Designing a double-coated cathode with high entropy oxides by microwave-assisted hydrothermal synthesis for highly stable Li–S batteries
Source abstract
Abstract
Abstract Nowadays, Li–S batteries are considered as one of the most promising alternatives to Li-ion technology in the near future, thanks to their high specific capacity and their significantly lower environmental impact and production costs. Consequently, many efforts have been directed to tackle with the inherent issues that affect Li–S batteries. One of the main problems is the so-called shuttle effect, which basically entails the unwanted migration of lithium polysulfides (LiPSs) from the cathode to the anode side, causing the degradation of the cell. Here, we report an effective strategy to restrain the shuttle effect and increase the kinetics at the cathode of the lithium–sulfur (Li–S) battery. A functional layer including high entropy oxides (HEO) coated onto the sulfur cathode allows to exploit the HEOs capability as promoter catalysts for the conversion of LiPSs. Pure HEO powders are synthesized by fast, highly efficient microwave irradiation, followed by heat treatment at 930 °C. The formation of highly crystalline HEO is confirmed by X-ray diffraction analysis. The LiPSs adsorption capability of HEO is evaluated by UV–vis and X-ray photoelectron spectroscopy analyses. The effect of the HEO-coated sulfur cathode on the electrochemical performance of the Li–S battery is studied by cyclic voltammetry and galvanostatic charge/discharge. The cell with double-coated cathode delivers an initial discharge capacity of 1173 mAh/g at C/10 with 45% capacity retention over 500 cycles at C/5, approaching ~ 99% coulombic efficiency. Graphical abstract
Source: crossref · Quality: baseline
Research context
OpenAlex topics: Advanced Battery Materials and Technologies · Advancements in Battery Materials · Thermal Expansion and Ionic Conductivity
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (51)
Show source-provided references
1. Pang Q, Kundu D, Nazar LF (2016) A graphene-like metallic cathode host for long-life and high-loading lithium–sulfur batteries. Mater Horiz 3:130–136. https://doi.org/10.1039/C5MH00246J10.1039/C5MH00246J ↗
2. Duffner F, Kronemeyer N, Tübke J et al (2021) Post-lithium-ion battery cell production and its compatibility with lithium-ion cell production infrastructure. Nat Energy 6:123–134. https://doi.org/10.1038/s41560-020-00748-810.1038/s41560-020-00748-8 ↗
3. Wild M, O’Neill L, Zhang T et al (2015) Lithium sulfur batteries, a mechanistic review. Energy Environ Sci 8:3477–3494. https://doi.org/10.1039/C5EE01388G10.1039/C5EE01388G ↗
4. Barghamadi M, Kapoor A, Wen C (2013) A review on Li–S batteries as a high efficiency rechargeable lithium battery. J Electrochem Soc 160:A1256–A1263. https://doi.org/10.1149/2.096308jes10.1149/2.096308jes ↗
5. Yuan H, Peng H-J, Li B-Q et al (2019) Conductive and catalytic triple-phase interfaces enabling uniform nucleation in high-rate lithium–sulfur batteries. Adv Energy Mater 9:1802768–1802776. https://doi.org/10.1002/aenm.20180276810.1002/aenm.201802768 ↗
6. Velasco JJ, Vélez P, Zoloff Michoff ME et al (2021) Role of the solvent in the activation of Li 2 S as cathode material: a DFT study. J Phys Condens Matter 33:344003–344014. https://doi.org/10.1088/1361-648X/ac08b910.1088/1361-648X/ac08b9 ↗
7. Zhang L, Wang Y, Niu Z, Chen J (2019) Advanced nanostructured carbon-based materials for rechargeable lithium–sulfur batteries. Carbon N Y 141:400–416. https://doi.org/10.1016/j.carbon.2018.09.06710.1016/j.carbon.2018.09.067 ↗
8. Liu X, Huang J-Q, Zhang Q, Mai L (2017) Nanostructured metal oxides and sulfides for lithium–sulfur batteries. Advanced Materials 29:1601759–1601784. https://doi.org/10.1002/adma.20160175910.1002/adma.201601759 ↗
9. Su Y-S, Manthiram A (2012) Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayer. Nat Commun 3:1–6. https://doi.org/10.1038/ncomms216310.1038/ncomms2163 ↗
10. Deng N, Liu Y, Li Q et al (2019) Functional mechanism analysis and customized structure design of interlayers for high performance Li–S battery. Energy Storage Mater 23:314–349. https://doi.org/10.1016/j.ensm.2019.04.04210.1016/j.ensm.2019.04.042 ↗
11. García-Soriano FJ, Para ML, Luque GL et al (2020) Improving the polysulfide barrier by efficient carbon nanofibers coating on separator/cathode for Li–S batteries. J Solid State Electrochem 24:2341–2351. https://doi.org/10.1007/s10008-020-04749-110.1007/s10008-020-04749-1 ↗
12. Zhao M, Peng Y-Q, Li B-Q et al (2021) Regulation of carbon distribution to construct high-sulfur-content cathode in lithium–sulfur batteries. J Energy Chem 56:203–208. https://doi.org/10.1016/j.jechem.2020.07.05410.1016/j.jechem.2020.07.054 ↗
13. Sun W, Ou X, Yue X et al (2016) A simply effective double-coating cathode with MnO2 nanosheets/graphene as functionalized interlayer for high performance lithium-sulfur batteries. Electrochim Acta 207:198–206. https://doi.org/10.1016/j.electacta.2016.04.13510.1016/j.electacta.2016.04.135 ↗
14. Fang J, Qin F, Li J et al (2015) Improved performance of sulfur cathode by an easy and scale-up coating strategy. J Power Sour 297:265–270. https://doi.org/10.1016/j.jpowsour.2015.06.15310.1016/j.jpowsour.2015.06.153 ↗
15. Versaci D, Cozzarin M, Amici J et al (2021) Influence of synthesis parameters on g-C3N4 polysulfides trapping: a systematic study. Appl Mater Today 25:101169–101182. https://doi.org/10.1016/j.apmt.2021.10116910.1016/j.apmt.2021.101169 ↗
16. Liu Z, Liu B, Guo P et al (2018) Enhanced electrochemical kinetics in lithium-sulfur batteries by using carbon nanofibers/manganese dioxide composite as a bifunctional coating on sulfur cathode. Electrochim Acta 269:180–187. https://doi.org/10.1016/j.electacta.2018.02.16010.1016/j.electacta.2018.02.160 ↗
17. Liu M, Deng N, Ju J et al (2019) A review: electrospun nanofiber materials for lithium–sulfur batteries. Adv Funct Mater 29:1905367–1905401. https://doi.org/10.1002/adfm.20190546710.1002/adfm.201905467 ↗
18. Kong L, Chen X, Li B-Q et al (2018) A bifunctional perovskite promoter for polysulfide regulation toward stable lithium–sulfur batteries. Adv Mater 30:1705219–1705226. https://doi.org/10.1002/adma.20170521910.1002/adma.201705219 ↗
19. Sun Q, Xi B, Li J-Y et al (2018) Nitrogen-doped graphene-supported mixed transition-metal oxide porous particles to confine polysulfides for lithium–sulfur batteries. Adv Energy Mater 8:1800595–1800605. https://doi.org/10.1002/aenm.20180059510.1002/aenm.201800595 ↗
20. Fan Q, Liu W, Weng Z et al (2015) Ternary hybrid material for high-performance lithium–sulfur battery. J Am Chem Soc 137:12946–12953. https://doi.org/10.1021/jacs.5b0707110.1021/jacs.5b07071 ↗
21. Wu F, Pollard TP, Zhao E et al (2018) Layered LiTiO2 for the protection of Li2S cathodes against dissolution: mechanisms of the remarkable performance boost. Energy Environ Sci 11:807–817. https://doi.org/10.1039/C8EE00419F10.1039/C8EE00419F ↗
22. Zhang Y, Zhao Y, Yermukhambetova A et al (2013) Ternary sulfur/polyacrylonitrile/Mg0.6Ni0.4O composite cathodes for high performance lithium/sulfur batteries. J Mater Chem A 1:295–301. https://doi.org/10.1039/C2TA00105E10.1039/C2TA00105E ↗
23. Zheng Y, Yi Y, Fan M et al (2019) A high-entropy metal oxide as chemical anchor of polysulfide for lithium–sulfur batteries. Energy Storage Mater 23:678–683. https://doi.org/10.1016/j.ensm.2019.02.03010.1016/j.ensm.2019.02.030 ↗
24. Rost CM, Sachet E, Borman T et al (2015) Entropy-stabilized oxides. Nat Commun 6:1–8. https://doi.org/10.1038/ncomms948510.1038/ncomms9485 ↗
25. Tavani F, Fracchia M, Pianta N et al (2020) Multivariate curve resolution analysis of operando XAS data for the investigation of the lithiation mechanisms in high entropy oxides. Chem Phys Lett 760:137968–137974. https://doi.org/10.1016/j.cplett.2020.13796810.1016/j.cplett.2020.137968 ↗
26. Sarkar A, Velasco L, Wang D et al (2018) High entropy oxides for reversible energy storage. Nat Commun 9:1–9. https://doi.org/10.1038/s41467-018-05774-510.1038/s41467-018-05774-5 ↗
27. Sarkar A, Wang Q, Schiele A et al (2019) High-entropy oxides: fundamental aspects and electrochemical properties. Adv Mater 31:1806236–1806245. https://doi.org/10.1002/adma.20180623610.1002/adma.201806236 ↗
28. Yuan K, Tu T, Shen C et al (2022) Self-ball milling strategy to construct high-entropy oxide coated LiNi0.8Co0.1Mn0.1O2 with enhanced electrochemical performance. J Adv Ceram 11:882–892. https://doi.org/10.1007/s40145-022-0582-610.1007/s40145-022-0582-6 ↗
29. Tian LY, Zhang Z, Liu S et al (2021) High-entropy spinel oxide nanofibers as catalytic sulfur hosts promise the high gravimetric and volumetric capacities for lithium–sulfur batteries. Energy Environ Mater 645–654. https://doi.org/10.1002/eem2.1221510.1002/eem2.12215 ↗
30. Sarkar A, Breitung B, Hahn H (2020) High entropy oxides: the role of entropy, enthalpy and synergy. Scripta Mater 187:43–48. https://doi.org/10.1016/j.scriptamat.2020.05.01910.1016/j.scriptamat.2020.05.019 ↗
31. Qiu N, Chen H, Yang Z et al (2019) A high entropy oxide (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O) with superior lithium storage performance. J Alloys Compd 777:767–774. https://doi.org/10.1016/j.jallcom.2018.11.04910.1016/j.jallcom.2018.11.049 ↗
32. Hong W, Chen F, Shen Q et al (2019) Microstructural evolution and mechanical properties of (Mg Co, Ni, Cu, Zn)O high-entropy ceramics. J Am Ceram Soc 102:2228–2237. https://doi.org/10.1111/jace.1607510.1111/jace.16075 ↗
33. Kheradmandfard M, Kashani-Bozorg SF, Noori-Alfesharaki AH et al (2018) Ultra-fast, highly efficient and green synthesis of bioactive forsterite nanopowder via microwave irradiation. Mater Sci Eng C 92:236–244. https://doi.org/10.1016/j.msec.2018.06.02610.1016/j.msec.2018.06.026 ↗
34. Kheradmandfard M, Minouei H, Tsvetkov N et al (2021) Ultrafast green microwave-assisted synthesis of high-entropy oxide nanoparticles for Li-ion battery applications. Mater Chem Phys 262:124265–124275. https://doi.org/10.1016/j.matchemphys.2021.12426510.1016/j.matchemphys.2021.124265 ↗
35. Biesuz M, Spiridigliozzi L, Dell’Agli G et al (2018) Synthesis and sintering of (Mg Co, Ni, Cu, Zn)O entropy-stabilized oxides obtained by wet chemical methods. J Mater Sci 53:8074–8085. https://doi.org/10.1007/s10853-018-2168-910.1007/s10853-018-2168-9 ↗
36. Nguyen TX, Patra J, Chang JK, Ting JM (2020) High entropy spinel oxide nanoparticles for superior lithiation–delithiation performance. J Mater Chem A 8:18963–18973. https://doi.org/10.1039/d0ta04844e10.1039/d0ta04844e ↗
37. Nguyen TX, Tsai CC, Patra J et al (2022) Co-free high entropy spinel oxide anode with controlled morphology and crystallinity for outstanding charge/discharge performance in Lithium-ion batteries. Chem Eng J 430:132658–132667. https://doi.org/10.1016/j.cej.2021.13265810.1016/j.cej.2021.132658 ↗
38. Sarkar A, Djenadic R, Usharani NJ et al (2017) Nanocrystalline multicomponent entropy stabilised transition metal oxides. J Eur Ceram Soc 37:747–754. https://doi.org/10.1016/j.jeurceramsoc.2016.09.01810.1016/j.jeurceramsoc.2016.09.018 ↗
39. Mao A, Xiang H-Z, Zhang Z-G et al (2019) Solution combustion synthesis and magnetic property of rock-salt (Co0.2Cu0.2Mg0.2Ni0.2Zn0.2)O high-entropy oxide nanocrystalline powder. J Magn Magn Mater 484:245–252. https://doi.org/10.1016/j.jmmm.2019.04.02310.1016/j.jmmm.2019.04.023 ↗
40. Berardan D, Meena AK, Franger S et al (2017) Controlled Jahn-Teller distortion in (MgCoNiCuZn)O-based high entropy oxides. J Alloys Compd 704:693–700. https://doi.org/10.1016/j.jallcom.2017.02.07010.1016/j.jallcom.2017.02.070 ↗
41. Lal MS, Sundara R (2019) High entropy oxides—a cost-effective catalyst for the growth of high yield carbon nanotubes and their energy applications. ACS Appl Mater Interfaces 11:30846–30857. https://doi.org/10.1021/acsami.9b0879410.1021/acsami.9b08794 ↗
42. Evers S, Yim T, Nazar LF (2012) Understanding the nature of absorption/adsorption in nanoporous polysulfide sorbents for the Li–S battery. J Phys Chem C 116:19653–19658. https://doi.org/10.1021/jp304380j10.1021/jp304380j ↗
43. Zhao X, Wang J, Sun X et al (2021) Hierarchical porous carbon with nano-MgO as efficient sulfur species micro-reactors for lithium-sulfur battery. J Electrochem Soc 168:40506–40514. https://doi.org/10.1149/1945-7111/abed2a10.1149/1945-7111/abed2a ↗
44. Barchasz C, Molton F, Duboc C et al (2012) Lithium/sulfur cell discharge mechanism: an original approach for intermediate species identification. Anal Chem 84:3973–3980. https://doi.org/10.1021/ac203224410.1021/ac2032244 ↗
45. Wang Y, Guo X, Chen C et al (2020) Alleviating the shuttle effect via bifunctional MnFe2O4/AB modified separator for high performance lithium sulfur battery. Electrochim Acta 354:136704. https://doi.org/10.1016/j.electacta.2020.13670410.1016/j.electacta.2020.136704 ↗
46. Ponraj R, Kannan AG, Ahn JH, Kim D-W (2016) Improvement of cycling performance of lithium–sulfur batteries by using magnesium oxide as a functional additive for trapping lithium polysulfide. ACS Appl Mater Interfaces 8:4000–4006. https://doi.org/10.1021/acsami.5b1132710.1021/acsami.5b11327 ↗
47. Usharani NJ, Shringi R, Sanghavi H et al (2020) Role of size, alio-/multi-valency and non-stoichiometry in the synthesis of phase-pure high entropy oxide (Co, Cu, Mg, Na, Ni, Zn)O. Dalton Trans 49:7123–7132. https://doi.org/10.1039/D0DT00958J10.1039/D0DT00958J ↗
48. Yuan Z, Peng H-J, Hou T-Z et al (2016) Powering lithium–sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts. Nano Lett 16:519–527. https://doi.org/10.1021/acs.nanolett.5b0416610.1021/acs.nanolett.5b04166 ↗
49. Liu Y-T, Han D-D, Wang L et al (2019) NiCo2O4 nanofibers as carbon-free sulfur immobilizer to fabricate sulfur-based composite with high volumetric capacity for lithium–sulfur battery. Adv Energy Mater 9:1803477. https://doi.org/10.1002/aenm.20180347710.1002/aenm.201803477 ↗
50. Tao X, Wang J, Liu C et al (2016) Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design. Nat Commun 7:11203. https://doi.org/10.1038/ncomms1120310.1038/ncomms11203 ↗
51. Su YS, Fu Y, Cochell T, Manthiram A (2013) A strategic approach to recharging lithium-sulphur batteries for long cycle life. Nat Commun 4:1–8. https://doi.org/10.1038/ncomms398510.1038/ncomms3985 ↗