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Li-ion intercalation materials with extremely high rate capability will blur the distinction between batteries and supercapacitors. We construct a series of nanoarchitectured intercalation materials including orthorhombic ( o -) Nb 2 O 5  hollow microspheres,  o -Nb 2 O 5 @carbon core-shell microspheres and tetragonal ( t -) NbO 2 @carbon core-shell microspheres, through a one-pot hydrothermal method with different post-treatments. These nanoarchitectured materials consist of small nanocrystals with highly exposed active surface, and all of them demonstrate good Li +  intercalation pseudocapacitive properties. In particular,  o -Nb 2 O 5  hollow microspheres can deliver the specific capacitance of 488.3 F g −1 , and good rate performance of 126.7 F g −1  at 50 A g −1 . The  o -Nb 2 O 5 @carbon core-shell microspheres show enhanced specific capacitance of 502.2 F g −1  and much improved rate performance (213.4 F g −1  at 50 A g −1 ). Furthermore, we demonstrate for the first time,  t -NbO 2  exhibits much higher rate capability than  o -Nb 2 O 5 . For discharging time as fast as 5.9 s (50 A g −1 ), it still exhibits a very high specific capacitance of 245.8 F g −1 , which is 65.2% retention of the initial capacitance (377.0 F g −1  at 1 A g −1 ). The unprecedented rate capability is an intrinsic feature of  t -NbO 2 , which may be due to the conductive lithiated compounds.

Nanoarchitectured Nb2O5 hollow, Nb2O5@carbon and NbO2@carbon Core-Shell Microspheres for Ultrahigh-Rate Intercalation Pseudocapacitors