Evaluating the Impact of Conjugation Break Spacer Incorporation in Poly(3,4-propylenedioxythiophene)-Based Cathode Binders for Lithium-Ion Batteries

Abstract

The driving force behind the significant advancement of conductive polymer binders for lithium-ion batteries (LIBs) stems from the poor binding strength, limited mechanical properties, and absence of electronic conductivity of the commonly used nonconjugated polymer binder, poly(vinylidene fluoride) (PVDF). With a goal to induce stretchability and deformability to the otherwise brittle conjugated backbone, we report here dihexyl-substituted poly(3,4-propylenedioxythiophene)-based (PProDOT-Hx 2 -based) conjugated polymers wherein conjugation break spacers (CBS, T-X-T) of varying alkyl spacer lengths (X = 6, 8, and 10) and varying contents (5, 10, and 20%) have been randomly incorporated into the PProDOT backbone, generating a family of nine random PProDOT-CBS copolymers. Electrochemical characterization revealed that three out of the nine PProDOT-CBS polymers (5% T-6-T, 5% T-8-T, and 10% T-6-T) are electrochemically stable over long-term cycling of 100 cycles. The electronic conductivity of the PProDOT-CBS polymers is consistent with previous literature reports on CBS polymers, where a decline in charge carrier mobility is observed with an increase in CBS content and spacer length, although no significant difference in ionic conductivity in these polymers was observed. This is supported by GIWAXS studies indicating a decrease in lamellar peak intensity with increasing CBS content and spacer length. Mechanical properties of the three selected PProDOT-CBS polymers were investigated by using the established "film-on-water" technique and a novel "film-on-solvent" technique that we report here for the first time, where the solvent used is the same as employed in the battery electrolyte. Both techniques showcase a generally lower tensile modulus (E) and higher crack onset strain (COS) of the PProDOT-CBS polymers relative to fully conjugated PProDOT-Hx 2 . Furthermore, significant enhancement in mechanical properties is observed with the "film-on-solvent" method, suggesting that electrolyte-induced swelling has a plasticizing effect on the polymers, accounting for their increased stretchability and deformability. Finally, cell testing of the PProDOT-CBS polymers with NCA cathodes aligned well with the electrochemical and mechanical studies, where a higher crack onset strain was crucial for higher capacity retention during long-term cycling. On the contrary, rate capability measurements proved that higher electronic conductivity is favored over mechanical properties during high rates of discharge. This work illustrates that the strategic introduction of CBS units into conjugated polymer binders is a viable method for the generation of stretchable conductive polymer binders for emerging high-capacity electrodes in LIBs.

Designer Conjugation-Break Spacer That Boosts Charge Transport in Semiconducting Terpolymers

“…Conjugated polymers (CPs) offer appealing advantages such as good solution processability, excellent mechanical flexibility, diverse molecular design, and tunable optoelectronic properties over inorganic silicon, which make them promising for applications in organic field-effect transistors (OFETs), − organic solar cells, − organic light-emitting diodes, and other electronic devices. − Great advances have been made in improving the charge carrier transport properties of CPs, primarily through the development of innovative electroactive building blocks. − It is well understood that rigid structures and coplanar geometries are favorable for strengthening intermolecular interactions and promoting tight interchain stacking, both being essential for effective intermolecular charge carrier transport. − In addition, in order to maximize the conjugation length to facilitate intrachain charge transport, those building blocks are designed to possess a fully π-conjugated skeleton, typically composed of sp 2 -hybridized carbons which constitute alternating single and double carbon–carbon bonds. − Constrained by these conventional perceptions, nonconjugated building blocks are typically excluded from being used for high-mobility CPs as they are electronically not favorable for charge delocalization and transport. In fact, for the rare instances where conjugation-break spacers (CBSs) have been incorporated into the backbone of CPs, the attention has been solely directed toward the use of flexible, nonconjugated moieties such as aliphatic or amide-containing segments, for regulating the solution processability and mechanical property of polymers. ,, While inclusion of such flexible linkers was successful in adjusting the solubility and film stretchability, , such modifications have inevitably compromised charge carrier transport after disrupting π-electron delocalization along the polymer backbone and weakening interchain interactions, potentially deterring further strategic use of CBS in CPs (Scheme a). , …”