A Polymetallic Metal‐Organic Framework‐Derived Strategy toward Synergistically Multidoped Metal Oxide Electrodes with Ultralong Cycle Life and High Volumetric Capacity

Metal-organic frameworks (MOFs) are very convenient self-templated precursors toward functional materials with tunable functionalities. Although a huge family of MOFs has been discovered, conventional MOF-derived strategies are largely limited to the sole MOF source based on a handful of the metal elements. The limitation in structure and functionalities greatly restrains the maximum performance of MOF-based materials for fulfilling the practical potential. This study reports a polymetallic MOF-derived strategy for easy synthesis of metal-oxide-based nanohybrids with precisely tailored multicomponent active dopants. A variety of MoO2-based nanohybrids with synergistical co-doping of W, Cu, and P are yielded by controlled pyrolysis of tailor-made polymetallic MOFs. The W doping induces the formation of MoxW1−xO2 solid solution with better activity. The homogeneous dispersion of Cu nanocrystallites in robust P-doped carbon skeleton creates a conductive network for fast charge transfer. Boosting by synergistically multidoping effect, the Mo0.8W0.2O2-Cu@P-doped carbon nanohybrids with optimized composition exhibit exceptionally long cycle life of 2000 cycles with high capacities but very slow capacity loss (0.043% per cycle), as well as high power output for lithium storage. Remarkably, the co-doping of heavy W and Cu elements in MoO2 with high density makes them particularly suitable for high volumetric lithium storage.