Redox-Active Ligand-Stabilized Lithium Iron Phosphate Nanoparticles for High-Performance Lithium-Ion Battery Cathode with High Capacities and Long-Term Stability
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Abstract
Abstract Developing cathodes that simultaneously deliver high capacity, superior rate capability, and long-term cycling stability remains a major challenge in lithium-ion batteries. Here, we report a high-performance textile cathode constructed via interfacial interaction-mediated assembly of high-energy porphyrin (PP) ligand-stabilized LiFePO 4 nanoparticles (LFP NPs). For this, 19 nm LFP NPs with olivine-type intercalation mechanism were covalently integrated with amine-functionalized PP to enable multi-electron redox activity, followed by encapsulation with multi-walled carbon nanotube (MWCNT) multilayers. Subsequent thermal annealing transformed the MWCNT layers into a covalently cross-linked conductive network. As a result, the textile cathode delivers an unprecedented specific capacity of ~260 mAh g −1 at ~0.1 C, excellent rate capability, and retains over 93% of its initial capacity after 2,000 cycles at 1 C with nearly 100% Coulombic efficiency. This work highlights interfacial interaction-mediated ligand assembly as a powerful strategy for next-generation high-capacity and durable cathodes.
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1. D. Liu, G. Cao, Engineering nanostructured electrodes and fabrication of film electrodes for efficient lithium ion intercalation. Energy Environ. Sci. 3(9), 1218–1237 (2010). https://doi.org/10.1039/B922656G10.1039/B922656G ↗
2. A. Manthiram, A reflection on lithium-ion battery cathode chemistry. Nat. Commun. 11(1), 1550 (2020). https://doi.org/10.1038/s41467-020-15355-010.1038/s41467-020-15355-0 ↗
3. G.G. Eshetu, H. Zhang, X. Judez, H. Adenusi, M. Armand et al., Production of high-energy Li-ion batteries comprising silicon-containing anodes and insertion-type cathodes. Nat. Commun. 12, 5459 (2021). https://doi.org/10.1038/s41467-021-25334-810.1038/s41467-021-25334-8 ↗
4. B. Lung-Hao Hu, F.-Y. Wu, C.-T. Lin, A.N. Khlobystov, L.-J. Li, Graphene-modified LiFePO4 cathode for lithium ion battery beyond theoretical capacity. Nat. Commun. 4, 1687 (2013). https://doi.org/10.1038/ncomms270510.1038/ncomms2705 ↗
5. T. Lai, L. Wang, Z. Liu, A.M. Bhayo, Y. Wang et al., Tackling challenges and exploring opportunities in cathode binder innovation. Nano-Micro Lett. 18(1), 9 (2025). https://doi.org/10.1007/s40820-025-01848-410.1007/s40820-025-01848-4 ↗
6. Y. Li, S. Yang, C. Li, W. Chen, W. Zhang et al., Constructing an interface layer with external resistance internal conduction on NCM cathode for improved stability and ion kinetics in lithium-ion batteries. Chem. Eng. J. 523, 168522 (2025). https://doi.org/10.1016/j.cej.2025.16852210.1016/j.cej.2025.168522 ↗
7. X. Zhang, T. Wu, J. Jian, S. Lin, D. Sun et al., Dual modification strategy for enhanced cycling and rate performance of Ni-rich cathode materials in lithium-ion batteries. Small 20(45), 2404488 (2024). https://doi.org/10.1002/smll.20240448810.1002/smll.202404488 ↗
8. X. Fan, G. Hu, B. Zhang, X. Ou, J. Zhang et al., Crack-free single-crystalline Ni-rich layered NCM cathode enable superior cycling performance of lithium-ion batteries. Nano Energy 70, 104450 (2020). https://doi.org/10.1016/j.nanoen.2020.10445010.1016/j.nanoen.2020.104450 ↗
9. M. Liu, Y. Ying, J. Liu, C. Li, R. Hu et al., Catalytic strategies enabled rapid formation of homogeneous and mechanically robust inorganic-rich cathode electrolyte interface for high-rate and high-stability lithium-ion batteries. Adv. Energy Mater. 14(48), 2403696 (2024). https://doi.org/10.1002/aenm.20240369610.1002/aenm.202403696 ↗
10. Y. Yang, Z. Li, Z. Yang, Q. Zhang, Q. Chen et al., Ultrafast lithium-ion transport engineered by nanoconfinement effect. Adv. Mater. 37(8), 2416266 (2025). https://doi.org/10.1002/adma.20241626610.1002/adma.202416266 ↗
11. K. Xia, Z. Yao, P. Zhao, Z. Liu, S. Zhao et al., Enabling 10C-rate fast charging in LiFePO4 based lithium-ion battery by balancing the electronic and ionic conductivity paths in cathode. Chem. Eng. J. 506, 160290 (2025). https://doi.org/10.1016/j.cej.2025.16029010.1016/j.cej.2025.160290 ↗
12. Y. Lu, J. Chen, Prospects of organic electrode materials for practical lithium batteries. Nat. Rev. Chem. 4(3), 127–142 (2020). https://doi.org/10.1038/s41570-020-0160-910.1038/s41570-020-0160-9 ↗
13. J. Hong, M. Lee, B. Lee, D.-H. Seo, C.B. Park et al., Biologically inspired pteridine redox centres for rechargeable batteries. Nat. Commun. 5, 5335 (2014). https://doi.org/10.1038/ncomms633510.1038/ncomms6335 ↗
14. M. Mao, S. Wang, Z. Lin, T. Liu, Y.-S. Hu et al., Electronic conductive inorganic cathodes promising high-energy organic batteries. Adv. Mater. 33(8), e2005781 (2021). https://doi.org/10.1002/adma.20200578110.1002/adma.202005781 ↗
15. Z. Chen, Y. Wang, Z. Ning, Q. Huang, J. Zhou et al., Conjugated microporous polymer/TiS2 composite cathode for high-performance lithium-rechargeable batteries. ACS Appl. Polym. Mater. 6(21), 13110–13119 (2024). https://doi.org/10.1021/acsapm.4c0220310.1021/acsapm.4c02203 ↗
16. L. Xu, M. Hong, J. Guo, F. Shen, D. Xu et al., Boosting Li+ diffusion in lithium-rich oxides through intrinsic structural design: insights and design principles. Nano-Micro Lett. 18(1), 273 (2026). https://doi.org/10.1007/s40820-026-02099-710.1007/s40820-026-02099-7 ↗
17. S. Cao, Y. Sun, Y. Li, A. Wang, W. Zhang et al., Multifunctional dipoles enabling enhanced ionic and electronic transport for high-energy batteries. Nano-Micro Lett. 18(1), 99 (2026). https://doi.org/10.1007/s40820-025-01926-710.1007/s40820-025-01926-7 ↗
18. L.S. de Vasconcelos, R. Xu, Z. Xu, J. Zhang, N. Sharma et al., Chemomechanics of rechargeable batteries: status, theories, and perspectives. Chem. Rev. 122(15), 13043–13107 (2022). https://doi.org/10.1021/acs.chemrev.2c0000210.1021/acs.chemrev.2c00002 ↗
19. X. Huang, Y. Zhou, Y. Zeng, X. Chen, F. He et al., Electron-donating/withdrawing groups functionalized porphyrin complex as high performance organic lithium batteries. Chem. Eng. J. 470, 144248 (2023). https://doi.org/10.1016/j.cej.2023.14424810.1016/j.cej.2023.144248 ↗
20. C. Cara, A. Musinu, V. Mameli, A. Ardu, D. Niznansky et al., Dialkylamide as both capping agent and surfactant in a direct solvothermal synthesis of magnetite and titania nanoparticles. Cryst. Growth Des. 15(5), 2364–2372 (2015). https://doi.org/10.1021/acs.cgd.5b0016010.1021/acs.cgd.5b00160 ↗
21. H. Dogari, R. Peymanfar, H. Ghafuri, Microwave absorbing characteristics of porphyrin derivates: a loop of conjugated structure. RSC Adv. 13(32), 22205–22215 (2023). https://doi.org/10.1039/D3RA03927G10.1039/D3RA03927G ↗
22. Y. Xia, W. Li, H. Xu, F. Wei, S. Ke et al., Tunable mesoporous porphyrin-based conjugated polymer capable of boosting four-electron Zn–I2 batteries. Adv. Funct. Mater. 35(11), 2417283 (2025). https://doi.org/10.1002/adfm.20241728310.1002/adfm.202417283 ↗
23. J. Fu, J. Wang, W. Yan, S. Cui, T. Zhang et al., Metalation of porphyrin units in a porous organic polymer stabilizing its anodic cycling performance in lithium-ion battery. J. Power. Sources 628, 235909 (2025). https://doi.org/10.1016/j.jpowsour.2024.23590910.1016/j.jpowsour.2024.235909 ↗
24. Y. Ko, H. Baek, Y. Kim, M. Yoon, J. Cho, Hydrophobic nanoparticle-based nanocomposite films using in situ ligand exchange layer-by-layer assembly and their nonvolatile memory applications. ACS Nano 7(1), 143–153 (2013). https://doi.org/10.1021/nn303452410.1021/nn3034524 ↗
25. A. Al-Ahmed, A. Sarı, M.A.J. Mazumder, G. Hekimoğlu, F.A. Al-Sulaiman, Thermal energy storage and thermal conductivity properties of Octadecanol-MWCNT composite PCMs as promising organic heat storage materials. Sci. Rep. 10, 9168 (2020). https://doi.org/10.1038/s41598-020-64149-310.1038/s41598-020-64149-3 ↗
26. B. Massoumi, R. Mohammad-Rezaei, M. Abbasian, M. Jaymand, Amine-functionalized carbon nanotubes as curing agent for polystyrene-modified novolac epoxy resin: synthesis, characterization and possible applications. Appl. Phys. A 125(5), 304 (2019). https://doi.org/10.1007/s00339-019-2599-410.1007/s00339-019-2599-4 ↗
27. X. Kang, T. He, H. Dang, X. Li, Y. Wang et al., Designing amino functionalized titanium-organic framework on separators toward sieving and redistribution of polysulfides in lithium-sulfur batteries. Nano-Micro Lett. 17(1), 277 (2025). https://doi.org/10.1007/s40820-025-01733-010.1007/s40820-025-01733-0 ↗
28. A. Maleki, U. Hamesadeghi, H. Daraei, B. Hayati, F. Najafi et al., Amine functionalized multi-walled carbon nanotubes: single and binary systems for high capacity dye removal. Chem. Eng. J. 313, 826–835 (2017). https://doi.org/10.1016/j.cej.2016.10.05810.1016/j.cej.2016.10.058 ↗
29. Y. Xin, M. Zhu, H. Zhang, X. Wang, High-entropy materials: a new paradigm in the design of advanced batteries. Nano-Micro Lett. 18(1), 1 (2025). https://doi.org/10.1007/s40820-025-01842-w10.1007/s40820-025-01842-w ↗
30. C. Scaggion, M. Marinato, G. Dal Sasso, L. Nodari, T. Saupe et al., A fresh perspective on infrared spectroscopy as a prescreening method for molecular and stable isotopes analyses on ancient human bones. Sci. Rep. 14(1), 1028 (2024). https://doi.org/10.1038/s41598-024-51518-510.1038/s41598-024-51518-5 ↗
31. R. von Hagen, H. Lorrmann, K.-C. Möller, S. Mathur, Electrospun LiFe1–yMnyPO4/C nanofiber composites as self-supporting cathodes in Li-ion batteries. Adv. Energy Mater. 2(5), 553–559 (2012). https://doi.org/10.1002/aenm.20110053410.1002/aenm.201100534 ↗
32. H. Wang, E. Rus, T. Sakuraba, J. Kikuchi, Y. Kiya et al., CO2 and O2 evolution at high voltage cathode materials of Li-ion batteries: a differential electrochemical mass spectrometry study. Anal. Chem. 86(13), 6197–6201 (2014). https://doi.org/10.1021/ac403317d10.1021/ac403317d ↗
33. B.L.D. Rinkel, J.P. Vivek, N. Garcia-Araez, C.P. Grey, Two electrolyte decomposition pathways at nickel-rich cathode surfaces in lithium-ion batteries. Energy Environ. Sci. 15(8), 3416–3438 (2022). https://doi.org/10.1039/D1EE04053G10.1039/D1EE04053G ↗
34. T. Zhao, H. Mahandra, R. Marthi, X. Ji, W. Zhao et al., An overview on the life cycle of lithium iron phosphate: synthesis, modification, application, and recycling. Chem. Eng. J. 485, 149923 (2024). https://doi.org/10.1016/j.cej.2024.14992310.1016/j.cej.2024.149923 ↗
35. P. Gao, Z. Chen, Z. Zhao-Karger, J.E. Mueller, C. Jung et al., A porphyrin complex as a self-conditioned electrode material for high-performance energy storage. Angew. Chem. Int. Ed. 56(35), 10341–10346 (2017). https://doi.org/10.1002/anie.20170280510.1002/anie.201702805 ↗
36. X. Chen, X. Feng, B. Ren, L. Jiang, H. Shu et al., High rate and long lifespan sodium-organic batteries using pseudocapacitive porphyrin complexes-based cathode. Nano-Micro Lett. 13(1), 71 (2021). https://doi.org/10.1007/s40820-021-00593-810.1007/s40820-021-00593-8 ↗
37. H.R. Byon, B.M. Gallant, S.W. Lee, Y. Shao-Horn, Role of oxygen functional groups in carbon nanotube/graphene freestanding electrodes for high performance lithium batteries. Adv. Funct. Mater. 23(8), 1037–1045 (2013). https://doi.org/10.1002/adfm.20120069710.1002/adfm.201200697 ↗
38. Q. Xu, Z. Liu, Y. Jin, X. Yang, T. Sun et al., A bipolar-type covalent organic framework on carbon nanotubes with enhanced density of redox-active sites for high-performance lithium-ion batteries. Energy Environ. Sci. 17(15), 5451–5460 (2024). https://doi.org/10.1039/d4ee00520a10.1039/d4ee00520a ↗
39. X. Peng, Y. Zhou, B. Chen, W. Cao, C. Sun et al., A porphyrin-phenylalkynyl-based conjugated organic polymer as a high-performance cathode for rechargeable organic batteries. ACS Appl. Mater. Interfaces (2024). https://doi.org/10.1021/acsami.4c1302310.1021/acsami.4c13023 ↗
40. Y. Sun, F. He, X. Huang, B. Ren, J. Peng et al., Ethynyl functionalized porphyrin complex as a new cathode for organic alkali metal batteries with excellent cycling stability. Chem. Eng. J. 451, 138734 (2023). https://doi.org/10.1016/j.cej.2022.13873410.1016/j.cej.2022.138734 ↗
41. X. Wang, Z. Chen, X. Xue, J. Wang, Y. Wang et al., Achieving stable lithium metal anode via constructing lithiophilicity gradient and regulating Li3N-rich SEI. Nano Energy 133, 110439 (2025). https://doi.org/10.1016/j.nanoen.2024.11043910.1016/j.nanoen.2024.110439 ↗
42. R. Soni, J.B. Robinson, P.R. Shearing, D.J.L. Brett, A.J.E. Rettie et al., Lithium-sulfur battery diagnostics through distribution of relaxation times analysis. Energy Storage Mater. 51, 97–107 (2022). https://doi.org/10.1016/j.ensm.2022.06.01610.1016/j.ensm.2022.06.016 ↗
43. G. Yang, B. Liu, F. Lai, K. Xue, X. Zhang et al., Low-temperature synthesis of amorphous LiF/Li₃BO₃ interfaces with F, B co-doped subsurface for long-cycling and high-rate Ni-rich cathodes. Nano Energy 140, 111009 (2025). https://doi.org/10.1016/j.nanoen.2025.11100910.1016/j.nanoen.2025.111009 ↗
44. K.-Y. Park, Y. Zhu, C.G. Torres-Castanedo, H.J. Jung, N.S. Luu et al., Elucidating and mitigating high-voltage degradation cascades in cobalt-free LiNiO2 lithium-ion battery cathodes. Adv. Mater. 34(3), 2106402 (2022). https://doi.org/10.1002/adma.20210640210.1002/adma.202106402 ↗
45. Z. Sun, H. Zhang, S. Wang, Y. Niu, K. Zhang et al., A novel ternary Li-rich Li4Fe0.5Mn0.5V(PO4)3 cathode for ultra-high-capacity Li-ion batteries with potential far beyond LFP via multi-electron reaction. Small 21(46), e04821 (2025). https://doi.org/10.1002/smll.20250482110.1002/smll.202504821 ↗
46. L. Wang, T. Liu, T. Wu, J. Lu, Strain-retardant coherent perovskite phase stabilized Ni-rich cathode. Nature 611(7934), 61–67 (2022). https://doi.org/10.1038/s41586-022-05238-310.1038/s41586-022-05238-3 ↗
47. Y. Zou, Y. Tang, Q. Zheng, H. Zhang, Y. Yan et al., Enabling the strengthened structural and interfacial stability of high-nickel LiNi0.9Co0.05Mn0.05O2 cathode by a coating-doping-microstructure regulation three-in-one strategy. Adv. Funct. Mater. 34(41), 2406068 (2024). https://doi.org/10.1002/adfm.20240606810.1002/adfm.202406068 ↗
48. Z. Zheng, F. Bei, L. Zhou, W. Xia, J. Sun et al., Efficient structural regulation platform for the controlled synthesis of LiFePO4 cathodes with shorter Li-ion diffusion paths. Langmuir 40(4), 2396–2404 (2024). https://doi.org/10.1021/acs.langmuir.3c0380110.1021/acs.langmuir.3c03801 ↗
49. J. Lin, Y.-H. Sun, X. Lin, Metal-organic framework-derived LiFePO4 cathode encapsulated in O, F-codoped carbon matrix towards superior lithium storage. Nano Energy 91, 106655 (2022). https://doi.org/10.1016/j.nanoen.2021.10665510.1016/j.nanoen.2021.106655 ↗
50. H. An, K. Park, LFP via nanoscale surface reforming with a tiny minimal amount of conductivity-enhancing material. Langmuir 41(3), 1821–1829 (2025). https://doi.org/10.1021/acs.langmuir.4c0428510.1021/acs.langmuir.4c04285 ↗
51. Y. Liu, J. Dong, J. Zhou, Y. Guan, Y. Wei et al., Interfacial evolution and accelerated aging mechanism for LiFePO4/graphite pouch batteries under multi-step indirect activation. Nano-Micro Lett. 18(1), 136 (2026). https://doi.org/10.1007/s40820-025-01971-210.1007/s40820-025-01971-2 ↗
52. W. Liu, J. Li, W. Li, H. Xu, C. Zhang et al., Inhibition of transition metals dissolution in cobalt-free cathode with ultrathin robust interphase in concentrated electrolyte. Nat. Commun. 11, 3629 (2020). https://doi.org/10.1038/s41467-020-17396-x10.1038/s41467-020-17396-x ↗
53. H. Ren, G. Zheng, Y. Li, S. Chen, X. Wang et al., Stabilizing LiCoO2 at 4.6 V by regulating anti-oxidative solvents. Energy Environ. Sci. 17(20), 7944–7957 (2024). https://doi.org/10.1039/d4ee02049a10.1039/d4ee02049a ↗
54. Y. Sun, C. Li, J. Chen, K. Zhang, W. Ji et al., In situ crystal structure growth and control for enhancing comprehensive performance in ultra-high nickel-layered lithium cathodes. Angew. Chem. Int. Ed. 65, e13466 (2026). https://doi.org/10.1002/anie.20251346610.1002/anie.202513466 ↗
55. Q. Li, Y. Wang, X. Wang, X. Sun, J.-N. Zhang et al., Investigations on the fundamental process of cathode electrolyte interphase formation and evolution of high-voltage cathodes. ACS Appl. Mater. Interfaces 12(2), 2319–2326 (2020). https://doi.org/10.1021/acsami.9b1672710.1021/acsami.9b16727 ↗
56. N. Wang, X. Zhang, Z. Ju, X. Yu, Y. Wang et al., Thickness-independent scalable high-performance Li–S batteries with high areal sulfur loading via electron-enriched carbon framework. Nat. Commun. 12, 4519 (2021). https://doi.org/10.1038/s41467-021-24873-410.1038/s41467-021-24873-4 ↗