This is their first fight after Zuko learned the true meaning of fire, and consequently the very first time Zuko has ever shown the ability to dismiss Azula's fire. You can plainly see that blocking her attacks has no visible strain on him, and he can plainly keep up with her attack speed. With Sokka's help Azula came dangerously close to death in a very short amount of time. Contrast his fight here with his bouts with her in book 2 where he was only able to survive against her through ducking and weaving and you can see how much closer they are as fighters. Also notice that Zuko wasn't afraid to face his sister. In fact he seemed eager to fight her.
Zuko again seemed pretty confident he wasn't marching to his death. He was fully aware it was his sister and was still confident he could at least match her long enough for the others to escape. I also see nothing in Azula's stance or technique that hint at her being a sloppier fighter, and she hadn't started seeing hallucinations yet, nor begun breaking down into hysterical sobbing. There's literally no indication that she isn't mentally capable enough to fight. This showdown ends after Zuko casually blows through all her attacks to get close, and the two have their attacks collide in a massive explosion that blasts both off the ship.
Zuko: "I can handle Azula."
Iroh: "Not alone. "You'll need help."
Zuko: You're right. How would you like to help me put Azula in her place?
As for this line of dialogue, notice that Zuko IS confident he can handle Azula. After all, his last two fights were very close. Iroh interrupts and says Zuko shouldn't go alone, to which Zuko agrees as he has tremendous respect for his uncle. Also keep in mind that Iroh was not around to see Zuko learn the true meaning of fire, and hasn't seen Zuko fight since book 2, so he has no way of knowing what Zuko's current skill level is to begin with. On top of that, we know that Iroh can be a worry wort when it comes to Zuko's safety.
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