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1.
A novel polymer electrolyte based on PMAML/PVDF-HFP blend   总被引:1,自引:0,他引:1  
A gel polymer electrolyte based on the blend of poly(methyl methacrylate-co-acrylonitrile-co-lithium methacrylate) (PMAML) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) was prepared and characterized. The synthesized PMAML were characterized by FTIR and NMR, respectively, and the surface morphology of the PMAML and PVDF-HFP blend membrane was also observed by scanning electron microscope (SEM). The electrochemical properties of composite electrolyte membranes were studied. The ionic conductivity of the polymer electrolyte composed of 75 wt.% 1 M LiBF4 in ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC=1:1 by weight) was about 2.6×10−3 S cm−1 at ambient temperature. The electrochemical window of the polymer electrolyte was about 4.6 V determined from the linear sweep voltammetry plot. The lithium ion polymer batteries were assembled by sandwiching gel polymer electrolyte between LiCoO2 cathode and mesophase carbon fibre (MPCF) anode. Charge-discharge test results display that lithium ion batteries with these gel polymer electrolytes have good electrochemical performance.  相似文献   

2.
Poly(acrylonitrile-butyl acrylate) gel polymer electrolyte was prepared for lithium ion batteries. The preparation started with synthesis of poly(acrylonitrile-butyl acrylate) by radical emulsion polymerization, followed by phase inversion to produce microporous membrane. Then, the microporous gel polymer electrolytes (MGPEs) was prepared with the microporous membrane and LiPF6 in ethylene carbonate/diethyl carbonate. The dry microporous membrane showed a fracture strength as high as 18.98 MPa. As-prepared gel polymer electrolytes presented ionic conductivity in excess of 3.0 × 10−3 S cm−1 at ambient temperature and a decomposition voltage over 6.6 V. The results showed that the as-prepared gel polymer electrolytes were promising materials for Li-ion batteries.  相似文献   

3.
Wanyu Chen 《Electrochimica acta》2008,53(13):4414-4419
An ionic complex of anionic and cationic monomers was obtained by protonation of (N,N-diethylamino)ethylmethacrylate with acrylic acid. A novel ionically crosslinked polyampholytic gel electrolyte was prepared through the free radical copolymerization of the ionic complex and acrylamide in a solvent mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate (1:1:1, v/v) containing 1 mol/L of LiPF6. The impedance analysis indicated that the ionic conductivity of the polyampholytic gel electrolyte was rather close to that of solution electrolytes in the absence of a polymer at the same temperature. The temperature dependence of the conductivity was found to be well in accord with the Arrhenius behavior. The formation processes of the solid electrolyte interphase (SEI) formed in both gel and solution electrolytes during the cycles of charge-discharge were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The cyclic voltammetry curves show a strong peak at a potential of 0.68 V and an increase of the interfacial resistance from 17.2 Ω to 35.8 Ω after the first cycle of charge-discharge. The results indicate that the formation process of SEI formed in both gel and solution electrolytes was similar which could effectively prevent the organic electrolyte from further decomposition and inserting into the graphite electrode. The morphologies of SEI formed in both gel and solution electrolytes were analyzed by field emission scanning electron microscopy. The results indicate that the SEI formed in the gel electrolyte showed a rough surface consisting of smaller solid depositions. Moreover, the SEI formed in the gel electrolyte became more compact and thicker as the cycling increased.  相似文献   

4.
Poly[(ethylene glycol)diacrylate]-poly(vinylidene fluoride), a gel polymer blend with ethylene carbonate:dimethyl carbonate:ethylmethyl carbonate (EC:DMC:EMC, 1:1:1 volume ratio) and containing 1.0 M of lithium hexafluoro phosphate (LiPF6) as liquid components, is employed as a gel polymer electrolyte for an electric double layer capacitor (EDLC). Its electrochemical characteristics is compared with that of liquid organic electrolyte mixture of ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate in a 1:1:1 volume ratio containing 1.0 M LiPF6 salt. The specific surface area of the activated carbon powder as an active material is 1908 m2/g. Liquid poly[(ethylene glycol)diacrylate] (PEGDA) oligomer with a high retention capability of liquid electrolytes is cured by UV irradiation and poly(vinylidene fluoride)-hexafluoropropylene (PVdF-HFP) copolymer with a porous structure endows polymer matrix with high mechanical strength.The specific capacitance of EDLC using the gel polymer electrolyte (GPE-EDLC) shows 120 F/g, which is better than the liquid organic electrolyte. Good cycling efficiency is observed for a GPE-EDLC with high retention capability of liquid components. The high specific capacitance and good cycling efficiency are most likely due to the polarization resistance of EDLC with the gel polymer electrolyte, which is lower than the liquid organic electrolyte. This may result from the distinguished adhesion between the activated carbon electrode and the gel polymer electrolyte, as well as high retention capability of liquid components.Power densities of GPE-EDLC and LOE-EDLC shows 1.88 kW/kg and 1.21 kW/kg, respectively. However, the energy densities are low in both electrolytes.The GPE-EDLC exhibits rectangular cyclic voltammogram similar to an ideal EDLC within operating voltage range of 0 V-2.5 V. It should be noted that a region of electric double layer means a wide voltage and a rapid formation. Redox currents of both EDLCs are not observed in the sweep region and the cyclic voltammograms are unchanged on repeated runs. The observed leakage current shows 49 μA after 720 s at a constant voltage of 2.5 V, due to the high ionic conductivity of 1.5 × 10−3 S cm−1 during storage time. Swelling and well-developed pore structures of the GPE blend films allow ions and solvents to move easily.  相似文献   

5.
A gel polymer electrolyte based on the blend of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and fully cyanoethylated cellulose derivative (DH-4-CN) was prepared and characterized. Thermal, mechanical, swelling, liquid electrolyte retention and electrochemical properties, as well as microstructures of the prepared polymer electrolytes, were investigated using thermogravimetric analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and scanning electron microscopy. The results showed that the addition of DH-4-CN could obviously improve the conductivity of PVDF-HFP based electrolyte. The maximum ionic conductivity of 4.36 mS cm−1 at 20 °C can be obtained for PVDF-HFP/DH-4-CN 14:1 in the presence of 1 M LiPF6 in EC and DMC (1:1, w/w). The dry blend membranes exhibit excellent thermal behavior. All the blend electrolytes are electrochemically stable up to about 4.8 V vs. Li/Li+ for all compositions. The results reveal that the composite polymer electrolyte qualifies as a potential application in lithium-ion battery.  相似文献   

6.
An admixture of commercial liquid electrolyte (LB302, 1 M solution of LiPF6 in 1:1 EC/DEC) and methyl methacrylate (MMA) was enclosed in CR2032 cells. The assembled cells were then -ray-irradiated using configurations of half cells and full cells. Through this in situ irradiation polymerization process, we obtained rechargeable lithium ion cells with poly(methyl methacrylate) (PMMA) based gel polymer electrolytes (GPE). Galvanostatic cycling, AC impedance spectroscopy, and cyclic voltammetry were employed to investigate the electrochemical properties of the cells and the gel polymer electrolyte. This PMMA-based gel polymer electrolyte was found to exhibit a high ionic conductivity (at least 10–3 S cm–1) at room temperature. Due to a significant increase in the charge transfer resistance between the GPE and the cathode, the cell impedance of a PMMA-based lithium ion cell is greater than that of a liquid-electrolyte-based cell. The discharge capacity of a LiNi0.8Co0.2O2/GPE/graphite is approximately 145 mAh g–1 for the first cycle and decreases to123 mAh g–1 after 20 cycles. In addition, a large initial cell impedance (LICI) was observed in the irradiated positive half cell. In this paper, we propose a possible mechanism related to the detachment of the PMMA layer from the lithium electrode. This detachment of the PMMA layer from the lithium electrode has not been explicitly discussed previously.  相似文献   

7.
Amphiphilic conetwork–structured copolymers containing different lengths of ethylene oxide (EO) chains as ionophilic units and methyl methacrylate (MMA) chains as ionophobic units were prepared by free radical copolymerization and characterized by FTIR and thermal analysis. Polymer gel electrolytes based on the copolymers complexed with liquid lithium electrolytes (dimethyl carbonate (DMC) : diethyl carbonate (DEC) : ethylene carbonate (EC) = 1 : 1 : 1 (W/W/W), LiPF6 1.0M) were characterized by differential scanning calorimetry and impedance spectroscopy. A maximum ion conductivity of 4.27 × 10?4 S/cm at 25oC was found for the polymer electrolyte based on (PEG2000‐b‐GMA)‐co‐MMA with long EO groups. Moreover, the effect of temperature on conductivity of the amphiphilic polymer electrolytes obeys the Arrhenius equation. The good room temperature conductivity of the polymer electrolytes is proposed to relate to the enhancement in the amorphous domain of the copolymers due to their amphiphilic conetwork structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

8.
Polymer nanocomposite gel electrolytes consisting of high molecular weight poly(methyl methacrylate) PMMA-clay nanocomposite, ethylene carbonate (EC)/propylene carbonate (PC) as plasticizer, and LiClO4 electrolyte are reported. Montmorillonite clay was ion exchanged with a zwitterionic surfactant (octadecyl dimethyl betaine) and dispersed in methyl methacrylate, which was then polymerized to synthesize PMMA-clay nanocomposites. The nanocomposite was dissolved in a mixture of EC/PC with LiClO4, heated and pressed to obtain polymer gel electrolyte. X-ray diffraction (XRD) of the gels indicated intercalated clay structure with d-spacings of 2.85 and 1.40 nm. In the gel containing plasticizer, the clay galleries shrink suggesting intercalation rather than partial exfoliation observed in the PMMA-clay nanocomposite. Ionic conductivity varied slightly and exhibited a maximum value of 8 × 10−4 S/cm at clay content of 1.5 wt.%. The activation energy was determined by modeling the conductivity with a Vogel-Tamman-Fulcher expression. The clay layers are primarily trapped inside the polymer matrix. Consequently, the polymer does not interact significantly with LiClO4 electrolyte as shown by FTIR. The presence of the clay increased the glass transition temperature (Tg) of the gel as determined by differential scanning calorimetry. The PMMA nanocomposite gel electrolyte shows a stable lithium interfacial resistance over time, which is a key factor for use in electrochemical applications.  相似文献   

9.
An ionic complex of anionic and cationic monomers was obtained by protonation of (N,N-diethylamino)ethylmethacrylate (DEA) with acrylic acid (AAc). Free radical copolymerization of the ionic complex and acrylamide (AAm), yielded the ionically crosslinked polyampholytic gel electrolytes [poly(AAc-DEA-AAm), designated as PADA] using two types of organic solvents containing a lithium salt. The PADA gel electrolyte exhibited good thermal stability shown by the DSC thermogram. The impedance analysis at temperatures ranging from −30 to 75 °C indicated that the ionic conductivities of the PADA gel electrolytes were rather close to those of liquid electrolytes. The temperature dependence of the ionic conductivities was found to be in accord with the Arrhenius equation. Moreover, the ionic conductivities of PADA gel electrolytes increased with an increase of the molar ratios of cationic/anionic monomers. The ionic conductivities of PADA gels prepared in solvent mixtures of propylene carbonate, ethyl methyl ether and dioxolane (3:1:1, v/v) were higher than those of PADA gels prepared in propylene carbonate only. Significantly, the ionic conductivities of two kinds of PADA gel electrolytes were in the range of 10−3 and 10−4 S cm−1 even at −30 °C. The electrochemical windows of PADA gel electrolytes measured by cyclic voltammetry were in the range from −1 V to 4.5 V.  相似文献   

10.
M. Deka 《Electrochimica acta》2010,55(5):1836-1364
In the present work, effect of organically modified montmorillonite (MMT) clays on PMMA-based electrolytes has been investigated. The nanocomposites have been prepared by solution intercalation technique with varying clay loading from 0 to 5 wt.%. The formation of partially exfoliated nanocomposites has been confirmed by XRD and TEM analyses. The obtained nanocomposites were soaked with 1 M LiClO4 in 1:1 (v/v) solution of propylene carbonate (PC) and diethyl carbonate (DEC) to get the required gel electrolytes. Surface morphology and structural conformation of the nanocomposite electrolytes have been examined by SEM and FTIR analyses, respectively. It has been observed that the ionic conductivity of the nanocomposite gel polymer electrolytes increases with the increase in clay loading and attains a maximum value of 1.3 × 10−3 S/cm at room temperature as revealed by ac impedance spectroscopy. Improvement of electrochemical and interfacial stabilities has also been observed in the gel electrolytes containing MMT fillers.  相似文献   

11.
Hu Cheng 《Electrochimica acta》2007,52(19):5789-5794
New gel polymer electrolytes containing 1-butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide (BMPyTFSI) ionic liquid are prepared by solution casting method. Thermal and electrochemical properties have been determined for these gel polymer electrolytes. The addition of BMPyTFSI to the P(EO)20LiTFSI electrolyte results in an increase of the ionic conductivity, and at high BMPyTFSI concentration (BMPy+/Li+ = 1.0), the ionic conductivity reaches the value of 6.9 × 10−4 S/cm at 40 °C. The lithium ion transference numbers obtained from polarization measurements at 40 °C were found to decrease as the amount of BMPyTFSI increased. However, the lithium ionic conductivity increased with the content of BMPyTFSI. The electrochemical stability and interfacial stability for these gel polymer electrolytes were significantly improved due to the incorporation of BMPyTFSI.  相似文献   

12.
In this present paper the influence of viscosity on the ionic dynamics of polymer gel electrolytes prepared by the Pechini polymeric precursor method is investigated by impedance spectroscopy, differential scanning calorimetric (DSC) and NMR techniques. Polymer gel electrolytes are formed by ethylene glycol (EG) and citric acid (CA) and lithium perchlorate. Room temperature conductivity of the order of 2.3 × 10−4 S/cm was obtained for the sample of EG/CA:LiClO4 with lower viscosity (η = 197 cP). The results show that the ionic conductivity of the electrolytes increases for decreasing viscosity. Proton (1H) and Lithium (7Li) NMR lineshapes and spin-lattice relaxation times were measured as a function of temperature and viscosity (197-868 cP). The 7Li relaxation process was found to be dominated by quadrupolar couplings. The activation energy extracted from the 1H and 7Li relaxation data (∼0.23 eV) was found to be independent of the viscosity of the gel electrolyte. The 7Li NMR relaxation results indicate an increase of the lithium ion mobility with decreasing viscosity.  相似文献   

13.
Polymer-clay nanocomposite (PCN) materials were prepared by intercalation of an alkyl-ammonium ion spacing/coupling agent and a polymer between the planar layers of a swellable-layered material, such as montmorillonite (MMT). The nanocomposite lithium polymer electrolytes comprising such PCN materials and/or a dielectric solution (propylene carbonate) were prepared and discussed. The chemical composition of the nanocomposite materials was determined with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy, which revealed that the alkyl-ammonium ion successfully intercalated the layer of MMT clay, and thus copolymer poly(vinylidene fluoride-hexafluoropropylene) entered the galleries of montmorillonite clay. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical properties of the lithium polymer electrolyte. Equivalent circuits were proposed to fit the EIS data successfully, and the significant contribution from MMT was thus identified. The resulting polymer electrolytes show high ionic conductivity up to 10−3 S cm−1 after gelling with propylene carbonate. The PCN materials exhibit good electrochemical stability and could be potentially used in lithium secondary battery.  相似文献   

14.
New polymer gel electrolytes containing ionic liquids were developed for modern chemical power sources—supercapacitors and lithium-ion batteries. Ternary systems polymer-ionic liquid-aprotic solvent as well as materials containing also lithium salts (LiClO4 or LiPF6) were prepared by direct, thermally initiated polymerisation. Poly(2-ethoxyethyl methacrylate) PEOEMA was combined with various ionic liquids based on 1-methylimidazole. Only 1-butyl-3-methylimidazolium hexafluorophosphate BMIPF6 formed a homogenous and slightly translucent polymer electrolyte, where aprotic solvents—propylene carbonate and ethylene carbonates were used as plasticisers. Materials were studied using the electrochemical and thermogravimetric methods and exhibit high ionic conductivity up to 0.94 mS cm−1 at 25 °C together with high electrochemical stability: the accessible potential window on the glassy carbon was found ca. 4.3 V. Prepared non-volatile materials are long-term and thermally stable up to 150 °C.  相似文献   

15.
Electrochemical intercalation of lithium into a natural graphite anode was investigated in electrolytes based on a room temperature ionic liquid consisting of trimethyl-n-hexylammonium (TMHA) cation and bis(trifluoromethanesulfone) imide (TFSI) anion. Graphite electrode was less prone to forming effective passivation film in 1 M LiTFSI/TMHA-TFSI ionic electrolyte. Reversible intercalation/de-intercalation of TMHA cations into/from the graphene interlayer was confirmed by using cyclic voltammetry, galvanostatic measurements, and ex situ X-ray diffraction technique. Addition of 20 vol% chloroethylenene carbonate (Cl-EC), ethylene carbonate (EC), vinyl carbonate (VC), or ethylene sulfite (ES) into the ionic electrolyte resulted in the formation of solid electrolyte interface (SEI) film prior to TMHA intercalation and allowed the formation of Li-C6 graphite interlayer compound. In the ionic electrolyte containing 20 vol% Cl-EC, the natural graphite anode exhibited excellent electrochemical behavior with 352.9 mAh/g discharge capacity and 87.1% coulombic efficiency at the first cycle. A stable reversible capacity of around 360 mAh/g was obtained in the initial 20 cycles without any noticeable capacity loss. Mechanisms concerning the significant electrochemical improvement of the graphite anode were discussed. Ac impedance and SEM studies demonstrated the formation of a thin, homogenous, compact and more conductive SEI layer on the graphite electrode surface.  相似文献   

16.
Organic-inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (D2000) complexed with LiClO4 via the co-condensation of an epoxy trialkoxysilane and tetraethoxysilane have been prepared and plasticized by a solution of ethylene carbonate (EC)/propylene carbonate (PC) mixture (1:1 by weight). The cross-linked hybrid network shows no solvent exudation and retains a large amount of plasticizer over 70 wt.% in stable state. The in situ built in silica network provides the hybrid electrolytes with good mechanical properties. The ionic conductivity of the dry hybrid electrolyte films was enhanced by two orders of magnitude via plasticization, reaching a maximum conductivity value of 4.0 × 10−3 S/cm at 30 °C. Variable temperature 7Li-{1H} magic angle spinning (MAS) NMR demonstrated that the Li+ cations can be complexed by the polymer network as well as by the plasticizing solvents, but not with the incorporated silica network. Furthermore, the 7Li chemical shift change indicated a progressive change in the lithium coordination from lithium-polymer to lithium-solvent with increasing temperatures. The role of the solvents and the mobility of the lithium ions were investigated by pulsed gradient spin echo (PGSE) NMR measurements to elucidate the behavior of the ionic conductivity.  相似文献   

17.
This paper discusses the preparation of microporous fibrous membranes from PVdF solutions with different polymer contents, using the electrospinning technique. Electrospun PVdF-based fibrous membranes with average fiber diameters (AFD's) of 0.45-1.38 μm have an apparent porosity and a mean pore size (MPS) of 80-89% and 1.1-4.3 μm, respectively. They exhibited a high uptake of the electrolyte solution (320-350%) and a high ionic conductivity of above 1 × 10−3 s/cm at room temperature. Their ionic conductivity increased with the decrease in the AFD of the fibrous membrane due to its high electrolyte uptake. The interaction between the electrolyte molecules and the PVdF with a high crystalline content may have had a minor effect on the lithium ion transfer in the fibrous polymer electrolyte, unlike in a nanoporous gel polymer electrolyte. The fibrous polymer electrolyte that contained a 1 M LiPF6-EC/DMC/DEC (1/1/1 by weight) solution showed a high electrochemical stability of above 5.0 V, which increased with the decrease in the AFD The interfacial resistance (Ri) between the polymer electrolyte and the lithium electrode slightly increased with the storage time, compared with the higher increase in the interfacial resistance of other gel polymer electrolytes. The prototype cell (MCMB/PVdF-based fibrous electrolyte/LiCoO2) showed a very stable charge-discharge behavior with a slight capacity loss under constant current and voltage conditions at the C/2-rate of 20 and 60 °C.  相似文献   

18.
Gel electrolytes based on lithium modified silica nano-particles   总被引:1,自引:0,他引:1  
In this work lithium modified silica (Li-SiO2) nano-particles were synthesized and used as a single ion lithium conductor source in gel electrolytes. It was found that Li-SiO2 exhibited good compatibility with DMSO, DMA/EC (a mixture of N,N-dimethyl acetamide and ethylene carbonate) and the ionic liquid, N-methyl-N-propyl pyrrolidinium bis(trifluoromethylsulfonyl) amide ([C3mpyr][NTf2]). Several gel electrolytes based on Li-SiO2 were obtained. These gel electrolytes were investigated by DSC, solid state NMR, conductivity measurements and cyclic voltammetry. Conductivities as high as 10−3 S/cm at room temperature were observed in these nano-particle gel electrolytes. The results of electrochemical tests showed that some of these materials were promising for using as lithium conductive electrolytes in electrochemical devices, with high lithium cycling efficiency evident.  相似文献   

19.
An EC/DEC [40:60% (v/v)] solvent mixture has been added in various amounts to the ionic liquid (IL) hexyltrimethylammonium bis(trifluoromethylsulfonyl)imide (N1116-NTf2) in the presence of LiNTf2 (lithium bis(trifluoromethylsulfonyl)imide) as lithium salt for possible use as electrolytes in lithium-ion batteries. These electrolytes exhibit a larger thermal stability than the reference electrolyte EC/DEC [40:60] + LiNTf2 1 M when the percentage of the IL exceeds 30% (v/v). All studied electrolytes are glass forming ones with an ideal glass transition temperature of ca. −85 °C(±5 °C), which has been determined by application of the VTF theory to conductivity and viscosity measurements and confirmed by DSC (Tg = −90 ± 5 °C). An electrochemical window of about 5 V versus Li/Li+ was measured at a glassy carbon electrode. The cycling ability of the optimized electrolyte N1116-NTf2/EC:DEC (40/60% (v/v)) + 1 M LiNTf2 has been investigated at a titanate oxide (Li4Ti5O12) and a cobalt oxide (LixCoO2) electrodes. Cycling the positive and the negative electrodes was conducted successfully with a high capacity and without any significant fading.  相似文献   

20.
In order to enhance the ionic conductivity of polyethylene oxide (PEO)-KOH based alkaline polymer electrolytes, three types of nano-powders, i.e., TiO2, β-Al2O3 and SiO2 were added to PEO-KOH complex, respectively, and the corresponding composite alkaline polymer electrolytes were prepared. The experimental results showed that the prepared polymer electrolytes exhibited higher ionic conductivities at room temperature, typically 10−3 S cm−1 as measured by ac impedance method, and good electrochemical stability. The electrochemical stability window of ca. 1.6 V was determined by cyclic voltammetry with stainless steel blocking electrodes. The influence of the film composition such as KOH, H2O and nano-additives on ion conductivity was investigated and explained. The temperature dependence of conductivity was also determined. In addition, polyvinyl alcohol (PVA)-sodium carboxymethyl cellulose (CMC)-KOH alkaline polymer electrolytes were obtained using solvent casting method. The properties of the polymer electrolytes were characterized by ac impedance, cyclic voltammetry and differential thermal analysis methods. The ionic conductivity of the prepared PVA-CMC-KOH-H2O electrolytes can reach the order of 10−2 S cm−1. The effect of CMC addition on the alkaline polymer electrolytes was also explained. The experimental results demonstrated that the PVA-CMC-KOH-H2O polymer electrolyte could be used in Ni/MH battery.  相似文献   

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