The success of polyacrylic acid (PAA) to suppress Li dendrite growth suggests that the mechanical properties of polymer-based coatings, including the modulus, toughness, and interfacial adhesion are important design criteria. However, the measurement of the adhesion of thin PAA, as well as other polymer coatings to the reactive Li-metal anode surface is limited experimentally and challenging computationally. In this paper, a strategy was proposed to estimate the adhesion and delamination of the PAA(polymer)/Li interface, based on the bonding nature at the simpler PAA (oligomer)/Li interfaces using density functional theory calculations. It has been shown that the carboxylic acid groups in PAA reacted strongly with metallic Li, which significantly enhances the interfacial adhesion through the Li-O bonds formation, Li ionization and its incorporation into PAA, and -H or -OH termination of Li after decomposition of the COOH functional group. During delamination, it was found that the most likely PAA delamination route involved breaking partial Li-O bonds and lifting some ionized Li atoms from the Li-metal, especially for the Li atoms that showed a charge closer to +1 or are bonded with two O atoms from PAA. Based on the average bonding energies from PAA(oligomer)/Li interface delamination calculations, the work of separation, Wsep, of the PAA(polymer)/Li interface was estimated to be ∼1.0 (J/m2). The high Wsep of PAA (polymer)/Li was comparable with the Li2O/Li interface and higher than Li2CO3/Li and LiF/Li interfaces. This order correlated well with the areal density of Li-O bonds, which can serve as a descriptor for the interfacial adhesion. This computational approach can be applied to other interfaces with polymer-based coatings.
Keywords: Li dendrite pevention; Li-metal battery; density functional theory; interface adhesion; polymer coatings.