The Boundary-Like Defect Type Vertical Graphene Enhances the Stability of Lithium Metal Batteries

Xiaodong Wang , Dingrong Guo , Peng Zhou , Ping Xu , Qi Liu , Liping Wang , Zhean Su , Feixianng Wu , Mingyu Zhang

Battery Energy ›› 2025, Vol. 4 ›› Issue (6) : e70029

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Battery Energy ›› 2025, Vol. 4 ›› Issue (6) : e70029 DOI: 10.1002/bte2.20240122
RESEARCH ARTICLE

The Boundary-Like Defect Type Vertical Graphene Enhances the Stability of Lithium Metal Batteries

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Abstract

The growth of lithium dendrites has been regarded as the biggest challenge for lithium metal batteries (LMBs). Vertical graphene (VG) is a promising inhibitor against lithium dendrites. However, there is no research on the effects of various defect types of VG on LMBs. Herein, we grew different defect types of VG on copper foam as LMBs anode and then studied their electrochemical properties in detail. As the synthesis temperature increases, the density of carbon nanosheets (CNS) gradually rises, causing the VG to transition from vacancy-like type to boundary-like type. The cycling test shows that the boundary-like type electrode exhibits the highest coulombic efficiency exceeding 97.9% after 200 cycles at 5 mA cm2 among various defect type electrodes. The superior electrochemical performance of the boundary-like type electrodes is attributed to their high defect content and abundant edge defects, which provide numerous nucleation sites for lithium and promote uniform deposition. Additionally, the unique three-dimensional morphology of VG offers sufficient space for lithium deposition, effectively inhibiting the growth of lithium dendrites. This study highlights that boundary-like type VG can effectively enhance the stability of LMBs, and provides a new idea for the application of VG to the anode of LMBs.

Keywords

defect type / lithium dendrites / LMBs anode / vertical graphene

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Xiaodong Wang, Dingrong Guo, Peng Zhou, Ping Xu, Qi Liu, Liping Wang, Zhean Su, Feixianng Wu, Mingyu Zhang. The Boundary-Like Defect Type Vertical Graphene Enhances the Stability of Lithium Metal Batteries. Battery Energy, 2025, 4(6): e70029 DOI:10.1002/bte2.20240122

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References

[1]

M. Li, J. Lu, Z. Chen, and K. Amine, “30 Years of Lithium-Ion Batteries,” Advanced Materials 30, no. 33 (2018): 1800561.

[2]

T. Kim, W. Song, D. Y. Son, L. K. Ono, and Y. Qi, “Lithium-Ion Batteries: Outlook on Present, Future, and Hybridized Technologies,” Journal of Materials Chemistry A 7, no. 7 (2019): 2942-2964.

[3]

M. Armand, P. Axmann, D. Bresser, et al., “Lithium-Ion Batteries-Current State of the Art and Anticipated Developments,” Journal of Power Sources 479 (2020): 228708.

[4]

Y. Guo, H. Li, and T. Zhai, “Reviving Lithium-Metal Anodes for Next-Generation High-Energy Batteries,” Advanced Materials 29, no. 29 (2017): 1700007.

[5]

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

[6]

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

[7]

Z. A. Ghazi, Z. Sun, C. Sun, et al., “Key Aspects of Lithium Metal Anodes for Lithium Metal Batteries,” Small 15, no. 32 (2019): 1900687.

[8]

Q. Wang, B. Liu, Y. Shen, et al., “Confronting the Challenges in Lithium Anodes for Lithium Metal Batteries,” Advanced Science 8, no. 17 (2021): 2101111.

[9]

J. Lai, R. Tan, H. Jiang, et al., “Development of an In Situ Polymerized Artificial Layer for Dendrite-Free and Stable Lithium Metal Batteries,” Battery Energy 3 (2024): 20230070.

[10]

S. Huang, W. Zhang, H. Ming, G. Cao, L. Z. Fan, and H. Zhang, “Chemical Energy Release Driven Lithiophilic Layer on 1 m2 Commercial Brass Mesh Toward Highly Stable Lithium Metal Batteries,” Nano Letters 19, no. 3 (2019): 1832-1837.

[11]

L. Fan, H. L. Zhuang, W. Zhang, Y. Fu, Z. Liao, and Y. Lu, “Stable Lithium Electrodeposition at Ultra-High Current Densities Enabled by 3D PMF/Li Composite Anode,” Advanced Energy Materials 8, no. 15 (2018): 1703360.

[12]

S. Ni, S. Tan, Q. An, and L. Mai, “Three Dimensional Porous Frameworks for Lithium Dendrite Suppression,” Journal of Energy Chemistry 44 (2020): 73-89.

[13]

S. S. Chi, Y. Liu, W. L. Song, L. Z. Fan, and Q. Zhang, “Prestoring Lithium Into Stable 3D Nickel Foam Host as Dendrite-Free Lithium Metal Anode,” Advanced Functional Materials 27, no. 24 (2017): 1700348.

[14]

Z. Hu, Z. Li, Z. Xia, et al., “PECVD-Derived Graphene Nanowall/Lithium Composite Anodes Towards Highly Stable Lithium Metal Batteries,” Energy Storage Materials 22 (2019): 29-39.

[15]

H. Ye, S. Xin, Y. X. Yin, and Y. G. Guo, “Advanced Porous Carbon Materials for High-Efficient Lithium Metal Anodes,” Advanced Energy Materials 7, no. 23 (2017): 1700530.

[16]

J. Xie, J. Ye, F. Pan, et al., “Incorporating Flexibility Into Stiffness: Self-Grown Carbon Nanotubes in Melamine Sponges Enable a Lithium-Metal-Anode Capacity of 15 Ma H Cm−2 Cyclable at 15 Ma Cm−2,” Advanced Materials 31, no. 7 (2019): 1805654.

[17]

S. S. Chi, X. G. Qi, Y. S. Hu, and L. Z. Fan, “3D Flexible Carbon Felt Host for Highly Stable Sodium Metal Anodes,” Advanced Energy Materials 8, no. 15 (2018): 1702764.

[18]

S. Xu, D. W. McOwen, C. Wang, et al., “Three-Dimensional, Solid-State Mixed Electron-Ion Conductive Framework for Lithium Metal Anode,” Nano Letters 18, no. 6 (2018): 3926-3933.

[19]

T. Zhang, H. Lu, J. Yang, et al., “Stable Lithium Metal Anode Enabled by a Lithiophilic and Electron/Ion Conductive Framework,” ACS Nano 14, no. 5 (2020): 5618-5627.

[20]

F. Ren, Z. Lu, H. Zhang, et al., “Pseudocapacitance Induced Uniform Plating/Stripping of Li Metal Anode in Vertical Graphene Nanowalls,” Advanced Functional Materials 28, no. 50 (2018): 1805638.

[21]

R. Fang, Z. Han, J. Li, et al., “Rationalized Design of Hyperbranched Trans-Scale Graphene Arrays for Enduring High-Energy Lithium Metal Batteries,” Science Advances 8, no. 34 (2022): eadc9961.

[22]

X. Ji, Z. Lin, J. Zeng, et al., “Controlling Structure of Vertically Grown Graphene Sheets on Carbon Fibers for Hosting Li and Na Metals as Rechargeable Battery Anodes,” Carbon 158 (2020): 394-405.

[23]

H. Shi, C. J. Zhang, P. Lu, Y. Dong, P. Wen, and Z. S. Wu, “Conducting and Lithiophilic Mxene/Graphene Framework for High-Capacity, Dendrite-Free Lithium-Metal Anodes,” ACS Nano 13, no. 12 (2019): 14308-14318.

[24]

J. Man, K. Liu, H. Zhang, et al., “Dendrite-Free Lithium Metal Anode Enabled by Ion/Electron-Conductive N-Doped 3D Carbon Fiber Interlayer,” Journal of Power Sources 489 (2021): 229524.

[25]

H. Song, T. He, J. Liu, et al., “Conformal Coating of Lithium-Zinc Alloy on 3D Conducting Scaffold for High Areal Capacity Dendrite-Free Lithium Metal Batteries,” Carbon 181 (2021): 99-106.

[26]

W. Zheng, X. Zhao, and W. Fu, “Review of Vertical Graphene and its Applications,” ACS Applied Materials & Interfaces 13, no. 8 (2021): 9561-9579.

[27]

C. Huang, Y. Mu, Y. Chu, et al., “A Review of Vertical Graphene and Its Energy Storage System Applications,” Journal of Chemical Physics 159, no. 21 (2023): 211001, https://doi.org/10.1063/5.0179107.

[28]

P. V. Shinde, R. Samal, and C. S. Rout, “Vertically Aligned Graphene-Analogous Low-Dimensional Materials: A Review on Emerging Trends, Recent Developments, and Future Perspectives,” Advanced Materials Interfaces 9, no. 9 (2022): 2101959.

[29]

X. Shan, J. Zhu, Z. Qiu, et al., “Ultrafast-Loaded Nickel Sulfide on Vertical Graphene Enabled by Joule Heating for Enhanced Lithium Metal Batteries,” Small 20, no. 35 (2024): 2401491.

[30]

S. Huang, H. Yang, J. Hu, et al., “Early Lithium Plating Behavior in Confined Nanospace of 3D Lithiophilic Carbon Matrix for Stable Solid-State Lithium Metal Batteries,” Small 15, no. 43 (2019): 1904216.

[31]

L. Dong, L. Nie, and W. Liu, “Water-Stable Lithium Metal Anodes With Ultrahigh-Rate Capability Enabled by a Hydrophobic Graphene Architecture,” Advanced Materials 32, no. 14 (2020): 1908494.

[32]

C. Yan, T. Xu, C. Ma, et al., “Dendrite-Free Li Metal Plating/Stripping Onto Three-Dimensional Vertical-Graphene @ Carbon-Cloth Host,” Frontiers in Chemistry 7 (2019): 714.

[33]

X. Wang, Y. Liu, Z. Su, Z. Mingyu, and Q. Huang, “Three Defect Types Transformation of Vertical Graphene by Elevating Temperature,” Vacuum 224 (2024): 113159.9.

[34]

A. Eckmann, A. Felten, A. Mishchenko, et al., “Probing the Nature of Defects in Graphene by Raman Spectroscopy,” Nano Letters 12, no. 8 (2012): 3925-3930.

[35]

L. G. Cançado, A. Jorio, E. H. M. Ferreira, et al., “Quantifying Defects in Graphene via Raman Spectroscopy at Different Excitation Energies,” Nano Letters 11, no. 8 (2011): 3190-3196.

[36]

Z. Ni, Y. Wang, T. Yu, and Z. Shen, “Raman Spectroscopy and Imaging of Graphene,” Nano Research 1 (2008): 273-291.

[37]

J. S. Park, A. Reina, R. Saito, J. Kong, G. Dresselhaus, and M. S. Dresselhaus, “G′ Band Raman Spectra of Single, Double and Triple Layer Graphene,” Carbon 47, no. 5 (2009): 1303-1310.

[38]

F. Banhart, J. Kotakoski, and A. V. Krasheninnikov, “Structural Defects in Graphene,” ACS Nano 5, no. 1 (2011): 26-41.

[39]

H. Estrade-Szwarckopf, “XPS Photoemission in Carbonaceous Materials: A “Defect” Peak Beside the Graphitic Asymmetric Peak,” Carbon 42, no. 8/9 (2004): 1713-1721.

[40]

A. Barinov, O. B. Malcioǧlu, S. Fabris, et al., “Initial Stages of Oxidation on Graphitic Surfaces: Photoemission Study and Density Functional Theory Calculations,” Journal of Physical Chemistry C 113, no. 21 (2009): 9009-9013.

[41]

R. A. Quinlan, M. Cai, R. A. Outlaw, S. M. Butler, J. R. Miller, and A. N. Mansour, “Investigation of Defects Generated in Vertically Oriented Graphene,” Carbon 64 (2013): 92-100.

[42]

X. X. Ma, X. Chen, Y. K. Bai, X. Shen, R. Zhang, and Q. Zhang, “The Defect Chemistry of Carbon Frameworks for Regulating the and Growth Behaviors in Lithium Metal Anodes,” Small 17, no. 48 (2021): 2007142.

[43]

Y. Mu, M. Han, J. Li, J. Liang, and J. Yu, “Growing Vertical Graphene Sheets on Natural Graphite for Fast Charging Lithium-Ion Batteries,” Carbon 173 (2021): 477-484.

[44]

O. Baranov, I. Levchenko, S. Xu, J. W. M. Lim, U. Cvelbar, and K. Bazaka, “Formation of Vertically Oriented Graphenes: What Are the Key Drivers of Growth?,” 2D Materials 5, no. 4 (2018): 044002.

[45]

X. Chen, Y. K. Bai, C. Z. Zhao, X. Shen, and Q. Zhang, “Lithium Bonds in Lithium Batteries,” Angewandte Chemie 132, no. 28 (2020): 11288-11291.

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2025 The Author(s). Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.

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