Conversationally, i agree that ex-wife seems much more common that former wife. In writing, though, the use of former doesn't seem so rare. Here's an interesting ngram.

However, these days, no one pays attention to such niceties, which means that everybody pretty much gets called whatever. Just ask them. Given the huge difference between how likely people are to capitalise the second component in ex-wife compared to co-founder, i think choose a rule and be consistent with it is terrible.

Scrubs Cast Dr Cox Ex Wife at Danita Foster blog

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