AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Energy Article
PDF (4.8 MB)
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript AI Chat Paper
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article | Open Access

Titanium-containing high entropy oxide (Ti-HEO): A redox expediting electrocatalyst towards lithium polysulfides for high performance Li-S batteries

Hassan Raza1,2,§, Junye Cheng1,§( ), Jingwei Wang1, Subash Kandasamy3, Guangping Zheng2( ), Guohua Chen3( )
Department of Materials Science, Shenzhen MSU-BIT University, Shenzhen 517182, China
Department of Mechanical Engineering, Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, China
School of Energy and Environment, City University of Hong Kong, Dat Chee Avenue, Kowloon, Hong Kong SAR, China

§ Hassan Raza and Junye Cheng contributed equally to this work.

Show Author Information

Graphical Abstract

Ti-containing high entropy oxide with increased electrical conductivities is beneficial for enhancing lithium polysulfide conversion kinetics and chemically restraining the shuttling effect in Li-S batteries.

Abstract

Since lithium sulfur (Li-S) energy storage devices are anticipated to power portable gadgets and electric vehicles owing to their high energy density (2600 Wh·kg–1); nevertheless, their usefulness is constrained by sluggish sulfur reaction kinetics and soluble lithium polysulfide (LPS) shuttling effects. High electrically conductive bifunctional electrocatalysts are urgently needed for Li-S batteries, and high-entropy oxide (HEO) is one of the most promising electrocatalysts. In this work, we synthesize titanium-containing high entropy oxide (Ti-HEO) (TiFeNiCoMg)O with enhanced electrical conductivity through calcining metal-organic frameworks (MOF) templates at modest temperatures. The resulting single-phase Ti-HEO with high conductivity could facilitate chemical immobilization and rapid bidirectional conversion of LPS. As a result, the Ti-HEO/S/KB cathode (with 70 wt.% of sulfur) achieves an initial discharge capacity as high as ~1375 mAh·g–1 at 0.1 C, and a low-capacity fade rate of 0.056% per cycle over 1000 cycles at 0.5 C. With increased sulfur loading (~5.0 mg·cm–2), the typical Li-S cell delivered a high initial discharge capacity of ~607 mAh·g–1 at 0.2 C and showcased good cycling stability. This work provides better insight into the synthesis of catalytic Ti-containing HEOs with enhanced electrical conductivity, which are effective in simultaneously enhancing the LPS-conversion kinetics and reducing the LPS shuttling effect.

Keywords

titanium containing high entropy oxide (Ti-HEOs)multi-metal-MOFs template methodelectrical conductivitylithium-sulfur batteriescatalytic conversion

Electronic Supplementary Material

Download File(s)
0116_ESM.pdf (1.3 MB)

References

[1]

Zhou, G. M.; Chen, H.; Cui, Y. Formulating energy density for designing practical lithium-sulfur batteries. Nat. Energy 2022, 7, 312–319.
Crossref Google Scholar
[2]

Xiang, Y. Y.; Lu, L. Q.; Kottapalli, A. G. P.; Pei, Y. T. Status and perspectives of hierarchical porous carbon materials in terms of high-performance lithium-sulfur batteries. Carbon Energy 2022, 4, 346–398.
Crossref Google Scholar
[3]

Manthiram, A.; Fu, Y. Z.; Chung, S. H.; Zu, C. X.; Su, Y. S. Rechargeable lithium-sulfur batteries. Chem. Rev. 2014, 114, 11751–11787.
Crossref Google Scholar
[4]

Seh, Z. W.; Sun, Y. M.; Zhang, Q. F.; Cui, Y. Designing high-energy lithium-sulfur batteries. Chem. Soc. Rev. 2016, 45, 5605–5634.
Crossref Google Scholar
[5]

Fang, R. P.; Zhao, S. Y.; Sun, Z. H.; Wang, D. W.; Cheng, H. M.; Li, F. More reliable lithium-sulfur batteries: Status, solutions and prospects. Adv. Mater. 2017, 29, 1606823.
Crossref Google Scholar
[6]

Bruce, P. G.; Freunberger, S. A.; Hardwick, L. J.; Tarascon, J. M. Li-O2 and Li-S batteries with high energy storage. Nat. Mater. 2012, 11, 19–29.
Crossref Google Scholar
[7]

Larcher, D.; Tarascon, J. M. Towards greener and more sustainable batteries for electrical energy storage. Nat. Chem. 2015, 7, 19–29.
Crossref Google Scholar
[8]

Boyjoo, Y.; Shi, H. D.; Tian, Q.; Liu, S. M.; Liang, J.; Wu, Z. S.; Jaroniec, M.; Liu, J. Engineering nanoreactors for metal-chalcogen batteries. Energy Environ. Sci. 2021, 14, 540–575.
Crossref Google Scholar
[9]

Zhang, J.; Li, M. N.; Younus, H. A.; Wang, B. S.; Weng, Q. H.; Zhang, Y.; Zhang, S. G. An overview of the characteristics of advanced binders for high-performance Li-S batteries. Nano Mater. Sci. 2021, 3, 124–139.
Crossref Google Scholar
[10]

Ji, X. L.; Nazar, L. F. Advances in Li-S batteries. J. Mater. Chem. 2010, 20, 9821–9826.
Crossref Google Scholar
[11]

Hagen, M.; Hanselmann, D.; Ahlbrecht, K.; Maça, R.; Gerber, D.; Tübke, J. Lithium-sulfur cells: The gap between the state-of-the-art and the requirements for high energy battery cells. Adv. Energy Mater. 2015, 5, 1401986.
Crossref Google Scholar
[12]

Majumder, S.; Shao, M. H.; Deng, Y. F.; Chen, G. H. Ultrathin sheets of MoS2/g-C3N4 composite as a good hosting material of sulfur for lithium-sulfur batteries. J. Power Sources 2019, 431, 93–104.
Crossref Google Scholar
[13]

Majumder, S.; Shao, M. H.; Deng, Y. F.; Chen, G. H. Two dimensional WS2/C nanosheets as a polysulfides immobilizer for high performance lithium-sulfur batteries. J. Electrochem. Soc. 2019, 166, A5386–A5395.
Crossref Google Scholar
[14]

Liang, X.; Hart, C.; Pang, Q.; Garsuch, A.; Weiss, T.; Nazar, L. F. A highly efficient polysulfide mediator for lithium-sulfur batteries. Nat. Commun. 2015, 6, 5682.
Crossref Google Scholar
[15]

Wang, H. Q.; Zhang, W. C.; Xu, J. Z.; Guo, Z. P. Advances in polar materials for lithium-sulfur batteries. Adv. Funct. Mater. 2018, 28, 1707520.
Crossref Google Scholar
[16]

Zhang, Z. W.; Peng, H. J.; Zhao, M.; Huang, J. Q. Heterogeneous/homogeneous mediators for high-energy-density lithium-sulfur batteries: Progress and prospects. Adv. Funct. Mater. 2018, 28, 1707536.
Crossref Google Scholar
[17]

Ji, X. L.; Lee, K. T.; Nazar, L. F. A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries. Nat. Mater. 2009, 8, 500–506.
Crossref Google Scholar
[18]

Xiao, Q. H. Q.; Yang, J. L.; Wang, X. D.; Deng, Y. R.; Han, P.; Yuan, N.; Zhang, L.; Feng, M.; Wang, C. A.; Liu, R. P. Carbon-based flexible self-supporting cathode for lithium-sulfur batteries: Progress and perspective. Carbon Energy 2021, 3, 271–302.
Crossref Google Scholar
[19]

Raza, H.; Bai, S. Y.; Cheng, J. Y.; Majumder, S.; Zhu, H.; Liu, Q.; Zheng, G. P.; Li, X. F.; Chen, G. H. Li-S batteries: Challenges, achievements and opportunities. Electrochem. Energy Rev. 2023, 6, 29.
Crossref Google Scholar
[20]

Shi, H. D.; Zhao, X. J.; Wu, Z. S.; Dong, Y. F.; Lu, P. F.; Chen, J.; Ren, W. C.; Cheng, H. M.; Bao, X. H. Free-standing integrated cathode derived from 3D graphene/carbon nanotube aerogels serving as binder-free sulfur host and interlayer for ultrahigh volumetric-energy-density lithium-sulfur batteries. Nano Energy 2019, 60, 743–751.
Crossref Google Scholar
[21]

Dong, Y. F.; Zheng, S. H.; Qin, J. Q.; Zhao, X. J.; Shi, H. D.; Wang, X. H.; Chen, J.; Wu, Z. S. All-MXene-based integrated electrode constructed by Ti3C2 nanoribbon framework host and nanosheet interlayer for high-energy-density Li-S batteries. ACS Nano 2018, 12, 2381–2388.
Crossref Google Scholar
[22]

Shi, H. D.; Qin, J. Q.; Huang, K.; Lu, P. F.; Zhang, C. F.; Dong, Y. F.; Ye, M.; Liu, Z. M.; Wu, Z. S. A two-dimensional mesoporous polypyrrole-graphene oxide heterostructure as a dual-functional ion redistributor for dendrite-free lithium metal anodes. Angew. Chem. 2020, 132, 12245–12251.
Crossref Google Scholar
[23]

Ci, H. N.; Shi, Z. X.; Wang, M. L.; He, Y.; Sun, J. Y. A review in rational design of graphene toward advanced Li-S batteries. Nano Res. Energy 2023, 2, e9120054.
Crossref Google Scholar
[24]

Sun, D. D.; Sun, Z. P.; Yang, D. H.; Jiang, X. F.; Tang, J.; Wang, X. B. Advances in boron nitride-based materials for electrochemical energy storage and conversion. EcoEnergy 2023, 1, 375–404.
Crossref Google Scholar
[25]

Shi, H. D.; Ren, X. M.; Lu, J. M.; Dong, C.; Liu, J.; Yang, Q. H.; Chen, J.; Wu, Z. S. Dual-functional atomic zinc decorated hollow carbon nanoreactors for kinetically accelerated polysulfides conversion and dendrite free lithium sulfur batteries. Adv. Energy Mater. 2020, 10, 2002271.
Crossref Google Scholar
[26]

He, J. R.; Manthiram, A. A review on the status and challenges of electrocatalysts in lithium-sulfur batteries. Energy Storage Mater. 2019, 20, 55–70.
Crossref Google Scholar
[27]

Wang, Y. C.; Pu, Y. R.; Yuan, L.; Zhang, Y.; Liu, C.; Wang, Q.; Wu, H. Synergistic effect of WN/Mo2C embedded in bioderived carbon nanofibers: A rational design of a shuttle inhibitor and an electrocatalyst for lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2022, 14, 18578–18588.
Crossref Google Scholar
[28]

Wang, S. N.; Hu, R. M.; Yuan, D.; Zhang, L.; Wu, C.; Ma, T. Y.; Yan, W.; Wang, R.; Liu, L.; Jiang, X. C. et al. Single-atomic tungsten-doped Co3O4 nanosheets for enhanced electrochemical kinetics in lithium-sulfur batteries. Carbon Energy 2023, 5, e329.
Crossref Google Scholar
[29]

Wang, Z. F.; Yan, Y. J.; Zhang, Y. G.; Chen, Y. X.; Peng, X. Y.; Wang, X.; Zhao, W. M.; Qin, C. L.; Liu, Q.; Liu, X. J. et al. Single-atomic Co-B2N2 sites anchored on carbon nanotube arrays promote lithium polysulfide conversion in lithium-sulfur batteries. Carbon Energy 2023, 5, e306.
Crossref Google Scholar
[30]

Shi, H. D.; Qin, J. Q.; Lu, P. F.; Dong, C.; He, J.; Chou, X. J.; Das, P.; Wang, J. M.; Zhang, L. Z.; Wu, Z. S. Interfacial engineering of bifunctional niobium (V)-based heterostructure nanosheet toward high efficiency lean-electrolyte lithium-sulfur full batteries. Adv. Funct. Mater. 2021, 31, 2102314.
Crossref Google Scholar
[31]

Abraham, A. M.; Boteju, T.; Ponnurangam, S.; Thangadurai, V. A global design principle for polysulfide electrocatalysis in lithium-sulfur batteries-A computational perspective. Battery Energy 2022, 1, 20220003.
Crossref Google Scholar
[32]

Rost, C. M.; Sachet, E.; Borman, T.; Moballegh, A.; Dickey, E. C.; Hou, D.; Jones, J. L.; Curtarolo, S.; Maria, J. P. Entropy-stabilized oxides. Nat. Commun. 2015, 6, 8485.
Crossref Google Scholar
[33]
Murty, B. S.; Yeh, J. W.; Ranganathan, S. High-entropy alloys: Basic concepts. In High Entropy Alloys. Murty, B. S.; Yeh, J. W.; Ranganathan, S., Eds.; Elsevier: Amsterdam, 2014; pp 13–35.
Crossref
[34]

Amiri, A.; Shahbazian-Yassar, R. Recent progress of high-entropy materials for energy storage and conversion. J. Mater. Chem. A 2021, 9, 782–823.
Crossref Google Scholar
[35]

Wang, Q. S.; Sarkar, A.; Li, Z. Y.; Lu, Y.; Velasco, L.; Bhattacharya, S. S.; Brezesinski, T.; Hahn, H.; Breitung, B. High entropy oxides as anode material for Li-ion battery applications: A practical approach. Electrochem. Commun. 2019, 100, 121–125.
Crossref Google Scholar
[36]

Ghigna, P.; Airoldi, L.; Fracchia, M.; Callegari, D.; Anselmi-Tamburini, U.; D’Angelo, P.; Pianta, N.; Ruffo, R.; Cibin, G. ; de Souza, D. O. et al. Lithiation mechanism in high-entropy oxides as anode materials for Li-ion batteries: An operando XAS study. ACS Appl. Mater. Interfaces 2020, 12, 50344–50354.
Crossref Google Scholar
[37]

Tian, L. Y.; Zhang, Z.; Liu, S.; Li, G. R.; Gao, X. P. High-entropy spinel oxide nanofibers as catalytic sulfur hosts promise the high gravimetric and volumetric capacities for lithium-sulfur batteries. Energy Environ. Mater. 2022, 5, 645–654.
Crossref Google Scholar
[38]

Sarkar, A.; Velasco, L.; Wang, D.; Wang, Q. S.; Talasila, G. ; de Biasi, L.; Kübel, C.; Brezesinski, T.; Bhattacharya, S. S.; Hahn, H. et al. High entropy oxides for reversible energy storage. Nat. Commun. 2018, 9, 3400.
Crossref Google Scholar
[39]

Chen, Y. W.; Fu, H. Y.; Huang, Y. Y.; Huang, L. Q.; Zheng, X. Y.; Dai, Y. M.; Huang, Y. H.; Luo, W. Opportunities for high-entropy materials in rechargeable batteries. ACS Mater. Lett. 2021, 3, 160–170.
Crossref Google Scholar
[40]

Tsau, C. H.; Yang, Y. C.; Lee, C. C.; Wu, L. Y.; Huang, H. J. The low electrical resistivity of the high-entropy alloy oxide thin films. Procedia Eng. 2012, 36, 246–252.
Crossref Google Scholar
[41]

Yang, Y. C.; Tsau, C. H.; Yeh, J. W. TiFeCoNi oxide thin film-A new composition with extremely low electrical resistivity at room temperature. Scr. Mater. 2011, 64, 173–176.
Crossref Google Scholar
[42]

Raza, H.; Cheng, J. Y.; Lin, C.; Majumder, S.; Zheng, G. P.; Chen, G. H. High-entropy stabilized oxides derived via a low-temperature template route for high-performance lithium-sulfur batteries. EcoMat 2023, 5, e12324.
Crossref Google Scholar
[43]

Raza, H.; Cheng, J. Y.; Chen, G. H.; Zheng, G. P. Low-temperature calcination of metal-organic frameworks (MOFs) to derive the high entropy stabilized oxide for high performance lithium-sulfur batteries. ECS Meet. Abstr. 2022, 1MA2022-0, 2432.
Crossref Google Scholar
[44]

Cheng, J. Y.; Ran, S. J.; Li, T.; Yan, M.; Wu, J.; Boles, S.; Liu, B.; Raza, H.; Ullah, S.; Zhang, W. J. et al. Achieving superior tensile performance in individual metal-organic framework crystals. Adv. Mater. 2023, 35, 2210829.
Crossref Google Scholar
[45]
Zhao, Y. H.; Lai, X. Q.; Wang, P. F.; Liu, Z. L.; Yi, T. F. Construction of metal-organic framework-derived Al-doped Na3V2(PO4)3 cathode materials toward high-performance rechargeable Na-ion battery. Energy Mater. Devices, in press, DOI: 10.26599/EMD.2024.9370002.
Crossref
[46]

Zheng, Y. N.; Yi, Y. K.; Fan, M. H.; Liu, H. Y.; Li, X.; Zhang, R.; Li, M. T.; Qiao, Z. A. A high-entropy metal oxide as chemical anchor of polysulfide for lithium-sulfur batteries. Energy Storage Mater. 2019, 23, 678–683.
Crossref Google Scholar
[47]

Kheradmandfard, M.; Minouei, H.; Tsvetkov, N.; Vayghan, A. K.; Kashani-Bozorg, S. F.; Kim, G.; Hong, S. I.; Kim, D. E. Ultrafast green microwave-assisted synthesis of high-entropy oxide nanoparticles for Li-ion battery applications. Mater. Chem. Phys. 2021, 262, 124265.
Crossref Google Scholar
[48]

Qiu, N.; Chen, H.; Yang, Z. M.; Sun, S.; Wang, Y.; Cui, Y. H. A high entropy oxide (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O) with superior lithium storage performance. J. Alloys Compd. 2019, 777, 767–774.
Crossref Google Scholar
[49]

Khan, N. A.; Akhavan, B.; Zheng, Z.; Liu, H. W.; Zhou, C. F.; Zhou, H. R.; Chang, L.; Wang, Y.; Liu, Y. P.; Sun, L. X. et al. Nanostructured AlCoCrCu0.5FeNi high entropy oxide (HEO) thin films fabricated using reactive magnetron sputtering. Appl. Surf. Sci. 2021, 553, 149491.
Crossref Google Scholar
[50]

Zhao, X. J.; Gao, T. Q.; Yuan, Y.; Fang, Z. Hollow slightly oxidized CoP confined into flyover-type carbon skeleton with multiple channels as an effective adsorption-catalysis matrix for robust Li-S batteries. Electrochim. Acta 2022, 422, 140512.
Crossref Google Scholar
[51]

Lin, H. B.; Yang, L. Q.; Jiang, X.; Li, G. C.; Zhang, T. R.; Yao, Q. F.; Zheng, G. W.; Lee, J. Y. Electrocatalysis of polysulfide conversion by sulfur-deficient MoS2 nanoflakes for lithium-sulfur batteries. Energy Environ. Sci. 2017, 10, 1476–1486.
Crossref Google Scholar
[52]

Li, W. L.; Qian, J.; Zhao, T.; Ye, Y. S.; Xing, Y.; Huang, Y. X.; Wei, L.; Zhang, N. X.; Chen, N.; Li, L. et al. Boosting high-rate Li-S batteries by an MOF-derived catalytic electrode with a layer-by-layer structure. Adv. Sci. 2019, 6, 1802362.
Crossref Google Scholar
[53]

Zhou, L.; Danilov, D. L.; Qiao, F.; Eichel, R. A.; Notten, P. H. L. ZnFe2O4 hollow rods enabling accelerated polysulfide conversion for advanced lithium-sulfur batteries. Electrochim. Acta 2022, 414, 140231.
Crossref Google Scholar
[54]

Wang, S. X.; Liu, X. Y.; Duan, H. H.; Deng, Y. F.; Chen, G. H. Fe3C/Fe nanoparticles embedded in N-doped porous carbon nanosheets and graphene: A thin functional interlayer for PP separator to boost performance of Li-S batteries. Chem. Eng. J. 2021, 415, 129001.
Crossref Google Scholar
[55]

Mu, J. W.; Jiang, H. L.; Yu, M.; Gu, S. H.; He, G. H.; Dai, Y.; Li, X. C. Thiophilic-lithiophilic hierarchically porous membrane-enabled full lithium-sulfur battery with a low N/P ratio. ACS Appl. Mater. Interfaces 2022, 14, 23408–23419.
Crossref Google Scholar
[56]

Abualela, S.; Lv, X. X.; Hu, Y.; Abd-Alla, M. D. NiO nanosheets grown on carbon cloth as mesoporous cathode for high-performance lithium-sulfur battery. Mater. Lett. 2020, 268, 127622.
Crossref Google Scholar
[57]

Bhargav, A.; He, J. R.; Gupta, A.; Manthiram, A. Lithium-sulfur batteries: Attaining the critical metrics. Joule 2020, 4, 285–291.
Crossref Google Scholar
[58]

Ye, H. L.; Li, Y. G. Towards practical lean-electrolyte Li-S batteries: Highly solvating electrolytes or sparingly solvating electrolytes. Nano Res. Energy 2022, 1, e9120012.
Crossref Google Scholar
[59]

Qi, C.; Li, H. L.; Wang, J.; Zhao, C. C.; Fu, C. M.; Wang, L. N.; Liu, T. X. Metal-organic-framework-derived porous carbon embedded with TiO2 nanoparticles as a cathode for advanced lithium-sulfur batteries. ChemElectroChem 2021, 8, 90–95.
Crossref Google Scholar
[60]

Liu, M. T.; Jhulki, S.; Sun, Z. F.; Magasinski, A.; Hendrix, C.; Yushin, G. Atom-economic synthesis of Magnéli phase Ti4O7 microspheres for improved sulfur cathodes for Li-S batteries. Nano Energy 2021, 79, 105428.
Crossref Google Scholar
[61]

Wu, H. W.; Hu, X. J.; Shao, M. H.; Zhang, S. W.; Chen, G. H. Encapsulating sulphur inside Magnéli phase Ti4O7 nanotube array for high performance lithium sulphur battery cathode. Can. J. Chem. Eng. 2022, 100, 2417–2431.
Crossref Google Scholar
[62]

Liu, H. T.; Liu, F.; Qu, Z. H.; Chen, J. L.; Liu, H.; Tan, Y. Q.; Guo, J. B.; Yan, Y.; Zhao, S.; Zhao, X. S. et al. High sulfur loading and shuttle inhibition of advanced sulfur cathode enabled by graphene network skin and N, P, F-doped mesoporous carbon interfaces for ultra-stable lithium sulfur battery. Nano Res. Energy 2023, 2, e9120049.
Crossref Google Scholar
[63]

Xiao, S. J.; Huang, L.; Lv, W.; He, Y. B. A highly efficient ion and electron conductive interlayer to achieve low self-discharge of lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2022, 14, 1783–1790.
Crossref Google Scholar
[64]

Knap, V.; Stroe, D. I.; Swierczynski, M.; Teodorescu, R.; Schaltz, E. Investigation of the self-discharge behavior of lithium-sulfur batteries. J. Electrochem. Soc. 2016, 163, A911–A916.
Crossref Google Scholar
Nano Research Energy
Volume 3 Issue 3,
September 2024
Article number: e9120116
DOI: 10.26599/NRE.2024.9120116
Cite this article:
Raza H, Cheng J, Wang J, et al. Titanium-containing high entropy oxide (Ti-HEO): A redox expediting electrocatalyst towards lithium polysulfides for high performance Li-S batteries. Nano Research Energy, 2024, 3: e9120116. https://doi.org/10.26599/NRE.2024.9120116

1966

Views

551

Downloads

1

Crossref

1

Scopus

Altmetrics
Received: 01 November 2023
Revised: 25 January 2024
Accepted: 01 February 2024
Published: 04 March 2024
© The Author(s) 2024. Published by Tsinghua University Press.

The articles published in this open access journal are distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Return