Photovoltaic systems are providing a growing share of power to the electric grid worldwide. As more and more of these systems are tied with battery energy storage to balance their intermittency, being able to ensure long and safe operation of these batteries will become critical. Because of their sporadic usage, far from the typical constant current or constant power, diagnosability without having to perform lengthy maintenance cycles will be a key factor to accelerate deployment.This work proposes a new methodology to enable the training of machine learning algorithms so they could be applied directly to photovoltaic (PV) battery charging data for opportunistic diagnosis. This is done by training the algorithms on synthetic voltage data under different degradations calculated from clear-sky model irradiance data. Validation was performed on synthetic voltage responses calculated from plane of array irradiance observations for a PV system located in Maui, HI, USA.Herein, we will present the result of our proof-of-concept study where we investigated the diagnosability of the voltage response of PV charged batteries under 18 different cloud coverages scenarios and for more than 10,000 different degradations. We also evaluated the effect of training conditions on clear-sky irradiance data by analyzing the resulting differences from training on 700,000 different voltage curves for a single day vs. 45,000 different voltage curves for of each of the 18 days used for cloud coverage estimation. In addition, we considered and quantified the effect of cell-to-cell variations. Training was performed on five state-of-the-art machine learning algorithms for battery diagnosis which included decision tree ensemble methods and neural networks. Finally, because the diagnosis was done outside of constant current, the capacity- and time-based information were decorrelated and compared. While time-base diagnosis is the most interesting for deployed systems, it was shown to be less accurate than its capacity counterpart for the tested algorithms. Yet, the accuracy of the diagnosis is still satisfactory for days where cloud effect is limited (average RMSE of 2.5% compared to 1.3% for capacity based if 50% or more clear skies).Summarizing, we will show that the degradation of PV-connected batteries could be diagnosed opportunistically without the need for maintenance cycles using well-trained state-of-art machine learning algorithms. Calculated RMSEs were below 2% for days with 50% or more clear skies considering more than 10,000 different degradation paths with 25% or less of the three thermodynamic degradation modes. In addition to the results themselves, and before real PV battery degradation data becomes available, this work is showing the significant benefits of using synthetic data to understand the expected variations and to start preparing adapted tools for when data become available.