Both cationic and anionic redox chemistry in a P2-type sodium layered oxide

Wang, Peng-Fei; Xiao, Yao; Piao, Nan; Wang, Qin-Chao; Ji, Xiao; Jin, Ting; Guo, Yu-Jie; Liu, Sufu; Deng, Tao; Cui, Chunyu; Chen, Long; Guo, Yu-Guo; Yang, Xiao-Qing; Wang, Chunsheng

doi:10.1016/j.nanoen.2020.104474

Title: Both cationic and anionic redox chemistry in a P2-type sodium layered oxide

Full Record
Other Related Research

Abstract

We report the demand for high energy Na-ion batteries has promoted intensive research on high energy oxygen redox chemistry in layered transition metal oxide cathodes. However, most layered cathodes with oxygen redox might suffer from irreversible electrochemical reaction, fast capacity decay and underlying O₂ release. Herein, we report that copper element with a strong electronegativaty can stablize Na-deficient P2-Na_2/3Mn_0.72Cu_0.22Mg_0.06O₂ phase to achieve both cationic and anionic redox chemistry. Hard and soft X-ray absorption spectra demonstrate that all Mn³⁺/Mn⁴⁺, Cu²⁺/Cu³⁺ and O^2-/(O₂)^n- participate in the redox reaction upon Na⁺ ions extraction and insertion. Density functional theory (DFT) calculations confirm that the strong covalency between copper and oxygen ensures the cationic and anionic redox activity in P2-Na_2/3Mn_0.72Cu_0.22Mg_0.06O₂ phase. The P2-Na_2/3Mn_0.72Cu_0.22Mg_0.06O₂ cathode could deliver stable cycling life with 87.9% capacity retention at 1C during 100 cycles, as well as high rate performance (70.3 mA h g^-1 cycled at 10C). In conclusion, our findings not only provide a promising guidelines to enhance the electrochemical performance of layered oxides based on anionic redox activity, but also explore the potential science behind oxygen redox process.

Authors:

Wang, Peng-Fei ^[1]; Xiao, Yao ^[2];

^[1]; Wang, Qin-Chao ^[3]; Ji, Xiao ^[1]; Jin, Ting ^[1]; Guo, Yu-Jie ^[2]; Liu, Sufu ^[1]; Deng, Tao ^[1]; Cui, Chunyu ^[1]; Chen, Long ^[1]; Guo, Yu-Guo ^[2];

^[3]; Wang, Chunsheng ^[1]

Univ. of Maryland, College Park, MD (United States)
Chinese Academy of Sciences (CAS), Beijing (China). CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Sciences (BNLMS), Inst. of Chemistry
Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:: 2020-01-10

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC)

OSTI Identifier:: 1593270

Alternate Identifier(s):: OSTI ID: 1592180

Report Number(s):: BNL-213544-2020-JAAM
Journal ID: ISSN 2211-2855

Grant/Contract Number:: SC0012704; EE0008202

Resource Type:: Accepted Manuscript

Journal Name:: Nano Energy

Additional Journal Information:: Journal Volume: 69; Journal Issue: C; Journal ID: ISSN 2211-2855

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Sodium-ion batteries; Cathode; Anionic redox; P2-type; Electrochemistry

Citation Formats


                    Wang, Peng-Fei, Xiao, Yao, Piao, Nan, Wang, Qin-Chao, Ji, Xiao, Jin, Ting, Guo, Yu-Jie, Liu, Sufu, Deng, Tao, Cui, Chunyu, Chen, Long, Guo, Yu-Guo, Yang, Xiao-Qing, and Wang, Chunsheng. Both cationic and anionic redox chemistry in a P2-type sodium layered oxide.  United States: N. p., 2020. 
Web.  doi:10.1016/j.nanoen.2020.104474.

Copy to clipboard


                    Wang, Peng-Fei, Xiao, Yao, Piao, Nan, Wang, Qin-Chao, Ji, Xiao, Jin, Ting, Guo, Yu-Jie, Liu, Sufu, Deng, Tao, Cui, Chunyu, Chen, Long, Guo, Yu-Guo, Yang, Xiao-Qing, & Wang, Chunsheng. Both cationic and anionic redox chemistry in a P2-type sodium layered oxide.  United States.  https://doi.org/10.1016/j.nanoen.2020.104474

Copy to clipboard


                    Wang, Peng-Fei, Xiao, Yao, Piao, Nan, Wang, Qin-Chao, Ji, Xiao, Jin, Ting, Guo, Yu-Jie, Liu, Sufu, Deng, Tao, Cui, Chunyu, Chen, Long, Guo, Yu-Guo, Yang, Xiao-Qing, and Wang, Chunsheng. Fri .  
"Both cationic and anionic redox chemistry in a P2-type sodium layered oxide".  United States.  https://doi.org/10.1016/j.nanoen.2020.104474.  https://www.osti.gov/servlets/purl/1593270.

Copy to clipboard


                    
@article{osti_1593270,

  title        = {Both cationic and anionic redox chemistry in a P2-type sodium layered oxide},

  author       = {Wang, Peng-Fei and Xiao, Yao and Piao, Nan and Wang, Qin-Chao and Ji, Xiao and Jin, Ting and Guo, Yu-Jie and Liu, Sufu and Deng, Tao and Cui, Chunyu and Chen, Long and Guo, Yu-Guo and Yang, Xiao-Qing and Wang, Chunsheng},

  abstractNote = {We report the demand for high energy Na-ion batteries has promoted intensive research on high energy oxygen redox chemistry in layered transition metal oxide cathodes. However, most layered cathodes with oxygen redox might suffer from irreversible electrochemical reaction, fast capacity decay and underlying O2 release. Herein, we report that copper element with a strong electronegativaty can stablize Na-deficient P2-Na2/3Mn0.72Cu0.22Mg0.06O2 phase to achieve both cationic and anionic redox chemistry. Hard and soft X-ray absorption spectra demonstrate that all Mn3+/Mn4+, Cu2+/Cu3+ and O2-/(O2)n- participate in the redox reaction upon Na+ ions extraction and insertion. Density functional theory (DFT) calculations confirm that the strong covalency between copper and oxygen ensures the cationic and anionic redox activity in P2-Na2/3Mn0.72Cu0.22Mg0.06O2 phase. The P2-Na2/3Mn0.72Cu0.22Mg0.06O2 cathode could deliver stable cycling life with 87.9% capacity retention at 1C during 100 cycles, as well as high rate performance (70.3 mA h g-1 cycled at 10C). In conclusion, our findings not only provide a promising guidelines to enhance the electrochemical performance of layered oxides based on anionic redox activity, but also explore the potential science behind oxygen redox process.},

  doi          = {10.1016/j.nanoen.2020.104474},

  journal      = {Nano Energy},

  number       = C,

  volume       = 69,

  place        = {United States},

  year         = {2020},

  month        = {1}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1016/j.nanoen.2020.104474

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 54 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Achieving High Stability and Performance in P2-Type Mn-Based Layered Oxides with Tetravalent Cations for Sodium-Ion Batteries

Journal Article Vanaphuti, Panawan ; Yao, Zeyi ; Liu, Yangtao ; ... - Small

We report P2-type sodium-manganese-based layered cathodes, owing to their high capacity from both cationic and anionic redox, are a potential candidate for Na-ion batteries to replace Li-ion technology in certain applications. Still, the structure instability originates from irreversible oxygen redox at high voltage remains a challenge. Here, a high sustainability cobalt-free P2- Na_0.72Mn_0.75Li_0.24X_0.01O₂ (X= Ti/Si) cathode is developed. The outstanding capacity retention and voltage retention after 150 cycles are obtained in Na half-cells. Our finding shows Ti locates on the surface while Si diffuses to the bulk of the particles. Thus, Ti can act as protective layer that alleviate sidemore »« less
https://doi.org/10.1002/smll.202201086

Full Text Available
Entropy and crystal-facet modulation of P2-type layered cathodes for long-lasting sodium-based batteries

Journal Article Fu, Fang ; Liu, Xiang ; Fu, Xiaoguang ; ... - Nature Communications

Abstract P2-type sodium manganese-rich layered oxides are promising cathode candidates for sodium-based batteries because of their appealing cost-effective and capacity features. However, the structural distortion and cationic rearrangement induced by irreversible phase transition and anionic redox reaction at high cell voltage (i.e., >4.0 V) cause sluggish Na-ion kinetics and severe capacity decay. To circumvent these issues, here, we report a strategy to develop P2-type layered cathodes via configurational entropy and ion-diffusion structural tuning. In situ synchrotron X-ray diffraction combined with electrochemical kinetic tests and microstructural characterizations reveal that the entropy-tuned Na _0.62 Mn _0.67 Ni _0.23 Cu _0.05 Mg _0.07 Timore »« less
https://doi.org/10.1038/s41467-022-30113-0
Oxygen redox chemistry in P2-Na_0.6Li_0.11Fe_0.27Mn_0.62O₂ cathode for high-energy Na-ion batteries

Journal Article Cao, Ming-Hui ; Li, Ren-Yan ; Lin, Shi-Ya ; ... - Journal of Materials Chemistry. A

Owing to the abundance of raw material reserves and low cost, Na-ion batteries (NIBs) have successfully gained widespread attention from academic and industrial communities in the past few decades. However, the insufficient cathode energy density is still one of the critical bottlenecks restricting the development of NIBs. Following a strategy of introducing Li+ into the transition-metal (TM) layer to enhance the oxygen redox reaction, a novel layered cathode material P2-Na_0.6Li_0.11Fe_0.27Mn_0.62O₂ (NLFMO) was designed and successfully synthesized. This NLFMO cathode not only delivers a large initial reversible capacity of 207.3 mA h g^-1, but also shows a good cycling performance (104.2more »« less
https://doi.org/10.1039/d1ta08471b

Full Text Available
Exploring the Charge Compensation Mechanism of P2-Type Na_0.6Mg_0.3Mn_0.7O₂ Cathode Materials for Advanced Sodium-Ion Batteries

Journal Article Cheng, Chen ; Ding, Manling ; Yan, Tianran ; ... - Energies

P2-type sodium layered transition metal oxides have been intensively investigated as promising cathode materials for sodium-ion batteries (SIBs) by virtue of their high specific capacity and high operating voltage. However, they suffer from problems of voltage decay, capacity fading, and structural deterioration, which hinder their practical application. Therefore, a mechanistic understanding of the cationic/anionic redox activity and capacity fading is indispensable for the further improvement of electrochemical performance. Here, a prototype cathode material of P2-type Na_0.6Mg_0.3Mn_0.7O₂ is comprehensively investigated, which presents both cationic and anionic redox behaviors during the cycling process. By a combination of soft X-ray absorption spectroscopy andmore »« less
https://doi.org/10.3390/en13215729

Full Text Available
Stabilizing Transition Metal Vacancy Induced Oxygen Redox by Co²⁺/Co³⁺ Redox and Sodium-Site Doping for Layered Cathode Materials

Journal Article Li, Xun‐Lu ; Bao, Jian ; Shadike, Zulipiya ; ... - Angewandte Chemie (International Edition)

Anionic redox is an effective way to boost the energy density of layer-structured metal-oxide cathodes for rechargeable batteries. However, inherent rigid nature of the TMO₆ (TM: transition metals) subunits in the layered materials makes it hardly tolerate the inner strains induced by lattice glide, especially at high voltage. Herein, P2-Na_0.8Mg0.13[Mn_0.6Co_0.2Mg_{0.07more » $$\square$$0.13}]O₂ ($$\square$$: TM vacancy) is designed that contains vacancies in TM sites, and Mg ions in both TM and sodium sites. Vacancies make the rigid TMO₆ octahedron become more asymmetric and flexible. Low valence Co²⁺/Co³⁺ redox couple stabilizes the electronic structure, especially at the charged state. Mg²⁺ in sodium sites can tune the interlayer spacing against O-O electrostatic repulsion. Time-resolved in situ X-ray diffraction confirms that irreversible structure evolution is effectively suppressed during deep desodiation benefiting from the specific configuration. X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations demonstrate that, deriving from the intrinsic vacancies, multiple local configurations of “_$$\square$$-O-_$$\square$$”, “Na-O-_$$\square$$”, “Mg-O-_$$\square$$” are superior in facilitating the oxygen redox for charge compensation than previously reported “Na-O-Mg”. The resulted material delivers promising cycle stability and rate capability, with a long voltage plateau at 4.2 V contributed by oxygen, and can be well maintained even at high rates. The strategy will inspire new ideas in designing highly stable cathode materials with reversible anionic redox for sodium-ion batteries.« less
https://doi.org/10.1002/anie.202108933

Full Text Available

Similar Records