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As to laws of war, that is usually driven by the Hague conventions. These are agreements which apply only to signatory nations conducting war against other signatory nations. However, in practice, many non-signatory nations have adopted them as guidelines towards general customs of war.
The 1899 convention states:
“This declaration states that, in any war between signatory powers, the parties will abstain from using "bullets which expand or flatten easily in the human body.”
The 1907 convention expands on this to prohibit:
“To employ arms, projectiles, or material calculated to cause unnecessary suffering”
To my knowledge, there has never been an international judicial finding that shotguns fit into either of those categories. The Germans did protest against the use of shotguns in WWI - arguing that they fell into the unnecessary suffering category since absent easy access to x-ray or antibiotics, and the general environment of the war, small shot wounds were difficult to treat, often became infected, and led to a slow, painful death.
Even today, different nations have different interpretations of these rules. For example, the American interpretation is much broader than the British or Swiss version.
.22 caliber shot shells would be considered #4 buckshot. It is about the lightest load you would use on a 100-200lb mammal and doesn’t meet the FBI’s criteria for penetration.
I’m sure some of the others will be along to address some of the common misunderstandings about shotgun use. So, I’ll just stick to your legal question.
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