If your silicone is peeling, strip down the tank and clean it thoroughly. Remove all plastic trim, and cut out the old silicone (on the inside of the tank only, try not to push between the pains of glass) with a sharp blade and scrape away all traces of silicone from the inside joints. Once all the internal silicone is off, test your structural silicone by applying outward pressure to the front and back pain. If they don't move and you don't hear any lovely creaking, you are good to re-seam. If you do hear any creaking or see movement, you will have to re-build the tank...
I'll assume you have a tank that has good structural silicone here. If the structural silicone has gone also, post back here and then set about taking the tank down to 5 separate pains of clean glass with all silicone and dirt removed. I'll get back to you with a "how to build a tank" guide that's more practical than the pin for a large® tank that 20g...
Wipe down the inside joints with any alcohol based cleaner (Mentholated spirits, white spirit, pain brush cleaner, nail varnish remover, Jhonson's Flea Spray...) and mask up the tank with masking tape. Silicone is messy stuff that can end up going every where, so control where it can go by masking off all placed you don't want it to go. Masking off the tank is slow, difficult and tedious, but is time and effort well spent and the job is neater and more professional looking when done
Now you have done a preliminary clean, and masked up, you wipe down with alcohol cleaner again. Open up your new tube of silicone and cut the nozle to the correct width of bead you wish to run, and then apply your silicone to all joint. Once you have enough on, lick your finger to dampen it and then smooth over all the joints, pressing out air bubbles and ensuring the silicone contacts all areas that are not covered by masking tape. Once smoothed over, use your clean hand to pull of the tape. From first application to tape removal, you mustn't take more than 5 mins, or the silicone will skin over and ruin the job. Don't rush, but don't go slow either
Let the tank sit and "cure" for at least 48 hours, or until you can no longer smell silicone, which ever come last
Now the tank is re-sealed and cured, water test it outside on a level surface that is lined with polystyrene. If it does not leak, drain it again and glue the trim back on, again leaving it 48 hours, before putting your tank to use again

You need the Polystyrene base lining, as the plastic trim making the "floating based" tanks float won't be there as usual if you happen to have a floating based tank...
All the best
Rabbut