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Coat grill rack with nonstick spray. Preheat grill to medium-high heat or prepare medium-high fire.
Cut each banana in half crosswise; cut each half in half lengthwise. Arrange bananas cut side up on a sheet pan; coat bananas with nonstick spray. In a small bowl, combine sugar, cinnamon, and cayenne pepper; sprinkle over bananas.
Arrange bananas, spiced side down, on hot grill rack. Grill until well marked, 2 to 3 minutes. Carefully turn bananas over and cook 2 more minutes. Remove from grill. Cut into 1-inch pieces and arrange on sheet pan. Freeze until completely firm, about 3 hours.
Place frozen bananas in a food processor; drizzle with almond milk and sprinkle with cocoa powder. Process on high until completely smooth, 2 to 3 minutes; stop to scrape sides of bowl occasionally. Serve right away (the texture will be similar to soft serve), or spoon into a container and freeze until scoopable, 1 to 2 hours.
Serving size: 2/3 cup