Hybrid Organosulfur Network/MWCNT Composite Cathodes for Li-S Batteries.

Lithium-sulfur (Li-S) batteries hold a promising position as candidates for next-generation high-energy storage systems. Here, we combine inverse vulcanization of sulfur with multiwalled carbon nanotubes (MWCNTs) to increase the conductivity of cathode materials for Li-S batteries. The mixing process of inversely vulcanized sulfur copolymer networks with MWCNTs is aided by shear in a two-roll mill to take advantage of the soft nature of the copolymer. The high-throughput mixing method demands a source of conductive carbon that can be intimately mixed with the S copolymer, rendering MWCNTs an excellent choice for this purpose. The resulting sulfur copolymer network-MWCNTs composites were thoroughly characterized in terms of structure, chemical composition, thermal, and electronic transport properties, and finally evaluated by electrochemical benchmarking. These promising hybrids yielded electrodes with high sulfur content and demonstrate stable electrochemical performance exhibiting a specific capacity of ca. 550 mAh·gsulfur-1 (380 mAh·gelectrode-1) even after 500 charge-discharge cycles at specific current of 167 mA·g-1 (corresponds to 0.1C discharge rate), and thus are superior to melt-infiltrated reference samples.

All-Carbon Monolithic Composites from Carbon Foam and Hierarchical Porous Carbon for Energy Storage.

We designed high-volumetric-energy-density supercapacitors from monolithic composites composed of self-standing carbon foam (CF) as the conducting matrix and embedded hierarchically organized porous carbon (PICK) as the active material. Using multiprobe scanning tunneling microscopy at selected areas, we were able to disentangle morphology-dependent contributions of the heterogeneous composite to the overall conductivity. Adding PICK is found to enhance the conductivity of the monoliths by providing additional links for the CF network, enabling high and stable performance. The resulting all-carbon CF-PICK composites were used as self-standing electrodes for symmetric supercapacitors without the need for a binder, additional conducting additive, metals as a current collector, or casting/drying steps. Supercapacitors achieved a capacitance of 181 F g-1 based on the entire mass of the monolithic electrode as well as an outstanding rate capability. Our symmetrical supercapacitors also delivered a record volumetric energy density of 19.4 mW h cm-3 when using aqueous electrolytes. Excellent cycling stability with almost quantitative retention of capacitance was found after 10,000 cycles in 6.0 M KOH as the electrolyte. Furthermore, charge-discharge testing at different currents demonstrated the fast charge-discharge capability of this material system that meets the requirements for practical applications.

Proximity-Induced Gap Opening by Twisted Plumbene in Epitaxial Graphene.

Besides graphene, further honeycomb 2D structures were successfully synthesized on various surfaces. However, almost flat plumbene hosting topologically protected edge states could not yet be realized. In this Letter, we investigated the intercalation of Pb on buffer layers on SiC(0001). Thereby, suspended and charge neutral graphene emerged, and the intercalated Pb formed plumbene honeycomb lattices, which are rotated by ±7.5° with respect to graphene. Along with this twist, a proximity-induced modulation of the hopping parameter in graphene opens a band gap of around 30 meV at the Fermi energy, giving rise to a metal-insulator transition. Moreover, the edges of the intercalated plumbene layers revealed edge states within the gap of the conduction bands at around 1 eV as expected for charge neutral plumbene.

Surface Transport Properties of Pb-Intercalated Graphene.

Intercalation experiments on epitaxial graphene are attracting a lot of attention at present as a tool to further boost the electronic properties of 2D graphene. In this work, we studied the intercalation of Pb using buffer layers on 6H-SiC(0001) by means of electron diffraction, scanning tunneling microscopy, photoelectron spectroscopy and in situ surface transport. Large-area intercalation of a few Pb monolayers succeeded via surface defects. The intercalated Pb forms a characteristic striped phase and leads to formation of almost charge neutral graphene in proximity to a Pb layer. The Pb intercalated layer consists of 2 ML and shows a strong structural corrugation. The epitaxial heterostructure provides an extremely high conductivity of σ=100 mS/□. However, at low temperatures (70 K), we found a metal-insulator transition that we assign to the formation of minigaps in epitaxial graphene, possibly induced by a static distortion of graphene following the corrugation of the interface layer.

High Mass Loading Asymmetric Micro-supercapacitors with Ultrahigh Areal Energy and Power Density.

High mass loading asymmetric micro-supercapacitors (MSCs) are key components for the development of high-performance energy and power supply systems. Here, a concept for achieving high mass loading electrodes is presented and applied to high mass loading micro-supercapacitors with ultrahigh areal energy and power density. The positive electrode is made from porous carbon with birnessite coverage and multiwalled carbon nanotubes (CNTs) as conducting additives (PIC-CNTs-MnO2). The negative electrode is prepared from hierarchically porous active carbon mixed with CNTs (PICK-CNTs). Both positive and negative electrode materials are tailored to ensure a high content of macro- and mesopores. MSCs with an optimized mass loading of 13.9 mg·cm-2 (maximum: 23.6 mg·cm-2) provide an ultrahigh areal capacitance of 1.13 F·cm-2 (volumetric capacitance: 22.6 F·cm-3), an outstanding energy of 627.8 µWh·cm-2, and a maximum power density of 64 mW·cm-2. About 85% of the initial capacitance remained after 5000 cycles. Moreover, shunt and tandem device testing confirmed a high uniformity of these MSCs, meeting the requirements of adjustable output currents and voltages in microchips.

Topological Surface State in Epitaxial Zigzag Graphene Nanoribbons.

Protected and spin-polarized transport channels are the hallmark of topological insulators, coming along with an intrinsic strong spin-orbit coupling. Here we identified such corresponding chiral states in epitaxially grown zigzag graphene nanoribbons (zz-GNRs), albeit with an extremely weak spin-orbit interaction. While the bulk of the monolayer zz-GNR is fully suspended across a SiC facet, the lower edge merges into the SiC(0001) substrate and reveals a surface state at the Fermi energy, which is extended along the edge and splits in energy toward the bulk. All of the spectroscopic details are precisely described within a tight binding model incorporating a Haldane term and strain effects. The concomitant breaking of time-reversal symmetry without the application of external magnetic fields is supported by ballistic transport revealing a conduction of G = e2/h.

The Weak 3D Topological Insulator Bi12 Rh3 Sn3 I9.

Topological insulators (TIs) gained high interest due to their protected electronic surface states that allow dissipation-free electron and information transport. In consequence, TIs are recommended as materials for spintronics and quantum computing. Yet, the number of well-characterized TIs is rather limited. To contribute to this field of research, we focused on new bismuth-based subiodides and recently succeeded in synthesizing a new compound Bi12 Rh3 Sn3 I9 , which is structurally closely related to Bi14 Rh3 I9 - a stable, layered material. In fact, Bi14 Rh3 I9 is the first experimentally supported weak 3D TI. Both structures are composed of well-defined intermetallic layers of ∞ 2 [(Bi4 Rh)3 I]2+ with topologically protected electronic edge-states. The fundamental difference between Bi14 Rh3 I9 and Bi12 Rh3 Sn3 I9 lies in the composition and the arrangement of the anionic spacer. While the intermetallic 2D TI layers in Bi14 Rh3 I9 are isolated by ∞ 1 [Bi2 I8 ]2- chains, the isoelectronic substitution of bismuth(III) with tin(II) leads to ∞ 2 [Sn3 I8 ]2- layers as anionic spacers. First transport experiments support the 2D character of this material class and revealed metallic conductivity.