250.66. Grounding electrode conductors are sized in accordance with the incoming service or feeder conductors to a building or structure.
You said you have 100 amp supply, but are likely increasing conductors size because of voltage drop. 250.66 don't care what the overcurrent protection is, it looks at the supply conductor size, so if you increased to 1 or 1/0 copper or 2/0 or 3/0 aluminum, what normally could have been an 8AWG GEC now must be at least 6 AWG. If you increased to 2/0 copper or 4/0 aluminum supply conductors you would need a 4 AWG GEC, even though you still have a 100 amp breaker on the supply side.
As others have mentioned already your EGC with the feeder needs increased as well if you increased ungrounded conductors because of voltage drop.