Is there any real difference in usage between ex- and former?
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My sense is that 'ex' carries just a slight note of dishonour, whereas 'former' carries no such nuance.
One speaks of 'former' Prime Ministers, and Presidents. I've never heard anyone speak of an ex-President, even of those that did behave dishonourably.
If a person was speaking of their 'ex-huband' or 'ex-wife', it would suggest to me that they were implying disfavour. 'My former wife' sounds softer.
An ex-clergyman sounds to me like one who has been 'unfrocked', a 'former clergyman' one who has retired; similarly with policemen.
Another take is that "ex" is a compound form, while "former" is an adjective. That would be "the difference in usage". But they both mean the same thing.
I don't think "ex" has a negative connotation.
Perhaps, in the President/Prime Minister case, "former" implies that he's still living.
On the other hand, no-one refers to the former spouse as "former husband (or wife)".
It's just one of those peculiarities of English. Nuances abound.