Yes and no. When you first hit the road, yes, you'll charge to 100%. However, along the way you'll charge up at a DC fast charge station. Those have what's called a charge curve, where it doesn't charge as fast as the battery charges. Think of it like filling a bike tire with a hand pump - the first few pumps are easy and the gauge jumps fast, but the last few are a lot harder and the needle barely moves. Much like air trying to resist higher pressure, more electrons repel each other as you charge the battery.

Ok, so charging. Charging from 10% to 80% takes roughly as long as charging from 80% to 100%. Rather than going to 100% at each charge, it's often beneficial to get just enough to get to the next charger with a little buffer room. Often you'll come out ahead if you just go to 80%ish (of course, if it's a long stretch to the next charger or you can skip a charge with more you may have reason to go beyond 80%)

Bigger range has its obvious advantages, but a bigger battery means you can take advantage of the charge curve a little more.