The additive effect of zwitterion and nano-particles on ion dissociation in polyelectrolytes

To realise the battery potential of gel polyelectrolytes greater ion dissociation, ultimately leading to higher conductivities, must be achieved. Higher conductivities will result through increasing the ion-dissociating properties of the gel polyelectrolyte. The poor degree of ion dissociation arises as the active ion tends to remain in close proximity to the backbone charge. Nano-particle inorganic oxides, and zwitterionic compounds have been shown to act as dissociation enhancers in certain polyelectrolyte systems. In an attempt to further increase ion dissociation the addition of both TiO₂ nano-particles and a zwitterionic compound based on 1-butylimidazolium-3-N-(butanesulphonate) were added to the gel polyelectrolyte system poly (Li-2-acrylamido-2-methyl-1-propane sulphonate-co-N,N′-dimethylacrylamide), poly(Li-AMPS-co-DMAA) to determine if a synergistic effect occurs. Two different solvents were used to determine the breadth of applicability of the additive effect. The use of both dissociators resulted in the maximum ionic conductivity being achieved at lower nano-particle concentrations when compared to an identical system without zwitterion.

Enhancement of ion dissociation in polyelectrolyte gels

High conductivity in single ion conducting polymer electrolytes is still the ultimate aim for many electrochemical devices such as secondary lithium batteries. Achieving effective ion dissociation in these cases remains a challenge since the active ion tends to remain in close proximity to the backbone charge as a result of a low degree of ion dissociation. A unique aspect of this dissociation problem in polyelectrolytes is the repulsion between the backbone charges created by dissociation. One way of enhancing ion dissociation in polyelectrolyte systems is to use copolymers in which only a fraction (<20%) of the mer units are charged and where the comonomer is itself chosen to be polar and preferably to be compatible with potential solvents. We have also found that certain dissociation enhancers based on ionic liquids or boroxine ring compounds can lead to high ionic conductivity. In the cases where an ionic liquid is used as the solvent in a polyelectrolyte gel, the viscosity of the ionic liquid and its hydrophilicity are critical to achieving high conductivity. Compounds based on the dicyanamide anion appear to be very effective ionic solvents; polyelectrolyte gels incorporating such ionic liquids exhibit conductivities as high as 10⁻² S/cm at room temperature. In the case of boroxine ring dissociation enhancers, gels based on poly(lithium-2-acrylamido-2-methyl-1-propanesulfonate) and ethylene carbonate produce conductivities approaching 10⁻³ S/cm. This paper will discuss these approaches for achieving higher conductivity in polyelectrolyte materials and suggest future directions to ensure single ion transport.

Boroxine ring compounds as dissociation enhancers in gel polyelectrolytes

In order to combine the advantages of both traditional gel electrolytes and polyelectrolytes, a novel polyelectrolyte which incorporates a boroxine ring-containing anion-trapping agent has been explored. Poly(lithium 2-acrylamido-2-methyl-1-propanesulfonate) (PAMPSLi), ethylene carbonate (EC) and tri(methoxyethoxyethoxyethoxy)boroxine (TME₃Bx) were combined to prepare various gel systems. The thermal properties and conductivities of these gels have been investigated. A conductivity of 10^−3.6 S cm⁻¹ at 20 °C has been achieved in a gel polyelectrolyte system with a molar ratio of [EC]:[TME3Bx]:[Li⁺]=24:1.7:1. Temperature-dependent NMR measurements indicated that a significant interaction exists between the boroxine ring and the polyelectrolyte.