Hi,
once you have extend the VG, either you add new LV or you perform a lvextend and resize2fs on your current volume.
You can have a look for instance at some
howto these operations might required you to umount the FS.
As Byte mentionned, what you are trying to do is not the best thing talking about data healthy (I do think that RAID0 and what I understood, you are planning to do is equivalent on this point).
Be also carrefull at what you are talking about : a "df " command is a FileSystem one, so you are meaning to increase your FS size over the two disks. This might not be the best choice, and I still do not understand this kind of layout.
But technically speaking, what you are asking about can be done ... at your own risk.
G.