Black Phosphorus-Based Nanocomposites as Anode Materials for Lithium-Ion Batteries: A Comprehensive Review

Abstract

Black phosphorus (BP) is a layered and two-dimensional substance that has been discussed as an anode material for lithium-ion batteries (LIBs) due to its exceptionally large theoretical capacity, anisotropic electrochemical characteristics, and bandgap control. However, pristine BP suffers from problems such as significant volume expansion, capacity fading, and low coulombic efficiency. To overcome these challenges, researchers have explored BP incorporated with various nanocomposites to not only improve structural stability and conductivity of BP, but also suppress its environmental degradation and optimize its electrochemical performance. This review focuses on modification strategies such as carbon-based hybridization, metal doping, and heterostructure engineering to address these challenges. It also systematically compares the strategy of synthesis of the BP-based nanocomposites, such as high-energy ball milling machine, chemical vapor deposition, liquid exfoliation, and their combination with various reinforcements. The electrochemical behavior of these composites, such as specific capacities, rate capability, cycling stability, among others are evaluated and compared, and the results are summarized in a tabular form to make them clear. In addition, this review explains how the BP-based nanocomposites can be used to transform the LIB technology while identifying key research directions to advance the versatility of these composites in real-world applications.

Keywords

anode / black phosphorus / electrochemical performance / Li-ion batteries / Na-ion batteries / nanocomposites / solid-state batteries

References

[1] A. Kumar, “Global Warming, Climate Change and Greenhouse Gas Mitigation.” in Biofuels: Greenhouse Gas Mitigation and Global Warming: Next Generation Biofuels and Role of Biotechnology, eds. A. Kumar, S. Ogita, and Y.-Y. Yau (Springer India, 2018), 1–16.

[2] K. C. Bhowmik, M. A. Rahman, Y. Ahmed, and T. B. Hai, “MXenes: Are They Ready for Direct Air Capture of CO2?,” Chemistry–An Asian Journal 20, no. 9 (2025): e202401822.

[3] S. Barua, M. A. Rahman, K. C. Bhowmik, M. M. Billah, and H. M. A. R. Maruf, “Transition Metal Oxides as Promising Air-Cathode Catalysts of Li-Air Batteries: A State-of-the-Art Review,” ChemistrySelect 10, no. 37 (2025): e04744.

[4] M. A. Rahman, X. Wang, and C. Wen, “High Energy Density Metal-Air Batteries: A Review,” Journal of the Electrochemical Society 160, no. 10 (2013): A1759–A1771.

[5] M. A. Rahman, X. Wang, and C. Wen, “A Review of High Energy Density Lithium–Air Battery Technology,” Journal of Applied Electrochemistry 44, no. 1 (2014): 5–22.

[6] K. Chandra Bhowmik, M. A. Rahman, M. M. Billah, and A. Paul, “From Lithium-Ion to Sodium-Ion Batteries for Sustainable Energy Storage: A Comprehensive Review on Recent Research Advancements and Perspectives,” Chemical Record 24, no. 12 (2024): e202400176.

[7] M. S. Whittingham, “Electrical Energy Storage and Intercalation Chemistry,” Science 192, no. 4244 (1976): 1126–1127.

[8] J. B. Goodenough and Y. Kim, “Challenges for Rechargeable Li Batteries,” Chemistry of Materials 22, no. 3 (2010): 587–603.

[9] T. Chen, Y. Jin, H. Lv, et al., “Applications of Lithium-Ion Batteries in Grid-Scale Energy Storage Systems,” Transactions of Tianjin University 26, no. 3 (2020): 208–217.

[10] L. J. Hounjet, “Comparing Lithium-and Sodium-Ion Batteries for Their Applicability Within Energy Storage Systems,” Energy Storage 4, no. 3 (2022): e309.

[11] A. Manthiram, “An Outlook on Lithium Ion Battery Technology,” ACS Central Science 3, no. 10 (2017): 1063–1069.

[12] T. F. Yi, L. Shi, X. Han, F. Wang, Y. Zhu, and Y. Xie, “Approaching High-Performance Lithium Storage Materials by Constructing Hierarchical CoNiO2@CeO2 Nanosheets,” Energy & Environmental Materials 4, no. 4 (2021): 586–595.

[13] J. Lu, Z. Chen, F. Pan, Y. Cui, and K. Amine, “High-Performance Anode Materials for Rechargeable Lithium-Ion Batteries,” Electrochemical Energy Reviews 1, no. 1 (2018): 35–53.

[14] J.-M. Tarascon and M. Armand, “Issues and Challenges Facing Rechargeable Lithium Batteries,” Nature 414, no. 6861 (2001): 359–367.

[15] M. A. Rahman, G. Song, A. I. Bhatt, Y. C. Wong, and C. Wen, “Nanostructured Silicon Anodes for High-Performance Lithium-Ion Batteries,” Advanced Functional Materials 26, no. 5 (2016): 647–678.

[16] F. Xin and M. S. Whittingham, “Challenges and Development of Tin-Based Anode With High Volumetric Capacity for Li-Ion Batteries,” Electrochemical Energy Reviews 3, no. 4 (2020): 643–655.

[17] W.-J. Zhang, “A Review of the Electrochemical Performance of Alloy Anodes for Lithium-Ion Batteries,” Journal of Power Sources 196, no. 1 (2011): 13–24.

[18] S. Das, K. C. Bhowmik, M. A. Rahman, and S. Barua, “Anatase TiO₂ as Anode of Lithium-Ion Batteries: A Comprehensive Review on Sustainable Synthesis and Electrochemical Properties,” Advanced Energy and Sustainability Research 6, no. 12 (2025): 2500190.

[19] S. Das, M. A. Rahman, M. S. Islam, and K. C. Bhowmik, “Experimental Investigation of Cycling Characteristics of Anatase TiO2 Nanotubes as Negative Electrode of Lithium-Ion Batteries,” Future Energy 4, no. 1 (2025): 1–7.

[20] S. Paul, M. A. Rahman, M. S. Islam, M. R. Islam, and S. E. T. Siddiqui, “Nanostructured Anatase TiO2 as Anode of High-Performance Lithium-Ion Batteries,” Battery Energy 1, no. 4 (2022): 20220018.

[21] M. A. Rahman, M. M. Rahman, and G. Song, “A Review on Binder-Free NiO-Ni Foam as Anode of High Performance Lithium-Ion Batteries,” Energy Storage 4, no. 3 (2022): e278.

[22] M. A. Rahman and C. Wen, “A Study of the Capacity Fade of Porous NiO/Ni Foam as Negative Electrode for Lithium-Ion Batteries,” Ionics 22, no. 2 (2016): 173–184.

[23] S.-E.-T. Siddiqui, M. A. Rahman, J. H. Kim, S. B. Sharif, and S. Paul, “A Review on Recent Advancements of Ni-NiO Nanocomposite as an Anode for High-Performance Lithium-Ion Battery,” Nanomaterials 12, no. 17 (2022): 2930.

[24] S.-E. T. Siddiqui, M. A. Rahman, M. S. Islam, J. H. Kim, and N. Barua, “Microstructured Pebble Stone Like Ni-NiO Composite as Anode of High-Performance Lithium-Ion Batteries,” Future Sustainability 2, no. 1 (2024): 1–13.

[25] S. Wang, C. Qu, J. Wen, et al., “Progress of Transition Metal Sulfides Used as Lithium-Ion Battery Anodes,” Materials Chemistry Frontiers 7, no. 14 (2023): 2779–2808.

[26] P. Shi, X. Q. Zhang, X. Shen, R. Zhang, H. Liu, and Q. Zhang, “Composite Lithium Anodes: A Review of Composite Lithium Metal Anode for Practical Applications,” Advanced Materials Technologies 5, no. 1 (2020): 2070002.

[27] H. Jin, Y. Huang, C. Wang, and H. Ji, “Phosphorus-Based Anodes for Fast Charging Lithium-Ion Batteries: Challenges and Opportunities,” Small Science 2, no. 6 (2022): 2200015.

[28] M. N. U. Chy, M. A. Rahman, J. H. Kim, N. Barua, and W. A. Dujana, “MXene as Promising Anode Material for High-Performance Lithium-Ion Batteries: A Comprehensive Review,” Nanomaterials 14, no. 7 (2024): 616.

[29] C. K. Chan, H. Peng, G. Liu, et al., “High-Performance Lithium Battery Anodes Using Silicon Nanowires,” Nature Nanotechnology 3, no. 1 (2008): 31–35.

[30] S. Chae, M. Ko, K. Kim, K. Ahn, and J. Cho, “Confronting Issues of the Practical Implementation of Si Anode in High-Energy Lithium-Ion Batteries,” Joule 1, no. 1 (2017): 47–60.

[31] H. Kim, M. Seo, M.-H. Park, and J. Cho, “A Critical Size of Silicon Nano-Anodes for Lithium Rechargeable Batteries,” Angewandte Chemie International Edition 49 (2010): 2146–2149.

[32] S. Chen, Z. Chen, X. Xu, C. Cao, M. Xia, and Y. Luo, “Scalable 2D Mesoporous Silicon Nanosheets for High-Performance Lithium-Ion Battery Anode,” Small 14, no. 12 (2018): 1703361.

[33] I. A. Courtney and J. R. Dahn, “Electrochemical and in Situ X-Ray Diffraction Studies of the Reaction of Lithium With Tin Oxide Composites,” Journal of the Electrochemical Society 144, no. 6 (1997): 2045–2052.

[34] Y. Li, Y. H. Zhao, L. L. Zhao, P. F. Wang, Y. Xie, and T. F. Yi, “Well-Dispersed Sb Particles Embedded on N-Doped Carbon Nanofibers Toward High-Performance Li-Ion Battery,” Rare Metals 43, no. 7 (2024): 2994–3006.

[35] M. Zhang, T. Wang, and G. Cao, “Promises and Challenges of Tin-Based Compounds as Anode Materials for Lithium-Ion Batteries,” International Materials Reviews 60, no. 6 (2015): 330–352.

[36] L. Zhang, H. B. Wu, and X. W. Lou, “Iron-Oxide-Based Advanced Anode Materials for Lithium-Ion Batteries,” Advanced Energy Materials 4, no. 4 (2014): 1300958.

[37] Y. Deng, L. Wan, Y. Xie, X. Qin, and G. Chen, “Recent Advances in Mn-Based Oxides as Anode Materials for Lithium Ion Batteries,” RSC Advances 4, no. 45 (2014): 23914–23935.

[38] A. Kumar Rai, L. Tuan Anh, C. J. Park, and J. Kim, “Electrochemical Study of NiO Nanoparticles Electrode for Application in Rechargeable Lithium-Ion Batteries,” Ceramics International 39, no. 6 (2013): 6611–6618.

[39] B. Wang, X. Y. Lu, K. Y. Wong, and Y. Tang, “Facile Solvothermal Synthesis and Superior Lithium Storage Capability of Co 3 O 4 Nanoflowers With Multi-Scale Dimensions,” Materials Chemistry Frontiers 1, no. 3 (2017): 468–476.

[40] A. Kim, E. Park, H. Lee, and H. Kim, “Highly Reversible Insertion of Lithium Into MoO₂ as an Anode Material for Lithium Ion Battery,” Journal of Alloys and Compounds 681 (2016): 301–306.

[41] L. Feng, Z. Xuan, Y. Zhang, C. Su, and J. Guo, “Recent Progress in Metal Oxide Based Materials as Anode Materials for Lithium-Ion Batteries,” Nano Biomedicine & Engineering 5, no. 1 (2013): 57–64.

[42] X.-Z. Li, N. Zhang, Y. R. Wu, et al., “Interconnected Bi₅Nb₃O₁₅@CNTs Network as High-Performance Anode Materials of Li-Ion Battery,” Rare Metals 41 (2022): 3401–3411.

[43] E. Ferg, R. J. Gummow, A. de Kock, and M. M. Thackeray, “Spinel Anodes for Lithium-Ion Batteries,” Journal of the Electrochemical Society 141, no. 11 (1994): L147–L150.

[44] J. Wang, H. Zhao, Y. Wen, et al., “High Performance Li₄Ti₅O₁₂ Material as Anode for Lithium-Ion Batteries,” Electrochimica Acta 113 (2013): 679–685.

[45] T.-T. Wei, P. Peng, Y. R. Ji, Y. R. Zhu, T. F. Yi, and Y. Xie, “Rational Construction and Decoration of Li5Cr7Ti6O25@C Nanofibers as Stable Lithium Storage Materials,” Journal of Energy Chemistry 71 (2022): 400–410.

[46] Y. Chen, X. Chen, and Y. Zhang, “A Comprehensive Review on Metal-Oxide Nanocomposites for High-Performance Lithium-Ion Battery Anodes,” Energy & Fuels 35, no. 8 (2021): 6420–6442.

[47] Y. Yong and L.-Z. Fan, “Silicon/Carbon Nanocomposites Used as Anode Materials for Lithium-Ion Batteries,” Ionics 19, no. 11 (2013): 1545–1549.

[48] P. Lian, X. Zhu, H. Xiang, Z. Li, W. Yang, and H. Wang, “Enhanced Cycling Performance of Fe₃O₄–Graphene Nanocomposite as an Anode Material for Lithium-Ion Batteries,” Electrochimica Acta 56, no. 2 (2010): 834–840.

[49] A. Kumar Rai, L. Tuan Anh, C. J. Park, and J. Kim, “Electrochemical Study of NiO Nanoparticles Electrode for Application in Rechargeable Lithium-Ion Batteries,” Ceramics International 39, no. 6 (2013): 6611–6618.

[50] N. Zhang, S. Y. Qi, Y. F. Guo, P. F. Wang, N. Ren, and T. F. Yi, “Approaching High-Performance Lithium Storage Materials of CoNiO2 Microspheres Wrapped Coal Tar Pitch-Derived Porous Carbon,” Dalton Transactions 52, no. 25 (2023): 8704–8715.

[51] L.-Q. Sun, M. J. Li, K. Sun, S. H. Yu, R. S. Wang, and H. M. Xie, “Electrochemical Activity of Black Phosphorus as an Anode Material for Lithium-Ion Batteries,” Journal of Physical Chemistry C 116, no. 28 (2012): 14772–14779.

[52] Y. Tian, H. Wang, H. Li, et al., “Recent Advances in Black Phosphorus/Carbon Hybrid Composites: From Improved Stability to Applications,” Journal of Materials Chemistry A 8, no. 9 (2020): 4647–4676.

[53] N. K. Chaudhari, H. Jin, B. Kim, D. San Baek, S. H. Joo, and K. Lee, “MXene: An Emerging Two-Dimensional Material for Future Energy Conversion and Storage Applications,” Journal of Materials Chemistry A 5, no. 47 (2017): 24564–24579.

[54] J. M. Tarascon and M. Armand, “Issues and Challenges Facing Rechargeable Lithium Batteries,” Nature 414, no. 6861 (2001): 359–367.

[55] S. Chen, Z. Chen, X. Xu, C. Cao, M. Xia, and Y. Luo, “Scalable 2D Mesoporous Silicon Nanosheets for High-Performance Lithium-Ion Battery Anode,” Small 14, no. 12 (2018): 1703361.

[56] I. A. Courtney and J. R. Dahn, “Electrochemical and In Situ X-Ray Diffraction Studies of the Reaction of Lithium With Tin Oxide Composites,” Journal of the Electrochemical Society 144, no. 6 (1997): 2045–2052.

[57] Z. Li, J. Ding, and D. Mitlin, “Tin and Tin Compounds for Sodium Ion Battery Anodes: Phase Transformations and Performance,” Accounts of Chemical Research 48, no. 6 (2015): 1657–1665.

[58] M. Armand and J. M. Tarascon, “Building Better Batteries,” Nature 451, no. 7179 (2008): 652–657.

[59] A. Staffolani, H. Darjazi, G. Carbonari, F. Maroni, S. Gabrielli, and F. Nobili, “Fe₃O₄/Graphene Composite Anode Material for Fast-Charging Li-Ion Batteries,” Molecules 26, no. 14 (2021): 4316.

[60] L. Zhang, J. Mu, Z. Wang, G. Li, Y. Zhang, and Y. He, “One-Pot Synthesis of NiO/C Composite Nanoparticles as Anode Materials for Lithium-Ion Batteries,” Journal of Alloys and Compounds 671 (2016): 60–65.

[61] H. Liu, K. Hu, D. Yan, et al., “Recent Advances on Black Phosphorus for Energy Storage, Catalysis, and Sensor Applications,” Advanced Materials 30, no. 32 (2018): 1800295.

[62] P. W. Bridgman, “Two New Modifications of Phosphorus,” Journal of the American Chemical Society 36, no. 7 (1914): 1344–1363.

[63] R. Fei and L. Yang, “Strain-Engineering the Anisotropic Electrical Conductance of Few-Layer Black Phosphorus,” Nano Letters 14, no. 5 (2014): 2884–2889.

[64] L. Li, Y. Yu, G. J. Ye, et al., “Black Phosphorus Field-Effect Transistors,” Nature Nanotechnology 9, no. 5 (2014): 372–377.

[65] D. J. Late, “Liquid Exfoliation of Black Phosphorus Nanosheets and Its Application as Humidity Sensor,” Microporous and Mesoporous Materials 225 (2016): 494–503.

[66] M. Zhang, Q. Wu, F. Zhang, et al., “2D Black Phosphorus Saturable Absorbers for Ultrafast Photonics,” Advanced Optical Materials 7, no. 1 (2019): 1800224.

[67] Y. Zhang, Y. Zheng, K. Rui, et al., “2D Black Phosphorus for Energy Storage and Thermoelectric Applications,” Small 13, no. 28 (2017): 1700661.

[68] Z. Guo, H. Zhang, S. Lu, et al., “From Black Phosphorus to Phosphorene: Basic Solvent Exfoliation, Evolution of Raman Scattering, and Applications to Ultrafast Photonics,” Advanced Functional Materials 25, no. 45 (2015): 6996–7002.

[69] J. Cheng, L. Gao, T. Li, et al., “Two-Dimensional Black Phosphorus Nanomaterials: Emerging Advances in Electrochemical Energy Storage Science,” Nano-Micro Letters 12, no. 1 (2020): 179.

[70] J. Zhu, G. Xiao, and X. Zuo, “Two-Dimensional Black Phosphorus: An Emerging Anode Material for Lithium-Ion Batteries,” Nano-Micro Letters 12, no. 1 (2020): 120.

[71] H. Liu, Y. Du, Y. Deng, and P. D. Ye, “Semiconducting Black Phosphorus: Synthesis, Transport Properties and Electronic Applications,” Chemical Society Reviews 44, no. 9 (2015): 2732–2743.

[72] X. Zhu, T. Zhang, Z. Sun, et al., “Black Phosphorus Revisited: A Missing Metal-Free Elemental Photocatalyst for Visible Light Hydrogen Evolution,” Advanced Materials 29, no. 17 (2017): 1605776.

[73] R. He, J. Hua, A. Zhang, et al., “Molybdenum Disulfide–Black Phosphorus Hybrid Nanosheets as a Superior Catalyst for Electrochemical Hydrogen Evolution,” Nano Letters 17, no. 7 (2017): 4311–4316.

[74] A. Favron, E. Gaufrès, F. Fossard, et al., “Photooxidation and Quantum Confinement Effects in Exfoliated Black Phosphorus,” Nature Materials 14, no. 8 (2015): 826–832.

[75] J. D. Wood, S. A. Wells, D. Jariwala, et al., “Effective Passivation of Exfoliated Black Phosphorus Transistors Against Ambient Degradation,” Nano Letters 14, no. 12 (2014): 6964–6970.

[76] M. T. Edmonds, A. Tadich, A. Carvalho, et al., “Creating a Stable Oxide at the Surface of Black Phosphorus,” ACS Applied Materials & Interfaces 7, no. 27 (2015): 14557–14562.

[77] Y. Zhao, Q. Zhou, Q. Li, X. Yao, and J. Wang, “Passivation of Black Phosphorus via Self-Assembled Organic Monolayers by Van Der Waals Epitaxy,” Advanced Materials 29, no. 6 (2017): 1603990.

[78] H. Tang, L. Yue, X. Mu, H. Xia, and H. Zhou, “Phosphorus-Based Anodes for Fast-Charging Lithium-Ion Batteries: Advances, Challenges and Prospects,” Energy Materials 5, no. 12 (2025): 500151.

[79] J. Zhang, Q. Shi, C. Lu, et al., “Recent Developments in Insertion Anode Materials for Li-Ion Batteries,” Materials Chemistry Frontiers 9, no. 14 (2025): 2161–2177.

[80] C. Zhang, M. Yu, G. Anderson, R. R. Dharmasena, and G. Sumanasekera, “The Prospects of Phosphorene as an Anode Material for High-Performance Lithium-Ion Batteries: A Fundamental Study,” Nanotechnology 28, no. 7 (2017): 075401.

[81] Y. Zhang, W. Sun, Z. Z. Luo, et al., “Functionalized Few-Layer Black Phosphorus With Super-Wettability Towards Enhanced Reaction Kinetics for Rechargeable Batteries,” Nano Energy 40 (2017): 576–586.

[82] L.-F. Gao, J. Y. Xu, Z. Y. Zhu, et al., “Small Molecule-Assisted Fabrication of Black Phosphorus Quantum Dots With a Broadband Nonlinear Optical Response,” Nanoscale 8, no. 33 (2016): 15132–15136.

[83] M. Qiu, Z. T. Sun, D. K. Sang, X. G. Han, H. Zhang, and C. M. Niu, “Current Progress in Black Phosphorus Materials and Their Applications in Electrochemical Energy Storage,” Nanoscale 9, no. 36 (2017): 13384–13403.

[84] A. E. Del Rio Castillo, V. Pellegrini, H. Sun, et al., “Exfoliation of Few-Layer Black Phosphorus in Low-Boiling-Point Solvents and Its Application in Li-Ion Batteries,” Chemistry of Materials 30, no. 2 (2018): 506–516.

[85] S. Zhao, W. Kang, and J. Xue, “The Potential Application of Phosphorene as an Anode Material in Li-Ion Batteries,” Journal of Materials Chemistry A: Materials for Energy and Sustainability 2, no. 44 (2014): 19046–19052.

[86] G.-C. Guo, D. Wang, X. L. Wei, et al., “First-Principles Study of Phosphorene and Graphene Heterostructure as Anode Materials for Rechargeable Li Batteries,” Journal of Physical Chemistry Letters 6, no. 24 (2015): 5002–5008.

[87] F. Zhou, X. S. Yang, J. Liu, et al., “In-Situ Introducing TiP2 Nanocrystals in Black Phosphorus Anode to Promote High Rate-Capacity Synergy,” Journal of Power Sources 499 (2021): 229979.

[88] K. S. Novoselov, A. K. Geim, S. V. Morozov, et al., “Electric Field Effect in Atomically Thin Carbon Films,” Science 306, no. 5696 (2004): 666–669.

[89] S. C. Dhanabalan, J. S. Ponraj, Z. Guo, S. Li, Q. Bao, and H. Zhang, “Emerging Trends in Phosphorene Fabrication Towards Next Generation Devices,” Advanced Science 4, no. 6 (2017): 1600305.

[90] S. Wu, K. S. Hui, and K. N. Hui, “2D Black Phosphorus: From Preparation to Applications for Electrochemical Energy Storage,” Advanced Science 5, no. 5 (2018): 1700491.

[91] S. Liang, M. N. Hasan, and J.-H. Seo, “Direct Observation of Raman Spectra in Black Phosphorus Under Uniaxial Strain Conditions,” Nanomaterials 9, no. 4 (2019): 566.

[92] F. I. Alzakia and S. C. Tan, “Liquid-Exfoliated 2D Materials for Optoelectronic Applications,” Advanced Science 8, no. 11 (2021): 2003864.

[93] L. Guan, B. Xing, X. Niu, et al., “Metal-Assisted Exfoliation of Few-Layer Black Phosphorus With High Yield,” Chemical Communications 54, no. 6 (2018): 595–598.

[94] A. Castellanos-Gomez, L. Vicarelli, E. Prada, et al., “Isolation and Characterization of Few-Layer Black Phosphorus,” 2D Materials 1, no. 2 (2014): 025001.

[95] J. R. Brent, N. Savjani, E. A. Lewis, S. J. Haigh, D. J. Lewis, and P. O'Brien, “Production of Few-Layer Phosphorene by Liquid Exfoliation of Black Phosphorus,” Chemical Communications 50, no. 87 (2014): 13338–13341.

[96] Y. Zhang, H. Wang, Z. Luo, et al., “An Air-Stable Densely Packed Phosphorene–Graphene Composite Toward Advanced Lithium Storage Properties,” Advanced Energy Materials 6, no. 12 (2016): 1600453.

[97] V. Nicolosi, M. Chhowalla, M. G. Kanatzidis, M. S. Strano, and J. N. Coleman, “Liquid Exfoliation of Layered Materials,” Science 340, no. 6139 (2013): 1226419.

[98] D. Hanlon, C. Backes, E. Doherty, et al., “Liquid Exfoliation of Solvent-Stabilized Few-Layer Black Phosphorus for Applications Beyond Electronics,” Nature Communications 6, no. 1 (2015): 8563.

[99] Y. Zhou, J. Chen, L. Yue, and D. Ren, “Preparation of High-Intensity Fluorescent Black Phosphorus Nanosheets,” Physica Status Solidi (a) 220, no. 13 (2023): 2200806.

[100] Y. Chen, X. Chen, J. Lin, Y. Zhuang, Z. Han, and J. Chen, “Electrochemical Detection of Alpha-Fetoprotein Based on Black Phosphorus Nanosheets Modification With Iron Ions,” Micromachines 13, no. 5 (2022): 673.

[101] P. Hashemi, D. Sabaghi, S. Yang, A. S. Nia, and X. Feng, “Electrochemical Exfoliation to Produce High-Quality Black Phosphorus,” Journal of Visualized Experiments (JoVE) 188 (2022): e64109, https://doi.org/10.3791/64109.

[102] L. Li, D. Zhang, J. Deng, Y. Gou, and J. Fang, “Electrochemical Exfoliation of Two-Dimensional Layered Black Phosphorus and Applications,” Journal of Energy Chemistry 49 (2020): 365–374.

[103] A. Ambrosi, Z. Sofer, and M. Pumera, “Electrochemical Exfoliation of Layered Black Phosphorus Into Phosphorene,” Angewandte Chemie International Edition 56, no. 35 (2017): 10443–10445.

[104] H. Xiao, M. Zhao, J. Zhang, et al., “Electrochemical Cathode Exfoliation of Bulky Black Phosphorus Into Few-Layer Phosphorene Nanosheets,” Electrochemistry Communications 89 (2018): 10–13.

[105] M. B. Erande, S. R. Suryawanshi, M. A. More, and D. J. Late, “Electrochemically Exfoliated Black Phosphorus Nanosheets–Prospective Field Emitters,” European Journal of Inorganic Chemistry 2015, no. 19 (2015): 3102–3107.

[106] A. S. Pawbake, M. B. Erande, S. R. Jadkar, and D. J. Late, “Temperature Dependent Raman Spectroscopy of Electrochemically Exfoliated Few Layer Black Phosphorus Nanosheets,” RSC Advances 6, no. 80 (2016): 76551–76555.

[107] Q. Li, J. T. Wu, Y. Liu, et al., “Recent Advances in Black Phosphorus-Based Electrochemical Sensors: A Review,” Analytica Chimica Acta 1170 (2021): 338480.

[108] M. Kumar, X. Xiong, Z. Wan, et al., “Ball Milling as a Mechanochemical Technology for Fabrication of Novel Biochar Nanomaterials,” Bioresource Technology 312 (2020): 123613.

[109] K. Deng, X. Li, X. Feng, H. Yang, and C. Wan, “High-Energy Ball Milling-Induced Facile Preparation and Controllable Surface Oxidation of Black Phosphorus for Improving Fire Safety of Epoxy Resin via Synergistic Effect,” Journal of Materials Research and Technology 29 (2024): 2339–2349.

[110] C. F. Burmeister, M. Hofer, P. Molaiyan, P. Michalowski, and A. Kwade, “Characterization of Stressing Conditions in a High Energy Ball Mill by Discrete Element Simulations,” Processes 10, no. 4 (2022): 692.

[111] H. X. Kho, S. Bae, S. Bae, B. W. Kim, and J. S. Kim, “Planetary Ball Mill Process in Aspect of Milling Energy,” Journal of Korean Powder Metallurgy Institute 21, no. 2 (2014): 155–164.

[112] E. Quartarone, T. Eisenmann, M. Kuenzel, et al., “Towards Advanced Sodium-Ion Batteries: Green, Low-Cost and High-Capacity Anode Compartment Encompassing Phosphorus/Carbon Nanocomposite as the Active Material and Aluminum as the Current Collector,” Journal of the Electrochemical Society 167, no. 8 (2020): 080509.

[113] S. V. Pedersen, F. Muramutsa, J. D. Wood, C. Husko, D. Estrada, and B. J. Jaques, “Mechanochemical Conversion Kinetics of Red to Black Phosphorus and Scaling Parameters for High Volume Synthesis,” npj 2D Materials and Applications 4, no. 1 (2020): 36.

[114] M. Mhadhbi, “Modelling of the High-Energy Ball Milling Process,” Advances in Materials Physics and Chemistry 11, no. 1 (2021): 31–44.

[115] Z. A. Lukman and M. S. M. Suan, “Characterization of Black Phosphorus Synthesized via Ball-Milling Technique for the Effect of Milling Media,” in International Conference and Exhibition on Sustainable Energy and Advanced Materials (Springer, 2023).

[116] W. Liu, Y. Zhu, S. Wang, and X. Zhang, “Preparation of Few-Layer Black Phosphorus by Wet Ball Milling Exfoliation,” Journal of Materials Science: Materials in Electronics 31, no. 12 (2020): 9543–9549.

[117] W. Cao, D. Lai, J. Yang, et al., “Research Progress on the Preparation Methods for and Flame Retardant Mechanism of Black Phosphorus and Black Phosphorus Nanosheets,” Nanomaterials 14, no. 10 (2024): 892.

[118] L. Zainul Abidin Lukman, N. Irwan Nurdin, and S. Mohd Shahadan Mohd Suan, “Characterization of Black Phosphorous Synthesized via Ball-Milling Technique for The Effect of Milling Media and Time,” Journal of Advanced Research in Micro and Nano Engieering 18, no. 1 (2024): 113–122.

[119] F. Zhou, L. Ouyang, M. Zeng, et al., “Growth Mechanism of Black Phosphorus Synthesized by Different Ball Milling Techniques,” Journal of Alloys and Compounds 784 (2019): 339–346.

[120] R. Gui, H. Jin, Z. Wang, and J. Li, “Black Phosphorus Quantum Dots: Synthesis, Properties, Functionalized Modification and Applications,” Chemical Society Reviews 47, no. 17 (2018): 6795–6823.

[121] C. C. Mayorga-Martinez, Z. Sofer, D. Sedmidubský, J. Luxa, B. Kherzi, and M. Pumera, “Metallic Impurities in Black Phosphorus Nanoflakes Prepared by Different Synthetic Routes,” Nanoscale 10, no. 3 (2018): 1540–1546.

[122] G. Tiouitchi, F. Elmanjli, O. Mounkachi, et al., “From Amorphous Red Phosphorus to a Few Layers of Black Phosphorus: A Low-Cost and Efficient Preparation Process,” Jordan Journal of Physics 13, no. 2 (2020): 149–155.

[123] L. Zhang, H. Huang, B. Zhang, et al., “Structure and Properties of Violet Phosphorus and Its Phosphorene Exfoliation,” Angewandte Chemie International Edition 59, no. 3 (2020): 1074–1080.

[124] Y. Da, Y. Zhou, S. Zhang, et al., “Fabrication of Single-Crystal Violet Phosphorus Flakes For Ultrasensitive Photodetection,” Small 20, no. 30 (2024): 2310276.

[125] N. Antonatos, J. Šturala, V. Mazánek, et al., “Black Phosphorus: Fundamental Properties and Influence of Impurities Induced by Its Synthesis,” ACS Applied Materials & Interfaces 14, no. 30 (2022): 34867–34874.

[126] Y. Wang, M. He, S. Ma, et al., “Low-Temperature Solution Synthesis of Black Phosphorus From Red Phosphorus: Crystallization Mechanism and Lithium Ion Battery Applications,” The Journal of Physical Chemistry Letters 11, no. 7 (2020): 2708–2716.

[127] L. Ding, P. Shao, Y. Yin, and F. Ding, “Synthesis of 2D Phosphorene: Current Status and Challenges,” Advanced Functional Materials 34, no. 32 (2024): 2316612.

[128] N. Antonatos, D. Bouša, S. Shcheka, S. M. Beladi-Mousavi, M. Pumera, and Z. Sofer, “In Situ Doping of Black Phosphorus by High-Pressure Synthesis,” Inorganic Chemistry 58, no. 15 (2019): 10227–10238.

[129] P. W. Bridgman, “Polymorphism, Principally of the Elements, Up to 50,000 Kg/cm²,” Physical Review 48, no. 11 (1935): 893–906.

[130] P. W. Bridgman, “Shearing Phenomena at High Pressures, Particularly in Inorganic Compounds,” Proceedings of the American Academy of Arts and Sciences 71, no. 9 (1937): 387–460.

[131] B. Deng, R. Frisenda, C. Li, X. Chen, A. Castellanos-Gomez, and F. Xia, “Progress on Black Phosphorus Photonics,” Advanced Optical Materials 6, no. 19 (2018): 1800365.

[132] N. Higashitarumizu, T. Kawashima, T. Smart, et al., “Mid-Infrared, Optically Active Black Phosphorus Thin Films on Centimeter Scale,” Nano Letters 24, no. 10 (2024): 3104–3111.

[133] L. Zhang, H. Huang, Z. Lv, et al., “Phonon Properties of Bulk Violet Phosphorus Single Crystals: Temperature and Pressure Evolution,” Acs Applied Electronic Materials 3, no. 3 (2021): 1043–1049.

[134] J. Wang, F. Liu, Y. Li, et al., “Enhancement of Broadband Reverse Saturable Absorption of Red/Black Phosphorus Heterojunction,” Molecules 29, no. 6 (2024): 1271.

[135] Y. Liu, Q. Liu, A. Zhang, et al., “Room-Temperature Pressure Synthesis of Layered Black Phosphorus–Graphene Composite for Sodium-Ion Battery Anodes,” ACS Nano 12, no. 8 (2018): 8323–8329.

[136] T. Bao, A. Bolag, X. Tian, and T. Ojiyed, “Synthesis of Black Phosphorene/P-Rich Transition Metal Phosphide NiP3 Heterostructure and Its Effect on the Stabilization of Black Phosphorene,” Crystals 13, no. 11 (2023): 1571.

[137] A. Ozawa, M. Yamamoto, T. Tanabe, S. Hosokawa, and T. Yoshida, “Black Phosphorus Synthesized by Solvothermal Reaction From Red Phosphorus and Its Catalytic Activity for Water Splitting,” Journal of Materials Chemistry A 8 (2020): 7368–7376.

[138] S. Zhu, Q. Liang, Y. Xu, H. Fu, and X. Xiao, “Facile Solvothermal Synthesis of Black Phosphorus Nanosheets From Red Phosphorus for Efficient Photocatalytic Hydrogen Evolution,” European Journal of Inorganic Chemistry 2020, no. 9 (2020): 773–779.

[139] N. Sultana, A. Degg, S. Upadhyaya, T. Nilges, and N. Sen Sarma, “Synthesis, Modification, and Application of Black Phosphorus, Few-Layer Black Phosphorus (FLBP), and Phosphorene: A Detailed Review,” Materials Advances 3, no. 14 (2022): 5557–5574.

[140] H. Wang, K. Hu, Z. Li, et al., “Black Phosphorus Nanosheets Passivation Using a Tripeptide,” Small 14, no. 35 (2018): 1801701.

[141] J. Sun, G. Zheng, H. W. Lee, et al., “Formation of Stable Phosphorus–Carbon Bond for Enhanced Performance in Black Phosphorus Nanoparticle–Graphite Composite Battery Anodes,” Nano Letters 14, no. 8 (2014): 4573–4580.

[142] L. Chen, G. Zhou, Z. Liu, et al., “Scalable Clean Exfoliation of High-Quality Few-Layer Black Phosphorus for a Flexible Lithium Ion Battery,” Advanced Materials 28 (2016): 510–517.

[143] Q. Jiang, J. Li, N. Yuan, Z. Wu, and J. Tang, “Black Phosphorus With Superior Lithium Ion Batteries Performance Directly Synthesized by the Efficient Thermal-Vaporization Method,” Electrochimica Acta 263 (2018): 272–276.

[144] T. Ramireddy, T. Xing, M. M. Rahman, et al., “Phosphorus–Carbon Nanocomposite Anodes for Lithium-Ion and Sodium-Ion Batteries,” Journal of Materials Chemistry A 3, no. 10 (2015): 5572–5584.

[145] C.-M. Park and H.-J. Sohn, “Black Phosphorus and Its Composite for Lithium Rechargeable Batteries,” Advanced Materials 19, no. 18 (2007): 2465–2468.

[146] R. Wang, X. Dai, Z. Qian, et al., “Boosting Lithium Storage in Free-Standing Black Phosphorus Anode via Multifunction of Nanocellulose,” ACS Applied Materials & Interfaces 12, no. 28 (2020): 31628–31636.

[147] Y. Shi, Z. Yi, Y. Kuang, et al., “Constructing Stable Covalent Bonding in Black Phosphorus/Reduced Graphene Oxide for Lithium Ion Battery Anodes,” Chemical Communications 56, no. 78 (2020): 11613–11616.

[148] S. Haghighat-Shishavan, M. Nazarian-Samani, M. Nazarian-Samani, et al., “Strong, Persistent Superficial Oxidation-Assisted Chemical Bonding of Black Phosphorus With Multiwall Carbon Nanotubes for High-Capacity Ultradurable Storage of Lithium and Sodium,” Journal of Materials Chemistry A 6, no. 21 (2018): 10121–10134.

[149] D. Zhao, L. Zhang, C. Fu, et al., “Hierarchical Phosphorus Hybrids With Carbon Nanotube Veins and Black Phosphorus Skins: Structure and Lithium Storage Properties,” Carbon 139 (2018): 1057–1062.

[150] H. Jin, S. Xin, C. Chuang, et al., “Black Phosphorus Composites With Engineered Interfaces for High-Rate High-Capacity Lithium Storage,” Science 370, no. 6513 (2020): 192–197.

[151] S. Yuan, G. Sun, J. Hong, and H. Jin, “Black Phosphorus/PANI/Carbon Nanotube Composite as a Lithium-Ion Battery Anode,” ACS Applied Nano Materials 7, no. 7 (2024): 7766–7772.

[152] Y. Zhang, W. Sun, Z. Z. Luo, et al., “Functionalized Few-Layer Black Phosphorus With Super-Wettability Towards Enhanced Reaction Kinetics for Rechargeable Batteries,” Nano Energy 40 (2017): 576–586.

[153] T.-H. Kim, K.-J. Jeon, and C.-M. Park, “Al, or Ti Composites as Superior Li-Ion Battery Anodes,” Chemical Engineering Journal 424 (2021): 130366.

[154] Y. Luo, H. Wu, L. Liu, et al., “TiO₂-Nanocoated Black Phosphorus Electrodes With Improved Electrochemical Performance,” ACS Applied Materials & Interfaces 10, no. 42 (2018): 36058–36066.

[155] J. Mei, Y. Zhang, T. Liao, X. Peng, G. A. Ayoko, and Z. Sun, “Black Phosphorus Nanosheets Promoted 2D-TiO₂-2D Heterostructured Anode for High-Performance Lithium Storage,” Energy Storage Materials 19 (2019): 424–431.

[156] S. Dong, L. Li, W. Ai, et al., “A Composite Anode Based on Intercalation and Conversion Mechanism for High-Rate Lithium-Ion Batteries,” Journal of Alloys and Compounds 1009 (2024): 176976.

[157] K. Roy, M. Wahid, D. Puthusseri, et al., “High Capacity, Power Density and Cycling Stability of Silicon Li-Ion Battery Anodes With a Few Layer Black Phosphorus Additive,” Sustainable Energy & Fuels 3, no. 1 (2019): 245–250.

[158] T. Yuan, X. Cui, J. Li, et al., “A High-Capacity Black Phosphorus-Graphite-Sn Anode for Lithium-Ion Batteries,” Materials Letters 343 (2023): 134376.

[159] P. Wang, H. Li, L. Song, et al., “How Does Nickel (Ni) Modify Two-Dimensional Black Phosphorus to Enhance Its Electrochemical Lithium Storage Performance?,” Journal of Alloys and Compounds 968 (2023): 172103.

[160] J. Jin, Y. Zheng, S. Huang, et al., “Directly Anchoring 2D Nico Metal–Organic Frameworks on Few-Layer Black Phosphorus for Advanced Lithium-Ion Batteries,” Journal of Materials Chemistry A 7, no. 2 (2019): 783–790.

[161] X. Li, W. Li, P. Shen, et al., “Layered GeP-Black P(Ge2P3): An Advanced Binary-Phase Anode for Li/Na-Storage,” Ceramics International 45, no. 12 (2019): 15711–15714.

[162] W. Li, P. Shen, J. Liao, et al., “Cu₂P₇-black P-MWCNTs (CuP₅/MWCNTs): An Advanced Hybrid Anode for Li/Na-Ion Batteries,” Materials Letters 253 (2019): 263–267.

[163] R. Meng, J. Huang, Y. Feng, et al., “Black Phosphorus Quantum Dot/Ti₃C₂ MXene Nanosheet Composites for Efficient Electrochemical Lithium/Sodium-Ion Storage,” Advanced Energy Materials 8, no. 26 (2018): 1801514.

[164] P. Lian, X. Li, L. Niu, et al., “High-Performance Black Phosphorus/Cnts/Mxene Ternary Composite as an Anode Material for Lithium-Ion Batteries,” SSRN Electronic Journal (2022), http://dx.doi.org/10.2139/ssrn.4088114.

[165] X. Chen, G. Xu, X. Ren, et al., “A Black/Red Phosphorus Hybrid as an Electrode Material for High-Performance Li-Ion Batteries and Supercapacitors,” Journal of Materials Chemistry A 5, no. 14 (2017): 6581–6588.

[166] F. Zhou, L. Liu, D. Dai, et al., “LiF-Induced In-Situ Engineering of a Dense Inorganic SEI for Superior Lithium Storage in Black Phosphorus Anode,” Journal of Colloid and Interface Science 680 (2025): 364–372.

[167] H. Kuai, C. Ji, X. Ma, X. Xiong, and S. Zhong, “Black Phosphorus Stabilized by Titanium Disulfide and Graphite via Chemical Bonds for High-Performance Lithium Storage,” Journal of Colloid and Interface Science 643 (2023): 1–8.

[168] S. Zhou, J. Li, L. Fu, et al., “Black Phosphorus/Hollow Porous Carbon for High Rate Performance Lithium-Ion Battery,” ChemElectroChem 7, no. 9 (2020): 2184–2189.

[169] M. Nagao, A. Hayashi, and M. Tatsumisago, “All-Solid-State Lithium Secondary Batteries With High Capacity Using Black Phosphorus Negative Electrode,” Journal of Power Sources 196, no. 16 (2011): 6902–6905.

[170] J. Yang, F. Mo, L. Huang, H. Liang, G. Sun, and S. Peng, “Building a C-P Bond to Unlock the Reversible and Fast Lithium Storage Performance of Black Phosphorus in All-Solid-State Lithium-Ion Batteries,” Materials Today Energy 20 (2021): 100662.

[171] Y. Zhang, L. Wang, H. Xu, J. Cao, D. Chen, and W. Han, “3D Chemical Cross-Linking Structure of Black Phosphorus@CNTs Hybrid as a Promising Anode Material for Lithium Ion Batteries,” Advanced Functional Materials 30, no. 12 (2020): 1909372.

[172] F. Zhou, L. Ouyang, J. Liu, X. S. Yang, and M. Zhu, “Chemical Bonding Black Phosphorus With TiO₂ and Carbon Toward High-Performance Lithium Storage,” Journal of Power Sources 449 (2020): 227549.

[173] K. Roy, M. Wahid, D. Puthusseri, et al., “High Capacity, Power Density and Cycling Stability of Silicon Li-Ion Battery Anode by Few Layer Black Phosphorous Additive,” Sustainable Energy & Fuels 3 (2019): 245–250.

[174] R. Amine, A. Daali, X. Zhou, et al., “A Practical Phosphorus-Based Anode Material for High-Energy Lithium-Ion Batteries,” Nano Energy 74 (2020): 104849.

[175] Y. Shi, Z. Yi, Y. Kuang, et al., “Constructing Stable Covalent Bonding in Black Phosphorus/Reduced Graphene Oxide for Lithium Ion Battery Anodes,” Chemical Communications 56, no. 78 (2020): 11613–11616.

[176] L. Pan, X. D. Zhu, K. N. Sun, Y. T. Liu, X. M. Xie, and X. Y. Ye, “Molecular Level Distribution of Black Phosphorus Quantum Dots on Nitrogen-Doped Graphene Nanosheets for Superior Lithium Storage,” Nano Energy 30 (2016): 347–354.

[177] F. Zhou, L. Liu, X. Hou, et al., “Synergistic Effect of Vinylene Carbonate and Fluoroethylene Carbonate in Constructing a Robust yet Flexible SEI for High Performance Black Phosphorus Anodes,” Journal of Alloys and Compounds 1036 (2025): 181804.

[178] T. Song, H. Chen, Z. Li, et al., “Creating an Air-Stable Sulfur-Doped Black Phosphorus-TiO2 Composite as High-Performance Anode Material for Sodium-Ion Storage,” Advanced Functional Materials 29, no. 22 (2019): 1900535.

[179] J. Pei, X. Gai, J. Yang, et al., “Producing Air-Stable Monolayers of Phosphorene and Their Defect Engineering,” Nature Communications 7, no. 1 (2016): 10450.

[180] T. Yang, I. Abdelwahab, H. Lin, et al., “Anisotropic Third-Order Nonlinearity in Pristine and Lithium Hydride Intercalated Black Phosphorus,” ACS Photonics 5, no. 12 (2018): 4969–4977.

[181] G.-L. Xu, Z. Chen, G. M. Zhong, et al., “Nanostructured Black Phosphorus/Ketjenblack–Multiwalled Carbon Nanotubes Composite as High Performance Anode Material for Sodium-Ion Batteries,” Nano Letters 16, no. 6 (2016): 3955–3965.

[182] M.-L. Lee, C. Y. Su, Y. H. Lin, et al., “Atomic Layer Deposition of TiO₂ on Negative Electrode for Lithium Ion Batteries,” Journal of Power Sources 244 (2013): 410–416.

[183] K.-Y. Chin, J. L. You, P. C. Chen, Y. C. Su, and S. M. Chang, “Influence of Binder Selection and Phosphorus-to-Graphite Ratios on the Electrical Performance of Transformed Black Phosphorus/Graphite Composite Anodes for Lithium-Ion Batteries,” Materials Science in Semiconductor Processing 200 (2025): 110004.

[184] J. W. Choi and D. Aurbach, “Promise and Reality of Post-Lithium-Ion Batteries With High Energy Densities,” Nature Reviews Materials 1, no. 4 (2016): 16013.

[185] H. Jin, T. Zhang, C. Chuang, et al., “Synergy of Black Phosphorus–Graphite–Polyaniline-Based Ternary Composites for Stable High Reversible Capacity Na-Ion Battery Anodes,” ACS Applied Materials & Interfaces 11, no. 18 (2019): 16656–16661.

[186] Y. Cheng, Y. Zhu, Y. Han, et al., “Sodium-Induced Reordering of Atomic Stacks in Black Phosphorus,” Chemistry of Materials 29, no. 3 (2017): 1350–1356.

[187] J. Tan, Z. Wang, J. Cui, et al., “PEO Composite Solid Polymer Electrolytes With the Synergistic Effect of Cryogenic Engineering and Trace BP Nanosheets for Nearly Room Temperature and 4 V Class All-Solid-State Lithium Batteries,” Sustainable Energy & Fuels 7, no. 3 (2023): 652–660.

[188] S. Jadhav, L. Kaulage, S. Saha, A. Bano, and S. Ogale, “Black Phosphorus Nanosheets as Efficient Ion Navigators at Room Temperature in Polyacrylonitrile-Based Composite Solid Polymer Electrolyte for Li-Ion Batteries,” Small 21, no. 41 (2025): e04995.

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