Abstract
Cation-disordered rocksalt (DRX) cathodes have recently emerged as a promising class of cobalt-free, high-capacity cathodes for lithium-ion batteries. To facilitate their commercialization, the development of scalable synthesis techniques providing control over composition and morphology is critical. To this end, a sol-gel synthesis route to prepare Mn-rich DRX cathodes with high capacities is presented here. Several compositions with varied Mn content and nominal F doping are successfully prepared using this technique. In-situ X-ray diffraction measurements demonstrate that DRX formation proceeds at moderate temperature (800 °C) through the sol-gel route, which enables intimate mixing among reactive intermediate phases that form at lower temperatures. All synthesized compositions possess cation short-range order, as evidenced by neutron pair distribution function and electron diffraction analysis. These DRX materials demonstrate promising electrochemical performance with reversible capacities up to 275 mAh g. Compared to the baseline oxide (Li1.2Mn0.4Ti0.4O2), the Mn-rich compositions exhibit improved cycling stability, with some showing an increase in capacity upon cycling. Overall, this study demonstrates the feasibility of preparing high-capacity DRX cathodes through a sol-gel based synthesis route, which may be further optimized to provide better control over the product morphology compared to traditional synthesis methods.
| Original language | English |
|---|---|
| Article number | 2203207 |
| Journal | Advanced Energy Materials |
| Volume | 13 |
| Issue number | 4 |
| DOIs | |
| State | Published - Jan 27 2023 |
Funding
S.P. and D.D. contributed equally to this work. Research conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) was sponsored by the Vehicle Technologies Office (VTO) under the Office of Energy Efficiency and Renewable Energy (EERE). Neutron scattering experiments were performed on the NOMAD beamline (BL-1B) at the Spallation Neutron Source, a DOE Office of Science User Facility operated by Oak Ridge National Laboratory. Some X-ray diffraction and scanning electron microscopy measurements were conducted at the Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. Ab-initio calculations were performed with support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program, of the U.S. Department of Energy (DOE) under contract no. DE-AC02- 05CH11231. The NMR experimental work reported here was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 and made use of the shared facilities of the UCSB MRSEC (NSF DMR 1720256), a member of the Material Research Facilities Network. The STEM/EDX experimental work reported here was performed under the support of the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the U.S. Department of Energy under Contract No. DE-LC-000L053 under the program of Next Generation Cathode and made use of the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. Department of Energy, Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the U.S. Department of Energy under Contract DE-AC05-76RLO1830. V.C.W. was supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE 1650114. N.J.S. was supported by the National Science Foundation Graduate Research Fellowship under grant No. DGE 1752814. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05–00OR22725 with the US Department of Energy (DOE). The publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan. S.P. and D.D. contributed equally to this work. Research conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) was sponsored by the Vehicle Technologies Office (VTO) under the Office of Energy Efficiency and Renewable Energy (EERE). Neutron scattering experiments were performed on the NOMAD beamline (BL‐1B) at the Spallation Neutron Source, a DOE Office of Science User Facility operated by Oak Ridge National Laboratory. Some X‐ray diffraction and scanning electron microscopy measurements were conducted at the Center for Nanophase Materials Sciences (CNMS), which is a DOE Office of Science User Facility. Ab‐initio calculations were performed with support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program, of the U.S. Department of Energy (DOE) under contract no. DE‐AC02‐ 05CH11231. The NMR experimental work reported here was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE‐AC02‐05CH11231 and made use of the shared facilities of the UCSB MRSEC (NSF DMR 1720256), a member of the Material Research Facilities Network. The STEM/EDX experimental work reported here was performed under the support of the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the U.S. Department of Energy under Contract No. DE‐LC‐000L053 under the program of Next Generation Cathode and made use of the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. Department of Energy, Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle for the U.S. Department of Energy under Contract DE‐AC05‐76RLO1830. V.C.W. was supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE 1650114. N.J.S. was supported by the National Science Foundation Graduate Research Fellowship under grant No. DGE 1752814.
Keywords
- cation disordered rocksalts
- lithium-ion battery cathodes
- manganese-rich
- sol-gel
- synthesis
