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1.
The structure of thick lead dioxide deposits (approximately 1 mm) formed in conditions likely to be met at the positive electrode during the charge/discharge cycling of a soluble lead-acid flow battery is examined. Compact and well adherent layers are possible with current densities >100 mA cm−2 in electrolytes containing 0.1–1.5 M lead(II) and methanesulfonic acid concentrations in the range 0–2.4 M; the solutions also contained 5 mM hexadecyltrimethylammonium cation, C16H33(CH3)3N+. From the viewpoint of the layer properties, the limitation is stress within the deposit leading to cracking and lifting away from the substrate; the stress appears highest at high acid concentration and high current density. There are, however, other factors limiting the maximum current density for lead dioxide deposition, namely oxygen evolution and the overpotential associated with the deposition of lead dioxide. A strategy for operating the soluble lead-acid flow battery is proposed.  相似文献   

2.
In order to adapt lead-acid batteries for use in hybrid electric vehicles, its specific energy must be improved. Specific energy is greatly dependant on active material utilization. In this study, we improve active material utilization in positive electrodes by the addition of electronically conductive additives. Titanium silicide particles (<44 μm diameter), titanium dioxide fibers (<10 μm, diameter), and titanium wire (76 μm, diameter) were incorporated into the positive electrode and each of their effects on discharge capacity and utilization of active material were examined. The percent mass of each additive was varied from 2–5%. Results indicate that titanium wire at 2.3 wt.% had the optimal effect of increasing the utilization by 12.3% (57 to 64% utilization) relative to control with no additive at a slow discharge rate (10 mA cm−2) without detrimental effect at fast discharge rate (50 mA cm−2). This additive also features reduction in weight and formation enhancement.  相似文献   

3.
The structure of lead deposits (approximately 1 mm thick) formed in conditions likely to be met at the negative electrode during the charge/discharge cycling of a soluble lead-acid flow battery is examined. The quality of the lead deposit could be improved by appropriate additives and the preferred additive was shown to be the hexadecyltrimethylammonium cation, C16H33(CH3)3N+, at a concentration of 5 mM. In the presence of this additive, thick layers with acceptable uniformity could be formed over a range of current densities (20–80 mA cm−2) and solution compositions. While electrolyte compositions with lead(II) concentrations in the range 0.1–1.5 M and methanesulfonic acid concentrations in the range 0–2.4 M have been investigated, the best quality deposits are formed at lower concentrations of both species. Surprisingly, the acid concentration was more important than the lead(II) concentration; hence a possible initial electrolyte composition is 1.2 M Pb(II) + 5 mM C16H33(CH3)3N+ without added acid.  相似文献   

4.
Nanoscale Co and Ni catalysts in silica were synthesized using sol–gel method for hydrogen production from steam reforming of methanol (SRM) in silicon microreactors with 50 μm channels. Silica sol–gel support with porous structure gives specific surface area of 452.35 m2 g−1 for Ni/SiO2 and 337.72 m2 g−1 for Co/SiO2. TEM images show the particles size of Ni and Co catalysts to be <10 nm. The EDX results indicate Co and Ni loadings of 5–6 wt.% in silica which is lower than the intended loading of 12 wt.%. The DTA and XRD data suggest that 450 °C is an optimum temperature for catalyst calcination when most of the metal hydroxides are converted to metal oxides without significant particle aggregation to form larger crystallites. SRM reactions show 53% methanol conversion with 74% hydrogen selectivity at 5 μL min−1 and 200 °C for Ni/SiO2 catalyst, which is higher than that for Co/SiO2. The activity of the metal catalysts decrease significantly after SRM reactions over 10 h, and it is consistent with the magnetization (VSM) results indicating that ∼90% of Co and ∼85% of Ni become non-ferromagnetic after 10 h.  相似文献   

5.
Plasma-fluorination of natural graphite samples with average particle sizes of 5 μm, 10 μm and 15 μm (NG5μm, NG10μm and NG15μm) was performed using CF4 and charge/discharge characteristics of surface-fluorinated samples were investigated in 1 mol dm−3 LiClO4–ethylene carbonate (EC)/diethyl carbonate (DEC)/propylene carbonate (PC) (1:1:1, v/v/v). Fluorine contents obtained by elemental analysis were in the range of 0.3–0.6 at.% and surface fluorine concentrations determined by X-ray photoelectron microscopy (XPS) were 14.8–17.3 at.%. Plasma-fluorination increased surface disorder of natural graphite samples though reduced surface areas due to its surface etching effect. Electrochemical decomposition of PC was highly reduced on surface-fluorinated NG10μm and NG15μm with high disorder. First coulombic efficiencies of plasma-fluorinated NG10μm and NG15μm increased by 9.7 and 19.3% at 150 mA g−1, respectively.  相似文献   

6.
Poly(vinylidene fluoride-co-hexafluoropropylene) {P(VdF-HFP)} membranes incorporating 0, 6 and 10 wt.% of nano-meter sized particles of SiO2 were prepared by electrospinning. These membranes served as host matrix for the preparation of polymer electrolytes (PEs) by activating with the non-volatile and safe room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonylimide) (BMITFSI). The membranes consisted of layers of fibers with average fiber diameter of 2–5 μm and had a porosity of ∼87%. PEs with SiO2 exhibited higher ionic conductivity with a maximum of 4.3 × 10−3 S cm−1 at 25 °C obtained with 6% SiO2. The optimum PE based on the membrane with 6% SiO2 exhibited better compatibility with lithium metal electrode on storage and resulted in enhanced charge–discharge performance in Li/LiFePO4 cells at room temperature, delivering the theoretical specific capacity of 170 mAh g−1 at 0.1 C-rate. The PEs exhibited a very stable cycle property as well, demonstrating their suitability for lithium battery applications.  相似文献   

7.
Spherical shape Cu–Sn alloy powders with fine size for lithium secondary battery were directly prepared by spray pyrolysis. The mean size and geometric standard deviation of the Cu–Sn alloy powders prepared at a temperature of 1100 °C were 0.8 μm and 1.2, respectively. The powders prepared at a temperature of 1100 °C with low flow rate of carrier gas as 5 l min−1 had main XRD peaks of Cu6Sn5 alloy and copper-rich Cu3Sn alloy phases. Cu and Sn components were well dispersed inside the submicron-sized alloy powders. The discharge capacities of the Cu6Sn5 alloy powders prepared at a flow rate of 5 l min−1 dropped from 485 to 313 mAh g−1 by the 20th cycle at a current density of 0.1 C. On the other hand, the discharge capacities of the Cu–Sn alloy powder prepared at a flow rate of 20 l min−1 dropped from 498 to 169 mAh g−1 by the 20th cycle at a current density of 0.1 C.  相似文献   

8.
Anode-supported solid oxide fuel cells (SOFC) comprising nickel + iron anode support and gadolinia-doped ceria (GDC) of composition Gd0.1Ce0.9O2−δ thin film electrolyte were fabricated, and their performance was evaluated. The ratio of Fe2O3 to NiO in the anode support was 3 to 7 on a molar basis. Fe2O3 and NiO powders were mixed in the desired proportions and discs were die-pressed. All other layers were sequentially applied on the anode support. The cell structure consisted of five distinct layers: anode support – Ni + Fe; anode functional layer – Ni + GDC; electrolyte – GDC; cathode functional layer – LSC (La0.6Sr0.4CoO3−δ) + GDC; and cathode current collector – LSC. Cells with three different variations of the electrolyte were made: (1) thin GDC electrolyte (∼15 μm); (2) thick GDC electrolyte (∼25 μm); and (3) tri-layer GDC/thin yttria-stabilized zirconia (YSZ)/GDC electrolyte (∼25 μm). Cells were tested with hydrogen as fuel and air as oxidant up to 650 °C. The maximum open circuit voltage measured at 650 °C was ∼0.83 V and maximum power density measured was ∼0.68 W cm−2. The present work shows that cells with Fe + Ni containing anode support can be successfully made.  相似文献   

9.
The negative electrode performance of the electroplated Al film electrode in the LiCl saturated AlCl3–1-ethyl-3-methylimizadolium chloride (EMIC) + SOCl2 melt as the electrolyte for use in non-flammable lithium secondary batteries was evaluated. In the cyclic voltammogram of the electroplated Al film electrode in the melt, the oxidation and reduction waves corresponding to the electrochemical insertion/extraction reactions of the Li+ ion were observed at 0–0.80 V vs. Li+/Li, which suggested that the electroplated Al film electrode operated well in the electrolyte. The almost flat potential profiles at about 0.40 V vs. Li+/Li on discharging were shown. The discharge capacity and charge–discharge efficiency was 236 mAh g−1 and 79.2% for the 1st cycle and it maintained 232 mAh g−1 and 77.9% after the 10th cycle. In addition, the initial charge–discharge efficiencies of the electroplated Al film electrode were higher than that of carbon electrodes. The main cathodic polarization reaction was the insertion of Li+ ions, and side reactions hardly occurred due to the decomposition reaction of the melt because the Li content corresponding to the electricity was almost totally inserted into the film after charging.  相似文献   

10.
Lithium metal is used as an anode material in a 3.0 V-class film-type MnO2||Li primary battery to increase the operating voltage and discharge capacity for application to active sensor tags of a radio-frequency identification system. A 20-μm thick lithium layer deposited homogeneously on a copper foil is prepared for the purpose of controlling the efficient utilization and lithium handling. A plasticized gel polymer electrolyte filled with SiO2 particles is also used to enhance the electrochemical stability and safety of the battery. A lithium primary battery with a lithium anode and a nonaqueous electrolyte is fabricated for the first time in the form of a film with a newly designed Nylon 6/Al/polypropylene pouch for perfect shielding. The fabricated 3.0 V-class film-type lithium primary battery passes several safety tests and achieves a discharge capacity and an energy density of more than 9 mAh cm−2 and 470 Wh L−1, respectively.  相似文献   

11.
It is known that negative plates of lead-acid batteries have low charge acceptance when cycled at high rates and progressively accumulate lead sulphate on high-rate partial-state-of-charge (HRPSoC) operation in hybrid-electric vehicle (HEV) applications. Addition of some carbon or graphite forms to the negative paste mix improves the charge efficiency and slows down sulfation of the negative plates. The present investigation aims to elucidate the contribution of electrochemically active carbon (EAC) additives to the mechanism of the electrochemical reactions of charge of the negative plates. Test cells are assembled with four types of EAC added to the negative paste mix in five different concentrations. Through analysis of the structure of NAM (including specific surface and pore radius measurements) and of the electrochemical parameters of the test cells on HRPSoC cycling, it is established that the electrochemical reaction of charge Pb2+ + 2e → Pb proceeds at 300-400 mV lower over-potentials on negative plates doped with EAC additives as compared to the charge potentials of cells with no carbon additives. Hence, electrochemically active carbons have a highly catalytic effect on the charge reaction and are directly involved in it. Consequently, the reversibility of the charge/discharge processes is improved, which eventually leads to longer battery cycle life. Thus, charging of the negative plates proceeds via a parallel mechanism on the surfaces of both Pb and EAC particles, at a higher rate on the EAC phase. Cells with EAC in NAM have the longest cycle life when their NAM specific surface is up to 4 m2 g−1 against 0.5 m2 g−1 for the lead surface. The proposed parallel mechanism of charge is verified experimentally on model Pb/EAC/PbSO4 and Pb/EAC electrodes. During the charge and discharge cycles of the HRPSoC test, the EAC particles are involved in dynamic adsorption/desorption on the lead sulfate and lead surfaces. Another effect of electrochemically active carbons is also evidenced namely that, above a definite concentration, some EAC forms reduce the mean pore radius of NAM. When it diminishes to less than 1.5 μm, access of sulfuric acid into the pores is impeded and PbO forms instead of PbSO4 in the pores of NAM during discharge. Thus, it may be presumed that electrochemically active carbons change the overall electrochemical reaction of charge and discharge of lead-acid cells when operated under HRPSoC cycling conditions.  相似文献   

12.
A new type of Li1−xFe0.8Ni0.2O2–LixMnO2 (Mn/(Fe + Ni + Mn) = 0.8) material was synthesized at 350 °C in air atmosphere using a solid-state reaction. The material had an XRD pattern that closely resembled that of the original Li1−xFeO2–LixMnO2 (Mn/(Fe + Mn) = 0.8) with much reduced impurity peaks. The Li/Li1−xFe0.8Ni0.2O2–LixMnO2 cell showed a high initial discharge capacity above 192 mAh g−1, which was higher than that of the parent Li/Li1−xFeO2–LixMnO2 (186 mAh g−1). We expected that the increase of initial discharge capacity and the change of shape of discharge curve for the Li/Li1−xFe0.8Ni0.2O2–LixMnO2 cell is the result from the redox reaction from Ni2+ to Ni3+ during charge/discharge process. This cell exhibited not only a typical voltage plateau in the 2.8 V region, but also an excellent cycle retention rate (96%) up to 45 cycles.  相似文献   

13.
Sn/Li2O composite coatings on stainless steel substrate, as anodes of thin-film lithium battery are carried out in SnCl2 and LiNO3 mixed solutions by using cathodic electrochemical synthesis and subsequently annealed at 200 °C. Through cathodic polarization tests, three major regions are verified: (I) O2 + 4H+ + 4e → 2H2O (∼0.25 to −0.5 V), (II) 2H+ + 2e → H2, Sn2+ + 2e → Sn, and NO3 + H2O + 2e → NO2 + 2OH (−0.5 to −1.34 V), and (III) 2H2O + 2e → H2 + 2OH (−1.34 to −2 V vs. Ag/AgCl). The coated specimens are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and charge/discharge tests. The nano-sized Sn particles embedded in Li2O matrix are obtained at the lower part of region II such as −1.2 V, while the micro-sized Sn with little Li2O at the upper part, such as −0.7 V. Charge/discharge cycle tests elucidated that Sn/Li2O composite film showed better cycle performance than Sn or SnO2 film, due to the retarding effects of amorphous Li2O on the further aggregation of Sn particles. On the other hand, the one tested for cut-off voltage at 0.9 V (vs. Li/Li+) is better than those at 1.2 and 1.5 V since the incomplete de-alloy at lower cut-off voltage may inhibit the coarsening of Sn particles, revealing capacity 587 mAh g−1 after 50 cycle, and capacity retention ratio C50/C2 81.6%, higher than 63.5% and 49.1% at 1.2 and 1.5 V (vs. Li/Li+), respectively.  相似文献   

14.
Electrochemically formed spinel-lithium manganese oxides were synthesized from manganese hydroxides prepared by a cathodic electrochemical precipitation from various concentrations of manganese nitrate solutions. Two types of manganese hydroxides were formed from diluted and concentrated Mn(NO3)2 aqueous solutions. Uniform and equi-sized disk shaped Mn(OH)2 crystals of 0.2–5 μm in diameter were obtained on a Pt substrate after the electrochemical precipitation from lower concentration of ranging from 2 mmol dm−3 to 2 mol dm−3 Mn(NO3)2 aq., while the grass blade-like precipitate which is ascribed to manganese hydroxide with 20–80 μm long and 1–5 μm wide were formed from concentrated Mn(NO3)2 aq.  相似文献   

15.
All-solid-state thin-filmed lithium-ion rechargeable batteries composed of amorphous Nb2O5 negative electrode with the thickness of 50–300 nm and amorphous Li2Mn2O4 positive electrode with a constant thickness of 200 nm, and amorphous Li3PO4−xNx electrolyte (100 nm thickness), have been fabricated on glass substrates with a 50 mm × 50 mm size by a sputtering method, and their electrochemical characteristics were investigated. The charge–discharge capacity based on the volume of positive electrode increased with increasing thickness of negative electrode, reaching about 600 mAh cm−3 for the battery with the negative electrode thickness of 200 nm. But the capacity based on the volume of both the positive and negative electrodes was the maximum value of about 310 mAh cm−3 for the battery with the negative electrode thickness of 100 nm. The shape of charge–discharge curve consisted of a two-step for the batteries with the negative electrode thickness more than 200 nm, but that with the thickness of 100 nm was a smooth S-shape curve during 500 cycles.  相似文献   

16.
Perovskite oxide La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF6428), a wonderful electronic–ionic conductor could be used as cathode of solid oxide fuel cell (SOFC). Graded cathode with coarse layer and fine layer, could improve the diffusion rate and electrochemical reaction activity of oxidant. The fabrication and properties of graded LSCF6428 cathode were discussed in this paper. First, pure perovskite LSCF6428 powders were prepared by citrate–EDTA method (CEM), citrate method (CM) and solid phase synthesis (SPS). The powders with higher specific surface area and smaller grain size are easier to be sintered and densified. Single LSCF6428 cathode with thickness of 30 μm was prepared by SPS powders, the porosity of cathode was high about 30% and pore size was about 5 μm. Graded LSCF6428 cathode including 30 μm outer layer and 10 μm inner layer was prepared by SPS and CM powders, respectively. Clear double-layer cathode was observed by SEM, which combined tightly and transited gradually. Porosity of outer layer is high about 30% and pore size is about 1–5 μm; inner layer is finer and pore size is about 0.2–1 μm. Based on the above research, 300 μm yttria stabilized zirconia (YSZ) electrolyte supported cell with single LSCF6428 cathode and double-layer LSCF6428 cathode were prepared, and the properties of two type cells were tested in H2. Power density of graded cell is 197 mW cm−2 at 950 °C, and improved about 46% comparing that of single layer LSCF6428 cell (135 mW cm−2).  相似文献   

17.
A simple method has been employed to prepare pillared layered Li1−2xCaxCoO2 cathode materials by cationic exchange under hydrothermal conditions. The synthesized materials were characterized by means of X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), field emission scanning electron microscope (FE-SEM) and galvanostatic charge–discharge cycling. The XRD data of the products show that they are single phases and retain the layered α-NaFeO2 type structure. The FE-SEM images of the materials prepared by hydrothermal method show uniform small particles, and the particle size of the materials is about 200 nm. The initial discharge specific capacities of layered LiCoO2 and pillared layered Li0.946Ca0.027CoO2 cathode materials calcined at 800 °C for 5 h within the potential range of 3.0–4.3 V (vs. Li+/Li) are 144.6 and 142.3 mAh g−1, respectively, and both materials retain good charge–discharge cycling performance. However, with increasing upper cutoff voltage, the pillar effect of Ca2+ in Li1−2xCaxCoO2 becomes more significant. The pillared layered Li0.946Ca0.027CoO2 has a higher capacity with an initial discharge specific capacity of 177.9 and 215.8 mAh g−1 within the potential range of 3.0–4.5 and 4.7 V (vs. Li+/Li), respectively, and retains good charge–discharge cycling performance.  相似文献   

18.
A solid oxide fuel cell with Sm0.2Ce0.8O1.9 (SDC) electrolyte of 10 μm in thickness and Ni–SDC anode of 15 μm in thickness on a 0.8 mm thick Ni–YSZ cermet substrate was fabricated by tape casting, screen printing and co-firing. A composite cathode, 75 wt.% Sm0.5Sr0.5CoO3 (SSCo) + 25 wt.% SDC, approximately 50 μm in thickness, was printed on the co-fired half-cell, and sintered at 950 °C. The cell showed a high electrochemical performance at temperatures ranging from 500 to 650 °C. Peak power density of 545 mW cm−2 at 600 °C was obtained. However, the cell exhibited severe internal shorting due to the mixed conductivity of the SDC electrolyte. Both the amount of water collected from the anode outlet and the open circuit voltage (OCV) indicated that the internal shorting current could reach 0.85 A cm−2 or more at 600 °C. Zr content inclusions were found at the surface and in the cross-section of the SDC electrolyte, which could be one of the reasons for reduced OCV and oxygen ionic conductivity. Fuel loss due to internal shorting of the thin SDC electrolyte cell becomes a significant concern when it is used in applications requiring high fuel utilization and electrical efficiency.  相似文献   

19.
Laser-printed thick-film electrodes (LiCoO2 cathode and carbon anode) are deposited onto metallic current collectors for fabricating Li-ion microbatteries. These microbatteries demonstrate a significantly higher discharge capacity, power and energy densities than those made by sputter-deposited thin-film techniques. This increased performance is attributed to the porous structure of the laser-printed electrodes, which allows improved ionic and electronic transport through the thick electrodes (∼100 μm) without a significant increase in internal resistance. These laser-printed electrodes are separated by a laser-cut porous membrane impregnated with a gel polymer electrolyte (GPE) in order to build mm-size scale solid-state rechargeable Li-ion microbatteries (LiCoO2/GPE/carbon). The resulting packaged microbatteries exhibit a power density of ∼38 mW cm−2 with a discharge capacity of ∼102 μAh cm−2 at a high discharge rate of 10 mA cm−2. The laser-printed microbatteries also exhibit discharge capacities in excess of 2500 μAh cm−2 at a current density of 100 μA cm−2. This is over an order of magnitude higher than that observed for sputter-deposited thin-film microbatteries (∼160 μAh cm−2).  相似文献   

20.
Several substituted titanates of formula Li4−xMgxTi5−xVxO12 (0 ≤ x ≤ 1) were synthesized (and investigated) as anode materials in rechargeable lithium batteries. Five samples labeled as S1–S5 were calcined (fired) at 900 °C for 10 h in air, and slowly cooled to room temperature in a tube furnace. The structural properties of the synthesized products have been investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transmission infrared (FTIR). XRD explained that the crystal structures of all samples were monoclinic while S1 and S3 were hexagonal. The morphology of the crystal of S1 was spherical while the other samples were prismatic in shape. SEM investigations explained that S4 had larger grain size diameter of 15–16 μm in comparison with the other samples. S4 sample had the highest conductivity 2.452 × 10−4 S cm−1. At a voltage plateau located at about 1.55 V (vs. Li +), S4 cell exhibited an initial specific discharge capacity of 198 mAh g−1. The results of cyclic voltammetry for Li4−xMgxTi5−xVxO12 showed that the electrochemical reaction was based on Ti4+/Ti3+ redox couple at potential range from 1.5 to 1.7 V. There is a pair of reversible redox peaks corresponding to the process of Li+ intercalation and de-intercalation in the Li–Ti–O oxides.  相似文献   

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