Você tem que definir um valor padrão.
ALTER TABLE mytable ADD COLUMN mycolumn character varying(50) NOT NULL DEFAULT 'foo';
... some work (set real values as you want)...
ALTER TABLE mytable ALTER COLUMN mycolumn DROP DEFAULT;
ALTER TABLE mytable ADD COLUMN mycolumn character varying(50) NOT NULL DEFAULT 'foo';
... some work (set real values as you want)...
ALTER TABLE mytable ALTER COLUMN mycolumn DROP DEFAULT;