Surface Characterization of Li-Substituted Compositionally Heterogeneous NaLi0.045Cu0.185Fe0.265Mn0.505O2 Sodium-Ion Cathode Material

Muhammad Mominur Rahman; Yan Zhang; Sihao Xia; Wang Hay Kan; Maxim Avdeev; Linqin Mu; Dimosthenis Sokaras; Thomas Kroll; Xi Wen Du; Dennis Nordlund; Yijin Liu; Feng Lin

doi:10.1021/acs.jpcc.9b01126

Surface Characterization of Li-Substituted Compositionally Heterogeneous NaLi_0.045Cu_0.185Fe_0.265Mn_0.505O₂ Sodium-Ion Cathode Material

Muhammad Mominur Rahman, Yan Zhang, Sihao Xia, Wang Hay Kan, Maxim Avdeev, Linqin Mu, Dimosthenis Sokaras, Thomas Kroll, Xi Wen Du, Dennis Nordlund, Yijin Liu, Feng Lin

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

The understanding of surface chemical and structural processes can provide some insights into designing stable sodium cathode materials. Herein, Li-substituted and compositionally heterogeneous NaLi_0.045Cu_0.185Fe_0.265Mn_0.505O₂ is used as a platform to investigate the interplay between Li substitution, surface chemistry, and battery performance. Li substitution improves the initial discharge capacity and energy density. However, there is no noticeable benefit in the long-term cycling stability of this material. The Li substitution in the transition-metal (TM) layer also seems to influence the transition-metal (TM) 3d-oxygen (O) 2p hybridization. Upon desodiation, the surface of active particles undergoes significant transition-metal reduction, especially Mn. Furthermore, the presence of electrolyte drastically accelerates such surface degradation. In general, the Li-substituted material experiences severe surface degradation, which is partially responsible for the performance degradation upon long-term cycling. While some studies have reported the benefits of Li substitution, the present study suggests that the effectiveness of the Li substitution strategy depends on the TM compositional distribution. More efforts are needed to improve the surface chemistry of Li-substituted sodium cathode materials.

Original language	English
Pages (from-to)	11428-11435
Number of pages	8
Journal	Journal of Physical Chemistry C
Volume	123
Issue number	18
DOIs	https://doi.org/10.1021/acs.jpcc.9b01126
State	Published - May 9 2019
Externally published	Yes

Funding

This work was supported by the Virginia Tech Department of Chemistry startup funds and Institute for Critical Technology and Applied Science at Virginia Tech. The Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility, is operated for the US Department of Energy, Office of Science by Stanford University. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The authors like to thank Dr Xu Feng of Surface Analysis Lab at Virginia Tech for his technical expertise with XPS depth-profiling analysis. The authors would further like to extend their gratitude toward Dr F. Marc Michel of Department of Geoscience, Virginia Tech for XRD pattern acquisition. W.H.K. appreciates for the beamtime in ECHIDNA granted from the Australian Centre for Neutron Scattering (CSNS) in ANSTO. W.H.K. also thank the support from the National Natural Science Foundation of China (11805034 and 21704105).

Funders	Funder number
Virginia Tech Department of Chemistry Startup Funds
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-AC02-76SF00515
Institute for Critical Technologies and Applied Science, Virginia Tech
National Natural Science Foundation of China	11805034, 21704105

Access to Document

10.1021/acs.jpcc.9b01126

Cite this

Rahman, M. M., Zhang, Y., Xia, S., Kan, W. H., Avdeev, M., Mu, L., Sokaras, D., Kroll, T., Du, X. W., Nordlund, D., Liu, Y., & Lin, F. (2019). Surface Characterization of Li-Substituted Compositionally Heterogeneous NaLi_0.045Cu_0.185Fe_0.265Mn_0.505O₂ Sodium-Ion Cathode Material. Journal of Physical Chemistry C, 123(18), 11428-11435. https://doi.org/10.1021/acs.jpcc.9b01126

@article{d1f70efd8d104cb79ab93492f21eeae2,

title = "Surface Characterization of Li-Substituted Compositionally Heterogeneous NaLi0.045Cu0.185Fe0.265Mn0.505O2 Sodium-Ion Cathode Material",

abstract = "The understanding of surface chemical and structural processes can provide some insights into designing stable sodium cathode materials. Herein, Li-substituted and compositionally heterogeneous NaLi0.045Cu0.185Fe0.265Mn0.505O2 is used as a platform to investigate the interplay between Li substitution, surface chemistry, and battery performance. Li substitution improves the initial discharge capacity and energy density. However, there is no noticeable benefit in the long-term cycling stability of this material. The Li substitution in the transition-metal (TM) layer also seems to influence the transition-metal (TM) 3d-oxygen (O) 2p hybridization. Upon desodiation, the surface of active particles undergoes significant transition-metal reduction, especially Mn. Furthermore, the presence of electrolyte drastically accelerates such surface degradation. In general, the Li-substituted material experiences severe surface degradation, which is partially responsible for the performance degradation upon long-term cycling. While some studies have reported the benefits of Li substitution, the present study suggests that the effectiveness of the Li substitution strategy depends on the TM compositional distribution. More efforts are needed to improve the surface chemistry of Li-substituted sodium cathode materials.",

author = "Rahman, {Muhammad Mominur} and Yan Zhang and Sihao Xia and Kan, {Wang Hay} and Maxim Avdeev and Linqin Mu and Dimosthenis Sokaras and Thomas Kroll and Du, {Xi Wen} and Dennis Nordlund and Yijin Liu and Feng Lin",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = may,

day = "9",

doi = "10.1021/acs.jpcc.9b01126",

language = "English",

volume = "123",

pages = "11428--11435",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

publisher = "American Chemical Society",

number = "18",

}

TY - JOUR

T1 - Surface Characterization of Li-Substituted Compositionally Heterogeneous NaLi0.045Cu0.185Fe0.265Mn0.505O2 Sodium-Ion Cathode Material

AU - Rahman, Muhammad Mominur

AU - Zhang, Yan

AU - Xia, Sihao

AU - Kan, Wang Hay

AU - Avdeev, Maxim

AU - Mu, Linqin

AU - Sokaras, Dimosthenis

AU - Kroll, Thomas

AU - Du, Xi Wen

AU - Nordlund, Dennis

AU - Liu, Yijin

AU - Lin, Feng

PY - 2019/5/9

Y1 - 2019/5/9

N2 - The understanding of surface chemical and structural processes can provide some insights into designing stable sodium cathode materials. Herein, Li-substituted and compositionally heterogeneous NaLi0.045Cu0.185Fe0.265Mn0.505O2 is used as a platform to investigate the interplay between Li substitution, surface chemistry, and battery performance. Li substitution improves the initial discharge capacity and energy density. However, there is no noticeable benefit in the long-term cycling stability of this material. The Li substitution in the transition-metal (TM) layer also seems to influence the transition-metal (TM) 3d-oxygen (O) 2p hybridization. Upon desodiation, the surface of active particles undergoes significant transition-metal reduction, especially Mn. Furthermore, the presence of electrolyte drastically accelerates such surface degradation. In general, the Li-substituted material experiences severe surface degradation, which is partially responsible for the performance degradation upon long-term cycling. While some studies have reported the benefits of Li substitution, the present study suggests that the effectiveness of the Li substitution strategy depends on the TM compositional distribution. More efforts are needed to improve the surface chemistry of Li-substituted sodium cathode materials.

AB - The understanding of surface chemical and structural processes can provide some insights into designing stable sodium cathode materials. Herein, Li-substituted and compositionally heterogeneous NaLi0.045Cu0.185Fe0.265Mn0.505O2 is used as a platform to investigate the interplay between Li substitution, surface chemistry, and battery performance. Li substitution improves the initial discharge capacity and energy density. However, there is no noticeable benefit in the long-term cycling stability of this material. The Li substitution in the transition-metal (TM) layer also seems to influence the transition-metal (TM) 3d-oxygen (O) 2p hybridization. Upon desodiation, the surface of active particles undergoes significant transition-metal reduction, especially Mn. Furthermore, the presence of electrolyte drastically accelerates such surface degradation. In general, the Li-substituted material experiences severe surface degradation, which is partially responsible for the performance degradation upon long-term cycling. While some studies have reported the benefits of Li substitution, the present study suggests that the effectiveness of the Li substitution strategy depends on the TM compositional distribution. More efforts are needed to improve the surface chemistry of Li-substituted sodium cathode materials.

UR - http://www.scopus.com/inward/record.url?scp=85065615382&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.9b01126

DO - 10.1021/acs.jpcc.9b01126

M3 - Article

AN - SCOPUS:85065615382

SN - 1932-7447

VL - 123

SP - 11428

EP - 11435

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 18

ER -

Surface Characterization of Li-Substituted Compositionally Heterogeneous NaLi_0.045Cu_0.185Fe_0.265Mn_0.505O₂ Sodium-Ion Cathode Material

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this