Heteroatom anchoring to enhance electrochemical reversibility for high-voltage P2-type oxide cathodes of sodium-ion batteries

Kai Liu; Susheng Tan; Xiao Guang Sun; Qingqing Zhang; Cheng Li; Hailong Lyu; Lianqi Zhang; Bishnu P. Thapaliya; Sheng Dai

doi:10.1016/j.nanoen.2024.109925

Heteroatom anchoring to enhance electrochemical reversibility for high-voltage P2-type oxide cathodes of sodium-ion batteries

Kai Liu, Susheng Tan, Xiao Guang Sun, Qingqing Zhang, Cheng Li, Hailong Lyu, Lianqi Zhang, Bishnu P. Thapaliya, Sheng Dai

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

5 Scopus citations

Abstract

P2-type cathode has received extensive attention due to its faster Na⁺ diffusion and a high theoretical capacity in sodium-ion batteries (SIBs). However, undesirable phase transformations have induced dramatic capacity decay of SIBs during the cycling process. In this study, heteroatom anchoring through Cu/Mg dual doping is introduced into P2-type Na_0.67Ni_0.33Mn_0.67O₂ cathode to enhance high-voltage electrochemical reversibility and modulate interfacial Na⁺ kinetics. The as-prepared Na_0.67Ni_0.23Mg_0.05Cu_0.05Mn_0.67O₂ exhibits an outstanding capacity retention (83.4 % after 2000 cycles at 10 C) and rate performance (73 mAh g⁻¹ at 10 C, accounting for 58.7 % of that at 0.1 C) over the voltage range of 2.5–4.4 V. Intensive explorations further manifest that the modified mechanism of dual-ion doping strategy is attributed to the synergistic coupling effect of a substantial change in Na occupancy distribution and an increase in oxygen vacancy buffer. Thus, the optimized cathode expedites Na⁺ diffusion and reduces detrimental phase transformation, which favors high-rate performance and long-term cycling stability. This study develops a route to rationally design high-voltage cathode materials for SIBs.

Original language	English
Article number	109925
Journal	Nano Energy
Volume	128
DOIs	https://doi.org/10.1016/j.nanoen.2024.109925
State	Published - Sep 2024

Funding

The material preparation and advanced electrochemical characterization were supported by the U.S. Department of Energy's Office of Science, Office of Basic Energy Science, Materials Sciences and Engineering Division. The scanning electron microscopy experiment was performed by a user project supported by the ORNL's Center for Nanophase Materials Sciences, which was sponsored by the U.S. Department of Energy, Office of Science, and Scientific User Facility Division. Prof. Tan appreciated the supporting for transmission electron microscopy facility at the University of Pittsburgh. Dr. Zhang was financially supported by the National Natural Science Foundation of China (No. 52202228), and funded by Science Research Project of Hebei Education Department (No. BJK2022011) and Central Funds Guiding the Local Science and Technology Development of Hebei Province (No. 236Z4404G). This manuscript also has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. This article has been contributed by US Government employees and the work is in the public domain in the USA. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan.\u201D With \u201CThis article has been authored by US Government employees and the work is in the public domain in the USA. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). The material preparation and advanced electrochemical characterization were supported by the U.S. Department of Energy\u2019s Office of Science, Office of Basic Energy Science, Materials Sciences and Engineering Division. The scanning electron microscopy experiment was performed by a user project supported by the ORNL\u2019s Center for Nanophase Materials Sciences, which was sponsored by the U.S. Department of Energy, Office of Science, and Scientific User Facility Division. Prof. Tan appreciated the supporting for transmission electron microscopy facility at the University of Pittsburgh. Dr. Zhang was financially supported by the National Natural Science Foundation of China (No. 52202228), and funded by Science Research Project of Hebei Education Department (No. BJK2022011) and Central Funds Guiding the Local Science and Technology Development of Hebei Province (No. 236Z4404G). This manuscript also has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. This article has been contributed to by US Government employees and the work is in the public domain in the USA. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan.

Keywords

Cu/Mg dual doping
High voltage
Oxygen vacancy
Phase transformation
Sodium ion batteries

Access to Document

10.1016/j.nanoen.2024.109925

Cite this

@article{ca8499d25f534e5b8e92ff2b5c8331cd,

title = "Heteroatom anchoring to enhance electrochemical reversibility for high-voltage P2-type oxide cathodes of sodium-ion batteries",

abstract = "P2-type cathode has received extensive attention due to its faster Na+ diffusion and a high theoretical capacity in sodium-ion batteries (SIBs). However, undesirable phase transformations have induced dramatic capacity decay of SIBs during the cycling process. In this study, heteroatom anchoring through Cu/Mg dual doping is introduced into P2-type Na0.67Ni0.33Mn0.67O2 cathode to enhance high-voltage electrochemical reversibility and modulate interfacial Na+ kinetics. The as-prepared Na0.67Ni0.23Mg0.05Cu0.05Mn0.67O2 exhibits an outstanding capacity retention (83.4 % after 2000 cycles at 10 C) and rate performance (73 mAh g−1 at 10 C, accounting for 58.7 % of that at 0.1 C) over the voltage range of 2.5–4.4 V. Intensive explorations further manifest that the modified mechanism of dual-ion doping strategy is attributed to the synergistic coupling effect of a substantial change in Na occupancy distribution and an increase in oxygen vacancy buffer. Thus, the optimized cathode expedites Na+ diffusion and reduces detrimental phase transformation, which favors high-rate performance and long-term cycling stability. This study develops a route to rationally design high-voltage cathode materials for SIBs.",

keywords = "Cu/Mg dual doping, High voltage, Oxygen vacancy, Phase transformation, Sodium ion batteries",

author = "Kai Liu and Susheng Tan and Sun, {Xiao Guang} and Qingqing Zhang and Cheng Li and Hailong Lyu and Lianqi Zhang and Thapaliya, {Bishnu P.} and Sheng Dai",

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

year = "2024",

month = sep,

doi = "10.1016/j.nanoen.2024.109925",

language = "English",

volume = "128",

journal = "Nano Energy",

issn = "2211-2855",

publisher = "Elsevier",

}

TY - JOUR

T1 - Heteroatom anchoring to enhance electrochemical reversibility for high-voltage P2-type oxide cathodes of sodium-ion batteries

AU - Liu, Kai

AU - Tan, Susheng

AU - Sun, Xiao Guang

AU - Zhang, Qingqing

AU - Li, Cheng

AU - Lyu, Hailong

AU - Zhang, Lianqi

AU - Thapaliya, Bishnu P.

AU - Dai, Sheng

PY - 2024/9

Y1 - 2024/9

N2 - P2-type cathode has received extensive attention due to its faster Na+ diffusion and a high theoretical capacity in sodium-ion batteries (SIBs). However, undesirable phase transformations have induced dramatic capacity decay of SIBs during the cycling process. In this study, heteroatom anchoring through Cu/Mg dual doping is introduced into P2-type Na0.67Ni0.33Mn0.67O2 cathode to enhance high-voltage electrochemical reversibility and modulate interfacial Na+ kinetics. The as-prepared Na0.67Ni0.23Mg0.05Cu0.05Mn0.67O2 exhibits an outstanding capacity retention (83.4 % after 2000 cycles at 10 C) and rate performance (73 mAh g−1 at 10 C, accounting for 58.7 % of that at 0.1 C) over the voltage range of 2.5–4.4 V. Intensive explorations further manifest that the modified mechanism of dual-ion doping strategy is attributed to the synergistic coupling effect of a substantial change in Na occupancy distribution and an increase in oxygen vacancy buffer. Thus, the optimized cathode expedites Na+ diffusion and reduces detrimental phase transformation, which favors high-rate performance and long-term cycling stability. This study develops a route to rationally design high-voltage cathode materials for SIBs.

AB - P2-type cathode has received extensive attention due to its faster Na+ diffusion and a high theoretical capacity in sodium-ion batteries (SIBs). However, undesirable phase transformations have induced dramatic capacity decay of SIBs during the cycling process. In this study, heteroatom anchoring through Cu/Mg dual doping is introduced into P2-type Na0.67Ni0.33Mn0.67O2 cathode to enhance high-voltage electrochemical reversibility and modulate interfacial Na+ kinetics. The as-prepared Na0.67Ni0.23Mg0.05Cu0.05Mn0.67O2 exhibits an outstanding capacity retention (83.4 % after 2000 cycles at 10 C) and rate performance (73 mAh g−1 at 10 C, accounting for 58.7 % of that at 0.1 C) over the voltage range of 2.5–4.4 V. Intensive explorations further manifest that the modified mechanism of dual-ion doping strategy is attributed to the synergistic coupling effect of a substantial change in Na occupancy distribution and an increase in oxygen vacancy buffer. Thus, the optimized cathode expedites Na+ diffusion and reduces detrimental phase transformation, which favors high-rate performance and long-term cycling stability. This study develops a route to rationally design high-voltage cathode materials for SIBs.

KW - Cu/Mg dual doping

KW - High voltage

KW - Oxygen vacancy

KW - Phase transformation

KW - Sodium ion batteries

UR - http://www.scopus.com/inward/record.url?scp=85197092765&partnerID=8YFLogxK

U2 - 10.1016/j.nanoen.2024.109925

DO - 10.1016/j.nanoen.2024.109925

M3 - Article

AN - SCOPUS:85197092765

SN - 2211-2855

VL - 128

JO - Nano Energy

JF - Nano Energy

M1 - 109925

ER -

Heteroatom anchoring to enhance electrochemical reversibility for high-voltage P2-type oxide cathodes of sodium-ion batteries

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this