Deciphering the Evolution of Current Distribution in Hybrid Silver Vanadium Oxide / Carbon Monofluoride Cathodes within Lithium Primary Batteries.

For batteries to function effectively all active material must be accessible requiring both electron and ion transport to each particle. A common approach to generating the needed conductive network is the addition of carbon to create a composite electrode. An alternative approach is the electrochemically induced formation of conductive reaction products where the electrochemically generated materials are in intimate contact with the active material contributing to effective connection of each active particle. This study probes silver vanadium oxide (Ag₂V₄O₁₁, SVO), carbon monofluoride (CF_x), and hybrid SVO/CF_x electrodes in lithium batteries. Ex situ XRD identifies Ag⁰ as a reduction product from SVO and LiF from CF_x that can be followed as a function of depth-of-discharge (DOD). Spatially-resolved operando energy dispersive x-ray diffraction reveals that the presence of SVO alleviates reaction heterogeneity in the electrodes which are electron transfer limited in the absence of sufficient Ag⁰. Synchrotron X-ray tomography on discharged cathodes reveals the distribution of silver particles where the particles are more closely spaced near the current collector indicating multiple nucleation sites for their formation. Finally, operando isothermal microcalorimetry is used to determine the heat dissipation of the parent and hybrid battery types. Using material enthalpy potentials, we determine the current distribution between the two active materials for the discharging hybrid cathode adding further insight to the diffraction analysis. Taken together, these results provide a comprehensive understanding of hybrid SVO/CF_x cathodes and give guidance on optimal compositions that balance power and energy density considerations.