I would not recommend you to start session just to get some unique id. Instead, use such things as uniqid() because it's intended to return unique id.
However, if you already have session, then, of course, use session_id() to get your session id - but do not rely on that, because "unique id" isn't same as "session id" in common sense: for example, multiple tabs in most browsers will use same process, thus, use same session identifier in result - and, therefore, different connections will have same id. It's your decision about desired behavior, I've mentioned this just to show the difference between session id and unique id.