Hi mat,
What you need for improving hill starting capability is more torque. Starting torque for these types of controllers is proportional to the current rating; 400 Amps in your case. Raising the battery voltage will not affect that.
The controller may or may not work with the extra 6 Volts. The charger would not fully charge the pack with the added battery.
I recommend you take a voltage and current measurement on the hill condition to see what is really happening with the battery and at the motor before doing any modifications.
Regards,
major