As a non-mathematician, it seems to me that the Law of Excluded Middle is merely an axiom when it comes to proofs that employ it.
Can we really rely on such proofs? In what sense are they valid?
EDIT
In the light of comments, my point is that yes, all proofs depend on axioms (I believe - I have never proved anything myself!) but, if we want to prove something in a specific field, how can we be certain that a proof is valid?
For example, I understand that there were mistaken proofs concerning factorisation because it was not realised that it was necessary to take into account complex numbers.
Therefore the main part of my question (i.e. In what sense are they valid?) really means, How does one decide whether or not this axiom is relevant in a particular field.
That depends on what you define as "valid".
Most mathematicians work with classical logic, i.e. logic in which the law of excluded middle is an accepted axiom. As David pointed out in the comment, there is also intuitionistic logic, in which the law of excluded middle is not accepted as axiom.
Since most mathematicians work with classical logic, most modern mathematical results are proved with the law of excluded middle assumed as an axiom. Thus, these proofs are "valid" in classical logic. On the other hand, if a proof uses the law of excluded middle somewhere (e.g. proof by contradiction), then it is not a "valid" proof in intuitionistic logic.
In summary, there is no single property determining whether a proof is "valid". Instead, we can only ask if a proof is valid in a certain class of logic.