Construction of multidimensional Bi@MoP/NC composite as advanced anode materials for sodium ion batteries

Abstract

A new flower-like Bi@MoP/NC composite is prepared using a two-step in situ polymerization process, followed by a phosphorization reaction. In this unique architecture, the MoP nanoparticles are embedded in an N-doped carbon layer and coated on the surface of the Bi core to form a flower-like structure. Similar to this MoP/C coating, MoP facilitates rapid ion diffusion and enhances the mechanical flexibility of the carbon layer. Therefore, the MoP/C composite layer can effectively improve the sodium storage reaction kinetics and buffer the volume change of Bi during sodiation/desodiation. Moreover, the flower-like structure can provide fast sodium ion diffusion channels and dissipate the inner stress during the sodiation/desodiation process. Accordingly, the Bi@MoP/NC composite shows outstanding sodium storage performance, including excellent long-term cycling stability (299.6 mAh g⁻¹ after 1500 cycles at 2.0 A g⁻¹) and superior rate capability (288.6 mAh g⁻¹ even at 10.0 A g⁻¹).

Keywords

sodium ion batteries / anode materials / flower-like structure / reaction kinetics

References

[1] Wang J, Li J, Zhang Q, et al.. Rational-designed high-performance anode materials for sodium-ion batteries: A review [J]. Advanced Composites and Hybrid Materials, 2024, 7(4): 119

[2] Zhou J, Reddy R C K, Zhong A, et al.. Metal–organic framework-based materials for advanced sodium storage: Development and anticipation [J]. Advanced Materials, 2024, 36(16): 2312471

[3] Zhou Z, Qian Y, Chen X, et al.. Challenges and strategies toward manganese hexacyanoferrate for high-performance sodium-ion batteries [J]. Advanced Functional Materials, 2024, 34(39): 2404938

[4] Zhang M, Wang S, Zhu J, et al.. Optimized heterostructures by preferred crystal orientation for ultrafast sodium storage [J]. Advanced Functional Materials, 2025, 35(29): 2500165

[5] Zhang M, Zhu J, Li Q, et al.. Effective stress dissipation by multi-dimensional architecture engineering for ultrafast and ultralong sodium storage [J]. Journal of Energy Chemistry, 2025, 101: 619-629

[6] Xu Z, Yoon G, Park K Y, et al.. Tailoring sodium intercalation in graphite for high energy and power sodium ion batteries [J]. Nature Communications, 2019, 10: 2598

[7] Li Y, Zhong X, Wu X, et al.. Bi/C nanosheet microspheres with an open pore structure as anodes for sodium ion batteries with high capacity, excellent rate performance and long cycle life [J]. Journal of Materials Chemistry A, 2021, 9(39): 22364-22372

[8] Wu X, Li Z, Feng W, et al.. Insights into electrolyte-induced temporal and spatial evolution of an ultrafast-charging bi-based anode for sodium-ion batteries [J]. Energy Storage Materials, 2024, 66: 103219

[9] Chen J, Liao S, Zhao J, et al.. operando magnetometry decodes fast sodium storage: Biomass-derived Bi@NSC anodes with triple-phase kinetics [J]. Chemical Engineering Journal, 2025, 520: 166439

[10] Chen L, He X, Chen H, et al.. N-Doped carbon encapsulating Bi nanoparticles derived from metal–organic frameworks for high-performance sodium-ion batteries [J]. Journal of Materials Chemistry A, 2021, 9(38): 22048-22055

[11] Pu B, Liu Y, Bai J, et al.. Iodine-ion-assisted galvanic replacement synthesis of bismuth nanotubes for ultrafast and ultrastable sodium storage [J]. ACS Nano, 2022, 16(11): 18746-18756

[12] Chen J, Fan X, Ji X, et al.. Intercalation of Bi nanoparticles into graphite results in an ultra-fast and ultrastable anode material for sodium-ion batteries [J]. Energy & Environmental Science, 2018, 11(5): 1218-1225

[13] Bai J, Liu Y, Pu B, et al.. Bio-inspired design of a self-supported bismuth microforest for high performance sodium storage [J]. Journal of Materials Chemistry A, 2024, 12(19): 11691-11700

[14] Yin H, Li Q, Cao M, et al.. Nanosized-bismuth-embedded 1D carbon nanofibers as highperformance anodes for lithium-ion and sodium-ion batteries [J]. Nano Research, 2017, 10(6): 2156-2167

[15] Lin Z, Qiu X, Zu X, et al.. Ultra-high-rate Bi anode encapsulated in 3D lignin-derived carbon framework for sodium-ion hybrid capacitors [J]. Rare Metals, 2024, 43(3): 1037-1047

[16] Zhang J, Li Y, Liu Y, et al.. Synergistic sodium storage in bismuth-loaded polycellular carbon spheres: High diffusion kinetics and stability [J]. Journal of Materials Chemistry A, 2025, 13(26): 20597-20609

[17] Zou X, Ye S, Ou C, et al.. Double-layer carbon coated on the micrometer bismuth by photothermal effect as anode for high-rate sodium-ion batteries [J]. Energy Storage Materials, 2024, 71: 103573

[18] Yan Z, Huang Z, Zhou H, et al.. Facile fabrication of MoP nanodots embedded in porous carbon as excellent anode material for potassium-ion batteries [J]. Journal of Energy Chemistry, 2021, 54: 571-578

[19] Wang Z, Yi Y, Zhao C, et al.. In situ electrochemical construction of bismuth nanoparticles: Harnessing intrinsic favorable heterointerfaces and structural confinement to augment sodium storage [J]. Advanced Functional Materials, 2025, 35(35): 2425694

[20] He Z, Han T, Liu W, et al.. 3D printed sodium-ion batteries via ternary anode design affording hybrid ion storage mechanism [J]. Advanced Energy Materials, 2024, 14(11): 2303296

[21] Huang Z, Hou H, Wang C, et al.. Molybdenum phosphide: A conversion-type anode for ultralong-life sodium-ion batteries [J]. Chemistry of Materials, 2017, 29(17): 7313-7322

[22] Pan Q, Zhang M, Zhang L, et al.. FeSe₂@C microrods as a superior long-life and high-rate anode for sodium ion batteries [J]. ACS Nano, 2020, 14(12): 17683-17692

[23] Pan Q, Zhang Q, Zheng F, et al.. Construction of MoS₂/C hierarchical tubular heterostructures for high-performance sodium ion batteries [J]. ACS Nano, 2018, 12(12): 12578-12586

[24] Ou X, Xiao Z, Zhang J, et al.. Enhancing the rapid Na⁺-storage performance via electron/ion bridges through GeS₂/graphene heterojunction [J]. ACS Nano, 2020, 14(10): 13952-13963

[25] Cao L, Gao X, Zhang B, et al.. Bimetallic sulfide Sb₂S₃@FeS₂ hollow nanorods as high-performance anode materials for sodium-ion batteries [J]. ACS Nano, 2020, 14(3): 3610-3620

[26] Wang C, Wang D, Ma X, et al.. Isotropy-induced stress relaxation and strong-tolerance for high-rate and long-duration sodium storage by amorphous structure engineering [J]. Advanced Functional Materials, 2022, 32(39): 2204687

[27] Zhang Y, Liu L, Zhao L, et al.. Sandwichlike CoMoP2/MoP heterostructures coupling N, P Co-doped carbon nanosheets as advanced anodes for high-performance lithium-ion batteries [J]. Advanced Composites and Hybrid Materials, 2022, 5(3): 2601-2610

[28] Chen D, Chen C, Yu H, et al.. Formation of N-doped carbon nanofibers decorated with MoP nanoflakes for dendrite-free lithium metal anode [J]. Advanced Functional Materials, 2024, 34(38): 2402951

[29] Zhang H, Bai Y, Li J, et al.. Ternary molybdenum oxyphosphide based hybrid nanotubes boosts sodium-ion diffusion kinetics enabled through oxygendeficient modulation [J]. Nano Energy, 2025, 135: 110625

[30] Yi Z, Liu Y, Li Y, et al.. Flexible membrane consisting of MoP ultrafine nanoparticles highly distributed inside N and P codoped carbon nanofibers as highperformance anode for potassium-ion batteries [J]. Small, 2020, 16(2): 1905301

[31] Wei S, Yang Y, Chen J, et al.. A fastcharging and ultra-stable sodium-ion battery anode enabled by N-doped Bi/BiOCl in a carbon framework [J]. Advanced Energy Materials, 2024, 14(37): 2401825

[32] Zhong X, Chen Y, Zhang W, et al.. Facile synthesis of a honeycomb-like nano-Bi/N-doped C composite as an anode for sodium-ion batteries with superb cycle stability [J]. ACS Sustainable Chemistry & Engineering, 2022, 10(27): 8856-8862

[33] Wang X, Yang M, Zeng T, et al.. Unveiling the potential of Bi/FeS-G nanocomposites: A pioneering approach to dual-functional anodes for highperformance lithium-ion and sodium-ion batteries [J]. Industrial & Engineering Chemistry Research, 2025, 64(3): 1825-1836

[34] Zhou S, Sun Z, Zhuang Z, et al.. Facile and scalable synthesis of bismuth oxyhalide nanosheets anodes for fast and durable sodium-ion storage [J]. Science China Materials, 2025, 68(3): 868-878

[35] Liu Y, Liu X, Wang X, et al.. Synergistic bimetallic effects of BiSb anodes enable long-stable sodium storage [J]. Advanced Functional Materials, 2025, 35(6): 2415092

[36] Tan C, Li Y, He W, et al.. TiO₂-coated MoP/phosphorus doped carbon nanorods for ultralong-life sodium ion batteries with high capacity [J]. Nanoscale, 2023, 15(30): 12686-12693

[37] Qin H, Zhang B, Wang C, et al.. Engineering the pin effect through selective doping and architecture design towards high-rate sodium storage performance [J]. Energy Storage Materials, 2022, 52: 189-200

[38] Zhang B, Xu B, Xiao Z, et al.. Inner-stressdissipative, rapid self-healing core-shell sulfide quantum dots for remarkable potassium-ion storage [J]. Energy Storage Materials, 2023, 56: 96-107

[39] Li J, Yu H, Zhao Y, et al.. Stress dissipation driven by multi-interface built-In electric fields and desert-rose-like structure for ultrafast and superior longterm sodium ion storage [J]. Angewandte Chemie International Edition, 2024, 63(12): e202318000

[40] Su Y, Johannessen B, Zhang S, et al.. Soft–rigid heterostructures with functional cation vacancies for fastcharging and high-capacity sodium storage [J]. Advanced Materials, 2023, 35(40): 2305149

[41] Rützler A, Büttner J, Oechsler J, et al.. Mesoporous N-doped carbon nanospheres as anode material for sodium ion batteries with high rate capability and superior power densities [J]. Advanced Functional Materials, 2024, 34(41): 2401188

[42] Hou S, Xie F, Wang X, et al.. Heterojunction-structured Ni_0.85Se/CoSe nanoparticles anchored on holey graphene for performance-enhanced sodium-ion batteries [J]. Journal of Colloid and Interface Science, 2025, 680: 334-344

[43] Wang S, Pang X, Huang D, et al.. Construction of Co9S8@C-MoS₂ heterostructure for fast charging and superior long-term cycling performance of sodium ion batteries [J]. Journal of Colloid and Interface Science, 2025, 680: 398-406

[44] Yu L, Li Z, Cai W, et al.. Bimetallic sulfide Sb₂S₃/FeS₂ heterostructure anchored in a carbon skeleton for fast and stable sodium storage [J]. Small, 2024, 20(46): 2404059

[45] Jiang Y, Li A, Pan Q, et al.. Yolk-shell FeS@N-doped carbon nanosphere as superior anode materials for sodium-ion batteries [J]. Journal of Colloid and Interface Science, 2024, 669: 137-145

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