Considering the natural abundance and low cost of sodium resources, sodium-ion batteries (SIBs) have received much attention for large-scale electrochemical energy storage. However, smart structure design strategies and good mechanistic understanding are required to enable advanced SIBs with high energy density. In recent years, the exploration of advanced cathode, anode and electrolyte materials, as well as advanced diagnostics have been extensively carried out. This review mainly focuses on the challenging problems for the attractive battery materials (i.e. cathode, anode and This article is protected by copyright. All rights reserved. 3 electrolytes) and summarizes the latest strategies to improve their electrochemical performance as well as presenting recent progress in operando diagnostics to disclose the physics behind the electrochemical performance, and to provide guidance and approaches to design and synthesize advanced battery materials. Outlook and perspectives on the future research to build better SIBs are also provided.
We have synthesized Ta thin films on Si substrates placed along a wall of a 2-cm-deep and 1-cm-wide trench, using both a mostly neutral Ta flux by conventional dc magnetron sputtering (dcMS) and a mostly ionized Ta flux by high-power pulsed magnetron sputtering (HPPMS). Structure of the grown films was evaluated by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The Ta thin film grown by HPPMS has a smooth surface and a dense crystalline structure with grains oriented perpendicular to the substrate surface, whereas the film grown by dcMS exhibits a rough surface, pores between the grains, and an inclined columnar structure. The improved homogeneity achieved by HPPMS is a direct consequence of the high ion fraction of sputtered species.
The ion to neutral ratio of the sputtered material have been studied for high power pulsed magnetron sputtering and compared with a continuous direct current (dc) discharge using the same experimental setup except for the power source. Optical emission spectroscopy (OES) was used to study the optical emission from the plasma through a side window. The emission was shown to be dominated by emission from metal ions. The distribution of metal ionized states clearly differed from the distribution of excited states, and we suggest the presence of a hot dense plasma surrounded by a cooler plasma. Sputtered material was ionized close to the target and transported into a cooler plasma region where the emission was also recorded. Assuming a Maxwell–Boltzmann distribution of excited states the emission from the plasma was quantified. This showed that the ionic contribution to the recorded spectrum was over 90% for high pulse powers. Even at relatively low applied pulse powers, the recorded spectra were dominated by emission from ions. OES analysis of the discharge in a continuous dc magnetron discharge was also made, which demonstrated much lower ionization.
The effect of the high pulse current and the duty cycle on the deposition rate in high power pulsed magnetron sputtering (HPPMS) is investigated. Using a Cr target and the same average target current, deposition rates are compared to dc magnetron sputtering (dcMS) rates. It is found that for a peak target current density ITpd of up to 570mAcm−2, HPPMS and dcMS deposition rates are equal. For ITpd>570mAcm−2, optical emission spectroscopy shows a pronounced increase of the Cr+∕Cr0 signal ratio. In addition, a loss of deposition rate, which is attributed to self-sputtering, is observed.
We demonstrate the creation of high-density plasma in a pulsed magnetron discharge. A 2.4 MW pulse, 100 μs wide, with a repetition frequency of 50 Hz is applied to a planar magnetron discharge to study the temporal behavior of the plasma parameters: the electron energy distribution function, the electron density, and the average electron energy. The electron density in the vicinity of the substrate, 20 cm below the cathode target, peaks at 8×1017 m−3, 127 μs after initiating the pulse. Towards the end of the pulse two energy groups of electrons are present with a corresponding peak in average electron energy. With the disapperance of the high-energy electron group, the electron density peaks, and the electron energy distribution appears to be Maxwellian like. Following the electron density peak, the plasma becomes more Druyvesteyn like with a higher average electron energy.
In this paper we present a study of how the magnetic field of a circular planar magnetron is affected when it is exposed to a pulsed high current discharge. Spatially resolved magnetic field measurements are presented and the magnetic disturbance is quantified for different process parameters. The magnetic field is severely deformed by the discharge and we record changes of several millitesla, depending on the spatial location of the measurement. The shape of the deformation reveals the presence of azimuthally drifting electrons close to the target surface. Time resolved measurements show a transition between two types of magnetic perturbations. There is an early stage that is in phase with the axial discharge current and a late stage that is not in phase with the discharge current. The later part of the magnetic field deformation is seen as a travelling magnetic wave. We explain the magnetic perturbations by a combination of E × B drifting electrons and currents driven by plasma pressure gradients and the shape of the magnetic field. A plasma pressure wave is also recorded by a single tip Langmuir probe and the velocity (∼10 3 m s −1 ) of the expanding plasma agrees well with the observed velocity of the magnetic wave. We note that the axial (discharge) current density is much too high compared to the azimuthal current density to be explained by classical collision terms, and an anomalous charge transport mechanism is required.
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