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The Large battery only charges the 12v battery when the VOLT is ON and running.
FWIW: On the Gen1 this isn't true since I have confirmed that breaking the circuit of the 12V AGM by pulling the negative lead off there is @13VDC being applied to the positive terminal of the 12V AGM whenever my Volt is plugged in and actively charging. If unplugged or when the charging cycle is complete, this @13VDC measured between B+ and chassis ground disappears.

I would expect the Gen2 to act more or less the same...

I have no idea why your button wouldn't work though...
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