I claim that the maximum dimension of a subspace of singular matrices of $M_n(\mathbb{R})$ is $n^2 - n$.
This number is achieved, for example, for the subspace of matrices having the first row equal to the zero vector.
Now assume by contradiction that there were a subspace $S$ of singular matrices of dimension $n^2 - n + 1$.
Firstly, there must be an element of $S$ having a nonzero entry in the first row and having all rows from $2$ to $n$ equal to $0$, by dimension considerations. To see why this is true, let A be the subspace of matrices of the form:
\begin{bmatrix}
* & * & * & \dots & * \\
0 & 0 & 0 & 0 & 0 \\
\vdots & \vdots & \vdots & \ddots & \vdots \\
0 & 0 & 0 & 0 & 0
\end{bmatrix}
Then $$\dim(A \cap S) = \dim(A) + \dim(S) - \dim(A + S) \geq n + n^2 - n + 1 - n^2 \geq 1$$ so there must be a nonzero matrix $X$ in $A \cap S$.
Thus $X$ looks like:
\begin{bmatrix}
a_{11} & * & * & \dots & * \\
0 & 0 & 0 & 0 & 0 \\
\vdots & \vdots & \vdots & \ddots & \vdots \\
0 & 0 & 0 & 0 & 0
\end{bmatrix}
WLOG assume $a_{11} \neq 0$ (otherwise permute the elements of the first row and apply below verbatim).
Consider next the subspace $M$ of $M_n(\mathbb{R})$ of matrices of the form:
\begin{bmatrix}
0 & 0 & 0 & \dots & 0 \\
0 & * & * & * & * \\
\vdots & \vdots & \vdots & \ddots & \vdots \\
0 & * & * & * & *
\end{bmatrix}
(it's like an embedding of $M_{n-1}(\mathbb{R})$ into $M_n(\mathbb{R})$).
Now $$\dim(S \cap M) = \dim(S) + \dim(M) - \dim(S + M) \geq n^2-n+1 + (n-1)^2 - n^2 = n^2 - 3n + 2 > (n-1)^2 -(n-1) + 1$$ so by our induction hypothesis it follows that $S \cap M$ contains a matrix $Y$ which when viewed as an $(n-1)$ by $(n-1)$ matrix is invertible (and also Y has the first row equal to $0$ in $M_n(\mathbb{R})$. But then $X+Y$ will have a nonzero determinant, contradiction.
Also, after solving this problem I found a more general problem (that implies it) here.