Athena was there to help Hercules in Labor #6:

Labor #6 Stymphalian Birds
To scare off the enormous flock of birds at a lake by the town of Stymphalos, Athena gave Hercules noisemaking clappers or krotala.

Athena was there to help Hercules in Labor #11:

Labor#11 Apples of the Hesperides
Athena may have helped Hercules hold up the world when the titan Atlas went to fetch the apples of the Hesperides for him, since, while Atlas was off fetching the apples, Hercules had agreed to support the world that was normally held up on the shoulders of the titan.

After Hercules brought the apples to his taskmaster Eurystheus (in completion of Labor #11), they had to be returned, so Athena took them back.

Athena was there to help Hercules in Labor #12:

Labor #12- Cerberus and Hades
Athena may have escorted Hercules and Cerberus out of the Underworld.

Athena helps Hercules in his madness:

Athena is said to have protected Hercules from killing more people than he did. After the murder of his children, when he was about to kill Amphitryon, Athena knocked him out, thereby preventing the murder of his mortal father.

Athena and Hercules:

Athena is the Greek goddess of wisdom, who was born fully grown and armed, from the head(ache) of her father Zeus. She was, thus, a warrior goddess, and was also a virginal goddess. Hercules is the Greek mythological semi-divine hero of all time, who bested fantastic beasts, made repeated trips to the the Underworld, and also went mad, due to the connivance of his step-mother, Hera. In his madness, Hercules killed his own children.

It was as a penance for this that he suffered the 12 labors which he performed for his cousin King Eurystheus.