Regulation of Lithium Nucleation by Designing a Biomimetic Carbon Frame for Super Compact and Non-Expanding Lithium Metal Anode

Abstract

Lithium metal is a compelling choice as an anode material for high-energy-density batteries, attributed to its elevated theoretical specific energy and low redox potential. Nevertheless, challenges arise due to its susceptibility to high-volume changes and the tendency for dendritic development during cycling, leading to restricted cycle life and diminished Coulombic efficiency (CE). Here, we innovatively engineered a kind of porous biocarbon to serve as the framework for a lithium metal anode, which boasts a heightened specific surface area and uniformly dispersed ZnO active sites, directly derived from metasequoia cambium. The porous structure efficiently mitigates local current density and alleviates the volume expansion of lithium. Also, incorporating the ZnO lithiophilic site notably reduces the nucleation overpotential to a mere 16 mV, facilitating the deposition of lithium in a compact form. As a result, this innovative material ensures an impressive CE of 98.5% for lithium plating/stripping over 500 cycles, a remarkable cycle life exceeding 1200 h in a Li symmetrical cell, and more than 82% capacity retention ratio after an astonishing 690 cycles in full cells. In all, such a rationally designed Li composite anode effectively mitigates volume change, enhances lithophilicity, and reduces local current density, thereby inhibiting dendrite formation. The preparation of a high-performance lithium anode frame proves the feasibility of using biocarbon in a lithium anode frame.

Keywords

Li nucleation / Li plating/stripping / lithium metal anode / porous biocarbon

References

[1] W. Xu, J. Wang, F. Ding, et al., “Lithium Metal Anodes for Rechargeable Batteries,” Energy and Environmental Science 7, no. 2 (2014): 513-537.

[2] J. Zhu, H. Zhang, F. Liu, and J. Chen, “Decorating Carbon Felt With Oxides by Dipping as Dendrite-Free Host for Lithium Metal Anode,” Ionics 26, no. 9 (2020): 4381-4390.

[3] C. Jin, O. Sheng, J. Luo, et al., “3D Lithium Metal Embedded Within Lithiophilic Porous Matrix for Stable Lithium Metal Batteries,” Nano Energy 37 (2017): 177-186.

[4] R. Zhang, N. W. Li, X. B. Cheng, Y. X. Yin, Q. Zhang, and Y. G. Guo, “Advanced Micro/Nanostructures for Lithium Metal Anodes,” Advanced Science 4, no. 3 (2017): 1600445.

[5] X. B. Cheng, R. Zhang, C. Z. Zhao, and Q. Zhang, “Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review,” Chemical Reviews 117, no. 15 (2017): 10403-10473.

[6] M. Jäckle and A. Groß, “Microscopic Properties of Lithium, Sodium, and Magnesium Battery Anode Materials Related to Possible Dendrite Growth,” Journal of Chemical Physics 141, no. 17 (2014): 174710.

[7] C. Ling, D. Banerjee, and M. Matsui, “Study of the Electrochemical Deposition of Mg in the Atomic Level: Why It Prefers the Non-Dendritic Morphology,” Electrochimica acta 76 (2012): 270-274.

[8] K. Yan, W. Fei, Y. Yao, F. Wu, and C. Zhang, “Optimization for Electrochemical Redox Performance of Li⁺/Li Couple Based on Steady-State Polarization Curve,” Electrochimica Acta 176 (2015): 836-844.

[9] B. Liu, J. G. Zhang, and W. Xu, “Advancing Lithium Metal Batteries,” Joule 2, no. 5 (2018): 833-845.

[10] Y. Li, D. Zhang, Y. Zhang, et al., “Biomass-Derived Microporous Carbon With Large Micropore Size for High-Performance Supercapacitors,” Journal of Power Sources 448 (2020): 227396.

[11] P. Hao, Z. Zhao, Y. Leng, et al., “Graphene-Based Nitrogen Self-Doped Hierarchical Porous Carbon Aerogels Derived From Chitosan for High Performance Supercapacitors,” Nano Energy 15 (2015): 9-23.

[12] T. Zhao, M. Wang, Y. Yao, et al., “Selective Elimination of the Reactive Groups of Porous Biochar 3D Host for Stable Lithium Anodes,” Electrochimica Acta 388 (2021): 138632.

[13] C. Zhao, Z. Wang, X. Tan, et al., “Implanting CNT Forest Onto Carbon Nanosheets as Multifunctional Hosts for High-Performance Lithium Metal Batteries,” Small Methods 3, no. 5 (2019): 1800546.

[14] B. Natalie, H. Steven, - Mohanty, et al., “Biocarbon Materials,” Nature Reviews Methods Primers 19, no. 1 (2024): 1-21.

[15] Q. Chen, X. Tan, Y. Liu, et al., “Biomass-Derived Porous Graphitic Carbon Materials for Energy and Environmental Applications,” Journal of Materials Chemistry A 8, no. 12 (2020): 5773-5811.

[16] T. Zhao, Y. Yao, Y. Yuan, et al., “A Universal Method to Fabricating Porous Carbon for Li-O₂ Battery,” Nano Energy 82 (2021): 105782.

[17] F. Yang, Y. Yao, Y. Xu, et al., “Evolution of the Porous Structure for Phosphoric Acid Etching Carbon as Cathodes in Li-O₂ Batteries: Pyrolysis Temperature-Induced Characteristics Changes,” Carbon Energy 6, no. 1 (2024): e372.

[18] T. Li, D. W. Kirk, and C. Q. Jia, “Monolithic Wood Biochar as Functional Material for Sustainability,” Canadian Journal of Chemical Engineering 99, no. 3 (2021): 640-656.

[19] J. Zhang and C. You, “Water Holding Capacity and Absorption Properties of Wood Chars,” Energy & Fuels 27, no. 5 (2013): 2643-2648.

[20] C. Yang, X. Zhang, T. Wang, et al., “Phenotypic Plasticity in the Structure of Fine Adventitious Metasequoia glyptostroboides Roots Allows Adaptation to Aquatic and Terrestrial Environments,” Plants 8, no. 11 (2019): 501-512.

[21] W. Huang, S. Liu, R. Yu, L. Zhou, Z. Liu, and L. Mai, “Single-Atom Lithiophilic Sites Confined Within Ordered Porous Carbon for Ultrastable Lithium Metal Anodes,” Energy & Environmental Materials 6, no. 3 (2023): e12466.

[22] C. Jin, O. Sheng, W. Zhang, et al., “Sustainable, Inexpensive, Naturally Multi-Functionalized Biomass Carbon for Both Li Metal Anode and Sulfur Cathode,” Energy Storage Materials 15 (2018): 218-225.

[23] B. Yu, T. Tao, S. Mateti, S. Lu, and Y. Chen, “Nanoflake Arrays of Lithiophilic Metal Oxides for the Ultra-Stable Anodes of Lithium-Metal Batteries,” Advanced Functional Materials 28, no. 36 (2018): 1803023.

[24] M. Chen, J. Zheng, O. Sheng, et al., “Sulfur-Nitrogen Co-Doped Porous Carbon Nanosheets to Control Lithium Growth for a Stable Lithium Metal Anode,” Journal of Materials Chemistry A 7, no. 31 (2019): 18267-18274.

[25] M. Wang, D. Li, Y. Yao, T. Zhao, and F. Wu, “Effect of Nitrogen Dopant Forms of Biochar Cathode on the Discharge Mechanism of Li-O₂ Battery,” Journal of the Electrochemical Society 168, no. 9 (2021): 090517.

[26] X. B. Cheng, T. Z. Hou, R. Zhang, et al., “Dendrite-Free Lithium Deposition Induced by Uniformly Distributed Lithium Ions for Efficient Lithium Metal Batteries,” Advanced Materials 28, no. 15 (2016): 2888-2895.

[27] L. Tan, S. Feng, X. Li, et al., “Oxygen-Induced Lithiophilicity of Tin-Based Framework Toward Highly Stable Lithium Metal Anode,” Chemical Engineering Journal 394 (2020): 124848.

[28] X. Liang, Q. Pang, I. R. Kochetkov, et al., “A Facile Surface Chemistry Route to a Stabilized Lithium Metal Anode,” Nature Energy 2, no. 9 (2017): 17119.

[29] Jy Kim, O. B. Chae, G. Kim, et al., “Spatial Control of Lithium Deposition by Controlling the Lithiophilicity With Copper(I) Oxide Boundaries,” Energy & Environmental Materials 6, no. 5 (2022): e12392.

[30] Z. Gou, Y. Yao, X. Geng, et al., “Dual Redox Mediators Assisted Hierarchically Porous Hollow Carbon Shell Cathode for Enhanced Performance Li-O₂ Battery,” Advanced Energy Materials 14, no. 18 (2024): 2304272.

[31] M. Wang, Y. Yao, Y. Tian, et al., “Atomically Dispersed Manganese on Carbon Substrate for Aqueous and Aprotic CO₂ Electrochemical Reduction,” Advanced Materials 35, no. 12 (2023): 2201658.

[32] X. Yan, L. Lin, Q. Chen, et al., “Multifunctional Roles of Carbon-Based Hosts for Li-Metal Anodes: A Review,” Carbon Energy 3, no. 2 (2021): 303-329.

[33] M. Jouiad, N. Al-Nofeli, N. Khalifa, F. Benyettou, and L. F. Yousef, “Characteristics of Slow Pyrolysis Biochars Produced From Rhodes Grass and Fronds of Edible Date Palm,” Journal of Analytical and Applied Pyrolysis 111 (2015): 183-190.

[34] Y. Yao, B. Gao, F. Wu, C. Zhang, and L. Yang, “Engineered Biochar From Biofuel Residue: Characterization and Its Silver Removal Potential,” ACS Applied Materials & Interfaces 7, no. 19 (2015): 10634-10640.

[35] M. Thommes, K. Kaneko, A. V. Neimark, et al., “Physisorption of Gases, With Special Reference to the Evaluation of Surface Area and Pore Size Distribution (IUPAC Technical Report),” Pure and Applied Chemistry 87, no. 9-10 (2015): 1051-1069.

[36] A. C. Ferrari and J. Robertson, “Resonant Raman Spectroscopy of Disordered, Amorphous, and Diamondlike Carbon,” Physical Review B 64, no. 7 (2001): 075414.

[37] L. Wang, K. Tang, M. Zhang, and J. Xu, “Facile Synthesis of Mn-Doped ZnO Porous Nanosheets as Anode Materials for Lithium Ion Batteries With a Better Cycle Durability,” Nanoscale Research Letters 10, no. 1 (2015): 280.

[38] D. Mandrino, M. Godec, and D. Nolan, “Oxide-State Evaluation of the Zinc and Aluminium in Metallic Thin Films Using Auger-Electron-Spectroscopy Depth Profiles,” Vacuum 98 (2013): 88-92.

[39] J.-M. Tarascon and M. Armand, “Issues and Challenges Facing Rechargeable Lithium Batteries,” Nature 414 (2001): 359-367.

[40] A. Pei, G. Zheng, F. Shi, Y. Li, and Y. Cui, “Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal,” Nano Letters 17, no. 2 (2017): 1132-1139.

[41] A. J. F. Bard and L. R. Faulkner, Electrochemical Methods, Fundamental Applications. (John Wiley & Sons, Inc, 2001).

[42] R. Tao, X. Bi, S. Li, et al., “Kinetics Tuning the Electrochemistry of Lithium Dendrites Formation in Lithium Batteries Through Electrolytes,” ACS Applied Materials & Interfaces 9, no. 8 (2017): 7003-7008.

[43] J. Qu, S. Wang, F. Wu, and C. Zhang, “Effect of Electrolyte Additives on the Cycling Performance of Li Metal and the Kinetic Mechanism Analysis,” ACS Applied Materials & Interfaces 13, no. 15 (2021): 18283-18293.

[44] X. Liu, G. Li, F. Wu, and C. Zhang, “Effect of Support Salts on Apparent Performance of Li Metal Anode in Ethylene Carbonate/Ethyl Methyl Carbonate Solvent and Dynamic Mechanism Analysis,” Electrochimica Acta 457 (2023): 142493.

[45] R. Akolkar, “Mathematical Model of the Dendritic Growth During Lithium Electrodeposition,” Journal of Power Sources 232 (2013): 23-28.

[46] K. Yan, Z. Lu, H.-W. Lee, et al., “Selective Deposition and Stable Encapsulation of Lithium Through Heterogeneous Seeded Growth,” Nature Energy 1, no. 3 (2016): 16010.

[47] Y. Cheng, J. Chen, Y. Chen, et al., “Lithium Host: Advanced Architecture Components for Lithium Metal Anode,” Energy Storage Materials 38 (2021): 276-298.

[48] W. Deng, W. Zhu, X. Zhou, and Z. Liu, “Graphene Nested Porous Carbon Current Collector for Lithium Metal Anode With Ultrahigh Areal Capacity,” Energy Storage Materials 15 (2018): 266-273.

[49] Y. Zhang, W. Luo, C. Wang, et al., “High-Capacity, Low-Tortuosity, and Channel-Guided Lithium Metal Anode,” Proceedings of the National Academy of Sciences United States of America 114, no. 14 (2017): 3584-3589.

[50] S. S. Zhang, K. Xu, and T. R. Jow, “EIS Study on the Formation of Solid Electrolyte Interface in Li-Ion Battery,” Electrochimica Acta 51, no. 8-9 (2006): 1636-1640.

[51] N. Ogihara, Y. Itou, T. Sasaki, and Y. Takeuchi, “Impedance Spectroscopy Characterization of Porous Electrodes Under Different Electrode Thickness Using a Symmetric Cell for High-Performance Lithium-Ion Batteries,” Journal of Physical Chemistry C 119, no. 9 (2015): 4612-4619.

[52] J. Guo, Z. Wen, M. Wu, J. Jin, and Y. Liu, “Vinylene Carbonate-LiNO₃: A Hybrid Additive in Carbonic Ester Electrolytes for SEI Modification on Li Metal Anode,” Electrochemistry Communications 51 (2015): 59-63.

RIGHTS & PERMISSIONS

2025 The Authors. Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.