You have to wait one week.

Note: Paid applications must pay their first weekly bill before they can
> send mail messages beyond the free quota. Once the first charge is cleared,
> each message sent above the free quota is charged at the normal paid rate.


https://developers.google.com/appengine/docs/python/mail/overview#Quotas_and_Limits

On Wed, Feb 6, 2013 at 8:51 PM, Jesús Espejo <[email protected]> wrote:
>
> Hello,
>
> I just activated billing for my app and i noticed a strange thing: Email
sending are limited to 100 emails per day. When i try to send more than
100, i receive an error "over quota". How i can change this? My app is a
paid app and i need to send more than 100 emails/day.
>
> Thanks in advance,
> Jesús.
>
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