Polyacrylonitrile block copolymers for the preparation of a thin carbon coating around TiO2 nanorods for advanced lithium-ion batteries.
Herein, a new method for the realization of a thin and homogenous carbonaceous particle coating, made by carbonizing RAFT polymerization derived block copolymers anchored on anatase TiO2 nanorods, is presented. These block copolymers consist of a short anchor block (based on dopamine) and a long, easily graphitizable block of polyacrylonitrile. The grafting of such block copolymers to TiO2 nanorods creates a polymer shell, which can be visualized by atomic force microscopy (AFM). Thermal treatment at 700 °C converts the polyacrylonitrile block to partially graphitic structures (as determined by Raman spectroscopy), establishing a thin carbon coating (as determined by transmission electron m…
Facile hybridization of Ni@Fe2O3 superparticles with functionalized reduced graphene oxide and its application as anode material in lithium-ion batteries
Abstract In our present work we developed a novel graphene wrapping approach of Ni@Fe2O3 superparticles, which can be extended as a concept approach for other nanomaterials as well. It uses sulfonated reduced graphene oxide, but avoids thermal treatments and use of toxic agents like hydrazine for its reduction. The modification of graphene oxide is achieved by the introduction of sulfate groups accompanied with reduction and elimination reactions, due to the treatment with oleum. The successful wrapping of nanoparticles is proven by energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy and Raman spectroscopy. The developed composite material shows strongly i…
Precursor Polymers for the Carbon Coating of Au@ZnO Multipods for Application as Active Material in Lithium-Ion Batteries
The synthesis of statistical and block copolymers based on polyacrylonitrile, as a source for carbonaceous materials, and thiol-containing repeating units as inorganic nanoparticle anchoring groups is reported. These polymers are used to coat Au@ZnO multipod heteroparticles with polymer brushes. IR spectroscopy and transmission electron microscopy prove the successful binding of the polymer onto the inorganic nanostructures. Thermogravimetric analysis is applied to compare the binding ability of the block and statistical copolymers. Subsequently, the polymer coating is transformed into a carbonaceous (partially graphitic) coating by pyrolysis. The obtained carbon coating is characterized by…
Stabilizing nanostructured lithium insertion materials via organic hybridization: A step forward towards high-power batteries
Abstract Herein, we present the electrochemical characterization of carbon-coated TiO 2 nanorods, obtained by carbonizing RAFT (reversible addition fragmentation chain transfer) polymerization derived block copolymers anchored on anatase TiO 2 nanorods. These carbon-coated TiO 2 nanorods show an improved electrochemical performance in terms of first cycle reversibility, specific capacity, cycling stability, and high rate capability. More importantly, however, the structural disordering observed in the uncoated TiO 2 nanorods by means of galvanostatic and potentiodynamic cycling as well as ex situ XRD analysis, does not occur for the carbon-coated material. Preventing this structural disorde…
Structural and dynamical characterization of melt PEO–salt mixtures
Abstract Salt doped poly ethylene oxide (PEO) mixtures were investigated by means of both small angle neutron scattering and QENS techniques aiming to characterize morphological and dynamical features in the melt state. These experimental evidences provide support to the proposed heterogeneous scenario for polymer electrolytes. In particular, the existence of PEO–cation complexes is proposed to play a major role in intramolecular cooperation and intermolecular transient crosslinks, which affects the mixture properties.
Segmental dynamics in polymer electrolytes
Polymer dynamics in poly(ethylene oxide) (PEO)–salt mixtures is investigated by means of quasi-elastic neutron scattering (QENS). In a previous study, we reported QENS data from the NEAT spectrometer (BENSC) that evidenced, for the first time, a dynamic heterogeneity in PEO–salt mixtures induced by salt addition. This finding is supported by molecular dynamics (MD) simulations carried out by Borodin et al. In agreement with MD simulations, our QENS data revealed two distinct processes: a fast motion corresponding to the bulk polymer and a slower relaxation, which we attribute to formation of PEO–cation complexes. In this paper we present new QENS data from the high-resolution spectrometer I…
Dynamic heterogeneity in polymer electrolytes. Comparison between QENS data and MD simulations
Abstract We have investigated the dynamics of poly(ethylene oxide) (PEO) lithium-based salt electrolytes (PEO–LiBETI) using quasi-elastic neutron scattering (QENS). Measurements were carried out on the spectrometer NEAT (HMI, Berlin) above the melting temperature of PEO ( T m ≈65°C). The experimental data fully support the Molecular Dynamics (MD)-derived model of a heterogeneous dynamics in dilute PEO-salt electrolytes. In agreement with MD simulations carried out on PEO–LiPF 6 , we find evidences for the existence of two dynamic processes: (a) a faster process that is described in terms of the pure PEO dynamics and (b) a second component which we identify with the slower motion of the PEO …
Multiple points of view of heteronuclear NOE: long range vs short range contacts in pyrrolidinium based ionic liquids in the presence of Li salts.
The nuclear Overhauser enhancement (NOE) is a powerful tool of NMR spectroscopy extensively used to gain structural information in ionic liquids (ILs). A general model for the distance dependence of intermolecular NOE in ILs was recently proposed showing that NOE spots beyond the first solvation shell and accounts for long-range effects. This conclusion prompted for a deep rethinking of the NOE data interpretation in ILs. In this paper we present an extensive and quantitative study of N-propyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR13TFSI), the homologue with bis(fluorosulfonyl)imide (PYR13FSI), and their mixtures with LiTFSI based on 1H-19F and 1H-7LiNOE correlation …
Extraordinary Performance of Carbon‐Coated Anatase TiO 2 as Sodium‐Ion Anode
The synthesis of in situ polymer‐functionalized anatase TiO2 particles using an anchoring block copolymer with hydroxamate as coordinating species is reported, which yields nanoparticles (≈11 nm) in multigram scale. Thermal annealing converts the polymer brushes into a uniform and homogeneous carbon coating as proven by high resolution transmission electron microscopy and Raman spectroscopy. The strong impact of particle size as well as carbon coating on the electrochemical performance of anatase TiO2 is demonstrated. Downsizing the particles leads to higher reversible uptake/release of sodium cations per formula unit TiO2 (e.g., 0.72 eq. Na+ (11 nm) vs only 0.56 eq. Na+ (40 nm)) while the …
Synthesis and characterization of carbon coated sponge-like tin oxide (SnOx) films and their application as electrode materials in lithium-ion batteries
Nanoporous metal oxides are widely used for the development of various functional nanostructures. We report on the synthesis of sponge-like tin oxide films on copper foil by anodization of electrochemically deposited tin films. The thin films are functionalized using a surface-anchoring carbon precursor-polymer (poly(acrylonitrile-b-dopamine acrylamide)) followed by annealing at elevated temperature to convert the polymer coating into a carbonaceous coating. The as prepared and the carbon coated films are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and Raman spectroscopy. Subsequently, both SnOx films are employed as a…
Carbon-Coated Anatase TiO2Nanotubes for Li- and Na-Ion Anodes
aInstitute of Physical Chemistry and MEET Battery Research Centre, University of Muenster, 48149 Muenster, Germany bHelmholtz-Institute Ulm (HIU), Electrochemistry I, 89081 Ulm, Germany cKarlsruher Institute of Technology (KIT), 76021 Karlsruhe, Germany dInstitute for Organic Chemistry, University of Mainz, 55128 Mainz, Germany eGraduate School Materials Science in Mainz, 55128 Mainz, Germany fInstitute for Inorganic and Analytical Chemistry, University of Mainz, 55128 Mainz, Germany gMax Planck Institute for Polymer Research, 55128 Mainz, Germany