Electrochemical properties of novel ionic liquids for electric double layer capacitor applications

An aliphatic quaternary ammonium salt which has a methoxyethyl group on the nitrogen atom formed an ionic liquid (room temperature molten salt) when combined with the tetrafluoroborate (BF₄⁻) and bis(trifluoromethylsulfonyl)imide [TFSI; (CF₃SO₂)₂N⁻] anions. The limiting oxidation and reduction potentials, specific conductivity, and some other physicochemical properties of the novel ionic liquids, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEME-BF₄) and DEME-TFSI have been evaluated and compared with those of 1-ethyl-3-methylimidazolium tetrafluoroborate. DEME-BF₄ is a practically useful ionic liquid for electrochemical capacitors as it has a quite wide potential window (6.0 V) and high ionic conductivity (4.8 mS cm⁻¹ at 25 °C). We prepared an electric double layer capacitor (EDLC) composed of a pair of activated carbon electrodes and DEME-BF₄ as the electrolyte. This EDLC (working voltage ∼2.5 V) has both, a higher capacity above room temperature and a better charge-discharge cycle durability at 100 °C when compared to a conventional EDLC using an organic liquid electrolyte such as a tetraethylammonium tetrafluoroborate in propylene carbonate.     

Molten lithium sulfonimide salt having poly(propylene oxide) tail

Poly(propylene oxide) (PPO) tailed lithium(trifluoromethyl sulfonylimide)s (TFSI-PPO) were prepared as non-onium type ionic liquid polymers. Introduction of PPO chain to the TFSI salt group resulted in lower the glass transition temperature (T_g) and induce the salt dissociation. The TFSI-PPO showed relatively high ionic conductivity owing to the high dissociation degree of the TFSI salt group. The maximum ionic conductivity of 3.3×10⁻⁶ S cm⁻¹ was observed at 30 °C for TFSI salt having PPO tail with number average molecular weight of 850. On the other hand, PPOs having the same salt moiety on both chain ends ((TFSI)₂-PPO) showed higher T_g than that of TFSI-PPOs. The lithium transference number of the (TFSI)₂-PPO with PPO chain length of Mn=2000 was 0.74 in spite of slightly lower ionic conductivity.     

Design and synthesis of ionic-conductive epoxy-based networked polymers

To develop ionic-conductive film-shaped electrolytes with high reliability, we designed and synthesized the following networked polymers with an epoxy/amine curing system using poly(ethylene glycol) as the main skeleton, and examined their fundamental properties such as ionic conductivity, thermal stability, and inflammability. (1) Networked polymers having quaternary ammonium salt structures. (2) Networked polymers having lithium sulfonate salt structures. (3) Networked polymers having lithium sulfonylimide salt structures. (4) Networked polymers swollen with ionic liquid solutions of lithium salts. Consequently, we found that networked polymers swollen with ionic liquid solutions containing lithium salts showed high ionic conductivity and high thermal stability with excellent non-flammability.     

Improved ionic conductivity of nitrile rubber/ionic liquid composites

Polymer electrolytes with high ionic conductivity and good elasticity were prepared by mixing nitrile rubber (poly(acrylonitrile-co-butadiene) rubber; NBR) with ionic liquid, N-ethylimidazolium bis(trifluoromethanesulfonyl)imide (EImTFSI). The NBR/EImTFSI composites were obtained as homogeneous and transparent films when the ionic liquid content was less than 60 wt%. Raman spectroscopy suggested the interaction between nitrile group of NBR and TFSI anion. Sample with ionic liquid content of 50 wt% showed the ionic conductivity of 1.2×10⁻⁵ S cm⁻¹ at 30 °C. Addition of lithium salt to this NBR/EImTFSI composite further enhanced the ionic conductivity to about 10⁻⁴ S cm⁻¹ without spoiling mechanical properties. DSC studies showed two glass transition temperatures for composites indicating microphase separation.     

Synthesis and characterization of two ionic liquids with emphasis on their chemical stability towards metallic lithium

Two room temperature ionic liquids (RTILs) without acidic protons, based on different cationic species (1-n-butyl-2,3-dimethylimidazolium) (BMMI) and N-n-butyl-N-methylpiperidinium (BMP) using (CF₃SO₂)₂N⁻ (TFSI) as anion, were prepared by quaternization of their respective amines with an appropriate alkyl halide, followed by ion exchange reaction. All relevant properties of these ionic liquids, such as, thermal stability, density, viscosity, electrochemical behavior, ionic conductivity and self-diffusion coefficients for both ionic species, were determined at different temperatures. In spite of their ionic conductivity being lower than 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonylimide) (BMITFSI), the absence of an acidic proton in both compounds is crucial to maintain their chemical stability towards metallic lithium and, thereby, to make possible the safe assembly of lithium ion batteries. Both ionic liquids without acidic protons do not react with metallic lithium; on the other hand, the formation of carbene species when BMITFSI was exposed to Li was confirmed by ¹H and ¹³C nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC-MS).     

Mixtures of ionic liquid and organic carbonate as electrolyte with improved safety and performance for rechargeable lithium batteries

In this paper we report the results of physical–chemical and electrochemical investigations performed on ternary mixtures of the room temperature ionic liquid (IL) N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₄TFSI), propylene carbonate (PC), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as electrolyte for lithium-ion batteries. The thermal stability, ionic conductivity, viscosity and electrochemical stability windows of all considered mixtures were investigated and compared with those of electrolytes based on the pure PYR₁₄TFSI and PC. The mixtures were also used as electrolyte in combination with LiFePO₄-based electrodes. The specific capacity and cycling stability of these systems were investigated at different C-rates, both at room temperature and 60 °C.     

Ion transport properties of lithium ionic liquids and their ion gels

A new series of lithium ionic liquids were prepared by introducing of two electron-withdrawing trifluoroacetyl groups in borate salts containing two methoxy-oligo(ethylene oxide) groups in the structures. Successive substitution reactions of oligo-ethylene glycol monomethyl ether and trifluroacetic acid from LiBH₄ yielded the lithium salts, which were clear and colorless liquids at room temperature. The fundamental physicochemical properties, such as density, thermal property, viscosity, ionic conductivity, self-diffusion coefficients, and electrochemical stability, were measured. The lithium ionic liquids had self-dissociation ability and conducted ions even in the absence of organic solvents. New polymer electrolytes, named ‘ion gels’, were prepared by radical cross-linking reactions of a poly(ethylene oxide-co-propylene oxide)tri-acrylate macromonomer in the presence the lithium ionic liquid. An increase in the glass transition temperatures (T_g) of the ion gels was very small even with increasing lithium ionic liquid concentration, and the T_g's were lower than that of the ionic liquid itself. The ionic conductivity of the ion gels surpassed that of the lithium ionic liquid in the bulk at certain compositions.     

Gel polymer electrolytes based on a novel quaternary ammonium salt for dye-sensitized solar cells

Gel polymer electrolytes were prepared with polyacrylonitrile (PAN) and solutions of a novel quaternary ammonium salt, polysiloxane with quaternary ammonium side groups (PSQAS), in a mixture of ethylene carbonate (EC) and propylene carbonate (PC). The influences of PAN content and salt concentration on the ionic conductivity have been investigated. The ionic conductivity can be further improved with the use of the mixtures of KI and PSQAS, which can be expected as inorganic-organic salts. The gel polymer electrolytes were used in the fabrication of the dye-sensitized solar cells with a nanoporous TiO₂ working electrode, cis-di(thiocyanato)-N,N-bis(2,2-bipyridyl-4,4-dicarboxylic acid) ruthenium(II) complex dye and a counter electrode based on platinized conducting glass. The cells showed open-circuit voltages (V _oc) around 0.6 V and short-circuit current densities (J _sc) larger than 7.5 mA cm^–2 under 60 mW cm^–2 irradiation. The fill factors (FF) and energy conversion efficiencies () of the cells were calculated to be higher than 0.56 and 4.4%, respectively.     

Cellulose triacetate‐based polymer gel electrolytes

New composite polymer gels were obtained from cellulose triacetate (CTA), N‐methyl‐N′‐propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr_1,3TFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Analysis by differential scanning calorimeter and scanning electron microscope showed that the ionic gel consisting of CTA, Pyr_1,3TFSI, and LiTFSI formed a completely homogeneous phase at the molar ratio of CTA/Pyr_1,3TFSI/LiTFSI = 1/3/1.5. The ionic conductivity of the polymer gel was significantly enhanced by the presence of LiTFSI. FTIR study strongly implies that the interaction of lithium ion with the carbonyl group of CTA could be responsible for the increase in conductivity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of polymer electrolytes based on the polymerized imidazolium ionic liquid and their applications in lithium batteries

The polymer electrolytes based on a polymerized ionic liquid (PIL) as polymer host and containing 1,2‐dimethyl‐3‐butylimidazolium bis(trifluoromethanesulfonyl)imide (BMMIM‐TFSI) ionic liquid, lithium TFSI salt, and nanosilica are prepared. The PIL electrolyte presents a high ionic conductivity, and it is 1.07 × 10^?3 S cm^?1 at 60°C, when the BMMIM‐TFSI content reaches 60% (the weight ratio of BMMIM‐TFSI/PIL). Furthermore, the electrolyte exhibits wide electrochemical stability window and good lithium stripping/plating performance. Preliminary battery tests show that Li/LiFePO₄ cells with the PIL electrolytes are capable to deliver above 146 mAh g^?1 at 60°C with very good capacity retention. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40928.     

Fast proton conductor under anhydrous condition synthesized from 12-phosphotungstic acid and ionic liquid

In this study, we synthesized a molecular hybrid conductor electrolyte using PWA ([H₃PW₁₂O₄₀·nH₂O]) and [1-butyl-3-methylimidazole][bis-(fluoromethanesulfonyl) amide] ([BMIM][TFSI]) ionic liquid. The [BMIM][TFSI] ionic liquid can interact with the strongly acidic PWA. The hybrids were hydrophilic, and included some water molecules in the structure of the hybrids. The water molecules remained up to 80 °C, contributing to improve conductivity under an anhydrous N₂ atmosphere. The conductivity of PWA-[BMIM][TFSI] hybrid under anhydrous conditions increased from 10⁻⁴ S/cm to 0.04 S/cm at 60 °C. The conductivity of the hybrids at each temperature was higher than that of pure PWA and [BMIM][TFSI] under anhydrous condition. It can be due to the protonic carriers.     

Effect of the alkyl group on the synthesis and the electrochemical properties of N-alkyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquids

The effect of the alkyl side group on the synthesis and the electrochemical properties of N-alkyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR_1ATFSI) ionic liquids (ILs) is reported. The investigation was focused on the PYR_1ATFSI ionic liquid family because of the interesting electrochemical properties of the members with propyl and butyl side chains. Side alkyl groups (A = C_nH_2n+1 with n ranging from 1 to 10) of different length and structure were used for the synthesis of PYR_1ATFSI materials. NMR and DSC have shown that the ionic liquids were correctly synthesized with the exception of the compounds with tertiary side chains. Most of the materials exhibited a conductivity higher than 10⁻³ S cm⁻¹ already at 12 °C. In the molten state a moderate conductivity decrease was observed with increasing the length and the branching of the side chain (C₂H_2n+1) group according with the change of viscosity of the ionic liquids. Most of the PYR_1ATFSI samples exhibited an electrochemical stability window exceeding 5 V.     

In situ FTIR study of the decomposition of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide ionic liquid during cathodic polarization of lithium and graphite electrodes

In this work we analyzed the cathodic reactions of an important ionic liquid (IL) based electrolyte solution, namely lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)/N-methyl-N-methylpyrrolidinium (BMP) TFSI. In situ FTIR spectroscopy was used for the analysis of gaseous products of the electrochemical decomposition of this IL solution during cathodic polarization of lithium metal and graphite electrodes. The main volatile product of the reductive decomposition of the anion in these BMPTFSI solutions is trifluoromethane. BMP cations decompose to mixtures of tertiary amines and hydrocarbons. The composition of the products is influenced by the nature of the anode material. Graphite possesses a catalytic activity in the electroreduction process of BMP cations which occurs along with their intercalation into the graphite structure. The liquid phase after cathodic polarization of graphite electrodes was analyzed by multinuclear NMR spectroscopy coupled with FTIR spectroscopy. ¹⁵N NMR and FTIR spectra revealed an increase in the Li cations content in the electrolyte solution, as a result of BMP cations decomposition during repeated cycling of graphite electrodes.     

Asymmetrical dicationic ionic liquids based on both imidazolium and aliphatic ammonium as potential electrolyte additives applied to lithium secondary batteries

Asymmetrical dicationic ionic liquids based on the combination of imidazolium and aliphatic ammonium cations with TFSI anion, MIC_nN₁₁₁-TFSI₂, have been synthesized for the first time, wherein MI represents imidazolium cation, N₁₁₁ represents trimethylammonium cation, and C_n represents spacer length. The physical and electrochemical properties of this family of ionic liquids were studied. 1-(3-Methylimidazolium-1-yl)ethane-(trimethylammonium) bi[bis(trifluoromethane-sulfonyl) imide] (MIC₂N₁₁₁-TFSI₂) shows solid-solid transition characteristics. 1-(3-Methylimidazolium-1-yl)pentane-(trimethylammonium) bi[bis(trifluoromethan-esulfonyl)imide] (MIC₅N₁₁₁-TFSI₂) has one of the lowest solid-liquid transformation temperatures among analogues, and belongs to the greatest thermal stable ionic liquids. Additionally, it has an order of conductivity of 10⁻¹ ms cm⁻¹, and electrochemical window of about 3.7 V at room temperature. To evaluate the potential of MIC₅N₁₁₁-TFSI₂ as an additive of electrolyte for lithium secondary batteries, cells composed of LiMn₂O₄ cathode/1 M LiPF₆ in EC:DMC (1:1, v/v) electrolytic solution containing 5 wt% of MIC₅N₁₁₁-TFSI₂/lithium metal anode have been prepared. The charge-discharge cycling test reveals that unlike the cases of Li/LiMn₂O₄ cells employing a conventional electrolyte with a monocationic ionic liquid, such as 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EtMeImTFSI) as an additive, the performances of Li/LiMn₂O₄ cells do not drop with the addition of MIC₅N₁₁₁-TFSI₂ at 1C rate, moreover, the cell exhibits better discharge capacity and cycle durability compared with the cell using the conventional electrolyte.     

A mechanism of ionic conduction of poly (vinylidene fluoride)-lithium perchlorate hybrid films

Polymeric solid electrolytes were prepared by the hybridisation of poly(vinylidene fluoride) and lithium perchlorate. These were obtained as films of about 0.1 mm thickness, and showed high lithium ionic conductivity of about 10^?5 (S cm^?1). The conductivity depended on the contents of lithium perchlorate and polar additives having high boiling temperature. The amount of lithium perchlorate and the logarithm of the conductivity showed linear relation up to a certain (critical) amount of lithium perchlorate. Beyond the critical value, crystals of lithium perchlorate grew in polymer matrix, and the conductivity was not increased so much. Viscosity and dielectric constant of the additives were potent factors to increase the conductivity of the hybrid film. Organic polar materials with lower viscosity such as N,N-dimethyl formamide or γ-butyrolactone strongly contributed to the improvement of lithium ionic conductivity. The activation energy of conduction decreased dramatically by increasing mole ratio of additive and lithium perchlorate. The lithium ions were considered to migrate in the conduction path which was formed by polymer matrix with organic additive molecules.     

Functionalized ionic liquids based on quaternary ammonium cations with three or four ether groups as new electrolytes for lithium battery

New functionalized ILs based on quaternary ammonium cations with three or four ether groups and TFSI⁻ anion were synthesized and characterized. Physical and electrochemical properties, including melting point, thermal stability, viscosity, conductivity and electrochemical stability were investigated for these ILs. Five ILs with lower viscosity in these ILs were applied in lithium battery as new electrolytes. Behavior of lithium redox and charge–discharge characteristics of lithium battery were investigated for these IL electrolytes with 0.6 mol kg⁻¹ LiTFSI. Lithium plating and striping on Ni electrode could be observed in these IL electrolytes. Li/LiFePO₄ cells using these IL electrolytes without additives had good capacity and cycle property at the current rate of 0.1 C, and the N(2o1)₃(2o2)TFSI and N2(2o1)₃TFSI electrolytes owned better rate property.     

Composition effects on ion transport in a polyelectrolyte gel with the addition of ion dissociators

The polymerization of lithium 2-acrylamido-2-methyl-1-propane sulphonic acid with N,N′-dimethylacrylamide has yielded polyelectrolyte gels which have the favourable property of being single ion conductors. The use of single ion conductors ensures that the transport number of lithium is close to unity. The mobility of the lithium ion is still quite low in these systems, resulting in low ionic conductivity. To increase ionic conductivity more charge carriers can be added however competing effects arise between increasing the number of charge carriers and decreasing the mobility of these charge carriers. In this paper the monomer ratio of the copolymer polyelectrolyte is varied to investigate the effect increasing the number of charge carriers has on the ionic conductivity and lithium ion and solvent diffusivity using pfg-NMR. Ion dissociators such as TiO₂ nano-particles and a zwitterionic compound based on 1-butylimidazolium-3-(N-butanesulfonate) have been added in an attempt to further increase the ionic conductivity of the system. It was found that the system with the highest ionic conductivity had the lowest solvent mobility in the presence of zwitterion. Without zwitterion the mobility of the solvent appears to determine the maximum ionic conductivity achievable.     

Gel electrolytes with ionic liquid plasticiser for electrochromic devices

The comparative performance of conducting polymer electrochromic devices (ECDs) utilising gel polymer electrolytes (GPEs) plasticised with ethylene carbonate/propylene carbonate or (N-butyl-3-methylpyridinium trifluoromethanesulphonylimide (P₁₄TFSI) has been made. Lithium perchlorate and lithium trifluoromethanesulphonylimide salts were used in the GPEs to provide enhanced ionic conductivity and inhibit phase separation of the polyethyleneoxide (PEO) and plasticiser. ECDs were assembled from cathodically colouring, polyethylenedioxythiophene (PEDOT), and anodically colouring, polypyrrole (PPy), conducting polymer electrochromes deposited by vapour deposition. The photopic contrast switching over the visible light spectrum, switching speeds and device stability of the ECDs were obtained. These studies demonstrate that the ionic liquid (IL) plasticised GPEs are a suitable replacement for pure IL based devices and volatile organic solvent plasticisers based upon ethylene carbonate/propylene carbonate mixtures.     

A new series of cross-linked (meth)acrylate polymer electrolytes for energy storage

A series of methacrylate-crosslinked polymers were investigated as potential polymer electrolytes for energy storage application. Methacrylate ester crosslinkers (25–50 mol.%) with different spacer lengths and MMA as comonomer were polymerised into thin films. Mixtures of ethylene carbonate and propylene carbonate (EC/PC) or alternatively the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM TFSI), both doped with lithium bis(trifluoromethane)sulfonimide (LiTFSI), fulfilled the role of electrolyte and porogen simultaneously. Ionic conductivity increased with increasing porogen content, Li ion concentration, and decreasing amounts of crosslinker (maximum values: 0.5 mS/cm (EC/PC) and 4.5 mS/cm (EMIM TFSI)). Thin films with permanent porosity were obtained for both electrolyte systems. The flexibility of the films increased with a lower concentration of crosslinker or the choice of a crosslinker with a longer spacer. The relationship between pore size, pore morphology, glass transition temperature and ionic conductivity on the other hand was complex and did not exhibit distinct trends. High thermal stability, ionic conductivity and tunable mechanical properties make these polymer thin films attractive candidates as in situ filled Li ion battery separator films either preformed or directly printed.     

The effect of ionic liquid fragment on the performance of polymer electrolytes

An ionic liquid 1‐methyl‐3‐[2‐(methacryloyloxy)ethyl]imidazolium bis(trifluoromethane sulfonylimide) (MMEIm‐TFSI) was synthesized and polymerized. Composite polymer electrolytes based on polymeric MMEIm‐TFSI (PMMEIm‐TFSI) and poly[(methyl methacrylate)‐co‐(vinyl acetate)] (P(MMA‐VAc)) were prepared, with lithium bis(trifluoromethane sulfonylimide) (LiTFSI) as target ions (Li⁺). DSC/TGA analysis showed good flexibility and thermal stability of the composite electrolyte membranes. The AC impedance showed that the ionic conductivity of the electrolytes increased with PMMEIm‐TFSI up to a maximum value of 1.78 × 10^?4 S cm^?1 when the composition was 25 wt% P(MMA‐VAc)/75 wt% PMMEIm‐TFSI/30 wt% LiTFSI at 30 °C. The composite electrolyte membrane (transmittance ≥ 90%) can also be used as the ion‐conductive layer material for electrochromic devices, and revealed excellent colorization performance. Copyright © 2011 Society of Chemical Industry