The error message shown by pgAdmin is misleading here and doesn't help.
PgAdmin uses pg_dump and other tools to perform certain actions like Import/Export or Backup. Before starting these external processes pgAdmin sets environmental variables for example:
'PGSSLMODE': 'disable' # Correct env variable
'PGSSLCERT': None # Malformed env variable, missing ''
Your issue is now that one of these variables is set incorrectly by pgAdmin and thus is malformed. Malformed means for example the quotes are missing like shown above. A env variable needs to be quoted.
Possible error cause:
You configured "Client certificate", "Client certificate key" and "Root certificate" inside the "SSL" tab of your connection and at least one of those files does NOT exist anymore, then your error will be shown.

I reported this bug/bad error handling here (requires a free forum account to view).