Freeze–thaw (F/T) and electrochemistry both are environment-friendly and efficient sludge treatment technologies. In this study, the sludge samples were frozen at − 15 °C, and 20% g/gTss activated carbon (AC) was added to the dissolved sludge. Finally, the uniformly mixed sludge was treated at a voltage of 15 V for 25 min. During the experiment, the effect of F/T on the floc structure was analyzed by a laser particle analyzer and scanning electron microscope. F/T treatment improved the dewatering performance of the sludge and promoted the aggregation of sludge flocs into larger particles either. At the same time, the median diameter (D50) increased from 45.27 to 128.94 μm. AC was added to the thawed sludge solution before electrochemical treatment (EP). The conductivity of AC enhanced the effect of EP, thereby cracking the sludge flocs. Therefore, the three-dimensional excitation–emission matrix (3D-EEM) intensity of tightly bound extracellular polymeric substances (TB-EPS) decreased significantly. The protein in TB-EPS decreased from 54 to 33%, and the D50 was also reduced to 105.3 μm. The final specific resistance of filtration and water content were reduced by 96.39% and 32.17%, respectively. The dehydrated cake elemental analysis showed that increased AC improved the sludge cake’s combustion efficiency significantly. Moreover, the preliminary economic analysis indicated that the cost of this research was low, which implied the potential application value of combined treatment.

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