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NASICON structured Li1+xAlxZr2-x(PO4)3 have been studied to replace LAGP and LATP in this paper. The effects of both annealing temperature and Al doping were investigated. Both the annealing temperature and Al doping exhibited an optimal value, which is 1100oC and 0.3, respectively. The doping of Al helped LiZr2(PO4)3 transfer from triclinic phase to rhombohedral phase and the conductivity of doped one was improved by one order of magnitude.