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13-07-2023 | Original Article

Tuning single-phase medium-entropy oxides derived from nanoporous NiCuCoMn alloy as a highly stable anode for Li-ion batteries

Authors: Zhen-Yang Yu, Qi Sun, Hao Li, Zhi-Jun Qiao, Wei-Jie Li, Shu-Lei Chou, Zhi-Jia Zhang, Yong Jiang

Published in: Rare Metals | Issue 9/2023

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Abstract

Incorporating four cations into a single-phase oxide is beneficial for maintaining structural stability during Li⁺ insertion/desertion because of the produced entropy-dominated phase stabilization effects. However, medium-entropy oxides exhibit inherently poor electron and ion conductivity. As such, in this work, a single-phase medium-entropy oxide of Ni_xCu_yCo_zMn_{1–x–y–z}O (named as NCCM@oxides(H₂)) is prepared by modified-NiCuCoMn alloy through the epitaxial-growing-based self-combustion and hydrogen reduction. During hydrogen reduction, some Cu ions are reduced to elemental Cu (defined as Cu⁰), which is distributed among the metal oxides, while generating extensive oxygen vacancies around Cu. The synergetic effect between nanoporous metal-core oxide-shell structure and enriched oxygen/Cu⁰ vacancies greatly enhances the electronic/ionic conductivity. In addition, the lattice of single-phase quaternary metal oxides has the configuration entropy stability, which enables the rock-salt structure to remain stable during repeated conversion reactions. Benefiting from the above-mentioned merits, the anode for Li-ion batteries with entropy-stabled NCCM@oxides(H₂) composite shows a high specific capacity of 699 mAh·g⁻¹ at 0.1 A·g⁻¹ and ultra-stable cycling stability, which maintains 618 and 489 mAh·g⁻¹ at 0.1 and 1.0 A·g⁻¹ after 200 cycles, respectively. This is the first use of this novel and simple strategy for modifying medium-entropy oxides, which paves the way for the development of high-entropy oxides as high-performance electrodes.

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previous article Preparation of double-shell Si@SnO2@C nanocomposite as anode for lithium-ion batteries by hydrothermal method

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[1]

Cavers H, Molaiyan P, Abdollahifar M, Lassi U, Kwade A. Perspectives on improving the safety and sustainability of high voltage lithium-ion batteries through the electrolyte and separator region. Adv Energy Mater. 2022;12(23):2200147. https://doi.org/10.1002/aenm.202200147.CrossRef

[2]

Zhang ZJ, Zhao J, Qiao ZJ, Wang JM, Sun SH, Fu WX, Zhang XY, Yu ZY, Dou YH, Kang JL, Yuan D, Feng YZ, Ma JM. Nonsolvent-induced phase separation-derived TiO₂ nanotube arrays/porous Ti electrode as high-energy-density anode for lithium-ion batteries. Rare Met. 2021;40(2):393. https://doi.org/10.1007/s12598-020-01571-6.CrossRef

[3]

Yan L, Zong LS, Zhang ZJ, Li JX, Wu HZ, Cui ZY, Kang JL. Oxygen vacancies activated porous MnO/graphene submicron needle arrays for high-capacity lithium-ion batteries. Carbon. 2022;190:402. https://doi.org/10.1016/j.carbon.2022.01.035.CrossRef

[4]

Eftekhari A. High-energy aqueous lithium batteries. Adv Energy Mater. 2018;8(24):1801156. https://doi.org/10.1002/aenm.201801156.CrossRef

[5]

Guo XB, Wang JC, Li GJ, Gao B, Bie CY, Zhang YP. Preparation and lithium-ion storage properties of vanadium nitride/nano silicon/carbon composite microspheres. Chin J Rare Metals. 2022;46(6):829. https://doi.org/10.13373/j.cnki.cjrm.XY2109002.CrossRef

[6]

Sun L, Liu YX, Shao R, Wu J, Jiang RY, Jin Z. Recent progress and future perspective on practical silicon anode-based lithium ion batteries. Energy Storage Materials. 2022;46:482. https://doi.org/10.1016/j.ensm.2022.01.042.CrossRef

[7]

Dong WJ, Xu JJ, Wang C, Lu Y, Liu XY, Wang X, Yuan XT, Wang Z, Lin TQ, Sui ML, Chen IW, Huang FQ. A robust and conductive black tin oxide nanostructure makes efficient lithium-ion batteries possible. Adv Mater. 2017;29(24):1700136. https://doi.org/10.1002/adma.201700136.CrossRef

[8]

Du WR, Du XF, Ma MB, Huang S, Sun XF, Xiong LL. Polymer electrode materials for lithium-ion batteries. Adv Funct Mater. 2022;32(21):2110871. https://doi.org/10.1002/adfm.202110871.CrossRef

[9]

Zhang ZJ, Li WJ, Chou SL, Han C, Liu HK, Dou SK. Effects of carbon on electrochemical performance of red phosphorus (P) and carbon composite as anode for sodium ion batteries. J Mater Sci Technol. 2021;68(30):140. https://doi.org/10.1016/j.jmst.2020.08.034.CrossRef

[10]

Liu SD, Kang L, Jun SC. Challenges and strategies toward cathode materials for rechargeable potassium-ion batteries. Adv Mater. 2021;33(47):2004689. https://doi.org/10.1002/adma.202004689.CrossRef

[11]

Zhao SQ, Guo ZQ, Yan K, Wan SW, He FR, Sun B, Wang GX. Towards high-energy-density lithium-ion batteries: strategies for developing high-capacity lithium-rich cathode materials. Energy Storage Mater. 2021;34:716. https://doi.org/10.1016/j.ensm.2020.11.008.CrossRef

[12]

Zhang Q, Zeng YP, Ling CS, Wang L, Wang ZY, Fan TE, Wang H, Xiao JR, Li XY, Qu BH. Boosting fast sodium ion storage by synergistic effect of heterointerface engineering and nitrogen doping porous carbon nanofibers. Small. 2022;18(13):2107514. https://doi.org/10.1002/smll.202107514.CrossRef

[13]

Liu JX, Wang JQ, Ni YX, Zhang K, Cheng FY, Chen J. Recent breakthroughs and perspectives of high-energy layered oxide cathode materials for lithium ion batteries. Mater Today. 2021;43:132. https://doi.org/10.1016/j.mattod.2020.10.028.CrossRef

[14]

Zhang SF, Zhang ZJ, Li HW, Yu ZY, Huang Q, Qiao ZJ, Zong LS, Yan L, Li JX, Kang JL. Ultrahigh areal capacity of self-combusted nanoporous NiCuMn/Cu flexible anode for Li-ion battery. Chem Eng J. 2020;383:123097. https://doi.org/10.1016/j.cej.2019.123097.CrossRef

[15]

Liu SD, Kang L, Zhang J, Jung E, Lee S, Jun SC. Structural engineering and surface modification of MOF-derived cobalt-based hybrid nanosheets for flexible solid-state supercapacitors. Energy Storage Mater. 2020;32:167. https://doi.org/10.1016/j.ensm.2020.07.017.CrossRef

[16]

Liu YF, Xiong LQ, Li PX, Fu HY, Hou ZC, Zhu L, Li WZ. Self-supported CuO nanoflake arrays on nanoporous Cu substrate as high-performance negative-electrodes for lithium-ion batteries. J Power Sour. 2019;428:20. https://doi.org/10.1016/j.jpowsour.2019.04.102.CrossRef

[17]

Yang Y, Yuan W, Zhang XQ, Wang C, Yuan YH, Huang Y, Ye YT, Qiu ZQ, Tang Y. A review on Fe_xO_y-based materials for advanced lithium-ion batteries. Renew Sustain Energy Rev. 2020;127:109884. https://doi.org/10.1016/j.rser.2020.109884.CrossRef

[18]

Hou CX, Wang B, Murugadoss V, Vupputuri S, Chao YF, Guo ZH, Wang CY, Du W. Recent advances in Co₃O₄ as anode materials for high-performance lithium-ion batteries. Eng Sci. 2020;11(5):19. https://doi.org/10.30919/es8d1128.CrossRef

[19]

Yao LH, Cao WQ, Zhao JG, Zheng Q, Wang YC, Jiang S, Pan QL, Song J, Zhu YQ, Cao MS. Regulating bifunctional flower-like NiFe₂O₄/graphene for green EMI shielding and lithium ion storage. J Mater Sci Technol. 2022;127:48. https://doi.org/10.1016/j.jmst.2022.04.010.CrossRef

[20]

Zong LS, Zhang ZJ, Yan L, Li P, Yu ZY, Qiao ZJ, Zhang SF, Kang JL. Multilayered interlaced SnO₂ nanosheets@porous copper tube textile as thin and flexible electrode for lithium-ion batteries. Electrochim Acta. 2021;385:138436. https://doi.org/10.1016/j.electacta.2021.138436.CrossRef

[21]

Langdon J, Manthiram A. A perspective on single-crystal layered oxide cathodes for lithium-ion batteries. Energy Storage Mater. 2021;37:143. https://doi.org/10.1016/j.ensm.2021.02.003.CrossRef

[22]

Cui ZH, Xie Q, Manthiram A. Zinc-doped high-nickel, low-cobalt layered oxide cathodes for high-energy-density lithium-ion batteries. ACS Appl Mater Interfaces. 2021;13(13):15324. https://doi.org/10.1021/acsami.1c01824.CrossRef

[23]

Chen Y, Chen XY, Zhang YL. A comprehensive review on metal-oxide nanocomposites for high-performance lithium-ion battery anodes. Energy Fuels. 2021;35(8):6420. https://doi.org/10.1021/acs.energyfuels.1c00315.CrossRef

[24]

Dyck O, Zhang LZ, Yoon M, Swett JL, Hensley D, Zhang C, Rack PD, Fowlkes JD, Lupini AR, Jesse S. Doping transition-metal atoms in graphene for atomic-scale tailoring of electronic, magnetic, and quantum topological properties. Carbon. 2021;173:205. https://doi.org/10.1016/j.carbon.2020.11.015.CrossRef

[25]

An YL, Fei HF, Zeng GF, Ci LJ, Xiong SL, Feng JK, Qian YT. Green, scalable, and controllable fabrication of nanoporous silicon from commercial alloy precursors for high-energy lithium-ion batteries. ACS Nano. 2018;12(5):4993. https://doi.org/10.1021/acsnano.8b02219.CrossRef

[26]

He W, Ye FJ, Lin J, Wang Q, Xie QS, Pei F, Zhang CY, Liu PF, Li XW, Wang LS, Qu BH, Peng DL. Boosting the electrochemical performance of Li-and Mn-rich cathodes by a three-in-one strategy. Nano-Micro Lett. 2021;13:205. https://doi.org/10.1007/s40820-021-00725-0.CrossRef

[27]

Wang D, Jiang SD, Duan CQ, Mao J, Dong Y, Dong KZ, Wang ZY, Luo SH, Liu YG, Qi XW. Spinel-structured high entropy oxide (FeCoNiCrMn)₃O₄ as anode towards superior lithium storage performance. J Alloys Compd. 2020;844:156158. https://doi.org/10.1016/j.jallcom.2020.156158.CrossRef

[28]

Vinnik DA, Trofimov EA, Zhivulin VE, Zaitseva OV, Gudkova SA, Starikov AY, Zherebtsov DA, Kirsanova AA, Habner M, Niewa R. High-entropy oxide phases with magnetoplumbite structure. Ceram Int. 2019;45(10):12942. https://doi.org/10.1016/j.ceramint.2019.03.221.CrossRef

[29]

Zheng YN, Yi YK, Fan MH, Liu HY, Li X, Zhang R, Li MT, Qiao ZA. A high-entropy metal oxide as chemical anchor of polysulfide for lithium-sulfur batteries. Energy Stor Mater. 2019;23:678. https://doi.org/10.1016/j.ensm.2019.02.030.CrossRef

[30]

Zhao J, Yang X, Huang Y, Du F, Zeng Y. Entropy stabilization effect and oxygen vacancies enabling spinel oxide highly reversible lithium-ion storage. ACS Appl Mater Interfaces. 2021;13(49):58674. https://doi.org/10.1021/acsami.1c18362.CrossRef

[31]

Xiao B, Wu G, Wang TD, Wei ZG, Sui YW, Shen BL, Qi JQ, Wei FX, Zheng JC. High-entropy oxides as advanced anode materials for long-life lithium-ion batteries. Nano Energy. 2022;95:106962. https://doi.org/10.1016/j.nanoen.2022.106962.CrossRef

[32]

Tian KH, Duan CQ, Ma Q, Li XL, Wang ZY, Sun HY, Luo SH, Wang D, Liu YG. High-entropy chemistry stabilizing spinel oxide (CoNiZnXMnLi)₃O₄ (X=Fe, Cr) for high-performance anode of Li-ion batteries. Rare Met. 2022;41(4):1265. https://doi.org/10.1007/s12598-021-01872-4.CrossRef

[33]

Sarkar A, Velasco L, Wang D, Wang QS, Talasila G, Biasi L, Kubel C, Brezesinski T, Bhattacharya SS, Hahn H, Breitung B. High entropy oxides for reversible energy storage. Nat Commun. 2018;9:783. https://doi.org/10.1038/s41467-018-05774-5.CrossRef

[34]

Qiu N, Chen H, Yang ZM, Sun S, Wang Y, Cui YH. A high entropy oxide (Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2O) with superior lithium storage performance. J Alloys Compd. 2019;777:767. https://doi.org/10.1016/j.jallcom.2018.11.049.CrossRef

[35]

Nguyen TX, Patra J, Chang JK, Ting JM. High entropy spinel oxide nanoparticles for superior lithiation–delithiation performance. J Mater Chem A. 2020;8(36):18963. https://doi.org/10.1039/D0TA04844E.CrossRef

[36]

Pan K, Zou F, Canova M, Zhu Y, Kim JH. Systematic electrochemical characterizations of Si and SiO anodes for high-capacity Li-ion batteries. J Power Sour. 2019;413:20. https://doi.org/10.1016/j.jpowsour.2018.12.010.CrossRef

[37]

Liu H, Xi C, Xin JH, Zhang GL, Zhang SF, Zhang ZJ, Huang Q, Li JX, Liu H, Kang J. Free-standing nanoporous NiMnFeMo alloy: an efficient non-precious metal electrocatalyst for water splitting. Chem Eng J. 2021;404:126530. https://doi.org/10.1016/j.cej.2020.126530.CrossRef

[38]

Shi YX, Pan XF, Li B, Zhao MM, Pang H. Co₃O₄ and its composites for high-performance Li-ion batteries. Chem Eng J. 2018;343:427. https://doi.org/10.1016/j.cej.2018.03.024.CrossRef

[39]

Mujtaba J, Sun HY, Zhao YY, Xiang GL, Xu SM, Zhu J. High-performance lithium storage based on the synergy of atomic-thickness nanosheets of TiO₂ (B) and ultrafine Co₃O₄ nanoparticles. J Power Sour. 2017;363:110. https://doi.org/10.1016/j.jpowsour.2017.07.076.CrossRef

[40]

Kang L, Zhang MY, Zhang J, Liu SD, Zhang N, Yao WJ, Ye Y, Luo C, Gong ZW, Cl W, Zhou XF, Wu X, Jun SC. Dual-defect surface engineering of bimetallic sulfide nanotubes towards flexible asymmetric solid-state supercapacitors. J Mater Chem A. 2020;8(47):25443. https://doi.org/10.1039/D0TA08979F.CrossRef

[41]

Yang J, Hu SY, Fang YR, Hoang S, Li L, Yang WW, Liang ZF, Wu J, Hu JP, Xiao W, Pan CQ, Luo Z, Ding J, Zhang LZ, Guo YB. Oxygen vacancy promoted O₂ activation over perovskite oxide for low-temperature CO oxidation. ACS Catal. 2019;9(11):9751. https://doi.org/10.1021/acscatal.9b02408.CrossRef

[42]

Zhang ZY, Li ML, Gao Y, Wei ZX, Zhang MN, Wang CZ, Zeng Y, Zou B, Chen G, Du F. Fast potassium storage in hierarchical Ca_0.5Ti₂(PO₄)₃@C microspheres enabling high-performance potassium-ion capacitors. Adv Funct Mater. 2018;28(36):1802684. https://doi.org/10.1002/adfm.201802684.CrossRef

[43]

Lokcu E, Toparli C, Anik M. Electrochemical performance of (MgCoNiZn)_1–xLi_xO high-entropy oxides in lithium-ion batteries. ACS Appl Mater Interfaces. 2020;12(21):23860. https://doi.org/10.1021/acsami.0c03562.CrossRef

[44]

Han ZY, Li XY, Li Q, Li HS, Xu J, Li N, Zhao GX, Wang X, Li HL, Li SD. Construction of the POMOF@polypyrrole composite with enhanced ion diffusion and capacitive contribution for high-performance lithium-ion batteries. ACS Appl Mater Interfaces. 2021;13(5):6265. https://doi.org/10.1021/acsami.0c20721.CrossRef

[45]

Zhang SF, Zhang ZZ, Zhang XY, Kang JL. Carbon coated Ni_xCo_yMn_1-_x_-_yO/Mn₃O₄ with robust deficiencies grown on nanoporous alloy for enhanced Li-ion storage. Electrochim Acta. 2020;332:135468. https://doi.org/10.1016/j.electacta.2019.135468.CrossRef

[46]

Liu CL, Luo SH, Huang HB, Wang ZY, Wang Q, Zhang YH, Liu YG, Zhai YC, Wang ZW. Potassium vanadate K_0.23V₂O₅ as anode materials for lithium-ion and potassium-ion batteries. J Power Sour. 2018;389:77. https://doi.org/10.1016/j.jpowsour.2018.04.014.CrossRef

[47]

Zhang M, He YX, Xu HJ, Ma C, Liang JF, Wang YY, Zhu J. Nb₂O₅ nanoparticles embedding in graphite hybrid as a high-rate and long-cycle anode for lithium-ion batteries. Rare Met. 2022;41(3):814. https://doi.org/10.1007/s12598-021-01863-5.CrossRef

[48]

Huang CY, Huang CW, Wu MC, Patra J, Nguyen TX, Chang MT, Clemens O, Ting JM, Li J, Chang JK. Atomic-scale investigation of Lithiation/Delithiation mechanism in high-entropy spinel oxide with superior electrochemical performance. Chem Eng J. 2021;420:129838. https://doi.org/10.1016/j.cej.2021.129838.CrossRef

[49]

Luo XF, Patra J, Chuang WT, Nguyen TX, Ting JM, Li J, Pao CW, Chang JK. Charge-discharge mechanism of high-entropy co-free spinel oxide toward Li⁺ storage examined using operando quick-scanning X-ray absorption spectroscopy. Adv Sci. 2022;9(21):2201219. https://doi.org/10.1002/advs.202201219.CrossRef

[50]

Sarkar A, Wang QS, Schiele A, Chellali MR, Bhattacharya SS, Wang D, Brezesinski T, Hahn H, Velasco L, Breitung B. High-entropy oxides: high-entropy oxides: fundamental aspects and electrochemical properties. Adv Mater. 2019;31(26):1970189. https://doi.org/10.1002/adma.201970189.CrossRef

[51]

Gao MJ, Le K, Wang GW, Wang Z, Wang FL, Liu W, Liu JR. Core-shell Cu_2-_xS@CoS₂ heterogeneous nanowire array with superior electrochemical performance for supercapacitor application. Electrochim Acta. 2019;323:134839. https://doi.org/10.1016/j.electacta.2019.134839.CrossRef

[52]

Zhou SH, Huang P, Xiong TZ, Yang F, Yang H, Huang YC, Li D, Deng JQ, Balogun MS. Sub-thick electrodes with enhanced transport kinetics via in situ epitaxial heterogeneous interfaces for high areal-capacity lithium ion batteries. Small. 2021;17(26):2100778. https://doi.org/10.1002/smll.202100778.CrossRef

[53]

Liu SD, Kang L, Zhang J, Jun SC, Yamauchi Y. Carbonaceous anode materials for non-aqueous sodium-and potassium-ion hybrid capacitors. ACS Energy Lett. 2021;6(11):4127. https://doi.org/10.1021/acsenergylett.1c01855.CrossRef

[54]

Yan YT, Lin JH, Liu T, Liu BS, Wang B, Qiao L, Tu JC, Cao J, Qi JL. Corrosion behavior of stainless steel-tungsten carbide joints brazed with AgCuX (X = In, Ti) alloys. Corros Sci. 2022;200:110231. https://doi.org/10.1016/j.corsci.2022.110231.CrossRef

[55]

Liu DH, Li WH, Zheng YP, Cui Z, Yan X, Liu DS, Wang JW, Zhang Y, Lü HY, Bai FY, Guo JZ, Wu XL. In situ encapsulating α-MnS into N, S-codoped nanotube-like carbon as advanced anode material: α→β phase transition promoted cycling stability and superior Li/Na-storage performance in half/full cells. Adv Mater. 2018;30(21):1706317. https://doi.org/10.1002/adma.201706317.CrossRef

[56]

Liu ZL, Wang XX, Wu ZY, Yang SJ, Yang SL, Chen SP, Wu XT, Chang XH, Yang PP, Zheng J, Liu XG. Ultrafine Sn₄P₃ nanocrystals from chloride reduction on mechanically activated Na surface for sodium/lithium ion batteries. Nano Res. 2020;13(11):3157. https://doi.org/10.1007/s12274-020-2987-2.CrossRef

[57]

Ling JK, Karuppiah C, Reddy MV, Pal B, Yang CC, Jose R. Unraveling synergistic mixing of SnO₂-TiO₂ composite as anode for Li-ion battery and their electrochemical properties. J Mater Res. 2021;36(20):4120. https://doi.org/10.1557/s43578-021-00313-3.CrossRef

Title: Tuning single-phase medium-entropy oxides derived from nanoporous NiCuCoMn alloy as a highly stable anode for Li-ion batteries
Authors: Zhen-Yang Yu
Qi Sun
Hao Li
Zhi-Jun Qiao
Wei-Jie Li
Shu-Lei Chou
Zhi-Jia Zhang
Yong Jiang
Publication date: 13-07-2023
Publisher: Nonferrous Metals Society of China
Published in: Rare Metals / Issue 9/2023
Print ISSN: 1001-0521
Electronic ISSN: 1867-7185
DOI: https://doi.org/10.1007/s12598-023-02293-1

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