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In a small bowl stir together the chili powder, smoked paprika, salt, garlic powder, black pepper, and 1 tablespoon of the brown sugar until well combined.
Trim the brisket’s fat cap to a ½-inch thickness and pat the meat dry. Rub the spice mixture all over the brisket until completely coated. (The rub can be applied up to 12 hours in advance. Cover and store the brisket in the refrigerator until ready to cook.)
Place the brisket in a 6-quart slow cooker with the fat cap facing up. In a medium bowl whisk together the barbecue sauce, broth, and soy sauce until smooth. Pour around and over the brisket. Top with the onion slices. Cover and cook on low until a thermometer inserted into the thickest portion of the brisket registers 205°F, 8 to 10 hours (or on high for 5 to 7 hours).
Transfer the brisket to a cutting board and let rest for 10 minutes. Meanwhile, ladle 1 cup of the liquid in the slow cooker into a small microwave-safe bowl. Whisk in the cornstarch and microwave on high until a thickened paste forms, about 1 minute 30 seconds. Whisk the paste and the remaining 3 tablespoons brown sugar into the liquid in the slow cooker until slightly thickened, about 2 minutes.
Thinly slice the brisket across the grain. Arrange the brisket slices on a serving platter and serve with the slow cooker barbecue sauce.