First, a clarification on terminology. The property that you are mentioning is what makes an outer measure a metric outer measure. Lebesgue measure is a metric outer measure, so we know that $m_*(E_1\bigcup E_2)= m_*(E_1) + m_*(E_2)$, where $E_1\bigcap E_2=\emptyset$ must be true if $d(E_1,E_2)>0$.
Now, to your question. An outer measure is additive on the $\sigma$-algebra of measurable sets $\mathcal{M}$. In fact, if $E_1, E_2 \in \mathcal{M}$, we have
$$
m_*(E_1\cup E_2)=m_*((E_1\cup E_2)\cap E_1)+m_*((E_1\cup E_2)\cap E_1^c)= m_*(E_1) + m_*(E_2),
$$
using the definition of measurable set.
So we need to look for a counterexample among non-measurable sets. Note that Solovay proved in 1970 that the existence of a non-measurable set is possible only if we assume the Axiom of Choice, so there won't be a trivial answer to your question.
The most famous construction of a non-measurable set is the Vitali set.
As in this answer by JDH, we can construct a Vitali set $V$ in such a way that is contained in $[0,a]$, for any $a \in (0,1)$. Also, since the inner measure of $V$ is zero, we have that $m_*([0,a]\setminus V)=a$ and then $[0,a]\setminus V$ is a non-measurable set of measure $a$.
Note that we must have $m_*(V)>0$, because a set is measurable if and only if its outer and inner measures coincide, and we know the latter to be zero.
Then we have, by setting $E_1=V$ and $E_2= [0,a]\setminus V$,
$$
a=m_*([0,a])=m_*(E_1 \cup E_2) < m_*(E_1)+m_*(E_2)=a + m_*(V).
$$