Philip Niehoff

Synthesis, structural characterisation and anti-proliferative activity of NHC gold amino acid and peptide conjugates

We report the synthesis of new NHC gold(I) and NHC gold(III) halide, amino acid and dipeptide complexes. Transmetallation of the N-phenylalanine-substituted NHC silver complex 3 with Me2SAuCl yields the phenylalanine-NHC gold(I) conjugate 4a. Halide exchange with LiBr and oxidation of 4a with Br2 in CH2Cl2 yields the phenylalanine-NHC Au(I) and Au(III) bromides 4b and 4c, respectively. Reaction of N-Boc protected cysteine methyl ester (Boc-Cys-OMe) or the dipeptide N-Boc-Leu-Cys-OMe with the NHC gold chloride 6a yields the (NHC)Au-S complexed amino acid and dipeptide derivatives 8 and 9. The NHC gold(III) complexes 4c and 6c were characterised by single crystal X-ray analysis. All of the tested gold carbene complexes showed significant anti-tumor activity on the HeLa, HepG2 and HT-29 cancer cell lines. The best compounds show activity comparable to the well-known anti-cancer drug cisplatin. There seems to be no clear cut structure-activity relationship in the compounds tested, nor did we observe a dependence on the metal oxidation state or the different halide substituents. Given the ease of preparation, stability and high activity of the compounds described herein, it may be possible to design tumor-specific anti-cancer agents based on NHC gold amino acid conjugates in the future.

Interface investigations of a commercial lithium ion battery graphite anode material by sputter depth profile X-ray photoelectron spectroscopy.

Here we provide a detailed X-ray photoelectron spectroscopy (XPS) study of the electrode/electrolyte interface of a graphite anode from commercial NMC/graphite cells by intense sputter depth profiling using a polyatomic ion gun. The uniqueness of this method lies in the approach using 13-step sputter depth profiling (SDP) to obtain a detailed model of the film structure, which forms at the electrode/electrolyte interface often noted as the solid electrolyte interphase (SEI). In addition to the 13-step SDP, several reference experiments of the untreated anode before formation with and without electrolyte were carried out to support the interpretation. Within this work, it is shown that through charging effects during X-ray beam exposure chemical components cannot be determined by the binding energy (BE) values only, and in addition, that quantification by sputter rates is complicated for composite electrodes. A rough estimation of the SEI thickness was carried out by using the LiF and graphite signals as internal references.

Composition and Growth Behavior of the Surface and Electrolyte Decomposition Layer of/on a Commercial Lithium Ion Battery LixNi1/3Mn1/3Co1/3O2 Cathode Determined by Sputter Depth Profile X-ray Photoelectron Spectroscopy

A detailed X-ray photoelectron spectroscopy (XPS) study of the surface and electrolyte decomposition layer of a LixNi1/3Mn1/3Co1/3O2 (NMC) cathode from commercial NMC/graphite cells by intense sputter depth profiling (SDP) using a polyatomic ion gun is provided. Cathodes of a cell after electrochemical formation and a cell at a state of initial capacity (SOIC) of 80%, which was reached after 2500 full cycles at 30 °C, are investigated.

Challenges of “Going Nano”: Enhanced Electrochemical Performance of Cobalt Oxide Nanoparticles by Carbothermal Reduction and In Situ Carbon Coating

The electrochemical performance of nano- and micron-sized Co(3)O(4) is investigated, highlighting the substantial influence of the specific surface area on the obtainable specific capacities as well as the cycling stability. In fact, Co(3)O(4) materials with a high surface area (i.e. a small particle size) show superior specific features, which are, however, accompanied by a rapid capacity fading, owing to the increased formation of an insulating polymeric surface film that results from transition-metal-catalyzed electrolyte decomposition. The simultaneous coating with carbon of Co(3)O(4) nanoparticles and in situ reduction of the Co(3)O(4) by a carbothermal route yields a CoO-Co-C nanocomposite. The formation of this material substantially enhances the long-term cycling stability and coulombic efficiency of the lithium-ion active material used. Although the metallic cobalt enhances the electronic conductivity within the electrode and remains electrochemically inactive (as revealed by in situ powder X-ray diffraction analysis), it might have a detrimental effect on the long-term cycling stability by catalytically inducing continuous electrolyte decomposition.

A 3D porous Li-rich cathode material with an in situ modified surface for high performance lithium ion batteries with reduced voltage decay

High crystallinity Li-rich porous materials integrated with an in situ formed surface containing carbonaceous compounds are synthesized through a facile approach. The rationally designed procedure involves the formation of a specific morphology of a hydroxide precursor assisted by a self-made template and subsequent high temperature treatment to obtain a Li1.2Mn0.56Ni0.16Co0.08O2 target product. The porous morphology is investigated using field-emission scanning electron microscopy and its surface area is quantitatively examined by gas sorption analysis coupled with the Brunauer–Emmett–Teller method. The crystallinity is characterized by X-ray diffraction and high-resolution transmission electron microscopy. X-ray photoelectron spectroscopy, CHN elemental analysis and small angle neutron scattering confirm the presence of carbonaceous compounds in the surface composition. The prepared material exhibits superior discharge rate capability and excellent cycling stability. It shows minor capacity loss after 100 cycles at 0.5C and retains 94.9% of its initial capacity after 500 cycles at 2C. Even more notably, the “voltage decay” during cycling is also significantly decreased. It has been found that carbonaceous compounds play a critical role in reducing the layered to spinel structural transformation during cycling. Therefore, the present porous Li-rich material with surface modified carbonaceous compounds represents an attractive material for advanced lithium-ion batteries.

Investigation of nano-sized Cu(II)O as a high capacity conversion material for Li-metal cells and lithium-ion full cells

In this study, self-prepared nanostructured CuO electrodes show no capacity decay for 40 cycles at 0.1C in Li metal cells. The reaction mechanisms of the CuO electrodes are investigated. With the help of in situ EIS, in situ XRD, TEM, XAS, SQUID, IC and GC-MS, it is found that the as-prepared CuO electrode undergoes significant phase and composition changes during the initial lithiation, with the transformation of CuO to nano-crystalline Cu. During the 1st delithiation, Cu is inhomogeneously oxidized, which yields a mixture of Cu2O, Cu2−xO and Cu. The incomplete conversion reaction during the 1st cycle is accompanied by the formation and partial decomposition of the solid electrolyte interphase (SEI) as the side reactions. Nevertheless, from the 1st to the 5th delithiation, the oxidation state of Cu approaches +2. After an additional formation step, the transformation to Cu and back to Cu2−xO remains stable during the subsequent long-term cycling with no electrolyte decomposition products detected. The LiNi1/3Mn1/3Co1/3O2 (NMC-111)/CuO full cells show high capacities (655.8 ± 0.6, 618.6 ± 0.9 and 290 ± 2 mA h g−1 at 0.1, 1 and 10C, respectively), within the voltage range of 0.7–4.0 V at 20 °C and a high capacity retention (85% after 200 cycles at 1C).

Coexistence of conversion and intercalation mechanisms in lithium ion batteries: Consequences for microstructure and interaction between the active material and electrolyte

Abstract Conversion-type lithium ion batteries experience severe and partly irreversible phase transitions during operation. Such phase transitions reduce the crystallite size and therefore enhance the exchange of the Li ions. Concurrently, the irreversible nature of the phase transitions may deteriorate the cycling stability and the long-term capacity of conversion-type batteries. In this contribution, the observed correlations between the crystal structures of compounds which are employed as anodes in conversion-type Li ion cells, the capacity and the long-term stability of these cells are discussed. The central characteristics affecting the performance of conversion-type Li ion cells seem to be the similarity of crystal structures of intermediately forming phases during the charge/discharge process, which facilitates strong local preferred orientation of nanocrystallites of neighboring phases and for the formation of local strain fields at partially coherent phase boundaries. The effect of the above-mentioned phenomena on capacity and cycle stability is argued from the point of view of a possibly impeded ion exchange. Equilibrium open circuit potentials are calculated using the CALPHAD method. However, it is shown that in order to better reproduce the experimentally determined plateau voltages, thermodynamic descriptions of the non-equilibrium intermediate phases have to be included. In addition, the stabilization of the conversion reaction by the electrolyte is pointed out.