Understanding the Role of Polymeric Binders in Water Based Lithium Ion Electrodes
Authors: Gordon Ronald , Willenbacher Norbert 
Published: February 2020

Polymers find application in Lithium ion Batteries (LiB) as binders, providing cohesion in the dry electrode layer as well as adhesion to the current collector. They may also be added as a thickener to control the flow and hence the processing behavior of the paste. Furthermore, polymeric binders can act as dispersing agents for active material or carbon black particles, thus strongly determining the component distribution in dry electrodes. Despite the vast amount of research activities in the field of LiB, the contribution of the binder to the cell performance still remains elusive. Therefore, the adsorption of carboxymethylcellulose (CMC) on LiFePO4 and graphite particles as active material was investigated. The flow behavior of the electrode pastes as well as the electrical conductivity, mechanical properties and microstructure of corresponding dry electrodes were thoroughly characterized.
Rheological measurements were carried out to study paste flow behavior as a function of CMC and solid particle concentration. The electrical conductivity of thin electrode layers was measured using the four point resistivity test. The adhesion force between electrode layer and current collector was determined via 90°-peel test. Thick electrode layers were prepared to investigate the cohesion in the electrode employing compression, bending and shear tests. Finally, the microstructure of the dry electrodes was characterize by means of scanning electron microscopy (SEM).
Yield stress and viscosity exhibit a pronounced minimum with increasing CMC concentration for both the cathode and anode pastes, indicating that CMC acts as dispersing agent at low concentrations and as a thickener at higher concentration when the equilibrium adsorption concentration is exceeded. Furthermore, the degree of substitution of CMC have no significant influence on the slurry viscosity, whereas higher molecular weights and CMC concentrations lead to significantly higher viscosities. Electrical conductivity of thin electrode layers increases with increasing CMC concentration and yields a pronounced maximum when the equilibrium adsorption concentration is covered, suggesting a critical polymer concentration at which electrode components ideally distribute. In addition, mechanical tests show no clear dependence of the adhesion strength on CMC concentration, irrespective of the degree of substitution or molecular weight, i.e. it does not contribute to the adhesive strength. In contrast, the cohesive strength of the electrode layers increases with higher polymer concentration and molecular weight, but decreases with increasing degree of substitution. Micrographs of the electrode layers show an alignment of the particles for electrodes based on high molecular weight CMC. Preliminary measurements exhibit higher adhesion strength when adding styrene butadiene rubber (SBR), whereas cohesion strength and electrical conductivity significantly decreases. This demonstrates that the optimum CMC concentration has to be chosen according to the required specifications with respect to cohesion and electrical performance.