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1.
The combination of a poly(ethylene glycol) (PEG) network and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) copolymer chains is one of the most efficient means for modifying PVDF-HFP gel electrolytes. Previous preparations tend to introduce contamination into the polymer gel electrolyte because of irradiation, high temperature or the initiator needed for crosslinking which might result in the electrochemical degradation. In order to overcome the above disadvantages, a new method has been developed to successfully prepare the semi-interpenetrating polymer networks of PVDF-HFP based electrolytes with crosslinked diepoxy polyethylene glycol (DIEPEG). In this process, impurities are avoided because of a moderate reaction temperature at 50 °C and poly(ethylenimine) (PEI) as the crosslinking agent. Microporous films with various compositions are prepared and characterized. Thermal, mechanical, swelling and electrochemical properties, as well as microstructures of the prepared polymer electrolytes have been investigated using thermogravimetric analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and scanning electron microscopy. The results show that the blend polymer electrolyte with PVDF-HFP/PEI + DIEPEG (60:40 w/w) has an ionic conductivity of 2.3 mS cm? 1 at room temperature in the presence of 1 M LiPF6 in EC and DMC (1:1 w/w). All the blend electrolytes are electrochemically stable up to 4.8 V versus Li/Li+. The results reveal that this new method may be very promising for improving PVDF-HFP based electrolytes.  相似文献   

2.
《Solid State Ionics》2006,177(9-10):843-846
We have synthesized poly(ethylene glycol) (PEG)-aluminate ester as a plasticizer for solid polymer electrolytes. The thermal stability, ionic conductivity and electrochemical stability of the polymer electrolyte which consist of poly(ethylene oxide) (PEO)-based copolymer, PEG–aluminate ester and lithium bis-trifluoromethanesulfonimide (LiTFSI) were investigated. Addition of PEG–aluminate ester increased the ionic conductivity of the polymer electrolyte, showing greater than 10 4 S cm 1 at 30 °C. The polymer electrolyte containing PEG–aluminate ester retained thermal stability of the non-additive polymer electrolyte and exhibited electrochemical stability up to 4.5 V vs. Li+/Li at 30 °C.  相似文献   

3.
Polyethylene oxide (PEO)-based electrolytes were crosslinked using electron beam (EB) irradiation. The gel contents of a polymer film were increased after irradiation doses of 0, 140, 280, and 420 kGy, with ionic conductivities of 0.831, 1.55, 6.08, and 7.95 (× 10? 5) S cm? 1 at 40 °C, respectively. The slight decrease in conductivity at higher temperatures after irradiation is due to the retardation of polymer motion by crosslinking. The electrolyte with higher EB dose amount exhibits higher conductivity due to stabilization of the amorphous state. The EB crosslinking with a co-bridging agent shows enhanced conductivities of 4.71, 6.59, and 7.18 (× 10? 5) S cm? 1 at 40 °C, after irradiation with 140, 280, and 420 kGy. Addition of the co-bridging agent is effective for developing a crosslinked structure with a smaller EB dose. Tensile strength becomes two to three times higher with irradiation compared to the non-treated polymer. Combination of the EB technique with a co-bridging agent is a simple and effective method to prepare strong dry polymer electrolyte films with improved room temperature conductivity.  相似文献   

4.
New solid electrolytes containing acetamide and lithium bioxalato borate (LiBOB) with different molar ratios have been investigated. Their melting points (Tm) are around 42 °C. The ionic conductivities and activation energies vary drastically below and above Tm, indicating a typical feature of phase transition electrolyte. The ionic conductivity of the LiBOB/acetamide electrolyte with a molar ratio of 1:8 is 5 × 10? 8 S cm? 1 at 25 °C but increases to 4 × 10? 3 S cm? 1 at 60 °C. It was found that anode materials, such as graphite and Li4Ti5O12, could not discharge and charge properly in this electrolyte at 60 °C due to the difficulty in forming a stable passivating layer on the anodes. However, a Li/LiFePO4 cell with this electrolyte can be charged properly after heating to 60 °C, but cannot be charged at room temperature. Although the LiBOB/acetamide electrolytes are not suitable for Li-ion batteries due to poor electrode compatibility, the current results indicate that a solid electrolyte with a slightly higher phase transition temperature than room temperature may find potential application in stationary battery for energy storage where the electrolyte is at high conductive liquid state at elevated temperature and low conductive solid state at low temperature. The interaction between acetamide and LiBOB in the electrolyte is also studied by Raman and FTIR spectroscopy.  相似文献   

5.
《Solid State Ionics》2006,177(7-8):741-747
A novel single ion conductive polymer electrolyte was developed by covalently linking an arylsulfonimide substituent to the polyphosphazene backbone. Polymeric single-ion conductors incorporate the anion of a salt either into the polymer backbone or as a pendent group linked to the polymer backbone. Immobilization of the anion could provide access to electrochemical devices that would be less vulnerable to increased resistance associated with salt concentration gradients at the interfaces during charging and discharging. In this work, an immobilized sulfonimide lithium salt is the source of lithium cations, while a cation-solvating cosubstituent, 2-(2-methoxyethoxy)ethoxy, was used to increase free volume and assist cation transport. The ionic conductivities showed a dependence on the percentage of lithiated sulfonimide substituent present. Increasing amounts of the lithium sulfonimide component increased the charge carrier concentration but decreased the ionic conductivity due to decreased macromolecular motion and possible increased shielding of the nitrogen atoms in the polyphosphazene backbone. Maximum ionic conductivity values of 2.45 × 10 6 S/cm at ambient temperature and 4.99 × 10 5 S/cm at 80 °C were obtained. Gel polymer electrolytes containing N-methyl-2-pyrrolidone gave ionic conductivities in the 10 3 S/cm range. The ion conduction process was investigated through model polymers that contained the non-immobilized sulfonimide — systems that had higher conductivities than their single ion counterparts.  相似文献   

6.
The search for anionic conductors based on solid polymer electrolytes is important for the development of photo-electrochemical (PEC) solar cells due to their many favourable chemical and physical properties. Although solid polymer electrolytes have been extensively studied as cation, mainly lithium ion, conductors for applications in secondary batteries, their use as anionic conductors have not been studied in greater detail. In a previous paper we reported the application of a PEO based iodide ion conducting electrolyte in a PEC solar cell. This electrolyte had the composition PEO: Pr4N+I? = 9:1 with 50 wt.% ethylene carbonate (EC). In this work we have studied the effect of incorporating alumina filler on the properties of this electrolyte. The investigation was extended to electrical and dielectric measurements including high frequency impedance spectroscopy and thermal analysis.In the DSC themograms two endothermic peaks have been observed on heating, one of these peaks is attributed with the melting of the PEO crystallites, while the other peak with a melting temperature ~ 30 °C is attributed to the melting of the EC rich phase. The melting temperature of both these peaks shows a marked variation with alumina content in the electrolyte. The temperature dependence of the conductivity shows that there is an abrupt conductivity increase in the first heating run evidently due to the melting of the EC rich phase. High conductivity values are retained at lower temperatures in the second heating. Conductivity isotherms show the existence of two maxima, one at ~ 5% Al2O3 content and the other at ~ 15%. The occurrence of these two maxima has been explained in terms of the interactions caused by alumina grains, the crystallinity and melting of the PEO rich phase. As seen from latent heat of melting, the crystallinity of the electrolyte has reduced considerably during the first heating run. In contrast to the conductivity enhancement caused by ceramic fillers in PEO-based cation containing electrolytes, no conductivity enhancement has been observed in the present PEO based anionic conducting materials by adding alumina except at low temperatures.  相似文献   

7.
《Solid State Ionics》2006,177(3-4):395-401
A series of new electrolyte materials based on a molecular plastic crystal doped by different iodide salts together with iodine have been prepared and characterized by thermal analysis, ionic conductivity, electrochemical and solid-state NMR diffusion measurements. In these materials, the plastic crystal phase of succinonitrile acts as a good matrix for the quaternary ammonium based iodides and iodine and appears to act in some cases as a solid-state “solvent” for the binary dopants. The materials were prepared by mixing the components in the molten state with subsequent cooling into the plastic crystalline state. This resulted in waxy-solid electrolytes in the temperature range from − 40 to 60 °C. The combination of structural variation of the cations, and fast redox couple diffusion (comparable with liquid-based electrolytes), as well as a high ionic conductivity of up to 3 × 10 3 S cm 1 at ambient temperature, make these materials very attractive for potential use in solid-state photoelectrochemical cells.  相似文献   

8.
《Solid State Ionics》2006,177(7-8):703-707
A polyphosphazene [NP(NHR)2]n with oligo[propylene oxide] side chains − R = –[CH(CH3)–CH2O]m–CH3 (m = 6  10) was synthesized by living cationic polymerisation and polymer-analogue substitution of chlorine from the intermediate precursor [NPCl2]n using the corresponding primary amine RNH2. The polymer had an average molecular weight of 3.3 × 105 D. Polymer electrolytes with different concentrations of dissolved lithium triflate (LiCF3SO3) were prepared. Mechanically stable polymer electrolyte membranes were formed using UV radiation induced crosslinking of the polymer salt mixture in the presence of benzophenone as photoinitiator. The glass transition temperature of the parent polymer was found to be − 75 °C before cross linking. It increases after crosslinking and with increasing amounts of salt to a maximum of − 55 °C for 20 wt.% LiCF3SO3. The ionic conductivity was determined by impedance spectroscopy in the temperature range 0–80 °C. The highest conductivity was found for a salt concentration of 20 wt.% LiCF3SO3: 6.5 × 10 6 S·cm 1 at 20 °C and 2.8 × 10 4 S cm 1 at 80 °C. The temperature dependence of the conductivities was well described by the MIGRATION concept.  相似文献   

9.
Polymer electrolytes based on the copolymer of N-vinylimidazolium tetrafluoroborate (VyImBF4) and poly(ethylene glycol) dimethacrylate (PEGDMA) have been prepared. Ethylene carbonate (EC) and LiClO4 are added to form gel polymer electrolytes. The chemical structure of the samples and the interactions between the various constituents are studied by FT-IR. TGA results show that these polymer electrolytes have acceptable thermal stability, are stable up to 155 °C. Measurements of conductivity are carried out as a function of temperature, VyImBF4 content in poly(VyImBF4-co-PEGDMA), and the concentration of EC and LiClO4. The conductivity increases with PEGDMA and EC content. The highest conductivity is obtained with a value of 2.90 × 10? 6 S cm? 1 at room temperature for VP1/EC(25 wt.%)–LiClO4 system, corresponding to the LiClO4 concentration of 0.70 mol kg? 1 polymer.  相似文献   

10.
《Solid State Ionics》2006,177(11-12):1091-1097
The effects of compositions on properties of PEO/KI/I2 salts polymer electrolytes were investigated to optimize the photovoltaic performance of solid state DSSCs. XRD pattern for the mole ratio 12:1 of [EO:KI] was showed the formation of complete amorphous complex. DSC results also confirmed the amorphous nature of the polymer electrolyte. The highest value of ionic conductivity is 8.36 × 10 5 S/cm at 303 K (ambient temperature) and 2.32 × 10 4 S/cm at 333 K (moderate temperature) for the mole ratio 12:1 of EO:KI complex. The effect of contribution of [I] and [I3] concentration with conductivity were also evaluated. FTIR spectrum reveals that the alkali metal cations were co-ordinated to ether oxygen of PEO. The formation of polyiodide ions, such as symmetric I3 (114 cm 1) and I5 (145 cm 1) caused by the addition of iodine was confirmed by FT Raman spectroscopic measurements. The optimum composition of PEO–KI–I2 polymer electrolyte system for higher conductivity at ambient and moderate temperatures was reported. A linear Arrhenius type behaviour was observed for all the PEO–KI polymer complexes. Transport number measurements were carried out for several polymer electrolyte compositions. Dye-sensitized solar cells were fabricated by using higher conductivity polymer electrolyte compositions and its photoelectrochemical performance was investigated. The fill factor, short-circuit current, photovoltage and energy conversion efficiency of the DSSC assembled with optimized electrolyte composition were calculated to be 0.563, 6.124 mA/cm2, 593 mV and 2.044% respectively.  相似文献   

11.
An amphiphilic hyperbranched-star polymer (HPE-g-MPEG) was synthesized by grafting methoxy poly(ethylene glycol) to the end of the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent. The synthesized amphiphilic hyperbranched-star polymer was blended with poly(vinylidene fluoride) (PVDF) to fabricate porous membranes via typical phase inversion process, and then the membranes were filled and swollen by a liquid electrolyte solution to form polymer electrolytes. The influences of HPE-g-MPEG on the morphology, crystallinity, liquid electrolyte uptake, mechanical properties of the porous membranes and the electrochemical properties of the activated membranes were investigated. It was found that the addition of HPE-g-MPEG resulted in a significant increase in porosity and a considerable reduction in crystallinity of the blend membranes, which favored the liquid electrolyte uptake and, consequently, led to a remarkable increase in ion conductivity at ambient temperature. The maximum ion conductivity observed in this study was 1.76 × 10? 3 S/cm at 20 °C for the blend membrane with a HPE-g-MPEG/PVDF ratio of 3/10 (w/w).  相似文献   

12.
Yuan Dong  Tianjie Ding  Li-Zhen Fan 《Ionics》2017,23(12):3339-3345
All-solid-state lithium batteries using flexible solid electrolytes instead of combustible organic liquid electrolytes are the ultimate solution to address the safety problem of commercialized lithium ion batteries. In this study, a free-standing and thermostable polymer/plastic crystal composite electrolyte (PPCE) based on polymerized trimethylolpropane trimethacrylate (TMPTMA)-1, 6-hexanediol diacrylate (HDDA) matrix, and plastic crystal electrolyte was prepared for all-solid-state lithium batteries. The polymerized TMPTMA-HDDA-based matrix of a porous network structure coupled with plastic crystal electrolyte (PCE) in the pores reveals good compatibility. The as-synthesized PPCE possesses excellent flexible performance, thermostability, and high conductivity, showing that PPCE can reach 8.53 × 10?4 S cm?1 with 7.5 wt% monomers (PPCE-7.5%) at 25 °C under a stability electrochemical window above 5.2 V. The assembled lithium batteries Li|PPCE|LiFePO4 exhibit high capacity and highly cycling stability at room temperature, indicating great potential of all-solid-state lithium batteries.  相似文献   

13.
《Solid State Ionics》2006,177(26-32):2683-2686
New type polymer electrolyte films based on poly(acrylonitrile), (PAN), and cyanoethylated poly(vinyl alcohol), (CN-PVA), were prepared and their conducting behaviors were investigated. CN-PVA was prepared from poly(vinyl alcohol), (PVA) and acrylonitrile in the presence of sodium hydroxide and quaternary ammonium halide as a phase transfer catalyst. Free standing PAN- and CN-PVA-based electrolyte films were prepared by casting the propylene carbonate (PC) solution containing PAN, CN-PVA and LiClO4 and removing some amount of PC. Ionic conductivity of the electrolyte film, (PAN)10(CN-PVA) 10(LiClO4)8(PC)4 composite film was 14.6 mS cm 1 at 30 °C and 22.4 mS cm 1 at 60 °C. FTIR results for the electrolyte films suggest that the nitrile groups in the CN-PVA matrix mainly interact with the lithium ions in the films and enhance dissolution of the lithium salt in the electrolyte films.  相似文献   

14.
《Solid State Ionics》2006,177(26-32):2417-2419
NH4PO3/SiO2 composite based electrolyte with SiO2 as supporting matrix was prepared. A thermogravimetric analysis was performed. Its electrochemical properties were investigated by an impedance spectroscopy within the temperature range of 100–300 °C under dry and humid atmospheres. The maximum conductivity is 6 mS cm 1 at 300 °C under dry N2 and 0.1 S cm 1 at 200 °C under humid N2.  相似文献   

15.
Gel polymer electrolytes (GPE) based on electrospun polymer membranes, poly(vinylidene fluoride-co-hexafluoropropylene), grafted poly(poly(ethylene glycol) methyl ether methacrylate) (PVDF-HFP-g-PPEGMA), and poly(vinylidene difluoride-co-hexafluoropropylene) (PVDF-HFP) are prepared for lithium ion batteries by incorporating with 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI). The uniform porosity and the compatibility of blend electrospun membranes avoiding the pore blocking are beneficial to enhance the electrolyte uptakes. The GPE based on the fibrous PVDF-HFP-g-PPEGMA/PVDF-HFP activated with 1 M LiTFSI (BMITFSI) show a maximum ionic conductivity of 2.3 × 10?3 S cm?1 at room temperature and electrochemical stability of up to 5.2 V. The Li/GPE/LiFePO4 cells with GPE based on PVDF-HFP-g-PPEGMA/PVDF-HFP blend electrospun membrane deliver specific capacities of 163, 141, and 125 mAh g?1 at 0.1, 0.5, and 1C rates, respectively, and remains well after 50 cycles for each rate. Therefore, the novel GPE have been demonstrated to be suitable for lithium-ion battery applications.  相似文献   

16.
《Solid State Ionics》2006,177(1-2):65-71
A comb-like EVOH based single ion polymer electrolyte (EVOH-g-SPEG) was synthesized by sulfonification of EVOH grafts 2-(2-chloroethoxy) ethanol (C4H9O2Cl)/2-[2-(2-chloroethxy) ethoxy] ethanol (C6H13O3Cl) with 1, 3-propane sultone. The main chain of the comb-like polymer is hydrophobic polyethylene segments; the side chain is hydrophilic poly (ethylene glycol) (PEG) segment, which can solubilize large amounts of inorganic salts. The sulfonic acid group was introduced onto the end of the PEG side chain. The acid form of SPE was successfully obtained by being dialyzed from the products with acid solution. The saturation water sorption of EVOH-g-SPEG membrane increased with the side chain length and the immersion time. The XRD results indicate that the water in SPE membrane region can destroy the membrane crystalline structure and the water absorption membranes are nearly amorphous. AFM phase images of the hydration membranes clearly show the hydrophilic domains, with sizes increasing from 10 to 35 nm as a function of the side chain length. A phase inversion could be observed when n  5, which was consistent with a rapid increase in water absorption. And the ion conductivity is also measured by AC impedance. The conductivity is greatly influenced by ion exchange capacity and water sorption. The comb-like EVOH-g-SPEG polymer electrolyte grafts with 2 PEG side chain provides the highest ionic conductivity (1.65 × 10 3 S cm 1). The comb-like polymer could be a candidate as new polymeric electrolyte material for fuel cells and other electrochemical devices.  相似文献   

17.
Doped lanthanum manganese chromite based perovskite, La0.7A0.3Cr0.5Mn0.5O3 ? δ (LACM, A = Ca, Sr, Ba), on yttria-stabilized zirconia (YSZ) electrolyte is investigated as potential electrode materials for solid oxide fuel cells (SOFCs). The electrical conductivity and electrochemical activity of LACM depend on the A-site dopant. The best electrochemical activity is obtained on the La0.7Ca0.3Cr0.5Mn0.5O3 ? δ/YSZ (LCCM/YSZ) composite electrodes. The conductivity of LCCM is 29.9 S cm? 1 at 800 °C in air, and the electrode polarization resistance (RE) of the LCCM/YSZ composite cathode for the O2 reduction reaction is 0.5 Ω cm2 at 900 °C. The effect of Gd-doped ceria (GDC) impregnation on the LCCM cathode polarization resistances is also studied. GDC impregnation significantly enhances the electrochemical activity of the LCCM cathode. In the case of the 6.02 mg cm? 2 GDC-impregnated LCCM cathode, RE is 0.4 Ω cm2 at 800 °C, ~ 60 times smaller than 24.4 Ω cm2 measured on a LCCM cathode without the GDC impregnation. Finally the electrochemical activities of the doped lanthanum manganese chromites for the H2 oxidation reaction are also investigated.  相似文献   

18.
《Solid State Ionics》2009,180(40):1640-1645
A facile synthetic route for the development of a new class of dilithium salts is described. Because of the presence of two lithium ions per molecule, these salts require lower concentrations than commonly used salts to achieve comparable ionic conductivities at ambient temperatures. An ionic conductivity of 3.55 × 10 3 S/cm at 30 °C was obtained using 0.5 M salt solution in 1:1 wt/wt ethylene carbonate:dimethyl carbonate. The salts exhibit excellent thermal stabilities to at least 350 °C and are electrochemically stable below 4.2 V versus lithium metal. The best salt was tested with a polymer electrolyte system. Incorporation of a polyethylene glycol-based borate ester plasticizer improved the ionic conductivity of the solid polymer electrolyte film up to 1.36 × 10 5 S/cm at 30 °C, which is 10 times higher than that of un-plasticized electrolyte films.  相似文献   

19.
《Solid State Ionics》2006,177(35-36):3129-3134
Substituted cyclotriphosphazenes were used to prepare lithium ion conducting polymer networks. Two types of compounds were synthesized starting with the precursor hexachlorocyclotriphosphazene (HCCP): Type I (CVEEP) in which all the chlorine atoms in HCCP were replaced by vinyloxyethoxyethoxy groups (VEE = –OCH2CH2OCH2CH2OCHCH2), and type II (CVMEEP) in which half of the chlorine was replaced by VEE and the other half by methoxyethoxyethoxy groups (MEE = –OCH2CH2OCH2CH2OCH3). The terminal vinyl groups were used to build up a network by a thermally initiated cross-linking of lithium salt containing membranes. Polymer electrolytes with dissolved LiSO3CF3 and LiN(SO2CF3)2 were investigated by impedance measurements. The ionic conductivity of CVMEEP with 10 wt.% LiSO3CF3 was 3.2 × 10 5 S/cm at 30 °C and 4.1 × 10 4 S/cm at 90 °C. Lower conductivity values in the range 10 8–10 9 S/cm were obtained at 30 °C for the highly crosslinked CVEEP. An interesting polymer electrolyte with good mechanical properties and a good conductivity of 1.3 × 10 5 S/cm (30 °C) was obtained from a solution of MEEP (= poly[bis(methoxy–ethoxy–ethoxy)phosphazene]) and LiSO3CF3 in CVEEP as an interpenetrating network.  相似文献   

20.
The effect of nano SiO2 and TiO2 fillers on the thermal, mechanical and electrochemical properties of PVA:PVdF:LiCF3SO3 have been investigated by three optimized systems of SPE (80PVA:20PVdF:15LiCF3SO3), CPE-I (SPE:8SiO2) and CPE-II (SPE:4TiO2). From the TGA curve least weight loss has been observed for CPE-II indicating high thermal stability compared to other systems. Stress–strain curve of the prepared samples confirm the enhancement of tensile strength in CPE-II compared to CPE-I and SPE. Conductivity studies show that addition of TiO2 filler slightly enhances ionic conductivity 3.7×10−3 S cm−1 compared to filler free system at 303 K. Dielectric plots have been analyzed and CPE-II possesses higher dielectric constant compared to CPE-I and filler free system. Temperature dependence of modulus plots has been studied for highest conductivity possessing sample. Wider electrochemical stability has been obtained for nano-composite polymer electrolytes. The results conclude that the prepared CPE-II shows the best performance and it will be well suited for lithium ion batteries.  相似文献   

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