Li_xVS_y nanocomposite electrodes for high-energy carbon-additive-free all-solid-state lithium-sulfur batteries

Abstract

All-solid-state (ASS) lithium-sulfur batteries are promising power sources with the potential for high capacity and safety. Lithium metal polysulfide cathodes can address issues arising from the low electronic conductivity of Li₂S and S. This study synthesized lithium vanadium polysulfides (Li_xVS_y) by the mechanochemical treatment of Li₂S and V₂S₃. The Li_xVS_ysystem contains nanocomposites of Li₂S and LiVS₂ in an amorphous matrix; lithiation and delithiation occur in both Li₂S and LiVS₂ during charging and discharging. LiVS₂ enhances the electronic conductivity of Li_xVS_y (~10^-1-10^-2 S cm^-1) and the reversibility of charge-discharge reactions because of its high electronic conductivity and layered structure. Therefore, ASS batteries with Li_xVS_y show high capacity (~650 mAh g^-1), even without conductive additives. Here, ASS full cells with high loading assembled using a composite cathode comprising Li₈VS_5.5 and a solid electrolyte in a 80:20 (wt.%) ratio (33 mg cm^-2) and a composite Si anode (10.4 mg cm^-2) exhibited a high areal capacity of 15 mAh cm^-2, resulting in calculation of high energy densities of 853 Wh L^-1 and 515 Wh kg^-1 when assuming the cells were enlarged and stacked. This study is expected to expedite research on the development of high-performance ASS batteries.

Keywords

Lithium-vanadium polysulfide cathodes / all-solid-state lithium-sulfur batteries / sulfide solid electrolytes / high energy density / nanocomposites

References

[1] Ji X.Advances in Li-S batteries.J Mater Chem2010;20:9821

[2] Manthiram A,Chung SH,Su YS.Rechargeable lithium-sulfur batteries.Chem Rev2014;114:11751-87

[3] Yamin H,Penciner J,Peled E.Lithium sulfur battery - oxidation reduction-mechanisms of polysulfides in Thf solutions.J Electrochem Soc1988;135:1045-8

[4] Shim J,Cairns EJ.The lithium/sulfur rechargeable cell: effects of electrode composition and solvent on cell performance.J Electrochem Soc2002;149:A1321

[5] Sakuda A,Tatsumisago M.Sulfide solid electrolyte with favorable mechanical property for all-solid-state lithium battery.Sci Rep2013;3:2261 PMCID:PMC3719077

[6] Fujita Y,Asakura T.Dynamic volume change of Li₂S-based active material and the influence of stacking pressure on capacity in all-solid-state batteries.Chem Mater2024;36:7533-40

[7] Kamaya N,Yamakawa Y.A lithium superionic conductor.Nat Mater2011;10:682-6

[8] Kato Y,Saito T.High-power all-solid-state batteries using sulfide superionic conductors.Nat Energy2016;1:201630

[9] Li Y,Kim H.A lithium superionic conductor for millimeter-thick battery electrode.Science2023;381:50-3

[10] Boulineau S,Tarascon J.Mechanochemical synthesis of Li-argyrodite Li₆PS₅X (X = Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application.Solid State Ion2012;221:1-5

[11] Yang X,Sun X.Towards high-performance solid-state Li-S batteries: from fundamental understanding to engineering design.Chem Soc Rev2020;49:2140-95

[12] Zhang W,Culver SP.The detrimental effects of carbon additives in Li₁₀GeP₂S₁₂-based solid-state batteries.ACS Appl Mater Interfaces2017;9:35888-96

[13] Strauss F,Maibach J.Influence of electronically conductive additives on the cycling performance of argyrodite-based all-solid-state batteries.RSC Adv2020;10:1114-9 PMCID:PMC9046990

[14] Walther F,Schneider Y.Influence of carbon additives on the decomposition pathways in cathodes of lithium thiophosphate-based all-solid-state batteries.Chem Mater2020;32:6123-36

[15] Fang R,Li Y,Goodenough JB.Achieving stable all-solid-state lithium-metal batteries by tuning the cathode-electrolyte interface and ionic/electronic transport within the cathode.Mater Today2023;64:52-60

[16] Balach J,Jaumann T.Metal-based nanostructured materials for advanced lithium-sulfur batteries.J Mater Chem A2018;6:23127-68

[17] Li X,Xiao B,Liang J.Inorganic polysulfide chemistries for better energy storage systems.Acc Chem Res2023;56:3547-57

[18] Sakuda A.Metal polysulfides as high capacity electrode active materials - toward superior secondary batteries based on sulfur chemistry.Electrochemistry2023;91:102003

[19] Kawasaki Y,Ayama T.Synthesis and electrochemical properties of Li₃CuS₂ as a positive electrode material for all-solid-state batteries.ACS Appl Energy Mater2021;4:20-4

[20] Otoyama M,Taguchi N,Sakaebe H.Mechanochemical synthesis and electrochemical properties of Li_xVS_y positive electrodes for all-solid-state batteries.ECS Adv2023;2:010501

[21] Ji Q,Wang J.Metallic vanadium disulfide nanosheets as a platform material for multifunctional electrode applications.Nano Lett2017;17:4908-16

[22] Cai L,Mwizerwa JP.Highly crystalline layered VS₂ nanosheets for all-solid-state lithium batteries with enhanced electrochemical performances.ACS Appl Mater Interfaces2018;10:10053-63

[23] Xu S,Zhou L,Kochetkov I.A high capacity all solid-state Li-sulfur battery enabled by conversion-intercalation hybrid cathode architecture.Adv Funct Mater2021;31:2004239

[24] Shigedomi T,Kishi T.Li₂S-V₂S₃ -LiI bifunctional material as the positive electrode in the all-solid-state Li/S battery.Chem Mater2022;34:9745-52

[25] Kwok CY,Kochetkov I,Nazar LF.High-performance all-solid-state Li₂S batteries using an interfacial redox mediator.Energy Environ Sci2023;16:610-8

[26] Izumi F.Three-dimensional visualization in powder diffraction.Solid State Phenomen2007;130:15-20

[27] Nakanishi K,Ohta T.XAFS measurements under atmospheric pressure in the soft X-ray region.Aip Conf Proc2010;1234:931-4

[28] Kiguchi M,Matsumura D,Ohta T.Interface structure of alkali-halide heteroepitaxial films studied by X-ray-absorption fine structure.Phys Rev B1999;60:16205-10

[29] Han F,Fan X.High-performance all-solid-state lithium-sulfur battery enabled by a mixed-conductive Li₂S nanocomposite.Nano Lett2016;16:4521-7

[30] Gamo H,Matsuda A.Understanding decomposition of electrolytes in all-solid-state lithium-sulfur batteries.Chem Mater2022;34:10952-63

[31] Kim JT,Nie HY.Manipulating Li₂S₂/Li₂S mixed discharge products of all-solid-state lithium sulfur batteries for improved cycle life.Nat Commun2023;14:6404 PMCID:PMC10570351

[32] Sun Z,Lv N.Insights on the properties of the O-doped argyrodite sulfide solid electrolytes (Li₆PS_5-xClO_x, x=0-1).ACS Appl Mater Interfaces2021;13:54924-35

[33] Murphy DW,Di Salvo FJ.Preparation and properties of LixVS2 (0 .ltoreq. x .ltoreq. 1).Inorg Chem1977;16:3027-31