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Title: Boosting Reversibility of Mn‐Based Tunnel‐Structured Cathode Materials for Sodium‐Ion Batteries by Magnesium Substitution

Abstract

Abstract Electrochemical irreversibility and sluggish mobility of Na + in the cathode materials result in poor cycle stability and rate capability for sodium‐ion batteries. Herein, a new strategy of introducing Mg ions into the hinging sites of Mn‐based tunnel‐structured cathode material is designed. Highly reversible electrochemical reaction and phase transition in this cathode are realized. The resulted Na 0.44 Mn 0.95 Mg 0.05 O 2 with Mg 2+ in the hinging Mn‐O 5 square pyramidal exhibits promising cycle stability and rate capability. At a current density of 2 C, 67% of the initial discharge capacity is retained after 800 cycles (70% at 20 C), much improved than the undoped Na 0.44 MnO 2 . The improvement is attribute to the enhanced Na + diffusion kinetics and the lowered desodiation energy after Mg doping. Highly reversible charge compensation and structure evolution are proved by synchrotron‐based X‐ray techniques. Differential charge density and atom population analysis of the average electron number of Mn indicate that Na 0.44 Mn 0.95 Mg 0.05 O 2 is more electron‐abundant in Mn 3d orbits near the Fermi level than that in Na 0.44 MnO 2 , leading to higher redox participation of Mn ions.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Department of Materials Science Fudan University Shanghai 200433 P. R. China
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1766591
Alternate Identifier(s):
OSTI ID: 1785839; OSTI ID: 1816202
Grant/Contract Number:  
SC0012704
Resource Type:
Published Article
Journal Name:
Advanced Science
Additional Journal Information:
Journal Name: Advanced Science Journal Volume: 8 Journal Issue: 9; Journal ID: ISSN 2198-3844
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; Mg substitution; cathode materials; phase transitions; sodium‐ion batteries

Citation Formats

Li, Xun‐Lu, Bao, Jian, Li, Yi‐Fan, Chen, Dong, Ma, Cui, Qiu, Qi‐Qi, Yue, Xin‐Yang, Wang, Qin‐Chao, and Zhou, Yong‐Ning. Boosting Reversibility of Mn‐Based Tunnel‐Structured Cathode Materials for Sodium‐Ion Batteries by Magnesium Substitution. Germany: N. p., 2021. Web. doi:10.1002/advs.202004448.
Li, Xun‐Lu, Bao, Jian, Li, Yi‐Fan, Chen, Dong, Ma, Cui, Qiu, Qi‐Qi, Yue, Xin‐Yang, Wang, Qin‐Chao, & Zhou, Yong‐Ning. Boosting Reversibility of Mn‐Based Tunnel‐Structured Cathode Materials for Sodium‐Ion Batteries by Magnesium Substitution. Germany. https://doi.org/10.1002/advs.202004448
Li, Xun‐Lu, Bao, Jian, Li, Yi‐Fan, Chen, Dong, Ma, Cui, Qiu, Qi‐Qi, Yue, Xin‐Yang, Wang, Qin‐Chao, and Zhou, Yong‐Ning. Thu . "Boosting Reversibility of Mn‐Based Tunnel‐Structured Cathode Materials for Sodium‐Ion Batteries by Magnesium Substitution". Germany. https://doi.org/10.1002/advs.202004448.
@article{osti_1766591,
title = {Boosting Reversibility of Mn‐Based Tunnel‐Structured Cathode Materials for Sodium‐Ion Batteries by Magnesium Substitution},
author = {Li, Xun‐Lu and Bao, Jian and Li, Yi‐Fan and Chen, Dong and Ma, Cui and Qiu, Qi‐Qi and Yue, Xin‐Yang and Wang, Qin‐Chao and Zhou, Yong‐Ning},
abstractNote = {Abstract Electrochemical irreversibility and sluggish mobility of Na + in the cathode materials result in poor cycle stability and rate capability for sodium‐ion batteries. Herein, a new strategy of introducing Mg ions into the hinging sites of Mn‐based tunnel‐structured cathode material is designed. Highly reversible electrochemical reaction and phase transition in this cathode are realized. The resulted Na 0.44 Mn 0.95 Mg 0.05 O 2 with Mg 2+ in the hinging Mn‐O 5 square pyramidal exhibits promising cycle stability and rate capability. At a current density of 2 C, 67% of the initial discharge capacity is retained after 800 cycles (70% at 20 C), much improved than the undoped Na 0.44 MnO 2 . The improvement is attribute to the enhanced Na + diffusion kinetics and the lowered desodiation energy after Mg doping. Highly reversible charge compensation and structure evolution are proved by synchrotron‐based X‐ray techniques. Differential charge density and atom population analysis of the average electron number of Mn indicate that Na 0.44 Mn 0.95 Mg 0.05 O 2 is more electron‐abundant in Mn 3d orbits near the Fermi level than that in Na 0.44 MnO 2 , leading to higher redox participation of Mn ions.},
doi = {10.1002/advs.202004448},
journal = {Advanced Science},
number = 9,
volume = 8,
place = {Germany},
year = {Thu Feb 18 00:00:00 EST 2021},
month = {Thu Feb 18 00:00:00 EST 2021}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/advs.202004448

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Works referenced in this record:

Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries
journal, September 2017


Suppressing the P2-O2 Phase Transition of Na 0.67 Mn 0.67 Ni 0.33 O 2 by Magnesium Substitution for Improved Sodium-Ion Batteries
journal, May 2016

  • Wang, Peng-Fei; You, Ya; Yin, Ya-Xia
  • Angewandte Chemie International Edition, Vol. 55, Issue 26
  • DOI: 10.1002/anie.201602202

Oxygen redox in hexagonal layered Na x TMO 3 (TM = 4d elements) for high capacity Na ion batteries
journal, January 2018

  • Assadi, M. H. N.; Okubo, Masashi; Yamada, Atsuo
  • Journal of Materials Chemistry A, Vol. 6, Issue 8
  • DOI: 10.1039/C7TA10826E

High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries
journal, August 2016

  • Zhou, Yong-Ning; Yue, Ji-Li; Hu, Enyuan
  • Advanced Energy Materials, Vol. 6, Issue 21
  • DOI: 10.1002/aenm.201600597

Utilizing Co 2+ /Co 3+ Redox Couple in P2-Layered Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 Cathode for Sodium-Ion Batteries
journal, July 2017


Polyanion-Type Electrode Materials for Sodium-Ion Batteries
journal, January 2017


Tuning P2-Structured Cathode Material by Na-Site Mg Substitution for Na-Ion Batteries
journal, December 2018

  • Wang, Qin-Chao; Meng, Jing-Ke; Yue, Xin-Yang
  • Journal of the American Chemical Society, Vol. 141, Issue 2
  • DOI: 10.1021/jacs.8b08638

Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes
journal, December 2019


Rod-shaped monoclinic CoMo2S4 with exceptionally reversible phase conversion for sodium storage
journal, October 2020


Study of the Insertion/Deinsertion Mechanism of Sodium into Na 0.44 MnO 2
journal, April 2007

  • Sauvage, F.; Laffont, L.; Tarascon, J. -M.
  • Inorganic Chemistry, Vol. 46, Issue 8
  • DOI: 10.1021/ic0700250

A Novel High Capacity Positive Electrode Material with Tunnel-Type Structure for Aqueous Sodium-Ion Batteries
journal, August 2015

  • Wang, Yuesheng; Mu, Linqin; Liu, Jue
  • Advanced Energy Materials, Vol. 5, Issue 22
  • DOI: 10.1002/aenm.201501005

High performance manganese-based layered oxide cathodes: overcoming the challenges of sodium ion batteries
journal, January 2017

  • Ortiz-Vitoriano, Nagore; Drewett, Nicholas E.; Gonzalo, Elena
  • Energy & Environmental Science, Vol. 10, Issue 5
  • DOI: 10.1039/C7EE00566K

Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2
journal, January 2018

  • Maitra, Urmimala; House, Robert A.; Somerville, James W.
  • Nature Chemistry, Vol. 10, Issue 3
  • DOI: 10.1038/nchem.2923

Comparative investigation on electrochemical properties of SmMgNi4, Sm2MgNi9 and SmNi5 compounds
journal, February 2017


Structurally stable Mg-doped P2-Na 2/3 Mn 1−y Mg y O 2 sodium-ion battery cathodes with high rate performance: insights from electrochemical, NMR and diffraction studies
journal, January 2016

  • Clément, Raphaële J.; Billaud, Juliette; Robert Armstrong, A.
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/C6EE01750A

Sur quelques nouvelles phases de formule NaxMnO2 (x ⩽ 1)
journal, February 1971

  • Parant, Jean-Paul; Olazcuaga, Roger; Devalette, Michel
  • Journal of Solid State Chemistry, Vol. 3, Issue 1
  • DOI: 10.1016/0022-4596(71)90001-6

Tunnel-structured Na0.66[Mn0.66Ti0.34]O2-F (x<0.1) cathode for high performance sodium-ion batteries
journal, November 2018


Single Crystalline Na 0.7 MnO 2 Nanoplates as Cathode Materials for Sodium-Ion Batteries with Enhanced Performance
journal, July 2013

  • Su, Dawei; Wang, Chengyin; Ahn, Hyo-jun
  • Chemistry - A European Journal, Vol. 19, Issue 33
  • DOI: 10.1002/chem.201301563

Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode
journal, January 2018


Recent Advances and Prospects of Cathode Materials for Sodium-Ion Batteries
journal, August 2015


P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries
journal, April 2012

  • Yabuuchi, Naoaki; Kajiyama, Masataka; Iwatate, Junichi
  • Nature Materials, Vol. 11, Issue 6
  • DOI: 10.1038/nmat3309

Jahn–Teller instability in spinel Li–Mn–O
journal, September 1999


Fe-Based Tunnel-Type Na 0.61 [Mn 0.27 Fe 0.34 Ti 0.39 ]O 2 Designed by a New Strategy as a Cathode Material for Sodium-Ion Batteries
journal, August 2015

  • Xu, Shuyin; Wang, Yuesheng; Ben, Liubin
  • Advanced Energy Materials, Vol. 5, Issue 22
  • DOI: 10.1002/aenm.201501156

New Insight into Ni-Rich Layered Structure for Next-Generation Li Rechargeable Batteries
journal, October 2017

  • Lee, Wontae; Muhammad, Shoaib; Kim, Taewhan
  • Advanced Energy Materials, Vol. 8, Issue 4
  • DOI: 10.1002/aenm.201701788

Ti-substituted tunnel-type Na0.44MnO2 oxide as a negative electrode for aqueous sodium-ion batteries
journal, March 2015

  • Wang, Yuesheng; Liu, Jue; Lee, Byungju
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7401

Structural and Thermodynamic Understandings in Mn‐Based Sodium Layered Oxides during Anionic Redox
journal, July 2020


Ab Initio Study of the Sodium Intercalation and Intermediate Phases in Na 0.44 MnO 2 for Sodium-Ion Battery
journal, March 2012

  • Kim, Heejin; Kim, Dong Jun; Seo, Dong-Hwa
  • Chemistry of Materials, Vol. 24, Issue 6
  • DOI: 10.1021/cm300065y

Research Development on Sodium-Ion Batteries
journal, October 2014

  • Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500192f