# Unraveling Charging and Discharging Processes in Organic Radical‐Based Electrodes: A Hierarchical Molecular and Quantum Mechanical Approach

## TL;DR

This study uses computational methods to understand how organic radical-based electrodes work during charging and discharging.

## Contribution

The paper introduces a hierarchical computational approach to analyze charge transfer in organic radical-based electrodes.

## Key findings

- Efficient intrastrand TEMPO-polythiophene charge transfer processes enhance conductivity.
- Short and rigid amid linkers are crucial for effective charge storage and transfer.
- The hierarchical approach reveals structure-property relationships in organic electrode materials.

## Abstract

Organic batteries represent a promising class of energy storage materials, due to their mechanical flexibility and sustainability. Typically, stable radicals, lacking intrinsic conductivity, are utilized as redox‐active materials. A recently introduced strategy to overcome this shortcoming is to incorporate stable radicals, i.e., (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO), into a polythiophene backbone. Thereby, an electrode material was obtained which does not require conductive additives. The current computational study aims to elucidate the functionality of this material by drawing in‐depth structure–property relationships utilizing a hierarchical molecular and quantum mechanical approach. Initially, structural properties of the electrode material's macroenvironment—containing the functionalized polythiophene, electrolyte, and solvent—were assessed in various charging states by molecular dynamics simulations. Subsequently, electronic properties were investigated by time‐dependent density functional theory for 564 microenvironments. Via this computational setup, the electronic communication within the material was assessed along intrastrand and interstrand CT processes involving the respective TEMPO and polythiophene units. Thereby, our hierarchical computational approach reveals that the intrinsic conductivity and charge storage capacity of the electrode material stems from efficient intrastrand TEMPO‐polythiophene CT processes along short and rigid amid linkers. These insights help to tailor improved conductive organic electrode materials with higher charging and discharging rate capabilities.

Charge transfer processes are investigated in p‐type organic electrode materials utilizing stable organic radicals incorporated in a conjugated backbone. Molecular dynamics simulations and time‐dependent density functional theory calculations allow us to evaluate charge transfer states as well as the underlying structure–property relationships.© 2026 WILEY‐VCH GmbH