Citation: Huang Fanyang, Jie Yulin, Li Xinpeng, Chen Yawei, Cao Ruiguo, Zhang Genqiang, Jiao Shuhong. Correlation between Li Plating Morphology and Reversibility of Li Metal Anode[J]. Acta Physico-Chimica Sinica, ;2021, 37(1): 200808. doi: 10.3866/PKU.WHXB202008081 shu

Correlation between Li Plating Morphology and Reversibility of Li Metal Anode

Hefei National Laboratory for Physical Sciences at the Microscale, Department of Materials Science and Engineering, CAS Key Laboratory of Materials for Energy Conversion, University of Science and Technology of China, Hefei 230026, China

Corresponding author: Jiao Shuhong, jiaosh@ustc.edu.cn

^†

Received Date: 27 August 2020
Revised Date: 27 September 2020
Accepted Date: 28 September 2020
Available Online: 19 October 2020
Fund Project: the National Natural Science Foundation of China 21776265the National Key Research and Development Program of China 2017YFA0206700the Anhui Provincial Natural Science Foundation 1908085ME122The project was supported by the National Key Research and Development Program of China (2017YFA0402802, 2017YFA0206700), the National Natural Science Foundation of China (51902304, 21776265), the Anhui Provincial Natural Science Foundation (1908085ME122), the Fundamental Research Funds for the Central Universities, China (Wk2060140026)the Fundamental Research Funds for the Central Universities, China Wk2060140026the National Key Research and Development Program of China 2017YFA0402802the National Natural Science Foundation of China 51902304

Commercialization of high-energy rechargeable batteries can promote the rapid development of portable electronics and electric vehicles. Li metal batteries (LMBs) have attracted considerable attention owing to their high theoretical energy density. Li metal anodes (LMAs) used in LMBs suffer from the disadvantages of high reactivity, interface instability and dendrite growth, which impede the practical development of the LMBs. Coulombic efficiency (CE), which depends on the type of electrolyte used, is one of the key parameters for evaluating the reversibility of battery systems. Herein, we use atomic force microscopy (AFM) to study the initial plating stages and growth of the lithium metal in different electrolytes, such as 1 mol·L^-1 lithium hexafluorophosphate (LiPF₆)-ethylene carbonate/dimethyl carbonate (EC/DMC, 1 : 1, V/V), 1 mol·L^-1 LiPF₆-EC/DMC (1 : 1, V/V) + 5% (mass fraction, w) fluoroethylene carbonate (FEC), 1 mol·L^-1 lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-1, 3-dioxolane/dimethoxyethane (DOL/DME, 1 : 1, V/V) + 2% (w) lithium nitrate (LiNO₃), and 4 mol·L^-1 lithium bis(fluorosulfonyl)imide (LiFSI)-DME, and further investigate the correlation between the CE of LMA and Li plating morphology. There are two types of Li morphologies in these electrolytes: strip-like and particle-like morphology. Since the specific surface area of particle-like deposits is much smaller than that of strip-like deposits, the particle-like morphology facilitates higher CE. (1) In the conventional carbonate electrolyte (1 mol·L^-1 LiPF₆-EC/DMC), Li predominantly forms strip-like deposits with large specific surface area, consuming much active Li (due to the side reaction between Li and the electrolyte). The dendrite morphology of the Li deposits lead to the formation of dead Li during the stripping process, which results in low CE. (2) FEC, an effective additive often used in carbonate electrolyte, can induce the transformation of Li plating morphology from strip-like to particle-like morphology. Therefore, the CE in FEC-containing electrolytes has been significantly improved with stable electrode/electrolyte interphase and small specific surface area of deposited Li. (3) In ether electrolytes, which have better compatibility with LMAs than carbonate electrolytes, Li metal exhibits a particle-like morphology and achieves high CE. (4) In the highly concentrated electrolyte (4 mol·L^-1 LiFSI-DME), Li metal grows into large particles without dendrite formation, which hampers the parasitic side reactions, and further enhances CE.
- Li metal anode,
- Coulombic efficiency,
- Plating morphology,
- Electrolyte,
- Atomic force microscopy
1. [1]
  Armand, M.; Tarascon, J. M. Nature 2008, 451, 652. doi: 10.1038/451652a doi: 10.1038/451652a
2. [2]
  Cano, Z. P.; Banham, D.; Ye, S.; Hintennach, A.; Lu, J.; Fowler, M.; Chen, Z. W. Nat. Energy 2018, 3, 279. doi: 10.1038/s41560-018-0108-1 doi: 10.1038/s41560-018-0108-1
3. [3]
  Choi, J. W.; Aurbach, D. Nat. Rev. Mater. 2016, 1, 16013. doi: 10.1038/natrevmats.2016.13 doi: 10.1038/natrevmats.2016.13
4. [4]
  Pathak, R.; Chen, K.; Gurung, A.; Reza, K. M.; Bahrami, B.; Pokharel, J.; Baniya, A.; He, W.; Wu, F.; Zhou, Y.; et al. Nat. Commun. 2020, 11, 93. doi: 10.1038/s41467-019-13774-2 doi: 10.1038/s41467-019-13774-2
5. [5]
  Yu, X.; Wang, L.; Ma, J.; Sun, X.; Zhou, X.; Cui, G. Adv. Energy Mater. 2020, 10, 1903939. doi: 10.1002/aenm.201903939 doi: 10.1002/aenm.201903939
6. [6]
  Lim, H. D.; Lee, B.; Bae, Y.; Park, H.; Ko, Y.; Kim, H.; Kim, J.; Kang, K. Chem. Soc. Rev. 2017, 46, 2873. doi: 10.1039/C6CS00929H doi: 10.1039/C6CS00929H
7. [7]
  Asadi, M.; Sayahpour, B.; Abbasi, P.; Ngo, A. T.; Karis, K.; Jokisaari, J. R.; Liu, C.; Narayanan, B.; Gerard, M.; Yasaei, P.; et al. Nature 2018, 555, 502. doi: 10.1038/nature25984 doi: 10.1038/nature25984
8. [8]
  Jung, J. W.; Cho, S. H.; Nam, J. S.; Kim, I. D. Energy Storage Mater. 2020, 24, 512. doi: 10.1016/j.ensm.2019.07.006 doi: 10.1016/j.ensm.2019.07.006
9. [9]
  Yin, Y. X.; Xin, S.; Guo, Y. G.; Wan, L. J. Angew. Chem. Int. Ed. 2013, 52, 13186. doi: 10.1002/anie.201304762 doi: 10.1002/anie.201304762
10. [10]
  Manthiram, A.; Fu, Y.; Chung, S. H.; Zu, C.; Su, Y. S. Chem. Rev. 2014, 114, 11751. doi: 10.1021/cr500062v doi: 10.1021/cr500062v
11. [11]
  Seh, Z. W.; Sun, Y.; Zhang, Q.; Cui, Y. Chem. Soc. Rev. 2016, 45, 5605. doi: 10.1039/c5cs00410a doi: 10.1039/c5cs00410a
12. [12]
  Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Chem. Rev. 2017, 117, 10403. doi: 10.1021/acs.chemrev.7b00115 doi: 10.1021/acs.chemrev.7b00115
13. [13]
  Sun, Y.; Liu, N.; Cui, Y. Nat. Energy 2016, 1, 16071. doi: 10.1038/nenergy.2016.71 doi: 10.1038/nenergy.2016.71
14. [14]
  Liu, F. F.; Zhang, Z. W.; Ye, S. F.; Yao, Y.; Yu, Y. Acta Phys. -Chim. Sin. 2021, 37, 2006021. doi: 10.3866/PKU.WHXB202006021
15. [15]
  Duan, H.; Yin, Y. X.; Shi, Y.; Wang, P. F.; Zhang, X. D.; Yang, C. P.; Shi, J. L.; Wen, R.; Guo, Y. G.; Wan, L. J. J. Am. Chem. Soc. 2018, 140, 82. doi: 10.1021/jacs.7b10864 doi: 10.1021/jacs.7b10864
16. [16]
  Jiao, S.; Zheng, J.; Li, Q.; Li, X.; Engelhard, M. H.; Cao, R.; Zhang, J. G.; Xu, W. Joule 2018, 2, 110. doi: 10.1016/j.joule.2017.10.007 doi: 10.1016/j.joule.2017.10.007
17. [17]
  Yan, C.; Cheng, X. B.; Yao, Y. X.; Shen, X.; Li, B. Q.; Li, W. J.; Zhang, R.; Huang, J. Q.; Li, H.; Zhang, Q. Adv. Mater. 2018, 30, e1804461. doi: 10.1002/adma.201804461 doi: 10.1002/adma.201804461
18. [18]
  Chen, L.; Fan, X.; Ji, X.; Chen, J.; Hou, S.; Wang, C. Joule 2019, 3, 732. doi: 10.1016/j.joule.2018.11.025 doi: 10.1016/j.joule.2018.11.025
19. [19]
  Wood, K. N.; Noked, M.; Dasgupta, N. P. ACS Energy Lett. 2017, 2, 664. doi: 10.1021/acsenergylett.6b00650 doi: 10.1021/acsenergylett.6b00650
20. [20]
  Pang, Q.; Liang, X.; Shyamsunder, A.; Nazar, L. F. Joule 2017, 1, 871. doi: 10.1016/j.joule.2017.11.009 doi: 10.1016/j.joule.2017.11.009
21. [21]
  Ye, H.; Yin, Y. X.; Zhang, S. F.; Shi, Y.; Liu, L.; Zeng, X. X.; Wen, R.; Guo, Y. G.; Wan, L. J. Nano Energy 2017, 36, 411. doi: 10.1016/j.nanoen.2017.04.056 doi: 10.1016/j.nanoen.2017.04.056
22. [22]
  Zhang, Y.; Qian, J.; Xu, W.; Russell, S. M.; Chen, X.; Nasybulin, E.; Bhattacharya, P.; Engelhard, M. H.; Mei, D.; Cao, R.; et al. Nano Lett. 2014, 14, 6889. doi: 10.1021/nl5039117 doi: 10.1021/nl5039117
23. [23]
  Jie, Y.; Liu, X.; Lei, Z.; Wang, S.; Chen, Y.; Huang, F.; Cao, R.; Zhang, G.; Jiao, S. Angew. Chem. Int. Ed. 2020, 59, 3505. doi: 10.1002/anie.201914250 doi: 10.1002/anie.201914250
24. [24]
  Zheng, G.; Lee, S. W.; Liang, Z.; Lee, H. W.; Yan, K.; Yao, H.; Wang, H.; Li, W.; Chu, S.; Cui, Y. Nat. Nanotechnol. 2014, 9, 618. doi: 10.1038/nnano.2014.152 doi: 10.1038/nnano.2014.152
25. [25]
  Lan, X.; Ye, W.; Zheng, H.; Cheng, Y.; Zhang, Q.; Peng, D. L.; Wang, M. S. Nano Energy 2019, 66, 104178. doi: 10.1016/j.nanoen.2019.104178 doi: 10.1016/j.nanoen.2019.104178
26. [26]
  Li, Y.; Li, Y.; Pei, A.; Yan, K.; Sun, Y.; Wu, C. L.; Joubert, L. M.; Chin, R.; Koh, A. L.; Yu, Y.; et al. Science 2017, 358, 506. doi: 10.1126/science.aam6014 doi: 10.1126/science.aam6014
27. [27]
  Li, Y.; Huang, W.; Li, Y.; Pei, A.; Boyle, D. T.; Cui, Y. Joule 2018, 2, 2167. doi: 10.1016/j.joule.2018.08.004 doi: 10.1016/j.joule.2018.08.004
28. [28]
  Wang, X.; Zhang, M.; Alvarado, J.; Wang, S.; Sina, M.; Lu, B.; Bouwer, J.; Xu, W.; Xiao, J.; Zhang, J. G.; et al. Nano Lett. 2017, 17, 7606. doi: 10.1021/acs.nanolett.7b03606 doi: 10.1021/acs.nanolett.7b03606
29. [29]
  Cao, X.; Ren, X.; Zou, L.; Engelhard, M. H.; Huang, W.; Wang, H.; Matthews, B. E.; Lee, H.; Niu, C.; Arey, B. W.; et al. Nat. Energy 2019, 4, 796. doi: 10.1038/s41560-019-0464-5 doi: 10.1038/s41560-019-0464-5
30. [30]
  Pei, A.; Zheng, G.; Shi, F.; Li, Y.; Cui, Y. Nano Lett. 2017, 17, 1132. doi: 10.1021/acs.nanolett.6b04755 doi: 10.1021/acs.nanolett.6b04755
31. [31]
  Chen, X.; Lai, J.; Shen, Y.; Chen, Q.; Chen, L. Adv. Mater. 2018, 30, e1802490. doi: 10.1002/adma.201802490 doi: 10.1002/adma.201802490
32. [32]
  Wang, S.; Liu, Q.; Zhao, C.; Lv, F.; Qin, X.; Du, H.; Kang, F.; Li, B. Energy Environ. Mater. 2018, 1, 28. doi: 10.1002/eem2.12002 doi: 10.1002/eem2.12002
33. [33]
  Zhao, W.; Song, W.; Cheong, L. Z.; Wang, D.; Li, H.; Besenbacher, F.; Huang, F.; Shen, C. Ultramicroscopy 2019, 204, 34. doi: 10.1016/j.ultramic.2019.05.004 doi: 10.1016/j.ultramic.2019.05.004
34. [34]
  Li, N. W.; Shi, Y.; Yin, Y. X.; Zeng, X. X.; Li, J. Y.; Li, C. J.; Wan, L. J.; Wen, R.; Guo, Y. G. Angew. Chem. Int. Ed. 2018, 57, 1505. doi: 10.1002/anie.201710806 doi: 10.1002/anie.201710806
35. [35]
  Aurbach, D. J. Electrochem. Soc. 1997, 144, 3355. doi: 10.1149/1.1838018 doi: 10.1149/1.1838018
36. [36]
  Aurbach, D.; Cohen, Y. J. Electrochem. Soc. 1996, 143, 3525. doi: 10.1149/1.1837248 doi: 10.1149/1.1837248
37. [37]
  Han, Y.; Jie, Y.; Huang, F.; Chen, Y.; Lei, Z.; Zhang, G.; Ren, X.; Qin, L.; Cao, R.; Jiao, S. Adv. Funct. Mater. 2019, 29, 1904629. doi: 10.1002/adfm.201904629 doi: 10.1002/adfm.201904629
38. [38]
  Chen, S.; Zheng, J.; Mei, D.; Han, K. S.; Engelhard, M. H.; Zhao, W.; Xu, W.; Liu, J.; Zhang, J. G. Adv. Mater. 2018, 30, 1706102. doi: 10.1002/adma.201706102 doi: 10.1002/adma.201706102
39. [39]
  Shi, F.; Pei, A.; Vailionis, A.; Xie, J.; Liu, B.; Zhao, J.; Gong, Y.; Cui, Y. Proc. Natl. Acad. Sci. U.S.A. 2017, 114, 12138. doi: 10.1073/pnas.1708224114 doi: 10.1073/pnas.1708224114
40. [40]
  Qian, J.; Henderson, W. A.; Xu, W.; Bhattacharya, P.; Engelhard, M.; Borodin, O.; Zhang, J. G. Nat. Commun. 2015, 6, 6362. doi: 10.1038/ncomms7362 doi: 10.1038/ncomms7362
41. [41]
  Yu, Z.; Wang, H.; Kong, X.; Huang, W.; Tsao, Y.; Mackanic, D. G.; Wang, K.; Wang, X.; Huang, W.; Choudhury, S.; et al. Nat. Energy 2020, 5, 526. doi: 10.1038/s41560-020-0634-5 doi: 10.1038/s41560-020-0634-5
42. [42]
  Adams, B. D.; Zheng, J.; Ren, X.; Xu, W.; Zhang, J. G. Adv. Energy Mater. 2018, 8, 1702097. doi: 10.1002/aenm.201702097 doi: 10.1002/aenm.201702097
43. [43]
  Jie, Y.; Ren, X.; Cao, R.; Cai, W.; Jiao, S. Adv. Funct. Mater. 2020, 30, 1910777. doi: 10.1002/adfm.201910777 doi: 10.1002/adfm.201910777
44. [44]
  Xu, K. Chem. Rev. 2004, 104, 4303. doi: 10.1021/cr030203g doi: 10.1021/cr030203g
45. [45]
  Wang, J.; Huang, W.; Pei, A.; Li, Y.; Shi, F.; Yu, X.; Cui, Y. Nature Energy 2019, 4, 664. doi: 10.1038/s41560-019-0413-3 doi: 10.1038/s41560-019-0413-3
46. [46]
  Yan, K.; Wang, J.; Zhao, S.; Zhou, D.; Sun, B.; Cui, Y.; Wang, G. Angew. Chem. Int. Ed. 2019, 58, 11364. doi: 10.1002/anie.201905251 doi: 10.1002/anie.201905251
1. [1]
  Feiya Cao , Qixin Wang , Pu Li , Zhirong Xing , Ziyu Song , Heng Zhang , Zhibin Zhou , Wenfang Feng . Magnesium-Ion Conducting Electrolyte Based on Grignard Reaction: Synthesis and Properties. University Chemistry, 2024, 39(3): 359-368. doi: 10.3866/PKU.DXHX202308094
2. [2]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
3. [3]
  Qiuyang LUO , Xiaoning TANG , Shu XIA , Junnan LIU , Xingfu YANG , Jie LEI . Application of a densely hydrophobic copper metal layer in-situ prepared with organic solvents for protecting zinc anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1243-1253. doi: 10.11862/CJIC.20240110
4. [4]
  Jiao CHEN , Yi LI , Yi XIE , Dandan DIAO , Qiang XIAO . Vapor-phase transport of MFI nanosheets for the fabrication of ultrathin b-axis oriented zeolite membranes. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 507-514. doi: 10.11862/CJIC.20230403
5. [5]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013
6. [6]
  Qin ZHU , Jiao MA , Zhihui QIAN , Yuxu LUO , Yujiao GUO , Mingwu XIANG , Xiaofang LIU , Ping NING , Junming GUO . Morphological evolution and electrochemical properties of cathode material LiAl_0.08Mn_1.92O₄ single crystal particles. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1549-1562. doi: 10.11862/CJIC.20240022
7. [7]
  Juan Yuan , Bin Zhang , Jinping Wu , Mengfan Wang . Design of a Comprehensive Experiment on Preparation and Characterization of Cu₂(Salen)₂ Nanomaterials with Two Distinct Morphologies. University Chemistry, 2024, 39(10): 420-425. doi: 10.3866/PKU.DXHX202402014
8. [8]
  Yutong Dong , Huiling Xu , Yucheng Zhao , Zexin Zhang , Ying Wang . The Hidden World of Surface Tension and Droplets. University Chemistry, 2024, 39(6): 357-365. doi: 10.3866/PKU.DXHX202312022
9. [9]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191
10. [10]
  Chunai Dai , Yongsheng Han , Luting Yan , Zhen Li , Yingze Cao . Ideological and Political Design of Solid-liquid Contact Angle Measurement Experiment. University Chemistry, 2024, 39(2): 28-33. doi: 10.3866/PKU.DXHX202306065
11. [11]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189
12. [12]
  Yingran Liang , Fei Wang , Jiabao Sun , Hongtao Zheng , Zhenli Zhu . Construction and Application of a New Experimental Device for Determination of Alkaline Metal Elements by Plasma Atomic Emission Spectrometry Based on Solution Cathode Glow Discharge: An Alternative Approach for Fundamental Teaching Experiments in Emission Spectroscopy. University Chemistry, 2024, 39(5): 380-387. doi: 10.3866/PKU.DXHX202312024
13. [13]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
14. [14]
  Yongmei Liu , Lisen Sun , Zhen Huang , Tao Tu . Curriculum-Based Ideological and Political Design for the Experiment of Methanol Oxidation to Formaldehyde Catalyzed by Electrolytic Silver. University Chemistry, 2024, 39(2): 67-71. doi: 10.3866/PKU.DXHX202308020
15. [15]
  Yanhui Zhong , Ran Wang , Zian Lin . Analysis of Halogenated Quinone Compounds in Environmental Water by Dispersive Solid-Phase Extraction with Liquid Chromatography-Triple Quadrupole Mass Spectrometry. University Chemistry, 2024, 39(11): 296-303. doi: 10.12461/PKU.DXHX202402017
16. [16]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
17. [17]
  Shuang Yang , Qun Wang , Caiqin Miao , Ziqi Geng , Xinran Li , Yang Li , Xiaohong Wu . Ideological and Political Education Design for Research-Oriented Experimental Course of Highly Efficient Hydrogen Production from Water Electrolysis in Aerospace Perspective. University Chemistry, 2024, 39(11): 269-277. doi: 10.12461/PKU.DXHX202403044
18. [18]
  Zitong Chen , Zipei Su , Jiangfeng Qian . Aromatic Alkali Metal Reagents: Structures, Properties and Applications. University Chemistry, 2024, 39(8): 149-162. doi: 10.3866/PKU.DXHX202311054
19. [19]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
20. [20]
  Tao Jiang , Yuting Wang , Lüjin Gao , Yi Zou , Bowen Zhu , Li Chen , Xianzeng Li . Experimental Design for the Preparation of Composite Solid Electrolytes for Application in All-Solid-State Batteries: Exploration of Comprehensive Chemistry Laboratory Teaching. University Chemistry, 2024, 39(2): 371-378. doi: 10.3866/PKU.DXHX202308057

Get Citation

PDF

XML

Metrics

PDF Downloads(19)
Abstract views(1498)
HTML views(393)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142