Can't get a job without experience, can't get experience without a job : it's an old problem. So why not work for nothing for a while to accumulate some experience (and perhaps to try out different types of work to see what suits you?)
I have to accept that some new professionals are saying that volunteering has been a help to them and has led to employment opportunities. That's great, if so. I've got a lot of reservations about this, but obviously it does get you that experience without which so many doors seem to be closed. I also know a number of young recent graduates who lead a double life: there's the work they get paid to do (shop assistants, barmen, waitresses) and then there's the thing they trained to do or the thing they aspire to, which doesn't pay (historical textiles, art history, fashion, playing in a band). Major couture houses rely heavily on interns, television companies and political parties use the free labour of eager aspirants hoping to get a foot on the ladder. There are far more young people working for free in some of these industries than there are ultimately opportunities for paid work. I wouldn't like to see libraries fall into this category.
People with private means are free to work for nothing, but that creates a difficult precedent for everyone else. With all the KPMG-inspired talk of volunteer-run libraries, a new strange attitude seems to be emerging: nice people don't expect to be paid for what they do, nice people wouldn't greedily insist on money for themselves to keep a service going, nice people offer their time. We all know, of course, that we need money to live on, and with that money we pay taxes and buy goods and services. Paid employment is an essential for most of us. The generosity of wealthy people with their time can have the effect of shutting other people out. If there is a plentiful supply of free labour, it may be that the employer will never need to offer paid work, which would create a vicious circle: you may gain experience but never then get the chance to get a paid job using it.
I qualified at a time when it would not have been expected or really acceptable to undertake voluntary work for any length of time. Quite a lot of contemporaries got into the workplace eventually after year-long low-paid placements on government-backed job creation schemes (e.g. the Manpower Services Commission). Some of these projects were very worthwhile, and while they were usually finite they sometimes led on to other things. I did work for the Church of England for nothing for experience for quite a while, at its request, but on reflection, while it was valuable experience, I am not sure that it did me any favours. That which is freely given is not always appreciated, and of course it may not be what is wanted - in which case it is much more difficult to tell someone so!
So, on the whole, I have deep reservations about voluntary work within a profession, except as short-term focused placements for those trying to acquire experience at the start of their careers. Voluntary work outside the profession is quite another thing, and there are lots of ways in which people with time to spare can make themselves useful, putting something back into society and gaining experience and some gratification at the same time.