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1.
A new functionalized ionic liquid (IL) based on cyclic quaternary ammonium cations with ester group and bis(trifluoromethanesulfonyl)imide ([TFSI]?) anion, namely, N-methyl-N-methoxycarbonylpiperidinium bis(trifluoromethanesulfonyl)imide ([MMOCPip][TFSI]), was synthesized and characterized. Physical and electrochemical properties, including Li-ion transference number, ionic conductivity, and electrochemical stability, were investigated. The electrochemical window of [MMOCPip][TFSI] was 6 V, which was wide enough to be used as a common electrolyte material. The Li-ion transference number of this IL electrolyte containing 0.1 M LiTFSI was 0.56. The half-cell tests indicated that the [MMOCPip][TFSI] obviously improved the cyclability of a Li/LiFePO4 cell. For the Li/LiFePO4 half-cells, after 20 cycles at room temperature at 0.1 C, the discharge capacity was 109.7 mAh g?1 with 98.7% capacity retention in the [MMOCPip][TFSI]/0.1 M LiTFSI electrolyte. The good electrochemical performance demonstrated that the [MMOCPip][TFSI] could be used as electrolyte for lithium-ion batteries.  相似文献   

2.
A piperidinium-based ionic liquid, N-methylpiperidinium-N-acetate bis(trifluoromethylsulfonyl)imide ([MMEPip][TFSI]), was synthesized and used as an additive to the electrolyte of LiFePO4 battery. The electrochemical performance of the electrolytes based on different contents of [MMEPip][TFSI] has been investigated. It was found that the [MMEPip][TFSI] significantly improved the high-rate performance and cyclability of the LiFePO4 cells. In the optimized electrolyte with 3 wt% [MMEPip][TFSI], 70 % capacity can be retained with an increase in rate to 3.5 C, which was 8 % higher than that of electrolyte without [MMEPip][TFSI]. For the Li/LiFePO4 half-cells, after 100 cycles at 0.1 C, the discharge capacity retention was 78 % in the electrolyte without ionic liquid. However, in the electrolyte with 3 wt% [MMEPip][TFSI], it displayed a high capacity retention of 91 %. The good electrochemical performances indicated that the [MMEPip][TFSI] additive would positively enhance the electrochemical performance of LiFePO4 battery.  相似文献   

3.
S. Abarna  G. Hirankumar 《Ionics》2017,23(7):1733-1743
Novel solid polymer electrolytes, poly(vinylalcohol)-lithium perchlorate (PVA-LiClO4) and PVA-LiClO4-sulfolane are prepared by solvent casting method. The experimental results show that sulfolane addition enhances the ionic conductivity of PVA-LiClO4 complex by three orders. The maximum ionic conductivity of 1.14 ± 0.20 × 10?2 S cm?1 is achieved for 10 mol% sulfolane-added electrolyte at ambient temperature. Polymer-salt-plasticizer interactions are analyzed through attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Lithium ion transference number is found by AC impedance spectroscopy combined with DC potentiostatic measurements. The results confirm that sulfolane improves the Li+ transference number of PVA-LiClO4 complex to 0.77 from 0.40. The electrochemical stability window of electrolytes is determined by cyclic voltammetry (CV). The broad electrochemical stability window of 5.45 V vs. lithium is obtained for maximum conducting electrolyte. All-solid-state cell is fabricated using maximum conducting electrolyte, and electrochemical impedance study is carried out. It reveals that electrolyte interfacial resistance with Li electrode is very low. The use of PVA-LiClO4-sulfolane as a viable electrolyte material for high-voltage lithium ion batteries is ensured.  相似文献   

4.
A new series of nanocomposite polymer electrolyte (NCPE) system comprising of polyethylene oxide (PEO) and polypropylene glycol (PPG) as blended polymer host, zinc trifluoromethanesulfonate [Zn(CF3SO3)2] as dopant salt and nanocrystalline alumina [Al2O3] as filler was prepared by solution casting technique. The present system consisting of five different compositions of 87.5 wt% (PEO:PPG)–12.5 wt% Zn(CF3SO3)2 + x wt% Al2O3 [where x = 1, 3, 5, 7 and 9, respectively] has been thoroughly characterized by various analytical techniques such as electrical impedance spectroscopy, X-ray diffraction (XRD) studies, differential scanning calorimetry (DSC), scanning electron microscopic (SEM) analysis and linear sweep voltammetry (LSV). The maximum room temperature ionic conductivity exhibited by the NCPE was found to be 2.1 × 10?4 S cm?1 for 3 wt% loading of Al2O3 which is an order higher than that of the optimized filler-free zinc salt doped polymer electrolyte system at 298 K. The evidence of a decrease in the degree of crystallinity responsible for the enhanced conductivity was revealed by the XRD data and further confirmed by DSC and SEM results. Moreover, the electrochemical stability window of the highly conducting electrolyte matrix has been experimentally determined by linear sweep voltammetry and found to be 3.6 V which is fairly adequate for the construction of zinc primary batteries as well as zinc-based rechargeable batteries at ambient conditions.  相似文献   

5.
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 (PYR1,4-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.  相似文献   

6.
Advanced Li-air battery architecture demands a high Li+ conductive solid electrolyte membrane that is electrochemically stable against metallic lithium and aqueous electrolyte. In this work, an investigation has been carried out on the microstructure, Li+ conduction behaviour and structural stability of Li7La3-x Y x Zr2O12 (x = 0.125, 0.25 and 0.50) prepared by conventional solid-state reaction technique. The phase analysis of Li7La3-x Y x Zr2O12 (x = 0.125, 0.25 and 0.50) sintered at 1200 °C by powder X-ray diffraction (PXRD) and Raman confirms the formation of high Li+ conductive cubic phase (\( Ia\overline{3}d \)) lithium garnets. Among the investigated lithium garnets, Li7La2.75Y0.25Zr2O12 sintered at 1200 °C exhibits a maximized room temperature total (bulk + grain boundary) Li+ conductivity of 3.21 × 10?4 S cm?1 along with improved relative density of 96 %. The preliminary investigation on the structural stability of Li7La2.75Y0.25Zr2O12 in the solutions of 1 M LiCl, dist. H2O and 1 M LiOH at 30 °C/50 °C indicates that the Li7La2.75Y0.25Zr2O12 is relatively stable against 1 M LiCl and dist. H2O. Further electrochemical investigation is essential for practical application of Li7La2.75Y0.25Zr2O12 as protective solid electrolyte membrane in aqueous Li-air battery.  相似文献   

7.
In this work, Li2ZrF6, a lithium salt additive, is reported to improve the interface stability of LiNi0.5Mn1.5O4 (LNMO)/electrolyte interface under high voltage (4.9 V vs Li/Li+). Li2ZrF6 is an effective additive to serve as an in situ surface coating material for high-voltage LNMO half cells. A protective SEI layer is formed on the electrode surface due to the involvement of Li2ZrF6 during the formation of SEI layer. Charge/discharge tests show that 0.15 mol L?1 Li2ZrF6 is the optimal concentration for the LiNi0.5Mn1.5O4 electrode and it can improve the cycling performance and rate property of LNMO/Li half cells. The results obtained by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) demonstrate that Li2ZrF6 can facilitate the formation of a thin, uniform, and stable solid electrolyte interface (SEI) layer. This layer inhibits the oxidation decomposition of the electrolyte and suppresses the dissolution of the cathode materials, resulting in improved electrochemical performances.  相似文献   

8.
LiTi2O4 anode material for lithium-ion battery has been prepared by a novel one-step solid-state reaction method using Li2CO3, TiO2, and carbon black as raw materials. X-ray diffraction, scanning electron microscopy, energy-dispersive spectrometry, and the determination of electrochemical properties show that the single phase of LiTi2O4 with spinel crystal structure is formed at 850?°C by this new method, and the lattice parameter is about 8.392?Å. The primary particle size of the LiTi2O4 powder is about 0.5–1.0 μm and its morphology is similar to a sphere. The lithium ion insertion voltage of LiTi2O4 anode material is about 1.50 V versus lithium metal, the initial discharge capacity is about 133.6 mAh g-1, the charge–discharge voltage plateau is very flat, and no solid electrolyte interface film is formed when working potential is more than 1.0 V. The reaction reversibility and the cycling stability are excellent, and the high rate performance is good.  相似文献   

9.
Fluoroethylene carbonate (FEC) is investigated as the electrolyte additive to improve the electrochemical performance of high voltage LiNi0.6Co0.2Mn0.2O2 cathode material. Compared to LiNi0.6Co0.2Mn0.2O2/Li cells in blank electrolyte, the capacity retention of the cells with 5 wt% FEC in electrolytes after 80 times charge-discharge cycle between 3.0 and 4.5 V significantly improve from 82.0 to 89.7%. Besides, the capacity of LiNi0.6Co0.2Mn0.2O2/Li only obtains 12.6 mAh g?1 at 5 C in base electrolyte, while the 5 wt% FEC in electrolyte can reach a high capacity of 71.3 mAh g?1 at the same rate. The oxidative stability of the electrolyte with 5 wt% FEC is evaluated by linear sweep voltammetry and potentiostatic data. The LSV results show that the oxidation potential of the electrolytes with FEC is higher than 4.5 V vs. Li/Li+, while the oxidation peaks begin to appear near 4.3 V in the electrolyte without FEC. In addition, the effect of FEC on surface of LiNi0.6Co0.2Mn0.2O2 is elucidated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The analysis result indicates that FEC facilitates the formation of a more stable surface film on the LiNi0.6Co0.2Mn0.2O2 cathode. The electrochemical impedance spectroscopy (EIS) result evidences that the stable surface film could improve cathode electrolyte interfacial resistance. These results demonstrate that the FEC can apply as an additive for 4.5 V high voltage electrolyte system in LiNi0.6Co0.2Mn0.2O2/Li cells.  相似文献   

10.
In order to study the influence of powder calcination temperature on lithium ion conductivity, synthesized Li1.3Ti1.7Al0.3(PO4)3 (LATP) was calcined at temperatures between 750 and 900 °C. The shape and size of the particles were characterized employing scanning electron microscopy (SEM), and specific surface area of the obtained powder was measured. The crystallinity grade of different heat-treated powders was calculated from XRD spectra. Posteriorly, all powders were sintered at 1100 °C employing field-assisted sintering (SPS), and the electrical properties were correlated to the calcination conditions. The highest ionic conductivity was observed for samples made out of powders calcined at 900 °C.  相似文献   

11.
Vinyl ethylene carbonate (VEC) is investigated as an electrolyte additive to improve the electrochemical performance of LiNi0.4Mn0.4Co0.2O2/graphite lithium-ion battery at higher voltage operation (3.0–4.5 V) than the conventional voltage (3.0–4.25 V). In the voltage range of 3.0–4.5 V, it is shown that the performances of the cells with VEC-containing electrolyte are greatly improved than the cells without additive. With 2.0 wt.% VEC addition in the electrolyte, the capacity retention of the cell is increased from 62.5 to 74.5 % after 300 cycles. The effects of VEC on the cell performance are investigated by cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), x-ray powder diffraction (XRD), energy dispersive x-ray spectrometry (EDS), scanning electron microscopy (SEM), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR). The results show that the films electrochemically formed on both anode and cathode, derived from the in situ decomposition of VEC at the initial charge–discharge cycles, are the main reasons for the improved cell performance.  相似文献   

12.
Lithium-rich cathode material Li[Li0.2Ni0.13Co0.13Mn0.54]O2 doped with trace Mo is successfully synthesized by a sol-gel method. The X-ray diffraction patterns show that trace Mo substitution increases the inter-layer space of the material, of which is benefiting to lithium ion insertion/extraction among the electrode materials. The (CV) tests demonstrate the decrease of polarization, and on the other hand, the lithium ion diffusion coefficient (D Li) of the modified material turns out to be larger, which indicates a faster electrochemical process. As a result, the Mo doped material possesses high rate performance and good cycling stability, and the initial discharge capacity reaches 149.3 mAh g?1 at a current density of 5.0 °C, and the residual capacity is 144.0 mAh g?1 after 50 cycles with capacity retention of 96.5 % in the potential range of 2.0–4.8 V at room temperature.  相似文献   

13.
A Li0.5FeV1.5O4 sample was synthesized using sol-gel route. The X-ray diffraction study indicates formation of spinel phase (with Fd3m space group) for this sample. LiO4, LiO6, and V-O bonds were identified from the Raman spectrum, while LiO4 and Fe-O bonds were identified from the FTIR spectrum of this sample phase. The FESEM study indicates formation of inhomogeneous grains. The surface area of 74.39 m2/g was estimated from the Brunauer-Emmett-Teller (BET) surface area analysis technique. The cyclic voltammetry study of Li0.5FeV1.5O4 indicates an anodic peak at 2.1 V while a cathodic peak at 1.98 V. The charge-discharge study exhibits two voltage plateaus respectively at 2.1 and at 4 V. Stable electrochemical capacity of 40 mAh/g for Li0.5FeV1.5O4 was found for 30 cycles. The electrochemical impedance spectroscopy study indicates smaller bulk resistance and higher ionic diffusion, i.e., less Warburg impedance for this phase. An energy density of 89 Wh/kg, a power density of 33 W/kg, and a 90% Coulombic efficiency was achieved with relatively good cyclic stability from Li0.5FeV1.5O4.  相似文献   

14.
Lithium-excess oxide shows great potential for its high specific capacity of exceeding 280 mAh g?1. However, the poor rate capability caused by the poor electrochemical kinetics condition as well as the structure instability block the way of its application. Here, we aimed to improve the kinetics circumstance for lithium ion transference through the material bulk by synthesizing lithium-excess oxide with high specific surface area. Petal-like nanoplates and nanoparticles with excellent electrochemical performance were obtained at different sintering temperatures and times by the electrospinning-sintering method, which facilitates the sufficient contact of electrode and electrolyte and helps to reduce the polarization during the electrochemical reaction process. Cyclic voltammetry tests verify that a portion of oxidized oxygen is reduced reversibly at 3.0 V and the reduction of oxygen contributes to the discharge capacity. Electrochemical impedance spectroscopy plots illustrate the ameliorative electrochemical kinetics is conductive to the oxidation of oxygen at 4.5 V.  相似文献   

15.
Solid electrolyte Li1.3Al0.3Ti1.7(PO4)3 was prepared by sol-gel method under different sintering conditions. The structural identification, surface morphology, electrochemical window, ionic conductivity, and activation energy of the Li1.3Al0.3Ti1.7(PO4)3 sintered pellets were investigated by X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. It is found that the sintering temperature and time have considerable effect on the properties of the Li1.3Al0.3Ti1.7(PO4)3 sintered pellets. The Li1.3Al0.3Ti1.7(PO4)3 pellet sintered at 900 °C for 2 h is denser than the pellets sintered at other conditions. Different sintering conditions result in the sintered pellet with different porosity. However, the sintering conditions have little effect on the electrochemical window of Li1.3Al0.3Ti1.7(PO4)3. Among the Li1.3Al0.3Ti1.7(PO4)3 pellets sintered at various conditions, the pellet sintered at 900 °C for 2 h shows the highest ionic conductivity of 3.46 × 10−4 S cm−1 and the lowest activation energy of 0.2821 eV.  相似文献   

16.
Nano-sized silica poly(methylmethacrylate)-based gel electrolyte containing lithium hexafluorophosphate (LiPF6) was synthesized by using different binary solvent mixture (propylene carbonate(PC) and dimethylformamide (DMF) in different volume ratio). Role of DMF in PC: Higher DMF content in PC-based electrolyte shows higher ionic conductivity at all polymer content and at wide temperature regions (10-70 °C). A small increment in ionic conductivity at lower content of polymer in liquid/gel electrolyte was observed and having maximum conductivity of 13.12 mS/cm at 25 °C. Stability (mechanically and electrically), viscosity and ionic conductivity of gel electrolytes were improved with the addition of nano-sized silica at ambient temperature. Ionic conductivity of nano-sized silica-based gel electrolyte does not change much over 5o–70 °C temperature range and is factor-wise only which make indispensable in different electrochemical devices. Also polymer gel electrolyte membranes as such and with dispersed silica nano-particles were characterized through scanning electron microscope to study the morphology of gel matrix.  相似文献   

17.
(Ni0.8Mn0.1Co0.1)(OH)2 and Co(OH)2 secondly treated by LiNi0.8Mn0.1Co0.1O2 have been prepared via co-precipitation and high-temperature solid-state reaction. The residual lithium contents, XRD Rietveld refinement, XPS, TG-DSC, and electrochemical measurements are carried out. After secondly treating process, residual lithium contents decrease drastically, and occupancy of Ni in 3a site is much lower and Li/Ni disorder decreases. The discharge capacity is 193.1, 189.7, and 182 mAh g?1 at 0.1 C rate, respectively, for LiNi0.8Mn0.1Co0.1O2-AP, -NT, and -CT electrodes between 3.0 and 4.2 V in pouch cell. The capacity retention has been greatly improved during gradual capacity fading of cycling at 1 C rate. The noticeably improved thermal stability of the samples after being treated can also be observed.  相似文献   

18.
The nanostructured Na3V2(PO4)3 (NVP) cathode material has been synthesized using the sol-gel route for different molar fractions of citric acid as a carbon source during the synthesis. The nanostructured NVP as cores with carbonic shell structures are fabricated with two different citric acid molar ratios. The thermal treatment has been optimized to convert the amorphous carbon shell into graphitic carbon to realize the better electrical conductivity and thus effective electron transfer during the electrochemical charge transfer process. The X-ray diffraction measurements confirmed the rhombohedral crystallographic phase (space group R-3c) with average crystallite size ~28 ± 5 nm. The coin cells are assembled in a hybrid rechargeable electrochemical cell configuration with lithium as a counter electrode and LiPF6-EC:DEC:DMC (1:1:1 ratio) as the electrolyte. The electrochemical charge/discharge measurements are carried out at C/10 and C/20 rates and the measured specific capacities are 80 and 120 mAhg?1 for samples with lower and higher citric acid molar ratios, respectively. The studies suggest that NVP can be used as an effective cathode material in hybrid electrochemical cells, and a higher concentration of citric acid may result in the effective carbonic shell for optimal electron transfer and thus enhanced electrochemical performance.  相似文献   

19.
A trilayer carbon nanotube (CNT)/Al2O3/polypropylene (PP) separator is prepared by means of simple tape casting of Al2O3 and CNT layers onto a commercial PP separator, respectively. The electrochemical performance of the trilayer separator in the lithium-sulfur batteries is compared with those of the PP and the Al2O3/PP separator. The CNT/Al2O3/PP separator exhibits the best electrochemical performance, including the cycling performance and rate capability. The CNT component in the trilayer separator acts as a matrix for capturing the polysulfide species and suppressing the migration of polysulfides to the lithium anode side and also reduces the charge transfer resistance of sulfur cathodes significantly. Meanwhile, the Al2O3 layer in the trilayer separator not only has the advantages on thermal stability and electrolyte intake but also can provide the strong shield for CNT from penetrating the separator.  相似文献   

20.
Zhenye Zhu  Fangyuan Cai  Jie Yu 《Ionics》2016,22(8):1353-1359
Li-rich layered-layered-Spinel structure spherical Li1.3Mn4/6Ni1/6Co1/6O2.40 particles was successfully prepared and coated with a uniform layer by a two-step co-precipitation method and evaluated in lithium cells. The structures and electrochemical properties of pristine Li1.3Mn4/6Ni1/6Co1/6O2.40 and AlF3-coated Li1.3Mn4/6Ni1/6Co1/6O2.40 were characterized. When the coating amount was 2 wt%, the cathode showed the best cycling performance and rate capability compared to others. The AlF3-coated Li1.3Mn4/6Ni1/6Co1/6O2.40 Li-ion cell cathode had a capacity retention of 90.07 % after 50 cycles at 0.5 C over 2.0–4.8 V, while the pristine Li1.3Mn4/6Ni1/6Co1/6O2.40 exhibited capacity retention of only 80.73 %. Moreover, the rate capability and cyclic performance also improved. Electrochemical impedance spectroscopy testing revealed that the improved electrochemical performance might attribute to the AlF3 coating layer which can suppress the increase of impedance during the charging and discharging process by preventing direct contact between the highly delithiated active material and electrolyte.  相似文献   

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