The NASICON framework is an attractive object for designing polyanion electrode materials for metal-ion batteries. Two new NASICON-structured (S.G. R-3c) niobium phosphates KNbTi(PO4)3 (a = 8.4307(1) Å, c = 23.3955(4) Å, V = 1440.11(5) Å3) and KNbV(PO4)3 (a = 8.4892(1) Å, c = 23.3042(4) Å, V = 1454.45(3) Å3) were synthesized by the Pechini sol–gel method. Rietveld refinement revealed the potassium atoms occupy only the A(1) 6-fold antiprismatic site in both structures. Nb K-edge XANES measurements confirmed the presence of Nb5+ in KNbV(PO4)3 and the mixed-valent Nb5+/4+ in KNbTi(PO4)3 phosphates. Electrochemical measurements showed that both compounds deliver the initial discharge capacity of 110–120 mAh g−1 at a C/10 rate in the Na-half cell. KNbV(PO4)3 also maintains a reversible K+ intercalation at about 1.5 V vs. K+/K with a significant hysteresis (∼0.35 V at a C/10 rate) indicating a sluggish K+ diffusion. The mobility of alkali metal ions within the framework of new phosphates is discussed in terms of bond valence site energy calculations.
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