Radical Polymer‐based Positive Electrodes for Dual‐Ion Batteries: Enhancing Performance with γ‐Butyrolactone‐based Electrolytes

Dual-ion batteries (DIBs) represent a promising alternative for lithium ion batteries (LIBs) for various niche applications. DIBs with polymer-based active materials, here poly(2,2,6,6-tetramethylpiperidinyl-N-oxyl methacrylate) (PTMA), are of particular interest for high power applications, though they require appropriate electrolyte formulations. As the anion mobility plays a crucial role in transport kinetics, Li salts are varied using the well-dissociating solvent γ-butyrolactone (GBL). Lithium difluoro(oxalate)borate (LiDFOB) and lithium bis(oxalate)borate (LiBOB) improve cycle life in PTMA||Li metal cells compared to other Li salts and a LiPF₆- and carbonate-based reference electrolyte, even at specific currents of 1.0 A g^-1 (≈10C), whereas LiDFOB reveals a superior rate performance, i. e., ≈90 % capacity even at 5.0 A g^-1 (≈50C). This is attributed to faster charge-transfer/mass transport, enhanced pseudo-capacitive contributions during the de-/insertion of the anions into the PTMA electrode and to lower overpotentials at the Li metal electrode.