Spell checking never seems to work, by default, in Libre Office on a Raspberry Pi.
To get it working:
# Go to:
https://extensions.libreoffice.org/extensions/english-dictionaries/
# Click on the Current Release or go to the below URL which
# is current as of now!
https://extensions.libreoffice.org/extensions/english-dictionaries/2017-01.01
# Download the .oxt file
# In Libre Office go to Tools / Extension Manager
# Add the .oxt file
# Spell checking now works!