in the ionic liquid, when measured in a symmetric configuration in voltage ranges of up to 0.6 and 2 V, respectively. The ordered mesoporous channels in the produced OM-CDC materials serve as ion-highways and allow for very fast ionic transport into the bulk of the OM-CDC particles. At room temperature the enhanced ion transport leads to 75% and 90% of the capacitance retention at current densities in excess of ∼10 A g(-1) in ionic liquid and aqueous electrolytes, respectively. The supercapacitors based on 250-300 μm OM-CDC electrodes demonstrate an operating frequency of up to 7 Hz in aqueous electrolyte. The combination of high specific capacitance and outstanding rate capabilities of the OM-CDC materials is unmatched by state-of-the art activated carbons and strictly microporous CDC materials.

Direct prediction of the desalination performance of porous carbon electrodes for capacitive deionization

Desalination by capacitive deionization (CDI) is an emerging technology for the energy- and cost-efficient removal of ions from water by electrosorption in charged porous carbon electrodes. A variety of carbon materials, including activated carbons, templated carbons, carbon aerogels, and carbon nanotubes, have been studied as electrode materials for CDI. Using carbide-derived carbons (CDCs) with precisely tailored pore size distributions (PSD) of micro- and mesopores, we studied experimentally and theoretically the effect of pore architecture on salt electrosorption capacity and salt removal rate. Of the reported CDC-materials, ordered mesoporous silicon carbide-derived carbon (OM SiC-CDC), with a bimodal distribution of pore sizes at 1 and 4 nm, shows the highest salt electrosorption capacity per unit mass, namely 15.0 mg of NaCl per 1 g of porous carbon in both electrodes at a cell voltage of 1.2 V (12.8 mg per 1 g of total electrode mass). We present a method to quantify the influence of each pore size increment on desalination performance in CDI by correlating the PSD with desalination performance. We obtain a high correlation when assuming the ion adsorption capacity to increase sharply for pore sizes below one nanometer, in line with previous observations for CDI and for electrical double layer capacitors, but in contrast to the commonly held view about CDI that mesopores are required to avoid electrical double layer overlap. To quantify the dynamics of CDI, we develop a two-dimensional porous electrode modified Donnan model. For two of the tested materials, both containing a fair degree of mesopores (while the total electrode porosity is ∼95 vol%), the model describes data for the accumulation rate of charge (current) and salt accumulation very well, and also accurately reproduces the effect of an increase in electrode thickness. However, for TiC-CDC with hardly any mesopores, and with a lower total porosity, the current is underestimated. Calculation results show that a material with higher electrode porosity is not necessarily responding faster, as more porosity also implies longer transport pathways across the electrode. Our work highlights that a direct prediction of CDI performance both for equilibrium and dynamics can be achieved based on the PSD and knowledge of the geometrical structure of the electrodes.

Tailoring porosity in carbon materials for supercapacitor applications

Within the different available electrochemical energy storage systems, supercapacitors stand out due to their high power densities and ultra-long cycle life. Their key-components are the electrode materials where the charge accumulation takes place and therefore many different approaches for the synthesis of carbonaceous electrode structures with well-defined pore systems are available. This review focuses on different strategies for tailoring porous carbon materials from the micropore level, over mesopores to macropores and even external or inter-particular porosity. A wide range of materials such as activated carbons, templated carbons, carbide-derived carbons, carbon nanotubes, carbon aerogels, carbon onions, graphenes and carbon nanofibers are presented, always in relation to their pore structure and potential use in supercapacitor devices.

Carbon Materials for Lithium Sulfur Batteries—Ten Critical Questions

Lithium-sulfur batteries are among the most promising electrochemical energy storage devices of the near future. Especially the low price and abundant availability of sulfur as the cathode material and the high theoretical capacity in comparison to state-of-the art lithium-ion technologies are attractive features. Despite significant research achievements that have been made over the last years, fundamental (electro-) chemical questions still remain unanswered. This review addresses ten crucial questions associated with lithium-sulfur batteries and critically evaluates current research with respect to them. The sulfur-carbon composite cathode is a particular focus, but its complex interplay with other hardware components in the cell, such as the electrolyte and the anode, necessitates a critical discussion of other cell components. Modern in situ characterisation methods are ideally suited to illuminate the role of each component. This article does not pretend to summarise all recently published data, but instead is a critical overview over lithium-sulfur batteries based on recent research findings.

Imine-linked polymer-derived nitrogen-doped microporous carbons with excellent CO2 capture properties.

A series of nitrogen-doped microporous carbons (NCs) was successfully prepared by direct pyrolysis of high-surface-area microporous imine-linked polymer (ILP, 744 m(2)/g) which was formed using commercial starting materials based on the Schiff base condensation under catalyst-free conditions. These NCs have moderate specific surface areas of up to 366 m(2)/g, pore volumes of 0.43 cm(3)/g, narrow micropore size distributions, and a high density of nitrogen functional groups (5.58-8.74%). The resulting NCs are highly suitable for CO2 capture adsorbents because of their microporous textural properties and large amount of Lewis basic sites. At 1 bar, NC-800 prepared by the pyrolysis of ILP at 800 °C showed the highest CO2 uptakes of 1.95 and 2.65 mmol/g at 25 and 0 °C, respectively. The calculated adsorption capacity for CO2 per m(2) (μmol of CO2/m(2)) of NC-800 is 7.41 μmol of CO2/m(2) at 1 bar and 25 °C, the highest ever reported for porous carbon adsorbents. The isosteric heats of CO2 adsorption (Qst) for these NCs are as high as 49 kJ/mol at low CO2 surface coverage, and still ~25 kJ/mol even at high CO2 uptake (2.0 mmol/g), respectively. Furthermore, these NCs also exhibit high stability, excellent adsorption selectivity for CO2 over N2, and easy regeneration and reuse without any evident loss of CO2 adsorption capacity.

Highly porous nitrogen-doped polyimine-based carbons with adjustable microstructures for CO2 capture

A series of highly porous nitrogen doped porous carbons (NPCs) have been successfully prepared using a novel porous polyimine as the precursor. The resulting NPCs have a high specific surface area of up to 3195 m2 g−1, high pore volume and micropore volume (up to 1.58 and 1.38 cm3 g−1, respectively), narrow micropore size distributions, and adjustable nitrogen (1.52–5.05 wt%) depending on the activation temperatures (600–750 °C). The CO2 uptakes of the NPCs prepared at higher temperatures (700–750 °C) are lower than those prepared at milder conditions (600–650 °C). At 1 bar, NPC-650 demonstrates the best CO2 capture performance and could efficiently adsorb CO2 molecules of 3.10 mmol g−1 (136 mg g−1) and 5.26 mmol g−1 (231.3 mg g−1), at 25 and 0 °C, respectively. The NPCs also show good a initial CO2/N2 adsorption selectivity of up to 23.4 and an adsorption ratio of CO2/N2 (6.6) at 1 bar. Meanwhile, these NPCs exhibit a high stability and facile regeneration/recyclability without evident loss of the CO2 capture capacities.

Carbide-Derived Carbon Monoliths with Hierarchical Pore Architectures†

Porous carbon materials are crucial components in catalysis, gas storage, electronics, and biochemistry. A hierarchical pore architecture in these materials is essential to achieve high surface areas combined with advanced mass transport kinetics. Widely used approaches for the generation of microor mesopores are activation and nanocasting. In contrast, macroporous carbon materials are primarily obtained by carbonization of polymeric precursor gels or replication of larger templates. A relatively new class of microand mesoporous carbon material with tunable porosity are carbide-derived carbon materials (CDCs). High-temperature chlorination of carbides leads to selective removal of metalor semi-metal atoms and allows control over the pore size of the resulting CDCs in a subngstrcm range by changing synthesis conditions or the carbide precursor. These materials have been studied for applications in gas storage and as electrode materials in supercapacitors because of their high specific surface areas. Recently, metal etching from pyrolyzed pre-ceramic components (polysilsesquioxanes or polysilazanes) was found to be a useful route towards carbide-derived carbon materials with enhanced porosity and gas-storage properties. A significant step towards ultrahigh specific surface area combined with a hierarchical mesoporous–microporous system was achieved using nanocasting of silica templates (SBA-15 or KIT-6) with polycarbosilane precursors and subsequent chlorine treatment of the resulting ordered mesoporous silicon carbides. These ordered mesoporous CDCs offer specific surface areas as high as 2800 mg 1 and total pore volumes of up to 2 cmg . Their mesostructure can be easily controlled by changing the silica hard template, resulting in excellent performance in protein adsorption, gas storage, and as electrodes for supercapacitors. However, such carbon materials are available only as nonstructured micrometer-sized powders and cannot be shaped into films without the addition of binders or the use of high mechanical stress, leading to structural deformation. Chlorine treatment of mechanically mixed Si/SiC precursors was found to be a useful route towards monolithic CDC with a hierarchical pore system. The presence of a free metal phase in the precursor system provides the opportunity to introduce a secondary macroporosity of 3 mm sized channels with a volume of 0.23 cmg 1 along with the microporous carbide-derived carbon material system. The introduction of large transport pores in polymerbased CDCs might be an alternative way to form materials that combine high surface areas with efficient fluid transport. The current literature describes a variety of routes for the production of highly macroporous ceramics from precursor polymers with controllable cell and window sizes. In particular, direct blowing of polycarbosilanes was found to be a useful approach for the generation of silicon carbide foams that might be suitable materials for the production of hierarchical CDCs. In the following, we describe a novel synthesis route for monolithic carbide-derived carbon materials, including micro-, meso-, and macroporous structures with extremely high specific surface area. They can be obtained by hightemperature chlorination of macroporous polymer-derived silicon carbide (SiC-PolyHIPE). A soft-templating approach starting from a high internal phase emulsion (HIPE) was used with an external oil phase consisting of liquid polycarbosilane SMP-10 and the cross-linker paradivinylbenzene. Using Span-80 as surfactant to stabilize the internal water phase, the application of oxidic or carbon hard templates and the corresponding template removal under harsh conditions is no longer necessary. After cross-linking the polymer chains, the resulting PolyHIPEs were pyrolyzed to silicon carbides at maximum temperatures of 700, 800, and 1000 8C and subsequently converted into CDCs by chlorine treatment at the maximum pyrolysis temperature (Supporting [*] M. Oschatz, L. Borchardt, Dr. I. Senkovska, N. Klein, Dr. R. Frind, Prof. Dr. S. Kaskel Department of Inorganic Chemistry Dresden University of Technology Bergstrasse 66, 01062 Dresden (Germany) E-mail: stefan.kaskel@chemie.tu-dresden.de

Stretchable and Semitransparent Conductive Hybrid Hydrogels for Flexible Supercapacitors

Conductive polymers showing stretchable and transparent properties have received extensive attention due to their enormous potential in flexible electronic devices. Here, we demonstrate a facile and smart strategy for the preparation of structurally stretchable, electrically conductive, and optically semitransparent polyaniline-containing hybrid hydrogel networks as electrode, which show high-performances in supercapacitor application. Remarkably, the stability can extend up to 35,000 cycles at a high current density of 8 A/g, because of the combined structural advantages in terms of flexible polymer chains, highly interconnected pores, and excellent contact between the host and guest functional polymer phase.

Kinetically Controlled Synthesis of PdNi Bimetallic Porous Nanostructures with Enhanced Electrocatalytic Activity

A class of 3D PdNi bimetallic nano-materials with porous nanostructures is synthesized using a facile and versatile approach at room temperature. Due to their porous nanostructures, their clean surfaces, as well as the synergistic effect between their compositions, the as-prepared PdNi exhibit greatly enhanced activity and stability towards methanol electrooxidation in an alkaline medium, holding great promise in fuel cells.