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Yeah, IPv6 is pretty important. I only have a few ESP8266 around the house and my DHCP pool is getting rapidly depleted...

You must have a lot of ESP8266 to deplete ~256^3 ips.

My home router can't really do more than about 100ish IPs.

Sounds more like time to get a new router vs changing all of your internal home network to ipv6

How is switching to IPv6 going to fix that problem?

Maybe ipv6 slaac would help compared to dhcp. Not by much, but maybe a bit

The router won't have to hold a NAT table for ipv6 devices, just relay router announcements.