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If all you want to do is boost the ignition system, I'd use a dc-dc converter. They're really cheap, and its easier.
I would not suggest making a 3 post battery. It'll unbalance the cells and you'll have to deal with that.
Other than that, I think a 5 cell setup would be worth a shot, though still pretty high of voltage off a fresh charge (16.75V). Definitely not 6 cell, thats gonna make your voltage too high.
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