journal article·2022-06-11Open access

High-Entropy Spinel Oxides Produced via Sol-Gel and Electrospinning and Their Evaluation as Anodes in Li-Ion Batteries

Beatrix Petrovičovà, Wenlei Xu, Maria Grazia Musolino, Fabiola Pantò, Salvatore Patanè, Nicola Pinna, Saveria Santangelo, Claudia Triolo

Applied Sciences· Volume 12· Issue 12

Abstract

In the last few years, high-entropy oxides (HEOs), a new class of single-phase solid solution materials, have attracted growing interest in both academic research and industry for their great potential in a broad range of applications. This work investigates the possibility of producing pure single-phase HEOs with spinel structure (HESOs) under milder conditions (shorter heat treatments at lower temperatures) than standard solid-state techniques, thus reducing the environmental impact. For this purpose, a large set of HESOs was prepared via sol-gel and electrospinning (by using two different polymers). Ten different equimolar combinations of five metals were considered, and the influence of the synthesis method and conditions on the microstructure, morphology and crystalline phase purity of the produced HESOs was investigated by a combination of characterization techniques. On the other hand, the presence of specific metals, such as copper, lead to the formation of minority secondary phase(s). Finally, two representative pure single-phase HESOs were preliminarily evaluated as active anode materials in lithium-ion batteries and possible strategies to enhance their rate capability and cyclability were proposed and successfully implemented. The approaches introduced here can be extensively applied for the optimization of HEO properties targeting different applications.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: High Entropy Alloys Studies · High-Temperature Coating Behaviors · Advanced materials and composites

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Dipartimento di Ingegneria Civile, dell’Energia, dell’Ambiente e dei Materiali (DICEAM), Università “Mediterranea”, Loc., Feo di Vito, 89122 Reggio Calabria, Italy

Institut für Chemie and IRIS Adlershof, Humboldt-Universität zu Berlin, Brook-Taylor Straße 2, 12489 Berlin, Germany

Istituto di Tecnologie Avanzate per l’Energia (ITAE) del Consiglio Nazionale delle Ricerche (CNR), 98126 Messina, Italy

Dipartimento di Scienze Matematiche e Informatiche, Scienze Fisiche e Scienze della Terra (MIFT), Università di Messina, 98166 Messina, Italy

National Reference Center for Electrochemical Energy Storage (GISEL), Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), 50121 Firenze, Italy

Funding

Italian Ministry of University and Research (MUR)

References (78)

Show source-provided references
1. A critical review of high entropy alloys and related concepts10.1016/j.actamat.2016.08.081 ↗
2. Breakthrough applications of high-entropy materials10.1557/jmr.2018.283 ↗
3. The emergent field of high entropy oxides: Design, prospects, challenges, and opportunities for tailoring material properties10.1063/5.0003149 ↗
4. High-entropy ceramics10.1038/s41578-019-0170-8 ↗
5. Nanostructured multi-element (TiZrNbHfTa)N and (TiZrNbHfTa)C hard coatings10.1016/j.surfcoat.2011.09.033 ↗
6. Mechanochemical-assisted synthesis of high-entropy metal nitride via a soft urea strategy10.1002/adma.201707512 ↗
7. Processing and properties of high-entropy ultra-high temperature carbides10.1038/s41598-018-26827-1 ↗
8. High-entropy carbide: A novel class of multicomponent ceramics10.1016/j.ceramint.2018.08.100 ↗
9. High-entropy metal diborides: A new class of high-entropy materials and a new type of ultrahigh temperature ceramics10.1038/srep37946 ↗
10. Data-driven design of ecofriendly thermoelectric high-entropy sulfides10.1021/acs.inorgchem.8b02379 ↗
11. Entropy-stabilized oxides10.1038/ncomms9485 ↗
12. High-entropy oxides: Fundamental aspects and electrochemical properties10.1002/adma.201806236 ↗
13. Synthesis and microstructure of the (Co, Cr, Fe, Mn, Ni)3O4 high entropy oxide characterized by spinel structure10.1016/j.matlet.2017.12.148 ↗
14. Facile synthesis and ferrimagnetic property of spinel (CoCrFeMnNi)3O4 high-entropy oxide nanocrystalline powder10.1016/j.molstruc.2019.05.073 ↗
15. Synthesis and sintering of (Mg, Co, Ni, Cu, Zn)O entropy-stabilized oxides obtained by wet chemical methods10.1007/s10853-018-2168-9 ↗
16. A high entropy oxide (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O) with superior lithium storage performance10.1016/j.jallcom.2018.11.049 ↗
17. High entropy oxides: The role of entropy, enthalpy and synergy10.1016/j.scriptamat.2020.05.019 ↗
18. Defect structure and transport properties of (Co, Cr, Fe, Mn, Ni)3O4 spinel-structured high entropy oxide10.1016/j.jeurceramsoc.2019.10.026 ↗
19. A five-component entropy-stabilized fluorite oxide10.1016/j.jeurceramsoc.2018.04.063 ↗
20. Low temperature synthesis and characterization of single phase multi-component fluorite oxide nanoparticle sols10.1039/C9RA04636D ↗
21. High-entropy layered oxide cathodes for sodium-ion batteries10.1002/anie.201912171 ↗
22. Synthesis and structures of high-entropy pyrochlore oxides10.1016/j.jeurceramsoc.2019.12.008 ↗
23. A new class of high-entropy perovskite oxides10.1016/j.scriptamat.2017.08.040 ↗
24. Rare earth and transition metal based entropy stabilised perovskite type oxides10.1016/j.jeurceramsoc.2017.12.058 ↗
25. Room-temperature synthesis of high-entropy perovskite oxide nanoparticle catalysts through ultrasonication-based method10.1002/cssc.201902705 ↗
26. Colossal dielectric constant in high entropy oxides10.1002/pssr.201600043 ↗
27. Multicomponent equiatomic rare earth oxides with a narrow band gap and associated praseodymium multivalency10.1039/C7DT02077E ↗
28. Room temperature lithium superionic conductivity in high entropy oxides10.1039/C6TA03249D ↗
29. Entropy-stabilized metal oxide solid solutions as CO oxidation catalysts with high-temperature stability10.1039/C8TA01772G ↗
30. High-entropy oxides for catalysis: Status and perspectives10.1016/j.apcata.2022.118478 ↗
31. High entropy oxides for reversible energy storage10.1038/s41467-018-05774-5 ↗
32. In operando synchrotron X-ray studies of a novel spinel (Ni0.2Co0.2Mn0.2Fe0.2Ti0.2)3O4 high-entropy oxide for energy storage applications10.1039/D0TA06455F ↗
33. Operando synchrotron transmission X-ray microscopy study on (Mg, Co, Ni, Cu, Zn)O high-entropy oxide anodes for lithium-ion batteries10.1016/j.matchemphys.2021.125105 ↗
34. Entropy-assisted high-entropy oxide with a spinel structure toward high-temperature infrared radiation materials10.1021/acsami.1c20055 ↗
35. Long-range antiferromagnetic order in a rocksalt high entropy oxide10.1021/acs.chemmater.9b00624 ↗
36. Triolo, C., Xu, W., Petrovičovà, B., Pinna, N., and Santangelo, S. (2022). Evaluation of entropy-stabilised (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O oxides produced via solvothermal method or electrospinning as anodes in lithium ion batteries. Adv. Funct. Mater., 2202892.10.1002/adfm.202202892 ↗
37. Single-phase formation mechanism and dielectric properties of sol-gel-derived Ba(Ti0.2Zr0.2Sn0.2Hf0.2Ce0.2)O3 high-entropy ceramics10.1016/j.jmst.2022.05.012 ↗
38. Characterization of novel high-entropy (La0.2Nd0.2Sm0.2Dy0.2Yb0.2)2Zr2O7 electrospun ceramic nanofibers10.1016/j.ceramint.2022.01.067 ↗
39. Low temperature synthesis of high-entropy (Y0.2Yb0.2Sm0.2Eu0.2Er0.2)2O3 nanofibers by a novel electrospinning method10.1016/j.jmst.2021.06.057 ↗
40. Sol–gel synthesis of spherical mesoporous high-entropy oxides10.1021/acsami.0c11899 ↗
41. Santangelo, S. (2019). Electrospun nanomaterials for energy applications: Recent advances. Appl. Sci., 9.10.3390/app9061049 ↗
42. Are electrospun carbon/metal oxide composite fibers relevant electrode materials for Li-Ion batteries?10.1149/2.0351614jes ↗
43. Are electrospun fibrous membranes relevant electrode materials for li-ion batteries? The case of the C/Ge/GeO2 composite fibers10.1002/adfm.201800938 ↗
44. Exploiting the condensation reactions of acetophenone to engineer carbon-encapsulated Nb2O5 nanocrystals for high-performance Li and Na energy storage systems10.1002/aenm.201902813 ↗
45. Spinel-structured high entropy oxide (FeCoNiCrMn)3O4 as anode towards superior lithium storage performance10.1016/j.jallcom.2020.156158 ↗
46. New spinel high-entropy oxides (FeCoNiCrMnXLi)3O4 (X = Cu, Mg, Zn) as the anode material for lithium-ion batteries10.1016/j.ceramint.2021.08.091 ↗
47. High entropy spinel-structure oxide for electrochemical application10.1016/j.cej.2021.133448 ↗
48. A new spinel high-entropy oxide (Mg0.2Ti0.2Zn0.2Cu0.2Fe0.2)3O4 with fast reaction kinetics and excellent stability as an anode material for lithium ion batteries10.1039/D0RA00255K ↗
49. Formation and properties of high entropy oxides in Co-Cr-Fe-Mg-Mn-Ni-O system: Novel (Cr, Fe, Mg, Mn, Ni)3O4 and (Co, Cr Fe,Mg, Mn)3O4 high entropy spinels10.1016/j.jeurceramsoc.2019.11.030 ↗
50. Liang, B., Ai, Y., Wang, Y., Liu, C., Ouyang, S., and Liu, M. (2020). Spinel-type (FeCoCrMnZn)3O4 high-entropy oxide: Facile preparation and supercapacitor performance. Materials, 13.10.3390/ma13245798 ↗
51. High entropy spinel oxide nanoparticles for superior lithiation–delithiation performance10.1039/D0TA04844E ↗
52. A new class of spinel high-entropy oxides with controllable magnetic properties10.1016/j.jmmm.2019.165884 ↗
53. CuO nanorods: A potential and efficient adsorbent in water purification10.1039/C4RA04619F ↗
54. Alhumaimess, M.S., Essawy, A.A., Kamel, M.M., Alsohaimi, I.H., and Hassan, H.M.A. (2020). Biogenic-mediated synthesis of mesoporous Cu2O/CuO nano-architectures of superior catalytic reductive towards nitroaromatics. Nanomaterials, 10.10.3390/nano10040781 ↗
55. In vitro evaluation of biodegradable magnesium alloys containing micro-alloying additions of strontium, with and without zinc10.1039/C5TB01516B ↗
56. Hu, G., Zhong, M., and Guo, C. (2019). Microstructures and high temperature tensile properties of As-Aged Mg-6Zn-1Mn-4Sn-(01, 0.5 and 1.0) Y alloys. Metals, 9.10.3390/met9010001 ↗
57. Formation and magnetic behaviour of manganese oxide nanoparticles10.1016/j.mseb.2010.01.049 ↗
58. Structural, Optical and room temperature magnetic study of Mn2O3 nanoparticles
59. Preparation and characterization of NiO nanoparticles by anodic arc plasma Method10.1155/2009/795928 ↗
60. Hong, S.J., Mun, H.J., Kim, B.J., and Kim, Y.S. (2021). Characterization of nickel oxide nanoparticles synthesized under low temperature. Micromachines, 12.10.3390/mi12101168 ↗
61. Morphology oriented surfactant dependent CoO and reaction time dependent Co3O4 nanocrystals from single synthesis method and their optical and magnetic properties10.1039/c3ce41502c ↗
62. Lattice vibration spectra. LIX. Single crystal infrared and Raman studies of spinel type oxides10.1016/0022-4596(91)90171-D ↗
63. High capacity and low cost spinel Fe3O4 for the Na-ion battery negative electrode materials10.1016/j.electacta.2014.09.081 ↗
64. Effect of rare earth doping on the vibrational spectra of spinel Mn-Cr ferrite10.1016/j.materresbull.2017.09.012 ↗
65. Raman fingerprint of chromate, aluminate and ferrite spinels10.1002/jrs.4764 ↗
66. Thermodynamic CoO–Co3O4 crossover using Raman spectroscopy in magnetic octahedron-shaped nanocrystals10.1002/jrs.5129 ↗
67. Nanodimensional spinel NiFe2O4 and ZnFe2O4 ferrites prepared by soft mechanochemical synthesis10.1063/1.4801962 ↗
68. Structural and electrical properties of CFO nanoparticle-filled PVA10.1007/s11664-019-07113-w ↗
69. Raman spectroscopic study of cation disorder in poly-and single crystals of the nickel aluminate spinel10.1088/0953-8984/19/18/186217 ↗
70. High entropy oxides (FeNiCrMnX)3O4 (X = Zn, Mg) as anode materials for lithium ion batteries10.1016/j.ceramint.2021.08.303 ↗
71. Co3O4 polyhedron@MnO2 nanotube composite as anode for high-performance lithium-ion batteries10.1002/smll.202008165 ↗
72. Lithiation mechanism in high-entropy oxides as anode materials for Li-ion batteries: An operando XAS study10.1021/acsami.0c13161 ↗
73. Multi-anionic and -cationic compounds: New high entropy materials for advanced Li-ion batteries10.1039/C9EE00368A ↗
74. Electrochemical performance of (MgCoNiZn)1−xLixO high-entropy oxides in lithium-ion batteries10.1021/acsami.0c03562 ↗
75. Fukushima, H., Kozu, T., Shima, H., Funakubo, H., Uchida, H., Katoda, T., and Nishida, K. (2015, January 24–27). Evaluation of oxygen vacancy in ZnO using Raman spectroscopy. Proceedings of the 2015 Joint IEEE International Symposium on the Applications of Ferroelectric (ISAF), International Symposium on Integrated Functionalities (ISIF), and Piezoelectric Force Microscopy Workshop (PFM), Singapore.10.1109/ISAF.2015.7172660 ↗
76. Characterization on of oxygen vacancies in SrTiO3 by means of inelastic and Raman speectroscopy10.1063/1.5115106 ↗
77. Reversible oxygen vacancy generation on pure CeO2 nanorods evaluated by in situ Raman spectroscopy10.1021/acs.jpcc.7b03155 ↗
78. Spinel-type high-entropy (Co0.2Mn0.2Fe0.2Zn0.2Ti0.2)3O4 oxides constructed from disordered cations and oxygen vacancies10.1016/j.jallcom.2021.163188 ↗