Abstract
The uneven deposition of lithium (Li) on current collectors causes serious dendrite growth and volume expansion. Commercial foamed copper (Cu) current collectors are unsuitable for Li anodes because of their large volume and mass and lithiophobic nature. Herein, a three-dimensional (3D) copper@tin (Cu@Sn) nanocone current collector with small volume, light weight, and lithiophilic nature was prepared by a simple electrodeposition method. The synergy of the nanoconical structure and lithiophilic Sn promotes the even deposition of Li and effectively inhibits the formation of Li dendrites. The resultant half batteries exhibit high Coulombic efficiency of 97.6% after 100 cycles at 1 mA cm−2, and the symmetrical Li battery demonstrates a prolonged lifespan of over 600 h at 1 mA cm−2. The full battery based on organic liquid electrolyte with LiFePO4 also exhibits a long lifespan of 550 cycles with high capacity retention of 95.1% at 1 C. Moreover, 3D Cu@Sn nanocone-based solid-state batteries exhibit excellent electrochemical performance and show no decay after 500 cycles at 1 C. Our work provides a strategy for fabricating 3D current collectors for high-energy-density Li metal batteries.
摘要
锂在集流体上的不均匀沉积将导致严重的枝晶生长和体积 膨胀等问题, 传统的商业化泡沫铜集流体由于具有较大的体积和 质量会降低电池的能量密度. 本文通过简单的电沉积方法制备了 体积小、重量轻, 具有亲锂性的3D Cu@Sn纳米锥集流体. 从成核 与沉积的角度出发, 纳米锥结构与亲锂的锡纳米颗粒的协同作用 促进了锂的均匀沉积, 可有效地抑制锂枝晶的生长. 组装的半电池 在1 mA cm−2下经过100次循环后, 库仑效率高达97.6%, 锂对称电 池在1 mA cm−2下可以稳定循环600 h. 将沉积金属锂后的Cu@Sn/Li复合负极与LiFePO4组装的液态全电池在1 C倍率下, 550个循环 之后, 容量保持率为95.1%. 此外, Cu@Sn纳米锥集流体在固态电池 Li/Cu@Sn∣PVDF–HFP–5 wt% SiO2∣LFP中也表现出优异的电化学 性能, 在1 C倍率下, 500个循环之后, 放电容量未发生衰减.
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References
Xu W, Wang J, Ding F, et al. Lithium metal anodes for rechargeable batteries. Energy Environ Sci, 2014, 7: 513–537
Hwang SM, Kim SY, Kim JG, et al. Electrospun manganese-cobalt oxide hollow nanofibres synthesized via combustion reactions and their lithium storage performance. Nanoscale, 2015, 7: 8351–8355
Lee J, Moon J, Han SA, et al. Everlasting living and breathing gyroid 3D network in Si@SiOx/C nanoarchitecture for lithium ion battery. ACS Nano, 2019, 13: 9607–9619
Xiao Z, Li Z, Meng X, et al. MXene-engineered lithium-sulfur batteries. J Mater Chem A, 2019, 7: 22730–22743
Yu W, Xue C, Hu B, et al. Oxygen- and dendrite-resistant ultra-dry polymer electrolytes for solid-state Li−O2 batteries. Energy Storage Mater, 2020, 27: 244–251
Hu X, Li Z, Chen J. Flexible Li−CO2 batteries with liquid-free electrolyte. Angew Chem Int Ed, 2017, 56: 5785–5789
Wang R, Zhang X, Cai Y, et al. Safety-reinforced rechargeable Li−CO2 battery based on a composite solid state electrolyte. Nano Res, 2019, 12: 2543–2548
Jung KN, Kim J, Yamauchi Y, et al. Rechargeable lithium-air batteries: a perspective on the development of oxygen electrodes. J Mater Chem A, 2016, 4: 14050–14068
Cheng XB, Zhang R, Zhao CZ, et al. Toward safe lithium metal anode in rechargeable batteries: A review. Chem Rev, 2017, 117: 10403–10473
Lin D, Liu Y, Cui Y. Reviving the lithium metal anode for high-energy batteries. Nat Nanotech, 2017, 12: 194–206
Albertus P, Babinec S, Litzelman S, et al. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat Energy, 2017, 3: 16–21
Liu H, Cheng XB, Jin Z, et al. Recent advances in understanding dendrite growth on alkali metal anodes. EnergyChem, 2019, 1: 100003
Ding F, Xu W, Graff GL, et al. Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. J Am Chem Soc, 2013, 135: 4450–4456
Ma Q, Sun X, Liu P, et al. Bio-inspired stable lithium-metal anodes by Co-depositing lithium with a 2D vermiculite shuttle. Angew Chem Int Ed, 2019, 58: 6200–6206
Yang Y, Xiong J, Lai S, et al. Vinyl ethylene carbonate as an effective SEI-forming additive in carbonate-based electrolyte for lithium-metal anodes. ACS Appl Mater Interfaces, 2019, 11: 6118–6125
Xu R, Zhang XQ, Cheng XB, et al. Lithium metal anodes: Artificial soft-rigid protective layer for dendrite-free lithium metal anode. Adv Funct Mater, 2018, 28: 1705838
Li NW, Yin YX, Yang CP, et al. An artificial solid electrolyte interphase layer for stable lithium metal anodes. Adv Mater, 2016, 28: 1853–1858
Kang D, Sardar S, Zhang R, et al. In-situ organic SEI layer for dendrite-free lithium metal anode. Energy Storage Mater, 2020, 27: 69–77
Pan K, Zhang L, Qian W, et al. A flexible ceramic/polymer hybrid solid electrolyte for solid-state lithium metal batteries. Adv Mater, 2020, 32: 2000399
Zhao CZ, Zhang XQ, Cheng XB, et al. An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes. Proc Natl Acad Sci USA, 2017, 114: 11069–11074
Zeng XX, Yin YX, Li NW, et al. Reshaping lithium plating/stripping behavior via bifunctional polymer electrolyte for room-temperature solid Li metal batteries. J Am Chem Soc, 2016, 138: 15825–15828
Wang SH, Yin YX, Zuo TT, et al. Stable Li metal anodes via regulating lithium plating/stripping in vertically aligned microchannels. Adv Mater, 2017, 29: 1703729
Yang CP, Yin YX, Zhang SF, et al. Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes. Nat Commun, 2015, 6: 8058
Zuo TT, Wu XW, Yang CP, et al. Graphitized carbon fibers as multifunctional 3D current collectors for high areal capacity Li anodes. Adv Mater, 2017, 29: 1700389
Qiu H, Tang T, Asif M, et al. 3D porous Cu current collectors derived by hydrogen bubble dynamic template for enhanced Li metal anode performance. Adv Funct Mater, 2019, 29: 1808468
Li Q, Zhu S, Lu Y. 3D porous Cu current collector/Li-metal composite anode for stable lithium-metal batteries. Adv Funct Mater, 2017, 27: 1606422
Yang Y, Xiong J, Zeng J, et al. VGCF 3D conducting host coating on glass fiber filters for lithium metal anodes. Chem Commun, 2018, 54: 1178–1181
Zhang C, Lv W, Zhou G, et al. Vertically aligned lithiophilic CuO nanosheets on a Cu collector to stabilize lithium deposition for lithium metal batteries. Adv Energy Mater, 2018, 8: 1703404
Lu LL, Zhang Y, Pan Z, et al. Lithiophilic Cu−Ni core-shell nanowire network as a stable host for improving lithium anode performance. Energy Storage Mater, 2017, 9: 31–38
Zhang D, Dai A, Wu M, et al. Lithiophilic 3D porous CuZn current collector for stable lithium metal batteries. ACS Energy Lett, 2020, 5: 180–186
Yue XY, Wang WW, Wang QC, et al. CoO nanofiber decorated nickel foams as lithium dendrite suppressing host skeletons for high energy lithium metal batteries. Energy Storage Mater, 2018, 14: 335–344
Chen L, Connell JG, Nie A, et al. Lithium metal protected by atomic layer deposition metal oxide for high performance anodes. J Mater Chem A, 2017, 5: 12297–12309
Chen KH, Sanchez AJ, Kazyak E, et al. Synergistic effect of 3D current collectors and ALD surface modification for high coulombic efficiency lithium metal anodes. Adv Energy Mater, 2019, 9: 1802534
Chen C, Pang Y, Zhang F, et al. Sharp Cu@Sn nanocones on Cu foam for highly selective and efficient electrochemical reduction of CO2 to formate. J Mater Chem A, 2018, 6: 19621–19630
Hwang SM, Lim YG, Kim JG, et al. A case study on fibrous porous SnO2 anode for robust, high-capacity lithium-ion batteries. Nano Energy, 2014, 10: 53–62
Xue H, Zhao J, Tang J, et al. High-loading nano-SnO2 encapsulated in situ in three-dimensional rigid porous carbon for superior lithium-ion batteries. Chem Eur J, 2016, 22: 4915–4923
Luo Z, Xu JC, Yuan B, et al. A novel 3D bimodal porous current collector with large interconnected spherical channels for improved capacity and cycling stability of Sn anode in Li-ion batteries. Mater Lett, 2018, 213: 189–192
Zhang Y, Wang C, Pastel G, et al. 3D wettable framework for dendrite-free alkali metal anodes. Adv Energy Mater, 2018, 8: 1800635
Luo Z, Liu C, Tian Y, et al. Dendrite-free lithium metal anode with lithiophilic interphase from hierarchical frameworks by tuned nucleation. Energy Storage Mater, 2020, 27: 124–132
Acknowledgements
This study was supported by the National Natural Science Foundation of China (51771094 and 21835004), the National Key R&D Program of China (2016YFB0901500), the Ministry of Education of China (B12015 and IRT13R30), and Tianjin Natural Science Foundation (18JCZDJC31500).
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Wang R and Shi F conceived the project and prepared the current collector. He X, Shi J, and Ma T helped with the characterization. Wang R and Shi F wrote the paper with support from Tao Z. All authors contributed to the general discussion.
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The authors declare that they have no conflict of interest.
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Experimental details and supporting data are available in the online version of the paper.
Rui Wang received her bachelor’s degree in applied chemistry from Central South University in 2017. Currently, she is a graduate student under the supervision of Prof. Zhanliang Tao at the College of Chemistry, Nankai University. Her research interest focuses on lithium metal anodes and solid-state electrolytes.
Faxing Shi received his bachelor’s degree from Central South University in 2017. He is a graduate student at the College of Chemistry, Nankai University. His research interests are the syntheses of novel metal nanomaterials and characterization of interface for nanostructures.
Zhanliang Tao received his PhD in inorganic chemistry from Nankai University in 2005 and is now a professor at the College of Chemistry, Nankai University. His research interest focuses on electrochemical energy storage and conversion.
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Wang, R., Shi, F., He, X. et al. Three-dimensional lithiophilic Cu@Sn nanocones for dendrite-free lithium metal anodes. Sci. China Mater. 64, 1087–1094 (2021). https://doi.org/10.1007/s40843-020-1528-5
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DOI: https://doi.org/10.1007/s40843-020-1528-5