Abstract
There is an urgent need for low-cost, resource-friendly, high-energy-density cathode materials for lithium-ion batteries to satisfy the rapidly increasing need for electrical energy storage. To replace the nickel and cobalt, which are limited resources and are associated with safety problems, in current lithium-ion batteries, high-capacity cathodes based on manganese would be particularly desirable owing to the low cost and high abundance of the metal, and the intrinsic stability of the Mn4+ oxidation state. Here we present a strategy of combining high-valent cations and the partial substitution of fluorine for oxygen in a disordered-rocksalt structure to incorporate the reversible Mn2+/Mn4+ double redox couple into lithium-excess cathode materials. The lithium-rich cathodes thus produced have high capacity and energy density. The use of the Mn2+/Mn4+ redox reduces oxygen redox activity, thereby stabilizing the materials, and opens up new opportunities for the design of high-performance manganese-rich cathodes for advanced lithium-ion batteries.
| Original language | English |
|---|---|
| Pages (from-to) | 185-190 |
| Number of pages | 6 |
| Journal | Nature |
| Volume | 556 |
| Issue number | 7700 |
| DOIs | |
| State | Published - Apr 1 2018 |
| Externally published | Yes |
Funding
Acknowledgements Work by J.L., D.A.K., D.-H.K., Z.L., R.J.C. and G.C. was supported by Robert Bosch LLC, Umicore Specialty Oxides and Chemicals, and the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Advanced Battery Materials Research (BMR) Program. This research, in part, used resources of the Advanced Photon Source, a US 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. Work at the Advanced Light Source is supported by DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE under contract no. DE-AC02-05CH11231. The computational work relied on resources provided by the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1548562. J.K.P. acknowledges NSF Graduate Research Fellowship (grant no. DGE-1106400). B.D.M. acknowledges support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the US DOE under contract no. DEAC02-05CH11231, under the Advanced Battery Materials Research (BMR) Program. The authors thank S.-H. Hsieh for assistance in the soft XAS experiments and the California NanoSystems Institute (CNSI) at the University of California Santa Barbara (UCSB) for experimental time on the 500MHz NMR spectrometer. The NMR experimental work reported here made use of the shared facilities of the UCSB MRSEC (NSF DMR 1720256), a member of the Material Research Facilities Network. Work by J.L., D.A.K., D.-H.K., Z.L., R.J.C. and G.C. was supported by Robert Bosch LLC, Umicore Specialty Oxides and Chemicals, and the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Advanced Battery Materials Research (BMR) Program. This research, in part, used resources of the Advanced Photon Source, a US 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. Work at the Advanced Light Source is supported by DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE under contract no. DE-AC02-05CH11231. The computational work relied on resources provided by the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1548562. J.K.P. acknowledges NSF Graduate Research Fellowship (grant no. DGE-1106400). B.D.M. acknowledges support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the US DOE under contract no. DEAC02- 05CH11231, under the Advanced Battery Materials Research (BMR) Program. The authors thank S.-H. Hsieh for assistance in the soft XAS experiments and the California NanoSystems Institute (CNSI) at the University of California Santa Barbara (UCSB) for experimental time on the 500 MHz NMR spectrometer. The NMR experimental work reported here made use of the shared facilities of the UCSB MRSEC (NSF DMR 1720256), a member of the Material Research Facilities Network.