Zeitschriftenaufsätze

The effects of automotive-related lithium-ion module design, i.e. module stiffness and initial compression during module assembly on cell aging, swelling and pressure evolution are still largely unknown. This paper presents the results of a long-term aging study of 12 large-format automotive graphite/NMC 622 pouch cells, cycled for different module stiffnesses and initial compressions using design of experiments. Statistical analysis of mechanical and aging data revealed significant nonlinear (interaction) effects of both factors on pressure evolution, capacity loss and increase in internal resistance of the cells. Pressure dependent cell aging is observed over 1000 cycles, which was related to loss of active material at the cathode from differential voltage analysis. Post-mortem analysis confirmed a cathode active material loss via half- and full-cell measurements of harvested electrodes. Cross-section SEM micrographs revealed increasing NMC-particle cracking with higher pressure. Based on this, a fatigue-based aging model was developed to describe the capacity loss due to pressure dependent particle cracking. The presented approach enables both improved modeling of pressure dependent aging and lifetime optimized module design

Memristive devices have led to an increased interest in neuromorphic systems. However, different device requirements are needed for the multitude of computation schemes used there. While linear and time-independent conductance modulation is required for machine learning, non-linear and time-dependent properties are necessary for neurobiologically realistic learning schemes. In this context, an adaptation of the resistance switching characteristic is necessary with regard to the desired application. Recently, bi-layer oxide memristive systems have proven to be a suitable device structure for this purpose, as they combine the possibility of a tailored memristive characteristic with low power consumption and uniformity of the device performance. However, this requires technological solutions that allow for precise adjustment of layer thicknesses, defect densities in the oxide layers, and suitable area sizes of the active part of the devices. For this purpose, we have investigated the bi-layer oxide system TiN/TiOx/HfOx/Au with respect to tailored I-V non-linearity, the number of resistance states, electroforming, and operating voltages. Therefore, a 4-inch full device wafer process was used. This process allows a systematic investigation, i.e. the variation of physical device parameters across the wafer as well as a statistical evaluation of the electrical properties with regard to the variability from device to device and from cycle to cycle. For the investigation, the thickness of the HfOx layer was varied between 2 nm and 8 nm, and the size of the active area of devices was changed between 100 [my]m^2 and 2500 [my]m^2. Furthermore, the influence of the HfOx deposition condition was investigated, which influences the conduction mechanisms from a volume-based, filamentary to an interface-based resistive switching mechanism. Our experimental results are supported by numerical simulations that show the contribution of the HfOx film in the bi-layer memristive system and guide the development of a targeting device.

The Fourier modal method (FMM) is certainly one of the most popular and general methods for the modeling of diffraction gratings. However, for non-lamellar gratings it is associated with a staircase approximation of the profile, leading to poor convergence rate for metallic gratings in TM polarization. One way to overcome this weakness of the FMM is the use of the fast Fourier factorization (FFF) first derived for the differential method. That approach relies on the definition of normal and tangential vectors to the profile. Instead, we introduce a coordinate system that matches laterally the profile and solve the covariant Maxwells equations in the new coordinate system, hence the name matched coordinate method (MCM). Comparison of efficiencies computed with MCM with other data from the literature validates the method.

Sodium-ion battery (SIB) is significant for grid-scale energy storage. However, a large radius of Na ions raises the difficulties of ion intercalation, hindering the electrochemical performance during fast charge/discharge. Conventional strategies to promote rate performance focus on the optimization of ion diffusion. Improving interface capacitive-like storage by tuning the electrical conductivity of electrodes is also expected to combine the features of the high energy density of batteries and the high power density of capacitors. Inspired by this concept, an oxide-metal sandwich 3D-ordered macroporous architecture (3DOM) stands out as a superior anode candidate for high-rate SIBs. Taking Ni-TiO2 sandwich 3DOM as a proof-of-concept, anatase TiO2 delivers a reversible capacity of 233.3 mAh g^-1 in half-cells and 210.1 mAh g^-1 in full-cells after 100 cycles at 50 mA g^-1. At the high charge/discharge rate of 5000 mA g^-1, 104.4 mAh g^-1 in half-cells and 68 mAh g^-1 in full-cells can also be obtained with satisfying stability. In-depth analysis of electrochemical kinetics evidence that the dominated interface capacitive-like storage enables ultrafast uptaking and releasing of Na-ions. This understanding between electrical conductivity and rate performance of SIBs is expected to guild future design to realize effective energy storage.

The use of vanadyl porphyrins either in synthetic compounds or naturally occurring in asphaltenes is investigated as a source of proton hyperpolarization via dynamic nuclear polarization (DNP) in nuclear magnetic resonance (NMR) experiments. The features of dynamics and location of the vanadyl VO2+ complex in aggregates within the oil asphaltene molecules are studied by means of DNP, electron paramagnetic resonance (EPR), and NMR field cycling relaxometry. Both the solid effect and Overhauser DNP were observed for the asphaltene solution in benzene, as well as in the solution and solid states for synthetic compounds. By comparison with a solution of synthetic vanadyl porphyrins, it is shown that vanadyl porphyrins in asphaltene aggregates are localized outside of the interface of the asphaltene aggregates and more exposed to the maltene molecules than free carbon-centered radicals associated with the core of asphaltene molecules. The perceptible contribution of scalar interaction is observed in solutions for both synthetic and asphaltene vanadyl porphyrins.