Molecular Layer Deposition for Surface Modification of Emerging Battery Systems

Abstract

In pursuing a fully electrified society, rechargeable batteries have become a commodity related to national security and prosperity. While state-of-the-art lithium-ion batteries (LIBs) are dominating portable electronics and quickly penetrating the market of electric vehicles, they also have become insufficient in energy density, cost, safety, and lifetime. To this end, new electrode chemistries are undergoing intensive investigation for next-generation LIBs and beyond technologies. Among potential anodes, silicon (Si), lithium (Li) metal, and sodium (Na) metal are among the most promising ones, ascribed to their extremely high capacities. On the cathode side, layer-structured metal oxides are still very compelling. However, all these electrode materials suffer from a series of issues, which hinder them from commercialization. Among various strategies to tackle these issues, surface modification is facile and effective for improving electrodes' performance, highly depending on the properties and quality of surface coatings. In this respect, molecular layer deposition (MLD) recently has emerged as a new technique enabling novel polymeric coatings, featuring its high-quality film coverage, unrivaled uniform and conformal coating, moderate process temperatures, and extremely accurate film growth at the molecular level. In this review, we present a comprehensive review on the MLD's latest applications for surface modification of next-generation high-energy LIBs, Li metal batteries (LMBs), Na-based batteries, and solid-state batteries. We expect that this article would ignite new sparks on searching novel solutions of emerging battery systems using MLD.

Keywords

lithium batteries / molecular layer deposition / solid-state batteries / sodium batteries / surface modification

References

[1] S. Zhang, “Status, Opportunities, and Challenges of Electrochemical Energy Storage,” Frontiers in Energy Research 1 (2013): 8, https://doi.org/10.3389/fenrg.2013.00008.

[2] G. E. Blomgren, “The Development and Future of Lithium Ion Batteries,” Journal of the Electrochemical Society 164, no. 1 (2017): A5019–A5025, https://doi.org/10.1149/2.0251701jes.

[3] R. Schmuch, R. Wagner, G. Hörpel, T. Placke, and M. Winter, “Performance and Cost of Materials for Lithium-Based Rechargeable Automotive Batteries,” Nature Energy 3, no. 4 (2018): 267–278, https://doi.org/10.1038/s41560-018-0107-2.

[4] X. Meng, “Interface Engineering of Lithium Metal Anodes via Atomic and Molecular Layer Deposition,” Inorganic Chemistry Frontiers 11, no. 3 (2024): 659–681, https://doi.org/10.1039/d3qi02241b.

[5] X. Meng, “Atomic-Scale Surface Modifications and Novel Electrode Designs for High-Performance Sodium-Ion Batteries via Atomic Layer Deposition,” Journal of Materials Chemistry A 5, no. 21 (2017): 10127–10149, https://doi.org/10.1039/c7ta02742g.

[6] C. Zhu, K. Han, D. Geng, H. Ye, and X. Meng, “Achieving High-Performance Silicon Anodes of Lithium-Ion Batteries via Atomic and Molecular Layer Deposited Surface Coatings: An Overview,” Electrochimica Acta 251 (2017): 710–728, https://doi.org/10.1016/j.electacta.2017.09.036.

[7] X. Wang and X.-B. Meng, “Surface Modifications of Layered LiNixMnyCozO₂ Cathodes via Atomic and Molecular Layer Deposition,” Rare Metals 42, no. 7 (2023): 2121–2156, https://doi.org/10.1007/s12598-022-02243-3.

[8] J. T. Frith, M. J. Lacey, and U. Ulissi, “A Non-Academic Perspective on the Future of Lithium-Based Batteries,” Nature Communications 14, no. 1 (2023): 420, https://doi.org/10.1038/s41467-023-35933-2.

[9] G. G. Eshetu, H. Zhang, X. Judez, et al., “Production of High-Energy Li-ion Batteries Comprising Silicon-Containing Anodes and Insertion-Type Cathodes,” Nature Communications 12, no. 1 (2021): 5459, https://doi.org/10.1038/s41467-021-25334-8.

[10] J. Liu, Z. Bao, Y. Cui, et al., “Pathways for Practical High-Energy Long-Cycling Lithium Metal Batteries,” Nature Energy 4, no. 3 (2019): 180–186, https://doi.org/10.1038/s41560-019-0338-x.

[11] S. Yari, A. Conde Reis, Q. Pang, and M. Safari, “Performance Benchmarking and Analysis of Lithium-Sulfur Batteries for Next-Generation Cell Design,” Nature Communications 16, no. 1 (2025): 5473, https://doi.org/10.1038/s41467-025-60528-4.

[12] A. D. Pathak, E. Cha, and W. Choi, “Towards the Commercialization of Li-S Battery: From Lab to Industry,” Energy Storage Materials 72 (2024): 103711, https://doi.org/10.1016/j.ensm.2024.103711.

[13] S.-T. Myung, K. Amine, and Y.-K. Sun, “Surface Modification of Cathode Materials From Nano- to Microscale for Rechargeable Lithium-Ion Batteries,” Journal of Materials Chemistry 20, no. 34 (2010): 7074–7095, https://doi.org/10.1039/c0jm00508h.

[14] J. Kim, Y.-W. Cho, S.-G. Woo, J.-N. Lee, and G.-H. Lee, “Advancements in Chemical Vapor Deposited Carbon Films for Secondary Battery Applications,” Small 21, no. 12 (2025): 2410570, https://doi.org/10.1002/smll.202410570.

[15] X. Y. Dai, L. P. Wang, J. Xu, Y. Wang, A. J. Zhou, and J. Z. Li, “Improved Electrochemical Performance of LiCoO₂ Electrodes With ZnO Coating by Radio Frequency Magnetron Sputtering,” ACS Applied Materials and Interfaces 6, no. 18 (2014): 15853–15859, https://doi.org/10.1021/am503260s.

[16] L. Sun, G. Yuan, L. Gao, et al., “Chemical Vapour Deposition,” Nature Reviews Methods Primers 1, no. 1 (2021): 5, https://doi.org/10.1038/s43586-020-00005-y.

[17] S. Lobe, A. Bauer, S. Uhlenbruck, and D. Fattakhova-Rohlfing, “Physical Vapor Deposition in Solid-State Battery Development: From Materials to Devices,” Advanced Science 8, no. 11 (2021): 2002044, https://doi.org/10.1002/advs.202002044.

[18] M. Qi, L. Wang, X. Huang, M. Ma, and X. He, “Surface Engineering of Cathode Materials: Enhancing the High Performance of Lithium-Ion Batteries,” Small 20, no. 38 (2024): 2402443, https://doi.org/10.1002/smll.202402443.

[19] M. Q. Snyder, S. A. Trebukhova, B. Ravdel, et al., “Synthesis and Characterization of Atomic Layer Deposited Titanium Nitride Thin Films on Lithium Titanate Spinel Powder as a Lithium-Ion Battery Anode,” Journal of Power Sources 165, no. 1 (2007): 379–385, https://doi.org/10.1016/j.jpowsour.2006.12.015.

[20] X. Meng, X. Q. Yang, and X. L. Sun, “Emerging Applications of Atomic Layer Deposition for Lithium-Ion Battery Studies,” Advanced Materials 24, no. 27 (2012): 3589–3615, https://doi.org/10.1002/adma.201200397.

[21] X. Meng, “Atomic Layer Deposition of Solid-State Electrolytes for Next-Generation Lithium-Ion Batteries and Beyond: Opportunities and Challenges,” Energy Storage Materials 30 (2020): 296–328, https://doi.org/10.1016/j.ensm.2020.05.001.

[22] X. Meng, “Atomic and Molecular Layer Deposition in Pursuing Better Batteries,” Journal of Materials Research 36, no. 1 (2021): 2–25, https://doi.org/10.1557/s43578-020-00054-9.

[23] X. Meng, “An Overview of Molecular Layer Deposition for Organic and Organic-Inorganic Hybrid Materials: Mechanisms, Growth Characteristics, and Promising Applications,” Journal of Materials Chemistry A 5, no. 35 (2017): 18326–18378, https://doi.org/10.1039/c7ta04449f.

[24] A. J. Loebl, C. J. Oldham, C. K. Devine, et al., “Solid Electrolyte Interphase on Lithium-Ion Carbon Nanofiber Electrodes by Atomic and Molecular Layer Deposition,” Journal of the Electrochemical Society 160, no. 11 (2013): A1971–A1978, https://doi.org/10.1149/2.020311jes.

[25] X. Meng, X. Wang, D. Geng, C. Ozgit-Akgun, N. Schneider, and J. W. Elam, “Atomic Layer Deposition for Nanomaterial Synthesis and Functionalization in Energy Technology,” Materials Horizons 4, no. 2 (2017): 133–154, https://doi.org/10.1039/c6mh00521g.

[26] Q. Sun, K. C. Lau, D. Geng, and X. Meng, “Atomic and Molecular Layer Deposition for Superior Lithium-Sulfur Batteries: Strategies, Performance, and Mechanisms,” Batteries & Supercaps 1, no. 2 (2018): 41–68, https://doi.org/10.1002/batt.201800043.

[27] N. P. Dasgupta, X. Meng, J. W. Elam, and A. B. Martinson, “Atomic Layer Deposition of Metal Sulfide Materials,” Accounts of Chemical Research 48, no. 2 (2015): 341–348, https://doi.org/10.1021/ar500360d.

[28] M. D. Groner, F. H. Fabreguette, J. W. Elam, and S. M. George, “Low-Temperature Al₂O₃ Atomic Layer Deposition,” Chemistry of Materials 16, no. 4 (2004): 639–645, https://doi.org/10.1021/cm0304546.

[29] R. L. Puurunen, “Surface Chemistry of Atomic Layer Deposition: A Case Study for the Trimethylaluminum/Water Process,” Journal of Applied Physics 97, no. 12 (2005): 121301, https://doi.org/10.1063/1.1940727.

[30] S. M. George, B. Yoon, and A. A. Dameron, “Surface Chemistry for Molecular Layer Deposition of Organic and Hybrid Organic−Inorganic Polymers,” Accounts of Chemical Research 42, no. 4 (2009): 498–508, https://doi.org/10.1021/ar800105q.

[31] H. Zhou and S. F. Bent, “Fabrication of Organic Interfacial Layers by Molecular Layer Deposition: Present Status and Future Opportunities,” Journal of Vacuum Science & Technology A 31, no. 4 (2013): 040801, https://doi.org/10.1116/1.4804609.

[32] H.-I. Shao, S. Umemoto, T. Kikutani, and N. Okui, “Layer-By-Layer Polycondensation of Nylon 66 by Alternating Vapour Deposition Polymerization,” Polymer 38, no. 2 (1997): 459–462, https://doi.org/10.1016/s0032-3861(96)00504-6.

[33] Y. Du and S. M. George, “Molecular Layer Deposition of Nylon 66 Films Examined Using in Situ FTIR Spectroscopy,” Journal of Physical Chemistry C 111, no. 24 (2007): 8509–8517, https://doi.org/10.1021/jp067041n.

[34] X. Meng, “Molecular Layer Deposition of Organic–Inorganic Hybrid Materials,” in Optoelectronic Organic-Inorganic Semiconductor Heterojunctions. 1st ed. (CRC Press, 2021), 37–70.

[35] A. A. Dameron, D. Seghete, B. B. Burton, et al., “Molecular Layer Deposition of Alucone Polymer Films Using Trimethylaluminum and Ethylene Glycol,” Chemistry of Materials 20, no. 10 (2008): 3315–3326, https://doi.org/10.1021/cm7032977.

[36] M. Vähä-Nissi, J. Sievänen, E. Salo, et al., “Atomic and Molecular Layer Deposition for Surface Modification,” Journal of Solid State Chemistry 214 (2014): 7–11, https://doi.org/10.1016/j.jssc.2013.11.040.

[37] Q. Peng, B. Gong, R. M. VanGundy, and G. N. Parsons, “‘Zincone’ Zinc Oxide−Organic Hybrid Polymer Thin Films Formed by Molecular Layer Deposition,” Chemistry of Materials 21, no. 5 (2009): 820–830, https://doi.org/10.1021/cm8020403.

[38] B. Yoon, J. L. O'Patchen, D. Seghete, A. S. Cavanagh, and S. M. George, “Molecular Layer Deposition of Hybrid Organic-Inorganic Polymer Films Using Diethylzinc and Ethylene Glycol,” Chemical Vapor Deposition 15, no. 4–6 (2009): 112–121, https://doi.org/10.1002/cvde.200806756.

[39] K. Van de Kerckhove, F. Mattelaer, J. Dendooven, and C. Detavernier, “Molecular Layer Deposition of ‘Vanadicone’, A Vanadium-based Hybrid Material, as an Electrode for Lithium-Ion Batteries,” Dalton Transactions 46, no. 14 (2017): 4542–4553, https://doi.org/10.1039/c7dt00374a.

[40] B. H. Lee, V. R. Anderson, and S. M. George, “Molecular Layer Deposition of Zircone and ZrO₂/zircone Alloy Films: Growth and Properties,” Chemical Vapor Deposition 19, no. 4–6 (2013): 204–212, https://doi.org/10.1002/cvde.201207045.

[41] R. A. Hall, S. M. George, Y. Kim, et al., “Growth of Zircone on Nanoporous Alumina Using Molecular Layer Deposition,” JOM 66, no. 4 (2014): 649–653, https://doi.org/10.1007/s11837-014-0933-z.

[42] B. H. Lee, V. R. Anderson, and S. M. George, “Growth and Properties of Hafnicone and HfO₂/hafnicone Nanolaminate and Alloy Films Using Molecular Layer Deposition Techniques,” ACS Applied Materials and Interfaces 6, no. 19 (2014): 16880–16887, https://doi.org/10.1021/am504341r.

[43] A. I. Abdulagatov, K. E. Terauds, J. J. Travis, A. S. Cavanagh, R. Raj, and S. M. George, “Pyrolysis of Titanicone Molecular Layer Deposition Films as Precursors for Conducting TiO₂/Carbon Composite Films,” Journal of Physical Chemistry C 117, no. 34 (2013): 17442–17450, https://doi.org/10.1021/jp4051947.

[44] O. Nilsen, K. R. Haug, T. Finstad, and H. Fjellvåg, “Molecular Hybrid Structures by Atomic Layer Deposition – Deposition of Alq₃, Znq₂ and Tiq₄ (Q = 8-hydroxyquinoline),” Chemical Vapor Deposition 19, no. 4–6 (2013): 174–179, https://doi.org/10.1002/cvde.201207043.

[45] A. Räupke, F. Albrecht, J. Maibach, et al., “Conformal and Highly Luminescent Monolayers of Alq₃ Prepared by Gas-Phase Molecular Layer Deposition,” ACS Applied Materials and Interfaces 6, no. 2 (2014): 1193–1199, https://doi.org/10.1021/am404918g.

[46] L. D. Salmi, M. J. Heikkilä, E. Puukilainen, T. Sajavaara, D. Grosso, and M. Ritala, “Studies on Atomic Layer Deposition of MOF-5 Thin Films,” Microporous and Mesoporous Materials 182 (2013): 147–154, https://www.sciencedirect.com/science/article/pii/S1387181113004125.

[47] L. D. Salmi, M. J. Heikkilä, M. Vehkamäki, E. Puukilainen, M. Ritala, and T. Sajavaara, “Studies on Atomic Layer Deposition of IRMOF-8 Thin Films,” Journal of Vacuum Science & Technology A 33, no. 1 (2015): 01A121, https://doi.org/10.1116/1.4901455.

[48] E. Ahvenniemi and M. Karppinen, “Atomic/Molecular Layer Deposition: A Direct Gas-Phase Route to Crystalline Metal-Organic Framework Thin Films,” Chemical Communications 52, no. 6 (2016): 1139–1142, https://doi.org/10.1039/c5cc08538a.

[49] M. Nisula and M. Karppinen, “Atomic/Molecular Layer Deposition of Lithium Terephthalate Thin Films as High Rate Capability Li-ion Battery Anodes,” Nano Letters 16, no. 2 (2016): 1276–1281, https://doi.org/10.1021/acs.nanolett.5b04604.

[50] C.-Y. Kao, J.-W. Yoo, Y. Min, and A. J. Epstein, “Molecular Layer Deposition of an Organic-based Magnetic Semiconducting Laminate,” ACS Applied Materials and Interfaces 4, no. 1 (2012): 137–141, https://doi.org/10.1021/am201506h.

[51] C.-Y. Kao, B. Li, Y. Lu, J.-W. Yoo, and A. J. Epstein, “Thin Films of Organic-Based Magnetic Materials of Vanadium and Cobalt Tetracyanoethylene by Molecular Layer Deposition,” Journal of Materials Chemistry C: Materials for Optical and Electronic Devices 2, no. 30 (2014): 6171–6176, https://doi.org/10.1039/c4tc00673a.

[52] B. Zhang, Y. Chen, J. Li, et al., “High Efficiency Cu-ZnO Hydrogenation Catalyst: The Tailoring of Cu-ZnO Interface Sites by Molecular Layer Deposition,” ACS Catalysis 5, no. 9 (2015): 5567–5573, https://doi.org/10.1021/acscatal.5b01266.

[53] T. Tynell, H. Yamauchi, and M. Karppinen, “Hybrid Inorganic–Organic Superlattice Structures With Atomic Layer Deposition/Molecular Layer Deposition,” Journal of Vacuum Science & Technology A 32, no. 1 (2014): 01A105, https://doi.org/10.1116/1.4831751.

[54] T. Tynell and M. Karppinen, “Zno: Hydroquinone Superlattice Structures Fabricated by Atomic/Molecular Layer Deposition,” Thin Solid Films 551 (2014): 23–26, https://doi.org/10.1016/j.tsf.2013.11.067.

[55] B. H. Lee, M. K. Ryu, S.-Y. Choi, K.-H. Lee, S. Im, and M. M. Sung, “Rapid Vapor-Phase Fabrication of Organic−Inorganic Hybrid Superlattices With Monolayer Precision,” Journal of the American Chemical Society 129, no. 51 (2007): 16034–16041, https://doi.org/10.1021/ja075664o.

[56] S. H. Cha, M. S. Oh, K. H. Lee, S. Im, B. H. Lee, and M. M. Sung, “Electrically Stable Low Voltage ZnO Transistors With Organic/Inorganic Nanohybrid Dielectrics,” Applied Physics Letters 92, no. 2 (2008): 023506, https://doi.org/10.1063/1.2827588.

[57] K. H. Lee, J.-M. Choi, S. Im, et al., “Low-Voltage-Driven Pentacene Thin-Film Transistor With an Organic-Inorganic Nanohybrid Dielectric,” Applied Physics Letters 91, no. 12 (2007): 123502, https://doi.org/10.1063/1.2786595.

[58] B. H. Lee, K. H. Lee, S. Im, and M. M. Sung, “Vapor-Phase Molecular Layer Deposition of Self-Assembled Multilayers for Organic Thin-Film Transistor,” Journal of Nanoscience and Nanotechnology 9, no. 12 (2009): 6962–6967, https://doi.org/10.1166/jnn.2009.1645.

[59] J. Huang, M. Lee, A. Lucero, and J. Kim, “Organic-Inorganic Hybrid Nano-Laminates Fabricated by Ozone-assisted Molecular-Atomic Layer Deposition,” Chemical Vapor Deposition 19, no. 4–6 (2013): 142–148, https://doi.org/10.1002/cvde.201207041.

[60] J. Huang, M. Lee, A. T. Lucero, L. Cheng, M.-W. Ha, and J. Kim, “7-Octenyltrichrolosilane/trimethyaluminum Hybrid Dielectrics Fabricated by Molecular-Atomic Layer Deposition on ZnO Thin Film Transistors,” Japanese Journal of Applied Physics 55, no. 6S1 (2016): 06GK04, https://doi.org/10.7567/jjap.55.06gk04.

[61] B. H. Lee, K. K. Im, K. H. Lee, S. Im, and M. M. Sung, “Molecular Layer Deposition of ZrO₂-Based Organic–Inorganic Nanohybrid Thin Films for Organic Thin Film Transistors,” Thin Solid Films 517, no. 14 (2009): 4056–4060, https://doi.org/10.1016/j.tsf.2009.01.173.

[62] K. Velasquez Carballo, M. Singh, and X. Meng, “Accurately Constituting Robust Interfaces for High-Performance High-Energy Lithium Metal Batteries,” Chemical Communications 61, no. 8 (2025): 1574–1588, https://doi.org/10.1039/d4cc05705h.

[63] X. Meng, K. C. Lau, H. Zhou, S. K. Ghosh, M. Benamara, and M. Zou, “Molecular Layer Deposition of Crosslinked Polymeric Lithicone for Superior Lithium Metal Anodes,” Energy Material Advances 2021 (2021): 9786201, https://doi.org/10.34133/2021/9786201.

[64] R. A. Ahmed, K. V. Carballo, K. P. Koirala, et al., “Lithicone-Protected Lithium Metal Anodes for Lithium Metal Batteries With Nickel-Rich Cathode Materials,” Small Structures 5, no. 11 (2024): 2400174, https://doi.org/10.1002/sstr.202400174.

[65] K. V. Carballo, X. Wang, M. Benamara, and X. Meng, “Effects of Cathode Loadings and Anode Protection on the Performance of Lithium Metal Batteries,” Nanotechnology 35, no. 7 (2024): 075401, https://doi.org/10.1088/1361-6528/ad0d25.

[66] X. Wang, J. Cai, K. Velasquez Carballo, F. Watanabe, and X. Meng, “Tackling Issues of Lithium Metal Anodes With a Novel Polymeric Lithicone Coating,” Chemical Engineering Journal 475 (2023): 146156, https://doi.org/10.1016/j.cej.2023.146156.

[67] X. Wang, K. Velasquez Carballo, A. Shao, J. Cai, F. Watanabe, and X. Meng, “A Novel Polymeric Lithicone Coating for Superior Lithium Metal Anodes,” Nano Energy 128 (2024): 109840, https://doi.org/10.1016/j.nanoen.2024.109840.

[68] X. Liang and A. W. Weimer, “An Overview of Highly Porous Oxide Films With Tunable Thickness Prepared by Molecular Layer Deposition,” Current opinion in solid state and Materials Science 19, no. 2 (2015): 115–125, https://doi.org/10.1016/j.cossms.2014.08.002.

[69] F. S. M. Hashemi, C. Prasittichai, and S. F. Bent, “A New Resist for Area Selective Atomic and Molecular Layer Deposition on Metal–Dielectric Patterns,” Journal of Physical Chemistry C 118, no. 20 (2014): 10957–10962, https://doi.org/10.1021/jp502669f.

[70] C. Prasittichai, K. L. Pickrahn, F. S. Minaye Hashemi, D. S. Bergsman, and S. F. Bent, “Improving Area-Selective Molecular Layer Deposition by Selective SAM Removal,” ACS Applied Materials and Interfaces 6, no. 20 (2014): 17831–17836, https://doi.org/10.1021/am504441e.

[71] Y.-S. Park, S.-E. Choi, H. Kim, and J. S. Lee, “Fine-Tunable Absorption of Uniformly Aligned Polyurea Thin Films for Optical Filters Using Sequentially Self-Limited Molecular Layer Deposition,” ACS Applied Materials and Interfaces 8, no. 18 (2016): 11788–11795, https://doi.org/10.1021/acsami.6b02142.

[72] D. Choudhury, S. K. Sarkar, and N. Mahuli, “Molecular Layer Deposition of Alucone Films Using Trimethylaluminum and Hydroquinone,” Journal of Vacuum Science & Technology A 33, no. 1 (2015): 01A115, https://doi.org/10.1116/1.4900934.

[73] X. Liang, D. M. King, P. Li, S. M. George, and A. W. Weimer, “Nanocoating Hybrid Polymer Films on Large Quantities of Cohesive Nanoparticles by Molecular Layer Deposition,” AIChE Journal 55, no. 4 (2009): 1030–1039, https://doi.org/10.1002/aic.11757.

[74] D. M. Piper, J. J. Travis, M. Young, et al., “Reversible High-Capacity Si Nanocomposite Anodes for Lithium-Ion Batteries Enabled by Molecular Layer Deposition,” Advanced Materials 26, no. 10 (2014): 1596–1601, https://doi.org/10.1002/adma.201304714.

[75] D. Molina Piper, Y. Lee, S.-B. Son, et al., “Cross-Linked Aluminum Dioxybenzene Coating for Stabilization of Silicon Electrodes,” Nano Energy 22 (2016): 202–210, https://doi.org/10.1016/j.nanoen.2016.02.021.

[76] Y. Ma, J. M. Martinez de la Hoz, I. Angarita, et al., “Structure and Reactivity of Alucone-Coated Films on Si and LixSiy Surfaces,” ACS Applied Materials and Interfaces 7, no. 22 (2015): 11948–11955, https://doi.org/10.1021/acsami.5b01917.

[77] T. Mu, Y. Zhao, C. Zhao, et al., “Stable Silicon Anodes by Molecular Layer Deposited Artificial Zincone Coatings,” Advanced Functional Materials 31, no. 21 (2021): 2010526, https://doi.org/10.1002/adfm.202010526.

[78] J.-B. Fang, S.-z. Chang, Q. Ren, T.-q. Zi, D. Wu, and A.-D. Li, “Tailoring Stress and Ion-Transport Kinetics via a Molecular Layer Deposition-Induced Artificial Solid Electrolyte Interphase for Durable Silicon Composite Anodes,” ACS Applied Materials and Interfaces 13, no. 27 (2021): 32520–32530, https://doi.org/10.1021/acsami.1c07572.

[79] J. Fang, J. Li, W. Zhang, et al., “Molecular Layer Deposited Mechanically and Chemically Robust Niobicone Interface Empowering Silicon Nanowire Anodes With Competent Cyclabilities,” Chemical Engineering Journal 484 (2024): 149387, https://doi.org/10.1016/j.cej.2024.149387.

[80] J. M. Wallas, B. C. Welch, Y. Wang, et al., “Spatial Molecular Layer Deposition of Ultrathin Polyamide to Stabilize Silicon Anodes in Lithium-Ion Batteries,” ACS Applied Energy Materials 2, no. 6 (2019): 4135–4143, https://doi.org/10.1021/acsaem.9b00326.

[81] T. Mu, Y. Sun, C. Wang, et al., “Long-Life Silicon Anodes by Conformal Molecular-Deposited Polyurea Interface for Lithium Ion Batteries,” Nano Energy 103 (2022): 107829, https://doi.org/10.1016/j.nanoen.2022.107829.

[82] Y. Lyu, X. Wu, K. Wang, et al., “An Overview on the Advances of LiCoO₂ Cathodes for Lithium-Ion Batteries,” Advanced Energy Materials 11, no. 2 (2021): 2000982, https://doi.org/10.1002/aenm.202000982.

[83] X. Wang, J. Cai, Y. Liu, et al., “Atomic-Scale Constituting Stable Interface for Improved LiNi_0.6Mn_0.2Co_0.2O₂ Cathodes of Lithium-Ion Batteries,” Nanotechnology 32, no. 11 (2021): 115401, https://doi.org/10.1088/1361-6528/abd127.

[84] Y. Liu, X. Wang, S. K. Ghosh, et al., “Atomic Layer Deposition of Lithium Zirconium Oxides for the Improved Performance of Lithium-Ion Batteries,” Dalton Transactions 51, no. 7 (2022): 2737–2749, https://doi.org/10.1039/d1dt03600a.

[85] H. Gao, J. Cai, G.-L. Xu, et al., “Surface Modification for Suppressing Interfacial Parasitic Reactions of a Nickel-Rich Lithium-Ion Cathode,” Chemistry of Materials 31, no. 8 (2019): 2723–2730, https://doi.org/10.1021/acs.chemmater.8b04200.

[86] X. Li, J. Liu, X. Meng, et al., “Significant Impact on Cathode Performance of Lithium-Ion Batteries by Precisely Controlled Metal Oxide Nanocoatings via Atomic Layer Deposition,” Journal of Power Sources 247 (2014): 57–69, https://doi.org/10.1016/j.jpowsour.2013.08.042.

[87] I. Bloom, L. Trahey, A. Abouimrane, et al., “Effect of Interface Modifications on Voltage Fade in 0.5Li₂MnO₃.0.5LiNi_0.375Mn_0.375CO_0.25O₂ Cathode Materials,” Journal of Power Sources 249 (2014): 509–514, https://doi.org/10.1016/j.jpowsour.2013.10.035.

[88] Y. Gao, J. Park, and X. Liang, “Synergic Titanium Nitride Coating and Titanium Doping by Atomic Layer Deposition for Stable- and High-Performance Li-Ion Battery,” Journal of the Electrochemical Society 165, no. 16 (2018): A3871–A3877, https://doi.org/10.1149/2.0671816jes.

[89] O. Tiurin, N. Solomatin, M. Auinat, and Y. Ein-Eli, “Atomic Layer Deposition (ALD) of Lithium Fluoride (LiF) Protective Film on Li-Ion Battery LiMn1.5Ni0.5O4 Cathode Powder Material,” Journal of Power Sources 448 (2020): 227373, https://doi.org/10.1016/j.jpowsour.2019.227373.

[90] J. Xie, A. D. Sendek, E. D. Cubuk, et al., “Atomic Layer Deposition of Stable LiAlF₄ Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling,” ACS Nano 11, no. 7 (2017): 7019–7027, https://doi.org/10.1021/acsnano.7b02561.

[91] X. Wang, J. Cai, Y. Ren, et al., “High-Performance LiNi_0.8Mn_0.1Co_0.1O₂ Cathode by Nanoscale Lithium Sulfide Coating via Atomic Layer Deposition,” Journal of Energy Chemistry 69 (2022): 531–540, https://doi.org/10.1016/j.jechem.2022.02.015.

[92] O. Lidor-Shalev, N. Leifer, M. Ejgenberg, et al., “Rosy, Molecular Layer Deposition of Alucone Thin Film on LiCoO₂ to Enable High Voltage Operation,” Batteries & Supercaps 4, no. 11 (2021): 1739–1748, https://doi.org/10.1002/batt.202100152.

[93] K. Egorov, W. Zhao, K. Knemeyer, A. N. Filippin, A. Giraldo, and C. Battaglia, “Mitigating First-Cycle Capacity Losses in NMC811 via Lithicone Layers Grown by Molecular Layer Deposition,” ACS Applied Materials and Interfaces 15, no. 16 (2023): 20075–20080, https://doi.org/10.1021/acsami.2c23158.

[94] Z. Ahaliabadeh, V. Miikkulainen, M. Mäntymäki, et al., “Stabilized Nickel-Rich-Layered Oxide Electrodes for High-Performance Lithium-Ion Batteries,” Energy & Environmental Materials 7, no. 6 (2024): e12741, https://doi.org/10.1002/eem2.12741.

[95] M. S. Whittingham, “Electrical Energy Storage and Intercalation Chemistry,” Science 192, no. 4244 (1976): 1126–1127, https://doi.org/10.1126/science.192.4244.1126.

[96] W. Xu, J. Wang, F. Ding, et al., “Lithium Metal Anodes for Rechargeable Batteries,” Energy & Environmental Science 7, no. 2 (2014): 513–537, https://doi.org/10.1039/c3ee40795k.

[97] L. Chen, Z. Huang, R. Shahbazian-Yassar, et al., “Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li-S Batteries With High Sulfur Mass Loading,” ACS Applied Materials and Interfaces 10, no. 8 (2018): 7043–7051, https://doi.org/10.1021/acsami.7b15879.

[98] Y. Zhao, L. V. Goncharova, Q. Sun, et al., “Robust Metallic Lithium Anode Protection by the Molecular-Layer-Deposition Technique,” Small Methods 2, no. 5 (2018): 1700417, https://doi.org/10.1002/smtd.201700417.

[99] K. R. Adair, C. Zhao, M. N. Banis, et al., “Highly Stable Lithium Metal Anode Interface via Molecular Layer Deposition Zircone Coatings for Long Life Next-Generation Battery Systems,” Angewandte Chemie International Edition 58, no. 44 (2019): 15797–15802, https://doi.org/10.1002/anie.201907759.

[100] Y. Sun, Y. Zhao, J. Wang, et al., “A Novel Organic ‘Polyurea’ Thin Film for Ultralong-Life Lithium-Metal Anodes via Molecular-Layer Deposition,” Advanced Materials 31, no. 4 (2019): 1806541, https://doi.org/10.1002/adma.201806541.

[101] Y. Zhao, M. Amirmaleki, Q. Sun, et al., “Natural SEI-Inspired Dual-Protective Layers via Atomic/Molecular Layer Deposition for Long-Life Metallic Lithium Anode,” Matter 1, no. 5 (2019): 1215–1231, https://doi.org/10.1016/j.matt.2019.06.020.

[102] X. Meng, Y. Liu, Y. Cao, Y. Ren, W. Lu, and J. W. Elam, “High-Performance High-Loading Lithium-Sulfur Batteries by Low Temperature Atomic Layer Deposition of Aluminum Oxide on Nanophase S Cathodes,” Advanced Materials Interfaces 4, no. 17 (2017): 1700096, https://doi.org/10.1002/admi.201700096.

[103] M. Yu, J. Ma, H. Song, et al., “Atomic Layer Deposited TiO₂ on a Nitrogen-Doped Graphene/Sulfur Electrode for High Performance Lithium-Sulfur Batteries,” Energy & Environmental Science 9, no. 4 (2016): 1495–1503, https://doi.org/10.1039/c5ee03902a.

[104] X. Li, A. Lushington, J. Liu, R. Li, and X. Sun, “Superior Stable Sulfur Cathodes of Li-S Batteries Enabled by Molecular Layer Deposition,” Chemical Communications 50, no. 68 (2014): 9757–9760, https://doi.org/10.1039/c4cc04097j.

[105] Y. Yang, G. Zheng, and Y. Cui, “A Membrane-Free Lithium/Polysulfide Semi-Liquid Battery for Large-Scale Energy Storage,” Energy & Environmental Science 6, no. 5 (2013): 1552–1558, https://doi.org/10.1039/c3ee00072a.

[106] Z. Wei Seh, W. Li, J. J. Cha, et al., “Sulphur-TiO₂ Yolk–Shell Nanoarchitecture With Internal Void Space for Long-Cycle Lithium-Sulphur Batteries,” Nature Communications 4, no. 1 (2013): 1331, https://doi.org/10.1038/ncomms2327.

[107] Y. Zhang, Y. Zhao, A. Yermukhambetova, Z. Bakenov, and P. Chen, “Ternary Sulfur/Polyacrylonitrile/Mg0.6Ni0.4O Composite Cathodes for High Performance Lithium/Sulfur Batteries,” Journal of Materials Chemistry A 1, no. 2 (2013): 295–301, https://doi.org/10.1039/c2ta00105e.

[108] X. Li, A. Lushington, Q. Sun, et al., “Safe and Durable High-Temperature Lithium–Sulfur Batteries via Molecular Layer Deposited Coating,” Nano Letters 16, no. 6 (2016): 3545–3549, https://doi.org/10.1021/acs.nanolett.6b00577.

[109] T. Yim, M.-S. Park, J.-S. Yu, et al., “Effect of Chemical Reactivity of Polysulfide Toward Carbonate-Based Electrolyte on the Electrochemical Performance of Li–S Batteries,” Electrochimica Acta 107 (2013): 454–460, https://doi.org/10.1016/j.electacta.2013.06.039.

[110] R. Elazari, G. Salitra, A. Garsuch, A. Panchenko, and D. Aurbach, “Sulfur-Impregnated Activated Carbon Fiber Cloth as a Binder-Free Cathode for Rechargeable Li-S Batteries,” Advanced Materials 23, no. 47 (2011): 5641–5644, https://doi.org/10.1002/adma.201103274.

[111] X. Pu, G. Yang, and C. Yu, “Liquid-Type Cathode Enabled by 3D Sponge-Like Carbon Nanotubes for High Energy Density and Long Cycling Life of Li-S Batteries,” Advanced Materials 26, no. 44 (2014): 7456–7461, https://doi.org/10.1002/adma.201403337.

[112] S. Evers and L. F. Nazar, “New Approaches for High Energy Density Lithium–Sulfur Battery Cathodes,” Accounts of Chemical Research 46, no. 5 (2013): 1135–1143, https://doi.org/10.1021/ar3001348.

[113] M. Nagao, Y. Imade, H. Narisawa, et al., “All-Solid-State Li–Sulfur Batteries With Mesoporous Electrode and Thio-LISICON Solid Electrolyte,” Journal of Power Sources 222 (2013): 237–242, https://doi.org/10.1016/j.jpowsour.2012.08.041.

[114] M. Nagao, A. Hayashi, and M. Tatsumisago, “Sulfur–Carbon Composite Electrode for All-Solid-State Li/S Battery With Li₂S–P₂S₅ Solid Electrolyte,” Electrochimica Acta 56, no. 17 (2011): 6055–6059, https://doi.org/10.1016/j.electacta.2011.04.084.

[115] C. Fu, B. M. Wong, K. N. Bozhilov, and J. Guo, “Solid State Lithiation-Delithiation of Sulphur in Sub-Nano Confinement: A New Concept for Designing Lithium-Sulphur Batteries,” Chemical Science 7, no. 2 (2016): 1224–1232, https://doi.org/10.1039/c5sc03419a.

[116] M. Vijayakumar, N. Govind, E. Walter, et al., “Molecular Structure and Stability of Dissolved Lithium Polysulfide Species,” Physical Chemistry Chemical Physics 16, no. 22 (2014): 10923–10932, https://doi.org/10.1039/c4cp00889h.

[117] M. Cuisinier, C. Hart, M. Balasubramanian, A. Garsuch, and L. F. Nazar, “Radical or Not Radical: Revisiting Lithium–Sulfur Electrochemistry in Nonaqueous Electrolytes,” Advanced Energy Materials 5, no. 16 (2015): 1401801, https://doi.org/10.1002/aenm.201401801.

[118] Y. Zhao, L. V. Goncharova, Q. Zhang, et al., “Inorganic-Organic Coating via Molecular Layer Deposition Enables Long Life Sodium Metal Anode,” Nano Letters 17, no. 9 (2017): 5653–5659, https://doi.org/10.1021/acs.nanolett.7b02464.

[119] K. Kaliyappan, T. Or, Y.-P. Deng, Y. Hu, Z. Bai, and Z. Chen, “Constructing Safe and Durable High-Voltage P2 Layered Cathodes for Sodium Ion Batteries Enabled by Molecular Layer Deposition of Alucone,” Advanced Functional Materials 30, no. 17 (2020): 1910251, https://doi.org/10.1002/adfm.201910251.

[120] C. Wang, Y. Zhao, Q. Sun, et al., “Stabilizing Interface Between Li10SnP2S12 and Li Metal by Molecular Layer Deposition,” Nano Energy 53 (2018): 168–174, https://doi.org/10.1016/j.nanoen.2018.08.030.

[121] S. Zhang, Y. Zhao, F. Zhao, et al., “Gradiently Sodiated Alucone as an Interfacial Stabilizing Strategy for Solid-State Na Metal Batteries,” Advanced Functional Materials 30, no. 22 (2020): 2001118, https://doi.org/10.1002/adfm.202001118.

RIGHTS & PERMISSIONS

2026 The Author(s). EcoEnergy published by John Wiley & Sons Australia, Ltd on behalf of China Chemical Safety Association.