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We discuss the details of ambipolar relaxation of the electric field in liquid asymmetric electrolytes to its stationary value. It is demonstrated that the account for finite boundary conditions modifies the existing concepts of this diffusion process. In particular, we succeeded to suggest a qualitatively correct explanation of the observed distribution of the electric fields over the bulk of the cuvette and its nonmonotonic behavior in measurements on the finite-size cuvette. We analyze the conditions of such an anomaly at the intermediate stages of the relaxation process.