I've started on the process, and will eventually have a complete alphabet with an indication of whether they are single or doubl letter encodings. I've done this using two colours, red for single, green for double. There are other obvious ways in.
For example, 26 Dn is a three letter solution with 6 cells to fill.
When I'd filled in all the letters of my initial sweep (solutions with equal number of cells to letters), I could look at some of my cold solved clues, for instance 1 Ac & 1 Dn and see that (from number of cells against number of letters) both must contain only one letter which is a double encoder, and as it happens, 4 letters in each were already demarcated in my singles list, so I could safely conclude that the initial letter is a double letter encoder. I then went through all my cold solved in a similar fashion and identified letters which MUST be double encoders.
Two of the letters in 3Dn are definite singles, so the last one must be a double. Cell 3 & cell 5 MUST have the same encoded single letter. As must third cell in 1 across and first cell of 25 Dn. Amazingly,it's helping me enormously to write this all out