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In this study, we investigated the effect of nanostructured Al2O3 particles on Li ion conducting, poly(ethylene oxide) (PEO)-based membranes prepared by electrospinning, solution casting and hot pressing. Pure PEO:LiBF4 solid polymer electrolytes (SPEs) and also plasticizer containing membranes were investigated with various amounts of Al2O3. In a first step, the best-performing composition of pure PEO:LiBF4 concerning the resulting ionic conductivity was identified and used as a standard for further experiments. In the following, the influence of the preparation method, the nature of the Al2O3, and the type of the plasticizer additives on the thermal and electrochemical properties for this standard composition were investigated. The Al2O3 composition was varied between 1 and 5 wt%. The ionic conductivity of bare electrospun PEO:LiBF4 SPE standard material has been improved by a factor ten to 1.9 × 10−6 S cm−1 at T = 293 K when 5 wt% of Al2O3 is added. For solution-casted PEO:LiBF4 standard compositions 18:1 with an initial ionic conductivity of 6.7 × 10−8 S cm−1, the addition of 2 wt% Al2O3 increased the performance to 1.4 × 10−7 S cm−1, both at T = 293 K. If succinonitrile and Al2O3 was admixed to the solution casted standard material, the ionic conductivity was further increased to reach 5.5 × 10−5 S cm−1 at T = 293 K. This material with a composition of 18:3:1 + 2 wt% Al2O3, outperforms the standard material by three orders of magnitude. [ABSTRACT FROM AUTHOR]

Surface coating is an effective concept to protect layered cathode active materials (CAMs) in lithium ion batteries from detrimental side reactions. Dry powder coating is a fast and cost‐effective coating process, and here we transfer this coating approach from Al2O3 to nanostructured fumed TiO2 and ZrO2 coatings on the same NMC (Li[Ni,Mn,Co]O2) material. Using similar processing, this allows a direct comparison of the characteristics of the achieved coating layers and their influence on the cycling performance of high‐nickel NMC. The nanostructured small oxide aggregates result in a quite homogeneous coating layer with a certain porosity around each CAM particle. Significantly enhanced long‐term cycling stability is observed, with a trend of increasing stability in the series ZrO2

Surface coating is a crucial method to mitigate the aging problem of high‐Ni cathode active materials (CAMs). By avoiding the direct contact of the CAM and the electrolyte, side reactions are hindered. Commonly used techniques like wet or ALD coating are time consuming and costly. Therefore, a more cost‐effective coating technique is desirable. Herein, a facile and fast dry powder coating process for CAMs with nanostructured fumed metal oxides are reported. As the model case, the coating of high‐Ni NMC (LiNi0.7Mn0.15Co0.15O2) by nanostructured fumed Al2O3 is investigated. A high coverage of the CAM surface with an almost continuous coating layer is achieved, still showing some porosity. Electrochemical evaluation shows a significant increase in capacity retention, cycle life and rate performance of the coated NMC material. The coating layer protects the surface of the CAM successfully and prevents side reactions, resulting in reduced solid electrolyte interface (SEI) formation and charge transfer impedance during cycling. A mechanism on how the coating layer enhances the cycling performance is hypothesized. The stable coating layer effectively prevents crack formation and particle disintegration of the NMC. In depth analysis indicates partial formation of LixAl2O3/LiAlO2 in the coating layer during cycling, enhancing lithium ion diffusivity and thus, also the rate performance. [ABSTRACT FROM AUTHOR]

The embedding of Ru nanoparticles into the otherwise unchanged metal-organic framework [[Zn.sub.4]O[(bdc).sub.3]] (MOF-5, bdc = 1,4-benzenedicarboxylate) is examined. Hydrogenolysis of the [[Ru(cod)(cot)].sub.3.5]@MOF-5 inclusion compound at the milder condition has not led to the formation of Ru nanoparticles.

The gas-phase loading of [Zn4O(bdc)3] (MOF-5; bdc = 1,4-benzenedicarboxylate) with the volatile compound [Ru(cod)(cot)] (cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene) was followed by solid-state 13C magic angle spinning (MAS) NMR spectroscopy. Subsequent hydrogenolysis of the adsorbed complex inside the porous structure of MOF-5 at 3 bar and 150 °C was performed, yielding ruthenium nanoparticles in a typical size range of 1.5-1.7 nm, embedded in the intact MOF-5 matrix, as confirmed by transmission electron microscopy (TEM), selected area electron diffraction (SAED), powder X-ray diffraction (PXRD), and X-ray absorption spectroscopy (XAS). The adsorption of CO molecules on the obtained Ru@MOF-5 nanocomposite was followed by IR spectroscopy. Solid-state 2H NMR measurements indicated that MOF-5 was a stabilizing support with only weak interactions with the embedded particles, as deduced from the surprisingly high mobility of the surface Ru-D species in comparison to surfactant-stabilized colloidal Ru nanoparticles of similar sizes. Surprisingly, hydrogenolysis of the [Ru(cod)(cot)]3.5@MOF-5 inclusion compound at the milder condition of 25 °C does not lead to the quantitative formation of Ru nanoparticles. Instead, formation of a ruthenium-cyclooctadiene complex with the arene moiety of the bdc linkers of the framework takes place, as revealed by 13C MAS NMR, PXRD, and TEM. [ABSTRACT FROM AUTHOR]

Three-dimensional covalent organic frameworks (COFs) have been demonstrated as a new class of templates for nanoparticles. Photodecomposition of the [Pd(η(3)-C(3) H(5))(η(5)-C(5)H(5))]@COF-102 inclusion compound (synthesized by a gas-phase infiltration method) led to the formation of the Pd@COF-102 hybrid material. Advanced electron microscopy techniques (including high-angle annular dark-field scanning transmission electron microscopy and electron tomography) along with other conventional characterization techniques unambiguously showed that highly monodisperse Pd nanoparticles ((2.4±0.5) nm) were evenly distributed inside the COF-102 framework. The Pd@COF-102 hybrid material is a rare example of a metal-nanoparticle-loaded porous crystalline material with a very narrow size distribution without any larger agglomerates even at high loadings (30 wt %). Two samples with moderate Pd content (3.5 and 9.5 wt %) were used to study the hydrogen storage properties of the metal-decorated COF surface. The uptakes at room temperature from these samples were higher than those of similar systems such as Pd@metal-organic frameworks (MOFs). The studies show that the H(2) capacities were enhanced by a factor of 2-3 through Pd impregnation on COF-102 at room temperature and 20 bar. This remarkable enhancement is not just due to Pd hydride formation and can be mainly ascribed to hydrogenation of residual organic compounds, such as bicyclopentadiene. The significantly higher reversible hydrogen storage capacity that comes from decomposed products of the employed organometallic Pd precursor suggests that this discovery may be relevant to the discussion of the spillover phenomenon in metal/MOFs and related systems., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)