This is originally the second Part of Track 24 (Hangeki no noroshi) of Movie 10 Strong World OST. It was originally played when the whole crew (except Nami, indeed) break into Shiki's Castle and walk slowly towards him.
In the anime it is played just after Luffy is thrown by Jinbei in front of the 3 Admirals in Episode 474 - that's also the titles source.

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