Enlarged interlayer of separator coating enabling high-performance lithiumsulfur batteries

Abstract

Lithiumsulfur batteries have been intensively studied due to their high theoretical energy density and abundant sulfur resources. However, their commercial application is hindered by the low redox kinetics and high sulfur losses. In principle, in the design of cathodes and separators, the adsorption toward lithium-polysulfides should be enhanced and the conversion of soluble high-order lithium-polysulfides should be catalyzed. Herein, a KV₃O₈·0.75H₂O separator is designed as an effective lithium-polysulfides mediator in lithiumsulfur batteries. The intercalated K⁺ would enlarge the interlayer spacing of vanadium oxides, preventing the collapse of the layer structure and improving the electrical/ion conductivity of the interface. Moreover, the KV₃O₈·0.75H₂O modified separator possess a prior adsorption and high redox kinetics toward lithium-polysulfides due to the enhanced diffusion kinetics, which guarantees the high-rate capability and efficient utilization of sulfur. As a result, lithiumsulfur batteries exhibit a high capacity of 1362 mAh·g¹ and a long lifespan with a low capacity loss of 0.073% per cycle. This work may provide an alternative way to establish a functional separator to balance the adsorption and conversion of polysulfides during the redox back and forth.

Graphical abstract

References

[1] Jin G F , Zhang J L , Dang B Y , Wu F C , Li J D . Engineering zirconium-based metal-organic framework-801 films on carbon cloth as shuttle-inhibiting interlayers for lithium−sulfur batteries. Frontiers of Chemical Science and Engineering, 2022, 16(4): 511–522

[2] Du B W , Luo Y H , Wu F C , Liu G H , Li J D , Xue W . Continuous amino-functionalized University of Oslo 66 membranes as efficacious polysulfide barriers for lithium−sulfur batteries. Frontiers of Chemical Science and Engineering, 2023, 17(2): 194–205

[3] Hong X , Wang R , Liu Y , Fu J , Liang J , Dou S . Recent advances in chemical adsorption and catalytic conversion materials for LiS batteries. Journal of Energy Chemistry, 2020, 42: 144–168

[4] Zhang T , Zhang L , Hou L . MXenes: synthesis strategies and lithium−sulfur battery applications. eScience, 2022, 2(2): 164–182

[5] Zhang J , Li M N , Younus A H , 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 Materials Science, 2021, 3(2): 124–139

[6] Ren L T , Liu J , Pato H A , Wang Y , Lu X W , Chandio A I , Zhou M Y , Liu W , Xu H J , Sun X M . Rational design of nanoarray structures for lithium–sulfur batteries: recent advances and future prospects. Materials Futures, 2023, 2(4): 042103

[7] Hu Y , Chen W , Lei T , Jiao Y , Huang J , Hu A , Gong C , Yan C , Wang X , Xiong J . Strategies toward high-loading lithium–sulfur battery. Advanced Energy Materials, 2020, 10(17): 2000082

[8] Ng S F , Lau M Y L , Ong W J . Lithium–sulfur battery cathode design: tailoring metal-based nanostructures for robust polysulfide adsorption and catalytic conversion. Advanced Materials, 2021, 33(50): 2008654

[9] Wu S Y , Li X , Zhang Y Z , Guan Q H , Wang J , Shen C Y , Lin H Z , Wang J T , Wang Y L , Zhan L . . Interface engineering of mxene-based heterostructures for lithium−sulfur batteries. Nano Research, 2023, 16(7): 9158–9178

[10] Li P , Lv H , Li Z , Meng X , Lin Z , Wang R , Li X . The electrostatic attraction and catalytic effect enabled by ionic-covalent organic nanosheets on MXene for separator modification of lithium–sulfur batteries. Advanced Materials, 2021, 33(17): 2007803

[11] Li X , Guan Q , Zhuang Z , Zhang Y , Lin Y , Wang J , Shen C , Lin H , Wang Y , Zhan L . . Ordered mesoporous carbon grafted mxene catalytic heterostructure as Li-ion kinetic pump toward high-efficient sulfur/sulfide conversions for Li–S battery. ACS Nano, 2023, 17(2): 1653–1662

[12] Li C , Liu R , Xiao Y , Cao F , Zhang H . Recent progress of separators in lithium–sulfur batteries. Energy Storage Materials, 2021, 40: 439–460

[13] Zhu D , Long T , Xu B , Zhao Y , Hong H , Liu R , Meng F , Liu J . Recent advances in interlayer and separator engineering for lithium–sulfur batteries. Journal of Energy Chemistry, 2021, 57: 41–60

[14] Tang J D , Zhao Q , Li F L , Hao Z D , Xu X L , Zhang Q Q , Liu J B , Jin Y H , Wang H . Two-dimensional materials towards separator functionalization in advanced Li–S batteries. Nanoscale, 2021, 13(45): 18883–18911

[15] Wang X X , Deng N P , Wei L Y , Yang Q , Xiang H Y , Wang M , Cheng B W , Kang W M . Recent progress in high-performance lithium sulfur batteries: the emerging strategies for advanced separators/electrolytes based on nanomaterials and corresponding interfaces. Chemistry An Asian Journal, 2021, 16(19): 2852–2870

[16] Song M , Tan H , Chao D L , Fan H J . Recent advances in Zn-ion batteries. Advanced Functional Materials, 2018, 28(41): 1802564

[17] Zuo S Y , Xu X J , Ji S M , Wang Z S , Liu Z B , Liu J . Cathodes for aqueous Zn-ion batteries: materials, mechanisms, and kinetics. Chemistry A European Journal, 2021, 27(3): 830–860

[18] Wang C , Cao Y , Luo Z , Li G , Xu W , Xiong C , He G , Wang Y , Li S , Liu H , Fang D . Flexible potassium vanadate nanowires on Ti fabric as a binder-free cathode for high-performance advanced lithium-ion battery. Chemical Engineering Journal, 2017, 307: 382–388

[19] Islam S , Alfaruqi M H , Putro D Y , Soundharrajan V , Sambandam B , Jo J , Park S , Lee S , Mathew V , Kim J . K⁺ intercalated V₂O₅ nanorods with exposed facets as advanced cathodes for high energy and high rate zinc-ion batteries. Journal of Materials Chemistry A, 2019, 7(35): 20335–20347

[20] Wan F , Huang S , Cao H , Niu Z . Freestanding potassium vanadate/carbon nanotube films for ultralong-life aqueous zinc-ion batteries. ACS Nano, 2020, 14(6): 6752–6760

[21] Qiu N , Yang Z M , Xue R , Wang Y , Zhu Y M , Liu W . Toward a high-performance aqueous zinc ion battery: potassium vanadate nanobelts and carbon enhanced zinc foil. Nano Letters, 2021, 21(7): 2738–2744

[22] Yang Y Q , Tang Y , Fang G Z , Shan L T , Guo J S , Zhang W Y , Wang C , Wang L B , Zhou J , Liang S Q . Li⁺ intercalated V₂O₅·nH₂O with enlarged layer spacing and fast ion diffusion as an aqueous zinc-ion battery cathode. Energy & Environmental Science, 2018, 11(11): 3157–3162

[23] Sambandam B , Soundharrajan V , Kim S , Alfaruqi M H , Jo J , Kim S , Mathew V , Sun Y K , Kim J . K₂V₆O₁₆·2.7H₂O nanorod cathode: an advanced intercalation system for high energy aqueous rechargeable Zn-ion batteries. Journal of Materials Chemistry A, 2018, 6(32): 15530–15539

[24] Baddour-Hadjean R , Thanh Nguyen Huynh L , Batyrbekuly D , Bach S , Pereira-Ramos J P . Bilayered potassium vanadate K_0.5V₂O₅ as superior cathode material for Na-ion batteries. ChemSusChem, 2019, 12(23): 5192–5198

[25] Zhang W , Tang C , Lan B , Chen L , Tang W , Zuo C , Dong S , An Q , Luo P . K_0.23V₂O₅ as a promising cathode material for rechargeable aqueous zinc ion batteries with excellent performance. Journal of Alloys and Compounds, 2020, 819: 152971

[26] Zhang X , Li X , Zhang Y , Li X , Guan Q , Wang J , Zhuang Z , Zhuang Q , Cheng X , Liu H . . Accelerated Li⁺ desolvation for diffusion booster enabling low-temperature sulfur redox kinetics via electrocatalytic carbon-grazfted-CoP porous nanosheets. Advanced Functional Materials, 2023, 33(36): 2302624

[27] Zhu Y H , Zhang Q , Yang X , Zhao E Y , Sun T , Zhang X B , Wang S , Yu X Q , Yan J M , Jiang Q . Reconstructed orthorhombic V₂O₅ polyhedra for fast ion diffusion in K-ion batteries. Chem, 2019, 5(1): 168–179

[28] Hao P F , Zhu T , Su Q , Lin J D , Cui R , Cao X X , Wang Y P , Pan A Q . Electrospun single crystalline fork-like K₂V₈O₂₁ as high-performance cathode materials for lithium-ion batteries. Frontiers in Chemistry, 2018, 6: 195

[29] Wan F , Zhang L L , Dai X , Wang X Y , Niu Z Q , Chen J . Aqueous rechargeable zinc/sodium vanadate batteries with enhanced performance from simultaneous insertion of dual carriers. Nature Communications, 2018, 9(1): 1656

[30] Hu P , Yan M Y , Zhu T , Wang X P , Wei X J , Li J T , Zhou L , Li Z H , Chen L N , Mai L Q . Zn/V₂O₅ aqueous hybrid-ion battery with high voltage platform and long cycle life. ACS Applied Materials & Interfaces, 2017, 9(49): 42717–42722

[31] Xie Z Q , Lai J W , Zhu X P , Wang Y . Green synthesis of vanadate nanobelts at room temperature for superior aqueous rechargeable zinc-ion batteries. ACS Applied Energy Materials, 2018, 1(11): 6401–6408

[32] Feng Y Q , Liu H , Liu Y , Li J Q . Tunable oxygen deficient in MoO_3x/MoO₂ heterostructure for enhanced lithium storage properties. International Journal of Energy Research, 2022, 46(5): 5789–5799

[33] Chen R , Wang Z Q , Chen Z X , Wang P J , Fang G Z , Zhou J , Tan X P , Liang S Q . Synthesis of K_0.25V₂O₅ hierarchical microspheres as a high-rate and long-cycle cathode for lithium metal batteries. Journal of Alloys and Compounds, 2019, 772: 852–860

[34] Baddour-Hadjean R , Boudaoud A , Bach S , Emery N , Pereira-Ramos J P . A comparative insight of potassium vanadates as positive electrode materials for Li batteries: influence of the long-range and local structure. Inorganic Chemistry, 2014, 53(3): 1764–1772

[35] Bach S , Boudaoud A , Emery N , Baddour-Hadjean R , Pereira-Ramos J P . K_0.5V₂O₅: a novel Li intercalation compound as positive electrode material for rechargeable lithium batteries. Electrochimica Acta, 2014, 119: 38–42

[36] Peng Z , Wei Q , Tan S , He P , Luo W , An Q , Mai L . Novel layered iron vanadate cathode for high-capacity aqueous rechargeable zinc batteries. Chemical Communications, 2018, 54(32): 4041–4044

[37] Ding Y C , Peng Y Q , Chen W Y , Niu Y J , Wu S G , Zhang X X , Hu L H . V-MOF derived porous V₂O₅ nanoplates for high performance aqueous zinc-ion battery. Applied Surface Science, 2019, 493: 368–374

[38] Singh M , Kumar P , Reddy G B . Effect of Ar, O₂, and N₂ plasma on the growth and composition of vanadium oxide nanostructured thin films. Advanced Materials Interfaces, 2018, 5(18): 1800612

[39] Cao K , Liu H , Li Y , Wang Y , Jiao L . Encapsulating sulfur in δ-MnO₂ at room temperature for Li–S battery cathode. Energy Storage Materials, 2017, 9: 78–84

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

Lu Q would like to acknowledge the financial supports from Joint Fund of Henan Province Science and Technology R&D Program (Grant No. 225200810093) and Startup Research of Henan Academy of Sciences (Grant No. 231817001). We also acknowledge financial supports from the National Natural Science Foundation of China (Grant No. 51272147), the Natural Science Foundation of Shaanxi Province (Grant No. 2015JM5208), the Graduate Innovation Found of Shaanxi University of Science and Technology, and Scientific Research Project of Chengdu Technological University (Grant No. 2023RC001). This work is also supported by the National Key R&D Program of China (Grant No. 2019YFC1520100). Feng Y acknowledge the financial supports from China Scholarship Council. The authors thank Andrea Voß (IFW Dresden) for technical support and ICP test. Beamtime allocation and support at beamline P65 of the PETRA III synchrotron (Deutsches Elektronen-Synchrotron, DESY, Hamburg, Germany) is gratefully acknowledged. Daria Mikhailova (IFW Dresden) is acknowledged for XAS measurement.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2385-5 and is accessible for authorized users.

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