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1.
《Ceramics International》2023,49(3):4473-4481
All solid-state lithium batteries (ASS-LBs) with polymer-based solid electrolytes are a prospective contender for the next-generation batteries because of their high energy density, flexibility, and safety. Among all-polymer electrolytes, PEO-based solid polymer electrolytes received huge consideration as they can dissolve various Li salts. However, the development of an ideal PEO-based solid polymer electrolyte is hindered by its insufficient tensile strength and lower ionic conductivity due to its semi-crystalline and soft chain structure. In order to lower the crystallization and improve the performance of PEO-based solid polymer electrolyte, tungsten trioxide (WO3) nanofillers were introduced into PEO matrix. Herein, a PEO20/LiTFSI/x-WO3 (PELI-xW) (x = 0%, 2.5%, 5%, 10%) solid composite polymer electrolyte was prepared by the tape casting method. The solid composite polymer electrolyte containing 5 wt% WO3 nanofillers achieved the highest ionic conductivity of 7.4 × 10-4 S cm-1 at 60 °C. It also confirms a higher Li-ion transference number of 0.42, good electrochemical stability of 4.3V, and higher tensile strength than a PEO/LiTFSI (PELI-0W) fillers-free electrolyte. Meanwhile, the LiFePO4│PELI-xW│Li ASS-LBs demonstrated high performance and cyclability. Based on these findings, it can be considered a feasible strategy for the construction of efficient and flexible PEO-based solid polymer electrolytes for next-generation solid-state batteries.  相似文献   

2.
A series of solid polymer electrolytes (SPEs) based on comb‐like nonionic waterborne polyurethane (NWPU) and LiClO4 are fabricated via a solvent free process. The NWPU‐based SPEs have sufficient mechanical strength which is beneficial to their dimensional stability. Differential scanning calorimetry analysis indicates that the phase separation occurs by the addition of the lithium salt. Scanning electron microscopy and X‐ray diffraction analyses illustrate the good compatibility between LiClO4 and NWPU. Fourier transform infrared study reveals the complicated interactions among lithium ions with the amide, carbonyl and ether groups in such SPEs. AC impedance spectroscopy shows the conductivity of the SPEs exhibiting a linear Arrhenius relationship with temperature. The ionic conductivity of the SPE with the mass content of 15% LiClO4 (SPE15) can reach 5.44 × 10?6 S cm?1 at 40 °C and 2.35 ×10?3 S cm?1 at 140 °C. The SPE15 possesses a wide electrochemical stability window of 0–5 V (vs. Li+/Li) and thermal stability at 140 °C. The excellent properties of this new NWPU‐based SPE are a promising solid electrolyte candidate for all‐solid‐state lithium ion batteries. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45554.  相似文献   

3.
To improve the electrochemical properties and enhance the mechanical strength of solid polymer electrolytes, series of composite polymer electrolytes (CPEs) were fabricated with hybrids of thermoplastic polyurethane (TPU) electrospun membrane, polyethylene oxide (PEO), SiO2 nanoparticles and lithium bis(trifluoromethane)sulfonamide (LiTFSI). The structure and properties of the CPEs were confirmed by SEM, XRD, DSC, TGA, electrochemical impedance spectroscopy and linear sweep voltammetry. The TPU electrospun membrane as the skeleton can improve the mechanical properties of the CPEs. In addition, SiO2 particles can suppress the crystallization of PEO. The results show that the TPU‐electrospun‐membrane‐supported PEO electrolyte with 5 wt% SiO2 and 20 wt% LiTFSI (TPU/PEO‐5%SiO2‐20%Li) presents an ionic conductivity of 6.1 × 10?4 S cm?1 at 60 °C with a high tensile strength of 25.6 MPa. The battery using TPU/PEO‐5%SiO2‐20%Li as solid electrolyte and LiFePO4 as cathode shows an attractive discharge capacity of 152, 150, 121, 75, 55 and 26 mA h g?1 at C‐rates of 0.2C, 0.5C, 1C, 2C, 3C and 5C, respectively. The discharge capacity of the cell remains 110 mA h g?1 after 100 cycles at 1C at 60 °C (with a capacity retention of 91%). All the results indicate that this CPE can be applied to all‐solid‐state rechargeable lithium batteries. © 2018 Society of Chemical Industry  相似文献   

4.
Electrospun poly[(vinylidene fluoride)‐co ‐hexafluoropropylene]/silica (PVdF‐HFP/SiO2) nanocomposite polymer membranes (esCPMs) were prepared by incorporating different weight percentages of SiO2 nanoparticles onto electrospun PVdF‐HFP by electrospinning technique. The surface morphology of electrospun PVdF‐HFP nanocomposite membranes was characterized by scanning electron microscopy. The effect of SiO2 nanoparticles incorporation onto electrospun PVdF‐HFP polymer membranes (esPMs) has been studied by XRD, DSC, TGA, and tensile analysis. The electrospun PVdF‐HFP/SiO2 based nanocomposite membrane electrolytes (esCPMEs) were prepared by soaking the corresponding esCPMs into 1 M LiPF6 in EC:DMC (1:1 vol/vol %). The ionic conductivity of the esCPMEs was studied by AC‐impedance studies and it was found that the incorporation of SiO2 nanoparticles into PVdF‐HFP membrane has improved the ionic conductivity from 1.320 × 10?3 S cm?1 to 2.259 × 10?3 S cm?1. The electrochemical stability of the esCPME was studied by linear sweep voltammetry studies and it was found to be 2.87 V. Finally, a prototype LiCo0.2Mn1.8O4//C Li‐ion capacitor (LIC) cell was fabricated with esCPME, which delivered a discharge capacitance of 128 F g?1 at the current density of 1 A g?1 and retained 86% of its discharge capacitance even after 10,000 cycles. These results demonstrated that the esCPMEs could be used as promising polymer membrane electrolyte for LICs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45177.  相似文献   

5.
This study describes a simple and effective method of synthesis of a polyurethane/graphene nanocomposite. Cationic waterborne polyurethane (CWPU) was used as the polymer matrix, and graphene oxide (GO) as a starting nanofiller. The CWPU/GO nanocomposite was prepared by first mixing a CWPU emulsion with a GO colloidal dispersion. The positively charged CWPU latex particles were assembled on the surfaces of the negatively charged GO nanoplatelets through electrostatic interactions. Then, the CWPU/chemically reduced GO (RGO) was obtained by treating the CWPU/GO with hydrazine hydrate in DMF. The results of X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Raman analysis showed that the RGO nanoplatelets were well dispersed and exfoliated in the CWPU matrix. The electrical conductivity of the CWPU/RGO nanocomposite could reach 0.28 S m?1, and the thermal conductivity was as high as 1.71 W m?1 K?1. The oxygen transmission rate (OTR) of the CWPU/RGO‐coated PET film was significantly decreased to 0.6 cmm?2 day?1, indicating a high oxygen barrier property. This remarkable improvement in the electrical and thermal conductivity and barrier property of the CWPU/RGO nanocomposite is attributed to the electrostatic interactions and the molecular‐level dispersion of RGO nanoplatelets in the CWPU matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43117.  相似文献   

6.
A new polymer electrolyte based on the biopolymer Agar‐Agar doped with ammonium thiocyanate (NH4SCN) has been prepared and characterized by FTIR analysis, X‐ray diffraction measurements, AC impedance spectroscopy, transference number measurements, and DSC analysis. The Fourier transform infrared analysis confirms the complex formation between agar and NH4SCN. The amorphous nature of the polymer electrolyte has been revealed from X‐ray diffraction analysis. The highest ionic conductivity has been observed for the sample of composition 1:1 between Agar and NH4SCN. As a function of temperature, the ionic conductivity of this sample exhibits Arrhenius behavior increasing from 1.03 × 10?3 S cm?1 at ambient temperature to 3.16 × 10?3 S cm?1 at 343 K. The transference number has been estimated by the dc polarization method, and it has been proven that the conducting species are predominantly cations. Using the highest conductivity polymer electrolyte, solid state electrochemical cell has been fabricated and cell parameters are reported. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44702.  相似文献   

7.
A new type of lithium salts, —SO2NLiSO2OCH2(CF2)nCH2Om— (LiPPFASI, where n = 2, 3, 4, 6, and 7), was used as salts in poly(ethylene oxide) (PEO)‐based solvent‐free electrolytes. The conductivity and electrochemical stability behaviors were studied. The results showed the electrolytes almost have a similar conductivity and the PEO–LiPPFASI (n = 3, EO/Li = 10) was the relatively better system under the experiment conditions. Moreover, most systems were found to be oxidatively stable up to 5.5 V versus Li/Li+ and the lithium deposition‐stripping process on the electrode was reversible for all the polymer electrolytes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1882–1885, 2001  相似文献   

8.
Nanocomposite polymer electrolytes (NCPEs) composed of poly(ethylene oxide), calcium phosphate [Ca3(PO4)2], and lithium perchlorate (LiClO4)/lithium bis(trifluoromethane sulfonyl)imide [LiN(CF3SO2)2 or LiTFSI] in various proportions were prepared by a hot‐press method. The membranes were characterized by scanning electron microscopy, differential scanning calorimetry, thermogravimetry–differential thermal analysis, ionic conductivity testing, and transference number studies. The free volume of the membranes was probed by positron annihilation lifetime spectroscopy at 30°C, and the results supported the ionic conductivity data. The NCPEs with LiClO4 exhibited higher ionic conductivities than the NCPE with LiTFSI as a salt. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

9.
Imidazolium‐functionalized norbornene and benzene‐functionalized norbornene were synthesized and copolymerized via ring‐opening metathesis polymerization to afford a polymeric ionic liquid (PIL) block copolymers {5‐norbornene‐2‐methyl benzoate‐block ‐5‐norbornene‐2‐carboxylate‐1‐hexyl‐3‐methyl imidazolium bis[(trifluoromethyl)sulfonyl]amide [P(NPh‐b ‐NIm‐TFSI)]} with good thermal stability. On this basis, the solid electrolyte, P(NPh‐b ‐NIm‐TFSI)–lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), through blending with LiTFSI, and the nanosilica composite electrolyte, P(NPh‐b ‐NIm‐TFSI)–LiTFSI–SiO2, through blending with LiTFSI and nanosilica, were prepared. The effects of the PILs and silica compositions on the properties, morphology, and ionic conductivity were investigated. The ionic conductivity was enhanced by an order of magnitude compared to that of polyelectrolytes with lower PIL compositions. In addition, the ionic conductivity of the nanosilica composite polyelectrolyte was obviously improved compared with that of the P(NPh‐b ‐NIm‐TFSI)–LiTFSI polyelectrolyte and increased progressively up to a maximum with increasing silica content when SiO2 was 10 wt % or lower. The best conductivity of the P(NPh‐b ‐NIm‐TFSI)–20 wt % LiTFSI–10 wt % SiO2 composite electrolyte with 7.7 × 10?5 S/cm at 25 °C and 1.3 × 10?3 S/cm at 100 °C were obtained, respectively. All of the polyelectrolytes exhibited suitable electrochemical stability windows. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44884.  相似文献   

10.
A comb‐like polyether, poly(3‐2‐[2‐(2‐methoxyethoxy)ethoxy]ethoxymethyl‐3′‐methyloxetane) (PMEOX), was reacted with hexamethylene diisocyanate and extended with butanediol in a one‐pot procedure to give novel thermoplastic elastomeric poly(ether urethane)s (TPEUs). The corresponding hybrid solid polymer electrolytes were fabricated through doping a mixture of TPEU and poly(vinylidene fluoride) with three kinds of lithium salts, LiClO4, LiBF4 and lithium trifluoromethanesulfonimide (LiTFSI), and were characterized using differential scanning calorimetry, thermogravimetric analysis and Fourier transform infrared spectroscopy. The ionic conductivity of the resulting polymer electrolytes was then assessed by means of AC impedance measurements, which reached 2.1 × 10?4 S cm?1 at 30 °C and 1.7 × 10?3 S cm?1 at 80 °C when LiTFSI was added at a ratio of O:Li = 20. These values can be further increased to 3.5 × 10?4 S cm?1 at 30 °C and 2.2 × 10?3 S cm?1 at 80 °C by introducing nanosized SiO2 particles into the polymer electrolytes. Copyright © 2006 Society of Chemical Industry  相似文献   

11.
Two types of 2D nanofillers, α‐zirconium phosphate (α‐ZrP) and graphene oxide (GO), were synthesized and incorporated into poly(vinyl alcohol) (PVA) with 1 wt % loading level at various α‐ZrP:GO (Z:G = 5:1, 2:1, 1:1, 1:2, and 1:5) ratios. The resulting nanocomposites were tested for barrier properties by casting films from solution. The structure and morphology of α‐ZrP and GO were characterized by Fourier‐transform infrared spectroscopy, atomic force microscope, scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction, which demonstrated successful preparation of exfoliated α‐ZrP and GO. The physical characteristics of the nanocomposite films, including thermal, mechanical, and gas barrier properties were investigated. The results indicated that the tensile strength, Young's modulus, and elongation at break of the PVA nanocomposite films with Z:G hybrid nanofiller improved compared to neat PVA. The glass transition temperature, melting temperature, and crystallinity also increased. Consequently there appears to be a synergistic effect with these two types of nanofillers that formed a specific macro structure of a “wall.” This macrostructure resulted in excellent O2 gas barrier properties with the PVA/Z:G‐5:1 nanocomposite films having the best performance. The of the PVA/Z:G‐5:1 nanocomposite decreased from 1.835 × 10?16 to 0.587 × 10?16 cm3 cm cm?2 s?1 Pa?1 compared with neat PVA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46455.  相似文献   

12.
The interaction behavior of solid‐state polymer electrolytes composed of poly(ethylene oxide) (PEO)/novolac‐type phenolic resin and lithium perchlorate (LiClO4) was investigated in detail by DSC, FTIR, ac impedance, DEA, solid‐state NMR, and TGA. The hydrogen bonding between the hydroxyl group of phenolic and ether oxygen of the PEO results in higher basicity of the PEO. The higher basicity of the ether group can dissolve the lithium salts more easily and results in a greater fraction of “free” anions and thus higher ionic conductivity. DEA results demonstrated that addition of the phenolic increases the dielectric constant because of the partially negative charge on the ether group induced by the hydrogen bonding interaction between ether oxygen and the hydroxyl group. The study showed that the blend of PEO(100)/LiClO4(25)/phenolic(15) possesses the highest ionic conductivity (1.5 × 10?5 S cm?1) with dimensional stability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1207–1216, 2004  相似文献   

13.
Lithium ion conductors with garnet‐type structure are promising candidates for applications in all solid‐state lithium ion batteries, because these materials present a high chemical stability against Li metal and a rather high Li+ conductivity (10?3–10?4 S/cm). Producing densified Li‐ion conductors by lowering sintering temperature is an important issue, which can achieve high Li conductivity in garnet oxide by preventing the evaporation of lithium and a good Li‐ion conduction in grain boundary between garnet oxides. In this study, we concentrate on the use of sintering additives to enhance densification and microstructure of Li7La3ZrNbO12 at sintering temperature of 900°C. Glasses in the LiO2‐B2O3‐SiO2‐CaO‐Al2O3 (LBSCA) and BaO‐B2O3‐SiO2‐CaO‐Al2O3 (BBSCA) system with low softening temperature (<700°C) were used to modify the grain‐boundary resistance during sintering process. Lithium compounds with low melting point (<850°C) such as LiF, Li2CO3, and LiOH were also studied to improve the rearrangement of grains during the initial and middle stages of sintering. Among these sintering additives, LBSCA and BBSCA were proved to be better sintering additives at reducing the porosity of the pellets and improving connectivity between the grains. Glass additives produced relative densities of 85–92%, whereas those of lithium compounds were 62–77%. Li7La3ZrNbO12 sintered with 4 wt% of LBSCA at 900°C for 10 h achieved a rather high relative density of 85% and total Li‐ion conductivity of 0.8 × 10?4 S/cm at room temperature (30°C).  相似文献   

14.
Poly(vinyl alcohol) (PVA) was used to prepare nanocomposites of multi‐wall carbon nanotubes (MWCNT) and functionalized carbon nanotubes (MWCNT‐NH2) in existence of 2‐carboxyethyl acrylate oligomers (CEA). Radiation‐induced crosslinking of the prepared matrix was carried out via gamma and ion beam irradiation. A comparative study of gamma and ion beam irradiation effect on the electrical conductivity of nanocomposite was conducted. The gelation of the gamma irradiated matrix outperforms the ion beam irradiated matrix. The order of gelation is PVA > (PVA/CEA) > (PVA/CEA)‐MWCNT > (PVA/CEA)‐MWCNT‐NH2. There is a significant reduction in the swelling of the nanocomposite. The formation of nanocomposites was confirmed by scanning electron microscopy, energy‐dispersive X‐ray (EDX) and FTIR examinations. The direct current electrical properties of PVA/nanocomposites are examined at room temperature by applying electric voltage from 1 to 20 V. The results revealed that the electrical conductivity is increased by adding the carbon nanotubes and irradiation by gamma and ion beam. At an applied electric voltage 20 V, in the electrical conductivity of the unirradiated PVA was from 9.20 × 10?8 S cm?1. After adding MWCNT an increase up to 4.70 × 10?5 S cm?1 was observed. While after ion beam irradiation, a further increase up to 9.30 × 10?5 S cm?1 was noticed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46146.  相似文献   

15.
The preparation and characterization of a polymer electrolyte films containing 80 wt % of poly (ethylene oxide) (PEO) and 20 wt % epoxidized natural rubber (ENR50) complexed with LiCF3SO3 has been reported. The ac impedance data showed good conducting properties of the solid polymer electrolyte (SPE) films. The greatest room temperature ionic conductivity of 7.5 × 10?5 S cm?1 was obtained at 25 wt % of LiCF3SO3 salt. This result has been supported by differential scanning calorimeter and X‐ray diffraction analysis. Analysis differential scanning calorimetry showed the relative percentage of crystallinity and Tm of PEO decreased with the increasing wt % of LiCF3SO3. Analysis with X‐ray diffraction suggested that the semicrystalline nature of PEO turned to amorphous due to the presence of LiCF3SO3. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

16.
Synthesis and ion transport characterization of a new K+-ion conducting nano-composite polymer electrolytes (NCPEs): (1?x) [70PEO:30KBr] + x SiO2, where 0 < x < 20 wt%, are reported. The present NCPEs have been cast using a novel hot-press technique in place of the traditional solution cast method. The conventional solid polymer electrolyte (SPE) composition: (70PEO:30KBr), identified as the highest conducting composition at room temperature, has been used as first-phase host matrix and nano-size (~8 nm) particles of SiO2 as second-phase dispersoid. As a consequence of dispersal of SiO2 in SPE host, two orders of conductivity enhancement have been observed in NCPE composition: [95(70PEO:30KBr) + 5SiO2] and this has been referred to as optimum conducting composition (OCC). The polymer-salt/nano-filler SiO2 complexation and thermal properties characterization were done with the help of XRD, FTIR, SEM, DSC and TGA studies. The ion transport behavior in NCPEs have been discussed on the basis of experimental measurements on some basic ionic parameters, viz. conductivity (σ), ionic mobility (μ), mobile ion concentration (n), ionic transference number (t ion), etc. The temperature-dependent conductivity studies of NCPE OCC have been done and activation energy (E a) value was determined using log σ?1/T Arrhenius plot.  相似文献   

17.
Polymer electrolytes of poly(ethylene oxide) matrix with lithium imide salt LiN(CF3SO2)2 were prepared by casting from solution. Thin films with compositions corresponding to molar ratios 6:1, 3:1 and 2:1 EO:Li were investigated by impedance spectroscopy, impedance spectroscopy simultaneous with polarizing microscope observation, X-ray diffraction and differential scanning calorimetry. The presence of PEO:LiTFSI stoichiometric complexes was found to significantly decrease conductivity at temperature of crystallization, which indicates that those complexes should be regarded as poorly conductive. Changes of properties of amorphous phase related to crystallization were also observed. Crystallization induced phase segregation, which in some cases caused considerable shift of the glass transition temperature of amorphous phase remaining in a semicrystalline system. For PEO:LiTFSI electrolyte with molar ratio of 3:1 EO:Li this effect was found to be responsible for enhancement of conductivity of semicrystalline sample in respect to the amorphous one, which was observed at low temperatures. Phase separation involving precipitation of LiTFSI salt was also found to be a likely explanation for significant enhancement of conductivity for PEO:LiTFSI 2:1 electrolyte subjected to rapid cooling below the glass transition temperature.  相似文献   

18.
Three new polymeric aromatic lithium sulfonylimides were used as salts in high molecular weight poly(ethylene oxide) (PEO) electrolytes. Their conductivity and electrochemical stability behaviors were investigated. The electrolytes with lithium poly[4,4′‐(hexafluoroisopropylidene)diphenoxy]sulfonylimide (LiPHFIPSI) showed a better conductive performance compared with the other two lithium salts. The best conductivity was obtained for PEO/LiPHFIPSI EO/Li = 16 (1.90 × 10?4 S/cm at 60°C). Thermal analysis indicated that the salts effectively decreased the crystallinity of PEO. Moreover, the electrolytes also had good electrochemical stability and their oxidative potential was to 5.5 V versus Li/Li+. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1802–1805, 2002  相似文献   

19.
A new poly(propylene carbonate)/poly(ethylene oxide) (PEO/PPC) polymer electrolytes (PEs) have been developed by solution‐casting technique using biodegradable PPC and PEO. The morphology, structure, and thermal properties of the PEO/PPC polymer electrolytes were investigated by scanning electron microscopy, X‐ray diffraction, and differential scanning calorimetry methods. The ionic conductivity and the electrochemical stability window of the PEO/PPC polymer electrolytes were also measured. The results showed that the Tg and the crystallinity of PEO decrease, and consequently, the ionic conductivity increases because of the addition of amorphous PPC. The PEO/50%PPC/10%LiClO4 polymer electrolyte possesses good properties such as 6.83 × 10?5 S cm?1 of ionic conductivity at room temperature and 4.5 V of the electrochemical stability window. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

20.
New composite polymer gels were obtained from cellulose triacetate (CTA), N‐methyl‐N′‐propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr1,3TFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Analysis by differential scanning calorimeter and scanning electron microscope showed that the ionic gel consisting of CTA, Pyr1,3TFSI, and LiTFSI formed a completely homogeneous phase at the molar ratio of CTA/Pyr1,3TFSI/LiTFSI = 1/3/1.5. The ionic conductivity of the polymer gel was significantly enhanced by the presence of LiTFSI. FTIR study strongly implies that the interaction of lithium ion with the carbonyl group of CTA could be responsible for the increase in conductivity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

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