Beyond point defects: a first-principles investigation of topological line defects in graphene as continuous catalytic highways for Li-S batteries

Abstract

Lithium-sulfur (Li-S) batteries have long been plagued by the shuttle effect and sluggish sulfur conversion, which limit their practical application. To address these issues, we propose and investigate several line-defect graphene configurations (including d5d7G, t5t7G, and 585G) as sulfur cathode host materials in Li-S batteries and evaluate their adsorption and catalytic potential using first-principles calculations. The results demonstrate that the continuous high-density linear defects are rich in active sites, which not only enhance the adsorption and the catalytic activity for lithium polysulfides (LiPSs), but also maintain a low barrier for Li⁺ diffusion. A qualitative correlation between the p-band center and the Gibbs free energy barrier is established, directly linking the defect topology to the catalytic activity. Comprehensive screening identifies the 585G configuration as the most promising candidate, as it exhibits the strongest polysulfide adsorption (E_a = -0.90 eV to -1.86 eV), the highest p-band center (-1.10 eV), and the lowest Gibbs free energy barrier (2.35 eV). This work provides insights into how the line-defect architectures govern the catalytic activity in graphene, offering a new design paradigm for the carbon-based sulfur hosts.

Keywords

Two-dimensional materials / first-principles calculations / lithium-sulfur batteries / line-defect graphene

References

[1] Li Q,Xia Q.Extra storage capacity in transition metal oxide lithium-ion batteries revealed by in situ magnetometry.Nat Mater2021;20:76-83

[2] Xu Z,Yang J,Nuli Y.High-voltage and intrinsically safe electrolytes for Li metal batteries.Nat Commun2024;15:9856 PMCID:PMC11564819

[3] Gui H,Cao Y.Hybridization-tuned dual-chain conjugated polythioether quinones for high-energy rechargeable magnesium batteries.Chem Sci2026;17:325-34 PMCID:PMC12603802

[4] Sun J,Chen L.Accelerating charging and elevating capacity of TiO₂ by interface space charge storage.Rare Met2025;44:5404-11

[5] Zhao Y,Zhu Y.The synergistic effect of heteronuclear diatom enhances the catalytic and adsorption ability of lithium-sulfur batteries.Appl Surf Sci2025;706:163600

[6] Zhou S,Liu S.Visualizing interfacial collective reaction behaviour of Li-S batteries.Nature2023;621:75-81

[7] Song H,Liu X.All-solid-state Li-S batteries with fast solid-solid sulfur reaction.Nature2025;637:846-53

[8] Zhou J,Tan S.Healable and conductive sulfur iodide for solid-state Li-S batteries.Nature2024;627:301-5

[9] Li J,Pan F.Engineering strategies for suppressing the shuttle effect in lithium-sulfur batteries.NanoMicro Lett2023;16:12

[10] Wang T,Ma Y,Wu Y.High-entropy materials regulating lithium polysulfides for advanced lithium-sulfur batteries.Chem Eng J2025;519:165580

[11] Zhang H,Li X.Atomically dispersed Co-Ru dimer catalyst boosts conversion of polysulfides toward high-performance lithium-sulfur batteries.Adv Mater2025;37:e2500950

[12] Zhang H,Liu R.Fe₃O₄-doped mesoporous carbon cathode with a plumber’s nightmare structure for high-performance Li-S batteries.Nat Commun2024;15:5451 PMCID:PMC11211388

[13] Liu R,Peng L.Establishing reaction networks in the 16-electron sulfur reduction reaction.Nature2024;626:98-104

[14] Cheng Q,Chen Z.Unveiling the capacity enhancement mechanism of carbon interlayers in lithium-sulfur batteries.Adv Energy Mater2025;15:2404757

[15] Saroha R,Cho SW,Park J.Polysulfide barrier comprising bismuth selenide nanocrystals well anchored within N-doped carbon microspheres for stable Li-S batteries.Energy Mater2025;5:500089

[16] Lu W,Dazon C,Pimenta V.MOF and related composites as selective functional separators and interlayers for Li-S batteries.Energy Mater2025;5:500075

[17] Xu Y,Gu F,Tian CS.Structure evolution at the gate-tunable suspended graphene-water interface.Nature2023;621:506-10

[18] Zhang J,Qian M.Optimizing electrocatalysis and domain effects of graphene on Li₂S cathodes for high-efficient-stable Li-S batteries.Small2025;21:e2409172

[19] Huangfu J,Di X.Controllable construction of active sites for catalytic conversion and spatial constraints applied to high‐performance lithium-sulfur batteries.Adv Energy Mater2025;15:2502210

[20] Tian J,Gao Q.Graphene-based nanomaterials as the cathode for lithium-sulfur batteries.Molecules2021;26:2507 PMCID:PMC8123287

[21] Klein BP,Deyerling J.One-step synthesis of graphene containing topological defects.Chem Sci2025;16:19403-13 PMCID:PMC12459200

[22] Zhang Y,Xu Y,Wang S.Design and regulation of defective electrocatalysts.Chem Soc Rev2024;53:10620-59

[23] Tiwari SK,Pandey R.Stone-wales defect in graphene.Small2023;19:e2303340

[24] Guo R,Xu W.Effect of intrinsic defects of carbon materials on the sodium storage performance.Adv Energy Mater2020;10:1903652

[25] Lv J,Liu J,Cheng Y.Interfacial charge transfer and defect engineering in the MoTe₂/graphene heterostructure for tailored carrier kinetics and nonlinear absorption.Adv Funct Materials2025;35:2505740

[26] Lu J,Sui X.In-situ construction of impurity-free defective graphene nanosheets as high-performance lithium-ion battery anodes via electron beam irradiation.Energy2026;344:139752

[27] Zhang N,Gao C.Rapid electron/ion transport in a 3D holey graphene aerogel framework toward high-loading Na-Se batteries.J Mater Chem A2026;14:18769-78

[28] Yi Z,Huo L.New insights into Li₂S₂/Li₂S adsorption on the graphene bearing single vacancy: a DFT study.Appl Surf Sci2020;503:144446

[29] Su F,Xie L.Critical role of surface defects in the controllable deposition of Li₂S on graphene: from molecule to crystallite.ACS Appl Mater Interfaces2020;12:53435-45

[30] Jia Y,Du A.Defect graphene as a trifunctional catalyst for electrochemical reactions.Adv Mater2016;28:9532-8

[31] Santos RMD,Galvão DS.Tuning penta-graphene electronic properties through engineered line defects.Sci Rep2020;10:8014 PMCID:PMC7229116

[32] Bhatt MD,Kim G.Various defects in graphene: a review.RSC Adv2022;12:21520-47 PMCID:PMC9347212

[33] Duman Ş,Libisch F.Line defects as valley filters in graphene.Phys Status Solidi (b)2025;262:2400418

[34] Zhang W,Zhang P,Jiang Y.Molecular dynamics study on the relaxation properties of bilayered graphene with defects.Bull Mater Sci2017;40:1255-61

[35] Gillen R.Family behavior and Dirac bands in armchair nanoribbons with 4-8 defect lines.J Phys Condens Matter2024;36

[36] Wang J,Zou G.Crystal-defect engineering of electrode materials for energy storage and conversion.Mater Today Nano2023;22:100336

[37] Wu B,Chen X.Structural modulation of nanographenes enabled by defects, size and doping for oxygen reduction reaction.Angew Chem Int Ed2025;64:e202415071

[38] Botello-Méndez AR,Terrones M,Charlier JC.One-dimensional extended lines of divacancy defects in graphene.Nanoscale2011;3:2868-72

[39] Khossossi N,Ainane A.Recent progress of defect chemistry on 2D materials for advanced battery anodes.Chem Asian J2020;15:3390-404 PMCID:PMC7702035

[40] Wang V,Liu J,Geng W.VASPKIT: a user-friendly interface facilitating high-throughput computing and analysis using VASP code.Comput Phys Commun2021;267:108033

[41] Rafiu R,Saikot MSH.Comprehensive first-principles analysis and device simulations of vacancy-ordered D₂CeX₆ double perovskites for high-efficiency lead-free solar cells.RSC Adv2025;15:44711-48

[42] Cabrera-Tinoco H,Valencia-Bedregal R.Pyridinic-N Coordination effect on the adsorption and activation of CO₂ by single vacancy iron-doped graphene.Langmuir2024;40:6703-17

[43] Abbasi R,Faez R.The geometric structure and electronic properties of van der Waals C-borophane/h-BC6N/Graphene heterostructure: a first-principles study.Physica B2025;699:416692

[44] Shi X,Nie C.SnHPO₄: a layered Tin(II) phosphate with enhanced birefringence.Inorg Chem2025;64:2127-32

[45] Varrassi L,Flage-larsen E.Automated workflow for accurate high-throughput GW calculations using plane waves.npj Comput Mater2025;11:1833

[46] González JE,Lima MP.Decoding Van der Waals impact on chirality transfer in perovskite structures: density functional theory insights.J Chem Inf Model2024;64:1306-18

[47] Tran TN,Hieu NH.Electric field enhances the electronic and diffusion properties of penta-graphene nanoribbon anodes in lithium-ion batteries.RSC Adv2024;14:33524-35 PMCID:PMC11495402

[48] He Q,Wang H,Liao X.Oxygen defects boost polysulfides immobilization and catalytic conversion: first-principles computational characterization and experimental design.Nano Res2020;13:2299-307

[49] Zhang H,Wang Y,Dai Y.Borophosphene: a potential anchoring material for lithium-sulfur batteries.Appl Surf Sci2021;562:150157

[50] Podlivaev A.Out-of-plane path of the Stone-Wales transformation in graphene.Phys Lett A2015;379:1757-61

[51] Chen J,Lin D.Anisotropic growth mechanism of epitaxial graphene on 4H-SiC.Appl Surf Sci2025;690:162596

[52] Li Y,Cong Y.Decoration of defective graphene with MoS₂ enabling enhanced anchoring and catalytic conversion of polysulfides for lithium-sulfur batteries: a first-principles study.Phys Chem Chem Phys2022;24:29214-22

[53] Lahiri J,Bozkurt P,Batzill M.An extended defect in graphene as a metallic wire.Nat Nanotechnol2010;5:326-9

[54] Kim K,Johnson RW.Selective metal deposition at graphene line defects by atomic layer deposition.Nat Commun2014;5:4781

[55] Chen J,Alem N.Controlled growth of a line defect in graphene and implications for gate-tunable valley filtering.Phys Rev B2014;89

[56] Guo H,Zheng Z,Ng AMC.Defect-enhanced performance of a 3D graphene anode in a lithium-ion battery.Nanotechnology2017;28:505402

[57] Dong C,Lian C.Scalable solid-phase synthesis of defect-rich graphene for oxygen reduction electrocatalysis.Green Energy Environ2023;8:224-32

[58] Sinthika S,Nimma Elizabeth R,Thapa R.Understanding the role of lithium bonds in doped graphene nanoribbons as cathode hosts for Li‐S batteries: a first‐principles study.Int J Energy Res2022;46:4405-16

[59] Guan L,Li L.Intrinsic defect-rich hierarchically porous carbon architectures enabling enhanced capture and catalytic conversion of polysulfides.ACS Nano2020;14:6222-31

[60] Chen H,Zheng M.Catalytic materials for lithium-sulfur batteries: mechanisms, design strategies and future perspective.Mater Today2022;52:364-88

[61] Ji L,Xue J.Flexible titanium nitride‐based membrane reactor for S₈/Li₂S and dendrite regulation in lithium‐sulfur batteries.Adv Energy Mater2025;15:2404738

[62] Jin L,Zhao H,Li Y.Unfolding the structure-property relationships of Li₂S anchoring on two-dimensional materials with high-throughput calculations and machine learning.J Energy Chem2023;82:31-9

[63] Zhou G,Wang T.Theoretical calculation guided design of single-atom catalysts toward fast kinetic and long-life Li-S batteries.Nano Lett2020;20:1252-61

[64] Zhou J,Zhu L.Deciphering the modulation essence of p bands in Co-based compounds on Li-S chemistry.Joule2018;2:2681-93

[65] Zhao Z,Li H.Synergetic effect of spatially separated dual co-catalyst for accelerating multiple conversion reaction in advanced lithium sulfur batteries.Nano Energy2021;81:105621

[66] Ma XX,Bai YK,Zhang R.The defect chemistry of carbon frameworks for regulating the lithium nucleation and growth behaviors in lithium metal anodes.Small2021;17:e2007142