There's no physical reason why something like a Segway can't be safe running that fast, but the problem is obviously much simpler at lower speeds.
The only way you could make a Segway safe at 25MPH would be to fully enclose it in a roll/crash cage and harness the rider. This is only for the rider's safety; you would have to go through a whole different process to arrive at a design that maximised pedestrian safety.
At which point it's a different device entirely.
Unless you have an idea for a scenario in which a Segway rapidly decelerates from 25-0MPH in a short space of time without chucking the rider at the scenery and/or pavement.
Some things can't be made safe in a practical way. A 25MPH Segway falls into that category, I think.