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1.
Hybrid polymer dry electrolytes comprised of poly(ethylene oxide) (PEO), polyacrylonitrile (PAN), and LiClO4 were investigated. The impedance spectroscopy showed that the effect of PAN on the ion conductivity of PEO‐based electrolytes depends on the concentration of lithium salt. When the mole ratio of lithium to oxygen is 0.062 (15%LiClO4‐PEO), adding PAN will increase the ionic conductivity. Differential scanning calorimetry, NMR, and IR data suggested that the enhanced conductivity was due to both the decreasing of the PEO crystallinity and increasing of the degree of ionization of lithium salt. There was obviously no interaction between PAN and lithium ions, and PAN acts as a reinforcing filler, and hence contributes to the mechanical strength besides reducing the crystallinity of the polymer electrolytes. When the LiClO4‐PEO‐PAN hybrid polymer electrolyte was heated at 200°C under N2, PAN crosslinked partially, which further decreased the crystallinity of PEO and increased the ionic conductivity, and at the same time prevented the recrystallization of PEO upon sitting at ambient environment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1530–1540, 2006  相似文献   

2.
We report the synthesis of all‐solid‐state polymeric electrolytes based on electrospun nanofibers. These nanofibers are composed of polyethylene oxide (PEO) as the matrix, lithium perchlorate (LiClO4) as the lithium salt and propylene carbonate (PC) as the plasticizer. The effects of the PEO, LiClO4 and PC ratios on the morphological, mechanical and electrochemical characteristics were investigated using the response surface method (RSM) and analysis of variance test. The prepared nanofibrous electrolytes were characterized using SEM, Fourier transform infrared, XRD and DSC analyses. Conductivity measurements and tensile tests were conducted on the prepared electrolytes. The results show that the average diameter of the nanofibers decreased on reduction of the PEO concentration and addition of PC and LiClO4. Fourier transport infrared analysis confirmed the complexation between PEO and the additives. The highest conductivity was 0.05 mS cm?1 at room temperature for the nanofibrous electrolyte with the lowest PEO concentration and the highest ratio of LiClO4. The optimum nanofibrous electrolyte showed stable cycling over 30 cycles. The conductivity of a polymer film electrolyte was 29 times lower than that of the prepared nanofibrous electrolyte with similar chemical composition. Furthermore, significant fading in mechanical properties was observed on addition of the PC plasticizer. The results obtained imply that further optimization might lead to practical uses of nanofibrous electrolytes in lithium ion batteries. © 2019 Society of Chemical Industry  相似文献   

3.
The solid polymeric nanocomposite electrolyte (SPNE) films based on the blend of amorphous poly(methyl methacrylate) (PMMA) and semicrystalline poly(ethylene oxide) (PEO) (PMMA:PEO = 80:20 wt %) doped with lithium perchlorate (LiClO4) salt and montmorillonite (MMT) clay nanofiller were prepared by classical solution cast, ultrasonic assisted solution cast and ultrasonication along with microwave irradiated solution cast followed by melt‐pressing methods. The X‐ray diffraction study of these electrolytes revealed the amorphous behavior with intercalated MMT structures. The suppressed crystallinity of PEO in the blend electrolyte complexes confirmed the existence of single discrete PEO chains confined within the PMMA domains. The dielectric relaxation spectroscopy of these materials was performed over the frequency range 20 Hz to 1 MHz, at ambient temperature. The presence of a singular relaxation peak in the loss tangent and electric modulus spectra of these electrolytes confirms a coupled cooperative chain segmental dynamics of the blend polymer owing to their miscible amorphous morphology. The behavior of transient complexes formed between the polymers functional groups, lithium cations and the intercalated MMT nanoplatelets was explored. The ambient temperature ionic conductivity of these electrolytes depends on the structural dynamics and the sample preparation methods. It is revealed that the presence of PEO in the PMMA matrix mainly governs the structural, dielectric, and ionic properties of these SPNE films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41311.  相似文献   

4.
The polymer nanocomposite (PNC) films consisted of poly(ethylene oxide) (PEO) and sodium cations montmorillonite (MMT) clay were prepared by aqueous solution casting and direct melt press compounding techniques, whereas the films of PEO with trimethyl octadecyl ammonium cations organo‐modified montmorillonite (OMMT) clay were formed by melt pressed technique. The clay concentrations in the nanocomposites used are 1, 2, 3, 5, 10, and 20 wt % of the PEO weight. The X‐ray diffraction patterns of these nanocomposites were measured in the angular range (2θ) of 3.8–30°. The values of basal spacing d001 of MMT/OMMT, clay gallery width Wcg, d‐spacings of PEO crystal reflections d120 and d112, and their corresponding crystallite size L, and the peaks intensity I (counts) were determined for these nanocomposites. Results reveal that the nanocomposites have intercalated clay structures and the amount of intercalation increases with the increase of clay concentration. As compared to melt pressed PEO–MMT nanocomposites, the amount of clay intercalation is higher in aqueous solution cast nanocomposites. At 20 wt % MMT dispersion in PEO matrix, the solution cast PEO–MMT nanocomposite almost changes into amorphous phase. The melt press compounded PEO–OMMT films show more intercalation as compared to the PEO–MMT nanocomposites prepared by same technique. In melt pressed nanocomposites, the PEO crystalline phase significantly reduces when clay concentration exceeds 3 wt %, which is evidenced by the decrease in relative intensity of PEO principal crystalline peaks. The effect of interactions between the functional group (ethylene oxide) of PEO and layered sheets of clay on both the main crystalline peaks of PEO was separately analyzed using their XRD parameters in relation to structural conformations of these nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39898.  相似文献   

5.
The nanocomposite films comprising polymer blends of poly(vinyl alcohol) (PVA), poly(vinyl pyrrolidone) (PVP), poly(ethylene oxide) (PEO), and poly(ethylene glycol) (PEG) with montmorillonite (MMT) clay as nanofiller were prepared by aqueous solution casting method. The X‐ray diffraction studies of the PVA–x wt % MMT, (PVA–PVP)–x wt % MMT, (PVA–PEO)–x wt % MMT and (PVA–PEG)–x wt % MMT nanocomposites containing MMT concentrations x = 1, 2, 3, 5 and 10 wt % of the polymer weight were carried out in the angular range (2θ) of 3.8–30°. The values of MMT basal spacing d001, expansion of clay gallery width Wcg, d‐spacing of polymer spherulite, crystallite size L and diffraction peak intensity I were determined for these nanocomposites. The values of structural parameters reveal that the linear chain PEO and PEG in the PVA blend based nanocomposites promote the amount of MMT intercalated structures, and these structures are found relatively higher for the (PVA–PEO)–x wt % MMT nanocomposites. It is observed that the presence of bulky ester‐side group in PVP backbone restricts its intercalation, whereas the adsorption behavior of PVP on the MMT nanosheets mainly results the MMT exfoliated structures in the (PVA–PVP)–x wt % MMT nanocomposites. The crystallinities of the PEO and PEG were found low due to their blending with PVA, which further decreased anomalously with the increase of MMT concentration in the nanocomposites. The decrease of polymer crystalline phase of these materials confirmed their suitability in preparation of novel solid polymer nanocomposite electrolytes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40617.  相似文献   

6.
Wendy Loyens 《Polymer》2005,46(18):7334-7345
The present study demonstrates the use of a simple and versatile melt-compounding route to prepare NaClO4-containing poly(ethylene oxide) PEO/clay nanocomposites combining excellent mechanical properties with a competitive level of the ionic conductivity. The nanostructure and the resulting thermal, mechanical and conductive properties of the salt-containing PEO/clay nanocomposites were found to be highly sensitive to the clay type, i.e. aspect ratio of the clay, to the presence of an organic modifier in the intergallery spacing, and to the salt concentration. The highest increase of the shear storage modulus is obtained in the presence of single silicate layers, thus an exfoliated nanostructure, having a high aspect ratio. These structures are only obtained with an (polar) organically modified clay (Cloisite 30B), regardless of the presence of salt. The use of non-organically modified clays (Cloisite Na+ and Laponite) resulted in intercalated nanocomposites, with only a minor improvement in stiffness. A strong interaction between the Na+ from NaClO4 and the Cloisite 30B silicate layers might be responsible for an increased PEO crystallinity and resultant additional increase in stiffness. A mechanism is proposed whereby the Na+ ions are drawn away from the PEO phase, to be complexed by the silicate layers, or even ion-exchanged with modifier cations. The addition of clay did not greatly affect the ion conductivity below the melt temperature of PEO. At higher temperatures, the nanocomposites displayed only slightly lower conductivities compared to the PEO/NaClO4 complex, due to the presence of the clay platelets.  相似文献   

7.
A method to produce nanocomposite polymer electrolytes consisting of poly(ethylene oxide) (PEO) as the polymer matrix, lithium tetrafluoroborate (LiBF4) as the lithium salt, and TiO2 as the inert ceramic filler is described. The ceramic filler, TiO2, was synthesized in situ by a sol–gel process. The morphology and crystallinity of the nanocomposite polymer electrolytes were examined by scanning electron microscopy and differential scanning calorimetry, respectively. The electrochemical properties of interest to battery applications, such as ionic conductivity, Li+ transference number, and stability window were investigated. The room‐temperature ionic conductivity of these polymer electrolytes was an order of magnitude higher than that of the TiO2 free sample. A high Li+ transference number of 0.51 was recorded, and the nanocomposite electrolyte was found to be electrochemically stable up to 4.5 V versus Li+/Li. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2815–2822, 2003  相似文献   

8.
Comb-shaped graft polymers were synthesized and complexed with a LiCF3SO3 salt to form a new class of polymer electrolytes. The polymers based on an acrylonitrile-butadiene copolymer (NBR) have pendant, short-chain poly(ethylene oxide) (PEO) grafted onto a butadiene unit. The characteristics of these polymer electrolytes were investigated in terms of number of pendant EO groups and grafting degree in the graft copolymer. The maximum conductivity was observed at the optimum side PEO chain length, and the PEO chain length for the maximum conductivity decreased with an increase in the grafting degree. And a solid 7Li NMR relaxation technique was used to study the local environments and dynamics of the ions in the polymer electrolytes. The maximum conductivity value obtained from our study was three orders of magnitude higher than that of classical PEO-based electrolytes at ambient temperature. These improved low temperature conducting polymers with higher relative mechanical strength are expected to be suitable for practical applications, such as in rechargeable lithium batteries or electrochromic devices.  相似文献   

9.
The morphological, structural, dielectric and electrical properties of aqueous solution-cast prepared poly(ethylene oxide)–zinc oxide (PEO–ZnO) nanocomposite films have been investigated as a function of ZnO nanoparticle concentrations up to 5 wt%. Scanning electron microscopy (SEM) images of these films show that the morphology of pristine PEO aggregated spherulites changes into fluffy, voluminous and highly porous with dispersion of ZnO nanoparticles into the PEO matrix. X-ray diffraction (XRD) study confirms that the crystalline phase of PEO greatly reduces at 1 wt% ZnO, and it again increases gradually with further increase of ZnO concentration. The dielectric relaxation spectroscopy (DRS) over the frequency range 20 Hz–1 MHz reveals that the real part of complex dielectric permittivity at audio frequencies decreases non-linearly whereas it remains almost constant at radio frequencies for these polymeric nanocomposites. Dispersion of nanosize ZnO particles into the PEO matrix reduces the values of dielectric permittivity which also exhibits a correlation with the dispersivity of ZnO nanoparticles. The relaxation peaks observed in the dielectric loss tangent and electric modulus spectra reveal that the electrostatic interactions of nanoscale ZnO particles with the ethylene oxide functional dipolar group of PEO monomer units decrease the local chain segmental dynamics of the polymer. Real part of ac conductivity spectra of these films have been analyzed by power law fit over the audio and radio frequency regions, respectively, and the obtained dc conductivity values for these regions differ by more than two orders of magnitude. The temperature dependent relaxation time and dc conductivity values of the nanodielectric material obey the Arrhenius relation of activation energies and confirm a correlation between dc conductivity and PEO chain segmental motion which is exactly identical to the characteristics of solid polymer electrolytes. Results imply that these nanocomposite materials can serve as low permittivity flexible nanodielectric for radio frequency microelectronic devices and also as electrical insulator for audio frequency operating conventional devices in addition to their suitability in preparation of solid polymer electrolytes.  相似文献   

10.
In this study, the polyethylene oxide (PEO)/SiO2 nanoparticles (NPs) nanocomposite films with various SiO2 NPs concentrations were prepared using an in situ formation of NPs in the polymer matrix for self-cleaning antireflected surface applications. The effect of SiO2 NPs in PEO/SiO2 NPs nanocomposite films on the structural, morphological, chemical, thermal, optical, and electrical properties of PEO/SiO2 NPs nanocomposite films was performed. According to the x-ray diffraction and the differential scanning calorimetry analysis, the crystallinity degree of the nanocomposite films decreases by increasing the SiO2 NPs concentrations. The bandgap energy of PEO/SiO2 NPs nanocomposite films decreases from 3.95 to 3.55 eV as the SiO2 NPs concentration increases up to 10 wt.%. The average electrical conductivity of the PEO/SiO2 NPs nanocomposite films increases from 5.1 × 10−7 to 2.0 × 10−6 S/cm as the SiO2 NPs concentration increases up to 10 wt.%. The refractive index decreases to 1.64 at 550 nm for the PEO/SiO2 NPs nanocomposite films with 10 wt.% of SiO2 NPs, and the water contact angle decreases to around 0° after thermal treatment, which confirms that the PEO/SiO2 NPs nanocomposite films can be used as self-cleaning antireflected surfaces.  相似文献   

11.
The oligo(ethylene oxide) modified layered double hydroxide (LDH) prepared by template method was added as a nanoscale nucleating agent into poly(ethylene oxide) (PEO) to form PEO/OLDH nanocomposite electrolytes. The effects of OLDH addition on morphology and conductivities of nanocomposite electrolytes were studied using wide-angle X-ray diffractometer, polarized optical microscopy, differential scanning calorimetry and ionic conductivity measurement. The results show that the exfoliated morphology of nanocomposites is formed due to the surface modification of LDH layers with PEO matrix compatible oligo(ethylene oxide)s. The nanoscale dispersed OLDH layers inhibit the crystal growth of PEO crystallites and result in a plenty amount of intercrystalline grain boundary within PEO/OLDH nanocomposites. The ionic conductivities of nanocomposite electrolytes are enhanced by three orders of magnitude compared to the pure PEO polymer electrolytes at ambient temperature. It can be attributed to the ease transport of Li+ along intercrystalline amorphous phase. This novel nanocomposite electrolytes system with high conductivities will be benefited to fabricate the thin-film type of Li-polymer secondary battery.  相似文献   

12.
Solvents and electrolytes play an important role in the fabrication of dye‐sensitized solar cells (DSSCs). We have studied the poly(ethylene oxide)‐poly(methyl methacrylate)‐KI‐I2 (PEO‐PMMA‐KI‐I2) polymer blend electrolytes prepared with different wt % of the 2‐mercaptopyridine by solution casting method. The polymer electrolyte films were characterized by the FTIR, X‐ray diffraction, electrochemical impedance and dielectric studies. FTIR spectra revealed complex formation between the PEO‐PMMA‐KI‐I2 and 2‐mercaptopyrindine. Ionic conductivity data revealed that 30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I2 electrolyte can show higher conductivity (1.55 × 10?5 S cm?1) than the other compositions (20, 40, and 50%). The effect of solvent on the conductivity and dielectric of solid polymer electrolytes was studied for the best composition (30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I2) electrolyte using various organic solvents such as acetonitrile, N,N‐dimethylformamide, 2‐butanone, chlorobenzene, dimethylsulfoxide, and isopropanol. We found that ac‐conductivity and dielectric constant are higher for the polymer electrolytes processed from N,N‐dimethylformamide. This observation revealed that the conductivity of the solid polymer electrolytes is dependent on the solvent used for processing and the dielectric constant of the film. The photo‐conversion efficiency of dye‐sensitized solar cells fabricated using the optimized polymer electrolytes was 3.0% under an illumination of 100 mW cm?2. The study suggests that N,N‐dimethylformamide is a good solvent for the polymer electrolyte processing due to higher ac‐conductivity beneficial for the electrochemical device applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42489.  相似文献   

13.
Lithium ion-conducting polymer blend electrolytes based on chitosan and methylcellulose complexed with lithium tetrafluoroborate (LiBF4) were prepared by a solution-casting method. The features of complexation of the solid polymer electrolytes were studied using X-ray diffraction techniques. Electrical conductivity of the prepared films was measured as a function of frequency at a different temperature. The increased trend of the electrical conductivity with increasing temperature and salt concentration can be attributed to increasing the mobility and number of lithium ions, respectively. The polymer electrolyte system exhibited Arrhenius-type, temperature-dependence ion conductivity behavior. Optical properties such as optical band gap, tail due to localized states and complex refractive index were estimated for present polymer electrolyte system from optical absorption measurement in the wavelength region 190–1100 nm. It was found that the optical direct band gap values shifted to lower energies upon addition of LiBF4 salt up to 40 wt% dopant concentration, and showed an increasing tendency for a further increase in dopant concentration. The high refractive index for this composition (2.44–2.63) at visible wavelengths eminently suitable for optical applications.  相似文献   

14.
Composite polymer electrolytes (CPEs) based on poly (ethylene oxide) (PEO) (Mol.Wt ∼6×105) complexed with LiN(CF3SO2)2 lithium salt and SrBi4Ti4O15 ferroelectric ceramic filler have been prepared as films. Citrate gel technique and conventional solid state technique were employed for the synthesis of the ferroelectric fillers in order to study the effect of particle size of the filler on ionic conductivity of the polymer electrolyte. Characterization techniques such as X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron microscopy (SEM) and temperature dependant DC conductivity studies were taken for the prepared polymer composite electrolytes. The broadening of DTA endotherms on addition of ceramic fillers to the polymer salt complex indicated the reduction in crystallinity. An enhancement in conductivity was observed with the addition of SrBi4Ti4O15 as filler to the (PEO)8-LiN(CF3SO2)2 polymer salt complexes. Among the investigated samples (PEO)8-LiN(CF3SO2)2 +10 wt% SrBi4Ti4O15 (citrate gel) polymer composite exhibits a maximum conductivity.  相似文献   

15.
All solid-state poly(ethylene oxide) (PEO) nanocomposite electrolytes were made containing nanoscale fillers of layered double hydroxides (LDHs). Two kinds of oligo(ethylene oxide) modified LDHs were prepared by template method, and added into PEO/LiClO4 matrix (with EO/Li molar ratio of 8) to study the effect on the ionic conductivity of PEO/LDH nanocomposite electrolytes. The structures of the modified LDHs were characterized by infrared spectra, thermogravimetric analysis and wide-angle X-ray diffraction. The results show that the oligo(ethylene oxide) with phosphonate anion can be effectively intercalated into the gallery region of LDHs and formed as an organic-inorganic hybrid (PLDH). With enhanced compatibility of LDH sheets by oligo(ethylene oxide) surface modification, the PEO/PLDH nanocomposite exhibits fully exfoliation morphology. The well dispersed LDH layers in PEO/LiClO4/PLDH nanocomposite electrolytes rendering the formation of amorphous phase, results in an enhancement of ionic conductivity by three orders of magnitude compared to the pure PEO/LiClO4 polymer electrolyte. This novel nanocomposite electrolytes system with high ionic conductivity will be benefited to fabricate the thin-film type of Li-polymer secondary battery. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

16.
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   

17.
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   

18.
The transparent and flexible solid polymer electrolytes (SPEs) were fabricated from polyacrylonitrile‐polyethylene oxide (PAN‐PEO) copolymer which was synthesized by methacrylate‐headed PEO macromonomer and acrylonitrile. The formation of copolymer is confirmed by Fourier‐transform infrared spectroscopy (FTIR) measurements. The ionic conductivity was measured by alternating current (AC) impedance spectroscopy. Ionic conductivity of PAN‐PEO‐LiClO4 complexes was investigated with various salt concentration, temperatures and molecular weight of PEO (Mn). And the maximum ionic conductivity at room temperature was measured to be 3.54 × 10?4 S/cm with an [Li+]/[EO] mole ratio of about 0.1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 461–464, 2006  相似文献   

19.
The synthesis, diffraction patterns, thermal stability, and ionic conductivity properties of methacrylate‐type polymers are analyzed here to assess their feasibility as polymer electrolytes. From the parent polymer, poly (N,N‐dimethylaminoethylmethacrylate), herein labeled PDMAEMA, a protonated derivative was used to prepare polymer/Montmorillonite nanocomposites with various clay contents (1, 3, and 5 wt %). AC spectroscopy provided the ionic conductivity data for the polymers and clay–polymer nanocomposites. Evidences of nanocomposite formation are shown using transmission electron microscopy and wide‐angle X‐ray diffraction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

20.
Preparation of polypropylene/mica nanocomposites via in situ polymerization is investigated. The nanocomposites were successfully synthesized using a Ziegler‐Natta catalyst based on MgCl2/modified mica/TiCl4. Muscovite mica was organically modified with quaternary ammonium salt, and with triethylaluminum. The treatment with triethylaluminum increased the disorder in the stacking of clay layers, producing a more active catalyst for propylene polymerization, although the mica containing catalysts had lower activity than the standard one prepared without clay. The nanostructure of the composites was characterized by X‐ray diffraction. The results showed that part of the mica layers were exfoliated in the polymer matrix, although tactoids were still present. Small‐angle X‐ray scattering analysis was used to determine how mica and its concentration influence the size of the polymer nanocrystals. Differential scanning calorimetry was used to investigate both melting and crystallization temperatures, as well as the crystallinity of the nanocomposite samples. Thermogravimetric analysis showed that polypropylene/mica nanocomposites presented much higher thermal stability than the polypropylene without mica, which means that mica had a barrier effect against heat. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45587.  相似文献   

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