The role of Li doping in layered/layered NaxLiyNi0.4Fe0.2Mn0.4O2 intergrowth electrodes for sodium ion batteries

Eric Gabriel; Pengbo Wang; Kincaid Graff; Shelly D. Kelly; Chengjun Sun; Changjian Deng; Inhui Hwang; Jue Liu; Cheng Li; Sarah Kuraitis; Jehee Park; Eungje Lee; Angel Conrado; Julie Pipkin; Max Cook; Stephanie McCallum; Yingying Xie; Zonghai Chen; Kamila M. Wiaderek; Andrey Yakovenko; Yang Ren; Yuming Xiao; Yuzi Liu; Elton Graugnard; Yan Yan Hu; Dewen Hou; Hui Xiong

doi:10.1016/j.nanoen.2024.110556

The role of Li doping in layered/layered Na_xLi_yNi_0.4Fe_0.2Mn_0.4O₂ intergrowth electrodes for sodium ion batteries

Eric Gabriel, Pengbo Wang, Kincaid Graff, Shelly D. Kelly, Chengjun Sun, Changjian Deng, Inhui Hwang, Jue Liu, Cheng Li, Sarah Kuraitis, Jehee Park, Eungje Lee, Angel Conrado, Julie Pipkin, Max Cook, Stephanie McCallum, Yingying Xie, Zonghai Chen, Kamila M. Wiaderek, Andrey YakovenkoYang Ren, Yuming Xiao, Yuzi Liu, Elton Graugnard, Yan Yan Hu, Dewen Hou, Hui Xiong

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

Abstract

The layered NaTMO₂ (TM = Ni, Fe, Mn) materials with the O3-type structure are attractive as positive electrodes for sodium ion batteries because of their high theoretical capacity. Additionally, Li doping in these materials has been shown to offer substantial enhancements to their electrochemical properties by promoting the formation of intergrowth structures, which intimately integrate the substituent phases. However, the influence of the specific Li content on the structural and electrochemical properties of the intergrowth materials requires investigation. Systematic variation of Li content in Na_xLi_yNi_0.4Fe_0.2Mn_0.4O₂ (NFM-Li_y) was conducted to identify the role of Li in modification of the intergrowth structure and electrochemical performance. Li contents of 0.15 and greater generate a layered/layered Na-O3/Li-O’3 intergrowth structure. ⁷Li and ²³Na solid-state nuclear magnetic resonance and x-ray absorption spectroscopy identify that when the total solubility for alkali ions in the layered structure is exceeded, Li continues to form the Li-O’3 phase while the excess Na forms residual sodium compounds such as Na₂O. Higher Li content is associated with improved capacity retention in the initial cycles from the superior stability of the mechanically linked Na-O3/Li-O’3 structure that suppresses the P3 to OP2 phase transition during charge. However, high Li contents are associated with increased rates of parasitic side reactions that reduce long-term cycling stability. These side reactions are connected to the instability of the cathode-electrolyte interphase, which can be partially mitigated by atomic layer deposition (ALD) coating with alumina, which significantly enhances the capacity retention and Coulombic efficiency. Overall, we find that the layered/layered Na-O3/Li-O’3 intergrowth structure is able to provide structural stability and suppress undesired phase transformations but is overwhelmed by the increased reactivity of the surface if not protected by surface coating.

Original language	English
Article number	110556
Journal	Nano Energy
Volume	134
DOIs	https://doi.org/10.1016/j.nanoen.2024.110556
State	Published - Feb 2025

Funding

This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences program under Award Number DE-SC0019121. E. Gabriel was supported by the DOE Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. ORISE is managed by ORAU under Contract No. DE-SC0014664. K. Graff acknowledges the support by U.S. National Science Foundation (NSF) (grant number DUE- 2111549). S. McCallum acknowledges the National Science Foundation (NSF) REU Site: Materials for Society (Award No. 1950305). This research used resources of the Advanced Photon Source and Center for Nanoscale Materials, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. Portions of this work were performed at HPCAT (Sector 16), APS, ANL. HPCAT operations are supported by DOE-NNSA's Office of Experimental Sciences. Work at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for U.S. DOE under Contract No. DEAC05\u201300OR22725. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences program under Award Number DE-SC0019121. E. Gabriel was supported by the DOE Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. ORISE is managed by ORAU under Contract No. DE-SC0014664. K. Graff acknowledges the support by U.S. National Science Foundation (NSF) (grant number DUE- 2111549). S. McCallum acknowledges the National Science Foundation (NSF) REU Site: Materials for Society (Award No.1950305). This research used resources of the Advanced Photon Source and Center for Nanoscale Materials, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. Portions of this work were performed at HPCAT (Sector 16), APS, ANL. HPCAT operations are supported by DOE-NNSA\u2019s Office of Experimental Sciences. Work at ORNL\u2019s Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for U.S. DOE under Contract No. DEAC05-00OR22725.

Keywords

Intergrowth
Layered oxides
Lithium doping
Positive electrodes
Sodium ion batteries
Surface coating

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10.1016/j.nanoen.2024.110556

Cite this

Gabriel, E., Wang, P., Graff, K., Kelly, S. D., Sun, C., Deng, C., Hwang, I., Liu, J., Li, C., Kuraitis, S., Park, J., Lee, E., Conrado, A., Pipkin, J., Cook, M., McCallum, S., Xie, Y., Chen, Z., Wiaderek, K. M., ... Xiong, H. (2025). The role of Li doping in layered/layered Na_xLi_yNi_0.4Fe_0.2Mn_0.4O₂ intergrowth electrodes for sodium ion batteries. Nano Energy, 134, Article 110556. https://doi.org/10.1016/j.nanoen.2024.110556

@article{9033070fbf7c4d6bb5463cc3aa8af6ff,

title = "The role of Li doping in layered/layered NaxLiyNi0.4Fe0.2Mn0.4O2 intergrowth electrodes for sodium ion batteries",

abstract = "The layered NaTMO2 (TM = Ni, Fe, Mn) materials with the O3-type structure are attractive as positive electrodes for sodium ion batteries because of their high theoretical capacity. Additionally, Li doping in these materials has been shown to offer substantial enhancements to their electrochemical properties by promoting the formation of intergrowth structures, which intimately integrate the substituent phases. However, the influence of the specific Li content on the structural and electrochemical properties of the intergrowth materials requires investigation. Systematic variation of Li content in NaxLiyNi0.4Fe0.2Mn0.4O2 (NFM-Liy) was conducted to identify the role of Li in modification of the intergrowth structure and electrochemical performance. Li contents of 0.15 and greater generate a layered/layered Na-O3/Li-O{\textquoteright}3 intergrowth structure. 7Li and 23Na solid-state nuclear magnetic resonance and x-ray absorption spectroscopy identify that when the total solubility for alkali ions in the layered structure is exceeded, Li continues to form the Li-O{\textquoteright}3 phase while the excess Na forms residual sodium compounds such as Na2O. Higher Li content is associated with improved capacity retention in the initial cycles from the superior stability of the mechanically linked Na-O3/Li-O{\textquoteright}3 structure that suppresses the P3 to OP2 phase transition during charge. However, high Li contents are associated with increased rates of parasitic side reactions that reduce long-term cycling stability. These side reactions are connected to the instability of the cathode-electrolyte interphase, which can be partially mitigated by atomic layer deposition (ALD) coating with alumina, which significantly enhances the capacity retention and Coulombic efficiency. Overall, we find that the layered/layered Na-O3/Li-O{\textquoteright}3 intergrowth structure is able to provide structural stability and suppress undesired phase transformations but is overwhelmed by the increased reactivity of the surface if not protected by surface coating.",

keywords = "Intergrowth, Layered oxides, Lithium doping, Positive electrodes, Sodium ion batteries, Surface coating",

author = "Eric Gabriel and Pengbo Wang and Kincaid Graff and Kelly, {Shelly D.} and Chengjun Sun and Changjian Deng and Inhui Hwang and Jue Liu and Cheng Li and Sarah Kuraitis and Jehee Park and Eungje Lee and Angel Conrado and Julie Pipkin and Max Cook and Stephanie McCallum and Yingying Xie and Zonghai Chen and Wiaderek, {Kamila M.} and Andrey Yakovenko and Yang Ren and Yuming Xiao and Yuzi Liu and Elton Graugnard and Hu, {Yan Yan} and Dewen Hou and Hui Xiong",

note = "Publisher Copyright: {\textcopyright} 2024 Elsevier Ltd",

year = "2025",

month = feb,

doi = "10.1016/j.nanoen.2024.110556",

language = "English",

volume = "134",

journal = "Nano Energy",

issn = "2211-2855",

publisher = "Elsevier",

}

Gabriel, E, Wang, P, Graff, K, Kelly, SD, Sun, C, Deng, C, Hwang, I, Liu, J , Li, C, Kuraitis, S, Park, J, Lee, E, Conrado, A, Pipkin, J, Cook, M, McCallum, S, Xie, Y, Chen, Z, Wiaderek, KM, Yakovenko, A, Ren, Y, Xiao, Y, Liu, Y, Graugnard, E, Hu, YY, Hou, D & Xiong, H 2025, 'The role of Li doping in layered/layered Na_xLi_yNi_0.4Fe_0.2Mn_0.4O₂ intergrowth electrodes for sodium ion batteries', Nano Energy, vol. 134, 110556. https://doi.org/10.1016/j.nanoen.2024.110556

TY - JOUR

T1 - The role of Li doping in layered/layered NaxLiyNi0.4Fe0.2Mn0.4O2 intergrowth electrodes for sodium ion batteries

AU - Gabriel, Eric

AU - Wang, Pengbo

AU - Graff, Kincaid

AU - Kelly, Shelly D.

AU - Sun, Chengjun

AU - Deng, Changjian

AU - Hwang, Inhui

AU - Liu, Jue

AU - Li, Cheng

AU - Kuraitis, Sarah

AU - Park, Jehee

AU - Lee, Eungje

AU - Conrado, Angel

AU - Pipkin, Julie

AU - Cook, Max

AU - McCallum, Stephanie

AU - Xie, Yingying

AU - Chen, Zonghai

AU - Wiaderek, Kamila M.

AU - Yakovenko, Andrey

AU - Ren, Yang

AU - Xiao, Yuming

AU - Liu, Yuzi

AU - Graugnard, Elton

AU - Hu, Yan Yan

AU - Hou, Dewen

AU - Xiong, Hui

PY - 2025/2

Y1 - 2025/2

N2 - The layered NaTMO2 (TM = Ni, Fe, Mn) materials with the O3-type structure are attractive as positive electrodes for sodium ion batteries because of their high theoretical capacity. Additionally, Li doping in these materials has been shown to offer substantial enhancements to their electrochemical properties by promoting the formation of intergrowth structures, which intimately integrate the substituent phases. However, the influence of the specific Li content on the structural and electrochemical properties of the intergrowth materials requires investigation. Systematic variation of Li content in NaxLiyNi0.4Fe0.2Mn0.4O2 (NFM-Liy) was conducted to identify the role of Li in modification of the intergrowth structure and electrochemical performance. Li contents of 0.15 and greater generate a layered/layered Na-O3/Li-O’3 intergrowth structure. 7Li and 23Na solid-state nuclear magnetic resonance and x-ray absorption spectroscopy identify that when the total solubility for alkali ions in the layered structure is exceeded, Li continues to form the Li-O’3 phase while the excess Na forms residual sodium compounds such as Na2O. Higher Li content is associated with improved capacity retention in the initial cycles from the superior stability of the mechanically linked Na-O3/Li-O’3 structure that suppresses the P3 to OP2 phase transition during charge. However, high Li contents are associated with increased rates of parasitic side reactions that reduce long-term cycling stability. These side reactions are connected to the instability of the cathode-electrolyte interphase, which can be partially mitigated by atomic layer deposition (ALD) coating with alumina, which significantly enhances the capacity retention and Coulombic efficiency. Overall, we find that the layered/layered Na-O3/Li-O’3 intergrowth structure is able to provide structural stability and suppress undesired phase transformations but is overwhelmed by the increased reactivity of the surface if not protected by surface coating.

AB - The layered NaTMO2 (TM = Ni, Fe, Mn) materials with the O3-type structure are attractive as positive electrodes for sodium ion batteries because of their high theoretical capacity. Additionally, Li doping in these materials has been shown to offer substantial enhancements to their electrochemical properties by promoting the formation of intergrowth structures, which intimately integrate the substituent phases. However, the influence of the specific Li content on the structural and electrochemical properties of the intergrowth materials requires investigation. Systematic variation of Li content in NaxLiyNi0.4Fe0.2Mn0.4O2 (NFM-Liy) was conducted to identify the role of Li in modification of the intergrowth structure and electrochemical performance. Li contents of 0.15 and greater generate a layered/layered Na-O3/Li-O’3 intergrowth structure. 7Li and 23Na solid-state nuclear magnetic resonance and x-ray absorption spectroscopy identify that when the total solubility for alkali ions in the layered structure is exceeded, Li continues to form the Li-O’3 phase while the excess Na forms residual sodium compounds such as Na2O. Higher Li content is associated with improved capacity retention in the initial cycles from the superior stability of the mechanically linked Na-O3/Li-O’3 structure that suppresses the P3 to OP2 phase transition during charge. However, high Li contents are associated with increased rates of parasitic side reactions that reduce long-term cycling stability. These side reactions are connected to the instability of the cathode-electrolyte interphase, which can be partially mitigated by atomic layer deposition (ALD) coating with alumina, which significantly enhances the capacity retention and Coulombic efficiency. Overall, we find that the layered/layered Na-O3/Li-O’3 intergrowth structure is able to provide structural stability and suppress undesired phase transformations but is overwhelmed by the increased reactivity of the surface if not protected by surface coating.

KW - Intergrowth

KW - Layered oxides

KW - Lithium doping

KW - Positive electrodes

KW - Sodium ion batteries

KW - Surface coating

UR - http://www.scopus.com/inward/record.url?scp=85211749486&partnerID=8YFLogxK

U2 - 10.1016/j.nanoen.2024.110556

DO - 10.1016/j.nanoen.2024.110556

M3 - Article

AN - SCOPUS:85211749486

SN - 2211-2855

VL - 134

JO - Nano Energy

JF - Nano Energy

M1 - 110556

ER -