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1.
We report blend-based plastic polymer electrolyte (i.e., polyethylene oxide (PEO)–polydimethyl siloxane (PDMS)–lithium hexafluorophosphate (LiPF6)) with substantial improvement in DC conductivity at ambient and subambient temperatures when compared with literature reports. Conductivity variation with salt concentration, investigated within ±30 °C range, indicates an optimum conductivity of 5.6?×?10?5 S cm?1 at 30 °C for Ö/Li ~10 with a further lowering by one order at 0 °C and it remains unaltered at ?10 °C. Enhanced conductivity in this blend electrolyte, though lower than two copolymer counterparts, is attributed to very low glass transition temperatures of the host polymers. X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggest an effective blending between the two polymers with an effective interaction between the Li salt and the blend polymer matrix. Raman spectroscopy results indicated that cation (Li+) coordination occurs at the C=Ö site in PEO out of the two electron-rich sites (i.e., CÖ and Si–Ö–Si) in the PEO–PDMS blend. The blend electrolytes are predominantly ionic (t ion ~97 %).  相似文献   

2.
Polyvinylidene difluoride (PVDF)–lithium bis(oxalato)borate (LiBOB) solid polymer electrolytes (SPEs) have been prepared by solution casting. The highest ionic conductivity achieved is 3.4610?3 S cm?1. Electrochemical potential window of the SPEs is found around 4.7 V. Interaction between PVDF and LiBOB is studied systematically. The changes of C–C, CF2, and CH2 vibration modes with an emerging shoulder are analyzed. At higher salt content, this shoulder becomes more prominent peak at the expense of CF2 vibration mode. This suggests the possible Li+?F coordination. Deconvolution of IR spectra region from 1750 to 1850 cm?1 has been carried out to estimate the relative percentage of free ions and contact ions. The finding is in good agreement with conductivity and XRD results. When more salt is present, the number of free ions percentage increases and the Full width at half-maximum (FWHM) of (110) plane is broadening. The Li+?F interaction breaks the folding patterns of polymer chain and enhances amorphousness domain.  相似文献   

3.
The plasticized composite solid polymer electrolytes (CSPE) involving polymer blends poly(methyl methacrylate)-poly(styrene-co-acrylonitrile) (PMMA-SAN), plasticizers ethylene carbonate (EC), and propylene carbonate (PC) with lithium triflate (LiCF3SO3) as salt and varying concentration of composite nano-filler zirconium oxide (ZrO2) is prepared by solution casting technique using THF as solvent. The powder X-ray diffraction (XRD) studies reveal amorphous nature of the CSPE samples. Fourier transform infrared (FT-IR) spectroscopy studies reveal interaction of Li+ ion with plasticizers, both C=O and OCH3 group of the PMMA, while nitrile group of SAN is inert. AC impedance and dielectric studies reveal that the ionic conductivity (σ), dielectric constant (ε’), and dielectric loss (ε”) of the prepared CSPE samples increase with increasing content of ZrO2 nano-filler up to 6 wt% and decrease with further additions. The temperature dependence of ionic conductivity follows Arrhenius relation and indicates ion-hopping mechanism. The sample Z2 (6 wt% ZrO2) with relaxation time τ of 8.13?×?107 s possess lowest activation energy (Ea?=?0.23 eV) and highest conductivity (2.32?×?104 S cm?1) at room temperature. Thermogravimetric analysis (TGA) reveals thermal stability of highest conducting sample Z2 up to 321 °C after complete removal of residual solvent, moisture, and its impurities. Differential scanning calorimetric (DSC) studies reveal absence of glass transition temperature (Tg) corresponding to atactic PMMA for the CSPE Z2, while isotactic PMMA component shows Tg around 70 °C, which is due to increased interaction of filler with PMMA leading to change in its tacticity. Scanning electron microscopy (SEM) analysis reveals blending of PMMA/SAN polymers and lithium triflate salt. The incorporation of nano-filler ZrO2 leads to change in surface topology of polymer matrix. Rough surface of the CSPE Z2 leads to new pathway for ionic conduction leading to maximum ionic conductivity.  相似文献   

4.
FTIR spectroscopic analysis has been carried out for liquid electrolytes containing lithium —(trifluormethanesulfonimide or imide) salt as the ion source, a binary solvent composed of γBL and DMF and gel electrolytes containing PMMA. These studies illustrate that for all electrolytes, the cation (Li+) — solvent interaction is predominant and occurs through the carbonyl oxygen and the electron rich nitrogen atom of the solvating medium i.e., the binary solvent. Ionic conductivity trends upon varying lithium imide concentration, exhibit a single maximum in both liquid and gel polymeric electrolytes. The conductivity at 25 °C (σ25) decline at high salt concentrations attributable to ion aggregation or cation-anion association, has been explained on the basis of detailed spectral analysis. Addition of PMMA as a gelatinizing agent to liquid electrolytes does not affect the conduction mechanism drastically, which is evident from conductivity measurements and is supplemented by spectral studies.  相似文献   

5.
《Solid State Ionics》1987,25(1):41-44
Complexes of alkali metal salts with various polymers have for some time been recognized as fast ionic conductors. Polymer electrolyte fast ion conductors are currently under consideration for use in high energy density electrochemical cells. In order to aid in our understanding of the mechanism of ionic conductivity we have examined systematically complexes of poly(ethylene oxide) (PEO) with the alkali metal salt series of Li+, Na+, K+, Rb+ and Cs+ with both tetraflouroborate (BF4-) and trifluoromethanesulfonate (CF3SO4-) anions. The ratio of monomer to salt was 10:1 in all cases. Complex impedance measurements were made on all samples in the temperature range 40°–125°C. With CF3SO4- as the anion a definite trend was apparent with the smallest cation Li+ being the worst conductor and Cs+, the largest cation, being the best. When BF4- salts are used, the Na+ complex is found to be the best conductor and Rb+ the worst. This study, in connection with our earlier studies, has shown that synergy between cation and anion in the polymer matrix is an important consideration in determining the ionic conductivity.  相似文献   

6.
A novel PEO-based blends solid polymer electrolytes doping liquid crystalline ionomers (LCI), PEO/PMMA/LiClO4/LCI, and PEO/LiClO4/LCI were prepared by solution casting technology. Scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS) analysis proved that LCI uniformly dispersed into the solid electrolytes and restrained phase separation of PEO and PMMA. Differential scanning calorimetry (DSC) results showed that LCI decreases the crystallinity of blends solid polymer electrolytes. Thermogravimetric analysis (TGA) proved LCI not only improved thermal stability of PEO/PMMA/LiClO4 blends but also prevent PEO/PMMA from phase separation. Infrared spectra results illustrated that there exists interaction among Li+ and O, and LCI that promotes the synergistic effects between PEO and PMMA. The EIS result revealed that the conductivity of the electrolytes increases with LiClO4 concentration in PEO/PMMA blends, but it increases at first and reaches maximum value of 2.53?×?10?4 S/cm at 1.0 % of LCI. The addition of 1.0 % LCI increases the conductivity of the electrolytes due to that LCl promoting compatibility and interaction of PEO and PMMA. Under the combined action of rigidity induced crystal unit, soft segment and the terminal ionic groups in LCI, PEO/PMMA interfacial interaction are improved, the reduction of crystallinity degree of PEO leads Li+ migration more freely.  相似文献   

7.
Polyethylene oxide (PEO) based polymer electrolytes with BaTiO3 as filler and Li(C2F5SO2)2N as salt have been examined in lithium polymer batteries. The aluminum disolution potential in PEO-Li(C2F5SO2)2N was estimated to be 4.1 V vs. Li/Li+ at 80 °C, which was compared to that of 3.8 V vs. Li/Li+ in PEO-Li(CF3SO2)2N. The electrical conductivity of the system was measured as a function of O/Li ratio. The highest conductivity was observed in O/Li=8. The conductivity was 1.65×10−3 S/cm at 80 °C and 1.5×10−5 S/cm at 25 °C. The interfacial resistance of Li/polymer electrolyte/Li annealed at 80 °C for 15 days was lower than 100 Ωcm2. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16 – 22, 2001.  相似文献   

8.
《Solid State Ionics》2006,177(26-32):2679-2682
The polymer electrolytes comprising blend of poly(vinyl acetate) (PVAc) and poly(methylmethacrylate) (PMMA) as a host polymer and LiClO4 as a dopant are prepared by solution casting technique. The amorphous nature of the polymer–salt complex has been confirmed by XRD analysis. The DSC thermograms show two Tg's for PVAc–PMMA blend. A decrease in Tg with the LiClO4 content reveals the increase of segmental motion. Conductance spectra results are found to obey the Jonscher's power law and the maximum dc conductivity value is found to be 1.76 × 10 3 S cm 1 at 303 K for the blend polymer complex with 20 wt.% LiClO4, which is suitable for the Li rechargeable batteries. The conductivity–temperature plots are found to follow an Arrhenius nature. The dc conductivity is found to increase with increase of salt concentration in the blend polymer complexes.  相似文献   

9.
《Solid State Ionics》1986,21(3):255-261
The electrical conductivity of substituted Li5GaO4 phases was investigated by complex impedance techniques. Substitution by divalent cations to increase the concentration of vacancies in Li5–2xZnxGaO4 did not enhance the ionic conductivity in β-Li5GaO4 -type solid solutions. High Li+ conduction was observed in Li5+xGa1–xMxO4 with M=Mg and Zn in the β-Li5GaO4 structure. The maximum conductivity at 300°C is 4.1 × 10–3 (ω-cm)–1 for Li5.4Ga0.6Zn0.4O4 and 1.3 × 10–3 (ω-cm)–1 for Li5.7Ga0.7Mg 0.3O4. These results are discussed in relation to the structural properties.  相似文献   

10.
The systems poly(butadiene-co-acrylonitrile) (PBAN) - lithium salts have been studied by means of X-ray and IR spectroscopy, optical microscopy and ac- and dc-conductivity measurements. X-ray and microscopy studies have confirmed that PBAN dissolves LiClO4 up to [CN]/[Li] ≈ 2: 1. IR spectra of the samples with LiAsF6, LiCF3SO3 and LiClO4 have indicated the coordination between Li+ and the polar CN groups of PBAN. So, PBAN was found to be a suitable polymer matrix for SPE. The polymer films exhibited predominant ionic conductivity. Measurements of conductivity and Li transport numbers versus temperature over a wide range of salt concentrations revealed the existence of two concentration regions (within the limits of salt solubility) corresponding to liquid-like and glass-like ion transport mechanisms. New solid polymer electrolyte with lithium single-ion conductivity of 10−3 S cm−1 at 25 – 95 °C was obtained. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997  相似文献   

11.
Free-standing composite polymer membranes comprising of high molecular weight poly (ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO4) and Li6La2BaTa2O12 (LLBTO) garnet oxide as filler were developed via standard solution-casting method. The as-synthesized composite membranes were investigated through powder x-ray diffraction (PXRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and impedance spectroscopy techniques for their phase, thermal, morphological, and electrical properties, respectively. The lithium ion conductivity of polymer composite membranes consisting of PEO8/LiClO4 with various weight percents (5, 10, 15, 20, 25, and 30) of LLBTO were evaluated. We demonstrated a significant enhancement in Li+ conductivity with the addition of LLBTO to the polymer-lithium salt complex. Among the investigated membranes, the composite containing 20 LLBTO wt% garnet oxide exhibits maximized room temperature (30 °C) Li+ conductivity of 2.03 × 10?4 S cm?1 and electrochemical stability greater than 4.5 V.  相似文献   

12.
《Current Applied Physics》2015,15(2):135-143
Solid polymer electrolytes consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend (50:50 wt/wt%) with lithium triflate (LiCF3SO3) as a dopant ionic salt at stoichiometric ratio [EO + (CO)]:Li+ = 9:1, poly(ethylene glycol) (PEG) as plasticizer (10 wt%) and montmorillonite (MMT) clay as nanofiller (3 wt%) have been prepared by solution cast followed by melt–pressing method. The X–ray diffraction study infers that the (PEO–PMMA)–LiCF3SO3 electrolyte is predominantly amorphous, but (PEO–PMMA)–LiCF3SO3–10 wt% PEG electrolyte has some PEO crystalline cluster, whereas (PEO–PMMA)–LiCF3SO3–10 wt% PEG–3 wt% MMT electrolyte is an amorphous with intercalated and exfoliated MMT structures. The complex dielectric function, ac electrical conductivity, electric modulus and impedance spectra of these electrolytes have been investigated over the frequency range 20 Hz to 1 MHz. These spectra have been analysed in terms of the contribution of electrode polarization phenomenon in the low frequency region and the dynamics of cations coordinated polymer chain segments in the high frequency region, and also their variation on the addition of PEG and MMT in the electrolytes. The temperature dependent dc ionic conductivity, dielectric relaxation time and dielectric strength of the plasticized nanocomposite electrolyte obey the Arrhenius behaviour. The mechanism of ions transportation and the dependence of ionic conductivity on the segmental motion of polymer chain, dielectric strength, and amorphicity of these electrolytes have been explored. The room temperature ionic conductivity values of the electrolytes are found ∼10−5 S cm−1, confirming their use in preparation of all-solid-state ion conducting devices.  相似文献   

13.
A solid polymer blend electrolyte is prepared using poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) polymers with different molecular weight percentage (wt%) of ammonium thiocyanate (NH4SCN) by solution casting technique with tetrahydrofuran (THF) as a solvent. The structural, morphological, vibrational, thermal and electrical properties of the prepared polymer blend electrolytes have been studied. The incorporation of NH4SCN into the polymeric matrix causes decrease in the degree of crystallinity of the samples. The complex formation between the polymer and salt has been confirmed by FTIR technique. The increase in T g with increase in salt concentration has been investigated. The maximum conductivity of 3.684?×?10?3 S cm?1 has been observed for the composition of 70PVAc/30PMMA/30 wt% of NH4SCN at 303 K. This value of ionic conductivity is five orders of magnitude greater than that of 70PVAc/30PMMA polymer membrane. Dielectric and transport studies have been done. The highest conducting polymer electrolyte is used to fabricate proton battery with the configuration Zn/ZnSO4·7H2O (anode) ||polymer electrolyte||PbO2/V2O5 (cathode). The open circuit voltage of the fabricated battery is 1.83 V, and its performance has been studied.  相似文献   

14.
Das  Avirup  Thakur  A. K. 《Ionics》2017,23(10):2845-2853

Polymer nanocomposite has been proven to improve the property of polymer salt complex. Organo-modified clay and inorganic oxides are the most commonly used filler for polymer nanocomposite (PNC). However, single wall carbon nanotube (SWCNT)/multiwall carbon nanotube (MWCNT) are becoming popular filler for PNC for their high surface area and high mechanical stability. In this work, a series of PNC sample has been prepared by using polyethylene oxide (PEO)-polydimethylsiloxane (PDMS) blend as polymer matrix, an optimized salt stoichiometry of Ö/Li ~15, and surface-modified MWCNT as filler. The effect of ion-polymer and ion-MWCNT interaction in the polymer nanocomposite has been investigated by using XRD, SEM, FTIR, and electrical study. X-ray diffraction pattern confirms the dispersion of MWCNT inside the polymer chain and modifies the structural parameter of the polymer matrix. FTIR spectra indicate inclusion of MWCNT inside the polymer salt complex which changes the ion dissociation/association in the polymer host matrix. Further, the changes in structural, thermal, and electrical property of the polymer salt complex system have been studied by using SEM, DSC, and impedance analysis. Dc conductivity study shows that optimized PNC sample has conductivity of 8.04 × 10−5 S cm−1. This is almost two order enhancement from pure polymer salt system (10−6 S cm−1).

  相似文献   

15.
A solid polymer electrolyte (SPE) composites consisting blend of poly(ethylene oxide) (PEO) and poly(ethylene glycol) (PEG) as the polymer host with LiCF3SO3 as a Li+ cation salt and TiO2 nanoparticle which acts as a filler were prepared using solution-casting technique. The SPE films were characterized by X-ray diffraction and Fourier transform infrared analysis to ensure complexation of the polymer composites. Frequency-dependent impedance spectroscopy observation was used to determine ionic conductivity and dielectric parameters. Ionic conductivity was found to vary with increasing salt and filler particle concentrations in the polymer blend complexes. The optimum ambient temperature conductivity achieved was 2.66?×?10?4?S?cm?1 for PEO (65 %), PEG (15 %), LiCF3SO3 (15 %), ethylene carbonate (5 %), and TiO2 (3 %) using weight percentage. The dielectric relaxation time obtained from a loss tangent plot is fairly consistent with the conductivity studies. Both Arrhenius and VTF behaviors of all the composites confirm that the conductivity mechanism of the solid polymer electrolyte is thermally activated.  相似文献   

16.
High molecular weight polymer poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP), ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIMFSI), and salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based free-standing and conducting ionic liquid-based gel polymer electrolytes (ILGPE) have been prepared by solution cast method. Thermal, electrical, and electrochemical properties of 80 wt% IL containing gel polymer electrolyte (GPE) are investigated by thermogravimetric (TGA), impedance spectroscopy, linear sweep voltammetry (LSV), and cyclic voltammetry (CV). The 80 wt% IL containing GPE shows good thermal stability (~?200 °C), ionic conductivity (6.42?×?10?4 S cm?1), lithium ion conductivity (1.40?×?10?4 S cm?1 at 30 °C), and wide electrochemical stability window (~?4.10 V versus Li/Li+ at 30 °C). Furthermore, the surface of LiFePO4 cathode material was modified by graphene oxide, with smooth and uniform coating layer, as confirmed by scanning electron microscopy (SEM), and with element content, as confirmed by energy dispersive X-ray (EDX) spectrum. The graphene oxide-coated LiFePO4 cathode shows improved electrochemical performance with a good charge-discharge capacity and cyclic stability up to 50 cycles at 1C rate, as compared with the without coated LiFePO4. At 30 °C, the discharge capacity reaches a maximum value of 104.50 and 95.0 mAh g?1 for graphene oxide-coated LiFePO4 and without coated LiFePO4 at 1C rate respectively. These results indicated improved electrochemical performance of pristine LiFePO4 cathode after coating with graphene oxide.  相似文献   

17.
The polymer–salt complex with high molecular weight poly(vinyl chloride) (PVC) as the host polymer and lithium sulphate (Li2SO4) as the dopant salt are constructed in the form of thin film. Ionic conductivity studies in the temperature range of 303–373 K are performed for polymer complexes with 75% and 85% PVC. Arrhenius and Vogel–Tamman–Fulcher (VTF) behaviour was observed before and after the Tg of polymer, respectively. Dielectric constant and electrical modulus were analyzed and it was concluded that the films had ion conducting potential. Fourier transform infrared (FTIR) study confirmed that complexation occurred between PVC and Li2SO4.  相似文献   

18.
Poly(nitriles) are among the polymer matrices providing high salt solubility and, in some cases, superionic lithium conductivity at ambient temperatures observed in highly concentrated solvent-free polymer electrolytes. However, the properties of these electrolytes in which ionic aggregation prevails remain difficult to reproduce and predict, as current theories do not adequately model their attributes. The development of new concepts for ion transport in highly concentrated solid polymer electrolytes (SPEs) requires a better understanding of the fundamentals of structure formation in a polymer–salt system over a wide concentration range including salt precipitation. In an attempt to approach this goal, a series of fundamental studies was carried out on the systems based on a rubbery random copolymer of butadiene and acrylonitrile (abbreviated as PBAN). In the present work, LiBr with monatomic halide anion was used as a lithium salt. The effect of LiBr concentration (0.05 to 3.35 mol kg?1) on phase composition, ion–molecular interactions, glass transition temperature, and ionic conductivity was studied by optical microscopy, FTIR, X-ray diffraction, DSC, and impedance measurements. The results were compared with those of PBAN–LiClO4 and PBAN–LiAsF6 studied previously. Low salt solubility and separation of a metastable cubic CsCl-type polymorph of LiBr were established. The highest conductivity of ~10?4 S cm?1 at >50 °C was observed for heterogeneous samples comprising this phase. While the conductivity of PBAN–LiBr was lower than that of PBAN–LiClO4 and PBAN–LiAsF6, this study provides a new insight into the nature of polymer electrolyte systems.  相似文献   

19.
Hybrid solid polymer electrolyte films comprising of poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA), LiClO4, and propylene carbonate are prepared by solution casting technique by varying the salt concentration. In this study, PVAc/PMMA polymer blend ratio is fixed as 25:75 on the basis of conductivity and mechanical stability of the film. X-ray diffraction, Fourier transform infrared impedance, thermogravimetry/differential thermal analysis and scanning electron microscopy studies are carried out for the polymer electrolytes. The maximum ionic conductivity is found to be 4.511 × 10−4 S cm−1 at 303 K for the plasticized polymer electrolyte with 8 wt.% of LiClO4. The ionic conductivity is found to decrease with an increase of LiClO4 concentration.  相似文献   

20.
Solid polymer electrolytes based on high molecular weight poly(ethylene oxide) (PEO) complexed with lithium difluoro(oxalato)borate (LiDFOB) salt in various EO:Li molar ratios from 30:1 to 8:1 were prepared by using solution casting technique. Ion–polymer interaction, structural, thermal, and ionic conductivity studies have been reported by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), polarized optical microscopy (POM), differential scanning calorimeter (DSC), and impedance analysis. FTIR spectral studies suggested that the interaction of Li+ cations with the ether oxygen of PEO, where a triple peak broad band centered at 1105 cm?1, corresponds to C–O–C stretching and extreme deformation occurs. XRD, POM, and DSC indicated that the inclusion of LiDFOB salt could reduce the crystallinity of PEO. The melting temperature of PEO shifted to lower temperature side by the addition of LiDFOB. The glass transition temperature obtained for the system 10:1 was ?38.2 °C. An increase in the ionic conductivity from 3.95?×?10?9 to 3.18?×?10?5 S/cm at room temperature (23 °C) was obtained through the addition of LiDFOB to a high molecular weight PEO. In addition, the ionic conductivity of the polymer electrolyte films followed an Arrhenius relation, and the activation energy decreased with increasing LiDFOB concentration.  相似文献   

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