We develop a theory of effects of electron-electron collisions on the Dyakonov-Perel' spin relaxation in multi-valley quantum wells. It is shown that the electron-electron scattering rate which governs the spin relaxation is different from that in a single-valley system. The theory is applied to Si/SiGe (001)-grown quantum wells where two valleys are simultaneously populated by free carriers. The dependences of the spin relaxation rate on temperature, electron concentration and valley-orbit splitting are calculated and discussed. We demonstrate that in a wide range of temperatures the electron-electron collisions can govern spin relaxation in high-quality Si/SiGe quantum wells.