In-Situ Crosslinkable Graphite for Mechanically Robust Dry-Processed Lithium-Ion Battery Electrodes

Abstract

The carbon footprint of lithium-ion battery (LIB) manufacturing is an emerging concern with the rapid expansion of LIBs into electric vehicles and large-scale energy storage systems. In this context, dry electrode processing, enabled by polytetrafluoroethylene (PTFE) binders, offers a solvent-free, energy-efficient alternative to conventional slurry-based fabrication methods. Moreover, the unique fibril morphology of PTFE supports high-mass-loading electrodes without sacrificing ion transport or rate capability. However, PTFE's low intrinsic adhesion compromises the mechanical integrity of dry-processed electrodes, hindering practical application. Herein, we introduce a surface modification strategy based on polydopamine–poly(acrylic acid) coatings on graphite, enabling in-situ crosslinking during dry-processed electrode fabrication. This approach enhances the electrode adhesion strength without degrading electrochemical performance. The crosslinked electrodes exhibit superior mechanical stability and retain 87.1% of their initial capacity after 500 cycles at 1 C (4.3 mA cm⁻²), demonstrating a scalable route to robust, high-performance dry-processed electrodes.

Keywords

dry-processed graphite electrode / in-situ crosslinking / lithium-ion battery / mechanical robustness / surface modification

References

[1] E. A. Olivetti, G. Ceder, G. G. Gaustad, and X. Fu, “Lithium-Ion Battery Supply Chain Considerations: Analysis of Potential Bottlenecks in Critical Metals,” Joule 1 (2017): 229–243.

[2] J.-M. Tarascon and M. Armand, “Issues and Challenges Facing Rechargeable Lithium Batteries,” Nature 414 (2001): 359–c367.

[3] B. Dunn, H. Kamath, and J.-M. Tarascon, “Electrical Energy Storage for the Grid: A Battery of Choices,” Science 334 (2011): 928–935.

[4] W. Jin, G. Song, J. K. Yoo, S. K. Jung, T. H. Kim, and J. Kim, “Advancements in Dry Electrode Technologies: Towards Sustainable and Efficient Battery Manufacturing,” ChemElectroChem 11 (2024): e202400288.

[5] H. Zhang, B. Xue, S. Li, et al., “Life Cycle Environmental Impact Assessment for Battery-Powered Electric Vehicles at the Global and Regional Levels,” Scientific Reports 13 (2023): 7952.

[6] S. Ahmed, P. A. Nelson, K. G. Gallagher, and D. W. Dees, “Energy Impact of Cathode Drying and Solvent Recovery During Lithium-Ion Battery Manufacturing,” Journal of Power Sources 322 (2016): 169–178.

[7] D. L. Wood, J. D. Quass, J. Li, S. Ahmed, D. Ventola, and C. Daniel, “Technical and Economic Analysis of Solvent-Based Lithium-Ion Electrode Drying With Water and NMP,” Drying Technology 36 (2018): 234–244.

[8] Y. Lu, C. Z. Zhao, H. Yuan, J. K. Hu, J. Q. Huang, and Q. Zhang, “Dry Electrode Technology, the Rising Star in Solid-State Battery Industrialization,” Matter 5 (2022): 876–898.

[9] M. Al-Shroofy, Q. Zhang, J. Xu, T. Chen, A. P. Kaur, and Y. T. Cheng, “Solvent-Free Dry Powder Coating Process for Low-Cost Manufacturing of LiNi1/3Mn1/3Co1/3O2 Cathodes in Lithium-Ion Batteries,” Journal of Power Sources 352 (2017): 187–193.

[10] H. Zhou, M. Liu, H. Gao, et al., “Dense Integration of Solvent-Free Electrodes for Li-Ion Supercabattery With Boosted Low Temperature Performance,” Journal of Power Sources 473 (2020): 228553.

[11] M. Ryu, Y. K. Hong, S. Y. Lee, and J. H. Park, “Ultrahigh Loading Dry-Process for Solvent-Free Lithium-Ion Battery Electrode Fabrication,” Nature Communications 14 (2023): 1316.

[12] D. W. Park, N. A. Cañas, N. Wagner, and K. A. Friedrich, “Novel Solvent-Free Direct Coating Process for Battery Electrodes and Their Electrochemical Performance,” Journal of Power Sources 306 (2016): 758–763.

[13] B. Ludwig, Z. Zheng, W. Shou, Y. Wang, and H. Pan, “Solvent-Free Manufacturing of Electrodes for Lithium-Ion Batteries,” Scientific Reports 6 (2016): 23150.

[14] Z. Wei, D. Kong, L. Quan, et al., “Removing Electrochemical Constraints on Polytetrafluoroethylene as Dry-Process Binder for High-Loading Graphite Anodes,” Joule 8 (2024): 1350–1363.

[15] S. Hong, J. K. Seo, C. Ha, S. M. Oh, and Y. J. Kim, “Dry-Processed Bimodal Cathode With Single-Crystalline Particles for High-Density and High-Performance Lithium-Ion Batteries,” Journal of Power Sources 638 (2025): 236621.

[16] K. Lee, Y. Jo, J. Seok Nam, H. Yu, and Y. J. Kim, “Dry-Film Technology Employing Cryo-Pulverized Polytetrafluoroethylene Binder for All-Solid-State Batteries,” Chemical Engineering Journal 487 (2024): 150221.

[17] H. Choi, D. Moon, J. Sheem, et al., “A Solvent-Free Process Enabled by Polytetrafluoroethlyene/Carbon Black Composites for Fabricating Electrodes for Lithium-Ion Batteries With a High Volumetric Energy,” Journal of Electrochemical Society 170 (2023): 090511.

[18] M. Yoo, C. W. Frank, S. Mori, and S. Yamaguchi, “Effect of Poly(Vinylidene Fluoride) Binder Crystallinity and Graphite Structure on the Mechanical Strength of the Composite Anode in a Lithium Ion Battery,” Polymer 44 (2003): 4197–4204.

[19] N. Lingappan, L. Kong, and M. Pecht, “The Significance of Aqueous Binders in Lithium-Ion Batteries,” Renewable and Sustainable Energy Reviews 147 (2021): 111227.

[20] Y. Suh, J. K. Koo, H. Im, and Y. J. Kim, “Astonishing Performance Improvements of Dry-Film Graphite Anode for Reliable Lithium-Ion Batteries,” Chemical Engineering Journal 476 (2023): 146299.

[21] J. K. Koo, J. Lim, J. Shin, et al., “Dry-Processed Ultra-High-Energy Cathodes (99.6 wt%, 4.0 g cm⁻³) Using Single-Crystalline Ni-Rich Oxides,” Energy Storage Materials 78 (2025): 104270.

[22] Y. Zhang, S. Lu, F. Lou, and Z. Yu, “Leveraging Synergies by Combining Polytetrafluorethylene With Polyvinylidene Fluoride for Solvent-Free Graphite Anode Fabrication,” Energy Technology 10 (2022): 2200732.

[23] H. Kim, J. H. Lim, T. Lee, et al., “Ozone-Treated Carbon Nanotube as a Conductive Agent for Dry-Processed Lithium-Ion Battery Cathode,” ACS Energy Letters 8 (2023): 3460–3466.

[24] Z. Du, C. J. Janke, J. Li, D. L. Wood III, and C. Daniel, “Method of Solvent-Free Manufacturing of Composite Electrodes Incorporating Radiation Curable Binders,” U.S. Patent No. US 11,289,689 B2 (2022).

[25] D. Song, D. Jung, I. Cho, M. H. Ryou, and Y. M. Lee, “Mussel-Inspired Polydopamine-Functionalized Super-P as a Conductive Additive for High-Performance Silicon Anodes,” Advanced Materials Interfaces 3 (2016): 1600270.

[26] R. Ponraj, X. Dai, D. G. Kim, D. K. Kim, and D. J. Kim, “Enhancing the Cycle Life of Lithium-Anode-Free Batteries Through Polydopamine-Coated Substrates,” Advanced Energy and Sustainability Research 4 (2023): 2300051.

[27] J. Seo, S. Hyun, J. Moon, J. Y. Lee, and C. Kim, “High Performance of a Polydopamine-Coated Graphite Anode With a Stable SEI Layer,” ACS Applied Energy Materials 5 (2022): 5610–5616.

[28] Y. Roh, D. Jin, E. Kim, et al., “Highly Improved Thermal Stability of the Ceramic Coating Layer on the Polyethylene Separator via Chemical Crosslinking Between Ceramic Particles and Polymeric Binders,” Chemical Engineering Journal 433 (2022): 134501.

[29] J. Kumberg, M. Müller, R. Diehm, et al., “Drying of Lithium-Ion Battery Anodes for Use in High-Energy Cells: Influence of Electrode Thickness on Drying Time, Adhesion, and Crack Formation,” Energy Technology 7 (2019): 1900722.

[30] Y. Itou, N. Ogihara, and S. Kawauchi, “Role of Conductive Carbon in Porous Li-Ion Battery Electrodes Revealed by Electrochemical Impedance Spectroscopy Using a Symmetric Cell,” Journal of Physical Chemistry C 124 (2020): 5559–5564.

[31] K. Y. Park, J. W. Park, W. M. Seong, et al., “Understanding Capacity Fading Mechanism of Thick Electrodes for Lithium-Ion Rechargeable Batteries,” Journal of Power Sources 468 (2020): 228369.

[32] T. T. Nguyen, A. Demortière, B. Fleutot, B. Delobel, C. Delacourt, and S. J. Cooper, “The Electrode Tortuosity Factor: Why the Conventional Tortuosity Factor is Not Well Suited for Quantifying Transport in Porous Li-Ion Battery Electrodes and What to Use Instead,” NPJ Computational Materials 6 (2020): 123.

[33] M. Ebner, D. W. Chung, R. E. García, and V. Wood, “Tortuosity Anisotropy in Lithium-Ion Battery Electrodes,” Advanced Energy Materials 4 (2014): 1301278.

[34] S. Hein, T. Danner, D. Westhoff, et al., “Influence of Conductive Additives and Binder on the Impedance of Lithium-Ion Battery Electrodes: Effect of Morphology,” Journal of the Electrochemical Society 167 (2020): 013546.

[35] W. Yao, M. Chouchane, W. Li, et al., “A 5 V-Class Cobalt-Free Battery Cathode With High Loading Enabled by Dry Coating,” Energy & Environmental Science 16 (2023): 1620–1630.

[36] D. Jang, S. Suh, H. Yoon, et al., “Enhancing Rate Capability of Graphite Anodes for Lithium-Ion Batteries by Pore-Structuring,” Applied Surface Science Advances 6 (2021): 100168.

[37] R. A. Zangmeister, T. A. Morris, and M. J. Tarlov, “Characterization of Polydopamine Thin Films Deposited at Short Times by Autoxidation of Dopamine,” Langmuir 29 (2013): 8619–8628.

[38] Y. Bie, J. Yang, X. Liu, J. Wang, Y. Nuli, and W. Lu, “Polydopamine Wrapping Silicon Cross-Linked With Polyacrylic Acid as High-Performance Anode for Lithium-Ion Batteries,” ACS Applied Material Interfaces 8 (2016): 2899–2904.

[39] J. Zhang, T. Ren, G. P. Nayaka, et al., “Design of Polydopamine-Encapsulation Multiporous Mno Cross-Linked With Polyacrylic Acid Binder for Superior Lithium Ion Battery Anode,” Journal of Alloys and Compounds 783 (2019): 341–348.

[40] H. Luo, C. Gu, W. Zheng, F. Dai, X. Wang, and Z. Zheng, “Facile Synthesis of Novel Size-Controlled Antibacterial Hybrid Spheres Using Silver Nanoparticles Loaded With Poly-dopamine Spheres,” RSC Advances 5 (2015): 13470–13477.

[41] C. Bak, K. G. Kim, H. Lee, et al., “Advanced Multilayer Model Electrode for Binder Distribution Within Composite Electrodes of Lithium Batteries,” Chemical Engineering Journal 483 (2024): 148913.

[42] J. Song, D. O. Shin, S. Byun, et al., “A New Perspective on the Advanced Microblade Cutting Method for Reliable Adhesion Measurement of Composite Electrodes,” Journal of Electrochemical Science and Technology 13 (2022): 227–236.

[43] J. Kim, S. Park, S. Hwang, and W. S. Yoon, “Principles and Applications of Galvanostatic Intermittent Titration Technique for Lithium-Ion Batteries,” Journal of Electrochemical Science and Technology 13 (2022): 19–31.

[44] W. Weppner and R. A. Huggins, “Determination of the Kinetic Parameters of Mixed-Conducting Electrodes and Application to the System Li₃Sb,” Journal of the Electrochemical Society 124 (1962): 1569–1578.

[45] S. Choi, N. Kim, D. Jin, et al., “Systematic Study on Li Dendrite Growth and Suppression in Pouch-Type Lithium-Ion Batteries With Misaligned Electrode Pairs,” Journal of Power Sources 579 (2023): 233265.

[46] N. Ogihara, S. Kawauchi, C. Okuda, Y. Itou, Y. Takeuchi, and Y. Ukyo, “Theoretical and Experimental Analysis of Porous Electrodes for Lithium-Ion Batteries by Electrochemical Impedance Spectroscopy Using a Symmetric Cell,” Journal of the Electrochemical Society 159 (2012): A1034.

[47] A. Shodiev, M. Chouchane, M. Gaberscek, et al., “Deconvoluting the Benefits of Porosity Distribution in Layered Electrodes on the Electrochemical Performance of Li-Ion Batteries,” Energy Storage Materials 47 (2022): 462–471.

[48] B. P. Matadi, S. Geniès, A. Delaille, et al., “Irreversible Capacity Loss of Li-Ion Batteries Cycled at Low Temperature Due to an Untypical Layer Hindering Li Diffusion into Graphite Electrode,” Journal of the Electrochemical Society 164 (2017): A2374.

[49] Z. M. Konz, E. J. McShane, and B. D. McCloskey, “Detecting the Onset of Lithium Plating and Monitoring Fast Charging Performance With Voltage Relaxation,” ACS Energy Letters 5 (2020): 1750–1757.

[50] Q. Liu, C. Du, B. Shen, et al., “Understanding Undesirable Anode Lithium Plating Issues in Lithium-Ion Batteries,” RSC Advances 6 (2016): 88683–88700.

[51] J. Li, L. Wang, and J. Xu, “Investigation of the Lithium Plating Triggering Criterion in Graphite Electrodes,” Journal of Materials Chemistry A 12 (2024): 12581–12591.

[52] M. H. Ryou, Y. M. Lee, J. K. Park, and J. W. Choi, “Mussel-Inspired Polydopamine-Treated Polyethylene Separators for High-Power Li-Ion Batteries,” Advanced Materials 23 (2011): 3066–3070.

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