Change the number 6 to whatever your total length needs to be:

SELECT REPLICATE('0',6-LEN(EmployeeId)) + EmployeeId

If the column is an INT, you can use RTRIM to implicitly convert it to a VARCHAR

SELECT REPLICATE('0',6-LEN(RTRIM(EmployeeId))) + RTRIM(EmployeeId)

And the code to remove these 0s and get back the 'real' number:

SELECT RIGHT(EmployeeId,(LEN(EmployeeId) - PATINDEX('%[^0]%',EmployeeId)) + 1)