Abstract
The efficient utilization of metallic lithium (Li) is the key to enable application of Li metal full-cell with low amount of excess Li, contributing to higher safety and energy density. Herein, we report an extraordinary Li metal full-cell with only 20% excess Li, which demonstrated significantly improved reversibility and high Coulombic efficiency. Ingenious simulated missile guidance and confinement system (SMGCS) was designed to guide and confine Li deposition through constructing compatible silver lithiophilic sites and nitrate layer. Silver sites act as effective Li nuclei to attract Li ions and direct the initial nucleation. The generated nitrate layer affords an interfacial environment favorable for confined and uniform deep Li deposition, which is theoretically verified by molecular dynamics (MD) simulations. The two combined merits offer a robust and dendrite-free Li deposition, enabling the application of Li metal full-cell with slight excess Li. They also result in an outperformed Li cycling efficiency of ca. 99% for over 300 cycles along with deep cycling at a high capacity of 10 mA h cm−2 in carbonate electrolytes. The unprecedented high degree of Li utilization opens a new avenue for the future development of highly efficient Li metal full cells.
摘要
金属锂的有效利用是实现锂金属全电池高安全性和高能量 密度应用的关键. 本文中, 我们报道了一种仅含20%过量锂且可逆 性和库仑效率显着提高的锂金属全电池. 我们通过设计巧妙的模 拟导弹制导约束系统(SMGCS), 构建兼容的亲锂银位点和硝酸盐 层来引导和限制锂的沉积. 银位点充当有效的锂沉积位点, 吸引锂 离子, 引导锂的初始成核. 生成的硝酸盐层提供了有利于均匀限域 且高容量锂沉积的界面环境, 这在理论上已通过分子动力学(MD) 模拟得到了验证. 这两种优点相结合, 实现了坚固且无枝晶的锂沉 积以及含有极少量过量锂的锂金属全电池的应用. 并且该锂金属 在碳酸酯电解液中表现出优异的循环效率(300次以上的循环中库 伦效率约99%), 还可以在10mA h cm−2 的高容量下进行深度循环. 本文中锂金属前所未有的高利用率为未来高效锂金属全电池的发 展开辟了一条新的道路.
Article PDF
Similar content being viewed by others
References
Xu W, Wang J, Ding F, et al. Lithium metal anodes for rechargeable batteries. Energy Environ Sci, 2014, 7: 513–537
Lin D, Liu Y, Cui Y. Reviving the lithium metal anode for high-energy batteries. Nat Nanotech, 2017, 12: 194–206
Goodenough JB, Kim Y. Challenges for rechargeable Li batteries. Chem Mater, 2009, 22: 587–603
Ma J, Meng F, Yu Y, et al. Prevention of dendrite growth and volume expansion to give high-performance aprotic bimetallic LiNa alloy-O2 batteries. Nat Chem, 2019, 11: 64–70
Zhao CZ, Chen PY, Zhang R, et al. An ion redistributor for dendrite-free lithium metal anodes. Sci Adv, 2018, 4: eaat3446
Li G, Liu Z, Huang Q, et al. Stable metal battery anodes enabled by polyethylenimine sponge hosts by way of electrokinetic effects. Nat Energy, 2018, 3: 1076–1083
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, 2018, 3: 16–21
Qiu F, Li X, Deng H, et al. A concentrated ternary-salts electrolyte for high reversible Li metal battery with slight excess Li. Adv Energy Mater, 2019, 9: 1803372
Liu Y, Lin D, Li Y, et al. Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode. Nat Commun, 2018, 9: 3656
Alvarado J, Schroeder MA, Pollard TP, et al. Bisalt ether electrolytes: a pathway towards lithium metal batteries with Ni-rich cathodes. Energy Environ Sci, 2019, 12: 780–794
Qian J, Henderson WA, Xu W, et al. High rate and stable cycling of lithium metal anode. Nat Commun, 2015, 6: 6362
Yamada Y, Wang J, Ko S, et al. Advances and issues in developing salt-concentrated battery electrolytes. Nat Energy, 2019, 4: 269–280
Shi Q, Zhong Y, Wu M, et al. High-capacity rechargeable batteries based on deeply cyclable lithium metal anodes. Proc Natl Acad Sci USA, 2018, 115: 5676–5680
Zhang XQ, Cheng XB, Chen X, et al. Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries. Adv Funct Mater, 2017, 27: 1605989
Markevich E, Salitra G, Chesneau F, et al. Very stable lithium metal stripping-plating at a high rate and high areal capacity in fluoroethylene carbonate-based organic electrolyte solution. ACS Energy Lett, 2017, 2: 1321–1326
Zhu B, Jin Y, Hu X, et al. Poly(dimethylsiloxane) thin film as a stable interfacial layer for high-performance lithium-metal battery anodes. Adv Mater, 2017, 29: 1603755
Yan K, Lee HW, Gao T, et al. Ultrathin two-dimensional atomic crystals as stable interfacial layer for improvement of lithium metal anode. Nano Lett, 2014, 14: 6016–6022
Gao Y, Zhao Y, Li YC, et al. Interfacial chemistry regulation via a skin-grafting strategy enables high-performance lithium-metal batteries. J Am Chem Soc, 2017, 139: 15288–15291
Lu LL, Ge J, Yang JN, et al. Free-standing copper nanowire network current collector for improving lithium anode performance. Nano Lett, 2016, 16: 4431–4437
Jin C, Sheng O, Luo J, et al. 3D lithium metal embedded within lithiophilic porous matrix for stable lithium metal batteries. Nano Energy, 2017, 37: 177–186
Yan K, Lu Z, Lee HW, et al. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nat Energy, 2016, 1: 16010
Liu W, Mi Y, Weng Z, et al. Functional metal-organic framework boosting lithium metal anode performance via chemical interactions. Chem Sci, 2017, 8: 4285–4291
Li W, Yao H, Yan K, et al. The synergetic effect of lithium polysulfide and lithium nitrate to prevent lithium dendrite growth. Nat Commun, 2015, 6: 7436
Li L, Jacobs R, Gao P, et al. Origins of large voltage hysteresis in high-energy-density metal fluoride lithium-ion battery conversion electrodes. J Am Chem Soc, 2016, 138: 2838–2848
Wang F, Yu HC, Chen MH, et al. Tracking lithium transport and electrochemical reactions in nanoparticles. Nat Commun, 2012, 3: 1201
Tu Z, Choudhury S, Zachman MJ, et al. Fast ion transport at solid-solid interfaces in hybrid battery anodes. Nat Energy, 2018, 3: 310–316
Yan C, Cheng XB, Yao YX, et al. An armored mixed conductor interphase on a dendrite-free lithium-metal anode. Adv Mater, 2018, 30: 1804461
Choudhury S, Tu Z, Stalin S, et al. Electroless formation of hybrid lithium anodes for fast interfacial ion transport. Angew Chem Int Ed, 2017, 56: 13070–13077
Canongia Lopes JN, Deschamps J, Pádua AAH. Modeling ionic liquids using a systematic all-atom force field. J Phys Chem B, 2004, 108: 2038–2047
Canongia Lopes JN, Pádua AAH. Molecular force field for ionic liquids composed of triflate or bistriflylimide anions. J Phys Chem B, 2004, 108: 16893–16898
Soetens JC, Millot C, Maigret B. Molecular dynamics simulation of Li+BF4 in ethylene carbonate, propylene carbonate, and dimethyl carbonate solvents. J Phys Chem A, 1998, 102: 1055–1061
Zhang R, Chen XR, Chen X, et al. Lithiophilic sites in doped graphene guide uniform lithium nucleation for dendrite-free lithium metal anodes. Angew Chem Int Ed, 2017, 56: 7764–7768
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
Li P, Lan H, Yan L, et al. Lithiation/delithiation behavior of silver nitrate as lithium storage material for lithium ion batteries. ACS Sustain Chem Eng, 2017, 5: 5686–5693
Cheng XB, Yan C, Peng HJ, et al. Sulfurized solid electrolyte interphases with a rapid Li+ diffusion on dendrite-free Li metal anodes. Energy Storage Mater, 2018, 10: 199–205
Acknowledgements
We acknowledge support from the National Natural Science Foundation of China (51622208, 21703149, and 51872193) and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).
Author information
Authors and Affiliations
Contributions
Zhou J, Zhou X, Qian T and Yan C conceived the idea and designed the experiment. Zhou J, Lu H, Ji H and Sun Y carried out the synthesis, characterization, electrochemical experiments and calculation. All authors participated in the data analysis and contributed to the manuscript writing.
Corresponding authors
Additional information
Conflict of interest
There are no conflicts to declare.
Supplementary information
Supporting data are available in the online version of the paper.
Jinqiu Zhou is a PhD student under the supervision of Prof. Chenglin Yan at Soochow University. Her research interests focus on lithium battery.
Haoliang Lu studies as a master under the supervision of Prof. Chenglin Yan at Soochow University. His research interests focus on zincion batteries, graphene energy storage and its applications.
Xi Zhou received his PhD degree from Nanjing University in 2016. Hs is now a Research Associate at the Institute of Chemical Industry of Forestry Products in Chinese Academy of Forestry. His research interests focus on biomass-based functional materials and their applications in energy storage, photoelectric sensor and biosorption.
Tao Qian received his PhD degree from Nanjing University in 2014. Hs is now a associate researcher at Soochow University. His research interests focus on energy conversion/storage including lithium battery and electrochemical catalysis.
Chenglin Yan joined Soochow University as a distinguished professor in 2014. He is now the Dean of the College of Energy. His research is totally related to novel design of lithium battery, electrochemical catalysts and their applications in energy storage and conversion.
Electronic Supplementary Material
Rights and permissions
About this article
Cite this article
Zhou, J., Lu, H., Zhou, X. et al. Highly efficient lithium utilization in lithium metal full-cell by simulated missile guidance and confinement systems. Sci. China Mater. 64, 830–839 (2021). https://doi.org/10.1007/s40843-020-1498-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-020-1498-8