I think you can do it all by mirroring. I have done it before when I had to move a preinstalled rootvg from a disk drawer to the internal disks. (the steps I had to take included steps to get the internal disks to be renamed hdisk0 and hdisk1 rather than hdisk14 and hdisk 15, although I probably didn't have to be that particular about it. I won't go into those steps here.)
The OS version I did this on is 4.3.3 and it was patched at the time to ML 5, I believe. the command mirrorvg is for version 4.2.1 or higher.
If doing a mirrorvg from two smaller disks to a larger disk doesn't work (you'd have to check the man pages for the correct syntax -- maybe mirrorvg rootvg hdisk<new disk number>?), you can accomplish the same thing by using the mklvcopy command. If you do use the mirrorvg command, you will have to also run the bosboot -a command and change your bootlist with the bootlist command.
To make it really simple, use smit.
First, of course, bring the new disk into rootvg.
The smit path to mirror LVs is:
System Storage Management/ Logical Volume Manager / set Characteristics of a Logical Volume / Add a Copy to a Logical Volume. The Add Copies to a Logical Volume screen is fairly easy to figure out.
Be sure to mirror a-l-l of the logical volumes, especially hd5. After you mirror hd5, you will have to run bosboot -a so the system knows where the additional boot LV is. you will also have to change your bootlist (both for normal and service mode) so the system know about the new disk that is bootable.
Once you get all of the logical volumes on the new, larger disk, test it by changing the bootlist for normal and put the new disk first. Boot the system and watch it come up and make sure it uses the new disk, rather than the older disk.
After you are sure you can boot on the new disk, you can break the mirrors (also using smit if you want). Again, be sure to run bosboot -a so the system knows the old BLV is gone. And, of course, change your bootlists so the old disk isn't listed.
Then, if you want to mirror from the new, larger disk to another disk the same size, just bring the second disk into rootvg and run a mirrorvg rootvg, or go through the LV by LV routine as above.
And finally, check to make sure quorum checking is off for rootvg. If you lose one of the disks of a 2 disk mirrored rootvg and quorum isn't turned off, losing one of the disks will bring the hole system down. To turn off quorum checking, use the smit path System Storage Management / Logical Volume Manger/ Set Characteristics of a Volume Group / Change a Volume Group.