Laplace inverted pulsed EPR relaxation to study contact between active material and carbon black in Li–organic battery cathodes

The addition of conductive additives during electrode fabrication is standard practice to mitigate a low intrinsic electronic conductivity of most cathode materials used in Li-ion batteries. To ensure an optimal conduction pathway, these conductive additives, which generally consist of carbon particles, need to be in good contact with the active compounds. Herein, we demonstrate how a combination of pulsed electron paramagnetic resonance (EPR) relaxometry and inverse Laplace transform (ILT) can be used to study such contact. The investigated system consists of PTMA (poly(2,2,6,6-tetramethylpiperidinyloxy-4-ylmethacrylate)) monomer radicals, which is a commonly used redox unit in organic radical batteries (ORB), mixed at different ratios with Super P carbon black (CB) as the conductive additive. Inversion recovery data were acquired to determine longitudinal (T1) relaxation time constant distributions. It was observed that not only the position and relative amplitude, but also the number of relaxation modes varies as the composition of PTMA monomer and CB is changed, thereby justifying the use of ILT instead of fitting with a predetermined number of components. A hypothesis for the origin of different relaxation modes was devised. It suggests that the electrode composition may locally affect the quality of electronic contact between the active material and carbon black.