The Volunteer doctype allows you to record the Volunter details.
Volunteer are simply contacts in your ERPNext database with one or more volunteering program. The contact may be an individual, a household, an organisation, or some other contact sub-type
To create new Volunteer go to:
Non Profit > Volunteer > New

Email: Email field is the id of Member doctype.
Volunteer Type: Volunteer Type is link field to Volunteer Type Doctype. Volunteer can select available Doctype.
Address and Contact Section: This Section linked to address and contact doctypes.
Volunteer Availability Section: This section is child table which contains select field about volunteer availability. a volunteer can select availability such as weekly, morning etc
Volunteer Skills Section: This section is child table which contains data field about the volunteer skills. a volunteer can add multiple skill for eg. Desk Job, Hospitality, Food management, computer operator etc.