Maybe the voltage regulator in the alternator going screwy?
My old Cavalier had a similar problem. Sometimes when starting the volts light would be on and it wouldn't charge. The mechanic showed me how to jump 2 wires at the alternator to give it a kick in the pants and get it to charge. It became so common that I wired a switch up to the dash so I didn't have to pop the hood every morning.
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Winter daily driver, parked most days right now

Summer daily driver
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