An improved preparation of 1-methyl-3-propylimidazolium iodide and its application in dye-sensitized solar cells

In this paper, we reported an improved preparation of 1-methyl-3-propylimidazolium iodide (MPII), which was the alkylation reaction of n-propyl iodide and 1-methylimidazole under solvent-free conditions by Teflon-lined, stainless autoclaves. It was shown that the resulting MPII was high pure, the conversion rate of 1-methylimidazole was close to 100% and the procedure was simple and eco-friendly. Moreover, the apparent diffusion coefficients of triiodide and iodide in the mixture with different ratios of MPII and 3-methoxypropionitrile were demonstrated by cyclic voltammetry using a Pt ultramicroelectrode. The dye-sensitized solar cells with the electrolyte, which was composed of 0.13 M I₂, 0.10 M LiI, 0.50 M 4-tert-butylpyrdine in the mixture of 3-methoxypropionitrile and MPII (weight ratio 0.65:1), gave short circuit photocurrent density of 14.82 mA/cm², open-circuit voltage of 0.69 V, and fill factor of 0.66, corresponding to the photoelectric conversion efficiency of 6.73% at the illumination (AM 1.5, 100 mW/cm²).     

Nonflammable gel electrolyte containing alkyl phosphate for rechargeable lithium batteries

A nonflammable polymeric gel electrolyte has been developed for rechargeable lithium battery systems. The gel film consists of poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP) swollen with lithium hexafluorophosphate (LiPF₆) solution in ternary solvent containing trimethyl phosphate (TMP). High ionic conductivity of 6.2 mS cm⁻¹ at 20 °C was obtained for the gel electrolyte consisting of 0.8 M LiPF₆/EC + DEC + TMP (55:25:20) with PVdF-HFP, which is comparable to that of the liquid electrolyte containing the same electrolytic salt. Addition of a small amount of vinylene carbonate (VC) in the gel electrolyte improved the rechargeability of a graphite electrode. The rechargeable capacity of the graphite in the gel containing VC was ca. 300 mAh g⁻¹, which is almost the same as that in a conventional liquid electrolyte system.     

Effects of addition of TiO2 nanoparticles on mechanical properties and ionic conductivity of solvent-free polymer electrolytes based on porous P(VdF-HFP)/P(EO-EC) membranes

To enhance the performance (i.e., mechanical properties and ionic conductivity) of pore-filling polymer electrolytes, titanium dioxide (TiO₂) nanoparticles are added to both a porous membrane and its included viscous electrolyte, poly(ethylene oxide-co-ethylene carbonate) copolymer (P(EO-EC)). A porous membrane with 10 wt.% TiO₂ shows better performance (e.g., homogeneous distribution, high uptake, and good mechanical properties) than the others studied and is therefore chosen as the matrix to prepare polymer electrolytes. A maximum conductivity of 5.1 × 10⁻⁵ S cm⁻¹ at 25 °C is obtained for a polymer electrolyte containing 1.5 wt.% TiO₂ in a viscous electrolyte, compared with 3.2 × 10⁻⁵ S cm⁻¹ for a polymer electrolyte without TiO₂. The glass transition temperature, T_g is lowered by the addition of TiO₂ (up to 1.5 wt.% in a viscous electrolyte) due to interaction between P(EO-EC) and TiO₂, which weakens the interaction between oxide groups of the P(EO-EC) and lithium cations. The overall results indicate that the sample prepared with 10 wt.% TiO₂ for a porous membrane and 1.5 wt.% TiO₂ for a viscous electrolyte is a promising polymer electrolyte for rechargeable lithium batteries.     

Solid-state Li/LiFePO4 polymer electrolyte batteries incorporating an ionic liquid cycled at 40 °C

The cycle behaviour and rate performance of solid-state Li/LiFePO₄ polymer electrolyte batteries incorporating the N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₃TFSI) room temperature ionic liquid (IL) into the P(EO)₂₀LiTFSI electrolyte and the cathode have been investigated at 40 °C. The ionic conductivity of the P(EO)₂₀LiTFSI + PYR₁₃TFSI polymer electrolyte was about 6 × 10⁻⁴ S cm⁻¹ at 40 °C for a PYR₁₃⁺/Li⁺ mole ratio of 1.73. Li/LiFePO₄ batteries retained about 86% of their initial discharge capacity (127 mAh g⁻¹) after 240 continuous cycles and showed excellent reversible cyclability with a capacity fade lower than 0.06% per cycle over about 500 cycles at various current densities. In addition, the Li/LiFePO₄ batteries exhibited some discharge capability at high currents up to 1.52 mA cm⁻² (2 C) at 40 °C which is very significant for a lithium metal-polymer electrolyte (solvent-free) battery systems. The addition of the IL to lithium metal-polymer electrolyte batteries has resulted in a very promising improvement in performance at moderate temperatures.     

P(DMS-co-EO)/P(EPI-co-EO) blend as a polymeric electrolyte

A new polymer electrolyte comprising the blend of poly(dimethylsiloxane-co-ethylene oxide) (P(DMS-co-EO)), and poly(epichlorohydrin-co-ethylene oxide) (P(EPI-co-EO)), with different concentrations of LiClO₄ is described. The polymer electrolyte was prepared by a solution-cast technique. The electrochemical properties were studied by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry techniques. The maximum ionic conductivity (σ=1.2×10⁻⁴ S cm⁻¹) was obtained for the P(DMS-co-EO)/P(EPI-co-EO) 15/85 and 20/80 blends with 6 wt.% LiClO₄. These same films had a wide electrochemical stability, higher than 5 V at room temperature. A stable passive layer at the interface between the polymer electrolyte and lithium metal was formed within the first few days and maintained during the follow storage period. UV-Vis absorption spectra of the blends showed a transparent polymer electrolyte in the visible region.     

Nanocomposite electrolytes with fumed silica in poly(methyl methacrylate): thermal,rheological and conductivity studies

Composite polymer electrolytes (CPEs), were prepared by adding hydrophilic fumed silica in different proportions upto 5 wt.% to gel polymeric electrolyte (GPE) comprising liquid electrolyte (1 M LiClO₄ in propylene carbonate) immobilized with 15 wt.% poly(methyl methacrylate) (PMMA). The effect of fumed silica content in the CPEs on the ionic conductivity and viscosity over a wide temperature range was investigated. The resultant CPEs showed room temperature conductivity (σ₂₅) as high as 3.8 mS cm⁻¹ along with viscosity value of 3700 P for 2 wt.% SiO₂ addition. Fumed silica addition both to the liquid electrolyte and to the GPE exhibits similar conductivity behaviour and this suggests a passive role of PMMA. The shear thinning behaviour, pointing towards easy processablity, high thermal stability and low volatility, makes these CPEs potential candidates as solid-like electrolytes for electrochemical devices.     

Electrochemical properties of the Li-ion polymer batteries with P(VdF-co-HFP)-based gel polymer electrolyte

Gel polymer electrolytes consisting of 25 wt.% P(VdF-co-HFP), 65 wt.% ethylene carbonate + propylene carbonate and 10 wt.% LiN(CF₃SO₂)₂ are prepared using by a solvent-casting technique. The electrodes are for use in lithium-ion polymer batteries. The electrochemical characteristics of the gel polymer electrolytes are evaluated by means of ac impedance and cyclic voltammetry. The charge–discharge performance of lithium polymer and lithium-ion polymer batteries is examined. A LiCoO₂ | gel polymer electrolyte (GPE) | mesocarbon microbeads (MCMB) cell delivers a discharge capacity of 146.8 and 144.5 mAh g⁻¹ on the first and the 20th cycle, respectively. The specific discharge capacity is greater than 140 mAh g⁻¹ for up to 20 cycle at all the current densities examined.     

A new class of alkaline polymer gel electrolyte for carbon aerogel supercapacitors

A carbon aerogel supercapacitor has been fabricated with an alkaline polymer gel electrolyte. The electrolyte, which also acts as a separator, has a thickness of 3 mm and a conductivity of around 10⁻² S cm⁻¹ at room temperature. The capacitor is characterized by means of cyclic voltammetry, impedance spectroscopy, and galvanostatic cycling. A specific capacitance of 9 F g⁻¹ is shown by cyclic voltammetry.     

Evaluation of nafion based double layer capacitors by electrochemical impedance spectroscopy

In this work some electrochemical characteristics of all solid double layer capacitors prepared by high surface carbon and Nafion polymer electrolyte are reported. Carbon composite electrodes with a Nafion loading of 30 wt.% were prepared and evaluated. Nafion 115 membrane, recast Nafion membrane and 1 M H₂SO₄ solution in a matrix of glass fiber have been used as electrolyte, in the double layer capacitors. The different double layer capacitors (DLCs) have been evaluated by electrochemical impedance spectroscopy. The capacitor with a recast Nafion electrolyte exhibits a proton conductivity of about 3×10⁻² S cm⁻¹ at ambient temperature, that is higher of that reported for solid electrolytes (10⁻³ to 10⁻⁴ S cm⁻¹) in the current literature on capacitors. A maximum of specific capacitance of 13 F/g of active materials (carbon+Nafion) corresponding to 52 F/g for a single electrode measured in a three-electrode arrangement has been achieved with the capacitor with recast Nafion. The capacitance of the capacitor with recast Nafion electrolyte, evaluated in low-frequency region below 10 mHz, was practically equivalent at that with sulphuric acid electrolyte. The interpretation of the characteristics of the microporous structure of carbon material of the electrodes by impedance analysis is also discussed.     

Electrochemical performances of lithium-ion polymer battery using LiNi1/3Co1/3Mn1/3O2 as cathode materials

In this work, a gel polymer electrolyte (GPE) was prepared using polyoxyalkylene glycol acrylate (POAGA) as a macromonomer. LiNi_1/3Mn_1/3Co_1/3O₂/GPE/graphite cells were prepared and their electrochemical properties were evaluated at various current densities and temperatures. The ionic conductivity of the GPE was more than 6.2 × 10⁻³ S cm⁻¹ at room temperature. The GPE had good electrochemical stability up to 5.0 V versus Li/Li⁺. POAGA-based cells were showed good electrochemical performances such as rate capability, low-temperature performance, and cycleability. No leakage of the electrolyte or an explosion was observed at the overcharge test.     

Improved performance of Li hybrid solid polymer electrolyte cells

The seminal research by Wright et al. on polyethylene oxide (PEO) solid polymer electrolyte (SPE) generated intense interest in all solid-state rechargeable lithium batteries. Following this a number of researchers have studied the physical, electrical and transport properties of thin film PEO electrolyte containing Li salt. These studies have clearly identified the limitations of the PEO electrolyte. Chief among the limitations are a low cation transport number (t₊), high crystallinity and segmental motion of the polymer chain, which carries the cation through the bulk electrolyte. While low t₊ leads to cell polarization and increase in cell resistance high T_g reduces conductivity at and around room temperatures. For example, the conductivity of PEO electrolyte containing lithium salt is <10⁻⁷ S cm⁻¹ at room temperature. Although modified PEO electrolytes with lower T_g exhibited higher conductivity (∼10⁻⁵ S cm⁻¹ at RT) the t₊ is still very low ∼0.25 for lithium ion. Numerous other attempts to improving t₊ have met with limited success. The latest approach involves integrating nano domains of inorganic moieties, such as silcate, alumosilicate, etc. within the polymer component. This approach yields an inorganic–organic component (OIC) based polymer electrolyte with higher conductivity and t₊ for Li⁺_. This paper describes the improved electrical and electrochemical properties of OIC-based polymer electrolyte and cells containing Li anode with either a TiS₂ cathode or Mag-10 carbon electrode. Several solid polymer electrolytes derived from silicate OIC and salt-in-polymer constituent based on Li triflate (LiTf) and PEO are studied. A typical composition of the SPE investigated in this work consists of 600 kDa PEO, lithium triflate (LiTf, LiSO₃CF₃) and 55% of silicate based on (3-glycidoxypropyl)trimethoxysilane and tetramethoxysilane at molar ratio 4:1 and 0.65 mol% of aluminum(tri-sec-butoxide) (GTMOS-Al1-900k-55%). Several pouch cells consisting of Li/OIC-based–SPE/cathode containing OIC-based–SPE–LiTf binder were fabricated and tested, these cells are called modified cells. The charge/discharge and impedance characteristics of the new cells (also called modified cells) are compared with that of the pouch cells containing the conventional PEO–LiTf electrolyte as the cathode binder, these cells are called non-modified cells. The new cells can be charged and discharged at 70 °C at higher currents. However, the old cells can be charged and discharged only at 80 °C or above and at lower currents. The cell impedance for the new cells is much lower than that for the old cells.     

Development of PVA based micro-porous polymer electrolyte by a novel preferential polymer dissolution process

A micro-porous polymer electrolyte based on PVA was obtained from PVA–PVC based polymer blend film by a novel preferential polymer dissolution technique. The ionic conductivity of micro-porous polymer electrolyte increases with increase in the removal of PVC content. Finally, the effect of variation of lithium salt concentration is studied for micro-porous polymer electrolyte of high ionic conductivity composition. The ionic conductivity of the micro-porous polymer electrolyte is measured in the temperature range of 301–351 K. It is observed that a 2 M LiClO₄ solution of micro-porous polymer electrolyte has high ionic conductivity of 1.5055 × 10⁻³ S cm⁻¹ at ambient temperature. Complexation and surface morphology of the micro-porous polymer electrolytes are studied by X-ray diffraction and SEM analysis. TG/DTA analysis informs that the micro-porous polymer electrolyte is thermally stable upto 277.9 °C. Chronoamperommetry and linear sweep voltammetry studies were made to find out lithium transference number and stability of micro-porous polymer electrolyte membrane, respectively. Cyclic voltammetry study was performed for carbon/micro-porous polymer electrolyte/LiMn₂O₄ cell to reveal the compatibility and electrochemical stability between electrode materials.     

Proton conducting behavior of a novel polymeric gel membrane based on poly(ethylene oxide)-grafted-poly(methacrylate)

A novel proton conducting polymeric gel membrane that consists of poly(ethylene oxide)-grafted-poly(methacrylate) (PEO-PMA) with poly(ethylene glycol) dimethyl ether (PEGDE) as a plasticizer doped with aqueous phosphoric acid (H₃PO₄) has been prepared and its physicochemical properties were studied in detail. The ionic conductivity was dependent much on the concentration of H₃PO₄, the immersion time, and content of the plasticizer. This type of proton conducting polymeric gels shares not only good mechanical properties but also thermal stability. Maximum conductivities up to 2.6×10⁻² S cm⁻¹ at room temperature (25 °C) and 2.8×10⁻² S cm⁻¹ at 70 °C were obtained for the composition of the polymer matrix to the plasticizer as 35/65 (in mass) after the H₃PO₄ doping from the aqueous solution with 2.93 mol l⁻¹. FT-IR spectra showed that these high proton conductivities are attributed to the presence of excesses free H₃PO₄ in the polymeric gel in addition to the hydrogen-bonded H₃PO₄ to the polymer matrix.     

A new polymer electrolyte system (PEO)n:NaPO3

A new Na⁺ ion conducting polymer electrolyte, based on poly(ethylene oxide) (PEO) and sodium meta phosphate (NaPO₃) is investigated. (PEO)_n:NaPO₃ polymer metal salt complexes with different [ethylene oxide]/Na ratios (n = 3, 4, 6, 8 and 10) are prepared by the solution casting method. Dissolution of the salt into the polymer host is confirmed by X-ray diffraction, differential scanning calorimetry (DSC) and scanning electron microscopy. Further, interaction of the polymer chains with the metal salt is substantiated by Fourier transform infrared spectroscopy. The electrical conductivity of the samples is measured over the temperature range 322–351 K. The temperature dependent conductivity exhibits two different activation energies, below and above the softening point of the polymer. The composition (PEO)₆:NaPO₃ is found to exhibit the least crystallinity but the highest conductivity 2.8 × 10⁻⁸ S cm⁻¹ at 351 K. The electronic transport number, measured by the dc polarization technique, shows that the conducting species are ionic in nature. The effect of ethylene carbonate on the best conducting composition is investigated by DSC and impedance spectroscopy. The addition of 20 wt.% ethylene carbonate, increases the amorphous phase and enhances the conductivity by two orders of magnitude.     

Ionic conductance of PDMAEMA/PEO polymeric electrolyte containing lithium salt mixed with plasticizer

Novel plasticized polymer electrolytes were synthesized with poly(N,N-dimethylamino-ethyl-methacrylate) (PDMAEMA), polyethylene oxide (PEO), LiTFSI as a salt, tetraethylene glycol dimethyl ether (tetraglyme), EC/PC and DEP as plasticizers. The ionic conductivity of various compositions of polymer electrolytes was investigated as a function of temperature, various concentrations of LiTFSI, plasticizers and various ratio of PDMAEMA/PEO. The ionic conductivity of PDMAEMA/PEO/LiTFSI (1.5 mol kg⁻¹) with DEP as a plasticizer (1.5 × 10⁻⁴ S cm⁻¹) exhibited lower than PDMAEMA/PEO/LiTFSI (1.2 mol kg⁻¹)/tetraglyme (5.24 × 10⁻⁴ S cm⁻¹) and PDMAEMA/PEO/LiTFSI (1.5 mol kg⁻¹)/EC + PC (2.1 × 10⁻⁴ S cm⁻¹). As increasing the PDMAEMA concentration up to 13.3%, the ionic conductivity was decreased rapidly. As increasing the PDMAEMA concentration the ionic conductivity was decreased due to high viscosity and some interactions reducing ion pairing. These plasticized polymer electrolytes were characterized by impedance spectroscopy and DSC.     

Ionic liquid–polymer gel electrolytes based on morpholinium salt and PVdF(HFP) copolymer

New ionic liquid–polymer gel electrolytes (IPGEs) are prepared from N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide (Mor_1,2TFSI) and poly(vinylidene fluoride)-hexafluoropropylene copolymer (PVdF(HFP)). To investigate the effect of propylene carbonate (PC) on the ionic conductivity of the IPGEs, the preparation methods are roughly divided into two groups according to the presence or absence of PC. The ionic conductivity for each IPGE is measured with increasing temperature and changing weight ratio of Mor_1,2TFSI. The results show that the ionic conductivity increases as the temperature and weight ratio of the Mor_1,2TFSI increase, and that the added PC improves the ionic conductivity of the IPGEs. In addition, thermogravimetric analysis and the data from infrared spectroscopy demonstrate the thermal stability of each IPGE and the presence of PC in the polymer network. Although the IPGEs that contain PC display high conductivity (∼1.1 × 10⁻² S cm⁻¹) at 60 °C, they are thermally unstable.     

Phase-separated polymer electrolyte based on poly(vinyl chloride)/poly(ethyl methacrylate) blend

The characteristics of polymer electrolytes based on a poly(vinyl chloride) (PVC)/poly(ethyl methacrylate) (PEMA) blend are reported. The PVC/PEMA based polymer electrolyte consists of an electrolyte-rich phase that acts as a conducting channel and a polymer-rich phase that provides mechanical strength. The dual phase was simply developed by a single-step coating process. The mechanical strength of the PVC/PEMA based polymer electrolyte was found to be much higher than that of a previously reported PVC/PMMA-based polymer electrolyte (poly(methyl methacrylate), PMMA) at the same PVC content, and even comparable with that of the PVC-based polymer electrolyte. The blended polymer electrolytes showed ionic conductivity of higher than 10⁻³ S cm⁻¹ and electrochemical stability up to at least 4.3 V. A prototype battery, which consists of a LiCoO₂ cathode, a MCMB anode, and PVC/PEMA-based polymer electrolyte, gives 92% of the initial capacity at 100 cycles upon repeated charge–discharge at the 1 C rate.     

Development of a biodegradable polymer electrolyte for rechargeable batteries

The possibility of producing a biodegradable polymer electrolyte based on poly-ɛ-caprolactone (PCL) with different concentrations of LiClO₄ has been investigated. The maximum ionic conductivity obtained at room temperature was 1.2 × 10⁻⁶ S cm⁻¹ for PCL complexed with 10 wt.% LiClO₄. In this mixture, complete biodegradation occurred after 110 days and was attributed to the presence of ester groups in the polymer matrix. The large electrochemical stability window of approximately 5 V showed that the PCL/LiClO₄ electrolyte had important electrochemical properties that would make it useful in the production of rechargeable batteries with a lower environmental impact.     

Effect of ball milling on structural and electrochemical properties of (PEO)nLiX (LiX = LiCF3SO3 and LiBF4) polymer electrolytes

Polymer electrolytes consisting of poly(ethylene oxide) (PEO) and lithium salts, such as LiCF₃SO₃ and LiBF₄ are prepared by the ball-milling method. This is performed at various times (2, 4, 8, 12 h) with ball:sample ratio of 400:1. The electrochemical and thermal characteristics of the electrolytes are evaluated. The structure and morphology of PEO–LiX polymer electrolyte is changed to amorphous and smaller spherulite texture by ball milling. The ionic conductivity of the PEO–LiX polymer electrolytes increases by about one order of magnitude than that of electrolytes prepared without ball milling. Also, the ball milled electrolytes have remarkably higher ionic conductivity at low temperature. Maximum ionic conductivity is found for the PEO–LiX prepared by ball milling for 12 h, viz. 2.52×10⁻⁴ S cm⁻¹ for LiCF₃SO₃ and 4.99×10⁻⁴ S cm⁻¹ for LiBF₄ at 90 °C. The first discharge capacity of Li/S cells increases with increasing ball milling time. (PEO)₁₀LiCF₃SO₃ polymer electrolyte prepared by ball milling show the typical two plateau discharge curves in a Li/S battery. The upper voltage plateau for the polymer electrolyte containing LiBF₄ differs markedly from the typical shape.     

Polymer electrolytes based on modified natural rubber for use in rechargeable lithium batteries

Modified natural rubber (NR) polymer hosts having low transition glass temperatures have been investigated. Three types of modified NR, namely 25% epoxidised NR (ENR-25), 50% ENR (ENR-50) and polymethyl methacrylate grafted NR (MG-49) were employed. Results are reported for ionic conductivity and thermal properties for both unplasticised and plasticised polymer electrolyte systems. The samples were in the form of free standing films with the thickness 0.2–0.5 mm and mixtures of ethylene carbonate (EC) and propylene carbonate (PC) were used as plasticisers. Unplasticised modified NR based systems exhibit ionic conductivities in 10⁻⁶–10⁻⁵ S cm⁻¹ range at ambient temperatures. Incorporating 50–100% of EC/PC by weight to the systems yielded mechanically stable films and ionic conductivities in 10⁻⁴–10⁻³ S cm⁻¹ range at ambient temperature. The thermal event of the systems has displayed an increasing trend of transition glass temperature at elevated salt concentration whereas incorporation of EC and PC into the systems leads to marked reduction in their T_g values.