柱状金属锂沉积物：电解液添加剂的影响

doi:10.3866/PKU.WHXB202007058

Abstract

Abstract:

With the booming growth market of electric vehicles and portable electronics, high-energy-density rechargeable lithium ion batteries are being extensively used to advance high-end devices. Lithium-ion batteries with graphite anodes approach the ceiling in energy density, but they cannot satisfy the current demand. Among the next-generation electrodes, lithium metal anodes are strong candidates because of their high theoretical capacity and the most negative electrochemical potential. However, lithium metal batteries have been abandoned because of their poor safety resulting from the growth of lithium dendrites during lithium deposition. Although several strategies have been proposed to suppress the generation of lithium dendrites as well as the side reactions between active lithium and the electrolyte, lithium metal anodes have not been practically applied so far. Various studies have been conducted on the factors influencing lithium deposition, with the aim of understanding the growth behavior of lithium dendrites. The electrolyte plays a crucial role in the performance of the working Li metal anode. In this study, a unique battery system is proposed to realize columnar lithium deposition, which is convenient for obtaining the length and diameter of lithium deposits. The influence of different electrolytes on lithium deposition was investigated by comparing the length-diameter (L/D) ratio of the lithium deposits in two kinds of electrolytes (1.0 mol·L^-1 LiPF₆-ethylene carbonate/diethyl carbonate (EC/DEC, 1 : 1 by volume) and 1.0 mol·L^-1 LiPF₆-5% (volume fraction) fluoroethylene carbonate (FEC)-EC/DEC (1 : 1 by volume)). The morphology of the lithium deposits was strongly affected by the electrolyte composition. In the electrolyte with the FEC additive, the diameter of columnar lithium increased from 0.3-0.6 μm to 0.7-1.3 μm, while the L/D ratio decreased from 12.5 to 5.6. The small L/D ratio can reduce the reactive area between the lithium metal anode and the electrolyte, which is beneficial for achieving high lithium utilization and a long lifespan. To probe the origin of this influence, the surface chemistry of the cycled lithium metal anode was investigated by X-ray photoelectron spectroscopy. The FEC additive can increase the proportion of lithium fluoride (LiF) in the solid electrolyte interphase, which is conducive for the rapid diffusion of lithium ions. As a result, fewer nucleation sites are formed, providing more space for the growth of lithium cores with a large diameter. Therefore, the addition of FEC leads to a decrease in the L/D ratio of columnar lithium.

Key words: Lithium metal battery, Columnar lithium, Electrolyte, Lithium fluoride, Length-diameter ratio

MSC2000:

O646

Shijie Yang, Xiangqun Xu, Xinbing Cheng, Xinmeng Wang, Jinxiu Chen, Ye Xiao, Hong Yuan, He Liu, Aibing Chen, Wancheng Zhu, Jiaqi Huang, Qiang Zhang. Columnar Lithium Metal Deposits: the Role of Non-Aqueous Electrolyte Additive[J].Acta Phys. -Chim. Sin., 2021, 37(1): 2007058.

Figures/Tables 7

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References 58

1	Chen X. R. ; Yao Y. X. ; Yan C. ; Zhang R. ; Cheng X. B. ; Zhang Q. Angew. Chem. Int. Ed. 2020, 132, 7817. doi: 10.1002/ange.202000375
2	Fan Y. ; Wang T. ; Legut D. ; Zhang Q. J. Energy Chem. 2019, 39, 160. doi: 10.1016/j.jechem.2019.01.021
3	Liu H. ; Cheng X. B. ; Huang J. Q. ; Yuan H. ; Lu Y. ; Yan C. ; Zhu G. L. ; Xu R. ; Zhao C. Z. ; Hou L. P. ; et al ACS Energy Lett. 2020, 5, 833. doi: 10.1021/acsenergylett.9b02660
4	Qiao Y. ; Li Q. ; Cheng X. B. ; Liu F. X. ; Yang Y. ; Lu Z. S. ; Zhao J. ; Wu J. W. ; Liu H. ; Yang S. T. ; et al ACS Appl. Mater. Interfaces 2020, 12, 5767. doi: 10.1021/acsami.9b18315
5	Shen Y. ; Zhang Y. ; Han S. ; Wang J. ; Peng Z. ; Chen L. Joule 2018, 2, 1674. doi: 10.1016/j.joule.2018.06.021
6	Feng Y. Q. ; Zheng Z. J. ; Wang C. Y. ; Yin Y. X. ; Ye H. ; Cao F. F. ; Guo Y. G. Nano Energy 2020, 73, 104731. doi: 10.1016/j.nanoen.2020.104731
7	Wan J. ; Xie J. ; Kong X. ; Liu Z. ; Liu K. ; Shi F. ; Pei A. ; Chen H. ; Chen W. ; Chen J. ; et al Nat. Nanotechnol. 2019, 14, 705. doi: 10.1038/s41565-019-0465-3
8	Ma Y. Y. ; Chen D. ; Yang Q. L. ; Yin Y. X. ; Bai X. P. ; Zhen S. Y. ; Fan C. ; Sun K. N. J. Energy Chem. 2020, 42, 49. doi: 10.1016/j.jechem.2019.06.008
9	Liu Y. ; Zheng L. ; Gu W. ; Shen Y. B. ; Chen L. W. Acta Phys. -Chim. Sin. 2021, 37, 2004058.
	刘亚; 郑磊; 谷巍; 沈炎宾; 陈立桅. 物理化学学报, 2021, 37, 2004058. doi: 10.3866/PKU.WHXB202004058
10	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 InfoMat. 2019, 1, 6. doi: 10.1002/inf2.12000
11	Kong L. ; Yan C. ; Huang J. Q. ; Zhao M. Q. ; Titirici M. M. ; Xiang R. ; Zhang Q. Energy Environ. Mater. 2018, 1, 100. doi: 10.1002/eem2.12012
12	Yan C. ; Cheng X. B. ; Tian Y. ; Chen X. ; Zhang X. Q. ; Li W. J. ; Huang J. Q. ; Zhang Q. Adv. Mater. 2018, 30, 1707629. doi: 10.1002/adma.201707629
13	Shi P. ; Li T. ; Zhang R. ; Shen X. ; Cheng X. B. ; Xu R. ; Huang J. Q. ; Chen X. R. ; Liu H. ; Zhang Q. Adv. Mater. 2019, 31, 1807131. doi: 10.1002/adma.201807131
14	Xu R. ; Xiao Y. ; Zhang R. ; Cheng X. B. ; Zhao C. Z. ; Zhang X. Q. ; Yan C. ; Zhang Q. ; Huang J. Q. Adv. Mater. 2019, 31, 1808392. doi: 10.1002/adma.201808392
15	Tong B. ; Chen X. ; Chen L. ; Zhou Z. ; Peng Z. ACS Appl. Energy Mater. 2018, 1, 4426. doi: 10.1021/acsaem.8b00821
16	Ye H. ; Zhang Y. ; Yin Y. X. ; Cao F. F. ; Guo Y. G. ACS Cent. Sci. 2020, 6, 661. doi: 10.1021/acscentsci.0c00351
17	Zhang W. ; Wu Q. ; Huang J. ; Fan L. ; Shen Z. ; He Y. ; Feng Q. ; Zhu G. ; Lu Y. Adv. Mater. 2020, 32, 2001740. doi: 10.1002/adma.202001740
18	Guo F. ; Chen P. ; Kang T. ; Wang Y. L. ; Liu C. H. ; Shen Y. B. ; Lu W. ; Chen L. W. Acta Phys. -Chim. Sin. 2019, 35, 1365.
	郭峰; 陈鹏; 康拓; 王亚龙; 刘承浩; 沈炎宾; 卢威; 陈立桅. 物理化学学报, 2019, 35, 1365. doi: 10.3866/PKU.WHXB201903008
19	Yue X. Y. ; Ma C. ; Bao J. ; Yang S. Y. ; Chen D. ; Wu X. J. ; Zhou Y. N. Acta Phys. -Chim. Sin. 2021, 37, 2005012.
	岳昕阳; 马萃; 包戬; 杨思宇; 陈东; 吴晓京; 周永宁. 物理化学学报, 2021, 37, 2005012. doi: 10.3866/PKU.WHXB202005012
20	Wang G. ; Xiong X. ; Xie D. ; Fu X. ; Ma X. ; Li Y. ; Liu Y. ; Lin Z. ; Yang C. ; Liu M. Energy Storage Mater. 2019, 23, 701. doi: 10.1016/j.ensm.2019.02.026
21	Zhang R. ; Shen X. ; Cheng X. B. ; Zhang Q. Energy Storage Mater. 2019, 23, 556. doi: 10.1016/j.ensm.2019.03.029
22	Shi P. ; Cheng X. B. ; Li T. ; Zhang R. ; Liu H. ; Yan C. ; Zhang X. Q. ; Huang J. Q. ; Zhang Q. Adv. Mater. 2019, 31, 1902785. doi: 10.1002/adma.201902785
23	Niu C. ; Lee H. ; Chen S. ; Li Q. ; Du J. ; Xu W. ; Zhang J. G. ; Whittingham M. S. ; Xiao J. ; Liu J. Nat. Energy 2019, 4, 551. doi: 10.1038/s41560-019-0390-6
24	Hobold G. M. ; Khurram A. ; Gallant B. M. Chem. Mater. 2020, 32, 2341. doi: 10.1021/acs.chemmater.9b04550
25	Chen Y. ; Luo Y. ; Zhang H. ; Qu C. ; Zhang H. ; Li X. Small Methods 2019, 3, 1800551. doi: 10.1002/smtd.201800551
26	Yao Y. X. ; Zhang X. Q. ; Li B. Q. ; Yan C. ; Chen P. Y. ; Huang J. Q. ; Zhang Q. InfoMat 2020, 2, 379. doi: 10.1002/inf2.12046
27	Fan H. ; Gao C. ; Jiang H. ; Dong Q. ; Hong B. ; Lai Y. J. Energy Chem. 2020, 49, 59. doi: 10.1016/j.jechem.2020.01.013
28	Liu H. ; Cheng X. B. ; Huang J. Q. ; Kaskel S. ; Chou S. ; Park H. S. ; Zhang Q. ACS Mater. Lett. 2019, 1, 217. doi: 10.1021/acsmaterialslett.9b00118
29	Zhang X. Q. ; Cheng X. B. ; Chen X. ; Yan C. ; Zhang Q. Adv. Funct. Mater. 2017, 27, 1605989. doi: 10.1002/adfm.201605989
30	Chen W. J. ; Zhao C. X. ; Li B. Q. ; Jin Q. ; Zhang X. Q. ; Yuan T. Q. ; Zhang X. ; Jin Z. ; Kaskel S. ; Zhang Q. Energy Environ. Mater. 2020, 3, 160. doi: 10.1002/eem2.12073
31	He Y. ; Zhang Y. ; Yu P. ; Ding F. ; Li X. ; Wang Z. ; Lv Z. ; Wang X. ; Liu Z. ; Huang X. J. Energy Chem. 2020, 45, 1. doi: 10.1016/j.jechem.2019.09.033
32	Chen J. X. ; Zhang X. Q. ; Li B. Q. ; Wang X. M. ; Shi P. ; Zhu W. C. ; Chen A. B. ; Jin Z. H. ; Xiang R. ; Huang J. Q. ; Zhang Q. J. Energy Chem. 2020, 47, 128. doi: 10.1016/j.jechem.2019.11.024
33	Yang Q. L. ; Li W. L. ; Dong C. ; Ma Y. Y. ; Yin Y. X. ; Wu Q. B. ; Xu Z. T. ; Ma W. ; Fan C. ; Sun K. N. J. Energy Chem. 2020, 42, 83. doi: 10.1016/j.jechem.2019.06.012
34	Li C. ; Liu S. ; Shi C. ; Liang G. ; Lu Z. ; Fu R. ; Wu D. Nat. Commun. 2019, 10, 1363. doi: 10.1038/s41467-019-09211-z
35	Wei Z. ; Ren Y. ; Sokolowski J. ; Zhu X. ; Wu G. InfoMat 2020, 2, 483. doi: 10.1002/inf2.12097
36	Liu H. ; Chen X. ; Cheng X. B. ; Li B. Q. ; Zhang R. ; Wang B. ; Chen X. ; Zhang Q. Small Methods 2019, 3, 1800354. doi: 10.1002/smtd.201800354
37	Shen X. ; Cheng X. ; Shi P. ; Huang J. ; Zhang X. ; Yan C. ; Li T. ; Zhang Q. J. Energy Chem. 2019, 37, 29. doi: 10.1016/j.jechem.2018.11.016
38	Shang Y. ; Chu T. ; Shi B. ; Fu K. Energy Environ. Mater. 2020, doi: 10.1002/eem2.12099
39	Lu D. ; Shao Y. ; Lozano T. ; Bennett W. D. ; Graff G. L. ; Polzin B. ; Zhang J. ; Engelhard M. H. ; Saenz N. T. ; Henderson W. A. ; et al Adv. Energy Mater. 2015, 5, 1702322. doi: 10.1002/aenm.201400993
40	Wood K. N. ; Kazyak E. ; Chadwick A. F. ; Chen K. H. ; Zhang J. G. ; Thornton K. ; Dasgupta N. P. ACS Cent. Sci. 2016, 2, 790. doi: 10.1021/acscentsci.6b00260
41	Yin X. ; Tang W. ; Jung I. D. ; Phua K. C. ; Adams S. ; Lee S. W. ; Zheng G. W. Nano Energy 2018, 50, 659. doi: 10.1016/j.nanoen.2018.06.003
42	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
43	Rodriguez R. ; Loeffler K. E. ; Edison R. A. ; Stephens R. M. ; Dolocan A. ; Heller A. ; Mullins C. B. ACS Appl. Energy Mater. 2018, 1, 5830. doi: 10.1021/acsaem.8b01194
44	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
45	Zhang X. Q. ; Chen X. ; Xu R. ; Cheng X. B. ; Peng H. J. ; Zhang R. ; Huang J. Q. ; Zhang Q. Angew. Chem. Int. Ed. 2017, 56, 14207. doi: 10.1002/anie.201707093
46	Qian J. ; Xu W. ; Bhattacharya P. ; Engelhard M. ; Henderson W. A. ; Zhang Y. ; Zhang J. G. Nano Energy 2015, 15, 135. doi: 10.1016/j.nanoen.2015.04.009
47	Cheng X. B. ; Zhao M. Q. ; Chen C. ; Pentecost A. ; Maleski K. ; Mathis T. ; Zhang X. Q. ; Zhang Q. ; Jiang J. ; Gogotsi Y. Nat. Commun. 2017, 8, 336. doi: 10.1038/s41467-017-00519-2
48	Michan A. L. ; Parimalam B. S. ; Leskes M. ; Kerber R. N. ; Yoon T. ; Grey C. P. ; Lucht B. L. Chem. Mater. 2016, 28, 8149. doi: 10.1021/acs.chemmater.6b02282
49	Nie M. ; Demeaux J. ; Young B. T. ; Heskett D. R. ; Chen Y. ; Bose A. ; Woicik J. C. ; Lucht B. L. J. Electrochem. Soc. 2015, 162, A7008. doi: 10.1149/2.0021513jes
50	Heine J. ; Hilbig P. ; Qi X. ; Niehoff P. ; Winter M. ; Bieker P. J. Electrochem. Soc. 2015, 162, A1094. doi: 10.1149/2.0011507jes
51	Jurng S. ; Brown Z. L. ; Kim J. ; Lucht B. L. Energy Environ. Sci. 2018, 11, 2600. doi: 10.1039/c8ee00364e
52	Ko J. ; Yoon Y. S. Ceram. Int. 2019, 45, 30. doi: 10.1016/j.ceramint.2018.09.287
53	Lang J. ; Long Y. ; Qu J. ; Luo X. ; Wei H. ; Huang K. ; Zhang H. ; Qi L. ; Zhang Q. ; Li Z. ; Wu H. Energy Storage Mater. 2019, 16, 85. doi: 10.1016/j.ensm.2018.04.024
54	Shin H. ; Park J. ; Han S. ; Sastry A. M. ; Lu W. J. Power Sources 2015, 277, 169. doi: 10.1016/j.jpowsour.2014.11.120
55	Jones J. ; Anouti M. ; Caillon-Caravanier M. ; Willmann P. ; Lemordant D. Fluid Phase Equilib. 2009, 285, 62. doi: 10.1016/j.fluid.2009.07.020
56	He M. ; Guo R. ; Hobold G. M. ; Gao H. ; Gallant B. M. Proc. Natl. Acad. Sci. U.S.A. 2020, 117, 73. doi: 10.1073/pnas.1911017116
57	Yang G. ; Li Y. ; Liu S. ; Zhang S. ; Wang Z. ; Chen L. Energy Storage Mater. 2019, 23, 350. doi: 10.1016/j.ensm.2019.04.041
58	Lee Y. ; Lee T. K. ; Kim S. ; Lee J. ; Ahn Y. ; Kim K. ; Ma H. ; Park G. ; Lee S. M. ; Kwak S. K. ; Choi N. S. Nano Energy 2020, 67, 104309. doi: 10.1016/j.nanoen.2019.104309

Reagent	Parameters	Company
Li mental	Thickness: 50, 600 μm	China Energy Lithium Co., Ltd. Aladdin
Cu	Thickness: 9 μm	China Energy Lithium Co., Ltd. Aladdin
CH₃CH₂OH	99.8%	Beijing Chemical Plant Co. LTD
CH₃COCH₃	99.8%	Beijing Chemical Plant Co. LTD
1 mol∙L⁻¹ LiPF₆-ethylene carbonate : diethyl carbonate (1 : 1 by volume)	99.8%	DoDoChem
Fluoroethylene carbonate	99.8%	DoDoChem
KAPTON tape	–	E. I. Du Pont Company
HCl	36.5%	Beijing Chemical Plant Co. LTD

Electrolyte	Diameter distribution/μm	Length distribution/μm	L/D ratio ^a
No FEC	0.3–0.6	4.5–5.5	12.5
5% FEC	0.7–1.3	4.9–5.9	5.6

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Columnar Lithium Metal Deposits: the Role of Non-Aqueous Electrolyte Additive

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