Let's start with a denumerable set $S$. The usual process to define a free vector space over $S$ is as follows:
A free vector space over $S$ consists of a tuple $(V,\alpha)$, satisfying the following universal property: Given any other $(W,\beta)$ there exists a unique linear map $\mu: V \to W$ that makes the following diagram commute. 
Of course to allow for the extra linear structure, $V$ should be "bigger" than $S$, so $V$ consists of all functions $S\to \mathbb{R}$. These functions are considered as "formal sums", namely a typical element of $V$ can be seen as $\phi=\sum a_i s_i$, $a_i \in \mathbb{R}$ and $s_i$ is a basis, $s_i : S \to \mathbb{R}$ that satisfies $s_i(s_j)=\delta_{ij}$. Aha, so $\sum a_i s_i$ acts on an element of $S$, say $s_k$ and gives $\left(\sum a_i s_i \right)(s_k)=a_k$. So far so good.
What happens if I try to free a vector space over a non-denumerable set $S$, say an interval of $\mathbb{R}$. By naive analogy should I get "formal integrals" as elements of the free vector space? Does this connect by any means to distributions?
First, the free vector space on $S$ is not the set $F(S, \mathbb{R})$ of functions $S \to \mathbb{R}$. That's too big. Indeed, in the universal property, consider $(W, \beta)$ to be $W = \mathbb{R}$ and $\beta(s) = 1$ for all $s \in S$. Then you cannot define $\mu(v)$ where $v \in V = F(S, \mathbb{R})$ is defined by $v(s) = 1$ for all $S$, because you would be computing $\sum_{s \in S} 1$ which doesn't converge in $\mathbb{R}$, because $S$ is infinite.
Instead, the free vector space $V$ on $S$ is a subset of $F(S, \mathbb{R})$. More precisely, it is the subset of functions $f : S \to \mathbb{R}$ such that $f(s) = 0$ for all but a finite number of members $s \in S$. I'll let you check the universal property, carefully this time.
Now, this doesn't depend at all on $S$ being denumerable. You can make the exact same definition for any set $S$, even not denumerable, and you'll still get the free vector space on $S$.
If you want to have a little bit more intuition about the free vector space, you were almost right with your description as formal sums $\phi = \sum_{s \in S} \phi_s s$, except that the coefficients $\phi_s$ need to be zero for all but a finite number of indices $s \in S$. Indeed, recall that in the definition of a basis, every element can be written as a linear combination of elements of the basis. And a linear combination is always a finite sum.