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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.
Polymer electrolyte membranes consisting of a novel hyperbranched polyether PHEMO (poly(3-{2-[2-(2-hydroxyethoxy) ethoxy] ethoxy}methyl-3′-methyloxetane)), PVDF-HFP (poly(vinylidene fluoride-hexafluoropropylene)) and LiTFSI have been prepared by solution casting technique. X-ray diffraction of the PHEMO/PVDF-HFP polymer matrix and pure PVDF-HFP revealed the difference in crystallinity between them. The effect of different amounts of PVDF-HFP and lithium salts on the conductivity of the polymer electrolytes was studied. The ionic conductivity of the prepared polymer electrolytes can reach 1.64 × 10? 4 S·cm? 1 at 30 °C and 1.75 × 10? 3 S·cm? 1 at 80 °C. Thermogravimetric analysis informed that the PHEMO/PVDF-HFP matrix exhibited good thermal stability with a decomposition temperature higher than 400 °C. The electrochemical experiments showed that the electrochemical window of the polymer electrolyte was around 4.2 V vs. Li+/Li. The PHEMO/PVDF-HFP polymer electrolyte, which has good electrochemical stability and thermal stability, could be a promising solid polymer electrolyte for polymer lithium ion batteries.  相似文献   

3.
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   

4.
Zheng Zhong  Qi Cao  Xianyou Wang  Na Wu  Yan Wang 《Ionics》2012,18(1-2):47-53
Composite nanofibrous membranes based on poly (vinyl chloride) (PVC)?Cpoly (methyl methacrylate) (PMMA) were prepared by electrospinning and then they were soaked in liquid electrolyte to form polymer electrolytes (PEs). The introduction of PMMA into the PVC matrix enhanced the compatibility between the polymer matrix and the liquid electrolyte. The composite nanofibrous membranes prepared by electrospinning involved a fully interconnected pore structure facilitating high electrolyte uptake and easy transport of ions. The ion conductivity of the PEs increased with the increase in PMMA content in the blend and the ion conductivity of the polymer electrolyte based on PVC?CPMMA (5:5, w/w) blend was 1.36?×?10?3 S cm?1 at 25?°C. The polymer electrolyte based on PVC?CPMMA (5:5, w/w) blend presented good electrochemical stability up to 5.0?V (vs. Li/Li+) and good interfacial stability with the lithium electrode. The promising results showed that nanofibrous PEs based on PVC?CPMMA were of great potential application in polymer lithium-ion batteries.  相似文献   

5.
The ionic liquid polymer electrolyte (IL-PE) membrane is prepared by ultraviolet (UV) cross-linking technology with polyurethane acrylate (PUA), methyl methacrylate (MMA), ionic liquid (Py13TFSI), lithium salt (LiTFSI), ethylene glycol dimethacrylate (EGDMA), and benzoyl peroxide (BPO). N-methyl-N-propyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py13TFSI) ionic liquid is synthesized by mixing N-methyl-N-propyl pyrrolidinium bromide (Py13Br) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The addition of Py13TFSI to polymer electrolyte membranes leads to network structures by the chain cross-linking. The resultant electrolyte membranes display the room temperature ionic conductivity of 1.37 × 10?3 S cm?1 and the lithium ions transference number of 0.22. The electrochemical stability window of IL-PE is about 4.8 V (vs. Li+/Li), indicating sufficient electrochemical stability. The interfacial resistances between the IL-PE and the electrodes have the less change after 10 cycles than before 10 cycles. IL-PE has better compatibility with the LiFePO4 electrode and the Li electrode after 10 cycles. The first discharge performance of Li/IL-PE/LiFePO4 half-cell shows a capacity of 151.9 mAh g?1 and coulombic efficiency of 87.9%. The discharge capacity is 131.9 mAh g?1 with 95.5% coulombic efficiency after 80 cycles. Therefore, the battery using the IL-PE exhibits a good cycle and rate performance.  相似文献   

6.
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   

7.
Rusi  C.-K. Sim  S. R. Majid 《Ionics》2017,23(5):1219-1227
Polyaniline (PANI) nanowire electrode was successfully prepared using electrodeposition method. The morphology, thickness, and electrochemical performance of PANI electrode can be controlled by varying the deposition scan rates. Lower deposition scan rate results in compact and aggregates of PANI nanowire morphology. The uniform nanowire of PANI was obtained at the applied scan rate of 100 mV s?1, and it was used as symmetric electrode coupled with H2SO4/polyvinyl alcohol (PVA) gel electrolyte. The different concentrations of H2SO4 acid in polymer electrolyte have influenced the electrochemical performance as well. The optimum specific capacitance and energy density of P100 PANI electrode in 3 M H2SO4/PVA gel polymer electrolyte was 377 F g?1 and 95.4 Wh kg?1 at the scan rate of 1 mV s?1. The good stability of the electrode in this system is applicable to many wearable electronics applications.  相似文献   

8.
A new functionalized ionic liquid (IL) based on cyclic quaternary ammonium cations with ester group and bis(trifluoromethanesulfonyl)imide ([TFSI]?) anion, namely, N-methyl-N-methoxycarbonylpiperidinium bis(trifluoromethanesulfonyl)imide ([MMOCPip][TFSI]), was synthesized and characterized. Physical and electrochemical properties, including Li-ion transference number, ionic conductivity, and electrochemical stability, were investigated. The electrochemical window of [MMOCPip][TFSI] was 6 V, which was wide enough to be used as a common electrolyte material. The Li-ion transference number of this IL electrolyte containing 0.1 M LiTFSI was 0.56. The half-cell tests indicated that the [MMOCPip][TFSI] obviously improved the cyclability of a Li/LiFePO4 cell. For the Li/LiFePO4 half-cells, after 20 cycles at room temperature at 0.1 C, the discharge capacity was 109.7 mAh g?1 with 98.7% capacity retention in the [MMOCPip][TFSI]/0.1 M LiTFSI electrolyte. The good electrochemical performance demonstrated that the [MMOCPip][TFSI] could be used as electrolyte for lithium-ion batteries.  相似文献   

9.
Polycarbonates (4a–d) with various side chain lengths were synthesized by the reaction of 1,4-bis(hydroxyethoxy)benzene derivatives and triphosgene in the presence of pyridine. The polymer electrolytes composed of 4a–d with lithium bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2, LiTFSI) were prepared, and their ionic conductivities and thermal and electrochemical properties were investigated. 4d-Based polymer electrolyte showed the highest ionic conductivity values of 1.0?×?10?4?S/cm at 80 °C and 1.5?×?10?6?S/cm at 30 °C, respectively, at the [LiTFSI]/[repeating unit] ratio of 1/2. Ionic conductivities of these polycarbonate-based polymer electrolytes showed the tendency of increase with increasing the chain length of oxyethylene moieties as side chains, suggestive of increased steric hindrance by side chains. Unique properties were observed for the 4a(n?=?0)-based polymer electrolyte without an oxyethylene moiety. All of polycarbonate-based polymer electrolytes showed good electrochemical and thermal stabilities as polymer electrolytes for battery application.  相似文献   

10.
Based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) and lithium tetrafluoroborate (LiBF4) salt along with blending plasticizers, ethylene carbonate (EC) and propylene carbonate (PC), high Li-ion-conducting gel polymer electrolyte films are developed. Their properties are characterized by various techniques. The ambient temperature ionic conductivity of the 85PVdF-HFP:15LiBF4 + 150(EC + PC) electrolyte film has a high value of 8.1 × 10?4 S cm?1. Its crystallinity, melting point, and electrochemical stability window are 9.5%, 115 °C, and 4.6 V, respectively. The mechanical testing shows that the Young’s modulus, yield strength, and breaking strain of this electrolyte film are 36.8 MPa, 3.4 MPa, and 320%, respectively. Lithium-ion batteries based on the gel polymer electrolyte film exhibit remarkable charge–discharge and cycling performances. The initial discharge capacity of this battery is as high as 165.1 mAh g?1 at 0.1 C and just shows a small capacity fading of 4.8% after 120 cycles, indicating that the 85PVdF-HFP:15LiBF4 + 150(EC + PC) system is an excellent electrolyte candidate for lithium-ion battery applications. The charge–discharge performance of the Li-ion cell fabricated with this gel polymer electrolyte film is apparently better than that of the previously reported Li-ion cells fabricated with other PVdF-HFP-based gel polymer electrolyte films.  相似文献   

11.
A new copolymer, poly(methyl methacrylate-co-butyl acrylate) (P(MMA-co-BA)), was synthesized by emulsion polymerization with different mass ratio of methyl methacrylate (MMA) and butyl acrylate (BA). The membranes were prepared by phase inversion and corresponding gel polymer electrolytes (GPEs) were obtained by immersing the membrane into a liquid electrolyte. In this design, the hard monomer MMA provided the copolymer with good electrolyte uptake, while the soft monomer BA provided the GPE with strong adhesion between the anode and cathode of lithium ion battery. The properties of the resulting product were investigated by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectra, scanning electron spectroscopy, linear sweep voltammetry, thermogravimetric analysis, cyclic voltammetry, electrochemical impedance spectroscopy and charge/discharge test. The results show that the obtained GPE based on P(MMA-co-BA) with the mass ratios of MMA and BA = 6:1 exhibits good conductivity (as high as 1.2 × 10?3 S cm?1) at room temperature and high electrochemical stability (up to 4.9 V vs. Li/Li+). With the application of the polyethylene (PE)-supported GPE in Li/Li(Li0.13Ni0.30Mn0.57)O2 battery, the battery presents good cyclic stability (maintaining 95.4 % of its initial discharge capacity after 50 cycles) at room temperature.  相似文献   

12.
A series of gel polymer electrolytes containing PVdF as homo polymer, a mixture of 1:1 Ethylene Carbonate (EC) : Propylene Carbonate (PC) as plasticizer and lithium-bistrifluoromethane sulphone imide [imide — LiN (CF3SO2)2] has been developed. Amounts of polymer (PVdF), plasticizer and the imide lithium salt have been varied as a function of their weight ratio composition in this regard. Dimensionally stable films possessing appreciable room temperature conductivity values have been obtained with respect to certain weight ratio compositions. However, conductivity data have been recorded at different possible temperatures, i.e., from 20 °C to 65 °C. XRD and DSC studies were carried out to characterize the polymer films for better amorphicity and reduced glass transition temperature, respectively. The electrochemical interface stability of the PVdF based gel polymer electrolytes over a range of storage period (24 h – 10 days) have been investigated using A.C. impedance studies. Test cells containing Li/gel polymer electrolyte (GPE)/Li have been subjected to undergo 50 charge-discharge cycles in order to understand the electrochemical performance behaviour of the dimensionally stable films of superior conductivity. The observed capacity fade of less than 20% even after 50 cycles is in favour of the electrochemical stability of the gel polymer electrolyte containing 27.5% PVdF −67.5 % EC+PC −5% imide salt. Cyclic voltammetry studies establish the possibility of a reversible intercalation — deintercalation process involving Li+ ions through the gel polymer electrolyte.  相似文献   

13.
Lithium bis(oxalate)borate (LiBOB) is a promising salt for lithium-ion batteries. However, it is necessary to exert the electrochemical performance of LiBOB by the appropriate solvent. With dimethyl sulfite (DMS) as mixed solvents, the electrochemical behavior of γ-butyrolactone (GBL) with LiBOB is studied in this paper. It shows that LiBOB-GBL/DMS electrolyte has high oxidation potential (>5.3 V) and satisfactory conductivities. When used in lithium and mesophase carbon microbead cells, the novel electrolyte exhibits not only excellent film-forming characteristics but also low impedances of the interface films. Besides, when used in LiFeO4/Li cells, compared to the cell with the electrolyte system of 1 mol L?1 LiPF6–ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1, v/v), LiBOB-based electrolyte exhibits several advantages, such as more stable cycle performance at room temperature and higher mean voltage.  相似文献   

14.
Ionic conductivity and redox stability domain of a new type of polymer electrolyte have been studied. The polymer electrolytes were prepared from a network of poly (dimethylsiloxane-grafted ethylene oxide) copolymer crosslinked by an aliphatic isocyanate (grafted PDMS) and containing 10 wt% LiClO4. Ionic conductivities higher than 10?5 ω?1 cm?1 are obtained above 30°C. The study of the electrochemical stability of the crosslinking agent suggests that the unreacted isocyanate groups are not stable. The electroactivity domain of the grafted PDMS-LiClO4 10 wt% electrolyte is larger than 3 V. The performances of a solid state battery using this electrolyte have been investigated. The first discharge and charge depths were 73%. The rechargeability behaviour have been compared with those of a Li/RuO2 battery with a linear high molecular weight P(EO)8-LiClO4 as electrolyte.  相似文献   

15.
To seek a promising candidate electrolyte at elevated temperature for lithium manganese oxide (LiMn2O4)/Li cells, the electrochemical performance of 0.7 mol L?1 LiBOB (lithium bis(oxalate)borate)-SL (sulfolane)/DEC (diethyl carbonate) (1:1, in volume) electrolyte was studied at 55 °C. The Mn dissolution in electrolyte was analyzed by inductively coupled plasma (ICP) analysis. AC impedance measurement and scanning electron microscopy (SEM) analysis were used to analyze the formation of the surface film on the LiMn2O4 electrode. The results demonstrate that the LiBOB-SL/DEC electrolyte can slow down the dissolution and erosion of Mn ions, and decrease the interface impedance. Moreover, the LiBOB-SL/DEC electrolyte could obviously improve the capacity retention, the operating voltage (4.05 V), and the rate performance of LiMn2O4/Li cells.  相似文献   

16.
S. Abarna  G. Hirankumar 《Ionics》2017,23(7):1733-1743
Novel solid polymer electrolytes, poly(vinylalcohol)-lithium perchlorate (PVA-LiClO4) and PVA-LiClO4-sulfolane are prepared by solvent casting method. The experimental results show that sulfolane addition enhances the ionic conductivity of PVA-LiClO4 complex by three orders. The maximum ionic conductivity of 1.14 ± 0.20 × 10?2 S cm?1 is achieved for 10 mol% sulfolane-added electrolyte at ambient temperature. Polymer-salt-plasticizer interactions are analyzed through attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Lithium ion transference number is found by AC impedance spectroscopy combined with DC potentiostatic measurements. The results confirm that sulfolane improves the Li+ transference number of PVA-LiClO4 complex to 0.77 from 0.40. The electrochemical stability window of electrolytes is determined by cyclic voltammetry (CV). The broad electrochemical stability window of 5.45 V vs. lithium is obtained for maximum conducting electrolyte. All-solid-state cell is fabricated using maximum conducting electrolyte, and electrochemical impedance study is carried out. It reveals that electrolyte interfacial resistance with Li electrode is very low. The use of PVA-LiClO4-sulfolane as a viable electrolyte material for high-voltage lithium ion batteries is ensured.  相似文献   

17.
Biodegradable polymer electrolyte films based on poly(ε-caprolactone) (PCL) in conjunction with lithium tetrafluoroborate (LiBF4) salt and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4) ionic liquid were prepared by solution cast technique. The structural, morphological, thermal, and electrical properties of these films were examined using X-ray diffraction (XRD), optical microscopy (OM), differential scanning calorimetry (DSC), and impedance spectroscopy. The XRD and OM results reveal that the pure PCL possesses a semi-crystalline nature and its degree of crystallinity decreases with the addition of LiBF4 salt and EMIMBF4 ionic liquid. DSC analysis indicates that the melting temperature and enthalpy are apparently lower for the 40 wt% EMIMBF4 gel polymer electrolyte as compared with the others. The ambient temperature electrical conductivity increases with increasing EMIMBF4 concentration and reaches a high value of ~2.83?×?10?4 S cm?1 for the 85 PCL:15 LiBF4 + 40 wt% EMIMBF4 gel polymer electrolyte. The dielectric constant and ionic conductivity follow the same trend with increasing EMIMBF4 concentration. The dominant conducting species in the 40 wt% EMIMBF4 gel polymer electrolyte determined by Wagner’s polarization technique are ions. The ionic conductivity of this polymer electrolyte (~2.83?×?10?4 S cm?1) should be high enough for practical applications.  相似文献   

18.
In this research, the effect of the different concentrations of NaSnO3 as the electrolyte additive in 0.7 mol L?1 NaCl solution on the electrochemical performances of the magnesium-8lithium (Mg-8Li) electrode are investigated by methods of potentiodynamic polarization, potentiostatic current-time, electrochemical impedance technique, and scanning electron microscopy (SEM). The corrosion resistance of the Mg-8Li electrode is improved when Na2SnO3 is added into the electrolyte solution. The potentiostatic current-time curves show that the electrochemical behaviors of the Mg-8Li electrode in the electrolyte solution containing 0.20 mmol L?1 Na2SnO3 is the best. The electrochemical impedance spectroscopy results indicate that the polarization resistance of the Mg-8Li electrode decreases in the following order with the concentrations of Na2SnO3: 0.05 mmol L?1?>?0.00 mmol L?1?>?0.30 mmol L?1?>?0.10 mmol L?1?>?0.20 mmol L?1. The scanning electron microscopy studies indicate that the electrolyte additive prevents the formation of the dense oxide film on the alloy surface and facilitates the peeling off of the oxidation products.  相似文献   

19.
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   

20.
Composite fibrous membranes based on poly(acrylonitrile)(PAN)-poly(vinyl chloride)(PVC) have been prepared by electrospinning. The fibrous membranes are made up of fibers of 850- to 1,300-nm diameters. These fibers are stacked in layers to produce a fully interconnected pore structure. Polymer electrolytes were prepared by immersing the fibrous membranes in 1 M LiClO4-PC solution for 60 min. The condition of pure PAN polymer electrolytes is jelly, which has poor mechanical performance and cannot be used. But when PVC with a good mechanical stiffener was added to PAN, the condition of composite PAN?CPVC polymer electrolytes becomes free-standing. In addition, the optimum electrochemical properties have been observed for the polymer electrolyte based on PAN?CPVC (8:2, w/w) to show ionic conductivity of 1.05?×?10?3 S cm?1 at 25 °C, anodic stability up to 4.9 V versus Li/Li+, and a good compatibility with lithium metal resulting in low interfacial resistance. The promising results showed that fibrous PEs based on PAN?CPVC (8:2, w/w) have good mechanical stability and electrochemical properties. This shows a great potential application in polymer lithium-ion batteries.  相似文献   

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