Can one of the capacitors in series get negative Voltage when discharging?
It depends on how they were charged to begin with.

If you charge the capacitors to the same voltage individually, then connect them in series and discharge them, then when the total voltage reaches zero, you'll find that the largest capacitor has a small positive bias on it and the smaller capacitors all have small negative biases.

On the other hand, if you connect the discharged capacitors in series and then charge them, you'll find that the largest capacitor ends up with the smallest relative voltage, and all of the smaller capacitors have larger voltages across them. When you discharge them, they all reach zero volts at the same time.