AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Lithiophilic N-doped carbon bowls induced Li deposition in layered graphene film for advanced lithium metal batteries

Xiaoyu Feng1,2,§, Hong-Hui Wu3,§, Biao Gao2, Michał Świętosławski4, Xin He5( ), Qiaobao Zhang1( )
Department of Materials Science and Engineering College of Materials Xiamen UniversityXiamen 361005 China
The State Key Laboratory of Refractories and Metallurgy Institute of Advanced Materials and Nanotechnology Wuhan University of Science and TechnologyWuhan 430081 China
School of Materials Science and Engineering University of Science and Technology BeijingBeijing 100083 China
Faculty of Chemistry Jagiellonian University ul. Gronostajowa 2Krakow 30-387 Poland
School of Chemical Engineering Sichuan UniversityChengdu 610065 China

§ Xiaoyu Feng and Hong-Hui Wu contributed equally to this work.

Show Author Information

Graphical Abstract

Abstract

Lithium (Li) metal with high theoretical capacity and low electrochemical potential is the most ideal anode for next-generation high-energy batteries. However, the practical implementation of Li anode has been hindered by dendritic growth and volume expansion during cycling, which results in low Coulombic efficiency (CE), short lifespan, and safety hazards. Here, we report a highly stable and dendrite-free Li metal anode by utilizing N-doped hollow porous bowl-like hard carbon/reduced graphene nanosheets (CB@rGO) hybrids as three-dimensional (3D) conductive and lithiophilic scaffold host. The lithiophilic carbon bowl (CB) mainly works as excellent guides during the Li plating process, whereas the rGO layer with high conductivity and mechanical stability maintains the integrity of the composite by confining the volume change in long-range order during cycling. Moreover, the local current density can be reduced due to the 3D conductive framework. Therefore, CB@rGO presents a low lithium metal nucleation overpotential of 18 mV, high CE of 98%, and stable cycling without obvious voltage fluctuation for over 600 cycles at a current density of 1 mA·cm–2. Our study not only provides a good CB@rGO host and pre-Lithiated CB@rGO composite anode electrode, but also brings a new strategy of designing 3D electrodes for those active materials suffering from severe volume expansion.

Keywords

dendrite inhibitionLi metal hostlithium metal batterybowl-like carbon/reduced graphene nanosheets hybrids

Electronic Supplementary Material

Video
12274_2021_3482_MOESM2_ESM.mp4
Download File(s)
12274_2021_3482_MOESM1_ESM.pdf (2.4 MB)

References

1

Liang, Y.; Zhao, C. Z.; Yuan, H; Chen, Y.; Zhang, W.; Huang, J. Q.; Yu D.; Liu, Y; Titirici, M. M.; Chueh, Y. L. et al. A review of rechargeable batteries for portable electronic devices. InfoMat. 2019, 1, 6–32.
Crossref Google Scholar
2

Wang, A. X.; Zhang, X. Y.; Yang, Y. W.; Huang, J. X.; Liu, X. J.; Luo, J. Y. Horizontal centripetal plating in the patterned voids of Li/graphene composites for stable lithium-metal anodes. Chem 2018, 4, 2192–2200.
Crossref Google Scholar
3

Wu, M.; Li, Y.; Liu, X.; Yang, S.; Ma, J.; Dou, S. Perspective on solid-electrolyte interphase regulation for lithium metal batteries. SmartMat. 2020, 2, 5–11.
Crossref Google Scholar
4

Pu, K. C.; Zhang, X.; Qu, X. L.; Hu, J. J.; Li, H. W.; Gao, M. X.; Pan, H. G.; Liu, Y. F. Recently developed strategies to restrain dendrite growth of Li metal anodes for rechargeable batteries. Rare Met. 2020, 39, 616–635.
Crossref Google Scholar
5

Winter, M.; Barnett, B.; Xu, K. Before Li ion batteries. Chem. Rev. 2018, 118, 11433–11456.
Crossref Google Scholar
6

Xu, W.; Wang, J. L.; Ding, F.; Chen, X. L.; Nasybulin, E.; Zhang, Y. H.; Zhang, J. G. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 2014, 7, 513–537.
Crossref Google Scholar
7

Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Toward safe lithium metal anode in rechargeable batteries: A review. Chem. Rev. 2017, 117, 10403–10473.
Crossref Google Scholar
8

Zhang, K.; Lee, G. H.; Park, M.; Li, W. J.; Kang, Y. M. Recent developments of the lithium metal anode for rechargeable non- aqueous batteries. Adv. Energy Mater. 2016, 6, 1600811.
Crossref Google Scholar
9

Zhamu, A.; Chen, G. R.; Liu, C. G.; Neff, D.; Fang, Q.; Yu, Z. N.; Xiong, W.; Wang, Y. B.; Wang, X. Q.; Jang, B. Z. Reviving rechargeable lithium metal batteries: Enabling next-generation high-energy and high-power cells. Energy Environ. Sci. 2012, 5, 5701–5707.
Crossref Google Scholar
10

Chen, X. R.; Zhao, B. C.; Yan, C.; Zhang, Q. Review on Li deposition in working batteries: From nucleation to early growth. Adv. Mater. 2021, 33, 2004128.
Crossref Google Scholar
11

Chen, X. R.; Yao, Y. X.; Yan, C.; Zhang, R.; Cheng, X. B.; Zhang, Q. A diffusion-reaction competition mechanism to tailor lithium deposition for lithium-metal batteries. Angew. Chem., Int. Ed. 2020, 59, 7743–7747.
Crossref Google Scholar
12

Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Wei, F.; Zhang, J. G.; Zhang, Q. A review of solid electrolyte interphases on lithium metal anode. Adv. Sci. 2016, 3, 1500213.
Crossref Google Scholar
13

Xu, R.; Zhang, X. Q.; Cheng, X. B.; Peng, H. J.; Zhao, C. Z.; Yan, C.; Huang, J. Q. Artificial soft-rigid protective layer for dendrite-free lithium metal anode. Adv. Funct. Mater. 2018, 28, 1705838.
Crossref Google Scholar
14

Chi, S. S.; Liu, Y. C.; Song, W. L.; Fan, L. Z.; Zhang, Q. Prestoring lithium into stable 3D nickel foam host as dendrite-free lithium metal anode. Adv. Funct. Mater. 2017, 27, 1700348.
Crossref Google Scholar
15

Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 2014, 114, 11503–11618.
Crossref Google Scholar
16

Cao, X.; Ren, X. D.; Zou, L. F.; Engelhard, M. H.; Huang, W.; Wang, H.; Matthews, B. E.; Lee, H.; Niu, C. J.; Arey, B. W. et al. Monolithic solid-electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization. Nat. Energy 2019, 4, 796–805.
Crossref Google Scholar
17

Ding, F.; Xu, W.; Graff, G. L.; Zhang, J.; Sushko, M. L.; Chen, X. L.; Shao, Y. Y.; Engelhard, M. H.; Nie, Z. M.; Xiao, J. et al. Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. J. Am. Chem. Soc. 2013, 135, 4450–4456.
Crossref Google Scholar
18

Wang, D. D.; Liu, H. D.; Li, M. Q.; Xia, D. W.; Holoubek, J.; Deng, Z.; Yu, M. Y.; Tian, J. H.; Shan, Z. Q.; Ong, S. P. et al. A long-lasting dual-function electrolyte additive for stable lithium metal batteries. Nano Energy 2020, 75, 104889.
Crossref Google Scholar
19

Liu, H. D.; Holoubek, J.; Zhou, H. Y.; Chen, A.; Chang, N.; Wu, Z. H.; Yu, S. C.; Yan, Q. Z.; Xing, X.; Li, Y. J. et al. Ultrahigh coulombic efficiency electrolyte enables Li|| span batteries with superior cycling performance. Mater. Today 2020, 42, 17–28.
Crossref Google Scholar
20

Liu, H. D.; Zhou, H. Y.; Lee, B. S.; Xing, X.; Gonzalez, M.; Liu, P. Suppressing lithium dendrite growth with a single-component coating. ACS Appl. Mater. Interfaces 2017, 9, 30635–30642.
Crossref Google Scholar
21

Gao, Y.; Yan, Z. F.; Gray, J. L.; He, X.; Wang, D. W.; Chen, T. H.; Huang, Q. Q.; Li, Y. C.; Wang, H. Y.; Kim, S. H. et al. Polymer- inorganic solid-electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions. Nat. Energy 2019, 18, 384–389.
Crossref Google Scholar
22

Liu, Q. C.; Xu, J. J.; Yuan, S.; Chang, Z. W.; Xu, D.; Yin, Y. B.; Li, L.; Zhong, H. X.; Jiang, Y. S.; Yan, J. M. et al. Artificial protection film on lithium metal anode toward long-cycle-life lithium-oxygen batteries. Adv. Mater. 2015, 27, 5241–5247.
Crossref Google Scholar
23

Zhou, H. Y.; Yu, S. C.; Liu, H. D.; Liu, P. Protective coatings for lithium metal anodes: Recent progress and future perspectives. J. Power Sources 2020, 450, 227632.
Crossref Google Scholar
24

Liu, H. D.; Yue, X. J.; Xing, X.; Yan, Q. Z.; Huang, J.; Petrova, V.; Zhou, H. Y.; Liu, P. A scalable 3D lithium metal anode. Energy Storage Mater. 2019, 16, 505–511.
Crossref Google Scholar
25

Li, H. P.; Ji, X. Y.; Liang, J. J. Dual-functional ion redistributor for dendrite-free lithium metal anodes. Rare Met. 2020, 39, 861–862.
Crossref Google Scholar
26

Shi, H. D.; Li, Y. G.; Lu, P. F.; Wu, Z. S. Single-atom cobalt coordinated to oxygen sites on graphene for stable lithium metal anodes. Acta Phys. –Chim. Sin. 2021, 37, 2008033.
Crossref Google Scholar
27

Huang, X.; Feng, X. Y.; Zhang, B.; Zhang, L.; Zhang, S. C.; Gao, B.; Chu, P. K.; Huo, K. F. Lithiated NiCo2O4 nanorods anchored on 3D nickel foam enable homogeneous Li plating/stripping for high-power dendrite-free lithium metal anode. ACS Appl. Mater. Interfaces 2019, 11, 31824–31831.
Crossref Google Scholar
28

Liu, K.; Pei, A.; Lee, H. R.; Kong, B.; Liu, N.; Lin, D. C.; Liu, Y. Y.; Liu, C.; Hsu, P. C.; Bao, Z. N. et al. Lithium metal anodes with an adaptive "solid-liquid" interfacial protective layer. J. Am. Chem. Soc. 2017, 139, 4815–4820.
Crossref Google Scholar
29

Sun, Y. M.; Zheng, G. Y.; Seh, Z. W.; Liu, N.; Wang, S.; Sun, J.; Lee, H. R.; Cui, Y. Graphite-encapsulated Li-metal hybrid anodes for high-capacity Li batteries. Chem 2016, 1, 287–297.
Crossref Google Scholar
30

Zheng, G. Y.; Lee, S. W.; Liang, Z.; Lee, H. W.; Yan, K.; Yao, H. B.; Wang, H. T.; Li, W. Y.; Chu, S.; Cui, Y. Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nat. Nanotechnol. 2014, 9, 618–623.
Crossref Google Scholar
31

Liu, S. F.; Xia, X. H.; Zhong, Y.; Deng, S. J.; Yao, Z. J.; Zhang, L. Y.; Cheng, X. B.; Wang, X. L.; Zhang, Q.; Tu, J. P. 3D TiC/C core/shell nanowire skeleton for dendrite-free and long-life lithium metal anode. Adv. Energy Mater. 2018, 8, 1702322.
Crossref Google Scholar
32

Zhao, Q.; Hao, X. G.; Su, S. M.; Ma, J. B.; Hu, Y.; Liu, Y.; Kang, F. Y.; He, Y. B. Expanded-graphite embedded in lithium metal as dendrite-free anode of lithium metal batteries. J. Mater. Chem. A 2019, 7, 15871–15879.
Crossref Google Scholar
33

Zheng, Z. M.; Wu, H. H.; Liu, H. D.; Zhang, Q. B.; He, X.; Yu, S. C.; Petrova, V.; Feng, J.; Kostecki, R.; Liu, P. et al. Achieving fast and durable lithium storage through amorphous FeP nanoparticles encapsulated in ultrathin 3D P-doped porous carbon nanosheets. ACS Nano 2020, 14, 9545–9561.
Crossref Google Scholar
34

Zhang, R.; Shen, X.; Cheng, X. B.; Zhang, Q. The dendrite growth in 3D structured lithium metal anodes: Electron or ion transfer limitation? Energy Storage Mater. 2019, 23, 556–565.
Crossref Google Scholar
35

Shi, P.; Li, T.; Zhang, R.; Shen, X.; Cheng, X. B.; Xu, R.; Huang, J. Q.; Chen, X. R.; Liu, H.; Zhang, Q. Lithiophilic LiC6 layers on carbon hosts enabling stable Li metal anode in working batteries. Adv. Mater. 2019, 31, 1807131.
Crossref Google Scholar
36

Zhao, H.; Lei, D. N.; He, Y. B.; Yuan, Y. F.; Yun, Q. B.; Ni, B.; Lv, W.; Li, B. H.; Yang, Q. H.; Kang, F. Y. et al. Compact 3D copper with uniform porous structure derived by electrochemical dealloying as dendrite-free lithium metal anode current collector. Adv. Energy Mater. 2018, 8, 1800266.
Crossref Google Scholar
37

Yun, Q. B.; He, Y. B; Lv, W.; Zhao, Y.; Li, B. H.; Kang, F. Y.; Yang, Q. H. Chemical dealloying derived 3D porous current collector for Li metal anodes. Adv. Mater. 2016, 28, 6932–6939.
Crossref Google Scholar
38

Lu, L. L.; Ge, J.; Yang, J. N.; Chen, S. M.; Yao, H. B.; Zhou, F.; Yu, S. H. Free-standing copper nanowire network current collector for improving lithium anode performance. Nano Lett. 2016, 16, 4431– 4437.
Crossref Google Scholar
39

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B: Condens. Matter Mater. Phys. 1996, 54, 11169.
Crossref Google Scholar
40

Zhang, H.; Liu, Z.; Liang, L.; Chen, L.; Qi, Y.; Harris, S. J.; Lu, P.; Chen, L. Understanding and predicting the lithium dendrite formation in Li-ion batteries: Phase field model. ECS Transactions 2014, 61, 1.
Crossref Google Scholar
41

Nan, Y.; Li, S. M.; Shi, Y. Z.; Yang, S. B.; Li, B. Gradient-distributed nucleation seeds on conductive host for a dendrite-free and high-rate lithium metal anode. Small 2019, 15, 1903520.
Crossref Google Scholar
42

Sharifi, T.; Hu, G.; Jia, X. E.; Wagberg, T. Formation of active sites for oxygen reduction reactions by transformation of nitrogen functionalities in nitrogen-doped carbon nanotubes. ACS Nano 2012, 6, 8904–8912.
Crossref Google Scholar
43

Rabchinskii, M. K.; Ryzhkov, S. A.; Kirilenko, D. A.; Ulin, N. V.; Baidakova, M. V.; Shnitov, V. V.; Pavlov, S. I.; Chumakov, R. G.; Stolyarova, D. Y.; Besedina, N. A. et al. From graphene oxide towards aminated graphene: Facile synthesis, its structure and electronic properties. Sci. Rep. 2020, 10, 1–12.
Crossref Google Scholar
44

Zhang, J.; Li, C. Q.; Peng, Z. K.; Liu, Y. S.; Zhang, J. M.; Liu, Z. Y.; Li, D. 3D free-standing nitrogen-doped reduced graphene oxide aerogel as anode material for sodium ion batteries with enhanced sodium storage. Sci. Rep. 2017, 7, 1–7.
Crossref Google Scholar
45

Zhang, Q.; Chen, H.; Luo, L.; Zhao, B.; Luo, H.; Han, X.; Wang, J.; Wang, C.; Yang, Y.; Zhu, T.; Liu, M. Harnessing the concurrent reaction dynamics in active Si and Ge to achieve high performance lithium-ion batteries. Energy Environ. Sci. 2018, 11, 669–681.
Crossref Google Scholar
46

Cheng, Y.; Zhang, L.; Zhang, Q.; Li, J.; Tang, Y.; Delmas, C.; Zhu, T.; Winter, M.; Wang, M.; Huang, J. Understanding all solid-state lithium batteries through in situ transmission electron microscopy. Mater. Today 2020, 42, 137–161.
Crossref Google Scholar
47

Li, Y.; Zhang, Q.; Yuan, Y.; Liu, H.; Yang, C.; Lin, Z.; Lu, J. Surface amorphization of vanadium dioxide (B) for K-ion battery. Adv. Energy Mater. 2020, 10, 2000717.
Crossref Google Scholar
48

Liu, S.; Wang, A.; Li, Q.; Wu, J.; Chiou, K.; Huang, J.; Luo, J. Crumpled graphene balls stabilized dendrite-free lithium metal anodes. Joule 2018, 2, 184–193.
Crossref Google Scholar
49

Zhang, C.; Liu, S.; Li, G.; Zhang, C.; Liu, X.; Luo, J. Incorporating ionic paths into 3D conducting scaffolds for high volumetric and areal capacity, high rate lithium-metal anodes. Adv. Mater. 2018, 30, 1801328.
Crossref Google Scholar
50

He, X.; Yang, Y.; Cristian, M. S.; Wang, J.; Hou, X.; Yan, B.; Li, J.; Zhang, T.; Paillard, E.; Swietoslawski, M. et al. Uniform lithium electrodeposition for stable lithium-metal batteries. Nano Energy 2020, 67, 104172.
Crossref Google Scholar
51

Zhao, L.; Wu, H. H.; Yang, C.; Zhang, Q.; Zhong, G.; Zheng, Z.; Chen, H.; Wang, J.; He, K.; Wang, B. et al. Mechanistic origin of the high performance of yolk@shell Bi2S3@N-doped carbon nanowire electrodes. ACS Nano 2018, 12, 12597–12611.
Crossref Google Scholar
Nano Research
Volume 15 Issue 1,
January 2022
Pages 352-360
DOI: 10.1007/s12274-021-3482-0
Cite this article:
Feng X, Wu H-H, Gao B, et al. Lithiophilic N-doped carbon bowls induced Li deposition in layered graphene film for advanced lithium metal batteries. Nano Research, 2022, 15(1): 352-360. https://doi.org/10.1007/s12274-021-3482-0
Topics:
Lithium batteries
Part of a topical collection:
The winners of “Top Papers Award” in 2022

1376

Views

103

Crossref

104

Web of Science

98

Scopus

16

CSCD

Altmetrics
Received: 15 February 2021
Revised: 29 March 2021
Accepted: 29 March 2021
Published: 21 April 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
Return