Annie, the Dark Child is an incredibly strong mage champion in League of Legends. Her spells are ridiculously powerful, and she should not be underestimated one bit. The only down side to Annie is that she may be quite squishy and that her movement speed is quite slow. These things can be fixed through the right rune set up or by purchasing items that give you extra health as well as Ability Power.
Annie's passive ability is Pyromania, which allows her to gain a stun once every five spell casts. Once the fourth spell has been cast, the next spell will also stun the target causing them to be unable to move, cast or attack. When Annie's stun is 'up', a white ring will appear around her, so all players are able to see that her next spell will also stun. This passive is a great fight initiator, or even an escape tool.
Annie's first ability is Disintegrate. Disintegrate grants Annie a mana infused fireball that deals magic damage to the target enemy. This can be casted on enemy champions as well as minions and monsters. If you kill a target with Disintegrate, then the cost of mana for that cast will be returned back to you. If you are able to master the art of last hitting minions, then you should have no problems during the early phases of laning as you basically have unlimited mana.
Annie's second ability is Incinerate. This is an AoE (area of effect) spell that deals magic damage to those enemies who are in the targeted area. If your stun is up and you cast Incinerate, then all the enemies who are in the area of the cast will be stunned. This can be a game changer; especially during those big team fights.
The third ability that Annie beholds is Molten Shield. When you activate this ability, Annie gains a shield around her for 15 seconds. This not only increases her armour and magic resistance, but also deals magic damage to enemies who auto attack Annie. It's kind of like a Thornmail (a defensive item in the League of Legends store).
Now, for Annie's ultimate ability: Tibbers! When Summon Tibbers has been activated, Annie releases her teddy bear from his prison to deal damage to enemies in the area. Not only can Tibbers auto attack, but he also deals a decent amount of AoE damage to those around him. Tibbers is also quite tanky (with 1200 health) and is able to take multiple hits from enemy turrets. Tibbers last 45 seconds.
If you are new to playing Annie, I would recommend levelling up Disintegrate over Incinerate and concentrate on last hitting those minions in the early stages of the game. It will save you from having to go back to the shop to recharge your mana. For items, as Annie is quite squishy " go with a Catalyst the Protector to start off with and build it into a Rod of Ages. You can stack Rod of Ages, so you could possibly buy two of them. Eventually, you'll want to look into buying a Rabadon's Deathcap as well as a Void Staff (especially if the enemy team start building Magic Resistance items).
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