[guided]We must prove the exact definiteness axiom: the operator norm is zero precisely for the zero operator.
First consider the zero operator. Let
\begin{align*}
0_{X,Y}:X&\to Y
\end{align*}
be the map defined by $0_{X,Y}x=0_Y$ for every $x\in X$. For every $x\in X$ satisfying $\|x\|_X\le 1$, the norm of the image is
\begin{align*}
\|0_{X,Y}x\|_Y=\|0_Y\|_Y=0.
\end{align*}
Therefore the set whose supremum defines $\|0_{X,Y}\|_{\mathcal L(X,Y)}$ contains only the number $0$, and hence
\begin{align*}
\|0_{X,Y}\|_{\mathcal L(X,Y)}=0.
\end{align*}
Now assume $T\in\mathcal L(X,Y)$ and
\begin{align*}
\|T\|_{\mathcal L(X,Y)}=0.
\end{align*}
We want to prove that $T$ sends every vector in $X$ to $0_Y$. Let $x\in X$ be arbitrary. If $x=0_X$, linearity gives $Tx=T0_X=0_Y$.
It remains to handle the case $x\ne 0_X$. The operator norm only controls vectors in the unit ball, so we scale $x$ into that unit ball. Define
\begin{align*}
u:=\frac{x}{\|x\|_X}\in X.
\end{align*}
Because $x\ne 0_X$, the norm axiom in $X$ gives $\|x\|_X>0$, so this definition is valid. By homogeneity of the norm on $X$,
\begin{align*}
\|u\|_X=\left\|\frac{x}{\|x\|_X}\right\|_X=1.
\end{align*}
Thus $u$ is one of the vectors appearing in the supremum defining the operator norm. Consequently,
\begin{align*}
0\le \|Tu\|_Y\le \|T\|_{\mathcal L(X,Y)}=0.
\end{align*}
So $\|Tu\|_Y=0$, and definiteness of the norm on $Y$ implies $Tu=0_Y$. Since $x=\|x\|_X u$, linearity of $T$ gives
\begin{align*}
Tx=T(\|x\|_X u)=\|x\|_X Tu=0_Y.
\end{align*}
Thus every $x\in X$ satisfies $Tx=0_Y$, so $T=0_{X,Y}$.[/guided]