The goal of this work has been to enhance the physical understanding of HPPC protocols as a means to diagnose battery degradation behavior. Such detailed physical information transcends the conventional lumped degradation modes, which merely offer insights into the "symptoms" of battery degradation. In this work, models for both current and voltage response during the pulse have been created, generating expressions directly relating physical degradation parameters and the observed response. Furthermore, we have demonstrated the benefits of using voltage pulses instead of current pulses, including stronger sensitivity with respect to degradation, explicit linear extraction of degradation mechanisms, faster optimization, and mitigated population effects relative to current pulses for phase separating materials. Discharge pulses are found to contain more information in cases of anode overpotential dominance, while charge pulses are better for cathode overpotential dominance. We have shown that it is possible extract the dominant degradation mechanisms from each electrode with a physics-based optimized HPPC protocol. This is key to tying together physics-based modeling with degradation diagnostics obtained from battery experiments without the need for "lumped" degradation modes commonly used in battery degradation . With these physical degradation parameters, we can diagnose the physical-driven reasons for battery failure and, in turn, design future batteries to mitigate capacity loss.