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.
Luffy Gear 5 Fanfic: In the heart of a new island, Luffy stood tall in his Gear 5 form. His body pulsed with a vibrant red energy as he faced the powerful new foe. 'I won't let you harm my friends!' he roared. With a swift motion, he stretched his arm like a rubber band, then snapped it forward, sending a shockwave of Haki towards the enemy. The foe tried to dodge but was caught in the blast, sent flying backwards. Luffy then bounced around the battlefield, his movements a blur, leaving trails of light as he continued his attack.
One interesting idea could be exploring new abilities Luffy discovers within Gear 5 that he hasn't shown in the official story yet. For example, he might be able to manipulate his surroundings in even more creative ways, like turning the air into rubbery substances to create platforms or traps.