Design of hybrid asymmetric capacitors in aqueous electrolyte using ZTC and ultraporous activated carbons

The use of two different materials as electrodes allows the construction of asymmetric and hybrid capacitors cells with enhanced energy and power density. This approach is especially well-suited for overcoming the limitations of pseudocapacitive materials that provide a huge capacitance boost, but in a limited potential window. In this work, we introduce the concepts and protocols that are required for a successful design of such systems, which is illustrated by the construction of an asymmetric hybrid cell where a zeolite-templated carbon and an ultraporous activated carbon have been combined.

Design of Activated Carbon/Activated Carbon Asymmetric Capacitors

Supercapacitors are energy storage devices that offer a high power density and a low energy density in comparison with batteries. Their limited energy density can be overcome by using asymmetric configuration in mass electrodes, where each electrode works within their maximum available potential window, rendering the maximum voltage output of the system. Such asymmetric capacitors are optimized using the capacitance and the potential stability limits of the electrodes, with the reliability of the design largely depending on the accuracy and the approach taken for the electrochemical characterization. Therefore, the performance could be lower than expected and even the system could break down, if a well thought out procedure is not followed. In this work, a procedure for the development of asymmetric supercapacitors based on activated carbons is detailed. Three activated carbon materials with different textural properties and surface chemistry have been systematically characterized in neutral aqueous electrolyte. The asymmetric configuration of the masses of both electrodes in the supercapacitor has allowed to cover a higher potential window, resulting in an increase of the energy density of the three devices studied when compared with the symmetric systems, and an improved cycle life.

A study of some low frequency applications of silicon capacitors. Internal research.

Mode of access: Internet.

Defects in PN junctions and MOS capacitors observed using thermally stimulated current and capacitance measurements, videotape script /

Includes bibliographical references (p. 14).

Radiation effects in metal-oxide-semiconductor capacitors

An investigation has been undertaken into the effects of various radiations on commercially made Al-SiO2-Si Capacitors (MOSCs). Detailed studies of the electrical and physical nature of such devices have been used to characterise both virgin and irradiated devices. In particular, an investigation of the nature and causes of dielectric breakdown in MOSCs has revealed that intrinsic breakdown is a two-stage process dominated by charge injection in a pre-breakdown stage; this is associated with localised high-field injection of carriers from the semiconductor substrate to interfacial and bulk charge traps which, it is proposed, leads to the formation of conducting channels through the dielectric with breakdown occurring as a result of the dissipation of the conduction band energy. A study of radiation-induced dielectric breakdown has revealed the possibility of anomalous hot-electron injection to an excess of bulk oxide traps in the ionization channel produced by very heavily ionizing radiation, which leads to intrinsic breakdown in high-field stressed devices. These findings are interpreted in terms of a modification to the model for radiation-induced dielectric breakdown based upon the primary dependence of breakdown on charge injection rather than high-field mechanisms. The results of a detailed investigation of charge trapping and interface state generation in such MOSCs due to various radiations has revealed evidence of neutron induced interface states, and of the generation of positive oxide charge in devices due to all of the radiations tested. In particular, the greater the linear energy transfer of the radiation, the greater the magnitude of charge trapped in the oxide and the greater the number of interface states generated. These findings are interpreted in terms of Si-H and Si-OH bond-breaking at the Si-SiO2 interface which is enhanced by charge carrier transfer to the interface and by anomalous charge injection to compensate for the excess of charge carriers created by the radiation.

New modular structure DC-DC converter without electrolytic capacitors for renewable energy applications

Electrolytic capacitors are extensively used in power converters but they are bulky, unreliable, and have short lifetimes. This paper proposes a new capacitor-free high step-up dc-dc converter design for renewable energy applications such as photovoltaics (PVs) and fuel cells. The primary side of the converter includes three interleaved inductors, three main switches, and an active clamp circuit. As a result, the input current ripple is greatly reduced, eliminating the necessity for an input capacitor. In addition, zero voltage switching (ZVS) is achieved during switching transitions for all active switches, so that switching losses can be greatly reduced. Furthermore, a three-phase modular structure and six pulse rectifiers are employed to reduce the output voltage ripple. Since magnetic energy stored in the leakage inductance is recovered, the reverse-recovery issue of the diodes is effectively solved. The proposed converter is justified by simulation and experimental tests on a 1-kW prototype.

Effects of alternating current voltage amplitude and oxide capacitance on mid-gap interface state defect density extractions in In0.53Ga 0.47As capacitors

This work looks at the effect on mid-gap interface state defect density estimates for In0.53Ga0.47As semiconductor capacitors when different AC voltage amplitudes are selected for a fixed voltage bias step size (100 mV) during room temperature only electrical characterization. Results are presented for Au/Ni/Al2O3/In0.53Ga0.47As/InP metal–oxide–semiconductor capacitors with (1) n-type and p-type semiconductors, (2) different Al2O3 thicknesses, (3) different In0.53Ga0.47As surface passivation concentrations of ammonium sulphide, and (4) different transfer times to the atomic layer deposition chamber after passivation treatment on the semiconductor surface—thereby demonstrating a cross-section of device characteristics. The authors set out to determine the importance of the AC voltage amplitude selection on the interface state defect density extractions and whether this selection has a combined effect with the oxide capacitance. These capacitors are prototypical of the type of gate oxide material stacks that could form equivalent metal–oxide–semiconductor field-effect transistors beyond the 32 nm technology node. The authors do not attempt to achieve the best scaled equivalent oxide thickness in this work, as our focus is on accurately extracting device properties that will allow the investigation and reduction of interface state defect densities at the high-k/III–V semiconductor interface. The operating voltage for future devices will be reduced, potentially leading to an associated reduction in the AC voltage amplitude, which will force a decrease in the signal-to-noise ratio of electrical responses and could therefore result in less accurate impedance measurements. A concern thus arises regarding the accuracy of the electrical property extractions using such impedance measurements for future devices, particularly in relation to the mid-gap interface state defect density estimated from the conductance method and from the combined high–low frequency capacitance–voltage method. The authors apply a fixed voltage step of 100 mV for all voltage sweep measurements at each AC frequency. Each of these measurements is repeated 15 times for the equidistant AC voltage amplitudes between 10 mV and 150 mV. This provides the desired AC voltage amplitude to step size ratios from 1:10 to 3:2. Our results indicate that, although the selection of the oxide capacitance is important both to the success and accuracy of the extraction method, the mid-gap interface state defect density extractions are not overly sensitive to the AC voltage amplitude employed regardless of what oxide capacitance is used in the extractions, particularly in the range from 50% below the voltage sweep step size to 50% above it. Therefore, the use of larger AC voltage amplitudes in this range to achieve a better signal-to-noise ratio during impedance measurements for future low operating voltage devices will not distort the extracted interface state defect density.

An ether-functionalised cyclic sulfonium based ionic liquid as an electrolyte for electrochemical double layer capacitors

A novel cyclic sulfonium cation-based ionic liquid (IL) with an ether-group appendage and the bis{(trifluoromethyl)sulfonyl}imide anion was synthesised and developed for electrochemical double layer capacitor (EDLC) testing. The synthesis and chemical-physical characterisation of the ether-group containing IL is reported in parallel with a similarly sized alkyl-functionalised sulfonium IL. Results of the chemical-physical measurements demonstrate how important transport properties, i.e. viscosity and conductivity, can be promoted through the introduction of the ether-functionality without impeding thermal, chemical or electrochemical stability of the IL. Although the apparent transport properties are improved relative to the alkyl-functionalised analogue, the ether-functionalised sulfonium cation-based IL exhibits moderately high viscosity, and poorer conductivity, when compared to traditional EDLC electrolytes based on organic solvents (propylene carbonate and acetonitrile). Electrochemical testing of the ether-functionalised sulfonium IL was conducted using activated carbon composite electrodes to inspect the performance of the IL as a solvent-free electrolyte for EDLC application. Good cycling stability was achieved over the studied range and the performance was comparable to other solvent free,
IL-based EDLC systems. Nevertheless, limitations of the attainable performance are primarily the result of sluggish transport properties and a restricted operative voltage of the IL, thus highlighting key aspects of this field which require further attention.

Binary Mixtures of 1-Butyl-1-Methylpyrrolidinium Bis{(trifluoromethyl)Sulfonyl}Imide and Aliphatic Nitrile Solvents As Electrolyte for Electrochemical Double Layer Capacitors (Invited).

Electrochemical double layer capacitors (EDLCs), also known as supercapacitors, are promising energy storage devices, especially when considering high power applications [1]. EDLCs can be charged and discharged within seconds [1], feature high power (10 kW·kg-1) and an excellent cycle life (>500,000 cycles). All these properties are a result of the energy storage process of EDLCs, which relies on storing energy by charge separation instead of chemical redox reactions, as utilized in battery systems. Upon charging, double layers are forming at the electrode/electrolyte interface consisting of the electrolyte’s ions and electric charges at the electrode surface.In state-of-the-art EDLC systems activated carbons (AC) are used as active materials and tetraethylammonium tetrafluoroborate ([Et4N][BF4]) dissolved in organic solvents like propylene carbonate (PC) or acetonitrile (ACN) are commonly used as the electrolyte [2]. These combinations of materials allow operative voltages up to 2.7 V - 2.8 V and an energy in the order of 5 Wh·kg-1[3]. The energy of EDLCs is dependent on the square of the operative voltage, thus increasing the usable operative voltage has a strong effect on the delivered energy of the device [1]. Due to their high electrochemical stability, ionic liquids (ILs) were thoroughly investigated as electrolytes for EDLCs, as well as, batteries, enabling high operating voltages as high as 3.2 V - 3.5 V for the former [2]. While their unique ionic structure allows the usage of neat ILs as electrolyte in EDLCs, ILs suffer from low conductivity and high viscosity increasing the intrinsic resistance and, as a result, a lower power output of the device. In order to overcome this issue, the usage of blends of ionic liquids and organic solvents has been considered a feasible strategy as they combine high usable voltages, while still retaining good transport properties at the same time.In our recent work the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide ([Pyrr14][TFSI]) was combined with two nitrile-based organic solvents, namely butyronitrile (BTN) and adiponitrile (ADN), and the resulting blends were investing regarding their usage in electrochemical double layer capacitors [4,5]. Firstly, the physicochemical properties were investigated, showing good transport properties for both blends, which are similar to the state-of-the-art combination of [Et4N][BF4] in PC. Secondly, the electrochemical properties for EDLC application were studied in depth revealing a high electrochemical stability with a maximum operative voltage as high as 3.7 V. In full cells these high voltage organic solvent based electrolytes have a good performance in terms of capacitance and an acceptable equivalent series resistance at cut-off voltages of 3.2 and 3.5 V. However, long term stability tests by float testing revealed stability issues when using a maximum voltage of 3.5 V for prolonged time, whereas at 3.2 V no such issues are observed (Fig. 1).Considering the obtained results, the usage of ADN and BTN blends with [Pyrr14][TFSI] in EDLCs appears to be an interesting alternative to state-of-the-art organic solvent based electrolytes, allowing the usage of higher maximum operative voltages while having similar transport properties to 1 mol∙dm-3 [Et4N][BF4] in PC at the same time.

The Effect of Package Geometry on Moisture Driven Degradation of Polymer Aluminum Capacitors

Polymer aluminum electrolytic capacitors were introduced to provide an alternative to liquid electrolytic capacitors. Polymer electrolytic capacitor electric parameters of capacitance and ESR are less temperature dependent than those of liquid aluminum electrolytic capacitors. Furthermore, the electrical conductivity of the polymer used in these capacitors (poly-3,4ethylenedioxithiophene) is orders of magnitude higher than the electrolytes used in liquid aluminum electrolytic capacitors, resulting in capacitors with much lower equivalent series resistance which are suitable for use in high ripple-current applications. The presence of the moisture-sensitive polymer PEDOT introduces concerns on the reliability of polymer aluminum capacitors in high humidity conditions. Highly accelerated stress testing (or HAST) (110ºC, 85% relative humidity) of polymer aluminum capacitors in which the parts were subjected to unbiased HAST conditions for 700 hours was done to understand the design factors that contribute to the susceptibility to degradation of a polymer aluminum electrolytic capacitor exposed to HAST conditions. A large scale study involving capacitors of different electrical ratings (2.5V – 16V, 100µF – 470 µF), mounting types (surface-mount and through-hole) and manufacturers (6 different manufacturers) was done to determine a relationship between package geometry and reliability in high temperature-humidity conditions. A Geometry-Based HAST test in which the part selection limited variations between capacitor samples to geometric differences only was done to analyze the effect of package geometry on humidity-driven degradation more closely. Raman spectroscopy, x-ray imaging, environmental scanning electron microscopy, and destructive analysis of the capacitors after HAST exposure was done to determine the failure mechanisms of polymer aluminum capacitors under high temperature-humidity conditions.

Improvement of carbon materials performance by nitrogen functional groups in electrochemical capacitors in organic electrolyte at severe conditions

N-doped activated carbon fibers have been synthesized by using chemically polymerized aniline as source of nitrogen. Commercial activated carbon fibers (A20) were chemically modified with a thin film of polyaniline (PANI) inside the microporosity of the carbon fibers. The modified activated carbon fibers were carbonized at 600 and 800 °C, respectively. In this way, activated carbon fibers modified with surface nitrogen species were prepared in order to analyze their influence in the performance of electrochemical capacitors in organic electrolyte. Symmetric capacitors were made of activated carbon fibers and N-doped activated carbon fibers and tested in a two-electrode cell configuration, using triethylmethylammonium tetrafluoroborate/propylene carbonate (TEMA-BF4/PC) as electrolyte. The effect of nitrogen species in the degradation or stabilization of the capacitor has been analyzed through floating durability tests using a high voltage charging (3.2 V). The results show higher stabilizing effect in carbonized samples (N-ACF) than in non-carbonized samples and pristine activated carbon fibers, which is attributed to the presence of aromatic nitrogen group, especially positively charged N-functional groups.

Lithium-ion capacitors with 2D Nb2CTx (MXene) - carbon nanotube electrodes

There is a growing interest to hybrid energy storage devices, such as lithium-ion capacitors, in which battery-type electrodes are combined with capacitor-type ones. It is anticipated that the energy density (either gravimetric or volumetric) of lithium-ion capacitors is improved if pseudocapacitive or fast insertion materials are used instead of conventional activated carbon (AC) in the capacitor-type electrode. MXenes, a new family of two-dimensional transition metal carbides, demonstrate metallic conductivity and fast charge-discharge behavior that make them suitable for this application. In this study, we move beyond single electrodes, half-cell studies and demonstrate three types of hybrid cells using Nb2CTx-carbon nanotube (CNT) films. It is shown that lithiated graphite/Nb2CTx-CNT, Nb2CTx-CNT/LiFePO4 and lithiated Nb2CTx-CNT/Nb2CTx-CNT cells are all able to operate within 3 V voltage windows and deliver capacities of 43, 24 and 36 mAh/g (per total weight of two electrodes), respectively. Moreover, the polarity of the electrodes can be reversed in the symmetric Nb2CTx-CNT cells from providing a positive potential between 0 and 3 V to a negative one from -3 to 0 V. It is shown that the volumetric energy density (50-70 Wh/L) of our first-generation devices with MXene electrodes exceeds that of a lithium titanate/AC capacitor.

Asymmetrical DC link voltage configuration for a diode-clamped inverter

There is a trade off between a number of output voltage levels and the reliability and efficiency of a multilevel converter. A new configuration of diode-clamped multilevel inverters with a different combination of DC link capacitors voltage has been proposed in this paper. Two different symmetrical and asymmetrical unequal arrangements for a four-level diode-clamped inverter have been compared, in order to find an optimum arrangement with lower switching losses and optimised output voltage quality. The simulation and hardware results for a four-level inverter show that the asymmetrical configuration can obtain more output voltage levels with the same number of components compared with a conventional four-level inverter and this will lead to the reduction of the harmonic content of the output voltage. A new family of multi-output DC-DC converters with a simple control strategy has been utilised as a front-end converter to supply the DC link capacitor voltages for the optimised configuration.