Ionic conduction in doped succinonitrile

Doping of lithium salts into the plastic crystal phase of succinonitrile does significantly increase ionic conductivity. This paper investigates the effect of anion (TFSA, Tf and BF₄) on the conductivity and diffusion of the mobile species using impedance spectroscopy and NMR. Room temperature conductivities up to 2.1×10^−4 S cm^−1 were obtained with 1 mol% lithium bis(trifluoromethanesulfonyl)amide in succinonitrile. Pulse field gradient NMR has shown that in all three systems investigated, both cation and anion are mobile in this lattice.

Room temperature fast-ion conduction in imidazolium halide salts

Fast-ion conduction has been observed in the iodide and bromide salts of 1-methyl-3-ethylimidazolium at ambient temperatures. The melting point of these two compounds is above 350 K and even at 273 K the ionic conductivity in the solid-state is greater than 10^−3S cm^−1. Cation diffusion coefficients have been measured using fringe field gradient and/or pulse field gradient ¹H NMR techniques, which indicated cation diffusion coefficients of the order of 10^−10 m² s^−1 in the solid-state. Remarkably, these values are up to an order of magnitude higher than the cation diffusion coefficient in the supercooled liquid at 293 K. The activation energy for diffusion in the solid-state is extremely small, as is typical of solid-state fast-ion conductors and indicates a change in transport mechanism from the melt to the crystal. The inability to detect an ¹²⁷I signal together with the modelling of the conductivity using the Nernst–Einstein equation suggests that the solid-state conduction is primarily due to cation diffusion. The solid-state fast-ion conduction is most likely related to vacancy diffusion along the cation layers in the crystal. The temperature dependence of the NMR signal intensity indicates that the number of mobile species is increasing with increasing temperature with an activation energy of approximately 20–30 kJ mol^−1.

Solid state lithium ion conduction in pyrrolidinium imide–lithium imide salt mixtures

The properties of the binary salt system based on mixtures of methyl ethyl pyrrolidinium bis(trifluoromethane sulfonyl) imide (P₁₂) and lithium bis(trifluoromethane sulfonyl) imide (Li imide) are reported. The lithium containing mixtures were found to be more than two orders of magnitude more conductive than the parent P₁₂ phase and the 33 mol% Li imide systems showed a solid state conductivity around 1×10^−4 S/cm at 20°C. This solid state conductivity is believed to take place in plastic crystal phases of the P₁₂ compound.

Fast ion conduction in molecular plastic crystals

Doping of lithium salts and acids into the plastic crystal phase of succinonitrile has shown for the first time of the possibility of creating solid state electrolytes based on plastic crystalline solvents where the matrix itself is neutral and hence not intrinsically conductive. These materials illustrate the concept of a solid state electrolyte solvent. Room temperature conductivities up to 3.4×10^−4 S cm^−1 were obtained with 5 wt.% lithium bis(trifluoromethanesulfonylamide) in succinonitrile. Pulsed field gradient NMR measurements indicate that both cation and anion are mobile in this lattice. Proton conductivity was also observed when methane sulfonic acid or glacial acetic acid was used as dopants, however, the conductivity in these systems is limited by the poor dissociating ability of these acids.

Decoupled ion conduction in poly(2-acrylamido-2-methyl-1-propane-sulfonic acid) homopolymers

As the focus on developing new polymer electrolytes continues to intensify in the area of alternative energy conversion and storage devices, the rational design of polyelectrolytes with high single ion transport rates has emerged as a primary strategy for enhancing device performance. Previously, we reported a series of sulfonate based copolymer ionomers based on using mixed bulky quaternary ammonium cations and sodium cations as the ionomer counterions. This led to improvements in the ionic conductivity and an apparent decoupling from the Tg of the ionomer. In this article, we have prepared a new series of ionomers based on the homopolymer of poly(2-acrylamido-2-methyl-1-propane-sulfonic acid) using differing sizes of the ammonium counter-cations. We observe a decreasing Tg with increasing the bulkiness of the quaternary ammonium cation, and an increasing degree of decoupling from Tg within these systems. Somewhat surprisingly, phase separation is observed in this homopolymer system, as evidenced from multiple impedance arcs, Raman mapping and SEM. The thermal properties, morphology and the effect of plasticizer on the transport properties in these ionomers are also presented. The addition of 10 wt% plasticizer increased the ionic conductivity between two and three orders of magnitudes leading to materials that may have applications in sodium based devices. This journal is

Increased ion conduction in dual cation [sodium][tetraalkylammonium] poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide-co-ethylacrylate] ionomers

© The Royal Society of Chemistry. Solid-state polymer electrolytes, as an alternative to traditional liquid electrolytes, have been intensively investigated for energy conversion and storage devices. The transport rate of single ions is the key to their high performance. For application in emerging sodium batteries, we have developed three dual-cation polymeric ionomers, which contain bulky tetraalkylammonium ions in addition to the sodium ion. The sizes and relative contents of the ammonium ions vary relative to the sodium ion contents. Comparative studies of ion dynamics, thermal properties, phase behaviours and ionic conductivities were carried out, taking advantage of various spectroscopic and thermal chemistry methods. The ion conductivities of the ionomers are greatly enhanced by the introduction of bulky counterions, as a result of the additional free volume and decreased sodium ion association. Raman spectroscopy and thermal analysis as well as the solid-state nuclear magnetic resonance studies are used to probe the conductivity behaviour.

NMR determination of ionic structure in plasticized polyether-urethane polymer electrolytes

Solid polymer electrolytes based on amorphous polyether-urethane networks combined with lithium or sodium salts and a low molecular weight cosolvent (plasticizer) have been investigated in our laboratories for several years. Conductivity enhancements of up to two orders of magnitude can be obtained whilst still retaining solid elastomeric properties. In order to understand the effects of the plasticizers and their mechanism of conductivity enhancement, multinuclear NMR has been employed to investigate ionic structure in polymer electrolyte systems containing NaCF₃SO₃, LiCF₃SO₃ and LiClO₃ salts.

With increasing dimethyl formamide (DMF) and propylene carbonate (PC) concentration the increasing cation chemical shift with fixed salt concentration indicates a decreasing anion-cation association consistent with an increased number of charge carriers. ¹³C chemical shift data for the same systems suggests that whilst DMF also decreases cation-polymer interactions, PC does the opposite, presumably by shielding cation-anion interactions. Temperature dependent ⁷Li spin-lattice relaxation times indicate the expected increase in ionic mobility upon plasticization with a shift of the T₁ minimum to lower temperatures. The magnitude of T₁ at the minimum increases upon addition of DMF whereas there is a slight decrease when PC is added. This also supports the suggestion that the DMF preferentially solvates the cation whereas the action of PC is limited to coulomb screening, hence freeing the anion.

Ionic conductivity in poly(diethylene glycol-carbonate)/sodium triflate complexes

New polymer electrolytes were synthesized and characterized based on a new polymer host. The motivation was to produce a host polymer with a high dielectric constant which should reduce ion clustering with an attendant increased conductivity. The new polymer host, poly(diethylene glycol carbonate) and its sodium triflate complexes were characterized by thermal analysis and AC impedance measurements. The polycarbonate backbone appears less flexible than the polyether hosts as evidenced by the higher glass transition temperatures. The conductivity for the sodium triflate complexes was measured as ~ 10^−5 S cm^−1 at 55 °C and the dielectric constant of the host polymer was found to be 3.6 at 3 GHz. The low conductivity is attributed to rigidity of the polycarbonate.

Fast ion conduction in an acid doped pentaglycerine plastic crystal

High proton conductivity has been achieved in the high temperature plastic crystal phase of pentaglycerine when doped with strong acids, including trifluoromethanesulfonic acid (triflic acid) and methanesulfonic acid. The solid–solid phase transition from the ordered to plastic phase in this material occurs at 86 °C and conductivities of 10^{− 3} S/cm were measured in the high temperature plastic phase on the addition of 1 mol% triflic acid. In the case of methanesulfonic acid, the conductivities showed a greater dependence on acid concentration and were lower than for triflic acid, as expected on the basis of acid strengths. Electrochemical characterisation shows a clear hydrogen reduction process indicating that the proton is the mobile species in the plastic phase.