Without finite fields: We wish to show that $\det(A)$ is necessarily odd (which we concluded from the $\Bbb F_2$ approach), which would imply $\det(A) \neq 0$. Fix a matrix $A$ of the described pattern.
Let $A^{(i,j)}$ denote the matrix in which we "flip" the sign of the $i,j$ entry. That is,
$$
A^{(i,j)}_{pq} = \begin{cases}
-A_{ij} & p=i,q=j\\
A_{ij} & \text{otherwise}
\end{cases}
$$
By applying the Laplace expansion of the determinant along the $i$th row, we see
$$
\det(A) - \det(A^{(i,j)}) = 2C_{ij}
$$
Where $C_{ij}$ is the cofactor associated with $i,j$. Notably, $C_{ij}$ is an integer.
So, flipping one sign won't change the parity of the derivative. Thus, is sufficient to show that the matrix $A$ whose off-diagonal entries are all $1$ has an odd determinant. But this is easy.
In particular, if $x$ is the column vector whose entries are all $1$, then we want to show that $\det(xx^T - I)$ is odd. We can do so either by considering the eigenvalues of the rank-$1$ matrix $xx^T$ or by Sylvester's determinant identity (or by row-reduction, or by observing that the matrix is circulant). Whichever way you choose, we find $\det(xx^T - I) = 1-n$, which is necessarily odd.
Another slick proof using finite fields (which avoids appealing to circulant matrices):
Consider the $n \times n$ matrix $B$ whose entries (from $\Bbb F_2$) are all $1$. Since $n$ is even, we find that $B^2 = nB = 0$. Since $B$ is nilpotent, its only eigenvalue is $0$ (with multiplicity $n$).
The matrix $A$ (taken modulo $2$) is given by $A = B + I$. Since $B$ has eigenvalue $0$ with multiplicity $n$, we may conclude that $A$ has eigenvalue $1$ with multiplicity $n$. Thus, $\det(A) = (1)^n = 1 \neq 0$.
Thus, we conclude that the determinant of an $A$ of the presented form is odd, hence non-zero.
Or, more simply: $B^2 = 0$. So, $A = B+I$ is invertible since
$$
A^2 = B^2 + 2B + I = 0 + 0 +I = I
$$