Welcome Paul,
If you added two batteries to the series and charged them how you described it would work IF the chargers are isolated.
Adding cells in series will decrease the current required for your normal driving and will increase your range. Normally adding new cells to old cells would be bad if you were going to charge them together, however if you charge them seperatially then you should be fine. Also running the dc/dc converter off part of the pack would be bad if you weren't charging seperatially.
It's not the ideal solution, but it would get you a little life and extra range out of the pack.