Niobium tungsten oxides for high-rate lithium-ion energy storage.
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Griffith, K., Wiaderek, K. M., Cibin, G., Marbella, L., & Grey, C. (2018). Niobium tungsten oxides for high-rate lithium-ion energy storage.. Nature, 559 (7715), 556-563. https://doi.org/10.1038/s41586-018-0347-0
The maximum power output and minimum charging time of a lithium-ion battery depend on both ionic and electronic transport. Ionic diffusion within the electrochemically active particles generally represents a fundamental limitation, so to achieve high rates of cycling, particles are frequently reduced to nanosize dimensions to the detriment of volumetric packing density, cost, stability, and sustainability. As an alternative to nanoscaling, here we show that two complex oxides, Nb16W5O55 and Nb18W16O93, which adopt crystallographic shear and bronze-like structures, respectively, can intercalate large quantities of lithium at surprisingly high rates even when their particles are micrometer-sized. Their lithium-ion diffusion coefficients (DLi) measured with pulsed field gradient NMR spectroscopy have room temperature values several orders-of-magnitude faster than typical electrode materials. Multielectron redox, buffered volume expansion, topologically frustrated Nb/W polyhedral arrangements, and rapid solid-state lithium transport lead to extremely high volumetric capacities and rate performance. Unconventional materials and mechanisms that enable lithiation of µm-sized particles in minutes have implications for high power applications, fast charging devices, all-solid-state batteries, and approaches to electrode design and material discovery.
K.J.G. gratefully acknowledges support from The Winston Churchill Foundation of the United States, the Herchel Smith Scholarship, and the Science and Technology Facilities Council Futures Early Career Award. K.J.G and C.P.G thank the EPSRC via the LIBATT grant (EP/P003532/1). L.E.M. was funded by the European Union’s Horizon 2020 – European Union research and innovation program under the Marie Skłodowska–Curie grant agreement No. 750294. We thank Dr. Ieuan Seymour, University of Cambridge, and Prof. Bruce Dunn, University of California, Los Angeles, for fruitful discussions. We thank Drs. Jeremy Skepper and Heather Greer, University of Cambridge, for assistance with the electron microscopy and Dr. Maxim Avdeev, Bragg Institute, for his bond valence sum mapping program. We thank Dr. Olaf Borkiewicz, Advanced Photon Source, Argonne National Laboratory and Alisha Kasam, University of Cambridge for diffraction data reduction scripts. We thank Diamond Light Source for access to beamline B18 (SP14956, SP16387, SP17913) that contributed to the results presented here. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE- AC02-06CH11357.
EPSRC (via University of Oxford) (EP/M009521/1)
European Commission Horizon 2020 (H2020) Marie Sk?odowska-Curie actions (750294)
External DOI: https://doi.org/10.1038/s41586-018-0347-0
This record's URL: https://www.repository.cam.ac.uk/handle/1810/282820