Vacancy-Enabled O3 Phase Stabilization for Manganese-rich Layered Sodium Cathodes

Xiao, Biwei; Wang, Yichao; Tan, Sha; Song, Miao; Li, Xiang; Zhang, Yuxin; Lin, Feng; Han, Kee Sung; Omenya, Fredrick O.; Amine, Khalil; Yang, Xiao-Qing; Reed, David M.; Hu, Yanyan; Xu, Gui-Liang; Hu, Enyuan; Li, Xin; Li, Xiaolin

doi:10.1002/ange.202016334

Title: Vacancy-Enabled O3 Phase Stabilization for Manganese-rich Layered Sodium Cathodes

Journal Article · Tue Apr 06 00:00:00 EDT 2021 · Angewandte Chemie International Edition

DOI:https://doi.org/10.1002/ange.202016334· OSTI ID:1781822

Xiao, Biwei ^[1]; Wang, Yichao ^[2]; Tan, Sha ^[3]; Song, Miao ^[1]; Li, Xiang ^[4]; Zhang, Yuxin ^[5]; Lin, Feng ^[5]; Han, Kee Sung ^[1]; Omenya, Fredrick O. ^[1]; Amine, Khalil ^[6]; Yang, Xiao-Qing ^[3]; Reed, David M. ^[1]; Hu, Yanyan ^[4]; Xu, Gui-Liang ^[7]; Hu, Enyuan ^[3]; Li, Xin ^[2]; Li, Xiaolin ^[1]

BATTELLE (PACIFIC NW LAB)
Harvard University
Brookhaven National Laboratory
Florida State University
Virginia Tech
Argonne National Laboratory
ARGONNE NATL LAB

Manganese-rich layered oxide materials hold great potential as low-cost and high-capacity cathodes for Na-ion batteries. However, they usually form P2 phase and suffer from fast capacity fade. In this work, an O3 phase sodium cathode has been developed out of a Li and Mn-rich layered material by leveraging the creation of transition metal (TM) and oxygen vacancies and the electrochemical exchange of Na and Li. The Mn-rich layered cathode material remains primarily O3 phase during sodiation/desodiation and can have a full sodiation capacity of ~220 mAh/g. It delivers ~160 mAh/g specific capacity between 2-3.8V with >86% retention over 250 cycles. Systematic characterizations and computational studies revealed that the TM and oxygen vacancies pre-formed in the sodiated material enables a “reversible” migration of TMs from the TM layer to the tetrahedral sites in the Na layer upon de-sodiation and sodiation. The migration creates metastable states, leading to increased kinetic barrier that prohibits a complete O3-P3 phase transition, hence stabilizing the structure and battery performance. This work provides a critical insight on the role of vacancies in TM migration and stabilization of phase transition, and sheds light on the future development of high performance and stable cathode materials for Na-ion batteries and beyond.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1781822

Report Number(s):: PNNL-SA-158592

Journal Information:: Angewandte Chemie International Edition, Vol. 60, Issue 15

Country of Publication:: United States

Language:: English

References (61)

From Charge Storage Mechanism to Performance: A Roadmap toward High Specific Energy Sodium-Ion Batteries through Carbon Anode Optimization Saurel, Damien; Orayech, Brahim; Xiao, Biwei Advanced Energy Materials, Vol. 8, Issue 17 https://doi.org/10.1002/aenm.201703268	journal	March 2018
Progress in High-Voltage Cathode Materials for Rechargeable Sodium-Ion Batteries You, Ya; Manthiram, Arumugam Advanced Energy Materials, Vol. 8, Issue 2 https://doi.org/10.1002/aenm.201701785	journal	September 2017
Challenges in Developing Electrodes, Electrolytes, and Diagnostics Tools to Understand and Advance Sodium-Ion Batteries Xu, Gui-Liang; Amine, Rachid; Abouimrane, Ali Advanced Energy Materials, Vol. 8, Issue 14 https://doi.org/10.1002/aenm.201702403	journal	February 2018
Hard Carbon as Sodium‐Ion Battery Anodes: Progress and Challenges Xiao, Biwei; Rojo, Teófilo; Li, Xiaolin ChemSusChem, Vol. 12, Issue 1 https://doi.org/10.1002/cssc.201801879	journal	November 2018
Sodium‐Ion Batteries Paving the Way for Grid Energy Storage Hirsh, Hayley S.; Li, Yixuan; Tan, Darren H. S. Advanced Energy Materials, Vol. 10, Issue 32 https://doi.org/10.1002/aenm.202001274	journal	July 2020
Recent developments on layered 3d-transtition metal oxide cathode materials for sodium-ion batteries Palaniyandy, Nithyadharseni Current Opinion in Electrochemistry, Vol. 21 https://doi.org/10.1016/j.coelec.2020.03.023	journal	June 2020
The Layered Oxides in Lithium and Sodium‐Ion Batteries: A Solid‐State Chemistry Approach Delmas, Claude; Carlier, Dany; Guignard, Marie Advanced Energy Materials, Vol. 11, Issue 2 https://doi.org/10.1002/aenm.202001201	journal	July 2020
Recent advances and prospects of layered transition metal oxide cathodes for sodium-ion batteries Gao, Rui-Min; Zheng, Zi-Jian; Wang, Peng-Fei Energy Storage Materials, Vol. 30 https://doi.org/10.1016/j.ensm.2020.04.040	journal	September 2020
P2-NaxVO2 system as electrodes for batteries and electron-correlated materials Guignard, Marie; Didier, Christophe; Darriet, Jacques Nature Materials, Vol. 12, Issue 1 https://doi.org/10.1038/nmat3478	journal	November 2012
P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries Yabuuchi, Naoaki; Kajiyama, Masataka; Iwatate, Junichi Nature Materials, Vol. 11, Issue 6 https://doi.org/10.1038/nmat3309	journal	April 2012
Controlling Surface Phase Transition and Chemical Reactivity of O3-Layered Metal Oxide Cathodes for High-Performance Na-Ion Batteries Song, Junhua; Wang, Kuan; Zheng, Jianming ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00700	journal	April 2020
Electrochemistry and Solid‐State Chemistry of NaMeO ₂ (Me = 3d Transition Metals) Kubota, Kei; Kumakura, Shinichi; Yoda, Yusuke Advanced Energy Materials, Vol. 8, Issue 17 https://doi.org/10.1002/aenm.201703415	journal	June 2018
Research Development on Sodium-Ion Batteries Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500192f	journal	October 2014
Adverse effects of interlayer-gliding in layered transition-metal oxides on electrochemical sodium-ion storage Sun, Yang; Guo, Shaohua; Zhou, Haoshen Energy & Environmental Science, Vol. 12, Issue 3 https://doi.org/10.1039/C8EE01006D	journal	January 2019
Understanding the Capacity Fading Mechanisms of O3‐Type Na[Ni _0.5 Mn _0.5 ]O ₂ Cathode for Sodium‐Ion Batteries Yu, Tae‐Yeon; Ryu, Hoon‐Hee; Han, Geumjae Advanced Energy Materials, Vol. 10, Issue 37 https://doi.org/10.1002/aenm.202001609	journal	July 2020
Layered Oxide Cathodes for Sodium-Ion Batteries: Phase Transition, Air Stability, and Performance Wang, Peng-Fei; You, Ya; Yin, Ya-Xia Advanced Energy Materials, Vol. 8, Issue 8 https://doi.org/10.1002/aenm.201701912	journal	November 2017
Layered Oxide Cathodes Promoted by Structure Modulation Technology for Sodium‐Ion Batteries Xiao, Yao; Abbasi, Nasir Mahmood; Zhu, Yan‐Fang Advanced Functional Materials, Vol. 30, Issue 30 https://doi.org/10.1002/adfm.202001334	journal	April 2020
A Long Cycle‐Life High‐Voltage Spinel Lithium‐Ion Battery Electrode Achieved by Site‐Selective Doping Liang, Gemeng; Wu, Zhibin; Didier, Christophe Angewandte Chemie International Edition, Vol. 59, Issue 26 https://doi.org/10.1002/anie.202001454	journal	April 2020
A Long Cycle‐Life High‐Voltage Spinel Lithium‐Ion Battery Electrode Achieved by Site‐Selective Doping Liang, Gemeng; Wu, Zhibin; Didier, Christophe Angewandte Chemie, Vol. 132, Issue 26 https://doi.org/10.1002/ange.202001454	journal	April 2020
Reining in dissolved transition-metal ions Asl, Hooman Yaghoobnejad; Manthiram, Arumugam Science, Vol. 369, Issue 6500 https://doi.org/10.1126/science.abc5454	journal	July 2020
Ti-Substituted NaNi _0.5 Mn _0.5- _x Ti _x O ₂ Cathodes with Reversible O3−P3 Phase Transition for High-Performance Sodium-Ion Batteries Wang, Peng-Fei; Yao, Hu-Rong; Liu, Xin-Yu Advanced Materials, Vol. 29, Issue 19 https://doi.org/10.1002/adma.201700210	journal	March 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 Wang, Peng-Fei; You, Ya; Yin, Ya-Xia Angewandte Chemie International Edition, Vol. 55, Issue 26 https://doi.org/10.1002/anie.201602202	journal	May 2016
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 Wang, Peng-Fei; You, Ya; Yin, Ya-Xia Angewandte Chemie, Vol. 128, Issue 26 https://doi.org/10.1002/ange.201602202	journal	May 2016
A Layered P2- and O3-Type Composite as a High-Energy Cathode for Rechargeable Sodium-Ion Batteries Guo, Shaohua; Liu, Pan; Yu, Haijun Angewandte Chemie International Edition, Vol. 54, Issue 20 https://doi.org/10.1002/anie.201411788	journal	April 2015
A Layered P2- and O3-Type Composite as a High-Energy Cathode for Rechargeable Sodium-Ion Batteries Guo, Shaohua; Liu, Pan; Yu, Haijun Angewandte Chemie, Vol. 127, Issue 20 https://doi.org/10.1002/ange.201411788	journal	April 2015
Roles of Coherent Interfaces on Electrochemical Performance of Sodium Layered Oxide Cathodes Huang, Qun; Liu, Jiatu; Xu, Sheng Chemistry of Materials, Vol. 30, Issue 14 https://doi.org/10.1021/acs.chemmater.8b01556	journal	June 2018
Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials Clément, Raphaële J.; Bruce, Peter G.; Grey, Clare P. Journal of The Electrochemical Society, Vol. 162, Issue 14 https://doi.org/10.1149/2.0201514jes	journal	January 2015
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release Hu, Enyuan; Yu, Xiqian; Lin, Ruoqian Nature Energy, Vol. 3, Issue 8 https://doi.org/10.1038/s41560-018-0207-z	journal	July 2018
Explore the Effects of Microstructural Defects on Voltage Fade of Li- and Mn-Rich Cathodes Hu, Enyuan; Lyu, Yingchun; Xin, Huolin L. Nano Letters, Vol. 16, Issue 10 https://doi.org/10.1021/acs.nanolett.6b01609	journal	September 2016
Electrochemical Activity of Li in the Transition-Metal Sites of O3 Li[Li[sub (1−2x)/3]Mn[sub (2−x)/3]Ni[sub x]]O[sub 2] Grey, Clare P.; Yoon, Won-Sub; Reed, John Electrochemical and Solid-State Letters, Vol. 7, Issue 9 https://doi.org/10.1149/1.1783113	journal	January 2004
Size‐Mediated Recurring Spinel Sub‐nanodomains in Li‐ and Mn‐Rich Layered Cathode Materials Xiao, Biwei; Liu, Hanshuo; Chen, Ning Angewandte Chemie International Edition, Vol. 59, Issue 34 https://doi.org/10.1002/anie.202005337	journal	June 2020
Size‐Mediated Recurring Spinel Sub‐nanodomains in Li‐ and Mn‐Rich Layered Cathode Materials Xiao, Biwei; Liu, Hanshuo; Chen, Ning Angewandte Chemie, Vol. 132, Issue 34 https://doi.org/10.1002/ange.202005337	journal	June 2020
Highly stable Li 1.2 Mn 0.54 Co 0.13 Ni 0.13 O 2 enabled by novel atomic layer deposited AlPO 4 coating Xiao, Biwei; Wang, Biqiong; Liu, Jian Nano Energy, Vol. 34 https://doi.org/10.1016/j.nanoen.2017.02.015	journal	April 2017
The Role of Metal Site Vacancies in Promoting Li–Mn–Ni–O Layered Solid Solutions McCalla, E.; Rowe, A. W.; Camardese, J. Chemistry of Materials, Vol. 25, Issue 13 https://doi.org/10.1021/cm401461m	journal	June 2013
High Capacity Li-Rich Positive Electrode Materials with Reduced First-Cycle Irreversible Capacity Loss Shunmugasundaram, Ramesh; Senthil Arumugam, Rajalakshmi; Dahn, J. R. Chemistry of Materials, Vol. 27, Issue 3 https://doi.org/10.1021/cm504583y	journal	January 2015
Highly Reversible Oxygen-Redox Chemistry at 4.1 V in Na _4/7− _x [□ _1/7 Mn _6/7 ]O ₂ (□: Mn Vacancy) Mortemard de Boisse, Benoit; Nishimura, Shin-ichi; Watanabe, Eriko Advanced Energy Materials, Vol. 8, Issue 20 https://doi.org/10.1002/aenm.201800409	journal	April 2018
β-NaMnO ₂ : A High-Performance Cathode for Sodium-Ion Batteries Billaud, Juliette; Clément, Raphaële J.; Armstrong, A. Robert Journal of the American Chemical Society, Vol. 136, Issue 49 https://doi.org/10.1021/ja509704t	journal	November 2014
Electrochemical Properties of Monoclinic NaMnO2 Ma, Xiaohua; Chen, Hailong; Ceder, Gerbrand Journal of The Electrochemical Society, Vol. 158, Issue 12 https://doi.org/10.1149/2.035112jes	journal	January 2011
Ab-initio structure determination of LiSbWO6 by X-ray powder diffraction Le Bail, A.; Duroy, H.; Fourquet, J. L. Materials Research Bulletin, Vol. 23, Issue 3 https://doi.org/10.1016/0025-5408(88)90019-0	journal	March 1988
In Operando XRD and TXM Study on the Metastable Structure Change of NaNi _1/3 Fe _1/3 Mn _1/3 O ₂ under Electrochemical Sodium-Ion Intercalation Xie, Yingying; Wang, Hong; Xu, Guiliang Advanced Energy Materials, Vol. 6, Issue 24 https://doi.org/10.1002/aenm.201601306	journal	September 2016
Insights into the structural effects of layered cathode materials for high voltage sodium-ion batteries Xu, Gui-Liang; Amine, Rachid; Xu, Yue-Feng Energy & Environmental Science, Vol. 10, Issue 7 https://doi.org/10.1039/C7EE00827A	journal	January 2017
Super Charge Separation and High Voltage Phase in Na _x MnO ₂ Chen, Xi; Wang, Yichao; Wiaderek, Kamila Advanced Functional Materials, Vol. 28, Issue 50 https://doi.org/10.1002/adfm.201805105	journal	October 2018
Jahn–Teller Assisted Na Diffusion for High Performance Na Ion Batteries Li, Xin; Wang, Yan; Wu, Di Chemistry of Materials, Vol. 28, Issue 18 https://doi.org/10.1021/acs.chemmater.6b02440	journal	September 2016
On the dynamics of transition metal migration and its impact on the performance of layered oxides for sodium-ion batteries: NaFeO ₂ as a case study Silván, Begoña; Gonzalo, Elena; Djuandhi, Lisa Journal of Materials Chemistry A, Vol. 6, Issue 31 https://doi.org/10.1039/C8TA02473A	journal	January 2018
Uncovering the roles of oxygen vacancies in cation migration in lithium excess layered oxides Qian, Danna; Xu, Bo; Chi, Miaofang Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/C4CP01799D	journal	January 2014
Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials Chen, Xi; Hwang, Sooyeon; Chisnell, Robin Advanced Functional Materials, Vol. 28, Issue 39 https://doi.org/10.1002/adfm.201803896	journal	July 2018
Origins of Bistability and Na Ion Mobility Difference in P2- and O3-Na _2/3 Fe _2/3 Mn _1/3 O ₂ Cathode Polymorphs Katcho, Nebil A.; Carrasco, Javier; Saurel, Damien Advanced Energy Materials, Vol. 7, Issue 1 https://doi.org/10.1002/aenm.201601477	journal	September 2016
Electrochemical and Structural Study of the Layered, “Li-Excess” Lithium-Ion Battery Electrode Material Li[Li _1/9 Ni _1/3 Mn _5/9 ]O ₂ Jiang, Meng; Key, Baris; Meng, Ying S. Chemistry of Materials, Vol. 21, Issue 13 https://doi.org/10.1021/cm900279u	journal	July 2009
Atomic Structure of Li ₂ MnO ₃ after Partial Delithiation and Re-Lithiation Wang, Rui; He, Xiaoqing; He, Lunhua Advanced Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1002/aenm.201200842	journal	June 2013
Li₂MnO₃-stabilized LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S. Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125 https://doi.org/10.1039/b702425h	journal	January 2007
Nanoscale Manipulation of Spinel Lithium Nickel Manganese Oxide Surface by Multisite Ti Occupation as High-Performance Cathode Xiao, Biwei; Liu, Hanshuo; Liu, Jian Advanced Materials, Vol. 29, Issue 47 https://doi.org/10.1002/adma.201703764	journal	October 2017
Understanding the Origins of Higher Capacities at Faster Rates in Lithium-Excess Li _x Ni _{2–4 x /3} Sb _{x /3} O ₂ Twu, Nancy; Metzger, Michael; Balasubramanian, Mahalingam Chemistry of Materials, Vol. 29, Issue 6 https://doi.org/10.1021/acs.chemmater.6b04691	journal	November 2016
NaTiO ₂ : a layered anode material for sodium-ion batteries Wu, Di; Li, Xin; Xu, Bo Energy & Environmental Science, Vol. 8, Issue 1 https://doi.org/10.1039/C4EE03045A	journal	January 2015
Layered-to-Rock-Salt Transformation in Desodiated Na _x CrO ₂ ( x 0.4) Bo, Shou-Hang; Li, Xin; Toumar, Alexandra J. Chemistry of Materials, Vol. 28, Issue 5 https://doi.org/10.1021/acs.chemmater.5b04626	journal	February 2016
Direct Observation of Alternating Octahedral and Prismatic Sodium Layers in O3‐Type Transition Metal Oxides Kim, Jae Chul; Kwon, Deok‐Hwang; Yang, Julia H. Advanced Energy Materials, Vol. 10, Issue 31 https://doi.org/10.1002/aenm.202001151	journal	June 2020
Understanding intercalation compounds for sodium-ion batteries and beyond Kaufman, Jonas L.; Vinckevičiūtė, Julija; Krishna Kolli, Sanjeev Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2152 https://doi.org/10.1098/rsta.2019.0020	journal	July 2019
A novel P3-type Na _2/3 Mg _1/3 Mn _2/3 O ₂ as high capacity sodium-ion cathode using reversible oxygen redox Song, Bohang; Hu, Enyuan; Liu, Jue Journal of Materials Chemistry A, Vol. 7, Issue 4 https://doi.org/10.1039/C8TA09422E	journal	January 2019
New Insights into the Performance Degradation of Fe-Based Layered Oxides in Sodium-Ion Batteries: Instability of Fe ³⁺ /Fe ⁴⁺ Redox in α-NaFeO ₂ Lee, Eungje; Brown, Dennis E.; Alp, Esen E. Chemistry of Materials, Vol. 27, Issue 19 https://doi.org/10.1021/acs.chemmater.5b02918	journal	September 2015
Identifying the Critical Role of Li Substitution in P2–Na _x [Li _y Ni _z Mn _{1– y – z} ]O ₂ (0 < x , y , z < 1) Intercalation Cathode Materials for High-Energy Na-Ion Batteries Xu, Jing; Lee, Dae Hoe; Clément, Raphaële J. Chemistry of Materials, Vol. 26, Issue 2 https://doi.org/10.1021/cm403855t	journal	December 2013
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries Kang, Kisuk; Shirley Meng, Ying; Breger, Julien Science, Vol. 311, Issue 5763, p. 977-980 https://doi.org/10.1126/science.1122152	journal	February 2006
Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes Eum, Donggun; Kim, Byunghoon; Kim, Sung Joo Nature Materials, Vol. 19, Issue 4 https://doi.org/10.1038/s41563-019-0572-4	journal	January 2020

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