In-situ construction of artificial interface layer using sodiophilic Bi₂S₃ nanowires for dendritic-free sodium-metal batteries

Abstract

Sodium metal anodes possess low redox potential and high theoretical capacity, yet they face the challenges of uncontrolled dendritic growth and unstable solid-electrolyte interphase (SEI). Herein, we report a straightforward synthesis of Bi₂S₃ nanowires, which are engineered as a sodiophilic artificial interface layer to facilitate uniform and dendrite-free Na plating-stripping. Density functional theory (DFT) calculations and experimental characterizations confirm that Bi₂S₃ with high Na⁺ adsorption energy undergoes a sequential in-situ conversion-alloying reaction with Na⁺, forming sodiophilic Na₃Bi alloy nucleation sites and a highly Na⁺-conductive Na₂S matrix. This composite interface synergistically lowers the Na nucleation energy barrier and accelerates Na⁺ diffusion kinetics, effectively suppressing dendritic Na growth. Besides, Bi₂S₃ displays a stronger affinity of PF₆ anions, facilitating the formation of NaF-rich SEI film with highly stable interface. Benefiting from these advantages, the Na/Bi₂S₃@Cu symmetric cell displays an extraordinary cycling lifespan of over 2,500 h at 2 mA cm^-2 and 2 mAh cm^-2, accompanied by an ultralow overpotential of 15 mV and a negligible interfacial resistance of 7.8 Ω even after 1,350 cycles. When paired with a commercial Na₃V₂(PO₄)₃/C cathode, the Na/Bi₂S₃ anode delivers superior long-term cycling stability and high-rate capability with capacity retention of 70% after 2,500 cycles at 10 C. This work provides an effective strategy for constructing stable sodiophilic interfaces for sodium metal anodes, which offers new fundamental insights for achieving high-performance sodium metal batteries.

Keywords

Sodium metal anode / sodiophilic Bi₂S₃ nanowires / artificial interface layer / Na⁺ diffusion kinetics / dendrite-free plating

References

[1] Turner JM.The matter of a clean energy future.Science2022;376:1361-1361

[2] Lukatskaya MR,Gogotsi Y.Multidimensional materials and device architectures for future hybrid energy storage.Nat Commun2016;7:12647 PMCID:PMC5023960

[3] Yang Z,Kintner-Meyer MC.Electrochemical energy storage for green grid.Chem Rev2011;111:3577-613

[4] Xu K.Electrolytes and interphases in Li-ion batteries and beyond.Chem Rev2014;114:11503-618

[5] Quilty CD,Li W.Electron and ion transport in lithium and lithium-ion battery negative and positive composite electrodes.Chem Rev2023:1327-63

[6] Wang H,Wu Q.Encapsulating silica/antimony into porous electrospun carbon nanofibers with robust structure stability for high-efficiency lithium storage.ACS Nano2018;12:3406-16

[7] Goodenough JB.Challenges for rechargeable Li batteries.Chem Mater2010;22:587-603

[8] Ruan J,Li Q.Current collector interphase design for high-energy and stable anode-less sodium batteries.Nat Sustain2025;8:530-41

[9] Chai W,Wang Z.HKUST-1 derived CuSx@C nanocomposites with TiO₂ coating and rich sulfur vacancies for excellent high-rate long-life sodium-ion batteries.J Power Sources2026;665:239009

[10] Liu P,Sun Z,Jiao L.Sodiophilic substrate induces NaF-rich solid electrolyte interface for dendrite-free sodium metal anode.Adv Mater2024;36:e2406058

[11] Yu Y,Yang Y.Highly sodiophilic heterostructures toward dendrite-free sodium metal batteries.Adv Funct Mater2024;34:2401914

[12] Rui X,Xu S.A low-temperature sodium-ion full battery: superb kinetics and cycling stability.Adv Funct Mater2021;31:2009458

[13] Huang F,Fang G.In-depth understanding of interfacial Na⁺ Behaviors in sodium metal anode: migration, desolvation, and deposition.Adv Mater2024;36:e2405310

[14] Gao W,Tan X.Sodiophilic design for sodium-metal batteries: progress and prospects.Energy Environ Sci2025;18:1630-57

[15] Shi D,Yang Y.NaBi_x/NaV_yO_z hybrid interfacial layer enables stable and dendrite-free sodium anodes.Small2024;20:e2402206

[16] Damircheli R,Ferrari VC.Highly uniform nitride-rich artificial solid electrolyte interphase enabled by nano-silicon nitride for superior performance in advanced sodium metal batteries.J Mater Chem A2024;12:31949-58

[17] Moorthy M,An SY,Han D.Recent trends in artificial SEI layers for controlling dendrite formation and enhancing cycle life: toward stable and durable sodium metal batteries.Small2025;21:e2502974 PMCID:PMC12393032

[18] Yin H,Wang Y.Artificial solid electrolyte interphase for sodium metal batteries: mechanistic insights and design strategies.Energy Environ Mater2025;8:e70077

[19] Sun H,Xu X.A safe and non-flammable sodium metal battery based on an ionic liquid electrolyte.Nat Commun2019;10:3302 PMCID:PMC6656735

[20] Wu Y,Ni J.Liquid metal-modified 3D Cu foam for dendrite-free sodium plating.Small2024;20:e2405357

[21] Chen R,He Q.Sb₂S₃ nanorod hierarchies enabling homogeneous sodium deposition for dendrite-free sodium-metal batteries.ACS Appl Energy Mater2022;5:10952-60

[22] Hu C,Zhang Y.Room-temperature all-solid-state sodium battery based on bulk interfacial superionic conductor.Nano Lett2021;21:10354-60

[23] Chen C,Tang Y.Emerging solutions to enable the efficient use of sodium metal anodes: progress and perspectives.Adv Funct Mater2024;34:2310833

[24] Chen Q,Hou Z.Building an artificial solid electrolyte interphase with high-uniformity and fast ion diffusion for ultralong-life sodium metal anodes.J Mater Chem A2020;8:16232-7

[25] Lu X,Shen S.Spatially confined in situ formed sodiophilic-conductive network for high-performance sodium metal batteries.Nano Lett2024;24:5490-7

[26] Xu P,Liu Z,Liang S.In situ construction of NaF-rich solid electrolyte interphase with metallic Ce sites for stable anode-free sodium metal batteries.Angew Chem Int Ed2025;64:e202515566

[27] Li Z,Tian W.3D Sb-based composite framework with gradient sodiophilicity for ultrastable sodium metal anodes.Adv Funct Mater2024;34:2301554

[28] Li Z,Lin G.Na (100)-textured electrode embedded with Sb-doped SnO₂ nanoparticles for dendrite-free sodium metal batteries.Adv Energy Mater2024;14:2402284

[29] Yang G,Sun C.High-performance sodium metal batteries with sodium-bismuth alloy anode.ACS Appl Energy Mater2020;3:12607-12

[30] Su D,Wang G.Bismuth: a new anode for the Na-ion battery.Nano Energy2015;12:88-95

[31] Zhou S,Zhang J.Single-atom engineering for synergistic nucleation and interfacial regulation enabling durable anode-free sodium metal batteries.Adv Mater2026;38:e13154

[32] Kyono A.Structural variations induced by difference of the inert pair effect in the stibnite-bismuthinite solid solution series (Sb,Bi)₂S₃.Am Mineral2004;89:932-40

[33] Li Y,Li B.Co-nucleus 1D/2D heterostructures with Bi₂S₃ nanowire and MoS₂ monolayer: one-step growth and defect-induced formation mechanism.ACS Nano2016;10:8938-46

[34] Yu H,Zhang J.Coordination regulation strategy in fabricating Bi₂S₃@CNFs composites with uniform dispersion for robust sodium storage.Inorg Chem2024;63:21441-9

[35] Yuan M,Xu T.Unlocking the ultrafast deposition kinetics within Bi-tailored core-shell structured carbon nanofibers for highly efficient and ultrastable sodium metal batteries.Angew Chem Int Ed2025;64:e202417930

[36] Zhu X,Wang W.Stable sodium metal anodes enabled by an in-situ generated mixed-ion/electron-conducting interface.Chem Eng J2022;446:136917

[37] Ma M,Yan Z.In situ synthesis of a bismuth layer on a sodium metal anode for fast interfacial transport in sodium-oxygen batteries.Batteries Supercaps2019;2:663-7

[38] Moorthy M,Ganesan BK.Ultra-high areal capacity, ultra-long life, dendrite-free sodium metal anode enabled by antimony-based Na-ion conducting artificial SEI layers.Chem Eng J2024;498:155234

[39] Dai J,Zhang R.Co-sputtering strategy to construct robust sodiophilic interfaces for anode-less sodium metal batteries.Chem Commun2024;60:11120-3

[40] Arab J,Kannojia HK,Dixit P.Fabrication of multiple through-holes in non-conductive materials by electrochemical discharge machining for RF MEMS packaging.J Mater Process Technol2019;271:542-53

[41] Sun B,Zhang J.Dendrite-free sodium-metal anodes for high-energy sodium-metal batteries.Adv Mater2018;30:1801334

[42] He G,Zhang T.Localized solvent-anchored carboxylate ester electrolyte enables wide temperature and fast charging sodium metal batteries.Adv Mater2026;38:e23324

[43] Zhang W,Sun G.Sodiophilic interface induces a NaF-rich solid electrolyte interface for stable sodium-metal batteries under harsh conditions.Nano Lett2025;25:6092-100