Because the positive terminal is charged by removing electrons from that end of the battery, which takes work. When you connect it to the negative end, you are allowing stray electrons to push towards the electron “holes” on the positive end.
In general, there aren’t many electrons that actually move from one end to the other. It is just that the lack of electrons on one end attracts all the electrons crowded in the metal conductors like they were cars on a highway at rush hour.
Negative is usually connected as ground because a large metal object usually has an excess of electrons which – if pulled away – won’t cause an imbalance of voltage in it. It can be called a current source (or sink, to ground excess current in the circuit).
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