Volume 1 Issue 3
September  2022
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Junbo Wang, Sren L Dreyer, Kai Wang, Ziming Ding, Thomas Diemant, Guruprakash Karkera, Yanjiao Ma, Abhishek Sarkar, Bei Zhou, Mikhail V Gorbunov, Ahmad Omar, Daria Mikhailova, Volker Presser, Maximilian Fichtner, Horst Hahn, Torsten Brezesinski, Ben Breitung, Qingsong Wang. P2-type layered high-entropy oxides as sodium-ion cathode materials[J]. Materials Futures, 2022, 1(3): 035104. doi: 10.1088/2752-5724/ac8ab9
Citation: Junbo Wang, Sren L Dreyer, Kai Wang, Ziming Ding, Thomas Diemant, Guruprakash Karkera, Yanjiao Ma, Abhishek Sarkar, Bei Zhou, Mikhail V Gorbunov, Ahmad Omar, Daria Mikhailova, Volker Presser, Maximilian Fichtner, Horst Hahn, Torsten Brezesinski, Ben Breitung, Qingsong Wang. P2-type layered high-entropy oxides as sodium-ion cathode materials[J]. Materials Futures, 2022, 1(3): 035104. doi: 10.1088/2752-5724/ac8ab9
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P2-type layered high-entropy oxides as sodium-ion cathode materials

© 2022 The Author(s). Published by IOP Publishing Ltd on behalf of the Songshan Lake Materials Laboratory
Materials Futures, Volume 1, Number 3
  • Received Date: 2022-07-14
  • Accepted Date: 2022-08-18
  • Revised Date: 2022-08-14
  • Publish Date: 2022-09-12
  • P2-type layered oxides with the general Na-deficient composition NaxTMO2 (x < 1, TM: transition metal) are a promising class of cathode materials for sodium-ion batteries. The open Na+ transport pathways present in the structure lead to low diffusion barriers and enable high charge/discharge rates. However, a phase transition from P2 to O2 structure occurring above 4.2 V and metal dissolution at low potentials upon discharge results in rapid capacity degradation. In this work, we demonstrate the positive effect of configurational entropy on the stability of the crystal structure during battery operation. Three different compositions of layered P2-type oxides were synthesized by solid-state chemistry, Na0.67(Mn0.55Ni0.21Co0.24)O2, Na0.67(Mn0.45Ni0.18Co0.24Ti0.1Mg0.03)O2 and Na0.67(Mn0.45Ni0.18Co0.18Ti0.1Mg0.03Al0.04Fe0.02)O2 with low, medium and high configurational entropy, respectively. The high-entropy cathode material shows lower structural transformation and Mn dissolution upon cycling in a wide voltage range from 1.5 to 4.6 V. Advanced operando techniques and post-mortem analysis were used to probe the underlying reaction mechanism thoroughly. Overall, the high-entropy strategy is a promising route for improving the electrochemical performance of P2 layered oxide cathodes for advanced sodium-ion battery applications.
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  • Conflict of interest

    There are no conflicts to declare.

    Author contributions

    J W, B B and Q W conceived the idea and designed the experiments. B B, H H and Q W supervised the project. S L D and T B conducted the DEMS measurements and analysed the data. K W and Z D performed the TEM measurements and analysed the data. T D, G K and M F collected the XPS spectra and analyzed the data. A S and Y M provided valuable suggestions during the whole project. B Z, M V G, A O and D M helped with the XAS measurements and analyzed the data. V P helped with the ICP-OES measurements. J W, B B and Q W prepared the initial manuscript. All authors discussed the results and contributed to discussion and reviewing the manuscript.

  • [1]
    Hwang J-Y, Myung S-T, Sun Y-K 2017 Sodium-ion batteries: present and future Chem. Soc. Rev. 46 3529-614 doi: 10.1039/c6cs00776g
    [2]
    Delmas C 2018 Sodium and sodium-ion batteries: 50 years of research Adv. Energy Mater. 8 1703137 doi: 10.1002/aenm.201703137
    [3]
    Tarascon J-M 2020 Na-ion versus Li-ion batteries: complementarity rather than competitiveness Joule 4 1616-20 doi: 10.1016/j.joule.2020.06.003
    [4]
    Palomares V, Casas-Cabanas M, Castillo-Martnez E, Han M H, Rojo T 2013 Update on Na-based battery materials. A growing research path Energy Environ. Sci. 6 2312-37 doi: 10.1039/c3ee41031e
    [5]
    Delmas C, Carlier D, Guignard M 2021 The layered oxides in lithium and sodium-ion batteries: a solid-state chemistry approach Adv. Energy Mater. 11 2001201 doi: 10.1002/aenm.202001201
    [6]
    Han M H, Gonzalo E, Singh G, Rojo T 2015 A comprehensive review of sodium layered oxides: powerful cathodes for Na-ion batteries Energy Environ. Sci. 8 81-102 doi: 10.1039/C4EE03192J
    [7]
    Clment R J, Bruce P G, Grey C P 2015 Reviewmanganese-based P2-type transition metal oxides as sodium-ion battery cathode materials J. Electrochem. Soc. 162 A2589-604 doi: 10.1149/2.0201514jes
    [8]
    Delmas C, Fouassier C, Hagenmuller P 1980 Structural classification and properties of the layered oxides Physica B+C 99 81-85 doi: 10.1016/0378-4363(80)90214-4
    [9]
    Hwang J-Y, Yoon C S, Belharouak I, Sun Y-K 2016 A comprehensive study of the role of transition metals in O3-type layered Na[NixCoyMnz]O2x = 1/3, 0.5, 0.6, and 0.8) cathodes for sodium-ion batteries J. Mater. Chem. A 4 17952-9 doi: 10.1039/C6TA07392A
    [10]
    Wang Y, Xiao R, Hu Y-S, Avdeev M, Chen L 2015 P2-Na0.6[Cr0.6Ti0.4]O2 cation-disordered electrode for high-rate symmetric rechargeable sodium-ion batteries Nat. Commun. 6 6954 doi: 10.1038/ncomms7954
    [11]
    T-Y Y, Hwang J-Y, Aurbach D, Sun Y-K 2017 Microsphere Na0.65[Ni0.17Co0.11Mn0.72]O2 cathode material for high-performance sodium-ion batteries ACS Appl. Mater. Interfaces 9 44534-41 doi: 10.1021/acsami.7b15267
    [12]
    Katcho N A, Carrasco J, Saurel D, Gonzalo E, Han M, Aguesse F, Rojo T 2017 Origins of bistability and Na ion mobility difference in P2- and O3-Na2/3Fe2/3Mn1/3O2 cathode polymorphs Adv. Energy Mater. 7 1601477 doi: 10.1002/aenm.201601477
    [13]
    Zhao C, et al 2020 Revealing high Na-content P2-type layered oxides as advanced sodium-ion cathodes J. Am. Chem. Soc. 142 5742-50 doi: 10.1021/jacs.9b13572
    [14]
    Lyu Y, Liu Y, Yu Z-E, Su N, Liu Y, Li W, Li Q, Guo B, Liu B 2019 Recent advances in high energy-density cathode materials for sodium-ion batteries Sustain. Mater. Technol. 21 e00098 doi: 10.1016/j.susmat.2019.e00098
    [15]
    Lee D H, Xu J, Meng Y S 2013 An advanced cathode for Na-ion batteries with high rate and excellent structural stability Phys. Chem. Chem. Phys. 15 3304-12 doi: 10.1039/c2cp44467d
    [16]
    Zhang J, Wang W, Wang W, Wang S, Li B 2019 Comprehensive review of P2-type Na2/3Ni1/3Mn2/3O2, a potential cathode for practical application of Na-Ion batteries ACS Appl. Mater. Interfaces 11 22051-66 doi: 10.1021/acsami.9b03937
    [17]
    Liu Q, Hu Z, Chen M, Zou C, Jin H, Wang S, Gu Q, Chou S 2019 P2-type Na2/3Ni1/3Mn2/3O2 as a cathode material with high-rate and long-life for sodium ion storage J. Mater. Chem. A 7 9215-21 doi: 10.1039/C8TA11927A
    [18]
    Liu T, et al 2019 Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery Nat. Commun. 10 4721 doi: 10.1038/s41467-019-12626-3
    [19]
    Kumakura S, Tahara Y, Kubota K, Chihara K, Komaba S 2016 Sodium and manganese stoichiometry of P2-type Na2/3MnO2 Angew. Chem., Int. Ed. Engl. 55 12760-3 doi: 10.1002/anie.201606415
    [20]
    Zhan C, Wu T, Lu J, Amine K 2018 Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodesa critical review Energy Environ. Sci. 11 243-57 doi: 10.1039/C7EE03122J
    [21]
    Zuo W, et al 2020 Highly-stable P2-Na0.67MnO2 electrode enabled by lattice tailoring and surface engineering Energy Storage Mater. 26 503-12 doi: 10.1016/j.ensm.2019.11.024
    [22]
    Cantor B, Chang I T H, Knight P, Vincent A J B 2004 Microstructural development in equiatomic multicomponent alloys Mater. Sci. Eng. A 375-377 213-8 doi: 10.1016/j.msea.2003.10.257
    [23]
    Yeh J-W, Chen S-K, Lin S-J, Gan J-Y, Chin T-S, Shun T-T, Tsau C-H, Chang S-Y 2004 Nanostructured high-entropy alloys with multiple principal elements: novel alloy design concepts and outcomes Adv. Eng. Mater. 6 299-303 doi: 10.1002/adem.200300567
    [24]
    Rost C M, Sachet E, Borman T, Moballegh A, Dickey E C, Hou D, Jones J L, Curtarolo S, Maria J-P 2015 Entropy-stabilized oxides Nat. Commun. 6 8485 doi: 10.1038/ncomms9485
    [25]
    Sarkar A, et al 2018 High entropy oxides for reversible energy storage Nat. Commun. 9 3400 doi: 10.1038/s41467-018-05774-5
    [26]
    Ma Y, Ma Y, Wang Q, Schweidler S, Botros M, Fu T, Hahn H, Brezesinski T, Breitung B 2021 High-entropy energy materials: challenges and new opportunities Energy Environ. Sci. 14 2883-905 doi: 10.1039/D1EE00505G
    [27]
    Ma Y, et al 2021 High-entropy metal-organic frameworks for highly reversible sodium storage Adv. Mater. 33 2101342 doi: 10.1002/adma.202101342
    [28]
    Wang Q, Velasco L, Breitung B, Presser V 2021 Highentropy energy materials in the age of big data: a critical guide to nextgeneration synthesis and applications Adv. Energy Mater. 11 2102355 doi: 10.1002/aenm.202102355
    [29]
    Zhao C, Ding F, Lu Y, Chen L, Hu Y-S 2020 High-entropy layered oxide cathodes for sodium-ion batteries Angew. Chem., Int. Ed. Engl. 59 264-9 doi: 10.1002/anie.201912171
    [30]
    Yang L, Chen C, Xiong S, Zheng C, Liu P, Ma Y, Xu W, Tang Y, Ong S P, Chen H 2021 Multiprincipal component P2-Na0.6(Ti0.2Mn0.2Co0.2Ni0.2Ru0.2O2 as a high-rate cathode for sodium-ion batteries JACS Au 1 98-107 doi: 10.1021/jacsau.0c00002
    [31]
    Wang Q, et al 2019 Multi-anionic and -cationic compounds: new high entropy materials for advanced Li-ion batteries Energy Environ. Sci. 12 2433-42 doi: 10.1039/C9EE00368A
    [32]
    Wang J, et al 2020 Lithium containing layered high entropy oxide structures Sci. Rep. 10 18430 doi: 10.1038/s41598-020-75134-1
    [33]
    Berkes B B, Jozwiuk A, Sommer H, Brezesinski T, Janek J 2015 Simultaneous acquisition of differential electrochemical mass spectrometry and infrared spectroscopy data for in situ characterization of gas evolution reactions in lithium-ion batteries Electrochem. Commun. 60 64-69 doi: 10.1016/j.elecom.2015.08.002
    [34]
    Berkes B B, Jozwiuk A, Vraar M, Sommer H, Brezesinski T, Janek J 2015 Online continuous flow differential electrochemical mass spectrometry with a realistic battery setup for high-precision, long-term cycling tests Anal. Chem. 87 5878-83 doi: 10.1021/acs.analchem.5b01237
    [35]
    Herklotz M, et al 2016 A novel high-throughput setup for in situ powder diffraction on coin cell batteries J. Appl. Crystallogr. 49 340-5 doi: 10.1107/S1600576715022165
    [36]
    Ravel B, Newville M 2005 ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT J. Synchrotron Radiat. 12 537-41 doi: 10.1107/S0909049505012719
    [37]
    Li J, et al 2019 P2Type Na0.67Mn0.8Cu0.1Mg0.1O2 as a new cathode material for sodium-ion batteries: insights of the synergetic effects of multi-metal substitution and electrolyte optimization J. Power Sources 416 184-92 doi: 10.1016/j.jpowsour.2019.01.086
    [38]
    Hasa I, Passerini S, Hassoun J 2017 Toward high energy density cathode materials for sodium-ion batteries: investigating the beneficial effect of aluminum doping on the P2-type structure J. Mater. Chem. A 5 4467-77 doi: 10.1039/C6TA08667E
    [39]
    Jung R, Metzger M, Maglia F, Stinner C, Gasteiger H A 2017 Chemical versus electrochemical electrolyte oxidation on NMC111, NMC622, NMC811, LNMO, and conductive carbon J. Phys. Chem. Lett. 8 4820-5 doi: 10.1021/acs.jpclett.7b01927
    [40]
    Risthaus T, et al 2018 A high-capacity P2 Na2/3Ni1/3Mn2/3O2 cathode material for sodium ion batteries with oxygen activity J. Power Sources 395 16-24 doi: 10.1016/j.jpowsour.2018.05.026
    [41]
    Mortemard de Boisse B, Carlier D, Guignard M, Bourgeois L, Delmas C 2014 P2-NaxMn1/2Fe1/2O2 phase used as positive electrode in Na batteries: structural changes induced by the electrochemical (De)intercalation process Inorg. Chem. 53 11197-205 doi: 10.1021/ic5017802
    [42]
    Wang J, et al 2020 Insights into P2-type layered positive electrodes for sodium batteries: from long- to short-range order ACS Appl. Mater. Interfaces 12 5017-24 doi: 10.1021/acsami.9b18109
    [43]
    Liu Z, Xu X, Ji S, Zeng L, Zhang D, Liu J 2020 Recent progress of P2-Type layered transition-metal oxide cathodes for sodium-ion batteries Chemistry A 26 7747-66 doi: 10.1002/chem.201905131
    [44]
    Z-Y L, Gao R, Sun L, Hu Z, Liu X 2015 Designing an advanced P2-Na0.67Mn0.65Ni0.2Co0.15O2 layered cathode material for Na-ion batteries J. Mater. Chem. A 3 16272-8 doi: 10.1039/C5TA02450A
    [45]
    Chen T, Liu W, Gao H, Zhuo Y, Hu H, Chen A, Zhang J, Yan J, Liu K 2018 A P2-type Na0.44Mn0.6Ni0.3Cu0.1O2 cathode material with high energy density for sodium-ion batteries J. Mater. Chem. A 6 12582-8 doi: 10.1039/C8TA04791J
    [46]
    Wang L, Sun Y-G, Hu -L-L, Piao J-Y, Guo J, Manthiram A, Ma J, Cao A-M 2017 Copper-substituted Na0.67Ni0.3-xCuxMn0.7O2 cathode materials for sodium-ion batteries with suppressed P2-O2 phase transition J. Mater. Chem. A 5 8752-61 doi: 10.1039/C7TA00880E
    [47]
    Yuan D, He W, Pei F, Wu F, Wu Y, Qian J, Cao Y, Ai X, Yang H 2013 Synthesis and electrochemical behaviors of layered Na0.67[Mn0.65Co0.2Ni0.15]O2 microflakes as a stable cathode material for sodium-ion batteries J. Mater. Chem. A 1 3895-9 doi: 10.1039/c3ta01430d
    [48]
    Yuan D, Hu X, Qian J, Pei F, Wu F, Mao R, Ai X, Yang H, Cao Y 2014 P2-type Na0.67Mn0.65Fe0.2Ni0.15O2 cathode material with high-capacity for sodium-ion battery Electrochim. Acta 116 300-5 doi: 10.1016/j.electacta.2013.10.211
    [49]
    Buchholz D, Moretti A, Kloepsch R, Nowak S, Siozios V, Winter M, Passerini S 2013 Toward Na-ion batteriessynthesis and characterization of a novel high capacity Na ion intercalation material Chem. Mater. 25 142-8 doi: 10.1021/cm3029615
    [50]
    Yoshida J, Guerin E, Arnault M, Constantin C, Mortemard de Boisse B, Carlier D, Guignard M, Delmas C 2014 New P2Na0.70Mn0.60Ni0.30Co0.10O2 layered oxide as electrode material for Na-ion batteries J. Electrochem. Soc. 161 A1987-91 doi: 10.1149/2.0121414jes
    [51]
    Luo C, Langrock A, Fan X, Liang Y, Wang C 2017 P2-type transition metal oxides for high performance Na-ion battery cathodes J. Mater. Chem. A 5 18214-20 doi: 10.1039/C7TA04515H
    [52]
    Lu Z, Dahn J R 2001 In Situ x-ray diffraction study of P2-Na2/3[Ni1/3Mn2/3]O2 J. Electrochem. Soc. 148 A1225 doi: 10.1149/1.1407247
    [53]
    Xu S, et al 2018 Suppressing the voltage decay of low-cost P2-type iron-based cathode materials for sodium-ion batteries J. Mater. Chem. A 6 20795-803 doi: 10.1039/C8TA07933A
    [54]
    Talaie E, Duffort V, Smith H L, Fultz B, Nazar L F 2015 Structure of the high voltage phase of layered P2-Na2/3-z[Mn1/2Fe1/2]O2 and the positive effect of Ni substitution on its stability Energy Environ. Sci. 8 2512-23 doi: 10.1039/C5EE01365H
    [55]
    Wang P-F, You Y, Yin Y-X, Wang Y-S, Wan L-J, Gu L, Guo Y-G 2016 Suppressing the P2-O2 phase transition of Na0.67Mn0.67Ni0.33O2 by magnesium substitution for improved sodium-ion batteries Angew. Chem., Int. Ed. Engl. 55 7445-9 doi: 10.1002/anie.201602202
    [56]
    Hwang J-Y, Kim J, Yu T-Y, Sun Y-K 2019 A new P2-type layered oxide cathode with extremely high energy density for sodium-ion batteries Adv. Energy Mater. 9 1803346 doi: 10.1002/aenm.201803346
    [57]
    Somerville J W, et al 2019 Nature of the Z-phase in layered Na-ion battery cathodes Energy Environ. Sci. 12 2223-32 doi: 10.1039/C8EE02991A
    [58]
    Zhang L, Tsolakidou C, Mariyappan S, Tarascon J-M, Trabesinger S 2021 Unraveling gas evolution in sodium batteries by online electrochemical mass spectrometry Energy Storage Mater. 42 12-21 doi: 10.1016/j.ensm.2021.07.005
    [59]
    Hatsukade T, Schiele A, Hartmann P, Brezesinski T, Janek J 2018 Origin of carbon dioxide evolved during cycling of nickel-rich layered NCM cathodes ACS Appl. Mater. Interfaces 10 38892-9 doi: 10.1021/acsami.8b13158
    [60]
    Papp J K, Li N, Kaufman L A, Naylor A J, Younesi R, Tong W, McCloskey B D 2021 A comparison of high voltage outgassing of LiCoO2, LiNiO2, and Li2MnO3 layered Li-ion cathode materials Electrochim. Acta 368 137505 doi: 10.1016/j.electacta.2020.137505
    [61]
    Strauss F, Payandeh S, Kondrakov A, Brezesinski T 2022 On the role of surface carbonate species in determining the cycling performance of all-solid-state batteries Mater. Futures 1 023501 doi: 10.1088/2752-5724/ac5b7d
    [62]
    Dreyer S L, Kondrakov A, Janek J, Brezesinski T 2022 In situ analysis of gas evolution in liquid- and solid-electrolyte-based batteries with current and next-generation cathode materials J. Mater. Res. doi: 10.1557/s43578-022-00586-2
    [63]
    Jung R, Metzger M, Maglia F, Stinner C, Gasteiger H A 2017 Oxygen release and its effect on the cycling stability of LiNixMnyCozO2 (NMC) cathode materials for Li-ion batteries J. Electrochem. Soc. 164 A1361-77 doi: 10.1149/2.0021707jes
    [64]
    Wandt J, Freiberg A T S, Ogrodnik A, Gasteiger H A 2018 Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries Mater. Today 21 825-33 doi: 10.1016/j.mattod.2018.03.037
    [65]
    Metzger M, Strehle B, Solchenbach S, Gasteiger H A 2016 Origin of H2 evolution in LIBs: H2O reduction vs. Electrolyte oxidation J. Electrochem. Soc. 163 A798-809 doi: 10.1149/2.1151605jes
    [66]
    Luo K, et al 2016 Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen Nat. Chem. 8 684-91 doi: 10.1038/nchem.2471
    [67]
    House R A, et al 2019 What triggers oxygen loss in oxygen redox cathode materials? Chem. Mater. 31 3293-300 doi: 10.1021/acs.chemmater.9b00227
    [68]
    Xu H, Guo S, Zhou H 2019 Review on anionic redox in sodium-ion batteries J. Mater. Chem. A 7 23662-78 doi: 10.1039/C9TA06389G
    [69]
    Park J-H, I-h K, Lee J, Park S, Kim D, Yu S-H, Sung Y-E 2021 Anionic redox reactions in cathodes for sodium-ion batteries ChemElectroChem 8 625-43 doi: 10.1002/celc.202001383
    [70]
    Solchenbach S, Hong G, Freiberg A T S, Jung R, Gasteiger H A 2018 Electrolyte and SEI decomposition reactions of transition metal ions investigated by on-line electrochemical mass spectrometry J. Electrochem. Soc. 165 A3304-12 doi: 10.1149/2.0511814jes
    [71]
    Schwenke K U, Solchenbach S, Demeaux J, Lucht B L, Gasteiger H A 2019 The impact of CO2 evolved from VC and FEC during formation of graphite anodes in lithium-ion batteries J. Electrochem. Soc. 166 A2035-47 doi: 10.1149/2.0821910jes
    [72]
    Wang B, Zhang F, Zhou X, Wang P, Wang J, Ding H, Dong H, Liang W, Zhang N, Li S 2021 Which of the nickel-rich NCM and NCA is structurally superior as a cathode material for lithium-ion batteries? J. Mater. Chem. A 9 13540-51 doi: 10.1039/D1TA01128F
    [73]
    Sathiya M, et al 2015 Origin of voltage decay in high-capacity layered oxide electrodes Nat. Mater. 14 230-8 doi: 10.1038/nmat4137
    [74]
    Li W, Liu X, Celio H, Smith P, Dolocan A, Chi M, Manthiram A 2018 Mn versus Al in layered oxide cathodes in lithium-ion batteries: a comprehensive evaluation on long-term cyclability Adv. Energy Mater. 8 1703154 doi: 10.1002/aenm.201703154
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