Sent some on-chain satoshis from Electrum to my Muun wallet at 4.1 sat/vB about two hours before time of this post.
Is this the Muun wallet you use?
https://muun.com/I did use this wallet but they claim to be self custodial. I am not sure why you sent your bitcoins from Electrum wallet to Muun wallet?
They are same in self custodial wallet and they all have Lightning Network. You can have Lightning Network on Electrum wallet too.
Will Muun cancelled the pending LN transaction after 24 hours or will it stay like that until on-chain fees are low again?
Transactions on Lightning Network are not on-chain, it's off-chain. Fee for Lightning Network transaction is very low but you have to pay on-chain transactions when you open or close your Lightning Network channel in Electrum wallet.
I don't know with Muun wallet, they provide a Lightning Network service for users and you don't have to open or close your own channel. It is strange because with such service, they are not self custodial.