I think you are right about the higher voltage. Even a generator or alternator puts out higher voltage.
The difference between a 10 amp charger and an 810 amp battery is about 800 amps of power. Enough to increase the size of the spark when attaching leads to a battery.
Of course the battery has to be outgassing when the spark occurs to get an explosion. I don't know when the maximum and minimums that a battery outgasses. I presume the 6 volt battery is at a low charge and the 12 volt has a full charge. The 12 volt with a running engine would have 13.6 volts going to it and maybe cause some outgassing. Opening the hood and quickly attaching leads would not let the gas dissipate and make things worse. Guess I'll see what others say about this. My 2 cents.
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