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Compounds of the 5 amino (ATCC) and 5 nitro 1,2,3,4 tetracyanocyclopentadienide (NTCC) ligand with iron(II) and iron(III), silver(I) and potassium(I) were prepared and characterized by electrochemical methods using EPR, cyclic voltammetry and Mößbauer spectroscopy as well as UV-Vis spectroscopy. The investigation sheds light on the free radical activity in non- as well as transition metal compounds, and shows signs of photoinduced electron transfer in transition metal compounds of the ligands. We characterized silver(I) and potassium compounds of the compounds via X-ray diffraction, with one of the structures exhibiting a porous coordination polymer.

We report the syntheses of various compounds within the pseudo-quaternary system of the type LiwNiₓCoyMnzOδ (δ≤1) (pre-NCMs). Four different compositions of this compound were realized as ultrasmall crystalline nanoparticles of 1–4 nm diameter using low-temperature solvothermal reaction conditions in tert-butanol at only 170 °C. All of the pre-NCMs crystallize in the rock-salt structure and their lithium content is between 20% and 30% with respect to the complete metal content. By adjusting the lithium content to 105% stoichiometry in the solvothermal reaction, the pre-NCMs can easily react to the respective Li(NiₓCoyMnz)O₂ (NCM) nanoparticles. Furthermore, nanosized desert-rose structured NCMs were obtained after addition of nanocellulose during the synthesis. By using the mixed metal monoxides as precursor for the NCMs, cation mixing between lithium and nickel is favored and gets more pronounced with increasing nickel content. The cation mixing effect compromises good electrochemical capacity retention, but the desert-rose structure nevertheless enables enhanced stability at high power conditions, especially for NCM333.

Crystals of the aminotetracyanocyclopentadienyl radical were obtained from the reaction of CaCl2 with Ag[C5(CN)4(NH2)] and recrystallization in MeOH, performed in sunlight. The radical was characterized by X-ray diffraction, EPR and UV Vis spectroscopy as well as by cyclovoltammetry and DFT calculations.

The construction of flexible electrochemical devices for energy storage and generation is of utmost importance in modern society. In this article, we report on the synthesis of flexible MoS2-based composite paper by high-energy shear force milling and simple vacuum filtration. This composite material combines high flexibility, mechanical strength and good chemical stability. Chronopotentiometric charge–discharge measurements were used to determine the capacitance of our paper material. The highest capacitance achieved was 33 mF·cm−2 at a current density of 1 mA·cm−2, demonstrating potential application in supercapacitors. We further used the material as a cathode for the hydrogen evolution reaction (HER) with an onset potential of approximately −0.2 V vs RHE. The onset potential was even lower (approximately −0.1 V vs RHE) after treatment with n-butyllithium, suggesting the introduction of new active sites. Finally, a potential use in lithium ion batteries (LIB) was examined. Our material can be used directly without any binder, additive carbon or copper current collector and delivers specific capacity of 740 mA·h·g−1 at a current density of 0.1 A·g−1. After 40 cycles at this current density the material still reached a capacity retention of 91%. Our findings show that this composite material could find application in electrochemical energy storage and generation devices where high flexibility and mechanical strength are desired.Keywords: flexible composites; hydrogen evolution reaction (HER); lithium ion batteries (LIBs); molybdenum disulfide; nanoarchitectonics; supercapacitors

The syntheses of a sterically demanding, multidentate bis(quinaldinyl)phenylphosphine oxide ligand and some Cu(I) and Ag(I) complexes thereof are described. By introducing a methylene group between the quinoline unit and phosphorus, the phosphine oxide ligand gains additional flexibility. This specific ligand design induces not only a versatile coordination chemistry but also a rarely observed and investigated behavior in solution. The flexibility of the birdlike ligand offers the unexpected opportunity of open-wing and closed-wing coordination to the metal. In fact, the determined crystal structures of these complexes show both orientations. Investigations of the ligand in solution show a strong dependency of the chemical shift of the CH2 protons on the solvent used. Variable-temperature, multinuclear NMR spectroscopy was carried out, and an interesting dynamic behavior of the complexes is observed. Due to the introduced flexibility, the quinaldinyl substituents change their arrangements from open-wing to closed-wing upon cooling, while still staying coordinated to the metal. This change in conformation is completely reversible when warming up the sample. Based on 2D NMR spectra measured at -80 °C, an assignment of the signals corresponding to the different arrangements was possible. Additionally, the copper(I) complex shows reversible redox activity in solution. The combination of structural flexibility of a multidentate ligand and the positive redox properties of the resulting complexes comprises key factors for a possible application of such compounds in transition-metal catalysis. Via a reorganization of the ligand, occurring transition states could be stabilized, and selectivity might be enhanced.

Freestanding electrodes are a promising way to increase the energy density of the batteries by decreasing the overall amount of electrochemically inactive materials. Freestanding antimony doped tin oxide (ATO)-based hybrid materials have not been reported so far, although this material has demonstrated excellent performance in conventionally designed electrodes. Two different strategies, namely electrospinning and freeze-casting, are explored for the fabrication of ATO-based hybrid materials. It is shown that the electrospinning of ATO/carbon based electrodes from polyvinyl pyrrolidone polymer (PVP) solutions was not successful, as the resulting electrode material suffers from rapid degradation. However, freestanding reduced graphene oxide (rGO) containing ATO/C/rGO nanocomposites prepared via a freeze-casting route demonstrates an impressive rate and cycling performance reaching 697 mAh g−¹ at a high current density of 4 A g−¹, which is 40 times higher as compared to SnO₂/rGO and also exceeds the freestanding SnO₂-based composites reported so far. Antimony doping of the nanosized tin oxide phase and carbon coating are thereby shown to be essential factors for appealing electrochemical performance. Finally, the freestanding ATO/C/rGO anodes are combined with freestanding LiFe₀.₂Mn₀.₈PO₄/rGO cathodes to obtain a full freestanding cell operating without metal current collector foils showing nonetheless an excellent cycling stability.

Oxygen evolution reaction (OER) is expected to be of great importance for the future energy conversion and storage in form of hydrogen by water electrolysis. Besides the traditional noble-metal or transition metal oxide-based catalysts, carbonaceous electrocatalysts are of great interest due to their huge structural and compositional variety and unrestricted abundance. This review provides a summary of recent advances in the field of carbon-based OER catalysts ranging from "pure" or unintentionally doped carbon allotropes over heteroatom-doped carbonaceous materials and carbon/transition metal compounds to metal oxide composites where the role of carbon is mainly assigned to be a conductive support. Furthermore, the review discusses the recent developments in the field of ordered carbon framework structures (metal organic framework and covalent organic framework structures) that potentially allow a rational design of heteroatom-doped 3D porous structures with defined composition and spatial arrangement of doping atoms to deepen the understanding on the OER mechanism on carbonaceous structures in the future. Besides introducing the structural and compositional origin of electrochemical activity, the review discusses the mechanism of the catalytic activity of carbonaceous materials, their stability under OER conditions, and potential synergistic effects in combination with metal (or metal oxide) co-catalysts.

To enable future large-scale generation of hydrogen via proton exchange membrane (PEM) electrolysis, utilization of scarce iridium-based catalysts required for the oxygen evolution reaction (OER) has to be significantly lowered. To address this question, the facile synthesis of a highly active TiO2 supported iridium oxide based OER catalyst with reduced noble metal content and an Ir-density of the catalyst powder as low as 0.05–0.08 gIr cm-3 is described in this work. A high surface area corrosion-resistant titania catalyst support homogeneously coated with a 1-2 nm thin layer of amorphous IrOOHx is oxidized in molten NaNO3 between 350-375°C. This procedure allows for a controllable phase transformation and crystallization to form a layer of interconnected IrO2 nanoparticles of ≈2 nm on the surface of the TiO2 support. The increase in crystallinity is thereby accompanied by a significant increase in conductivity of up to 11 S cm-1 for a 30 wt% Ir loaded catalyst. Oxidized samples further display a significantly increased stability with less detectable Ir dissolution under OER conditions. With a mass-based activity of 59 A g-1 at an overpotential of 300 mV, the electrocatalytic activity is maintained at the level of the highly active amorphous IrOOHx phase used as precursor and outperforms it at higher current densities through the increased conductivity. MEA measurements with catalyst loadings of 0.2-0.3 mg cm-2 further confirm the high catalytic activity and initial stability at industrially relevant current densities. The introduced synthesis approach therefore shows a path for the fabrication of novel highly active and atom-efficient oxide supported catalysts with complex nanostructures and thin homogenous nanoparticle coatings that allows a future large-scale application of PEM electrolysis technology without restrictions by the natural abundance of iridium.

In this chapter, after having introduced the basics of electrochemical storage and types of secondary batteries, detailed focus is given on: (i) anode ceramic materials, (ii) cathode active materials, and (iii) separators and solid electrolytes. Chemistries of interest are based on lithium and sodium, covering both current commercial applications as well as technologies under development such as solid-state batteries.

Freestanding electrodes for lithium ion batteries are considered as a promising option to increase the total gravimetric energy density of the cells due to a decreased weight of electrochemically inactive materials. We report a simple procedure for the fabrication of freestanding LiFe0.2Mn0.8PO4 (LFMP)/rGO electrodes with a very high loading of active material of 83 wt%, high total loading of up to 8 mg cm−2, high energy density, excellent cycling stability and at the same time very fast charging rate, with a total performance significantly exceeding the values reported in the literature. The keys to the improved electrode performance are optimization of LFMP nanoparticles via nanoscaling and doping; the use of graphene oxide (GO) with its high concentration of surface functional groups favoring the adhesion of high amounts of LFMP nanoparticles, and freeze-casting of the GO-based nanocomposites to prevent the morphology collapse and provide a unique fluffy open microstructure of the freestanding electrodes. The rate and the cycling performance of the obtained freestanding electrodes are superior compared to their Al-foil coated equivalents, especially when calculated for the entire weight of the electrode, due to the extremely reduced content of electrochemically inactive material (17 wt% of electrochemically inactive material in case of the freestanding compared to 90 wt% for the Al-foil based electrode), resulting in 120 mAh g−1electrode in contrast to 10 mAh g−1electrode at 0.2 C. The electrochemical performance of the freestanding LFMP/rGO electrodes is also considerably better than the values reported in literature for freestanding LFMP and LMP composites, and can even keep up with those of LFP-based analogues. The freestanding LFMP/rGO reported in this work is additionally attractive due to its high gravimetric energy density (604 Wh kg−1LFMP at 0.2C). The obtained results demonstrate the advantage of freestanding LiFe0.2Mn0.8PO4/rGO electrodes and their great potential for applications in lithium ion batteries.

Construction of flexible electrochemical devices for energy storage and generation is of utmost importance in the modern society. In this article, we report the synthesis of flexible MoS2 based composite paper by high-energy shear force milling and simple vacuum filtration. This composite material combines high flexibility, mechanical strength and good chemical stability. Chronopotentiometric charge-discharge measurements were used to determine the capacitance of our paper material. Highest capacitance of 33 mF cm-2 was achieved at current density of 1 mA cm-2 showing potential application in supercapacitors. We further used the material as a cathode for hydrogen evolution reaction (HER) with an onset potential of ca. -0.2 V vs RHE. The onset potential was even lower (ca. -0.1 V vs RHE) after treatment with n-butyllithium suggesting the introduction of new active sites. Finally, a potential use in Lithium ion batteries (LIB) was examined. Our material can be used directly without any binder, additive carbon or copper current collector and delivers specific capacity of 740 mA h g-1 at a current density of 0.1 A g-1. After 40 cycles at this current density the material still reached a capacity retention of 91%. Our findings show that this composite material could find application in electrochemical energy storage and generation devices where high flexibility and mechanical strength are desired.

We report the formation of crystalline dispersible LixCo1–xOy (with y⩽1) nanoparticles with an unusual rock-salt phase containing ∼15 at. % Li in the crystalline structure. This is the first time t...

'Black' TiO2 -in the widest sense, TiO2 reduced by various treatments-has attracted tremendous scientific interest in recent years because of some outstanding properties; most remarkably in photocatalysis. While the material effects visible light absorption (the blacker, the better), black titania produced by high pressure hydrogenation was recently reported to show another highly interesting feature; noble-metal-free photocatalytic H2 generation. In a systematic investigation of high-temperature hydrogen treatments of anatase nanoparticles, TEM, XRD, EPR, XPS, and photoelectrochemistry are used to characterize different degrees of surface hydrogenation, surface termination, electrical conductivity, and structural defects in the differently treated materials. The materials' intrinsic activity for photocatalytic hydrogen evolution is coupled neither with their visible light absorption behavior nor the formation of amorphous material, but rather must be ascribed to optimized and specific defect formation (gray is better than black). This finding is further confirmed by using a mesoporous anatase matrix as a hydrogenation precursor, which, after conversion to the gray state, even further enhances the overall photocatalytic hydrogen evolution activity.

Phosphorus and arsenic belong to the 5th group of elements – so-called pnictogens. These materials are among the most intensively studied nanomaterials with layered structure. In this contribution we report the synthesis of arsenic – black phosphorus alloys. Two samples with various black phosphorus and arsenic content together with pure black phosphorus were exfoliated using shear force milling. Extensive analyses have revealed the successful synthesis of AsP alloys with good crystallinity and composition close to that of the intended value. Testing these materials for lithium ion batteries (LIBs) shows that there is a huge capacity loss after the initial charge/discharge cycles. Such a drop was attributed to a delithiation of the lithium rich phase and a loss of proper electrical contact. After the initial capacity loss, the Coulombic efficiencies in the subsequent cycles reached 90–99%. Moreover, both of the alloys exhibited higher capacity than pure black phosphorus sample, indicating that alloying with arsenic is an advantageous technique. The results of this work show the fundamental charge storage capabilities of AsP alloys a can serve as a starting point for the synthesis of advanced materials based on AsP alloys.

A series of bis(pyrazolyl)methane copper complexes were found to catalyze a fast palladium-free Sonogashira coupling reaction of several iodoarenes with terminal alkynes such as phenylacetylene, propargyl benzyl ether, and (tert-butyl-dimethyl)silylacetylene. These reactions proceed with CuCl2·2H2O (10 mol-%) under aerobic conditions and the corresponding chelate ligand (10 mol-%), with its tailored facial coordination mode, is crucial for the success of the reaction. The coupling can also be carried out in water with liquid aryl halides and a phase-transfer catalyst.

Herein, recent progress in the field of tin oxide (SnO2)‐based nanosized and nanostructured materials as conversion and alloying/dealloying‐type anodes in lithium‐ion batteries and beyond (sodium‐ and potassium‐ion batteries) is briefly discussed. The first section addresses the importance of the initial SnO2 micro‐ and nanostructure on the conversion and alloying/dealloying reaction upon lithiation and its impact on the microstructure and cyclability of the anodes. A further section is dedicated to recent advances in the fabrication of diverse 0D to 3D nanostructures to overcome stability issues induced by large volume changes during cycling. Additionally, the role of doping on conductivity and synergistic effects of redox‐active and ‐inactive dopants on the reversible lithium‐storage capacity and rate capability are discussed. Furthermore, the synthesis and electrochemical properties of nanostructured SnO2/C composites are reviewed. The broad research spectrum of SnO2 anode materials is finally reflected in a brief overview of recent work published on Na‐ and K‐ion batteries., A matter of size and structure: Large volume changes during SnO2 conversion and alloying of an anode limit its stability upon cycling. A brief overview of how primary particle size, nanostructuring, and composite formation influence the electrode performance and stability in SnO2 anode‐based lithium‐ion batteries is provided and complemented by recent reports on corresponding sodium and potassium systems.

'Black' TiO

Tin oxide-based materials attract increasing attention as anodes in lithium-ion batteries due to their high theoretical capacity, low cost, and high abundance. Composites of such materials with a carbonaceous matrix such as graphene are particularly promising, as they can overcome the limitations of the individual materials. The fabrication of antimony-doped tin oxide (ATO)/graphene hybrid nanocomposites is described with high reversible capacity and superior rate performance using a microwave assisted in situ synthesis in tert-butyl alcohol. This reaction enables the growth of ultrasmall ATO nanoparticles with sizes below 3 nm on the surface of graphene, providing a composite anode material with a high electric conductivity and high structural stability. Antimony doping results in greatly increased lithium insertion rates of this conversion-type anode and an improved cycling stability, presumably due to the increased electrical conductivity. The uniform composites feature gravimetric capacity of 1226 mAh g(-1) at the charging rate 1C and still a high capacity of 577 mAh g(-1) at very high charging rates of up to 60C, as compared to 93 mAh g(-1) at 60C for the undoped composite synthesized in a similar way. At the same time, the antimony-doped anodes demonstrate excellent stability with a capacity retention of 77% after 1000 cycles.