Phenothiazine Polymers as Versatile Electrode Materials for Next-Generation Batteries.

Organic battery electrode materials are key enablers of different postlithium cell chemistries. As a p-type compound with up to two reversible redox processes at relatively high potentials of 3.5 and 4.1 V vs. Li/Li, phenothiazine is an excellently suited redox-active group. It can easily be functionalized and incorporated into polymeric structures, a prerequisite to obtain insolubility in liquid battery electrolytes. Phenothiazine tends to exhibit π-interactions (π*-π*-interactions) to stabilize its radical cationic form, which can increase the stability of the oxidized form but can also strongly influence its cycling performance as a battery electrode material. In recent years, we investigated a broad range of phenothiazine-based polymers as battery electrode materials, providing insight into the effect of π-interactions on battery performance, leading to design principles for highly functional phenothiazine-based polymers, and enabling the investigation of full cells. We observed that π-interactions are particularly expressed in "mono"-oxidized forms of poly-(3-vinyl--methylphenothiazine) (PVMPT) and are enabled in the battery electrode due to the solubility of oxidized PVMPT in many carbonate-based liquid electrolytes. PVMPT dissolves during charge and is redeposited during discharge as a stable film on the positive electrode, however, still retaining half of its charge. This diminishes its available specific capacity to half of the theoretical value. We followed three different strategies to mitigate dissolution and inhibit the formation of π-interactions in order to access the full specific capacity for the one-electron process: Adjusting the electrolyte composition (type and ratio of cyclic vs. linear carbonate), encapsulating PVMPT in highly porous conductive carbons or cross-linking the polymer to X-PVMPT. All three strategies are excellently suited to pursue full-cell concepts using PVMPT or X-PVMPT as positive electrode material. The extent of π-interactions could also be modified by structural changes regarding the polymer backbone (polystyrene or polynorbornene) or exchanging the heteroatom sulfur in phenothiazine by oxygen in phenoxazine. By changing the molecular design and attaching electron-donating methoxy groups to the phenothiazine units, its second redox process can be reversibly enabled, even in carbonate-based electrolytes. Studies by us as well as others provided a selection of high-performing phenothiazine polymers. Their applicability was demonstrated as positive electrode in full cells of different configurations, including dual-ion battery cells using an inorganic or organic negative electrode, anion-rocking-chair cells as examples of all-organic batteries, or even an aluminum battery with a performance exceeding that of aluminum-graphite battery cells. In changing the design concept to conjugated phenothiazine polymers, a higher intrinsic semiconductivity can result, enabling the use of a lesser amount of the conductive carbon additive in the composite electrode. It also provides a handle to alter the optical properties of the polymers, for instance by designing donor-acceptor type conjugated polymers with visible-light absorption, where we demonstrated an application in a photobattery. This Account provides an overview of these findings, also in the context of other literature in the field. It highlights phenothiazine polymers as versatile electrode materials for next-generation batteries.