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I have no expertise on this subject, but lots of interest in seeing someone give it a try!
There should be multiple safety systems in place to protect from these voltages. Even though I have been extremely attentive while handling supercapacitors, I have twice accidentally arc'd the pack with a brief but spectacular display of sparks... on just 13 volts.
The safety systems should allow a tired brain to make mistakes, forget things, and still remain safe.
How about making the double-voltage system and doing a series of increasing tests to verify all components are able to handle it? If some measured parameter approaches a limit, either engineer a solution, or abandon the idea and go dual motor / parallel batteries.
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