Stabilizing lattice oxygen redox in layered sodium transition metal oxide through spin singlet state

Xuelong Wang, Liang Yin, Arthur Ronne, Yiman Zhang, Zilin Hu, Sha Tan, Qinchao Wang, Bohang Song, Mengya Li, Xiaohui Rong, Saul Lapidus, Shize Yang, Enyuan Hu, Jue Liu

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

Reversible lattice oxygen redox reactions offer the potential to enhance energy density and lower battery cathode costs. However, their widespread adoption faces obstacles like substantial voltage hysteresis and poor stability. The current research addresses these challenges by achieving a non-hysteresis, long-term stable oxygen redox reaction in the P3-type Na2/3Cu1/3Mn2/3O2. Here we show this is accomplished by forming spin singlet states during charge and discharge. Detailed analysis, including in-situ X-ray diffraction, shows highly reversible structural changes during cycling. In addition, local CuO6 Jahn-Teller distortions persist throughout, with dynamic Cu-O bond length variations. In-situ hard X-ray absorption and ex-situ soft X-ray absorption study, along with density function theory calculations, reveal two distinct charge compensation mechanisms at approximately 3.66 V and 3.99 V plateaus. Notably, we observe a Zhang-Rice-like singlet state during 3.99 V charging, offering an alternative charge compensation mechanism to stabilize the active oxygen redox reaction.

Original languageEnglish
Article number7665
JournalNature Communications
Volume14
Issue number1
DOIs
StatePublished - Dec 2023

Funding

The work done at Brookhaven National Laboratory is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US Department of Energy through the Advanced Battery Materials Research (BMR) Program under contract no. DE-SC0012704. Neutron powder diffraction measurements used resources at the Spallation Neutron Source (POWGEN and NOMAD instruments), a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research used resources of beamlines 7-BM (QAS) and 23-ID-2 (IOS) of the National Synchrotron Light Source II (NSLS-II) at Brookhaven National Laboratory (Contract No. DE-SC0012704 and DE-SC0012653). We acknowledge the use of facilities within the Eyring Materials Center at Arizona State University supported in part by NNCI_ECCS-1542160. The DFT calculations were performed using computational resources at the Center for Functional Nanomaterials (CFN), which is a U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory. The authors also acknowledge the Beijing Super Cloud Center (BSCC) and the Beijing Beilong Super Cloud Computing Co. Ltd for providing HPC resources that have contributed to the DFT results reported within this paper ( http://www.blsc.cn/ ) This research used 11-BM beamline and electrochemistry laboratory 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. J.L. would like to thank partial finacial support from ORNL LDRD # 10761 - Operando neutron diffraction for battery research. The work done at Brookhaven National Laboratory is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US Department of Energy through the Advanced Battery Materials Research (BMR) Program under contract no. DE-SC0012704. Neutron powder diffraction measurements used resources at the Spallation Neutron Source (POWGEN and NOMAD instruments), a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research used resources of beamlines 7-BM (QAS) and 23-ID-2 (IOS) of the National Synchrotron Light Source II (NSLS-II) at Brookhaven National Laboratory (Contract No. DE-SC0012704 and DE-SC0012653). We acknowledge the use of facilities within the Eyring Materials Center at Arizona State University supported in part by NNCI_ECCS-1542160. The DFT calculations were performed using computational resources at the Center for Functional Nanomaterials (CFN), which is a U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory. The authors also acknowledge the Beijing Super Cloud Center (BSCC) and the Beijing Beilong Super Cloud Computing Co. Ltd for providing HPC resources that have contributed to the DFT results reported within this paper (http://www.blsc.cn/) This research used 11-BM beamline and electrochemistry laboratory 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. J.L. would like to thank partial finacial support from ORNL LDRD # 10761 - Operando neutron diffraction for battery research.

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