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In a lot of places, peak supply is during the day now. Overnight conditions are more about a lack of demand than a surplus of supply (although they're sort of equivalent), but really the most effective use would be charge while the sun shines, dump the battery onto the grid when you get home, and then charge slowly overnight after the end of peak. Assuming there's no downsides from cycling your battery and you and the system have perfect knowledge of your evening plans.