Bi-static sensing is crucial for exploring the potential of networked sensing capabilities in integrated sensing and communications (ISAC). However, it suffers from the challenging clock asynchronism issue. CSI ratio-based sensing is an effective means to address the issue. Its performance bounds, particular for Doppler sensing, have not been fully understood yet. This work endeavors to fill the research gap. Focusing on a single dynamic path in high-SNR scenarios, we derive the closed-form CRB. Then, through analyzing the mutual interference between dynamic and static paths, we simplify the CRB results by deriving close approximations, further unveiling new insights of the impact of numerous physical parameters on Doppler sensing. Moreover, utilizing the new CRB and analyses, we propose novel waveform optimization strategies for noise- and interference-limited sensing scenarios, which are also empowered by closed-form and efficient solutions. Extensive simulation results are provided to validate the preciseness of the derived CRB results and analyses, with the aid of the maximum-likelihood estimator. The results also demonstrate the substantial enhanced Doppler sensing accuracy and the sensing capabilities for low-speed target achieved by the proposed waveform design.