The Air Stability of Sodium Layered Oxide NaTMO<sub>2</sub> (100) Surface Investigated via DFT Calculations

Air stability caused by the H<sub>2</sub>O/CO<sub>2</sub> reaction at the layered oxide NaTMO<sub>2</sub> surface is one of the main obstacles to commercializing sodium-ion batteries (SIBS). The H<sub>2</sub>O and CO<sub>2</sub> adsorption...

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Main Authors: Hui Li, Qing Xue, Shengyi Li, Xuechun Wang, Yijie Hou, Chang Sun, Cun Wang, Guozheng Sheng, Peng Sheng, Huitao Bai, Li Xu, Yumin Qian
Format: Article
Language:English
Published: MDPI AG 2025-07-01
Series:Nanomaterials
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Online Access:https://www.mdpi.com/2079-4991/15/14/1067
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author Hui Li
Qing Xue
Shengyi Li
Xuechun Wang
Yijie Hou
Chang Sun
Cun Wang
Guozheng Sheng
Peng Sheng
Huitao Bai
Li Xu
Yumin Qian
author_facet Hui Li
Qing Xue
Shengyi Li
Xuechun Wang
Yijie Hou
Chang Sun
Cun Wang
Guozheng Sheng
Peng Sheng
Huitao Bai
Li Xu
Yumin Qian
author_sort Hui Li
collection DOAJ
description Air stability caused by the H<sub>2</sub>O/CO<sub>2</sub> reaction at the layered oxide NaTMO<sub>2</sub> surface is one of the main obstacles to commercializing sodium-ion batteries (SIBS). The H<sub>2</sub>O and CO<sub>2</sub> adsorption properties on the (100) surface of sodium layered transition metal oxide NaTMO<sub>2</sub> (TM = Co, Ni, Mo, Nd) are calculated using the DFT method to study the surface air stability. This study showed that the material bulk phase (symmetry), surface site, element type, and surface termination are all (though not the only) important factors that affect the adsorption strength. Contrary to previous studies, the P phase is not always more air-stable than the O phase; our calculations showed that the NaNiO<sub>2</sub> O phase is more stable than the P phase. The calculated band center and occupation showed a direct relationship with the adsorption energy. The Na site adsorption for CO<sub>2</sub> and H<sub>2</sub>O showed the same V-shape trend. However, the TM adsorption for CO<sub>2</sub> and H<sub>2</sub>O showed a different trend. With an increased t<sub>2</sub>g band center, CO<sub>2</sub> adsorption strength increases. There is no clear trend for H<sub>2</sub>O adsorption. Our calculations showed that the electronic structure of the surface atomic of adsorption site plays a decisive role in CO<sub>2</sub> and H<sub>2</sub>O adsorption strength. This study demonstrated an effective method for obtaining a stability parameter regarding the electronic structure, which can be used to screen the air-stable layered oxide sodium cathode in the future.
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series Nanomaterials
spelling doaj-art-48625e17a90146da9c019d2cb199e5632025-08-20T03:56:45ZengMDPI AGNanomaterials2079-49912025-07-011514106710.3390/nano15141067The Air Stability of Sodium Layered Oxide NaTMO<sub>2</sub> (100) Surface Investigated via DFT CalculationsHui Li0Qing Xue1Shengyi Li2Xuechun Wang3Yijie Hou4Chang Sun5Cun Wang6Guozheng Sheng7Peng Sheng8Huitao Bai9Li Xu10Yumin Qian11Beijing Institute of Smart Energy, Beijing 102209, ChinaBeijing Institute of Smart Energy, Beijing 102209, ChinaBeijing Institute of Smart Energy, Beijing 102209, ChinaKey Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement, Ministry of Education, School of Physics, Beijing Institute of Technology, Beijing 100081, ChinaKey Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement, Ministry of Education, School of Physics, Beijing Institute of Technology, Beijing 100081, ChinaKey Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement, Ministry of Education, School of Physics, Beijing Institute of Technology, Beijing 100081, ChinaKey Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement, Ministry of Education, School of Physics, Beijing Institute of Technology, Beijing 100081, ChinaKey Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement, Ministry of Education, School of Physics, Beijing Institute of Technology, Beijing 100081, ChinaBeijing Institute of Smart Energy, Beijing 102209, ChinaBeijing Institute of Smart Energy, Beijing 102209, ChinaBeijing Institute of Smart Energy, Beijing 102209, ChinaKey Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement, Ministry of Education, School of Physics, Beijing Institute of Technology, Beijing 100081, ChinaAir stability caused by the H<sub>2</sub>O/CO<sub>2</sub> reaction at the layered oxide NaTMO<sub>2</sub> surface is one of the main obstacles to commercializing sodium-ion batteries (SIBS). The H<sub>2</sub>O and CO<sub>2</sub> adsorption properties on the (100) surface of sodium layered transition metal oxide NaTMO<sub>2</sub> (TM = Co, Ni, Mo, Nd) are calculated using the DFT method to study the surface air stability. This study showed that the material bulk phase (symmetry), surface site, element type, and surface termination are all (though not the only) important factors that affect the adsorption strength. Contrary to previous studies, the P phase is not always more air-stable than the O phase; our calculations showed that the NaNiO<sub>2</sub> O phase is more stable than the P phase. The calculated band center and occupation showed a direct relationship with the adsorption energy. The Na site adsorption for CO<sub>2</sub> and H<sub>2</sub>O showed the same V-shape trend. However, the TM adsorption for CO<sub>2</sub> and H<sub>2</sub>O showed a different trend. With an increased t<sub>2</sub>g band center, CO<sub>2</sub> adsorption strength increases. There is no clear trend for H<sub>2</sub>O adsorption. Our calculations showed that the electronic structure of the surface atomic of adsorption site plays a decisive role in CO<sub>2</sub> and H<sub>2</sub>O adsorption strength. This study demonstrated an effective method for obtaining a stability parameter regarding the electronic structure, which can be used to screen the air-stable layered oxide sodium cathode in the future.https://www.mdpi.com/2079-4991/15/14/1067DFTsurface electron structureair stabilitysodium ion battery
spellingShingle Hui Li
Qing Xue
Shengyi Li
Xuechun Wang
Yijie Hou
Chang Sun
Cun Wang
Guozheng Sheng
Peng Sheng
Huitao Bai
Li Xu
Yumin Qian
The Air Stability of Sodium Layered Oxide NaTMO<sub>2</sub> (100) Surface Investigated via DFT Calculations
Nanomaterials
DFT
surface electron structure
air stability
sodium ion battery
title The Air Stability of Sodium Layered Oxide NaTMO<sub>2</sub> (100) Surface Investigated via DFT Calculations
title_full The Air Stability of Sodium Layered Oxide NaTMO<sub>2</sub> (100) Surface Investigated via DFT Calculations
title_fullStr The Air Stability of Sodium Layered Oxide NaTMO<sub>2</sub> (100) Surface Investigated via DFT Calculations
title_full_unstemmed The Air Stability of Sodium Layered Oxide NaTMO<sub>2</sub> (100) Surface Investigated via DFT Calculations
title_short The Air Stability of Sodium Layered Oxide NaTMO<sub>2</sub> (100) Surface Investigated via DFT Calculations
title_sort air stability of sodium layered oxide natmo sub 2 sub 100 surface investigated via dft calculations
topic DFT
surface electron structure
air stability
sodium ion battery
url https://www.mdpi.com/2079-4991/15/14/1067
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