There is a great second hand charity store called Emmaus that sells loads of stuff; clothes, furniture, electrics, books.. the list goes on.. Their main store is near the tram stop Geestemuenderstrasse which is north on line 12. On their website I read that there is a second smaller store at Florastrasse but I haven't been there yet so don't know what it's like. If you want to check out the website...
http://www.emmaus-koeln.de/It is a charity shop though so if you're wanting money for your stuff it's not the place. I know of a good second hand shop for clothes that might buy things. If you walk from Rudolfplatz towards Neumarkt it is on the right hand side after the huge Sparkasse. Hope that helps!