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When Iroh teaches Zuko how redirect lightning, he instructions Zuko to move the lightning from his arm, down to his stomach, and out the other arm. Iroh called the stomach the “Sea of Chi”, or a vast ocean in Irohs case.
In Zuko’s final Agni Kai with a Azula, he is able to redirect the lightning, but at great cost. Zuko wasn’t able to maintain proper form when he was jumping in to save Katara, and got hurt and a chest scar as a result.
My theory on how Zuko got that scar is this: Zuko didn’t have time to redirect most of the lighting through his arms. Instead, he caught most of it directly in his stomach. Then from the stomach, he could release it from his other arm. However, Zuko got very hurt because the lighting burned through flesh on its way to the stomach.
My Evidence: His chest scar is exactly over where his stomach should be.