sed 's/\B/\&/g'
\B - Matches everywhere but on a word boundary; that is it matches if the character to the left and the character to the right are either both “word” characters or both “non-word” characters. GNU sed manual.
Information: GNU sed manual, regular expression extensions.
Testing:
sed 's/\B/\&/g' <<< '12345'
1&2&3&4&5