Features of emission electrode activation leading to enhancement of negative ion emission in cesium-free discharges are discussed. In some ion sources with cesium-free discharges, the emission of negative ions has been increased significantly by emission electrode activation using strong heating of the negative biased electrode by discharge plasma. A simple explanation of this enhancement is that it is due to an accumulation on the emission surface of the plasma electrode of impurities with low ionization potential that decreases in surface work function and increases the secondary emission of negative ions similar to "Cesiation." The negative biasing of emission surface is important for accumulation and trapping the impurities on the emission surface. To effectively control the activation process it is important to directly detect the evolution of the work function and the impurity concentration during electrode activation with enhancement of negative ion emission.