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Preheat oven to 375F. Grease bottom of 9" round cake pan.
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In a small bowl, pour boiling water over cocoa powder and whisk until smooth. Set aside and let cool.
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In a small bowl, mix flour, baking soda, baking powder and salt. Set aside.
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In a large bowl or mixer, cream softened butter and sugar until light and fluffy.
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Beat egg in.
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Mix in vanilla.
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Add flour mixture and cocoa mixture, alternating each. (Add flour, add cocoa, add flour, add cocoa, etc.)
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Pour batter into pan.
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Bake in oven for 18-23 minutes.
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Set the cake aside until cool.
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Once cooled, put the cake into a large bowl and crumble it into small crumbs.
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Add frosting in a bit at a time until the cake can hold a ball shape but is still crumbly. (it shouldn't be mostly frosting.)
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Using your hands, a spoon, or a small ice cream scoop, scoop out two balls of the cake and frosting mixture.
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Put a Peanut M&M's next to one ball and smush the other ball onto the other side of the Peanut M&M's (so it's a Peanut M&M's sandwich...kind of) then roll into one ball. The cake ball should be ~2 inches in diameter.
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Put the ball on a plate and repeat until you've used up all the cake.
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Melt ~2 oz of baking chocolate over a double boiler or in the microwave in a mug or small microwave safe bowl.
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Dip the cake pop sticks or the blunt end of the skewer into the melted chocolate, then insert into the cake ball about half way and set on a plate. Repeat for all the cake pops.
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Freeze cake pops for about 20 minutes.
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Meanwhile, crush ~1/4 cup of Peanut M&M's using a food processors, rolling pin, hammer, or whatever tool you use to crush things and put into a shallow bowl or plate.
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When the freezer time is almost up, melt the remaining chocolate in a mug, making sure there's enough to completely cover the cake pop when dipped.
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Remove cake balls from freezer.
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Dip cake balls into the melted chocolate until covered. Let the excess drip off.
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While the chocolate is still wet, roll the cake pop in the crushed Peanut M&M's.
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Let the cake pop dry by sticking it into some styrofoam, or a cup filled with Peanut M&M's (the M&M's will help cold the cake pops up.)
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Put the cake pops back into the freezer to let the chocolate set.
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Enjoy!