Getting caught up finally! Thing 22 talks about volunteering as a way to get experience in areas that your job doesn't cover. While this sounds fantastic in theory I have no idea how I would fit it in in the real world. I have spent the last few years trying to get a full time job so there is no way that I would willingly choose to work part time. Even in the periods that I have been working part time at the library I have had to go and get another job in order to pay the bills so volunteering just wasn't an option. If you can afford to do it I think it's a great use of time but unfortunately it's not possible for everyone.
There are ways round this. You could ask your current employer for more responsibility on a sort of voluntary basis. However, I think you have to be careful not to be taken advantage of here. I have managed to increase my skills recently by attending conferences and getting more involved in the profession in general. Presenting a poster at Umbrella was as much about improving my public speaking skills as anything else and it was a very rewarding experience.
I think volunteering is something that employers definitely respond to since it shows that you are willing to go out there and go the extra mile to learn something new. However, they also need to be aware that not everyone has this luxury and that people may go about gaining experience in different ways. I think that as long as you can gain skills somewhere this will help you in your future career, for example just involving myself in following cpd23 shows that I am interested in developing new skills. Hopefully this will be enough for now.