Thermionic emission is the emission of charged particles from a charged surface (usually metal), which is caused by the vibration energy of the particles overcoming the electrical potential holding them to the surface. An example of this would be your cathode ray tube where a charged filament is heated (by passing a large current through it), the electrons on the surface of the filament (remember charge always resides on the surface of a conductor) gain enough thermal energy to 'break free'.
For more detail google: Thermionic Emission