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1.
Despite the extensive employment of binary/ternary mixed-carbonate electrolytes (MCEs) for Li-ion batteries, the role of each ingredient with regards to the solvation structure, transport properties, and reduction behavior is not fully understood. Herein, we report the atomistic modeling and transport property measurements of the Gen2 (1.2 M LiPF6 in ethylene carbonate (EC) and ethyl methyl carbonate (EMC)) and EC-base (1.2 M LiPF6 in EC) electrolytes, as well as their mixtures with 10 mol% fluoroethylene carbonate (FEC). Due to the mixing of cyclic and linear carbonates, the Gen2 electrolyte is found to have a 60% lower ion dissociation rate and a 44% faster Li+ self-diffusion rate than the EC-base electrolyte, while the total ionic conductivities are similar. Moreover, we propose for the first time the anion–solvent exchange mechanism in MCEs with identified energetic and electrostatic origins. For electrolytes with additive, up to 25% FEC coordinates with Li+, which exhibits a preferential reduction that helps passivate the anode and facilitates an improved solid electrolyte interphase. The work provides a coherent computational framework for evaluating mixed electrolyte systems.

The different roles of the anion, cyclic and linear carbonates, and additive in mixed-carbonate electrolytes are revealed. The anion–solvent exchange mechanism and factors influencing the solid electrolyte interphase (SEI) formation are deciphered.  相似文献   

2.

Performance of dye-sensitized nano-crystalline TiO2 thin film-based photo-electrochemical solar cells (PECSCs) containing gel polymer electrolytes is largely governed by the nature of the cation in the electrolyte. Dependence of the photovoltaic performance in these quasi-solid state PECSCs on the alkaline cation size has already been investigated for single cation iodide salt-based electrolytes. The present study reports the ionic conductivity dependence on the nature of alkaline cations (counterion) in a gel polymer electrolyte based on binary iodides. Polyacrylonitrile-based gel polymer electrolyte series containing binary iodide salts is prepared using one of the alkaline iodides (LiI, NaI, KI, RbI, and CsI) and tetrapropylammonium iodide (Pr4NI). All the electrolytes based on binary salts have shown conductivity enhancement compared to their single cation counterparts. When combined with Pr4NI, each of the Li+, Na+, K+, Rb+, and Cs+ cation containing iodide salts incorporated in the gel electrolytes has shown a room temperature conductivity enhancement of 85.59, 12.03, 12.71, 20.77, and 15.36%, respectively. The conductivities of gel electrolytes containing binary iodide systems with Pr4NI and KI/RbI/CsI are higher and have shown values of 3.28, 3.43, and 3.23 mS cm−1, respectively at room temperature. The influence of the nature of counterions on the performance of quasi-solid state dye-sensitized solar cells is investigated by assembling two series of cells. All the binary cationic solar cells have shown more or less enhancements of open circuit voltage, short circuit current density, fill factor, and efficiency compared to their single cation counterparts. This work highlights the importance of employing binary cations (a large and a small) in electrolytes intended for quasi-solid state solar cells. The percentage of energy conversion efficiency enhancement shown for the PECSCs made with electrolytes containing Pr4NI along with Li+, Na+, K+, Rb+, and Cs+ iodides is 260.27, 133.65, 65.27, 25.32, and 8.36%, respectively. The highest efficiency of 4.93% is shown by the solar cell containing KI and Pr4NI. However, the highest enhancements of ionic conductivity as well as the energy conversion efficiency were exhibited by the PECSC made with Li+-containing binary cationic electrolyte.

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3.
Herein, we report the micellization and the clouding of a nonionic surfactant, poly(ethylene glycol) t-octylphenyl ether (Triton X-100), in aqueous solutions in the absence and presence of (chloride salt) electrolytes. In the absence and presence of electrolytes, the critical micelle concentration (CMC) of Triton X-100 was measured by surface tension measurements. Upon increasing the temperature as well as the concentration of electrolytes, the CMCs decreased. The surface properties and the thermodynamic parameters of the micellar systems were evaluated. From these evaluated thermodynamic parameters, it was found that in the presence of an electrolyte, the stability of the micellar system is high. The cloud points (CPs) of Triton X-100 were also measured in the absence and presence of metallic ions of electrolytes. Upon the addition of metallic ions of chloride salts (electrolytes), the decrease in CP values was observed and the order was found to be: K+ > Na+ > Li+ > NH+4.  相似文献   

4.
Solid polymer electrolyte membranes were prepared by complexing tetrapropylammoniumiodide (Pr4N+I?) salt with polyethylene oxide (PEO) plasticized with ethylene carbonate (EC), and these were used in photoelectrochemical (PEC) solar cells fabricated with the configuration glass/FTO/TiO2/dye/electrolyte/Pt/FTO/glass. The PEO/Pr4N+I?+I2?=?9:1 ratio gave the best room temperature conductivity for the electrolyte. For this composition, the plasticizer EC was added to increase the conductivity, and a further conductivity enhancement of four orders of magnitude was observed. An abrupt increase in conductivity occurs around 60–70 wt% EC; the room temperature conductivity was 5.4?×?10?7 S cm?1 for 60 wt% EC and 4.9?×?10?5 S cm?1 for the 70 wt% EC. For solar cells with electrolytes containing PEO/Pr4N+I?+I2?=?9:1 and EC, IV curves and photocurrent action spectra were obtained. The photocurrent also increased with increasing amounts of EC, up to three orders of magnitude. However, the energy conversion efficiency of this cell was rather low.  相似文献   

5.
Thermal stability, flammability, and electrochemical performances of the cyclic carbonate-based electrolytes [where γ-butyrolactone (GBL) is a main component (at least 50 vol.%) among of EC and PC with LiBF4] have been examined in comparison with contemporary (EC/EMC, 1:3 vol.%, 1 M LiPF6) electrolyte by DSC, accelerating rate calorimetry (ARC), AC impedance, and cyclic voltammetry (CV). This study shows that GBL-based electrolytes have perfect thermal stability and will improve Li-ion battery safety (including flammability) without performance trade-off with the accurate combination of active materials and separator. Several types of negative electrode materials (such as hard carbon, MCMB, and SWF) have been tested to evaluate GBL-based electrolyte influence on SEI formation and battery performance. Finally, GBL-based electrolytes show not only equal electrochemical performance in comparison to commonly used electrolytes (EC/EMC in this study) but it will notably improve battery safety.  相似文献   

6.
Zn-Ti-O composite thin film prepared on FTO by sol-gel technique is discovered presenting electrochromic behavior in electrolytes with Li+ ion (LiClO4) and K+ (KCl) as well. The observed EC colored/bleached switching is electrolyte dependent which is blue-green/transparent in LiClO4 and gray-blue/transparent in KCl, respectively. Accordantly, the respective most optical modulation (ΔT) between colored and bleached states is ~?32% (710 nm) in LiClO4 and ~?37% (600 nm) in KCl. The finding of appreciable steady EC durability with appealing visual optical contrast (ΔT) in conventionally fabricated Zn-Ti-O thin film using with bigger/heavier K+ electrolyte helps expanding the applicable components in EC device.  相似文献   

7.
A new plasticized nanocomposite polymer electrolyte based on poly (ethylene oxide) (PEO)-LiTf dispersed with ceramic filler (Al2O3) and plasticized with propylene carbonate (PC), ethylene carbonate (EC), and a mixture of EC and PC (EC+PC) have been studied for their ionic conductivity and thermal properties. The incorporation of plasticizers alone will yield polymer electrolytes with enhanced conductivity but with poor mechanical properties. However, mechanical properties can be improved by incorporating ceramic fillers to the plasticized system. Nanocomposite solid polymer electrolyte films (200–600 μm) were prepared by common solvent-casting method. In present work, we have shown the ionic conductivity can be substantially enhanced by using the combined effect of the plasticizers as well as the inert filler. It was revealed that the incorporating 15 wt.% Al2O3 filler in to PEO: LiTf polymer electrolyte significantly enhanced the ionic conductivity [σ RT (max)?=?7.8?×?10?6 S cm?1]. It was interesting to observe that the addition of PC, EC, and mixture of EC and PC to the PEO: LiTf: 15 wt.% Al2O3 CPE showed further conductivity enhancement. The conductivity enhancement with EC is higher than PC. However, mixture of plasticizer (EC+PC) showed maximum conductivity enhancement in the temperature range interest, giving the value [σ RT (max)?=?1.2?×?10?4 S cm?1]. It is suggested that the addition of PC, EC, or a mixture of EC and PC leads to a lowering of glass transition temperature and increasing the amorphous phase of PEO and the fraction of PEO-Li+ complex, corresponding to conductivity enhancement. Al2O3 filler would contribute to conductivity enhancement by transient hydrogen bonding of migrating ionic species with O–OH groups at the filler grain surface. The differential scanning calorimetry thermograms points towards the decrease of T g , crystallite melting temperature, and melting enthalpy of PEO: LiTf: Al2O3 CPE after introducing plasticizers. The reduction of crystallinity and the increase in the amorphous phase content of the electrolyte, caused by the filler, also contributes to the observed conductivity enhancement.  相似文献   

8.
The effect of cation on the performance of activated carbon (AC)/graphite capacitor has been studied. Electrolytes using Li+ and four kinds of quaternary alkyl ammonium cations have been picked up for this investigation. The relationship between the ionic radii of cations and the specific capacitance of AC negative electrode in corresponding electrolytes has been correlated. The state of Li+ dissolved in PC (propylene carbonate) solvent has also been clarified.  相似文献   

9.
Electric double-layer capacitors (EDLCs) are composed of two activated carbon (AC) electrodes and an electrolyte/separator, in which the ACs contain numbers of surface oxygen functionalities (SOFs). In this work, the effect of SOFs on the EDLC’s capacitance in non-aqueous electrolytes is studied by using a 1.0 m (molality) LiPF6 3:7 (wt.) ethylene carbonate-ethyl methyl carbonate electrolyte and a commercial activated carbon. Results show that the SOFs on one hand contribute to Faradic pseudocapacitance, and on the other hand adversely reduce the EDLC’s performances, including the initial reversibility, coulombic efficiency, and capacitance retention. It is found that the AC behaves significantly different in the Li/AC half cells and in the AC/AC full cells and that the SOF’s pseudocapacitance increases with widening the EDLC’s operating voltage. The latter is attributed to the large-voltage hysteresis of the redox of SOFs. In this paper, the AC’s unique behaviors in Li salt electrolyte are presented, and a possible mechanism for the observed behaviors is proposed.  相似文献   

10.
A random copolymer of ethylene oxide with CO2, namely, poly(ethylene carbonate/ethylene oxide) (P(EC/EO)), has been synthesized as a novel candidate for polymer electrolytes. Electrolyte composed of P(EC/EO) and lithium bis(fluorosulfonyl)imide has an ionic conductivity of 0.48 mS cm−1 and a Li transference number (t +) of 0.66 at 60 °C. To study ion‐conductive behavior of P(EC/EO)‐based electrolytes, the Fourier transform infrared (FT‐IR) technique is used to analyze the interactions between Li+ and functional groups of the copolymer. The carbonate groups may interact preferentially with Li+ rather than the ether groups in P(EC/EO). This study suggests that copolymerization of carbonate and flexible ether units can realize both high conductivity and t + for polymer electrolytes. High‐performance P(EC/EO) electrolyte is expected to be a candidate material for use in all‐solid‐state batteries.

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11.
Electrolytes of 1 M blend salts (LiPF6 and tetraethylammonium tetrafluoroborate, Et4NBF4) have been investigated in supercapacitor battery system with composite LiMn2O4 and activated carbon (AC) cathode, and Li4Ti5O12 anode. The results obtained with the blend salts electrolytes are compared with those obtained with cells build using standard 1 M LiPF6 dissolved in ethylene carbonate + dimethyl carbonate + ethyl (methyl) carbonate (EC + DMC + EMC, 1:1:1 wt.%) as electrolyte. It is found that the blend salts electrolyte performs better on both electrochemical and galvanostatic cycling stability, especially cycled at 4 C rate. When the concentration of LiPF6 is 0.2 M and Et4NBF4 is 0.8 M, the capacity retention of the battery is 96.23% at 4 C rate after 5,000 cycles, much higher than that of the battery with standard 1 M LiPF6 electrolyte, which is only 62.35%. These results demonstrate that the blend salts electrolyte can improve the galvanostatic cycling stability of the supercapacity battery. Electrolyte of 0.2 M LiPF6 + 0.8 M Et4NBF4 in EC + DMC + EMC (1:1:1 wt.%) is a promising electrolyte for (LiMn2O4 + AC)/Li4Ti5O12.  相似文献   

12.
In the present work, nanofibrous composite polymer electrolytes consist of polyethylene oxide (PEO), ethylene carbonate (EC), propylene carbonate (PC), lithium perchlorate (LiClO4), and titanium dioxide (TiO2) were designed using response surface method (RSM) and synthesized via an electrospinning process. Morphological properties of the as‐prepared electrolytes were studied using SEM. FTIR spectroscopy was conducted to investigate the interaction between the components of the composites. The highest room temperature ionic conductivity of 0.085 mS.cm?1 was obtained with incorporation of 0.175 wt. % TiO2 filler into the plasticized nanofibrous electrolyte by EC. Moreover, the optimum structure was compared with a film polymeric electrolyte prepared using a film casting method. Despite more amorphous structure of the film electrolyte, the nanofibrous electrolyte showed superior ion conductivity possibly due to the highly porous structure of the nanofibrous membranes. Furthermore, the mechanical properties illustrated slight deterioration with incorporation of the TiO2 nanoparticles into the electrospun electrolytes. This investigation indicated the great potential of the electrospun structures as all‐solid‐state polymeric electrolytes applicable in lithium ion batteries.  相似文献   

13.
Poly (acrylate-co-imide)-based gel polymer electrolytes are synthesized by in situ free radical polymerization. Infrared spectroscopy confirms the complete polymerization of gel polymer electrolytes. The ionic conductivity of gel polymer electrolytes are measured as a function of different repeating EO units of polyacrylates. An optimal ionic conductivity of the poly (PEGMEMA1100-BMI) gel polymer electrolyte is determined to be 4.8 × 10–3 S/cm at 25 °C. The lithium transference number is found to be 0.29. The cyclic voltammogram shows that the wide electrochemical stability window of the gel polymer electrolyte varies from −0.5 to 4.20 V (vs. Li/Li+). Furthermore, we found the transport properties of novel gel polymer electrolytes are dependent on the EO design and are also related to the rate capability and the cycling ability of lithium polymer batteries. The relationship between polymer electrolyte design, lithium transport properties and battery performance are investigated in this research.  相似文献   

14.
The polymer electrolytes composed of poly(acrylonitrile‐co‐lithium methacrylate) [P(AN‐co‐LiMA)], ethylene carbonate (EC), and LiClO4 salts have been prepared. The ion groups in the P(AN‐co‐LiMA) were found to prevent EC from crystallization through their ion–dipole interactions with the polar groups in the EC. This suppression of the EC crystallization could lead to the enhancement of the ion conductivity at subambient temperature. The polymer electrolytes based on the PAN ionomer with 4 mol % ion content exhibited ion conductivities of 2.4 × 10−4 S/cm at −10°C and 1.9 × 10−3 S/cm at 25°C by simply using EC as a plasticizer. In the polymer electrolytes based on the PAN ionomer, ion motions seemed to be coupled with the segmental motions of the polymer chain due to the presence of the ion–dipole interaction between the ion groups in the ionomer and the polar groups in the EC, while the ion transport in the PAN‐based polymer electrolytes was similar to that of the liquid electrolytes. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 247–252, 1999  相似文献   

15.
It is established that the reaction of recharging trioxalate complexes of ruthenium(III) occurs in the case of solutions with excess supporting oxalate salts of alkali metals K+, Na+, and Cs+ in reversible conditions, and limiting recharge currents are caused by diffusion. At the same time, values of diffusion coefficients for complex anion [Ru(C2O4)3]–3 decrease by almost two times upon going from potassium to sodium and cesium electrolytes. Substantial differences in the limiting currents in solutions containing excess amounts of the above salts are explained by the formation, at least in the case of cesium and sodium electrolytes, of ionic associates whose reduction rate at a fixed potential is lower than that of nonassociated anion [Ru(C2O4)3]–3. With solution dilution by supporting salts, transition is observed from reversible recharge conditions to absolutely irreversible conditions and a change in the above sequence of the effect of supporting cations on the recharge rate; at a fixed potential, the process decelerates in the series Cs+ > K+ > Na+. The reduction wave of the ruthenium(II) oxalate complexes in solutions with excess supporting electrolyte happens to depend on pH and, probably, is determined by simultaneous formation of adsorbed atoms of hydrogen (or ruthenium hydride) on atoms of ruthenium(0).  相似文献   

16.
The structural and electric properties of chitosan electrolytes doped by three different ammonium salts [CH3COONH4, NH4Cl, and (NH4)2SO4] were discussed. The chitosan electrolytes were prepared by solution casting technique. The results show that the addition of ammonium salts leads to: The formation of complexation between ammonium salts and chitosan matrix, the destruction of crystal forms, and the enhancement of amorphous nature. With the rise of salt content, both the glass transition temperature and the activation energy show a “V”‐type trend, whereas the conductivity exhibits a reverse trend. For different ammonium salts, the electric properties of the chitosan electrolyte are different due to the Coulomb force between anion of salts and functional groups. The CH3COONH4 doped chitosan electrolyte exhibits the optimum electric properties, whereas those of (NH4)2SO4 doped chitosan electrolyte are worst. The chitosan electrolyte doped with 40 wt % CH3COONH4 has the lowest glass transition temperature of 369 K, the lowest activation energy of 0.19 eV, and the highest ionic conductivity of 2.87 × 10?4 S cm?1 at room temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 880–885, 2010  相似文献   

17.
Porous carbon materials with high surface area and different pore structure have been successfully prepared by phenolic resin combined with polyvinyl alcohol (PVA) and KOH as activation agents. The surface morphology, structure, and specific surface area of the carbon materials were studied by scanning electron microscopy, X-ray diffraction, and nitrogen sorption measurement, respectively. Furthermore, the effects of specific surface area, pore structure, and electrolyte on electrochemical properties were investigated by galvanostatic charge–discharge measurement. The results show that KOH–PVA-activated carbon materials display specific capacitance as high as 218 F?g?1 in 30 wt.% KOH aqueous electrolyte, 147 F?g?1 in 1 M LiPF6/(ethylene carbonate (EC) + dimethyl carbonate) (1:1?v/v), and 115 F?g?1 in 1 M Et3MeNBF4/propylene carbonate organic electrolyte, respectively. In addition, the carbon materials demonstrate long-term cycle stability, especially the AK3P-0.30 in aqueous electrolyte and the AK2P-0.30 with excellent rate capability in organic electrolyte. These reveal that the existence of a micro-mesoporous structure of activated carbon is beneficial to store energy in an aqueous supercapacitor and broad pore size distribution of activated carbon is favorable to energy storage in an organic supercapacitor. The carbon materials with pore size distribution in different ranges improve the electrochemical performance of supercapacitor in different electrolytes. A new pore-expand agent (PVA combining with KOH) was used to obtain porous carbons with enhanced properties for supercapacitor.  相似文献   

18.
High-performance and low-cost electrochemical capacitors (ECs) are essential for large-scale applications in energy storage. In this work, the specific capacitance of active carbon (AC) electrode was significantly improved through the combination of introducing functional groups on the surface of AC and adding redox-active molecules (K3Fe(CN)6) into 2?M KOH aqueous electrolytes. The surface-oxygen functionalized AC (FAC) was synthesized using HNO3 echoed as the electrode and 2?M KOH with 0.1?M K3Fe(CN)6 as the electrolyte. The surface functional groups of the AC not only contribute to the pseudocapacitance but also increase the active sites of the electrode/electrolyte interface, which enhances the electrochemical activity of the Fe(CN)63?/Fe(CN)64? redox pair, thus leading to high capacitance. In the redox electrolyte, the specific capacitance was much higher in 229.17?F?g?1 (1?A?g?1) achieved for those FAC than in raw AC (only 147.06?F?g?1). Similarly, the FAC electrode suggested high energy density and extended cycling stability in the KOH?+?K3Fe(CN)6 electrolyte.  相似文献   

19.
In the present work, boron-doped multicomponent gel polymer electrolytes composed of host polymer, sulfonated polysulfone (SPSU) and the additives; ionic liquid, 1-ethyl-3-methyl-imidazolium tetrafluoroborate (IL), H3BO3, polyphosphoric acid (PPA) were prepared. Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) techniques were used to characterize the sulfonated polysulfone-based electrolytes. Ion conductivity of these gel electrolytes were studied by dielectric impedance analyzer within the temperature from ?20 to 100°C. The ionic conductivity of the SPSU-5IL-1PPA and SPSU-5IL-1H3BO3-1PPA were measured as 4.8 × 10?3 and 9 × 10?4 S cm?1, respectively. Supercapacitor having activated carbon-based composite electrode and electrolyte was constructed with the configuration: Al/C/electrolyte/C/Al. The electrochemical properties and ion transfer characteristics of the supercapacitor were investigated by the cyclic voltammetry (CV). Galvanostatic charge—discharge experiments exhibited good electrochemical reversibility and produced a specific capacitance value of 120 F g?1 at 1 A g?1. The symmetric supercapacitor system was retained almost 85% of its initial activity after 1000 cycle.  相似文献   

20.
New polymer electrolytes based on poly(ester diacrylate) (PEDA), LiClO4, and additives of ethylene carbonate (EC) have a Li+ ion conductivity comparable with that of liquid electrolytes. The conductivity first decreases by an order of magnitude at an EC content of ??5 wt.% and then increases by three orders of magnitude at 55 wt.% EC. To understand the nature of this extreme dependence, a comprehensive study using IR spectroscopy and quantum chemical modeling was performed. It was found that the changes in the IR spectra with an increase in the EC content were stepwise to form at final stage the same absorption peaks that were observed for the IR spectra of LiClO4 solutions in EC. The density functional theory studies of the energy and structures of mixed Li+ complexes and LiClO4 with EC and PEDA, which was modeled by oligomers H-((CH2)2COO(CH2)2O) n -CH3 (n ?? 10) showed a stronger binding of the lithium ion with the polymer matrix in the mixed complexes with one EC molecule at a low content of EC resulting, most likely, in a decrease in the conductivity. Less stable mixed complexes with three EC molecules can be formed with an increase in the EC fraction and they become unstable in EC excess because of the transition of the Li+ ions to solvate complexes containing only EC molecules.  相似文献   

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