Exporting Very Large Database from mysql 5.5
There wouldn't be anything broken , mysqlworkbench is a pretty mature software.
You just need to watch the filesystem of the storage where you are going to store the file.
ntfs would be fine, but fat32 will limit you to around 4GB.

However, if you are just looking for an exporter with UI, Navicat Premium is more comfortable in my opinion. Hope it helps.