As per this answer, the list of the main 64 yoginis, a group of Sahacharis of the Devi, includes personalities like Bhadrakali and Kalaratri. Which indicates the Devi Kali could be separate from Devi Uma herself.
We could possibly take support from the Devi Mahatmya. The Devi Mahatmya recounts the incident of the killing of great Asuras like Mahisha, Shumbha and Nishumbha. In Shumbha Nishumbha story, Devi Kalika aka Kalaratri emerges from Devi Kaushiki, in order to kill Canda Munda:
Out from the surface of her forehead, which was rugged with frowns, issued suddenly Kālī of the terrible countenance.
-Devi Mahatmya, Markandeya Purana, Chapter 87.
Here too one can see Devi Kali possibly as a separate Devi emerging from Devi Kaushiki. The description of Kali too is one that terrifies people, that is often associated with the yoginis like Dakini, Shakini.
One more thing is funny. If Devi is impartial to all her subjects, her killing Asuras herself is a little odd. Instead, the same task could be accomplished by one of her Bhrtyas, viz. The yoginis.
I would therefore like to know whether the Devi Kali is among the 64 yoginis as a separate Devi or is it a form of Devi Parvati herself. What then is the difference between Yogini Kali and Kali, form of Devi.
Can it be said that all the devis who killed Asuras were among the Yoginis and not the Devi herself, considering impartiality?