This question pertains to Grumpy Parsnip's answer here: Fiber bundle with null-homotopic fiber inclusion
The claim is: If $F\to E\to B$ is a fiber bundle with $F\to E$ nullhomotopic, then the LES of homotopy groups breaks into split SES's:
$$0\to \pi_i(E)\to \pi_i(B)\to \pi_{i-1}(F)\to 0$$
In the answer linked above, it is claimed that a splitting is given as follows:
$$\begin{align} & \pi_{i-1}(F)\to \pi_i(E,F)\stackrel{\cong}{\to}\pi_i(B) \\ &[f]\mapsto[(\widetilde{f},f)] \end{align}$$
where $\widetilde f:D^i\to E$ is an extension of the composite $S^{i-1}\stackrel{f}{\to} F\to E$ which is nullhomotopic.
What's not clear to me is why this is well-defined. That is, why is the boundary map $\pi_i(E,F)\to \pi_{i-1}(F)$ injective? Is this true for arbitrary pairs of spaces $(E,F)$ with $F\hookrightarrow E$ nullhomotpic?