Absolutely. Look at intraday electricity prices, and you see that the energy is cheapest when the sun is shining.

Problem is, if you use it for cooling, it's strictly better to use the electricity directly (chances are the sun is shining when it's hot).

And if you use it for heating (at least from day to night), the round-trip efficiency is probably still better for batteries, or electric heating + hot water storage, because you can use heat pumps which are say, 5x more efficient than burning fuel.