Abstract: To enhance the ionic conductivity in solid phase polyelectrolyte systems for lithium ion battery applications demands effective control of the phase properties. Here, we report on a strategy involving a layer-by-layer methodology of two polyelectrolytes, poly(ethylene oxide) (PEO) and poly(acrylic) acid (PAA) and carboxylic acid functionalized multi-walled carbon nanotubes (MWNTs). Optimization of the assembly strategy revealed that undoped and lithium-ion doped stacking of four layers provides excellent film growth and improvement of the ionic conductivity of up to 10â 5 S cmâ 1, which exceeds conventional assemblies of lithium-ion doped [PEO/PAA] by up to two orders of magnitude. Although ionic conductivity was most effectively enhanced for ultrathin films (< 100 nm), [PEO/PAA/PEO/(PAA + MWNT)] stacking still provides an ionic conductivity of > 10â 6 S cmâ 1 for thick films (> 2 μm). The improvement of ionic conductivity was attributed to (i) interfacial phase mixing (blending) of the two polyelectrolytes, (ii) the MWNT contribution in the interfacial region, and (iii) the preferential adsorption of lithium-ions along the carbon nanotubes. This study involved a series of scanning probe methods including lateral force microscopy, and electrostatic force microscopy.
Abstract: Ion conductivities of layer-by-layer (LBL) assemblies of solid thin film polyelectrolyte systems involving poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) were found to be a strong function of the number of bilayer stacks, n, with conductivities approaching 10â 7 S/cm for n < 10, compared to 10â 9 S/cm for n ⥠10 and 10â 10 S/cm for bulk PEO. Increased ion conductivity for low LBL stack numbers (n < 10) originated to part from an effective suppression of the PEO crystallization via PEO/PAA blending, which could be inferred from local glass transition temperature measurements involving shear modulation force microscopy. Another phenomenon responsible for high conductivity in thin films was found in the in-plane phase heterogeneity of PEO and PAA. Increased ion conductivity for larger LBL stacks (n ⥠10) were attributed to low concentration autoblending caused by PEO-PAA hydrogen bonding, and an average layer thickness of noticeably less than 100 nm. The effect of interfacial constraints was evident in the degree of intermixing, addressed by a thin film extended Fox blend analysis, in the glass and melting transitions of PEO and PAA pure film components. While the glass transition value of PAA decreased by 55% to 46 °C for an 8 nm film, the melting transition for PEO decreased by 15% to 64 °C caused by surface tension effects.
Abstract: The scanning force microscope (SFM) was used to investigate morphology of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blend. The effect of solvent and dewetting in surface structure of PEO film was reported. The results manifested that the crystallization of PEO could be suppressed completely in ultrathin region via using chloroform as a solvent, and the branched-like crystallization was recovered after dewetting. Also, the effect of thickness, the ratio of PEO/PAA and dewetting in surface morphology of PEOâPAA blend films were investigated. These results showed that the crystallization was highly dependent on the ratio of PEO/PAA and the thickness of blend film. Furthermore, we assembled the PEO/PAA layer-by-layer film by spin-casting method for the first time, which exhibited highly efficiency. As a complementary tool, we also used lateral force microscopy (LFM) to explore surface information of these films. The result was indicative of interfacial constraints in ultrathin region, and also was supported by the results showing the spin-casting PEO/PAA blends rather than heterogeneous mixture.
