The determinant of $J_n - I_n$ is nonzero in the base field if and only if $J_n - I_n$ is invertible: so let's compute $\operatorname{det}(J_n - I_n)$. Recall that for a diagonalizable matrix its determinant is just the product of its eigenvalues (with multiplicity): we will show that $J_n - I_n$ is diagonalizable and compute these eigenvalues.
First I claim that there are $n - 1$ linearly independent eigenvectors of $J_n - I_n$ all with eigenvalue $-1$ given by (check this):
$$
\begin{bmatrix}
-1\\1\\0\\0\\\vdots\\0
\end{bmatrix},
\begin{bmatrix}
-1\\0\\1\\0\\\vdots\\0
\end{bmatrix},
\cdots,
\begin{bmatrix}
-1\\0\\0\\0\\\vdots\\1
\end{bmatrix}.
$$
Next I claim that the vector
$$
\begin{bmatrix}
1\\1\\1\\\vdots\\1
\end{bmatrix}
$$
of all ones is an eigenvector with eigenvalue $n - 1$ (check this too).
This pins down all of the eigenvalues with multiplicity of $J_n - I_n$: we have $\det(J_n - I_n) = -1 \cdot -1 \cdot \cdots \cdot -1 \cdot (n - 1) = (-1)^{n-1}( n - 1)$. In particular $J_n - I_n$ is invertible if and only if $n - 1$ is nonzero in the base field. This is always the case as long as the characteristic of the base field does not divide $n - 1$, as you say.