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Pistons in brakes make a big difference. It is nothing like pistons in engines. When hydraulic pressure engages the caliper piston, it presses inward on the pad, against the rotor, slowing the vehicle. In a single piston setup, there is one large piston and a relatively small brake pad doing the work. In a four piston, they are using the same amount of hydraulic pressure as the single piston (depending on the master cylinder pushrod and booster, but let's imagine it's the same) but because there are four pistons and a much larger pad that pressure is applied to a greater surface area of the rotor, increasing stopping power dramatically.
Hope that helps.
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