The ground state electronic properties of the strongly correlated transition metal Ni are usually not accessible from the excitation spectra measured in photoelectron spectroscopy. We show that the bottom of the Ni d band along [111] can be probed through the energy dependence of the phase of quantum-well states in Ag/Ni(111). Our model description of the quantum-well energies measured by angle-resolved photoemission determines the bottom of the Lambda(1) d band of Ni as 2.6 eV, in full agreement with standard local density theory and at variance with the values of 1.7-1.8 eV from direct angle-resolved photoemission experiments of Ni