Christian Reitz

Pseudocapacitive Contributions to Charge Storage in Highly Ordered Mesoporous Group V Transition Metal Oxides with Iso-Oriented Layered Nanocrystalline Domains

Amphiphilic block copolymers are very attractive as templates to produce inorganic architectures with nanoscale periodicity because of their ability to form soft superstructures and to interact with inorganic materials. In this paper, we report the synthesis and electrochemical properties of highly ordered mesoporous T-Nb(2)O(5), L-Ta(2)O(5), and TaNbO(5) solid solution thin films with iso-oriented layered nanocrystalline domains. These oxide materials were fabricated by coassembly of inorganic sol-gel reagents with a poly(ethylene-co-butylene)-b-poly(ethylene oxide) diblock copolymer, referred to as KLE. We establish that all materials employed here are highly crystalline and have an ordered cubic pore-solid architecture after thermal treatment. We also demonstrate that these group V transition metal oxides can be readily produced with a high degree of crystallographic alignment on virtually any substrate in contrast to classical solution-phase epitaxy which requires the use of a single-crystalline substrate to achieve oriented crystal growth. Moreover, we show the benefits of producing a material with both a mesoporous morphology and crystallographically oriented domains. Mesoporous T-Nb(2)O(5) films exhibit high levels of pseudocapacitive charge storage and much higher capacities than mesoporous amorphous films of the same initial Nb(2)O(5) composition. Part of this high capacity stems from very facile intercalation pseudocapacitance. This process occurs at rates comparable to traditional redox pseudocapacitance in high surface area Nb(2)O(5) because of the periodic nanoscale porosity, the iso-orientation of the layered nanocrystalline pore walls, and the mechanical flexibility of periodic porous materials.

Ordered mesoporous α-Fe2O3 (hematite) thin-film electrodes for application in high rate rechargeable lithium batteries.

Herein is reported the synthesis of ordered mesoporous α-Fe(2)O(3) thin films produced through coassembly strategies using a poly(ethylene-co-butylene)-block-poly(ethylene oxide) diblock copolymer as the structure-directing agent and hydrated ferric nitrate as the molecular precursor. The sol-gel derived α-Fe(2)O(3) materials are highly crystalline after removal of the organic template and the nanoscale porosity can be retained up to annealing temperatures of 600 °C. While this paper focuses on the characterization of these materials using various state-of-the-art techniques, including grazing-incidence small-angle X-ray scattering, time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy, and UV-vis and Raman spectroscopy, the electrochemical properties are also examined and it is demonstrated that mesoporous α-Fe(2)O(3) thin-film electrodes not only exhibit enhanced lithium-ion storage capabilities compared to bulk materials but also show excellent cycling stabilities by suppressing the irreversible phase transformations that are observed in microcrystalline α-Fe(2)O(3).

Soft-templating synthesis of mesoporous magnetic CuFe2O4 thin films with ordered 3D honeycomb structure and partially inverted nanocrystalline spinel domains

Combining sol-gel chemistry with polymer templating strategies enables production of CuFe(2)O(4) thin films with both an ordered cubic network of 17 nm diameter pores and tunable spinel domain sizes. These nanocrystalline materials contain only minor structural defects with λ = 0.85 ± 0.02 and exhibit multiple functionalities, including superparamagnetic behavior (T(B)≈ 310 K) and redox- and photoactivity.

Hierarchical Carbon with High Nitrogen Doping Level: A Versatile Anode and Cathode Host Material for Long-Life Lithium-Ion and Lithium-Sulfur Batteries.

Nitrogen-rich carbon with both a turbostratic microstructure and meso/macroporosity was prepared by hard templating through pyrolysis of a tricyanomethanide-based ionic liquid in the voids of a silica monolith template. This multifunctional carbon not only is a promising anode candidate for long-life lithium-ion batteries but also shows favorable properties as anode and cathode host material owing to a high nitrogen content (>8% after carbonization at 900 °C). To demonstrate the latter, the hierarchical carbon was melt-infiltrated with sulfur as well as coated by atomic layer deposition (ALD) of anatase TiO2, both of which led to high-quality nanocomposites. TiO2 ALD increased the specific capacity of the carbon while maintaining high Coulombic efficiency and cycle life: the composite exhibited stable performance in lithium half-cells, with excellent recovery of low rate capacities after thousands of cycles at 5C. Lithium-sulfur batteries using the sulfur/carbon composite also showed good cyclability, with reversible capacities of ∼700 mA·h·g(-1) at C/5 and without obvious decay over several hundred cycles. The present results demonstrate that nitrogen-rich carbon with an interconnected multimodal pore structure is very versatile and can be used as both active and inactive electrode material in high-performance lithium-based batteries.

Field-driven migration of bipolar metal particles on solid electrolytes

A metal particle, which is not electronically contacted but is electrically contacted by a purely cation conducting solid electrolyte, is driven into the direction of the anode when an external electric field is applied. The particle behaves as a bipolar electrode. During the field-driven movement, the metal particle changes its morphology and spreads across the surface. This process is studied in situ with an optical microscope and ex situ with a scanning electron microscope. It is discussed as an example of morphological instabilities in solid state transport.

Nanocrystalline NaTaO3 thin film materials with ordered 3D mesoporous and nanopillar-like structures through PIB-b-PEO polymer templating: towards high-performance UV-light photocatalysts

Ordered mesoporous NaTaO3 thin films with both 3D honeycomb and nanopillar-like structures were successfully produced through sol–gel templating using a novel amphiphilic diblock copolymer, PIB53-b-PEO45, as the structure-directing agent. These nanocrystalline materials not only exhibit enhanced UV-light photocatalytic activity but are also able to maintain stable performance.

Microwave synthesis of high-quality and uniform 4 nm ZnFe2O4 nanocrystals for application in energy storage and nanomagnetics

Summary Magnetic nanocrystals with a narrow size distribution hold promise for many applications in different areas ranging from biomedicine to electronics and energy storage. Herein, the microwave-assisted sol–gel synthesis and thorough characterization of size-monodisperse zinc ferrite nanoparticles of spherical shape is reported. X-ray diffraction, 57Fe Mössbauer spectroscopy and X-ray photoelectron spectroscopy all show that the material is both chemically and phase-pure and adopts a partially inverted spinel structure with Fe3+ ions residing on tetrahedral and octahedral sites according to (Zn0.32Fe0.68)tet[Zn0.68Fe1.32]octO4±δ. Electron microscopy and direct-current magnetometry confirm the size uniformity of the nanocrystals, while frequency-dependent alternating-current magnetic susceptibility measurements indicate the presence of a superspin glass state with a freezing temperature of about 22 K. Furthermore, as demonstrated by galvanostatic charge–discharge tests and ex situ X-ray absorption near edge structure spectroscopy, the as-prepared zinc ferrite nanocrystals can be used as a high-capacity anode material for Li-ion batteries, showing little capacity fade – after activation – over hundreds of cycles. Overall, in addition to the good material characteristics, it is remarkable that the microwave-based synthetic route is simple, easily reproducible and scalable.

Sub-50 nm Channel Vertical Field-Effect Transistors using Conventional Ink-Jet Printing

A printed vertical field-effect transistor is demonstrated, which decouples critical device dimensions from printing resolution. A printed mesoporous semiconductor layer, sandwiched between vertically stacked drive electrodes, provides <50 nm channel lengths. A polymer-electrolyte-based gate insulator infiltrates the percolating pores of the mesoporous channel to accumulate charge carriers at every semiconductor domain, thereby, resulting in an unprecedented current density of MA cm-2 .

In situ tuning of magnetization via topotactic lithium insertion in ordered mesoporous lithium ferrite thin films

The synthesis and characterization of cubic mesostructured lithium ferrite (α-LiFe5O8) with 20 nm diameter pores and nanocrystalline walls is reported. The material is prepared in the form of thin films by sol–gel dip-coating using a poly(isobutylene)-block-poly(ethylene oxide) amphiphilic diblock copolymer as the porogen. Electron microscopy, X-ray scattering and diffraction, time-of-flight secondary ion mass spectrometry, Raman and X-ray photoelectron spectroscopy all show that α-LiFe5O8 can be templated to produce high-quality films that are chemically and phase-pure and thermally stable to over 600 °C. Magnetometry measurements indicate ferrimagnetic behavior below 300 K, with the coercivity exhibiting a T1/2 dependence. This novel mesoporous spinel material – when used as an electrode in secondary battery cells – can reversibly store charge via topotactic Li insertion, which allows for the intriguing possibility of tuning the magnetization at room temperature in a facile and controlled manner. The general approach is simple and should be applicable to a variety of other magnetic materials that are capable of reacting electrochemically with Li to produce reduced phases.

Synthesis, structural characterisation and proton conduction of two new hydrated phases of barium ferrite BaFeO2.5−x(OH)2x

Materials exhibiting mixed electronic and proton conductivity are of great interest for applications ranging from electrodes for proton conducting ceramic fuel cells to hydrogen separation membranes. In this work, we report a detailed investigation of the effect of water incorporation in BaFeO2.5 on the structure and conductivity. BaFeO2.5 is shown to be topochemically transformed to two different hydrated modifications, low-water (LW-) and high-water (HW-) BaFeO2.5. A combined analysis of neutron and X-ray diffraction data was used to determine the crystal structure of LW-BaFeO2.5 (BaFeO2.33(OH)0.33), which shows a unique ordering pattern of anion vacancies for perovskite type compounds, with structural relaxations around vacancies being similar to the chemically similar compound BaFeO2.33F0.33. Approximate proton positions were determined using the bond valence method. Conductivity studies of hydrated and pure BaFeO2.5 (with additional comparison to oxidized BaFeO2.5) show a significant enhancement of the conductivity on water incorporation, which can be attributed to proton conductivity. This is the first report of significant grain proton conduction (∼10−6 to 10−7 S cm−1) in an iron based perovskite. Water uptake is further shown to be completely reversible, with reformation of BaFeO2.5 when heating the compound to temperatures above ∼450 K under Ar.