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In a 6-quart slow cooker, whisk together the coconut milk, peanut butter, rice vinegar, brown sugar, soy sauce and curry paste until smooth.
Stir in the onions, lemongrass and garlic.
Add the chicken and stir to combine.
Cover and cook on low until an instant-read thermometer inserted into the thickest part of a chicken breast registers 165°F (74°C), about 3 ½–4 hours.
Combine the broccoli with 2 tablespoons water in a bowl and microwave on high until crisp-tender, 4 minutes. Alternatively, steam the broccoli on the stove, 3 minutes. Drain.
Place chicken breasts and broccoli on a serving platter, set aside.
In a small bowl, combine the potato starch with 1 tablespoon cold water.
Add to the slow cooker, adjust heat to high, and cook, stirring frequently, until the sauce has thickened, about 2 minutes.
Pour over the chicken and broccoli and serve.