Comb-shaped single ion conductors have been synthesized by (1) sulfonation of small molecule chloroethyleneglycols, which, after ion exchange to the Li+ salt were then converted to the acrylate by reaction with acryloyl chloride and copolymerized with polyethylene glycol monomethyl ether acrylate (Mn = 454, n = 8) (PAE8-co-E3SO3Li); (2) sulfonation of chloride end groups grafted on to prepolymers of polyacrylate ethers (PAE8-g-EnSO3Li, n = 2, 3). The highest conductivity at 25°C of 2.0 × 10−7Scm−1 was obtained for the PAE8-co-E3SO3Li with a salt concentration of EO/Li = 40. The conductivity of PAE8-g-E3SO3Li is lower than that of PAE8-co-E3SO3Li at similar salt concentrations, which is related to the incomplete sulfonation of the grafted polymer that leads to a lower concentration of Li+. The addition of 50wt.% of plasticizer, PC/EMC (1/1, v/v), to PAE8-g-E2SO3Li increases the ambient conductivity by three orders of magnitude, which is due to the increased ion mobility in a micro-liquid environment and an increase concentration of free ions as a result of the higher dielectric constant of the solvent. A symmetrical Li/Li cell with an electrolyte membrane consisting of 75wt.% PC/EMC (1/1, v/v) was cycled at a current density of 100μAcm−2 at 85°C. The cycling profile showed no concentration polarization after a break-in period during the first few cycles, which was apparently due to reaction of the solvent at the lithium metal surface that reacted with lithium metal to form a stable SEI layer.

The behavior of polymer electrolytes in lithium batteries is reviewed in the context of molecular scale models as well as on the system scale. It is shown how the molecular structure of the electrolyte strongly influences ion transport through the polymer as well as across the interfaces and determines the values of a number of parameters needed for system models that can predict the performance of the battery (e.g. κ, D, t0+ and i0). The interaction of the electrolyte with the electrodes not only leads to transfer of the lithium ion across the interface but also to side reactions that profoundly influence the calendar and life cycle of the battery. Typically these electrochemically induced side reactions generate the SEI layer, but inherent instability of the bulk electrolyte may also play a role in the formation of surface layers. These various reactions can lead to changes in the mechanical properties of the separator and electrode structure that promote life-limiting phenomena such as dendrite growth, passivation and morphology changes. The rheological model of Eisenberg is drawn upon to show how the interactions of the electrolyte with surfaces can lead to distinct changes in mechanical and transport properties that may limit the battery performance and lead to diminished performance with time. The molecular level models may be combined with the rheological models to provide workable models of the interfaces and bulk electrolyte dynamics that in turn can be used to provide a more accurate level of performance prediction from the system models. This connects molecular structure with battery performance and guides the design and synthesis of new and better materials.

Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation, and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5×10−5 S/cm at 25°C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5–6 units long, there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles.