Although I know a lot of email clients will pre-fetch or otherwise cache images.
That is not even a given already.
Many email clients – be they web-based, or standalone applications – have privacy controls that prevent images from being automatically loaded, to prevent tracking of who read a (specific) email.
On the other hand, there’s clients like f.e. gmail’s web interface, that tries to establish the standard of downloading all referenced external images, presumably to mitigate/invalidate such attempts at user tracking – if a large majority of gmail users have those images downloaded automatically, whether they actually opened the email or not, the data that can be gained for analytical purposes becomes watered down.
I am unaware of any that pre-fetch regular links like some link
Let’s stay on gmail for example purposes, but others will behave similarly: Since Google is always interested in “what’s out there on the web”, it is highly likely that their crawlers will follow that link to see what it contains/leads to – for their own indexing purposes.
If it is, is there a sort of no-follow type of rel attribute that can be added to the link to help prevent this?
rel=no-follow concerns ranking rather than crawling, and a no-index (either in robots.txt or via meta element/rel attribute) also won’t keep nosy bots from at least requesting the URL.
Plus, other clients involved – such as a firewall/anti-virus/anti-madware – might also request it for analytical purposes without any user actively triggering it.
If you want to be (relatively) sure that any action is triggered only by a (specific) human user, then use URLs in emails or other kind of messages over the internet only to lead them to a website where they confirm an action to be taken via a form, using method=POST; whether some kind of authentication or CSRF protection might also be needed, might go a little beyond the context of this question.