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1.
Room temperature ionic liquids (RTILs) with high safety characteristic usually have high viscosity and melting point, which is adverse for the application of RTIL-based electrolytes in Li-ion batteries. In this investigation, a promising RTIL, i.e. PP13TFSI consisting of N-methyl-N-propylpiperidinium (PP13) cation and bis(trifluoromethanesulfonyl)imide (TFSI) anion is synthesized. The effect of the content of Li salt in the electrolytes containing PP13TFSI and LiTFSI on the ionic conductivity and cell performance is investigated. The electrolyte of 0.3 mol kg−1 LiTFSI/PP13TFSI is recommended for its higher lithium transference number and discharge capacity in the LiCoO2/Li cell than other electrolytes. In addition, it is found that, by introducing 20% diethyl carbonate (DEC) as a co-solvent into pure RTIL electrolyte, the rate capability and low-temperature performance of the LiCoO2/Li cells are improved obviously, without sacrificing its safety characteristics. It suggests that a component with low viscosity and melting point, i.e. DEC, is necessary to effectively overcome the shortcomings of RTIL for the application in Li-ion batteries.  相似文献   

2.
The rapid thermal annealing (RTA) process was employed to obtain crystalline LiCoO2 thin films. XRD analyses of the LiCoO2 thin film show increased crystallinity with an increase in the RTA time. The Auger electron spectroscopic analysis of the LiCoO2 film strongly suggests that the RTA process is more advantageous to obtain a stable inter layer between the substrate and the deposited film and between each deposited layer than the conventional annealing process. All-solid-state thin film cells composed of Li/lithium phosphorous oxynitride (Lipon)/LiCoO2 systems were fabricated using the LiCoO2 cathode treated with RTA. The optimum condition of RTA would be 900 s at 650 °C, which exhibited a good rate capability for high power applications. Two cells were connected in parallel to obtain a higher discharge current, and they showed a specific capacity of 38.4 μAh cm−2 μm−1 even at a 25C rate (current density: 7.96 mA cm−2).  相似文献   

3.
In order to improve the discharge capacity in lithium ion microbatteries, a thick-film cathode was fabricated by a screen printing using LiCoO2 pastes. The printed cathode showed a different discharge curves when the cell was tested using various (liquid, gel and solid-state) electrolytes. When a cell test was performed with organic liquid electrolyte, the maximum discharge capacity was 200 μAh cm−2, which corresponded to approximately 133 mAh g−1 when the loading weight of LiCoO2 was calculated. An all-solid-state microbattery could be assembled using sputtered LiPON electrolyte, an evaporated Li anode, and printed LiCoO2 cathode films without delamination or electrical problems. However, the highest discharge capacity showed a very small value (7 μAh cm−2). This problem could be improved using a poly(vinylidene fluoride-hexafluoro propylene) (PVDF-HFP) gel electrolyte, which enhanced the contact area and adhesion force between cathode and electrolyte. The discharge value of this cell was measured as approximately 164 μAh cm−2 (≈110 mAh g−1). As the PVDF-HFP electrolyte had a relatively soft contact property with higher ionic conductance, the cell performance was improved. In addition, the cell can be fabricated in a leakage-free process, which can resolve many safety problems. According to these results, there is a significant possibility that a film prepared using the aforementioned paste with screen printing and PVDF-HFP gel electrolyte is feasible for a microbattery.  相似文献   

4.
Polyaniline layers of different morphologies ranging from open and “sponge-like” structures to compact and “pebble-like” surfaces were synthesized from perchlorate solutions and employed as cathode in the galvanic cell with Zn anode and NH4Cl/ZnCl2 electrolyte. Cathodic properties of synthesized layers were investigated by the constant current charging/discharging method in 500 cycles. Specific charge capacities and specific energies obtained form the current-time curves strongly depend on the morphology of investigated layers and discharge conditions. The results unambiguously show that charging/discharging reaction of polyaniline layers is limited to relatively thin layer at polymer/solution boundary. Specific charge capacities are inversely related to both the polymer thickness and the discharge current density. In the limit of zero current densities the specific charge capacity as high as 245 A h kg−1 could be achieved for porous structures of polyaniline layers. Specific capacitance higher than 400 F g−1 obtained at 2 mA cm−2 current density makes polyaniline a promising material for the application in electrochemical supercapacitors. The electrochemical behaviour of the layers was investigated by cyclic voltammetry and electrochemical impedance spectroscopy before and after 500 cycles of charging/discharging experiments. Both, cyclic voltammetry and electrochemical impedance spectroscopy showed that some polyaniline layers develop an increased charged transfer resistance at the carbon support/polymer interface during charging/discharging process. The increased charge transfer resistance does not affect the overall specific charge of the layers. The low-frequency capacities in impedance spectra are attributed to charging/discharging of polymer/electrolyte interface and seem to be related to the specific charge capacities obtained by extrapolation to zero current density discharge reaction.  相似文献   

5.
The use of self-organized TiO2 nanotube arrays electrochemically grown onto Si is investigated for the fabrication of an alternative electrode dedicated to on-chip Li-ion 2D microbatteries. Discharge/charge curves and cycling performance are studied in lithium-anode electrochemical test cells for both amorphous and crystalline titania nanotubes. At 5 μA cm−2 amorphous TiO2 nanotube layers onto Si deliver a maximum areal capacity of 89 μAh cm−2 in the first reversible discharge and 56 μAh cm−2 over 50 cycles. We demonstrate that these nanostructured thin film electrodes showing such electrochemical performances are compatible with IC technology.  相似文献   

6.
We have incorporated polymer additives such as poly(ethylene glycol) dimethyl ether (PEGDME) and tetra(ethylene glycol) dimethyl ether (TEGDME) into N-methyl-N-butylpyrrolidinium bis(trifluoromethane sulfonyl)imide (PYR14TFSI)-LiTFSI mixtures. The resulting PYR14TFSI + LiTFSI + polymer additive ternary electrolyte exhibited relatively high ionic conductivity as well as remarkably low viscosity over a wide temperature range compared to the PYR14TFSI + LiTFSI binary electrolytes. The charge/discharge cyclability of Li/LiFePO4 cells containing the ternary electrolytes was investigated. We found that Li/PYR14TFSI + LiTFSI + PEGDME (or TEGDME)/LiFePO4 cells containing the two different polymer additives showed very similar discharge capacity behavior, with very stable cyclability at room temperature (RT). Li/PYR14TFSI + LiTFSI + TEGDME/LiFePO4 cells can deliver about 127 mAh/g of LiFePO4 (74.7% of theoretical capacity) at 0.054 mA/cm2 (0.2C rate) at RT and about 108 mAh/g of LiFePO4 (63.4% of theoretical capacity) at 0.023 mA/cm2 (0.1C rate) at −1 °C for the first discharge. The cell exhibited a capacity fading rate of approximately 0.09-0.15% per cycle over 50 cycles at RT. Consequently, the PYR14TFSI + LiTFSI + polymer additive ternary mixture is a promising electrolyte for cells using lithium metal electrodes such as the Li/LiFePO4 cell reported here. These cells showed the capability of operating over a significant temperature range (∼0-∼30 °C).  相似文献   

7.
J.-H. Shin 《Electrochimica acta》2005,50(19):3859-3865
Solvent-free P(EO)20LiTFSI + PYR14TFSI polymer electrolyte films with PYR14+/Li+ mole ratios ranging from 0.96 to 3.22 were prepared by hot-pressing mixtures composed of PEO, LiTFSI and PYR14TFSI of selected stoichiometries. The PYR14TFSI room temperature ionic liquid (RTIL) is homogeneously incorporated into the P(EO)20LiTFSI membrane without phase separation. For a PYR14+/Li+ mole ratio of 3.22, the ionic conductivity was about 2 × 10−4 S/cm at 20 °C, i.e., more than one order of magnitude higher than that of the RTIL-free electrolyte. The electrochemical stability window of the polymer electrolyte containing the RTIL was about 6 V (versus Ag/Ag+). Li/V2O5 cells with the polymer electrolyte (PYR14+/Li+ = 1.92) showed a 60% capacity retention after 80 cycles at 40 °C (the initial capacity was 210 mA h/g). Li/V2O5 cells (PYR14+/Li+ = 1.28) held at 30 °C delivered about 93 mA h/g (at 0.057 mA/cm2), which corresponds to approximately 34% utilization of the active material. These results suggest that the incorporation of the RTILs into PEO-based polymer electrolytes is very promising for the future realization of solid-state lithium metal polymer batteries operating near ambient temperatures.  相似文献   

8.
Anhydrous proton-conducting inorganic-organic hybrid membranes were prepared by sol-gel process with tetramethoxysilane/methyl-trimethoxysilane/trimethylphosphate and 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonyl) imide [EMI][TFSI] ionic liquid as precursors. These hybrid membranes were studied with respect to their structural, thermal, proton conductivity, and hydrogen permeability properties. The Fourier transform infrared spectroscopy (FT-IR) and 31P, 1H, and 13C nuclear magnetic resonance (NMR) measurements have shown good chemical stability, and complexation of PO(OCH3)3 with [EMI][TFSI] ionic liquid in the studied hybrid membranes. Thermal analysis including TG and DTA confirmed that the membranes were thermally stable up to 330 °C. Thermal stability of the hybrid membranes was significantly enhanced by the presence of inorganic SiO2 framework and high stability of [TFSI] anion. The effect of [EMI][TFSI] ionic liquid addition on the microstructure of the membranes was studied by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) micrographs and no phase separation at the surfaces of the prepared membranes was observed and also homogeneous distribution of all elements was confirmed. Proton conductivity of all the prepared membranes was measured from −20 °C to 150 °C, and high conductivity of 5.4 × 10−3 S/cm was obtained for 40 wt% [EMI][TFSI] doped 40TMOS-50MTMOS-10PO(OCH3)3 (mol%) hybrid membrane, at 150 °C under anhydrous conditions. The hydrogen permeability was found to decrease from 1.61 × 10−11 to 1.39 × 10−12 mol/cm s Pa for 40 wt% [EMI][TFSI] doped hybrid membrane as the temperature increases from 20 °C to 150 °C. For 40 wt% [EMI][TFSI] doped hybrid membrane, membrane electrode assemblies were prepared and a maximum power density value of 0.22 mW/cm2 at 0.47 mA/cm2 as well as a current density of 0.76 mA/cm2 were obtained at 150 °C under non-humidified conditions when utilized in a H2/O2 fuel cell.  相似文献   

9.
Composite cathodes based on La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) are investigated for lower operating temperature (<750 °C) applications of a solid oxide fuel cell (SOFC). To enhance a charge transfer, a bi-layer SOFC cathode is proposed, which has a LSCF–Ce0.9Gd0.1O1.95 (GDC) composite layer and a pure LSCF layer. The bi-layer cathode SOFC shows a current density of 0.65 A cm−2 at 0.8 V and 660 °C, which is higher than a LSCF–GDC composite single-layer cathode SOFC cell of 0.35 A cm−2. The charge transfer polarizations in the bi-layer cathode SOFC are 0.14 Ω cm2 and 0.35 Ω cm2 at 760 °C and 660 °C, respectively, which are lower than those in the single-layer cathode cell of 0.23 Ω cm2 and 0.66 Ω cm2. The impedances characterized with a fitting model show that the lowered charge transfer polarization in the bi-layer cathode is a dominant factor in reducing the total polarization of SOFC.  相似文献   

10.
Electroactive polypyrrole-Fe2O3 nanocomposite materials were prepared by chemical polymerization of pyrrole in aqueous Fe2O3 colloidal solution, using FeCl3 as oxidant and tosylate anions (TS) as doping agent. The nanocomposite material named (PPyTSNC) was studied by X-ray diffraction analysis, Fourier Transform Infra-Red spectroscopy and thermogravimetric analysis. Their electrochemical storage properties were investigated on composite electrodes using 80% in weight of active materials in different immidazolium and pyrrolidinium based room temperature ionic liquids (RTILs) as electrolytes. Cyclic voltammetry and constant current charge discharge cycling showed high charge storage properties of the nanocomposite based electrodes in 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide (EMITFSI) and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) (respectively 72 mAh/g and 62 mAh/g at 1 mA/cm2 discharge current) which are more than twice higher than the values obtained with pure PPy. These improvements in capacities have been attributed to the PPyTSNC morphology modification which ensures a large incorporation of the electrolyte inside the nanostructure. The specific capacitances of the nanocomposite electrodes reached 210 F/g and 190 F/g in EMITFSI and PYR14TFSI and their cyclability has shown only 3-5% capacitance loss after one thousand cycles for both ionic liquids.  相似文献   

11.
Edy Marwanta 《Polymer》2005,46(11):3795-3800
Polymer electrolytes with high ionic conductivity and good elasticity were prepared by mixing nitrile rubber (poly(acrylonitrile-co-butadiene) rubber; NBR) with ionic liquid, N-ethylimidazolium bis(trifluoromethanesulfonyl)imide (EImTFSI). The NBR/EImTFSI composites were obtained as homogeneous and transparent films when the ionic liquid content was less than 60 wt%. Raman spectroscopy suggested the interaction between nitrile group of NBR and TFSI anion. Sample with ionic liquid content of 50 wt% showed the ionic conductivity of 1.2×10−5 S cm−1 at 30 °C. Addition of lithium salt to this NBR/EImTFSI composite further enhanced the ionic conductivity to about 10−4 S cm−1 without spoiling mechanical properties. DSC studies showed two glass transition temperatures for composites indicating microphase separation.  相似文献   

12.
New functionalized ILs based on quaternary ammonium cations with three or four ether groups and TFSI anion were synthesized and characterized. Physical and electrochemical properties, including melting point, thermal stability, viscosity, conductivity and electrochemical stability were investigated for these ILs. Five ILs with lower viscosity in these ILs were applied in lithium battery as new electrolytes. Behavior of lithium redox and charge–discharge characteristics of lithium battery were investigated for these IL electrolytes with 0.6 mol kg−1 LiTFSI. Lithium plating and striping on Ni electrode could be observed in these IL electrolytes. Li/LiFePO4 cells using these IL electrolytes without additives had good capacity and cycle property at the current rate of 0.1 C, and the N(2o1)3(2o2)TFSI and N2(2o1)3TFSI electrolytes owned better rate property.  相似文献   

13.
A gel polymer electrolyte (GPE) is prepared from polymethylmethacrylate interpenetrating polymer network, benzoyl peroxide, and 1.1 M LiPF6/EC-DEC (1:1 vol.%). The LiCoO2/graphite cells are prepared and their electrochemical properties were evaluated at various current densities and temperatures. The viscosity of the precursor containing 5 vol.% curable mixture is around 4.6 mPa s. The ionic conductivity of the GPE at 20 °C is around 5.8×10−3 S cm−1. The GPE has good electrochemical stability up to 4.8 V vs. Li/Li+. The capacity of the cell at 1.0C rate is 82% of the discharge capacity at 0.2C rate. The capacity of the cell at −10 °C is 86% of the discharge capacity at 20 °C. Discharge capacity of the cell with GPE is stable with charge-discharge cycling.  相似文献   

14.
The 30-cell nickel-yttria stabilized zirconia (Ni-YSZ) hydrogen electrode-supported planar solid oxide electrolyzer (SOE) stack modules were manufactured and tested at 800 °C in steam electrolysis mode for hydrogen production. The electrolysis efficiency of the stack modules was higher than 100% at a total steam and hydrogen flow of 2.1 sccm cm−2, a H2O/H2 ratio of 80/20, and a current density of <0.2 A cm−2. The electrolysis efficiency, current efficiency, and actual hydrogen production rate of the stack modules increased with increasing H2O/H2 ratio at a constant current density. However, the electrolysis and current efficiencies decreased steadily at high current densities. During hydrogen production, the stack modules were operated at 800 °C and a constant current density of 0.15 A cm−2 for up to 1100 h. A steam conversion rate of 62% and current efficiency of 87.4% were obtained; the actual hydrogen production rate reached as high as 103.6 N L h−1. Post-mortem analysis showed that delamination of the LSM–YSZ oxygen electrode mainly occurred in the steam and air inlet area of the 10×10 cm2 cells.  相似文献   

15.
SnOx thin films were prepared by reactive radio frequency magnetron sputtering with different sputtering powers. X-ray photoelectron spectroscopy suggested that all the films have similar chemical stoichiometry as SnO1.5. X-ray diffraction and transmission electro microscopy results showed that crystal size of the SnOx thin films gradually increases with increase of sputtering power from 50 to 150 W. Cyclic voltammetry and galvanostatic charge/discharge cycling measurements indicated that the electrochemical properties of SnOx films strongly rely on their crystal sizes as well as surface morphologies. The SnOx film deposited at sputtering power of 120 W exhibits the best electrochemical performances. It could deliver a reversible capacity of 670 μAh cm−2 μm−1 at 50 μA cm−2 in the voltage range of 0.1-1.2 V up to 50 cycles.  相似文献   

16.
Self-assembled monolayers of dodecanethiol (C12SH-SAMs) on polycrystalline gold were prepared under ultrasonic irradiation at 100 W (the actual ultrasonic power intensity is about 0.1 W cm−2 including the heat loss) for different time and investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). CV experiments show that the differential capacitance Cd values of the C12SH-SAM prepared under ultrasonic irradiation at 100 W (0.1 W cm−2) for 15 min are independent of the scan rate, the thickness d value of this monolayer is 17.5 Å, the tilt angle φ value of the molecules in this monolayer from the gold surface normal was calculated to be 30° and the difference value of the current density at −0.2 and 0.5 V (Δip) is only 0.69 μA cm−2. From the EIS experiments, we find that the phase angle value at 1 Hz Φ1 Hz of the C12SH-SAM prepared under ultrasonic irradiation at 100 W (0.1 W cm−2) for 15 min is 89°, the charge transfer resistance Rct value of this monolayer is 1.40 × 106 Ω cm2 and the surface coverage θ value of this monolayer was calculated to be 99.997% from Rct. These results indicate that the C12SH-SAM of almost defect-free structure and very low ionic permeability can be formed under ultrasonic irradiation at 100 W (0.1 W cm−2) in a short time (15 min).  相似文献   

17.
Sixteen new guanidinium salts based on small cations and TFSI anion were prepared and characterized. Physical and electrochemical properties of these products, including melting point, thermal stability, viscosity, conductivity and electrochemical window were investigated. Reducing symmetry of cations can reduce the melting points, and 12 products are liquids at room temperature. The viscosities of cg22TFSI, cg12TFSI and cg13TFSI were 45, 46 and 52 mPa s at 25 °C, respectively. Electrochemical and thermal stabilities of these ILs permitted them to become promising electrolytes used in electrochemical devices.  相似文献   

18.
To achieve a high-energy-density lithium electrode, high-density LiFePO4/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO4 as a precursor, glucose as a C source, and Li2CO3 as a Li source, in a pipe furnace under an atmosphere of 5% H2-95% N2. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO4/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO4/carbon composite powder with a carbon content of 7% reached 1.80 g m−3. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g−1, respectively, with a volume capacity of 300.6 mAh cm−3, at a 0.1C rate. At a rate of 5C, the LiFePO4/carbon composite shows a high discharge capacity of 98.3 mAh g−1 and a volume capacity of 176.94 mAh cm−3.  相似文献   

19.
Normal pulse voltammetric method was used to synthesize nanofibers of polyaniline (PANi) in HCl solution on a platinum electrode. The influences of the synthesis parameters, such as potential increment, pulse duration and monomer concentration on the electrochemical properties of the PANi films were investigated. Scanning electron microscopic micrographs clearly revealed the formation a nanofiber structure with average diameter in range 70-100 nm under optimum experimental conditions. The electrochemical properties of PANi films were studied with the impedance analysis, cyclic voltammetry and charge/discharge capacities. FT-IR results revealed that the PANi nanofibers were in emeraldine salt form. The film was employed as a positive electrode (cathode) for a PANi-Zn secondary battery containing 1.0 M ZnCl2 and 0.5 M NH4Cl as electrolyte. The cells were charged and discharged under a pulse current of 0.31 mA cm−2. It was found that the maximum capacity of the PANi-Zn battery is 235.60 Ah kg−1 with a columbic efficiency of 97-100% over a wide range of current density of 0.3-5.6 mA cm−2. The specific energy was 287.43 Wh kg−1 and the PANi cathode exhibited good recycleability.  相似文献   

20.
A series of coal-based activated carbons representing a wide range of mesopore content, from 16.7 to 86.9%, were investigated as an electrode in electric double layer capacitors (EDLCs) in 1 mol l−1 H2SO4 and 6 mol l−1 KOH electrolytic solutions. The activated carbons (ACs) used in this study were produced from chemically modified lignite, subbituminous and bituminous coals by carbonization and subsequent activation with steam. The BET surface area of ACs studied ranged from 340 to 1270 m2 g−1. The performance of ACs as EDLC electrodes was characterized using voltammetry, galvanostatic charge/discharge and impedance spectroscopy measurements. For the carbons with surface area up to 1000 m2 g−1, the higher BET surface area the higher specific capacitance (F g−1) for both electrolytes. The surface capacitance (μF cm−2) increases also with the mesopore content. The optimum range of mesopore content in terms of the use of ACs studied for EDLCs was found to be between 20 and 50%. A maximum capacitance exceeding 160 F g−1 and a relatively high surface capacitance about 16 μF cm−2 measured in H2SO4 solution were achieved for the AC prepared from a sulfonated subbituminous coal. This study shows that the ACs produced from coals exhibit a better performance as an electrode material of EDLC in H2SO4 than in KOH electrolytic solutions. For KOH, the capacitance per unit mesopore surface is slightly lower than that referred to unit micropore surface (9.1 versus 10.1 μF cm−2). However, in the case of H2SO4 the former capacitance is double and even higher compared with the latter (23.1 versus 9.8 μF cm−2). On the other hand, the capacitance per micropore surface area is the same in both electrolytes used, about 10.0 μF cm−2.  相似文献   

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