Interesting question! Alas, I'm not a volcanologist but here goes..
For reference, the first man-made object that was launched into space most likely wasn't Sputnik, but a man-hole cover accidentally blasted into space during the Pascal-A nuclear test (yield 55 tons!) of the Operation Plumbbob. So technically it is possible for an object to reach escape velocity from a single impulse such as an explosion, be it volcanic or nuclear. This means that with bit of handwavium it certainly makes for a plotline that is not too far fetched!
Now, to the question what it would actually mean.
First: The type of volcano.
For an explosive eruption you need a very specific type of volcano and lava. If you have a shield volcano, such as volcanoes in Hawaii, where the lava is easily flowing basaltic lava (mafic lava), you can't have a sufficiently explosive eruption regardless of the size of the eruption.
Instead, you need a stratovolcano – or the conic type you often see in photographs (eg. Mt. Fuji) – with highly viscous, felsic lavas that can lead to very explosive eruptions.
Second: Size of the eruption
Contrary to what one might think, I'm not at all certain that having a super-colossal or larger (VEI 7+) eruption would be the ideal setting. You're heaving a lot of mass instead of launching relatively small mass, rifle-like orbital debris we're looking for; $E_k = \frac{1}{2}mv^2 \rightarrow v = \sqrt{\frac{2E_k}{m}}$ after all.
In terms of energy, even a "small" volcanic explosion provides enough power to launch an object to orbit. According to this, the maximum elastic energy yield of an eruption is $10^{19}$ Joules, or equivalent energy of ~160 000 Hiroshima bombs or ~2 million Pascal-As.
Third: Plausibility.
Is the scenario plausible? Possibly? The ash from Mount Pinatubo in 1991 eruption reached 34 kilometres and the rocks from 1883 Krakatoa flew at least 50 kilometres (laterally). That's just two data points from the past 150 years. Furthermore, we can't very easily track individual sub-kilogram objects launched into space so it could have happened before, even up to escape velocity itself.
As the problem is not the size of eruption, but rapid release of energy and sufficiently durable ejecta, in order to make the scenario more plausible you could add in an obsidian monolith rock collapsing into the caldera before the eruption that acts as a cork.
This might be enough handwavium necessary for the high pressures and the ensuing explosion that could launch obsidian shrapnel unto the ISS!
Edit and fourth: Physics!
After discussing with GOATnine (see comments) I had an idea! The amount of heat transferred to the object is roughly the kinetic energy of the air mass above it accelerated to launch speed of the projectile. This is because the object moving at $v>>c$ would just punch a hole to a static atmosphere. This is, of course, only a ball park number that only works for really fast projectiles...and we're disregarding so many effects here (shape, ablation, DRAG, etc..)
In any case, the mass of air is simply $F = PA_c \rightarrow \frac{m}{A_c} = \frac{P}{a} = 1 \text{ bar} / 10 $m/s$^2 \sim 10 000 $kg/m$^2$ and the energy for heating is thus
$$E_h(v_0, A_c)= \frac{1}{2}mv^2 \sim A_c v^2 \cdot 5 000 \text{kg/m}^2$$ where $A_c$ is the cross-sectional area of the object.
What we have to resist that is the ablation of the material, i.e. heating it up to vaporization temperature and beyond. We choose aluminium oxide, as that's pretty hard obsidian material to melt. It has $\rho = 3960$ kg/m$^3$, melting point of 2324 K and boiling point ~3300 K, with heat capacities of $c_{solid} = 1200$ J/(kg$\cdot$K) and $c_{liquid} =$1127 J/(kg$\cdot$K). Finally, the phase changes $H_{solid} \sim 1 × 10^6 $ J/kg & $H_{liquid} \sim 20 \times 10^6 $ J/kg.
Starting from 290 K gives us $\Delta T_s = 2035$ K and $\Delta T_l = 1000$ K for
$$H_{tot} / m = \Delta T_s c_{solid} + \Delta T_l c_{liquid} + H_{solid} + H_{liquid} \sim 25 \text{ MJ/kg}$$
Now, we assume sphere so the mass is $m = \rho \frac{4}{3} \pi r^3$ while $A_c = \pi r^2$ so we have $$m = \frac{4}{3\sqrt{\pi}} \rho A_c^\frac{3}{2} \sim A_c^\frac{3}{2} 3000 \text{ kg/m}^3$$
Plugging that as mass gives us the total heat capacity in terms of $A_c$
$$H_{tot} = A_c^\frac{3}{2} \cdot 7.5 \text{ GJ/m}^3$$
And setting that as larger than heating energy
$$\begin{align}
H_{tot} & > E_h \\
A_c^\frac{3}{2} \cdot 7.5 \text{ GJ/m}^3 & > A_c v^2 \cdot 5 000 \text{kg/m}^2 \\
\frac{v^2}{\sqrt{A_c}} & < 1.5 \cdot 10^6 \text{m/s}^2
\end{align}
$$but as $A_c$ here is just $\pi r^2$ the solution relates radius and velocity into a simple relation:
$$ \frac{v^2}{r} < 2.7 \cdot 10^6 \text{m/s}^2 \longrightarrow \\
f(r) > \frac{v^2}{2.7 \cdot 10^6 \text{m/s}^2} \lor f(v) < \sqrt{r \cdot 2.7 \cdot 10^6 \text{m/s}^2}
$$
So, what does that tell us? At escape velocity $v = 11.2$ km/s we get that the radius has to be around 50 meters or over. Now, this is not enough to launch the object into space as we're ignoring drag here (heh). If we guesstimate that with drag we need double the delta-v to LEO to reach LEO we have $v = 18$ km/s and $f(r) > 120$ meters.
Still plausible? Perhaps...but unlikely! However, we can definitely rule out the manhole cover from ever reaching space: The whopping 50+ km/s translates roughly to a 1 kilometer object!
n.b. with a bit of tweaking you can convert that relation to a function of m or to different materials.