Trimming of microring resonators by photooxidation of a plasma-polymerized organosilane cladding material

As the complexity of microphotonic devices grows, the ability to precisely trim microring resonators becomes increasingly important. Photo-oxidation trimming uses UV irradiation to oxidize a cladding layer composed of polymerized hexamethyldisilane (6M2S) deposited with plasma-enhanced chemical vapor deposition (PECVD). PECVD 6M2S has optical properties that are compatible with microring devices, and its high cross linking renders it insoluble. Photo-oxidation decreases the refractive index of PECVD 6M2S by nearly 4%, permitting large resonance shifts that are not feasible with thermal trimming techniques. Resonance shifts from single-mode, 100 microm diameter Si3N4 (n =2.2) rings were as large as 12.8 nm for the TE mode and 23.5 nm for the TM mode.     

General equivalent circuit of batteries and fuel cells

A general electrical circuit is described whose properties are analogous to those of fuel cells and batteries. It is shown how this equivalent circuit model can show the influence of changes in material parameters upon the output of such physical systems. As an example, the significance of the transference numbers of minority electronic and ionic charge carriers in the electrolyte on the output voltage of fuel cells and batteries is readily seen. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Comparative study between silicon-rich oxide films obtained by LPCVD and PECVD

A comparative study of compositional and optical properties of silicon-rich oxide (SRO) films deposited by low-pressure chemical vapor deposition (LPCVD) and plasma-enhanced chemical vapor deposition (PECVD) is presented. Infrared spectra revealed the presence of hydrogen bonded to silicon atoms in the SRO–PECVD films, whereas in SRO–LPCVD films the IR spectra looked like the stoichiometric thermal silicon oxide. Moreover, X-ray photoelectron spectroscopy (XPS) studies showed that the SRO–PECVD films contain a higher content of nitrogen than SRO–LPCVD films. In spite of differences, the SRO films obtained by both methods show a strong room-temperature photoluminescence (PL). However, the highest PL intensity was emitted by SRO films obtained by LPCVD.     

(Ce0.8Sm0.2O2-δ/Y2O3:ZrO2)N超晶格电解质薄膜的制备及表征

采用脉冲激光沉积技术(PLD), 在MgO单晶基底上, 依次沉积氧化钐掺杂的氧化铈(Ce_0.8Sm_0.2O_2-δ, SDC)和钇稳定氧化锆(8 mol%Y₂O₃:ZrO₂, YSZ)制备了五种(SDC/YSZ)_N (N=3, 5, 10, 20, 30) 超晶格电解质薄膜. 利用X射线衍射(XRD)、高分辨透射电子显微镜(HR-TEM)和交流阻抗对其形貌、相结构和电学性能进行了表征. 结果显示, (SDC/YSZ)_N超晶格电解质薄膜之间形成了明显的界面和较好的超晶格结构; 薄膜表面颗粒生长均匀、致密、平滑, 在薄膜的界面处没有元素相互扩散也未出现裂纹, 外延生长良好; 电导率随着(SDC/YSZ)_N超晶格电解质界面数的增加而增加, 而活化能则随之减少, 是较为理想的低温固体氧化物燃料电池电解质.     

Evaluation of solid electrolyte cells with a versatile electrochemical technique

Voltage losses in fuel cells and other solid electrolyte systems are due to several mass transport and kinetics processes at the electrode/electrolyte interface as well as to ohmic contributions from the electrolyte, electrodes, current collectors and contact resistances. Electrochemical impedance spectroscopy (EIS) has been in use for several decades in fuel cell research and is quite effective in determining the contribution of individual electrode and electrolyte processes. However, data acquisition and analysis can be time-consuming and the technique has many limitations whilst cell performance and operating conditions are varying rapidly with time especially when the cells are under current load. The galvanostatic current interruption (GCI) technique is fast and can be used under a wide range of operating as well as for rapidly varying loads and cell performance conditions. In this paper a totally new and very simple way of adapting commercially available equipment has been described to perform high quality, reliable and fast GCI measurements over a range of different currents in one sequence without having to use an electronic switch or a solid state relay or a separate fast data logging system. Its versatility has been demonstrated with a number of standard RC circuits simulating slow electrode and fast electrolyte processes and by evaluating a number of solid oxide fuel cell materials. The GCI technique has been shown to be able to determine the composition of all standard test circuits within ±1 % of those determined from the EIS technique and actual values of circuit components. The technique has been applied to investigating solid electrolyte cells and produced excellent results.     

Perborate as novel fuel for enhanced performance of membraneless fuel cells

This paper presents the development of membraneless sodium perborate fuel cell using acid/alkaline electrolyte. In the acid/alkaline electrolyte, perborate works both as an oxidant as well as reductant. Sodium perborate affords hydrogen peroxide in aqueous medium. The cell converts the energy released by H₂O₂ decomposition with H⁺ and OH^? ions into electricity and produces water and oxygen. Such a novel design eliminates the need of a membrane, in which acid and alkaline electrolytes contact with each other. At room temperature, the laminar flow-based microfluidic membraneless fuel cell can reach a maximum power density of 34 mW/cm² with the molar ratio of [Perborate]/[NaOH]?=?1 as fuel and [Perborate]/[H₂SO₄]?=?2 as oxidant. The paper reports for the first time the use of sodium perborate as the oxidant and reductant. The developed fuel cell emits no CO₂, features no proton exchange membrane, inexpensive catalysts, and simple planar structure, which enables high design flexibility and easy integration of the microscale fuel cell into actual microfluidic systems and portable power applications.     

Novel solid acid fuel cell based on a superprotonic conductor Tl3H(SO4)2

We have fabricated a fuel cell based on a superprotonic conductor, a Tl₃H(SO₄)₂ crystal, and have measured the electrical properties of this fuel cell. It is found that the open-circuit voltage in the fuel cell based on the Tl₃H(SO₄)₂ crystal increases by supplying H₂ fuel gas and typically becomes 0.83 V. Moreover, we have observed that the cell voltage decreases with increasing current density, as observed in fuel cells such as proton exchange membrane fuel cell, solid oxide fuel cell, etc. These results indicate that it is possible to use the Tl₃H(SO₄)₂ crystal as the electrolyte of a solid acid fuel cell. In addition, we suggest that the selection of the electrode and the preparation of the very thin electrolyte are extremely important to achieve high-efficiency of power generation of this fuel cell.     

Oxygen-ion conducting electrolyte materials for solid oxide fuel cells

Oxygen-ion conducting solid electrolyte systems have been reviewed with specific emphasis on their use in solid oxide fuel cells. The relationships between phase assemblage, electrolyte stability and ionic conductivity have been discussed. The role of parameters such as sintering temperature and atmosphere which influence the segregation of impurities, present in the starting ceramic powders, at grain boundaries and at the external surface of the electrolyte compacts has been emphasised. The stability of various electrolyte materials in contact with other fuel cell components and in fuel environments has been discussed in detail. The ageing behaviour at fuel cell operating temperatures has been described. Data on ionic conductivity, mechanical and thermal properties have been presented for a number of electrolyte materials.     

Reactive sputtering deposition and electrochemical characterisation of thin solid electrolyte membranes for solid oxide fuel cells

Solid oxide fuel cells directly convert the chemical energy of a fuel into electricity. To enhance the efficiency of the fuel cells, the thickness of the gastight solid electrolyte membranes should be as thin as possible. Y₂O₃-stabilised ZrO₂ (YSZ) electrolyte films were prepared by reactive sputtering deposition using Zr/Y targets in Ar/O₂ atmospheres. The films were 5 – 8 μm thin and were deposited onto anode substrates made of a NiO/YSZ composite. After deposition of a cathode with the composition La_0.65Sr_0.35MnO₃ the electrochemical properties of such a fuel cell were tested under operating conditions at temperatures between 600 °C and 850 °C. Current-voltage curves were recorded and impedance measurements were performed to calculate apparent activation energies from the fitted resistance data. The conductivity of the YSZ films varied between 4.6·10⁻⁶ S/cm and 2.2·10⁻⁵ S/cm at 400 °C and the fuel cell gave a reasonable power density of 0.4 W/cm² at 0.7 V and 790 °C using H₂ with 3 % H₂O as fuel gas. The gas compositions were varied to distinguish the electrochemical processes of the anode and cathode in the impedance spectra. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Amorphous silicon solar cells on nano‐imprinted commodity paper without sacrificing efficiency

Paper is a cheap substrate which is in principle compatible with the process temperature applied in the plasma enhanced chemical vapour deposition (PECVD) and hot wire CVD (HWCVD) of thin film silicon solar cells. The main drawback of paper for this application is the porosity due to its fibre like structure. The feature size (micrometre scale) is larger than the thickness of the applied photovoltaic layers. To overcome this problem, UV curable lacquer was used to planarize the surface. Plain 80 grams printer paper was taken as a substrate and the lacquer smoothens the rough surface of the paper such that a designed nanostructure can be imprinted for light scattering. In this manner single junction amorphous silicon solar cells with a HWCVD deposited intrinsic layer were processed on paper, without any concessions to the process temperature of 200 °C. The cell performance is comparable to that of reference cells grown on stainless steel, proving that solar cells can be deposited on paper substrates without sacrificing performance. PV on paper could be applied as ”disposable” power source for gadgets, electronic labelling, remote sensing systems, etc. (Internet of Things). (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Influence of fuel and media on membraneless sodium percarbonate fuel cell

This paper reports the media flexibility of membraneless sodium percarbonate fuel cell (MLSPCFC) using acid/alkaline bipolar electrolyte in which the anode is in acidic media while the cathode is in alkaline media, or vice versa. Investigation of the cell operation is conducted by using formic acid as a fuel and sodium percarbonate as an oxidant for the first time under ‘acid–alkaline media’ configurations. The MLSPCFC architecture enables interchangeable operation with different media combinations. The experimental results indicate that operating under acid–alkaline media conditions significantly improves the fuel cell performance compared with all-acidic and all-alkaline conditions. The effects of flow rates and the concentrations of various species at both the anode and cathode on the cell performance are also investigated. It has been demonstrated that the laminar flow-based microfluidic membraneless fuel cell can reach a maximum power density of 25.62 mW cm^?2 with a fuel mixture flow rate of 0.3 mL min^?1 at room temperature.     

PECVD制备AZO（ZnO:Al）透明导电薄膜

采用PECVD（等离子体增强化学气相沉积）工艺在普通玻璃和Si基上制备出了方块电阻低至89 Ω,可见光透过率高达79%,对基体附着力强的多晶态的AZO（ZnO:Al）薄膜.采用PECVD法制备AZO薄膜是一种有益的尝试,AZO透明导电薄膜不仅具有与ITO（透明导电薄膜,如In₂O₃:Sn）可比拟的光电特性,而且价格低廉、无毒,在氢等离子体环境中更稳定,所获结果对实际工艺条件的选择具有一定借鉴作用和参考价值. 关键词： AZO（ZnO:Al） 等离子体增强化学气相沉积 透明导电薄膜     

Ionic liquid-based electrolyte with dual-functional LiDFOB additive toward high-performance LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> batteries

Manganese oxide-based cathodes are one of the most promising lithium-ion battery (LIB) cathode materials due to their cost-effectiveness, high discharge voltage plateau (above 4.0 V vs. Li/Li⁺), superior rate capability, and environmental benignity. However, these batteries using conventional LiPF₆-based electrolytes suffer from Mn dissolution and poor cyclic capability at elevated temperature. In this paper, the ionic liquid (IL)-based electrolytes, consisting of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfon)imidate (PYR_1,4-TFSI), propylene carbonate (PC), lithium bis(trifluoromethanesulfon)imide (LiTFSI), and lithium oxalyldifluoroborate (LiDFOB) additive, were explored for improving the high temperature performance of the LiMn₂O₄ batteries. It was demonstrated that LiTFSI-ILs/PC electrolyte associated with LiDFOB addition possessed less Mn dissolution and Al corrosion at the elevated temperature in LiMn₂O₄/Li batteries. Cyclic voltammetry and electrochemical impedance spectroscopy implied that this kind of electrolyte also contributed to the formation of a highly stable solid electrolyte interface (SEI), which was in accordance with the polarization measurement and the Li deposition morphology of the symmetric lithium metal cell, thus beneficial for improving the cycling performance of the LiMn₂O₄ batteries at the elevated temperature. Cyclic voltammetry and electrochemical impedance spectroscopy implied that the cells using this kind of electrolyte exhibited better interfacial stability, which was further verified by the polarization measurement and the Li deposition morphology of the symmetric lithium metal cell, thus beneficial for improving the cycling performance of the LiMn₂O₄ batteries at the elevated temperature. These unique characteristics would endow this kind of electrolyte a very promising candidate for the manganese oxide-based batteries.     

Studies on modified anode polymer hydrogen sensor

An improved polymer electrolyte membrane (PEM) fuel cell based amperometric hydrogen sensor that operates at room temperature has been developed. The electrolyte used in the sensor is PVA/H₃PO₄ blend, which is a proton conducting solid polymer electrolyte. A blend of palladium and platinum coated on the membrane is used as anode and platinum as cathode. The sensor functions as a fuel cell, H₂/Pd-Pt//PVA-H₃PO₄//Pt/O₂, and the short circuit current is found to be linearly related to the hydrogen concentration. The present study aims at investigating the dependence of sensor behaviour on the anode composition. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Quantifying phosphoric acid in high‐temperature polymer electrolyte fuel cell components by X‐ray tomographic microscopy

Synchrotron‐based X‐ray tomographic microscopy is investigated for imaging the local distribution and concentration of phosphoric acid in high‐temperature polymer electrolyte fuel cells. Phosphoric acid fills the pores of the macro‐ and microporous fuel cell components. Its concentration in the fuel cell varies over a wide range (40–100 wt% H₃PO₄). This renders the quantification and concentration determination challenging. The problem is solved by using propagation‐based phase contrast imaging and a referencing method. Fuel cell components with known acid concentrations were used to correlate greyscale values and acid concentrations. Thus calibration curves were established for the gas diffusion layer, catalyst layer and membrane in a non‐operating fuel cell. The non‐destructive imaging methodology was verified by comparing image‐based values for acid content and concentration in the gas diffusion layer with those from chemical analysis.     

Small particle size multiphase Li-alloy anodes for lithium-ionbatteries

An impressive improvement of the cycling performance of Li-alloy anodes (M + Li⁺ +e⁻ Li_xM) in rechargeable organic electrolyte lithium batteries can be achieved by replacing compact or large particle size metallic host matrices M (e.g. Sn or Sb) with small particle size (micro- or nano-scale) multiphase metallic host materials like Sn/SnSb_n or Sn/SnAg_n. Electrochemical alloy deposition is a convenient way to prepare sub-micrometer particles of Sn and SnSb_n or Sn and SnAg_n. During the first lithium insertion these small particle size multiphase matrix materials are expanded to a porous material, however, without formation of major cracks. This seems not only to be related with the small absolute changes in the size of the individual particles, but also with the fact that the more reactive particles are allowed to expand in a soft and ductile surrounding of still unreacted material.     

Characterization in MCFC conditions of high-temperature, potentiostatically deposited Co-based thin films on NiO cathode

Molten carbonate fuel cell (MCFC) is one of the most advanced high-temperature devices to convert chemical energy into electrical energy without pollution. It can be used in cogeneration as electrical and thermal generator because of its high working temperature (650 °C). Nevertheless, its commercialization is still limited. In fact, its lifetime is mostly reduced by the dissolution of the cathode into the corrosive molten carbonate electrolyte. One of the ways to overcome this problem is to modify or protect the state-of-the-art cathode. In the last case, the deposit must present conductivity as good as the classical NiO porous cathode one but a lower solubility in the electrolyte. For this reason, thin films of cobalt(III) were electrodeposited. A classical three-electrode cell was used to deposit Co-based thin films by chronoamperometry in aqueous solution, at relatively high temperature (80 °C). The deposition conditions lead to homogeneous, covering, and crystallized films. The microstructure and the crystallinity of the deposits were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements. Then, their electrochemical properties were studied in the molten carbonate electrolyte under a mixture of CO₂ and air. In situ measurements such as chronopotentiometry at I = 0 (open-circuit potential) or impedance spectroscopy were carried out during 48 h. Moreover, ex situ measurements such as inductively coupled plasma atomic emission spectroscopy to evaluate the solubility, or SEM and XRD measurements were performed to characterize the thin Co-based films in such molten carbonate fuel cell working cathodic conditions.     

XPS investigation of the PTFE induced hydrophobic properties of electrodes for low temperature fuel cells

In electrodes of low temperature fuel cells like polymer electrolyte membrane fuel cells (PEFC) or alkaline fuel cells (AFC) the reactants and the water must be transported. For this purpose the pore system in the electrodes needs a hydrophilic character for the transport of the water and a hydrophobic character for the transport of the gases. The degree of the hydrophobicity determines whether the pore system will be flooded by the reaction water. In the case of PEFC, this is also determined by the degree of the required humidification of the reaction gases. In AFC hydrophobicity determines the extension of the three-phase reaction zone. Caused by the strong influence of hydrophobicity on the transport processes, the electrochemical performance and the optimized operation conditions are also affected by hydrophobicity.Typically polytetrafluoro-ethylene (PTFE) is used to make the electrodes hydrophobic, because PTFE has a high chemical stability. Hydrophobicity depends on the concentration of PTFE on the electrode surface. The PTFE concentration, which is related to the hydrophobic character, can be determined by XPS. The changes in the PTFE content and structure of the electrode of a PEFC was investigated by cyclic voltammetry and XPS and correlated with the performance of the cell in long-term operation. With both methods an initial significant increase in free and electrochemically active surface platinum area is observed. This activation is associated with a degradation of the PTFE in the electrode which is responsible for the hydrophobic properties of the electrode. With further operation the performance of the cell decreases because the water management becomes more critical. Generally, it is shown that XPS can be used for the investigation of the hydrophobicity of electrodes prepared by various manufacturing techniques as well as of changes in their hydrophobicity induced by the electrochemical operation.     

Role of Acid Treatment of the Carbon Support in the Growth of Atomic-Layer-Deposited Pt Nanoparticles for PEMFC Fabrication

Ultrathin films or particles of atomic layer deposition (ALD) on high surface can improve the activity and durability of catalyst fields, so depending on the surface state, the ALD growth mechanism on porous materials should be systematically investigated and optimized to improve their characteristics of catalysts. Herein, a Pt catalyst used in polymer electrode membrane fuel cell (PEMFC) applications is synthesized through fluidized-bed-reactor ALD on carbon black whose surface is modified through treatment with citric acid. The functional groups, analyzed through X-ray photoelectron spectroscopy (XPS), are found to be maximized after 60 min of acid treatment with stirring. Compared with bare carbon (untreated), the acid-treated carbon presents rich oxidized functional groups and abundant defects but lower surface areas and pore volumes. After ALD Pt deposition, highly dense, uniform, and well-dispersed Pt nanoparticles (NPs) are observed on the carbon black subjected to acid treatment, because of the favorable surface modifications for ALD growth resulting from the acid treatment. The ALD-Pt NPs on the acid-treated carbon exhibit larger electrochemical active surface areas, improved oxygen reduction reactions, and PEMFC performances, when compared with that of NPs on bare carbon with similar Pt weight loading.     

具有可渗透阳极的自呼吸微流体燃料电池性能特性

微流体燃料电池去除了质子交换膜,避免了膜退化、水管理等问题,是微型燃料电池领域新的研究热点。本文构建了具有可渗透阳极和空气自呼吸阴极的微流体燃料电池,采用甲酸溶液作为燃料对其性能特性进行了实验研究。结果表明:具有可渗透阳极的自呼吸微流体燃料电池性能随燃料浓度或流量的增加先升高后下降,随电解液浓度的增加而升高;阳极侧反应产生的CO₂气泡对自呼吸微流体燃料电池的性能和燃料利用率的影响较大,适当提高燃料流量有利于气泡的排除。