TL, DR: One claim cited in the question is actually wrong in the generality it is stated there, and some short arguments given for it are flawed; however, the issue can be fixed in sufficient special cases if one invokes more structure theory (as alluded to in Lubin's answer, which is, of course, entirely correct).
1. The exercise quoted in the OP is exercise 1a to chapter II, section 3 in Fesenko/Vostokov, page 55 here (they use $F$ where we use $K$). But part of what is claimed there, namely, that
for $ \alpha_n := \sum_{i=1}^n \theta_i \pi^i$ (where $ \theta_i \in \mathcal{O}_{K_{i+1}} \setminus \mathcal{O}_{K_i}$), we have $\lim_{n \to \infty} \alpha_n \notin K^{ur}$
is actually wrong unless one is more restrictive about what $\theta_i$ are allowed.
Example. Since $17$ is my favourite number, I will show an example where $\lim_{n \to \infty} \alpha_n = 17 p$ which quite obviously is $\in K^{ur}$.
Indeed, let $K = \mathbb Q_p, \pi =p$, $K_i := \mathbb Q_p(\zeta_{p^i-1})$, and let
$$\theta_1 := 17 - p \zeta_{p^2-1}$$
and for $i \ge 2$,
$$\theta_i := \zeta_{p^{i}-1} - p \zeta_{p^{i+1}-1}.$$
Then $\theta_i \in \mathcal{O}_{K_{i+1}} \setminus \mathcal{O}_{K_i}$ but we also have $$\alpha_n = 17p - p^{n+1} \zeta_{p^{n+1}-1}$$ for all $n$, so as claimed $\lim_{n \to \infty} \alpha_n = 17p \in \mathbb Z \subset K^{ur}$.
2. The issue with supposed arguments showing that the limit is $\notin K^{ur}$, like in the OP
if it is in the union, it belongs to one of the $K_i$'s, but this contradicts the fact that $\alpha_j \notin K_j$ [maybe $K_i$ is meant here, but it does not matter] for $j > i$.
is that while the first implication (that it belongs to some $K_i$) is true, and while it is also true that $\alpha_j \notin K_i$ for any $j \ge i$ (this holds true in my example in 1 too), these things just do not contradict each other. In a comment it is written
each $\alpha_i \in K_i \setminus K_{i-1}$, so when you make $i$ go to infinity, it will not be in any $K_i$. The limit exists, but it is not in any finite extension.
but these vague words contain an invalid conclusion from the terms of a sequence to its limit; as the example shows, we can very well have a sequence whose individual terms leave any finite extension, but that tells us more or less nothing about its limit.
I admit at first those claims sounded plausible to me too, but I also assume once one sees what the issue is, one sees how I made up my example, and how one can easily make many more.
3. How we can save what we want:
Of course e.g. Lubin is well aware of these things, but politely hides them a little in his answer, in the short remarks about uniqueness of certain representations. This idea does provide us with examples where the argument goes through. One just has to put a little more work into this, as in
Example: If in the situation described in 1 we instead let $$\theta_i := \zeta_{p^{i+1}-1},$$ then indeed $\lim \alpha_n \notin K^{ur}$.
Namely, the completion $\widehat{K^{ur}}$ is a field with a discrete valuation, uniformizer $p$, residue field $\mathbb F_p^{alg}$, and (by definition) complete. Hence, by general structure theory for such fields, once we fix a set of representatives $R \subset \mathcal{O}_{\widehat{K^{ur}}}$ of the residue field, then the standard series representation with such representatives is unique, i.e. if $\sum \beta_n p^n = \sum \gamma_n p^n$ and all $\beta_i, \gamma_i \in R$, then for all $n$ we have $\beta_n =\gamma_n$. But the joke is that we can choose a set of such representatives which is compatible with our tower of fields $K_i$; for example, letting $R_i := \mu_{p^i-1}$ (all roots of unity of order $p^i-1$) and $R:= \bigcup R_i$, now we can put the supposed arguments in 2 on solid ground: Namely, if $\alpha:=\lim \alpha_n \in K^{ur} = \bigcup K_i$, then it is in some $K_i$; but because $R_{i}$ is also a set of representatives of the residue field of the complete field $K_i$, this means there is also a representation
$$\alpha = \sum \gamma_n \cdot p^n \qquad \qquad (I)$$
with all $\gamma_n \in R_i$. But in $\widehat K^{ur}$, of course we still have
$$\alpha = \sum \zeta_{p^{n+1}-1} \cdot p^n \qquad \qquad (II).$$
Now because $\zeta_{p^{j+1}-1} \notin R_i$ for all $j \ge i$, but $R_i \subset R$, the expressions $I$ and $II$ contradict the uniqueness of series representations with coefficients in $R$ in the field $\widehat{K^{ur}}$.
(It's also fun to see where exactly this kind of proof breaks down in my example in 1. It happens not where one might first think: The series representations $\alpha = 17 p$ versus $\alpha = \sum \theta_i p^i$ do not contradict each other, because they do not share the same set of representatives as coefficients.)