I don't homeschool, but had a couple of suggestions in general.
Library day can be designated to one day a week. Ours is Sunday. We are on their email list so they actually email us 1 day in advance which books are due. (which is helpful if we've checked out many on different Sundays) We can also renew them online. Check this out as it can save that hassle. During super busy times I just renew everything, it wont let you renew if a book is on hold so I don't feel I'm keeping a book away from anyone. It also emails you if a book you have on hold has come in.
I'm not sure what shopping/errands you are running every day, egad I would go crazy with so many errands. My bills are paid online, I had my kids on the same dentist/doctor schedule (unless due to illness of course) so even those were one day events every..what, six months? I'm simply not understand what exactly the running around entails that it is consuming practically every day of the week.
I loved the schedule peanut suggested.
Hard work doesn't hurt kids but if the kids are watching dad not take responsibility for the family, thereby making them do more work than you possibly would have them do if he was helping, that can build resentment throughout the whole household. What are some things that you do specifically for the hubby that you can back off from to give yourself some more "relaxing kid time" or "relaxing me time"?
Volunteering is great, neglecting your family responsibilities is not.