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1.
A new plasticized nanocomposite polymer electrolyte based on poly (ethylene oxide) (PEO)-LiTf dispersed with ceramic filler (Al2O3) and plasticized with propylene carbonate (PC), ethylene carbonate (EC), and a mixture of EC and PC (EC+PC) have been studied for their ionic conductivity and thermal properties. The incorporation of plasticizers alone will yield polymer electrolytes with enhanced conductivity but with poor mechanical properties. However, mechanical properties can be improved by incorporating ceramic fillers to the plasticized system. Nanocomposite solid polymer electrolyte films (200–600 μm) were prepared by common solvent-casting method. In present work, we have shown the ionic conductivity can be substantially enhanced by using the combined effect of the plasticizers as well as the inert filler. It was revealed that the incorporating 15 wt.% Al2O3 filler in to PEO: LiTf polymer electrolyte significantly enhanced the ionic conductivity [σ RT (max)?=?7.8?×?10?6 S cm?1]. It was interesting to observe that the addition of PC, EC, and mixture of EC and PC to the PEO: LiTf: 15 wt.% Al2O3 CPE showed further conductivity enhancement. The conductivity enhancement with EC is higher than PC. However, mixture of plasticizer (EC+PC) showed maximum conductivity enhancement in the temperature range interest, giving the value [σ RT (max)?=?1.2?×?10?4 S cm?1]. It is suggested that the addition of PC, EC, or a mixture of EC and PC leads to a lowering of glass transition temperature and increasing the amorphous phase of PEO and the fraction of PEO-Li+ complex, corresponding to conductivity enhancement. Al2O3 filler would contribute to conductivity enhancement by transient hydrogen bonding of migrating ionic species with O–OH groups at the filler grain surface. The differential scanning calorimetry thermograms points towards the decrease of T g , crystallite melting temperature, and melting enthalpy of PEO: LiTf: Al2O3 CPE after introducing plasticizers. The reduction of crystallinity and the increase in the amorphous phase content of the electrolyte, caused by the filler, also contributes to the observed conductivity enhancement.  相似文献   

2.
Four quaternary alkyl ammonium salts were used in an organophilic procedure, performed on montmorillonite clay, and resulted in intercalation in dimethylformamide (DMF) or ethylene carbonate (EC)/propylene carbonate (PC) as a cosolvent between poly(vinylidene fluoride) (PVdF) and the organophilic clay. An examination using X‐ray diffraction revealed that PVdF entered galleries of montmorillonite clay, and it exhibited exfoliation and intercalation phenomena when it was analyzed with transmission electron microscopy. Gel PVdF nanocomposite electrolyte materials were successfully prepared by the addition of the appropriate percentages of DMF or PC/EC as a cosolvent, organophilic clay, and lithium perchlorate to PVdF. The maximum ionic conductivity was 1.03 × 10?2 S/cm, and the materials exhibited better film formation, solvent‐maintaining capability, and dimensional stability than electrolyte films without added organophilic clays. The results of cyclic voltammetry testing showed that the addition of the organophilic clays significantly enhanced the electrochemical stability of the polymer electrolyte system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3873–3882, 2002  相似文献   

3.
In the present work, nanofibrous composite polymer electrolytes consist of polyethylene oxide (PEO), ethylene carbonate (EC), propylene carbonate (PC), lithium perchlorate (LiClO4), and titanium dioxide (TiO2) were designed using response surface method (RSM) and synthesized via an electrospinning process. Morphological properties of the as‐prepared electrolytes were studied using SEM. FTIR spectroscopy was conducted to investigate the interaction between the components of the composites. The highest room temperature ionic conductivity of 0.085 mS.cm?1 was obtained with incorporation of 0.175 wt. % TiO2 filler into the plasticized nanofibrous electrolyte by EC. Moreover, the optimum structure was compared with a film polymeric electrolyte prepared using a film casting method. Despite more amorphous structure of the film electrolyte, the nanofibrous electrolyte showed superior ion conductivity possibly due to the highly porous structure of the nanofibrous membranes. Furthermore, the mechanical properties illustrated slight deterioration with incorporation of the TiO2 nanoparticles into the electrospun electrolytes. This investigation indicated the great potential of the electrospun structures as all‐solid‐state polymeric electrolytes applicable in lithium ion batteries.  相似文献   

4.
A star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized, and its corresponding gel polymer electrolyte based on lithium perchlorate and plasticizers EC/PC with the character being colorless and highly transparent has been also prepared. The polymer host was characterized and confirmed to be of a star network and an amorphous structure by FTIR, ^1H NMR and XRD studies. The polymer host hold good mechanical properties for pentaerythritol cross-linking. Maximum ionic conductivity of the prepared polymer electrolyte has reached 8.83 × 10 ^-4 S·cm^-1 at room temperature. Thermogravimetry (TG) of the polymer electrolyte showed that the thermal stability was up to at least 150 ℃. The gel polymer electrolyte was further evaluated in electrochromic devices fabricated by transparent PET-ITO and electrochromically active viologen derivative films, and its excellent performance promised the usage of the gel polymer electrolyte as ionic conductor material in electrochrornic devices.  相似文献   

5.
The novel single-ionic conductive gel polymer electrolyte was prepared from polyvinylidene fluoride (PVDF), propylene glycol carbonate (PC) and a new fluorine-containing ionomer. Cation-carbonyl interaction behavior, morphology and ionic conductive properties of this gel polymer electrolyte were studied by infrared spectra analysis (IR), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and complex impedance analysis. The results showed that the fluorine-containing ionomer was miscible with both PVDF and PC, and that the carbonyl groups in the ionomer and PC could bond competitively with the cation. Both the content of fluorine-containing ionomer and the content of PC had a great effect on morphology and ionic conductive properties of the samples. For this new gel polymer electrolyte, an ionic conductivity of above 10−4 S cm−1 at room temperature could be reached, and this electrolyte system was a single-ionic kind gel polymer electrolyte with the transport number of the sodium ion exceed 0.99 (t+>0.99).  相似文献   

6.
New polymer electrolyte films of lithium tetrafluoroborate (LiBF4)-complexed poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) embedded with different quantities of 1-ethyl-3methylimidazolium tetrafluoroborate (EMIMBF4) ionic liquid were prepared by solution casting. The prepared films were characterized using various techniques: X-ray diffraction, scanning electron microscopy, impedance spectroscopy and electrochemical measurements. The pure PVdF-HFP possessed a semi-crystalline structure and its amorphicity increased with the addition of LiBF4 salt and EMIMBF4 ionic liquid. The size and interconnection of pores in the films were enhanced by EMIMBF4. Impedance measurements indicated that the room-temperature ionic conductivity of the films increased with increasing EMIMBF4 concentration until 15 wt.%, being up to 0.202 × 10−4 S cm−1, and then decreased with further increasing EMIMBF4 concentration. In addition, the temperature-dependent ionic conductivity of the polymer electrolyte films followed an Arrhenius relation and the 15 wt.% EMIMBF4-incorporated gel polymer electrolyte film exhibited a low activation energy for ionic conduction, being about 0.28 eV. Finally, the electrochemical stability window of the 85PVdF-HFP:15LiBF4+15 EMIMBF4 gel polymer electrolyte films was evaluated as approximately 4.4 V, which is a promising value for ion battery applications.  相似文献   

7.
In this work, the influence of 2-mercaptobenzimidazole (2-MCBI) on poly(vinylidinefluoride-co-hexafluoropropylene)/KI/I2 (PVDF-HFP/KI/I2) polymer electrolytes were studied. The pure and different weight percentage ratios (20, 30, 40 and 50%) of 2-MCBI doped PVDF-HFP/KI/I2 electrolytes were prepared by a solution casting technique. The as-prepared polymer electrolyte films were characterized using various techniques such as Fourier transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC), X-ray diffractometer (XRD), alternating current (AC)-impedance analysis. The addition of 2-MCBI with pure PVDF-HFP/KI/I2 was found to increase the ionic conductivity of electrolyte. Among the various additions, 30 wt% 2-MCBI doped PVDF-HFP/KI/I2 showed the highest room temperature ionic conductivity values than the others. The dye-sensitized solar cell (DSSC) fabricated using this optimized polymer electrolyte achieved a high power conversion efficiency of 4.40% than the pure PVDF-HFP/KI/I2 (1.74%) at similar experimental conditions. Thus, the 2-MCBI doped polymer electrolyte has proven to be an effective substitute to the liquid electrolyte in DSSCs.  相似文献   

8.
A proton-conducting nanocomposite gel polymer electrolyte (GPE) system, [35{(25 poly(methylmethacrylate) (PMMA) + 75 poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP))?+?xSiO2}?+?65{1 M NH4SCN in ethylene carbonate (EC) + propylene carbonate (PC)}], where x?=?0, 1, 2, 4, 6, 8, 10, and 12, has been reported. The free standing films of the gel electrolyte are obtained by solution cast technique. Films exhibit an amorphous and porous structure as observed from X-ray diffractometry (XRD) and scanning electron microscopy (SEM) studies. Fourier transform infrared spectrophotometry (FTIR) studies indicate ion–filler–polymer interactions in the nanocomposite blend GPE. The room temperature ionic conductivity of the gel electrolyte has been measured with different silica concentrations. The maximum ionic conductivity at room temperature has been observed as 4.3?×?10?3?S?cm?1 with 2 wt.% of SiO2 dispersion. The temperature dependence of ionic conductivity shows a typical Vogel-Tamman-Fulcher (VTF) behavior. The electrochemical potential window of the nanocomposite GPE film has been observed between ?1.6 V and 1.6 V. The optimized composition of the gel electrolyte has been used to fabricate a proton battery with Zn/ZnSO4·7H2O anode and PbO2/V2O5 cathode. The open circuit voltage (OCV) of the battery has been obtained as 1.55 V. The highest energy density of the cell has been obtained as 6.11 Wh?kg?1 for low current drain. The battery shows rechargeability up to 3 cycles and thereafter, its discharge capacity fades away substantially.  相似文献   

9.
Poly(ethylene glycol)‐based networked polymers that had lithium sulfonate salt structures on the network were prepared by heating a mixture of poly(ethylene glycol) diglycidyl ether (PEGGE), poly(ethylene glycol) bis(3‐aminopropyl) terminated (PEGBA), and an ionic epoxy monomer, lithium 3‐glycidyloxypropanesulfonate (LiGPS). Flexible self‐standing networked polymer films showed high thermal stability, low crystallinity, low glass transition temperature, and good mechanical strength. The materials were ion conductive at room temperature even under a dry condition, although the ionic conductivity was rather low (10?6 to 10?5 S/m). The ionic conductivity increased with the increase in temperature to above 1 × 10?4 S/m at 90 °C. The film samples became swollen by immersing in propylene carbonate (PC) or PC solution of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The samples swollen in PC showed higher ionic conductivity (ca.1 × 10?3 S/m at room temperature), and the samples swollen in LiTFSI/PC showed much higher ionic conductivity (nearly 1 S/m at room temperature). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3113–3118, 2010  相似文献   

10.
Networked polymers that had poly(ethylene glycol) (PEG) chains and lithium sulfonylimide salt structures were prepared by curing a mixture of poly(ethylene glycol) diglycidyl ether and lithium 3‐glycidyloxypropanesulfonyl‐trifluoromethanesulfonylimide with poly(ethylene glycol) bis(3‐aminopropyl) terminated. The obtained flexible self‐standing networked polymer films showed high thermal and mechanical stability with relatively high ionic conductivity. The room temperature ionic conductivity under a dry condition was in the range of 10?5 ~ 10?4 S m?1, which is one order of magnitude higher than the corresponding networked polymers having lithium sulfonate salt structures (10?6 ~ 10?5 S m?1). The film sample became swollen by immersing in propylene carbonate (PC) or PC solution of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The sample swollen in PC showed higher ionic conductivity (7.2 × 10?3 S m?1 at room temperature), and the sample swollen in 1.0 M LiTFSI/PC showed much higher ionic conductivity (8.2 × 10?1 S m?1 at room temperature). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

11.
New poly (vinylidenefluoride-co-hexafluoro propylene) (PVDF-HFP)/CeO2-based microcomposite porous polymer membranes (MCPPM) and nanocomposite porous polymer membranes (NCPPM) were prepared by phase inversion technique using N-methyl 2-pyrrolidone (NMP) as a solvent and deionized water as a nonsolvent. Phase inversion occurred on the MCPPM/NCPPM when it is treated by deionized water (nonsolvent). Microcomposite porous polymer electrolytes (MCPPE) and nanocomposite porous polymer electrolytes (NCPPE) were obtained from their composite porous polymer membranes when immersed in 1.0 M LiClO4 in a mixture of ethylene carbonate/dimethyl carbonate (EC/DMC) (v/v = 1:1) electrolyte solution. The structure and porous morphology of both composite porous polymer membranes was examined by scanning electron microscope (SEM) analysis. Thermal behavior of both MCPPM/NCPPM was investigated from DSC analysis. Optimized filler (8 wt% CeO2) added to the NCPPM increases the porosity (72%) than MCPPM (59%). The results showed that the NCPPE has high electrolyte solution uptake (150%) and maximum ionic conductivity value of 2.47 × 10−3 S cm−1 at room temperature. The NCPPE (8 wt% CeO2) between the lithium metal electrodes were found to have low interfacial resistance (760 Ω cm2) and wide electrochemical stability up to 4.7 V (vs Li/Li+) investigated by impedance spectra and linear sweep voltammetry (LSV), respectively. A prototype battery, which consists of NCPPE between the graphite anode and LiCoO2 cathode, proves good cycling performance at a discharge rate of C/2 for Li-ion polymer batteries.  相似文献   

12.
A free standing polymer electrolytes films, containing poly(glycidyl methacrylate) (PGMA) as the polymer host, lithium perchlorate (LiClO4), and ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide [Bmim][TFSI] as a plasticizer was successfully prepared via the solution casting method. The XRD analysis revealed the amorphous nature of the electrolyte. ATR-FTIR and thermal studies confirmed the interaction and complexation between the polymer host and the ionic liquid. The maximum ionic conductivity of the solid polymer electrolyte was found at 2.56 × 10–5 S cm–1 by the addition of 60 wt % [Bmim][TFSI] at room temperature and increased up to 3.19 × 10–4 S cm–1 at 373 K, as well as exhibited a transition of temperature dependence of conductivity: Arrhenius-like behavior at low and high temperatures.  相似文献   

13.
In last few decades, polymer electrolyte is the most promising candidate for the fabrication of electrochemical devices. In current work, the influence of adding the room-temperature ionic liquid (trifluoromethanesulfonic chloride – CClF3O2S) in polyethylene oxide (PEO): ammonium iodide (NH4I) polymer electrolyte has been studied. The IL-doped polymer electrolyte films are synthesized by solution casting method with varying stoichiometric ratios. Several experimental techniques including optical polarizing microscope, impedance spectroscopy, X-ray diffraction, Linear sweep voltammetry, Ionic transference number thermal analysis, and electrical conductivity measurements at room temperature have been studied in detail. The complex material's maximum conductivity has been determined to be 3.3 × 10−5 S cm−1 at room temperature. The POM images show the increase in amorphous region which further confirm the improvement in ionic conductivity. Ionic transference number 0.96 shows the system is purely ionic in nature. The ESW of the IL doped polymer electrolyte is also sawed to be 3.32 V which is suitable for the fabrication of electrochemical devices.  相似文献   

14.
The gel polymer electrolyte based on semi-IPN (interpenetrating polymer network) structure for the protection of lithium metal electrode was successfully developed by ultraviolet (UV) radiation-curing method. A curable mixed solution consists of linear polymer (Kynar 2801), crosslinking agent (1,6-hexanediol diacrylate), liquid electrolyte (ethylene carbonate (EC)/propylene carbonate (PC)/1 M LiClO4), oligo(ethylene glycol) borate (OEGB) anion receptor, and photoinitiator (methyl benzoylformate). The OEGB was synthesized by the dehydrocoupling reaction of hydroxyl group in di(ethylene glycol) methyl ether with hydrogen in BH3 and characterized by 1H NMR. The presence of OEGB anion receptor in the protection layer could lead to an enhancement in the ionic conductivity, electrochemical stability, and the interfacial properties. The deposited lithium exhibited particle-like shape resulting from the introduction of the protection layer onto the lithium electrode surface. The unit cell based on the lithium anode protected with gel polymer electrolyte containing OEGB showed higher discharge capacity than that of the unit cell without OEGB after 100 cycles at C/2 rate (1.25 mA cm−2).  相似文献   

15.
以丙烯腈(AN)、甲基丙烯酸甲酯(MMA)、丙烯醛(A)为单体,采用乳液聚合法制成一种共聚物———聚(丙烯腈 甲基丙烯酸甲酯 丙烯醛) (PAMA) .将PAMA作为第二共聚物与聚(偏氟乙烯 六氟丙烯) (PVDF -HFP)共混,并向反应体系中添加纳米级SiO2 ,充分混合后利用二次相转移法制得薄膜,并对所得薄膜的断面形貌、吸附性能、热性能、导电性能等进行了测试.研究发现,SiO2 的加入增大了膜中微孔体积,改善了微孔分布,且增大了电解液的吸附量;共聚物PAMA的组成影响薄膜的吸附性能,其中极性较大的丙烯醛单元和丙烯腈单元起着决定性作用;PAMA含量的增加使得共混膜吸附电解液量增加.制得共混膜的离子电导率达2 . 30×10 - 3S cm .  相似文献   

16.
In this work, the use of a polyethylene oxide-based nanocomposite polymer electrolyte (NCPE) in a redox capacitor with polypyrrole electrodes has been studied. To the best of our knowledge, not much work has been reported in the literature on redox capacitors fabricated using NCPEs. The composition of the polyethylene oxide (PEO)-based NCPE was fine tuned to obtain films with the highest ionic conductivity. They were mechanically stable to handle for any purpose without damaging the film. The optimized composition was {[(10PEO:NaClO4) molar ratio]: 75 wt.% propylene carbonate (PC)}: 5 wt.% TiO2. This electrolyte film showed an ambient temperature ionic conductivity of 5.42 × 10?3 S cm?1. It was employed in a redox capacitor with polypyrrole electrodes polymerized in the presence of sodium perchlorate in non-aqueous medium. Performance of the redox capacitors were observed using cycling voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge discharge test. It was possible to observe a satisfactory capacitive behavior in the range 58–83 F/g. Further, the redox capacitors had the ability to retain for continuous charge discharge processes.  相似文献   

17.
Thermally stable, flexible polymer gel electrolytes with high ionic conductivity are prepared by mixing the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (C4mpyrTFSI), LiTFSI and poly(vinylidene difluoride-co-hexafluoropropylene (PVDF-HFP). FT-IR and Raman spectroscopy show that an amorphous film is obtained for high (60 %) C4mpyrTFSI contents. Thermogravimetric analysis (TGA) confirms that the polymer gels are stable below ∼300 °C in both nitrogen and air environments. Ionic conductivity of 1.9×10−3 S cm−2 at room temperature is achieved for the 60 % ionic liquid loaded gel. Germanium (Ge) anodes maintain a coulombic efficiency above 95 % after 90 cycles in potential cycling tests with the 60 % C4mpyrTFSI polymer gel.  相似文献   

18.
Poly(vinylidene fluoride-co-hexaflouro propylene) is a well-known material for polymer electrolyte membranes (PEMs) due to its low cost, high mechanical integrity and excellent chemical resistance; however, its pure form has limited characteristics that require further modification to achieve optimum results. Therefore, the different dosages of polyaniline (PANI) (10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt%) were incorporated into PVDF-HFP blend to fabricate PVDF-HFP/PANI polymer electrolyte membrane by using breath-figure method. The FTIR peaks of PVDF-HFP and PVDF-HFP/PANI membrane confirms the successful incorporation of PANI into PVDF-HFP blend, while TGA, DSC and XRD analysis shows the PANI effect on stability and ionic conductivity of PVDF-HFP membrane. The PVDF-HFP/PANI membrane with 30 wt% PANI found superior with the highest porosity of 83%, electrolyte uptake of 270% and ionic conductivity of 1.96 mS cm−1; however, the other concentrations of PANI were also effective and enhanced the performance of PVDF-HFP membrane. This shows the improved performances of PVDF-HFP membrane were attributed to successful incorporation of PANI and the proposed membrane can be a suitable alternative PEM or a separator for energy devices.  相似文献   

19.
PEO/LiClO_4纳米SiO_2复合聚合物电解质的电化学研究   总被引:8,自引:0,他引:8  
将实验室制备的纳米二氧化硅和市售纳米二氧化硅粉末与PEO LiClO4复合 ,制得了复合PEO电解质 .它们的室温离子电导率可比未复合的PEO电解质提高 1~ 2个数量级 ,最高可以达到 1 2 4× 10 - 5S cm .离子电导率的提高有两方面的原因 :一是无机二氧化硅粉末的加入抑制了PEO的结晶 ,是二氧化硅粉末和聚合物电解质之间形成的界面对电导率的提高也有一定的作用 .在进一步加入PC EC(碳酸丙烯酯 碳酸乙烯酯 )混合增塑剂后制得的复合凝胶PEO电解质 ,可使室温离子电导率再提高 2个数量 ,达到 2× 10 - 3 S cm .用这种复合凝胶PEO电解质组装了Li|compositegelelectrolyte|Li半电池 ,并测量了该半电池的交流阻抗谱图随组装后保持时间的变化 ,实验观察到在保持时间为 144h以内钝化膜的交流阻抗迅速增大 ,但在随后的时间内逐渐趋于平稳 ,表明二氧化硅粉末的加入可以有效地抑制钝化膜的生长  相似文献   

20.
The potential applications of carbon black are expected to grow as science and technology improve offering up new possibilities for innovation throughout disciplines included in the field of energy storage. The present work shows the influence of carbon black to improve the ionic conductivity of the polymer electrolyte. The synthesis of polyethylene oxide: ammonium iodide based polymer electrolyte incorporated with carbon black varying from 0.01 to 0.06 wt% with respect to PEO: NH4I system by solution casting method. Different characterizations like polarized optical microscopy (POM), impedance spectroscopy, and ionic transference number (tion) are studied in detail. The maximum ionic conductivity is achieved at 0.05 wt% carbon black shows 1.20 × 10−5 S cm−1 at ambient temperature. In accordance with POM data, the amorphous region has increased whereas the crystalline region has shrunk which further indicated the increase in ionic conductivity . The value of (tion) is calculated to be 0.97 which shows the system is ionic in nature. PEO based polymer electrolyte doped carbon black can be used for the fabrication of energy storage devices.  相似文献   

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