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It depends on whether she has a Kindle 3G with wi-fi, or an older one. If she has one with wi-fi, if you send a book to her free.kindle.com email address (and your email address is registered with her Manage Your Kindle page as being allowed to email to her Kindle), no charge is incurred. If something is delivered via 3G, there is a 15 cent per megabyte charge. Most books are less than a megabyte in size.
Library books normally have DRM, and would not work on her Kindle (until library lending is enabled later this year, but she would have to download it herself).
If she has a current Kindle, and can't download anything, how could she get email?
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