RESUMEN
Mechanical properties of hydrogels with reversible transition metal-polymer crosslinks can be flexibly tuned depending on the dissociation kinetics of the metal bond. We use rheology to investigate the sol-gel transition of a Fe(III)-poly(acrylic acid) network with varying crosslinker content and model the corresponding mechanical relaxation at different stages of gelation. The system transitions from an unentangled chain regime to a crosslink dissociation dominated regime, where the relaxation is governed by two timescales with different activation energies. To account for the interplay of chain and crosslinker dynamics, a time-temperature-superposition procedure is introduced for both processes separately, thus separating the dynamic processes in these thermorheologically complex dynamic networks. The activation energy of chain relaxation remains unchanged whether or not the chain participates in the network. To model contributions to the dynamic modulus of each process, we combine concepts from fractional viscoelasticity with a generalized Maxwell model, which describes the dynamics of an unentangled chain solution with reversible crosslinks. This allows us to quantify the evolution of viscoelastic parameters in the course of gelation, where we find that the terminal relaxation time of the gels increases less than expected at high crosslinker contents. This result is attributed to a facilitated crosslink exchange mechanism and a lower pH of the gel matrix.
RESUMEN
Li metal batteries (LMBs) containing cross-linked polymer electrolytes (PEs) are auspicious candidates for next-generation batteries. However, the wetting behavior of PEs on uneven Li metal surfaces has been neglected in most studies. Herein, it is shown that microscale defect sites with curved edges play an important role in a wettability-dependent electrodeposition. The wettability and the viscoelastic properties of PEs are correlated, and the impact of wettability on the nucleation and diffusion near the Li|PE interface is distinguished. It is found that the curvature of the edges is a key factor for the investigation of wetting phenomena. The appearance of microscale defects and phase separation are identified as main causes for erratic nucleation. It is emphasized that the implementation of stable and consistent long-term cycling performance of LMBs using PEs requires a deeper understanding of the "soft-solid"-solid contact between PEs and inherently rough Li metal surfaces.