Luffy uses Gear 5 in a significant battle towards the later part of the manga. But the exact chapter or arc can vary depending on how you're reading it.
I think it's in a relatively recent chapter, but the exact one might vary depending on where you're reading the manga. You might need to check the latest updates.
Well, in the fanfiction, Gear 4 Luffy might have had some new and unexpected interactions. Maybe he could have teamed up with some other pirates in a different way. Since he was in such a powerful form, he could have inspired more of the pirates to fight back more bravely against the Marines. And his presence in Gear 4 could have also affected the admirals' strategies, making them more cautious or forcing them to use their more powerful techniques earlier.
It would likely make the storyline more exciting. Gear 4 Luffy is extremely powerful, so his presence in Marineford would change the power dynamics. He could defeat more enemies quickly.