This achievement is related to the single player campaign so you should not be able to miss this.
*** Spoiler - click to reveal ***This will unlock while playing through the mission "To Stand Alone." it will unlock after you finish fighting all the AIM enemies when you try to break into the prison. Then after the cutscene introducing black widow and once you gain control of her then it will pop.
Please message me if you have any questions and if you down vote this please let me know why so I can make this solution better.
Have fun Avenging.