The mathematical statement $$\exists h\in \mathbb{R} \quad \dfrac{1}{h}=5 $$ seems a mathematical statement that is true.
However, its negation $$\forall h\in \mathbb{R} \quad \dfrac{1}{h}\neq 5$$ is not a mathematical statement, because it claims that $\displaystyle\frac10\ne5,$ which is nonsense since $0$ does not have a multiplicative inverse.
Consequently, the two statements either are not negations of each other or are mathematically nonsense. Which is it?
And how do I formalise “there exists a real number whose multiplicative inverse is $5$” ?
Assuming we interpret division to mean the usual notion of division in the real numbers, you're correct that the statement $(\exists h \in \mathbb{R})(1/h = 5)$ doesn't quite make sense, for the reason you stated. A more formal way of putting it is that $1/h = 5$ is not, in fact, a predicate with domain $\mathbb{R}$, so we can't quantify it over $\mathbb{R}$.
There are a few ways to correct this:
In practice, issues like this are often somewhat informally glossed over, because the intended meaning of the statement is clear and there's no ambiguity, as all these ways of resolving the formal syntactical issue lead to the same conclusion. But it's good to understand how a slightly informal notation like that can be correctly rewritten/reinterpreted to resolve any formal syntactical problems.