π–π interactions in a phenothiazine-based organic redox polymer lead to an ultra-high cycling stability of a lithium–organic battery.

Although the lithium-metal anode has the advantages of both high gravimetric and volumetric capacities (3862 Ah kg −1 and 2085 Ah L −1 ) [13] and is already successfully used in primary batteries, it is still plagued by a series of issues that limit its successful operation in rechargeable applications, when organic solvent based electrolytes are used. [14] One of them is the nature of the lithium-metal dissolution and redeposition in the discharge and charge process together with the composition of the solid electrolyte interphase (SEI) [15,16] that is formed immediately after electrolyte addition and continues to form, grow and alter during cycling, [17] which limits the rechargeability in these battery systems and decreases their safety. [15,18,19] The SEI, though not being a homo geneous single phase, varies in composition and thickness and these differences lead to inhomogeneous and thus locally different current densities during the discharge and charge process, which can ultimately cause the formation of high surface area lithium (HSAL) during lithium deposition (charging) and hole/pit formation during dissolution (discharging). [20][21][22] In the worst case, the HSAL morphology takes the form of dendrites, i.e., small needle like lithium deposits that can grow through the separator from the anode towards the cathode. This process can lead to an internal short circuit of the cell resulting in local overheating and possibly cause a cell fire due to an increased reactivity with the electrolyte and the low melting point of lithium (180.54 °C). [23] Practical approaches to improve the rechargeable lithiummetal anode from the electrode material's point of view concentrate on either using coated lithium powder [24,25] or foil [26] and lithium with surface micropatterning. [27,28] The main underlying principle is increasing the specific surface area thus decreasing the effective current density and the resulting overpotential. However, the behavior of the lithium-metal electrode is quite complex and electrolyte-dependent [22,[29][30][31] and there is a need to identify the optimal conditions under which lithium-metal electrodes can cycle with both an increased reversibility and low overpotentials. [32] As-received lithium-metal foil contains several contaminants, [33] particularly on the surface. [34] In addition, even a new lithium foil that is considered to be smooth shows a non-negligible surface roughness that Lithium metal as an electrode material possesses a native surface film, which leads to a rough surface and this has a negative impact on the cycling behavior. A simple, fast, and reproducible technique is shown, which makes it possible to flatten and thin the native surface film of the lithium-metal anode. Atomic force microscopy and scanning electron microscopy images are presented to verify the success of the method and X-ray photoelectron spectroscopy measurements reveal that the chemical composition of the lithium surface is also changed. Furthermore, galvanostatic measurements indicate superior c...

Organic cathode materials are a sustainable alternative to transition metal oxide‐based compounds in high voltage rechargeable batteries due to their low toxicity and availability from less‐limited resources. Important criteria in their design are a high specific capacity, cycling stability, and rate capability. Furthermore, the cathode should contain a high mass loading of active material and be compatible with different anode materials, allowing for its use in a variety of cell designs. Here, cross‐linked poly(3‐vinyl‐N‐methylphenothiazine) as cathode‐active material is presented, which shows a remarkable rate capability (up to 10C) and cycling stability at a high and stable potential of 3.55 V versus Li/Li+ and a specific capacity of 112 mAh g−1. Its use in full cells with a high mass loading of 70 wt% is demonstrated against lithium titanate as intercalation material as well as lithium metal, which both show excellent performance. Through comparison with poly(3‐vinyl‐N‐methylphenothiazine) the study shows that changing the structure of the redox‐active polymer through cross‐linking can lead to a change in charge/discharge mechanism and cycling behavior of the composite electrode. Poly(3‐vinyl‐N‐methylphenothiazine) in its cross‐ and non‐cross‐linked form both show excellent results as cathode‐active materials with variable specifications regarding specific capacity, cycling stability, and rate capability.