Coat a slow cooker with nonstick spray. In a large bowl, whisk together the flour, sugar, cocoa powder, baking powder, and salt. In a second bowl, whisk together the milk, melted butter, and vanilla.: The aroma of warm butter will be missing here, but greasing the bowl prevents the cake from sticking to the sides, giving you clean edges when serving. You should feel the slickness across the inner surface as you spray, and the visual sheen is a good cue that the bowl is ready. If you skip this you risk tearing the cake when you scoop it out, so do not be tempted to omit the spray.
Make a well in the middle of the dry ingredients. Pour the wet ingredients in to the well and whisk until smooth. Pour into the bottom of a slow cooker.: As you whisk these dry ingredients, you will see the mixture lighten and become uniform in color, releasing a concentrated cocoa scent. Combining them thoroughly ensures even leavening and prevents pockets of baking powder or salt. A common mistake is rushing this step, which can leave lumps or uneven rise, so whisk until the texture looks even and smooth.
Whisk together the sugar, brown sugar, cocoa powder until evenly combined. Sprinkle evenly over the batter in the slow cooker.: The wet mix should look glossy and cohesive, with tiny ribbons of butter dispersing into the milk. This emulsion delivers moisture and richness to the batter, which translates to a tender top layer. If your melted butter is too hot it can cook the milk slightly, so allow it to cool a bit before combining to keep the mixture smooth.
Pour the hot water over the top of the batter and topping. Do not stir. Cover and cook on HIGH for 3 to 4 hours or LOW for 5 hours, or until a toothpick inserted in to the middle of the cake comes out clean with a few crumbs attached.: Creating a well gives you a place to pour the wet ingredients so they incorporate gently, helping to avoid overmixing. As you pour the wet into the center and whisk outward, you will notice the batter becoming silkier and more homogeneous. Overworking here can develop gluten and yield a tougher cake, so stop whisking once smooth.
Serve with ice cream or whipped cream, spooning the chocolate sauce from the bottom of the slow cooker over the top. Garnish with maraschino cherries if desired.: The batter should be free of streaks and feel slightly thick, with a glossy sheen from the butter. The tactile cue of smoothness means the flour is hydrated and ready to set in the cooker. If you still see dry specks, they will create dry pockets in the cake, so whisk until the batter appears even.
Pour into the bottom of a slow cooker: When you pour the batter into the prepared slow cooker, it should settle into an even layer that looks velvety on top. The visual uniformity helps the cake bake evenly across the surface. If the batter pools on one side because the cooker is not level, rotate the cooker gently to level it before continuing, otherwise the bake will be uneven.
Whisk together the sugar, brown sugar, cocoa powder until evenly combined: This topping mix should smell deeply chocolatey and have a slightly damp, sand like texture when properly combined. Ensuring the sugars and cocoa are uniform prevents streaks of overly sweet or bitter sauce once the water is added. If you notice clumps, press them through the sieve or break them up, because unmixed clumps will create uneven sauce pockets.
Sprinkle evenly over the batter in the slow cooker: Even distribution is crucial so the saucy layer forms consistently under the cake. As you sprinkle, the surface should be fully covered in a thin, uniform dusting rather than concentrated piles. Uneven sprinkling can create areas that are too sweet or too dry, so take a moment to spread the mixture gently with the back of a spoon if needed.
Pour the hot water over the top of the batter and topping: The steam rising from the hot water is part of the sensory experience, and when poured slowly you will see the granulated topping begin to dissolve. Do not stir, because the separation between the cake batter and the sauce is what creates the lava effect. If the water is not hot enough the sugars may not dissolve fully, resulting in a thinner sauce, so use very warm water from a kettle.
Do not stir: Resisting the urge to mix after adding water is hard, but this restraint is essential. The cake sets on top while the liquid works beneath, creating that molten center. Stirring would homogenize the layers and you would lose the contrast, so step back and trust the process.
Cover and cook on HIGH for 3 to 4 hours or LOW for 5 hours, or until a toothpick inserted in to the middle of the cake comes out clean with a few crumbs attached: You will notice a sweet, chocolate steam as the cooker warms, and the top will shift from glossy to set and slightly matte. The toothpick test should reveal a mostly set top with a few moist crumbs, signaling that the bottom remains saucy. A mistake is opening the lid too often to check, which releases heat and extends cook time, so try to minimize lid lifts.
Serve with ice cream or whipped cream, spooning the chocolate sauce from the bottom of the slow cooker over the top: The final contrast between warm cake and cold ice cream is the moment of payoff, and you will hear a soft hiss as the hot sauce meets the cold topping. Spoon generously so each bite has both cake and sauce. If you let the dessert sit too long before serving, the sauce will thicken and lose some of its silkiness, so serve soon after uncovering.
Garnish with maraschino cherries if desired: The bright pop of the cherries adds color and a hint of sweet acidity that complements the chocolate. Place them on top right before serving so they keep their shine. Leaving them in the cooker during storage can make them soggy, so add them at plating time.