Novel ionic liquid electrolyte for electrochemical double layer capacitors

A novel oxygen containing spiro ammonium salt, oxazolidine-3-spiro-1’-pyrrolidinium tetrafluoroborate (OPBF₄) was synthesized using an innovative technique for use as electrolyte in electrochemical double layer capacitors (EDLC). Comparison of OPBF₄ with commercially available, tetraethyl ammonium tetrafluoroborate (TEABF₄) showed higher voltage window and higher capacitance for the OPBF₄ compound. Moreover, molarity of 3 M was produced with OPBF₄ as compared to a maximum of 1.5 M for TEABF₄ in acetonitrile (AN). This is especially important to enable the fabrication of higher energy density EDLC. This is the first report of testing OPBF₄ compound in an EDLC device, and it qualifies as a reasonable alternative to TEABF₄ for high performance ultracapacitors.     

Fluorination effect of activated carbon electrodes on the electrochemical performance of electric double layer capacitors

The surface of phenol-based activated carbon (AC) was fluorinated at room temperature with different F₂:N₂ gas mixtures for use as an electrode material in an electric double-layer capacitor (EDLC). The effect of surface fluorination on EDLC electrochemical performance was investigated. The specific capacitance of the fluorinated AC-based EDLC was measured in a 1 M H₂SO₄ electrolyte, in which it was observed that the specific capacitances increased from 375 and 145 F g⁻¹ to 491 and 212 F g⁻¹ with the scan rates of 2 and 50 mV s⁻¹, respectively, in comparison to those of an unfluorinated AC-based EDLC when the fluorination process was optimized via 0.2 bar partial F₂ gas pressure. This enhancement in capacitance can be attributed to the synergistic effect of increased polarization on the AC surface, specific surface area, and micro and mesopore volumes, all of which were induced by the fluorination process. The observed increase in polarization was derived from a highly electronegative fluorine functional group that emerged due to the fluorination process. The increased surface area and pore volume of the AC was derived from the physical function of the fluorine functional group.     

Novel ionic liquid based electrolyte for double layer capacitors with enhanced high potential stability

Developing electrolyte with high electrochemical stability is the most effective way to improve the energy density of double layer capacitors (DLCs), and ionic liquid is a promising choice. Herein, a novel ionic liquid based high potential electrolyte with a stabilizer, succinonitrile, was proposed to improve the high potential stability of the DLC. The electrolyte with 7.5 wt% succinonitrile added has a high ionic conductivity of 41.1 mS cm^-1 under ambient temperature, and the DLC adopting this electrolyte could be charged to 3.0 V with stable cycle ability even under a discharge current density of 6 A g^-1. Moreover, the energy density could be increased by 23.4% when the DLC was charged to 3.0 V compared to that charged to 2.7 V.     

Influence of electrolyte characteristics on the electrochemical parameters of electrical double layer capacitors

Electrical double layer capacitors based on ideally polarizable nanoporous carbon electrodes in propylene carbonate with the addition of different 1 M Me₃EtNBF₄, Me₂Et₂NBF₄, MeEt₃NBF₄, Et₄NBF₄, Et₃PrNBF₄ and Et₃BuNBF₄ electrolytes have been tested by cyclic voltammetry, chronoamperometry and electrochemical impedance methods. The limits of ideal polarizability, low-frequency limiting capacitance and series resistance, time constant, Ragone plots (energy density vs. power density dependencies) and other characteristics have been discussed. The influence of the electrolyte molar mass on the electrochemical characteristics of the nanoporous carbon electrode cells has been established. The applicability limits of the Srinivasan and Weidner model have been tested.     

Electrochemical behavior of activated carbon electrodes in electric double layer capacitors with tetrametylammonium bis(oxalato)borate electrolyte synthesized by microwave irradiation

The electrochemical behavior of electric double layer capacitors (EDLCs) with tetramethylammonium bis(oxalato)borate electrolyte and electrodes based on various activated carbons (ACs) was studied. Tetraalkylammonium bis(oxalate)borate salts were synthesized by means of microwave (MW) irradiation. The specific conductivities of salt solutions were determined. It was shown that the efficiency of electric double layer capacitors increases with an increase in specific surface area and a decrease in the purity of carbon materials.     

Protic ionic liquid-based gel polymer electrolyte: structural and ion transport studies and its application in proton battery

Proton-conducting free standing gel polymer electrolyte (GPE) films containing protic ionic liquid, 1-butyl-3-methylimidazolium hydrogen sulphate, immobilized in blend of poly(vinylidenefluoride-co-hexafluoropropylene) and poly(vinylpyrrolidone) have been prepared by solution-cast technique. Films have been characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), differential scanning calorimetry (DSC), complex impedance spectroscopy, and cyclic voltammetry. Ionic conductivity of the semicrystalline and porous GPE films has been obtained as ~3.9?×?10^?3 S cm^?1 at room temperature. Protonic nature of conduction in the films has been established by performing cyclic voltammetry and complex impedance spectroscopy on the cells having both blocking (stainless steel) and both reversible electrodes (Zn + ZnSO₄.7H₂O). The electrochemical stability window of the films has been found as ~3.8 V. The highest conducting film has been used as a separator and proton conductor to fabricate a proton battery of configuration Zn + ZnSO₄.7H₂O |GPE film| PbO₂ + V₂O₅. The battery shows an open circuit voltage of ~1.62 V. Energy density of the cell has been obtained as 35.2 W h kg^?1 for low current drain. Rechargeability of the cell has been tested for ten cycles. The maximum discharge capacity of the cell has been obtained as ~2.50 mA h g^?1 during the first discharge cycle.     

Highly porous LiMnPO4 in combination with an ionic liquid-based polymer gel electrolyte for lithium batteries

A porous well defined LiMnPO₄ cathode material is synthesized by a sol-gel method. The electrochemical performance of the cathode material is evaluated in a cell with an ionic liquid-based polymer electrolyte (0.5 M LITFSI in EMImTFSI) and a lithium metal electrode. The results are compared to a cell with a traditional organic carbonate-based electrolyte (1 M LiPF₆ in EC/DMC). The cell with the ionic liquid-based polymer electrolyte presents an enhanced electrochemical intercalation performance of lithium ions, a high electrochemical stability window of 5 V, and an excellent cycling ability as compared with the organic based counterpart. Furthermore, the ionic liquid-based polymer gel electrolyte effectively prevents the dissolution of manganese — otherwise a common problem.     

Fabrication and evaluation of a polymer Li-ion battery with microporous gel electrolyte

This paper introduces an easy method for the fabrication of polymer Li-ion batteries with microporous gel electrolyte (MGE). The MGE is a multiphase electrolyte, which is composed of liquid electrolyte, gel electrolyte, and polymer matrix. The MGE not only has high ionic conductivity and good adhesion to the electrodes at low temperatures, but also retains good mechanical strength at elevated temperatures. Therefore, the MGE batteries are able to operate over a wide temperature range. During battery fabrication, the MGE is formed in situ by introducing liquid electrolyte into a swellable microporous polymer membrane and then heating or cycling the battery. In this work, the chemical compatibility of MGE with metal lithium during 60 °C storage and with LiMn₂O₄ cathode during cycling was studied. In addition, graphite/MGE/LiMn₂O₄ Li-ion batteries were made and evaluated.     

Fabrication and characterization of supported dual acidic ionic liquids for polymer electrolyte membrane fuel cell applications

In this study, we proposed an innovative and versatile method for preparation of highly stable and conductive supported ionic liquid (IL) membranes for proton exchange fuel cell applications. Novel covalently supported dual acidic IL membranes were prepared by radiation induced grafting of 4-vinyl pyridine (4-VP) onto poly(ethylene-co-tetrafluoroethylene) (ETFE) film followed by post-functionalization via sequential treatments with 1,4-butane sultone and sulfuric acid to introduce pyridinium alkyl sulfonate/hydrogen sulfate moieties. The advantage of our approach lies in grafting polymers with highly reactive functional groups suitable for efficient post-sulfonation. The membranes displayed better swelling and mechanical properties compared to Nafion 112 despite having more than 3 times higher ion exchange capacity (IEC). The proton conductivity reached superior values to Nafion above 80 °C. Particularly, the membrane with ion exchange capacity of 3.41 displayed a proton conductivity of 259 mScm⁻¹ at 95 °C. This desired conductivity value is attributed to the high IEC of the membranes as well as dissociation of the hydrophobic ETFE polymer and hydrophilic pyridinium alkyl sulfonate groups. Such appealing properties make the supported IL membranes promising for proton exchange membrane fuel cells (PEMFC).     

Microfluidic cells with interdigitated array gold electrodes: Fabrication and electrochemical characterization

Microfluidic flow cells combined with an interdigitated array (IDA) electrode and/or individually driven interdigitated electrodes were fabricated and characterized for application as detectors for flow injection analysis. The gold electrodes were produced by a process involving heat transfer of a toner mask onto the gold surface of a CD-R and etching of the toner-free gold region by short exposure to iodine-iodide solution. The arrays of electrodes with individual area of 0.01 cm² (0.10 cm of length × 0.10 cm of width and separated by gaps of 0.05 or 0.03 cm) were assembled in microfluidic flow cells with 13 or 19 μm channel depth. The electrochemical characterization of the cells was made by voltammetry under stationary conditions and the influence of experimental parameters related to geometry of the channels and electrodes were studied by using K₄Fe(CN)₆ as model system. The obtained results for peaks currents (I_p) are in excellent agreement with the expected ones for a reversible redox system under stationary thin-layer conditions. Two different configurations of the working electrodes, E_i, auxiliary electrode, A, and reference electrode, R, on the chip were examined: E_i/R/A and R/E_i/A, with the first presenting certain uncompensated resistance. This is because the potentiostat actively compensates the iR drop occurring in the electrolyte thin layer between A and R, but not from R to each E_i. This is confirmed by the smaller difference between the cathodic and anodic peak potentials for the second configuration. Evaluation of the microfluidic flow cells combined with (individually driven) interdigitated array electrodes as biamperometric or amperometric detectors for FIA reveals stable and reproducible operation, with peak heights presenting relative standard deviations of less than 2.2%. For electrochemically reversible species, FIA peaks with enhanced current signal were obtained due to redox cycling under flow operation. The versatility of microfluidic flow cells, produced by simple and low-cost technique, associated with the rich information content of electrochemical techniques with arrays of electrodes, opens many future research and application opportunities.     

Physical and electrochemical characterization of activated carbons with high mesoporous ratio for supercapacitors based on ionic liquid as the electrolyte

A series of activated carbons with high mesoporous ratio were prepared by KOH reactivation based on activated carbon as the precursor. As the KOH/AC mass ratio was increased to 4:1, the mesoporous ratio increases from 60% to 76%, and the average pore size from 2.23 to 3.14?nm. Moreover, the specific capacitance for the activated carbon in ionic liquid 1-ethyl-3-methylmidazolium tetrafluoroborate ([EMIm]BF₄) can reach the maximum value of 189?F?g^?1 (8.0???F?cm^?2). In addition, the decrease of specific capacitance for activated carbons by KOH reactivation with current density increase shows two regimes, suggesting that activated carbons with high mesoporous ratio are much fit for charge?Cdischarge at larger current density.     

Charge storage mechanism of MnO2 cathodes in Zn/MnO2 batteries using ionic liquid-based gel polymer electrolytes

Cathode reactions in Zn/MnO₂ batteries using aqueous electrolytes have been usually interpreted by the reduction of Mn^4 + to Mn^3 + while protons and/or cations penetrate inside the cathode. However, until now, the MnO₂ storage charge mechanism using a non-aqueous gel polymer electrolyte (GPE) has not been investigated. In this work, ionic liquid-based GPEs including BMIM Tf and ZnTf₂ have been employed in Zn/MnO₂ batteries. Different states of charge of MnO₂ cathodes used in Zn/IL-GPE/MnO₂ batteries have been analyzed by XPS and EDX techniques. XPS analysis showed that Mn^4 + is reduced during the discharge process at the same time as Zn^2 + cations are incorporated into the cathode. Besides, Zn^2 + cations insertion is accompanied by triflate anions.     

Application of a novel binder for activated carbon-based electrical double layer capacitors with nonaqueous electrolytes

In this work, we have fabricated activated carbon electrodes using the binder LA135 and assembled electrical double layer capacitors with nonaqueous electrolytes of 1 M tetraethyl ammonium tetrafluoroborate (Et₄NBF₄) in propylene carbonate (PC), 1 M Et₄NBF₄ in acetonitrile (AN), and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) ionic liquid, respectively. The main chemical compositions of the binder are polyacrylonitrile and styrene–butadiene rubber. Scanning electron microscope images show that the conductive agents have been uniformly dispersed on the activated carbons in the electrode. The thermal stabilities of electrodes using different binders are studied by thermogravimetric analysis. The electrochemical properties of cells in different nonaqueous electrolytes are characterized by cyclic voltagramms, electrochemical impedance spectra, galvanostatic charge–discharge, leakage current, and cycle life measurements. The capacitor in Et₄NBF₄/AN has the lowest internal resistance and superior high-rate capability, and the one in Et₄NBF₄/PC has the smallest leakage current. The capacitor in EMIMBF₄ has the energy density as high as 35.4 Wh?kg^?1 at a current density of 0.2 A g^?1 (based on the total mass of active materials), which is 1.6 times higher than that of capacitor in PC electrolyte. Besides, the electrochemical properties of capacitors with different binders are comparatively studied. The capacitor using LA135 has the highest specific capacitance and moderate internal resistance comparing with the ones using poly(tetrafluoroethylene), sodium carboxymethyl cellulose + styrene–butadiene rubber or poly (vinylidene fluoride).     

Preparation and characterization of lithium ion conducting ionic liquid-based biodegradable corn starch polymer electrolytes

Thin films of biodegradable corn starch-based biopolymer electrolytes were prepared by solution casting technique. Lithium hexafluorophosphate (LiPF₆) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BmImTf) were employed as lithium salt and ionic liquid, respectively. With reference to the temperature dependence study, Arrhenius relationship was observed. The highest ionic conductivity of (6.00 ± 0.01) × 10⁻⁴ S cm⁻¹ was obtained at 80 °C. Based on x-ray diffraction (XRD) result, the peaks became broader with doping of ionic liquid revealing the higher amorphous region of the biopolymer electrolytes. Ionic liquid-based biopolymer electrolytes exhibited lower glass transition temperature (T _g).     

Effect of MgO nanoparticles on ionic conductivity and electrochemical properties of nanocomposite polymer electrolyte

This paper analyzes the comparison between the performances and morphologies of the PMMA gel and composite electrolyte membrane with nanosized MgO particles. These polymer electrolytes were studied in detailed using XRD, DSC, SEM and AC impedance analysis. The conductivity enhancement has been attributed to the addition of ceramic filler that yields a significant increase of surface to volume ratio related to the decrease in glass transition temperature values in the composite polymer electrolyte. Good interfacial stability at the electrode/electrolyte interface resulted on account of the improved ion dissociation by ceramic filler and a rise in the room temperature conductivity (8.14 × 10⁻³ S cm⁻¹) due to the iono-covalent or Lewis acid–base bonds to the ions and ether oxygen base groups was also observed. Further enhancement of conductivity has been observed on MgO surface, as Lewis-acidic sites interact with both PMMA and ClO₄⁻ ions. The percentage of swelling was found to increase with increasing soaking periods upto 12 h. Beyond that soaking period, it was found that there was a negligible increase in the % of swelling.     

Solid-state graphene-based supercapacitor with high-density energy storage using ionic liquid gel electrolyte: electrochemical properties and performance in storing solar electricity

Journal of Solid State Electrochemistry - The electrochemical properties and high-density energy storage performance of graphene nano-platelet-based solid-state electrical double-layer...     

Synthesis and characterization of mixing soft-segmented waterborne polyurethane polymer electrolyte with room temperature ionic liquid

Composite polymer electrolytes based on mixing soft-segment waterborne polyurethane(WPU)and 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide(BMImTFSI)have been prepared and characterized.The addition of BMImTFSI results in an increase of the ionic conductivity.At high BMImTFSI concentration(BMImTFSI/WPU=3 in weight ratio),the ionic conductivity reaches 4.27×10~(-3)S/cm at 30℃.These composite polymer electrolytes exhibit good thermal and electrochemical stability,which are high enough to be...     

Highly conductive nanostructured C-TiO2 electrodes with enhanced electrochemical stability and double layer charge storage capacitance

The present work reports the structural and electrochemical properties of carbon-modified nanostructured TiO(2) electrodes (C-TiO(2)) prepared by anodizing titanium in a fluoride-based electrolyte followed by thermal annealing in an atmosphere of methane and hydrogen in the presence of Fe precursors. The C-TiO(2) nanostructured electrodes are highly conductive and contain more than 1 × 10(10) /cm(2) of nanowires or nanotubes to enhance their double layer charge capacitance and electrochemical stability. Electrogenerated chemiluminescence (ECL) study shows that a C-TiO(2) electrode can replace noble metal electrodes for ultrasensitive ECL detection. Dynamic potential control experiments of redox reactions show that the C-TiO(2) electrode has a broad potential window for a redox reaction. Double layer charging capacitance of the C-TiO(2) electrode is found to be 3 orders of magnitude higher than an ideal planar electrode because of its high surface area and efficient charge collection capability from the nanowire structured surface. The effect of anodization voltage, surface treatment with Fe precursors for carbon modification, the barrier layer between the Ti substrate, and anodized layer on the double layer charging capacitance is studied. Ferrocene carboxylic acid binds covalently to the anodized Ti surface forming a self-assembled monolayer, serving as an ideal precursor layer to yield C-TiO(2) electrodes with better double layer charging performance than the other precursors.