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1.
The behaviour of several solvents in rechargeable lithium cells employing two different structure type cathodes, ns-V6O13 a framework oxide, and TiS2 a layered material, was compared. Excellent cycling behaviour and high energy were obtained for the Li/ns-V6O13 cell at current densities as high as 5 mA cm−2 in the temperature range 25 to −40 °C. Cells utilizing an electrolyte of 2 M LiAsF6 in methyl formate were discharged at a current density of 2 mA cm−2 at −40 °C with 37% cell efficiency at an energy density of 255 W h kg−1 (based on active material). Use of an LiAsF6/2-MeTHF electrolyte with ns-V6O13 resulted in satisfactory cycle-life, but at significantly reduced capacities than observed with the LiAsF6/MF electrolyte. This is attributed to the lower conductivities of 2-MeTHF solutions.

The results for Li/TiS2 cells are in direct contrast with those observed for ns-V6O13. Use of MF solutions with TiS2 results in extremely low capacities while capacities and cycle life in 2-MeTHF solutions are quite good. These differences are attributed to a combination of factors including solvent co-intercalation, ion salvation, and solvent decomposition.  相似文献   


2.
The characteristics of polyaniline/graphite composites (PANi/G) have been studied in aqueous electrolyte. PANi/G films with different graphite particle sizes were deposited on a platinum electrode by means of cyclic voltammetry. The film was employed as a positive electrode (cathode) for a Zn-PANi/G secondary battery containing 1.0 M ZnCl2 and 0.5 M NH4Cl electrolyte at pH 4.0. The cells were charged and discharged under a constant current of 0.6 mA cm−2. The assembled battery showed an open-circuit voltage (OCV) of 1.55 V. All the batteries were discharge to a cut off voltage of 0.7 V. Maximum discharge capacity of the Zn-PANi/G battery was 142.4 Ah kg−1 with a columbic efficiency of 97–100% over at least 200 cycles. The mid-point voltage (MPV) and specific energy were 1.14 V and 162.3 Wh kg−1, respectively. The constructed battery showed a good recycleability. The structure of these polymer films was characterized by FTIR and UV–vis spectroscopies. Electrochemical impedance spectroscopy (EIS) was used as a powerful tool for investigation of charge transfer resistance in cathode material. The scanning electron microscopy (SEM) was employed as a morphology indicator of the cathodes.  相似文献   

3.
Vehicle trials with the first sodium/nickel chloride ZEBRA batteries indicated that the pulse power capability of the battery needed to be improved towards the end of the discharge. A research programme led to several design changes to improve the cell which, in combination, have improved the power of the battery to greater than 150 W kg−1 at 80% depth of discharge. Bench and vehicle tests have established the stability of the high power battery over several years of cycling. The gravimetric energy density of the first generation of cells was less than 100 Wh kg−1. Optimisation of the design has led to a cell with a specific energy of 120 Wh kg−1 or 86 Wh kg−1 for a 30 kWh battery. Recently, the cell chemistry has been altered to improve the useful capacity. The cell is assembled in the over-discharged state and during the first charge the following reactions occur: at 1.6 V: Al+4NaCl=NaAlCl4+3Na; at 2.35 V: Fe+2NaCl=FeCl2+2Na; at 2.58 V: Ni+2NaCl=NiCl2+2 Na. The first reaction serves to prime the negative sodium electrode but occurs at too low a voltage to be of use in providing useful capacity. By minimising the aluminium content more NaCl is released for the main reactions to improve the capacity of the cell. This, and further composition optimisation, have resulted in cells with specific energies in excess of 140 Wh kg−1, which equates to battery energies>100 Wh kg−1. The present production battery, as installed in a Mercedes Benz A class electric vehicle, gives a driving range of 205 km (128 miles) in city and hill climbing. The cells with improved capacity will extend the practical driving range to beyond 240 km (150 miles).  相似文献   

4.
The cycling behaviour of an electroplated lithium-zinc alloy film electrode is examined in 1 M LiC1O4/propylene carbonate. The cycle life depends on the utilization of lithium in the alloy and is improved by dispersion of 2 to 4 wt.% iron. This improvement is more effective when the discharge cutoff potential is 0.5 V versus Li+/Li. In this case, the life cycle is about 150 cycles at 250 mA h g−1 of lithium utilization. The reason for improvement is possibly the suppression of electrode disintegration and the appropriate choice of alloy phases.  相似文献   

5.
《Solar Energy》2000,68(6):209-515
Various mixed Fe/V-oxides can be used as anodes in Li+ rocking chair batteries, however, their small optical modulation during the insertion/extraction of Li+ ions makes them candidates for the counter electrodes in electrochromic (EC) devices. The sol–gel route in combination with dip-coating deposition was used for the preparation of Fe/V-oxide films with molar ratios Fe:V=0.1:1, 1:2, 1:1 and 2:1. X-ray diffraction combined with Fourier transform infrared (FT-IR) spectroscopy studies of films and powders reveal that heating of xerogel films at 400°C produces films with nanosized FeVO4 (Fe:V=1:1) and Fe2V4O13 (Fe:V=1:2) grains, while the corresponding crystalline powders were obtained at 500°C (8 h). Charge capacities (Q) of Fe/V-oxide films (300 and 400°C) were determined using cyclic voltammetry (CV) from 1.5 to −1.5 V vs. Ag/AgCl (4.8 to 1.8 V vs. Li) in 1 M LiClO4/propylene carbonate (PC) electrolyte. Our results revealed that Q values of Fe/V-oxide films are up to 20 mC cm−2 depending on the thickness (40–100 nm), temperature of heating and the Fe:V molar ratio (1:2, 1:1). During the first 300 cycles the cycling stability of the Fe-containing films is better than that of V2O5 crystalline films. UV-visible spectra of charged/discharged films revealed that these films, similar to V2O5 films, exhibit a mixed anodic/cathodic electrochromism. It was established that with regard to the colouring/bleaching changes of V2O5 crystalline films, the Fe/V-oxide films exhibit smaller cathodic colouring at wavelengths λ>600 nm and higher visible transmittance. IR spectroscopy of charged/discharged Fe/V-oxide films confirmed that the reduction of Fe3+ prevents the overreduction of V5+ to V3+, which takes place in V2O5 films cycled in the same potential range.  相似文献   

6.
Screen-printing technology was developed to fabricate Ce0.8Sm0.2O1.9 (SDC) electrolyte films onto porous NiO–SDC green anode substrates. After sintering at 1400 °C for 4 h, a gas-tight SDC film with a thickness of 12 μm was obtained. A novel cathode material of Ba0.5Sr0.5Co0.8Fe0.2O3−δ was subsequently applied onto the sintered SDC electrolyte film also by screen-printing and sintered at 970 °C for 3 h to get a single cell. A fuel cell of Ni–SDC/SDC (12 μm)/Ba0.5Sr0.5Co0.8Fe0.2O3−δ provides the maximum power densities of 1280, 1080, 670, 370, 180 and 73 mW cm−2 at 650, 600, 555, 505, 455 and 405 °C, respectively, using hydrogen as fuel and stationary air as oxidant. When dry methane was used as fuel, the maximum power densities are 876, 568, 346 and 114 mW cm−2 at 650, 600, 555 and 505 °C, respectively. The present fuel cell shows excellent performance at lowered temperatures.  相似文献   

7.
Polyaniline (PAn), synthesized by electro-polymerization, has exhibited good reversibility in an LiClO4/propylene carbonate electrolyte. The reversible specific capacity reaches 120 A h kg−1. PAn appears to be a candidate positive electrode for a secondary lithium battery because of its reversibility, high-rate discharge performance, and low self-discharge. The compatibility of the electrolyte between PAn and lithium electrodes is an important problem to be solved.  相似文献   

8.
Porous, thin films of copper molybdenum sulfides (Cu3+δMo6S7.9), that have been prepared by the technique of painting and subsequent reaction with mixed H2/H2S gases at 500 °C, have been used as a cathode material for lithium secondary batteries. The test cell comprised: Li/2 M LiClO4 in PC-THF (4:6)/Cu3+δMo6S7.9 (porous, thin film). The discharge reaction proceeded via the intercalation of lithium ions into the structural interstices of the cathode material.

The first discharge curve of the cell showed that the porous film could incorporate up to 18 lithium ions per formula unit. The capacity of the thin film was four times higher than that previously reported for powder or pressed-pellet electrodes. The theoretical energy density was 675 W h kg−1, i.e., higher than that of TiS2 (455 W h kg−1) which is one of the best materials for high-energy lithium batteries. From X-ray diffraction studies of the lithium incorporated in the thin film at each discharge step, it is suggested that there are four incorporation reactions of lithium ions into the cathode. Finally, cycling tests have been conducted at room temperature.  相似文献   


9.
《Solar Energy》2000,68(6):523-540
Layered LixCoO2 and LixNiO2 thin films (x1) were prepared by a peroxo wet chemistry route from Li(I), Co(II) and Ni(II) acetate precursors and the addition of H2O2. Structural changes during the processing of xerogel to final oxide were followed by X-ray diffraction and infrared spectroscopy. Electrochromic properties were determined with in-situ potentiodynamic, potentiostatic and galvanostatic spectroelectrochemical measurements. Single dipped films with composition Li0.99Co1.01O2 or Li0.94Ni1.06O2 exhibited stable voltammetric response in 1 M LiClO4/propylene carbonate electrolyte after about 60 cycles. The total charge exchanged in a reversible charging/discharging cycle was about ±30 mC cm−2 for Li0.99Co1.01O2 and ±20 mC cm−2 for Li0.94Ni1.06O2 oxide films. Galvanostatic measurements showed that about 1/2 (x0.5) and 2/3 (x0.3) of Li+ ions could be reversibly removed from the structure of Li0.99Co1.01O2 and Li0.94Ni1.06O2 films, respectively. Practical applicability of Li0.99Co1.01O2 and Li0.94Ni1.06O2 oxide films was studied in electrochromic devices with WO3(H+)Li+ormolyteLi0.99Co1.01O2 and WO3(H+)Li+ormolyteLi0.94Ni1.06O2 configuration. The monochromatic transmittance Ts (λ=633 nm) of dark blue coloured devices was extremely low (Ts3%), whereas in bleached state the value reached around Ts70%.  相似文献   

10.
The electrochemical performances of Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag composite cathodes have been investigated in intermediate temperature solid oxide fuel cells. The Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag cathodes prepared by ball milling followed by firing at 920 °C show the maximum performance (power density: 0.15 W cm−2 at 800 °C) at 3 wt.% Ag. On the other hand, the Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag composite cathodes with 0.1 mg cm−2 (0.5 wt.%) Ag that were prepared by an impregnation of Ag into Nd0.6Sr0.4Co0.5Fe0.5O3−δ followed by firing at 700 °C (but the electrolyte–Nd0.6Sr0.4Co0.5Fe0.5O3−δ assembly was prepared first by firing at 1100 °C) exhibit much better performance (power density: 0.27 W cm−2 at 800 °C) than the composite cathodes prepared by ball milling, despite a much smaller amount of Ag due to a better dispersion and an enhanced adhesion. AC impedance analysis indicates that the Ag catalysts dispersed in the porous Nd0.6Sr0.4Co0.5Fe0.5O3−δ cathode reduce the ohmic and the polarization resistances due to an increased electronic conductivity and enhanced electrocatalytic activity.  相似文献   

11.
H. Schwarz   《Biomass & bioenergy》1993,5(6):413-419
In Austria it is planned to use Miscanthus sinensis ‘Giganteus’ as a renewable energy source. The influence of site, age of crop and time of harvest on yield, water content, nitrogen content and quality was investigated. In the first year the yield was 0.7 to 2 t dry matter ha−1, in the second year 7.9 to 15.5 t ha−1 and in the third year 17.4 to 24.5 t ha−1. In February of the first year the water content was 40 to 50%, in the second year 34 to 49% and in the third year 24 to 38%. Sufficient precipitation (about 800 mm) in mild climates is required for high yields. On sites with more rain the water content of the plants was higher. Water and nitrogen content decreased significantly during the six week period from January to the end of February. In February of the first year the nitrogen content was 7.8 to 16.6 g kg−1 dry matter, in the second year 3.7 to 6.2 g kg−1 and in the third year 2.6 to 7.5 g kg−1. The calorific value was as high as that of firewood (18 to 19 MJ kg−1 ). The ash content exceeded firewood but was lower than that of straw. By the third year of cultivation 60 to 150 kg N ha−1, 100 to 200 kg K20 ha−1, 10 to 35 kg P2 O5 ha−1, 10 to 25 kg MgO ha−1 and 20 to 35 kg CaO ha−1 had to be taken up by the harvest at the end of February.  相似文献   

12.
PolyStor has teamed with Hawker Eternacell (US) to develop a BB-2590/U rechargeable lithium-ion battery under contract with the US Army CECOM (Ft. Monmouth, NJ, USA). The concept involves using commercially available ICR-18650 cylindrical lithium-ion cells. The individual cells have a high specific energy of 135 Wh kg−1 and an energy density of 335 Wh dm−3. Electronic circuitry was developed to provide pack protection, charge equalization and battery management (fuel gauging). PolyStor's rechargeable BB-2590/U battery provides 4.5 Ah at 28 V nominal or 9.0 Ah at 14 V nominal, translating into 108 Wh kg−1 and 150 Wh dm−3. The key developments are discussed in this paper.  相似文献   

13.
Rate constants for the reaction of isocyanate radicals (NCO) in its electronic ground state ( 2Π) with oxygen atoms were determined at 2.5 Torr total pressure in the temperature range 302–757 K. Excimer laser photolysis (ELP) of chlorine isocyanate (ClNCO) produced NCO radicals detected by laser-induced fluorescence (LIF). The reaction NCO + O exhibits a negative temperature dependence, described by the two-parameter equation: kNCO+O(T) = (4.3−2.2+3.2) × 10−8 × T−1.14−0.12+0.08 cm3 molecule−1 s−1. Measurements at 298 K and total pressures of 2.5 and 9.9 Torr, respectively, indicated a slight pressure dependence. For the reaction of NCO radicals with hydrogen atoms, the rate constant kNCO+H = (2.2 ± 1.5) × 10−11 cm3 molecule−1 s−1was obtained at 298 K and a total pressure of 2.6 Torr for the first time by a direct measurement. From a single measurement k = (3.8 ± 1.6) × 10−11 cm3 molecule−1 s−1 was determined at 548 K and 2.4 Torr total pressure. In addition, rate constants for the reactions of NCO radicals with molecular oxygen (O2), carbon dioxide (CO2), molecular hydrogen (H2), and carbon monoxide (CO), which is a dissociation product of CO2 in a microwave discharge, were measured at two different temperatures. At room temperature these reactions were slow and at the detection limit of the ELP/LIF technique. However, at elevated temperatures at least the rate constants of the reactions NCO + O2 and NCO + H2 become significantly larger and, therefore, should be taken into account, when modeling combustion processes under certain conditions.  相似文献   

14.
Mesoporous Ce0.8Sm0.2O1.9 (SDC) oxide with high surface area was prepared by a novel glycine-nitrate combustion process with in situ created nickel oxide as template, and applied as the catalytic layer for methane-fueled solid-oxide fuel cells (SOFCs) operated at reduced temperatures. The weight ratio of nickel oxide to SDC in the synthesis process was found to have significant effect on both the crystallite size and the textural properties of the resulted SDC powder. In particular, when it was at 9, the thermally stable and well-crystallized SDC powder showed a mesoporous structure with narrow pore-size distribution, high surface area (77 m2 g−1) and large pore volume (0.2276 cm3 g−1), even after the calcination at 700 °C for 3 h. The mesoporous SDC was found to favor free gas diffusion with no gas diffusion polarization occurred even at high current density both for hydrogen and methane fuels. The SOFC with Ru impregnated mesoporous SDC catalytic layer displayed promising performance with a peak power density of 462 mW cm−2 at 650 °C.  相似文献   

15.
The cathode is a key component in low temperature solid oxide fuel cells. In this study, composite cathode, 75 wt.% Sm0.5Sr0.5CoO3 (SSC) + 25 wt.% Sm0.2Ce0.8O1.9 (SDC), was applied on the cermet supported thin SDC electrolyte cell which was fabricated by tape casting, screen-printing, and co-firing. Single cells with the composite cathodes sintered at different temperatures were tested from 400 to 650 °C. The best cell performance, 0.75 W cm−2 peak power operating at 600 °C, was obtained from the 1050 °C sintered cathode. The measured thin SDC electrolyte resistance Rs was 0.128 Ω cm2 and total electrode polarization Rp(a + c) was only 0.102 Ω cm2 at 600 °C.  相似文献   

16.
Ultralife Batteries delivered the world's first commercial shipments of solid polymer rechargeable batteries in 1997. The battery consists of a LixMn2O4 based cathode, graphite anode and proprietary polymeric separator. Energy density of the batteries exceeds 120 W h kg−1 and 200 W h dm−3 at the C rate. Pulse capability up to 5 C has been demonstrated. More than 90% of the initial C rate capacity remains after 500 continuous cycles at room temperature. These solid polymer rechargeable batteries also show good low and high temperature performance and have good safety characteristics.  相似文献   

17.
Hydrated nickel oxide NiOxHy films were deposited onto indium tin oxide (ITO) coated glass by two methods (i) colloidal precipitation and (ii) anodic electrodeposition. The electrochromic properties of hydrated nickel oxide films were studied by transmittance measurements (UV/VIS/NIR), and Fourier transform infrared reflectance spectroscopy as a function of the key deposition parameters. The solar transmittance was calculated for films switched in both bleached and coloured states. The best results were achieved for films produced by anodic electrodeposition from stable solutions with solar transmittance Ts(bleached) = 0.82 and Ts(coloured) = 0.22. Corresponding optimum values for the films produced by colloidal precipitation were solar transmittance Ts(bleached = 0.82 and Ts(coloured) = 0.47. Fourier transform spectrophotometry was used for elucidating changes in hydration, hydroxylation and for the characterization of structural characteristics in the bleached and coloured states. It was found that free OH stretching vibration at 3647 cm−1 corresponds to Ni(OH)2 for both anodic and colloidal deposited films in the reduced (bleached) state. In the oxidised state hydrogen bonded OH at 3360 cm−1 is observed.  相似文献   

18.
This study examines the effect of hydrogen peroxide (H2O2) on the open-circuit voltage (OCV) of a proton exchange membrane fuel cell (PEMFC) and the reduction of H2O2 in the membrane using a ruthenium/carbon catalyst (Ru/C) at the anode. Each cathode and anode potential of the PEMFC in the presence of H2O2 is examined by constructing a half-cell using 1.0 M H2SO4 solution as an electrolyte and Ag/AgCl as the reference electrode. H2O2 is added to the H2SO4 solution and the half-cell potential is measured at each H2O2 concentration. The cathode potential is affected by the H2O2 concentration while the anode potential remains stable. A Ru catalyst is used to reduce the level of H2O2 formation through O2 cross-over at the interface of a membrane and the anode. The Ru catalyst is known to produce less H2O2 through oxygen reduction at the anode of PEMFC than a Pt catalyst. A Ru/C layer is placed between the Nafion® 112 membrane and anode catalyst layer and the cell voltage under open-circuit condition is measured. A single cell is constructed to compare the OCV of the Pt/C only anode with that of the Ru/C-layered anode. The level of hydrogen cross-over and the OCV are determined after operation at a current density of 1 A cm−2 for 10 h and stabilization at open-circuit for 1 h to obtain an equilibrium state in the cell. Although there is an increase in the OCV of the cell with the Ru/C layer at the anode, excessive addition of Ru/C has an adverse effect on cell performance.  相似文献   

19.
Electrochromic niobia (Nb205) coatings were prepared by the sot-gel spin-coating and d.c. magnetron sputtering techniques. Parameters were investigated for the process fabrication of sol-gel spin coated Nb205 films exhibiting high coloration efficiency comparable with that d.c. magnetron sputtered niobia films. X-ray diffraction studies (XRD) showed that the sot-gel deposited and magnetron sputtered films heat treated at temperatures below 450°C, were amorphous, whereas those heat treated at higher temperatures were slightly crystalline. X-ray photoelectron spectroscopy (XPS) studies showed that the stoichiometry of the films was Nb205. The refractive index and electrochromic coloration were found to depend on the preparation technique. Both films showed low absorption and high transparency in the visible range. We found that the n, k values of the sot-gel deposited films to be lower than for the sputtered films. The n and k values were n = 1.82 and k = 3 × 10−3, and n = 2.28 and K = 4 × 10−3 at 530 urn for sot-gel deposited and sputtered films, respectively. The electrochemical behavior and structural changes were investigated in 1 M LiC104/propylene carbonate solution. Using the electrochemical measurements and X-ray photoelectron spectroscopy, the probable electrode reaction with the lithiation and delithiation is Nb2O5 + x Li+ + x e ↔ LixNb205. Cyclic voltametric (CV) measurements showed that both Nb205 films exhibits electrochemical reversibility beyond 1200 cycles without change in performance. “In situ” optical measurement revealed that those films exhibit an electrochromic effect in the spectral range 300 < λ < 2100 nm but remain unchanged in the infrared spectral range. The change in visible transmittance was 40% for 250 nm thick electrodes. Spectroelectrochemical measurements showed that spin coated films were essentially electrochemically equivalent to those prepared by d.c. magnetron sputter deposition.  相似文献   

20.
Oxidative conversion of propane to propylene and ethylene over a V2O5/CeO2/SA5205 (V:Ce=1:1) catalyst, with or without steam and limited O2, has been studied at different temperatures (700–850 °C), C3H8/O2 ratio (4.0), H2O/C3H8 ratio (0.5) and space velocity (3000 cm3 g−1 h−1). The propane conversion, selectivity for propylene and net heat of reaction (ΔHr) are strongly influenced by the reaction temperature and presence of steam in the reactant feed. In the presence of steam and limited O2, the process involves a coupling of endothermic thermal cracking and exothermic oxidative conversion reactions of propane which occur simultaneously. Because of the coupling of exothermic and endothermic reactions, the process operates in an energy-efficient and safe manner. The net heat of reaction can be controlled by the reaction temperature and concentration of O2. The process exothermicity is found to be reduced drastically with increasing temperature. Due to the addition of steam in the feed, no coke formation was observed in the process.  相似文献   

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