You are going to want to hash passwords and not encrypt them. An encryption can be undone with the key. The password the user types in is called the plaintext password, the plaintext password should NEVER be written or stored anywhere.
When something is hashed, it is a one way translation, a hash cannot easily be translated back to its plaintext form, so when someone enters their password, you hash it and then compare it with the hashed password stored in the database.
A few hashing algorithms are MD5, SHA1, etc- in PHP, you can use the crypt function to hash a password. I should note that MD5 and SHA1 are not as secure anymore as they are very fast, which means that they can be brute forced fairly quickly (there are also databases where you can reverse engineer the hashes fairly quickly). You should use PHP's crypt function.
tl;dr - Hash passwords, don't encrypt them (for security, especially eCommerce).