Perhaps a fashion designer who has always been overshadowed by Marinette's designs. This person gets akumatized when they see all the love and attention that Ladybug (who is Marinette) gets. They become a villain who uses their fashion - themed powers to create outfits that make people act in love - crazed ways. The Love Patrol would then have to deal with this designer - turned - villain and their wacky fashion - induced love spells.
A new villain could be introduced. For example, a Cupid - like figure who has gone bad. This villain could be jealous of all the love Ladybug and Chat Noir are trying to protect and decides to use his powers to turn love into chaos. He could shoot arrows that make people fall out of love or into obsessive and harmful love, which would be a big challenge for the Love Patrol.
Hawkmoth could be the main villain as always. He might see the Valentine's Day spirit or all the love in the air during the Love Patrol's time as an opportunity to akumatize someone. Maybe he akumatizes a jilted lover who then goes on a rampage against happy couples in Paris.
A new character could be introduced as the main villain. Maybe a corrupt police officer who turns to the dark side. He could use his knowledge of the law and the city's security systems to commit crimes and frame the Miraculous heroes. He would be a formidable opponent as he has insider knowledge.
An evil alien warlord could be the main villain. This warlord could be bent on conquering Earth and other planets in the universe. He might see the Miraculouses as a threat and try to destroy Ladybug and Chat Noir first.
Hawkmoth is an obvious choice. His whole mission is to obtain the Miraculouses, and in a death fanfiction, he could succeed in a more devious way than in the original series, directly or indirectly causing Ladybug's death.
A possible main villain could be a character from Ladybug's past who has discovered her identity and is using that knowledge to create chaos. They could be blackmailing her or trying to steal her Miraculous by setting up elaborate mysteries and traps for her to solve.
One possible plot could be that Ladybug and Chat Noir form a special 'Love Patrol' to protect the city during a Valentine's Day event. They notice that an akumatized villain is targeting couples and spreading hate. As they fight, they also start to realize their own feelings for each other more deeply. They use their powers in creative ways, like Ladybug's Lucky Charm creating heart - shaped objects that help them in the battle.
Hawk Moth would be an obvious choice as he is the main villain in the series. He could be extra devious during Christmas, trying to ruin the festive mood for everyone in Paris. He might akumatize people who are feeling left out or jealous during the holidays.
The main villain could be a pirate captain who has found a dark Miraculous. He uses its power to control other pirates and turn them into his minions. He wants to use the power of the Ladybug and Cat Noir Miraculous to become the most powerful being on the seas.
Ladybug and Chat Noir would likely be main characters as well. Since it's a Miraculous Ladybug fanfiction, they are important figures in that universe. They would interact with the son of the villain, either as enemies at first or as potential allies. And then there could be the villain parent. This character would have a big influence on the son's life and actions, constantly pulling him towards the path of villainy.
A time - traveler from the future could also be an interesting main villain. This character could have seen a dark future where the Miraculouses were misused and has come back to the present to destroy them all. But in his quest, he doesn't care who gets hurt, and Emma has to stop him from changing the past and future in a bad way.
A villain that has the power to steal emotions could be a great choice. Imagine this villain targeting Edendaphne's friends and allies, draining their positive emotions. Edendaphne would have to find a way to not only stop the villain but also restore the emotions of those affected. It would be a very emotional and intense story.