According to the postgres documentation, you add a key to an hstore column as follows:
UPDATE tab SET h = h || (\'c\' => \'3\');
But it seem
To avoid this you need to ensure the hstore is created as empty and not null. You can add an empty hstore to an existing table:
ALTER TABLE htest ADD h HSTORE NOT NULL DEFAULT '';
Or you can alter your existing hstore to empty:
ALTER TABLE htest ALTER COLUMN h SET NOT NULL;
ALTER TABLE htest ALTER COLUMN h SET DEFAULT '';
Please note that exiting values cannot be null when you set the column to 'NOT NULL'.