锂金属负极的可逆性与沉积形貌的关联

doi:10.3866/PKU.WHXB202008081

物理化学学报 >> 2021, Vol. 37 >> Issue (1): 2008081.doi: 10.3866/PKU.WHXB202008081

所属专题：金属锂负极

锂金属负极的可逆性与沉积形貌的关联

黄凡洋, 揭育林, 李新鹏, 陈亚威, 曹瑞国, 章根强, 焦淑红()

中国科学技术大学，中国科学院能量转换材料重点实验室，材料科学与工程系，合肥微尺度物质科学国家研究中心，合肥 230026

收稿日期:2020-08-27 录用日期:2020-09-28 发布日期:2020-10-19
通讯作者: 焦淑红 E-mail:jiaosh@ustc.edu.cn
作者简介:第一联系人：
^†These authors contribute equally to this work.
基金资助:
国家重点研发计划(2017YFA0402802);国家重点研发计划(2017YFA0206700);国家自然科学基金(51902304);国家自然科学基金(21776265);安徽省自然科学基金(1908085ME122);中央高校基本科研基金(Wk2060140026)

Correlation between Li Plating Morphology and Reversibility of Li Metal Anode

Fanyang Huang, Yulin Jie, Xinpeng Li, Yawei Chen, Ruiguo Cao, Genqiang Zhang, Shuhong Jiao()

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

Received:2020-08-27 Accepted:2020-09-28 Published:2020-10-19
Contact: Shuhong Jiao E-mail:jiaosh@ustc.edu.cn
About author:Jiao Shuhong. E-mail:jiaosh@ustc.edu.cn; Tel.: +86-551-63601807
Supported by:
the National Key Research and Development Program of China(2017YFA0402802);the National Key Research and Development Program of China(2017YFA0206700);the National Natural Science Foundation of China(51902304);the National Natural Science Foundation of China(21776265);the Anhui Provincial Natural Science Foundation(1908085ME122);the Fundamental Research Funds for the Central Universities, China(Wk2060140026)

摘要/Abstract

摘要：

高能量密度二次电池的商业化将会推动便携式电子设备和电动车的飞速发展。锂金属电池因具有较高的理论能量密度而受到研究者的广泛关注。然而，锂金属负极较低的库仑效率(CE)和枝晶生长等问题，严重制约了锂金属电池的发展。库仑效率是衡量电池体系可逆性的关键参数之一，锂金属负极的库仑效率在不同电解液中存在较大的差异，本文以四种常见的电解液为例，包括1 mol·L^-1六氟磷酸锂-碳酸乙烯酯/碳酸二甲酯电解液，1 mol·L^-1六氟磷酸锂-碳酸乙烯酯/碳酸二甲酯+ 5% (w)氟代碳酸乙烯酯电解液，1 mol·L^-1双(三氟甲烷磺酰)亚胺锂-乙二醇二甲醚/1, 3二氧戊环+ 2% (w)硝酸锂电解液，以及4 mol·L^-1双氟磺酰亚胺锂-乙二醇二甲醚电解液，利用原子力显微镜研究了不同电解液体系中锂金属的生长行为，探讨了锂金属沉积形貌与其库仑效率之间的联系，为发展高效的锂金属负极提供了参考依据。

关键词: 锂金属负极, 库仑效率, 沉积形貌, 电解液, 原子力显微镜

Abstract:

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.

Key words: Li metal anode, Coulombic efficiency, Plating morphology, Electrolyte, Atomic force microscopy

MSC2000:

O646

黄凡洋, 揭育林, 李新鹏, 陈亚威, 曹瑞国, 章根强, 焦淑红. 锂金属负极的可逆性与沉积形貌的关联[J]. 物理化学学报, 2021, 37(1): 2008081.

Fanyang Huang, Yulin Jie, Xinpeng Li, Yawei Chen, Ruiguo Cao, Genqiang Zhang, Shuhong Jiao. Correlation between Li Plating Morphology and Reversibility of Li Metal Anode[J]. Acta Phys. -Chim. Sin., 2021, 37(1): 2008081.

图/表 6

表1

图1

图2

图3

图4

图5

参考文献 46

1	Armand M. ; Tarascon J. M. Nature 2008, 451, 652. doi: 10.1038/451652a
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
3	Choi J. W. ; Aurbach D. Nat. Rev. Mater. 2016, 1, 16013. doi: 10.1038/natrevmats.2016.13
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
5	Yu X. ; Wang L. ; Ma J. ; Sun X. ; Zhou X. ; Cui G. Adv. Energy Mater. 2020, 10, 1903939. doi: 10.1002/aenm.201903939
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
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
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
9	Yin Y. X. ; Xin S. ; Guo Y. G. ; Wan L. J. Angew. Chem. Int. Ed. 2013, 52, 13186. doi: 10.1002/anie.201304762
10	Manthiram A. ; Fu Y. ; Chung S. H. ; Zu C. ; Su Y. S. Chem. Rev. 2014, 114, 11751. doi: 10.1021/cr500062v
11	Seh Z. W. ; Sun Y. ; Zhang Q. ; Cui Y. Chem. Soc. Rev. 2016, 45, 5605. doi: 10.1039/c5cs00410a
12	Cheng X. B. ; Zhang R. ; Zhao C. Z. ; Zhang Q. Chem. Rev. 2017, 117, 10403. doi: 10.1021/acs.chemrev.7b00115
13	Sun Y. ; Liu N. ; Cui Y. Nat. Energy 2016, 1, 16071. doi: 10.1038/nenergy.2016.71
14	Liu F. F. ; Zhang Z. W. ; Ye S. F. ; Yao Y. ; Yu Y. Acta Phys. -Chim. Sin. 2021, 37, 2006021.
	刘凡凡; 张志文; 叶淑芬; 姚雨; 余彦. 物理化学学报, 2021, 37, 2006021. doi: 10.3866/PKU.WHXB202006021
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
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
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
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
19	Wood K. N. ; Noked M. ; Dasgupta N. P. ACS Energy Lett. 2017, 2, 664. doi: 10.1021/acsenergylett.6b00650
20	Pang Q. ; Liang X. ; Shyamsunder A. ; Nazar L. F. Joule 2017, 1, 871. doi: 10.1016/j.joule.2017.11.009
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
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
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
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
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
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
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
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
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
30	Pei A. ; Zheng G. ; Shi F. ; Li Y. ; Cui Y. Nano Lett. 2017, 17, 1132. doi: 10.1021/acs.nanolett.6b04755
31	Chen X. ; Lai J. ; Shen Y. ; Chen Q. ; Chen L. Adv. Mater. 2018, 30, e1802490. doi: 10.1002/adma.201802490
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
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
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
35	Aurbach D. J. Electrochem. Soc. 1997, 144, 3355. doi: 10.1149/1.1838018
36	Aurbach D. ; Cohen Y. J. Electrochem. Soc. 1996, 143, 3525. doi: 10.1149/1.1837248
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
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
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
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
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
42	Adams B. D. ; Zheng J. ; Ren X. ; Xu W. ; Zhang J. G. Adv. Energy Mater. 2018, 8, 1702097. doi: 10.1002/aenm.201702097
43	Jie Y. ; Ren X. ; Cao R. ; Cai W. ; Jiao S. Adv. Funct. Mater. 2020, 30, 1910777. doi: 10.1002/adfm.201910777
44	Xu K. Chem. Rev. 2004, 104, 4303. doi: 10.1021/cr030203g
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
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

Reagent	Parameters	Company
1 mol·L^-1 LiPF₆ in ethylene carbonate/dimethyl carbonate (1 : 1, V/V)	/	DoDoChem
1 mol·L^-1 LiTFSI in 1, 3-dioxolane/dimethoxyethane (1 : 1, V/V) + 2% (w) LiNO₃	/	DoDoChem
Fluoroethylene carbonate	≥ 99.95%	DoDoChem
Dimethoxyethane	≥ 99.95%	DoDoChem
Lithium bis(fluorosulfonyl)imide	≥ 99.8%	DoDoChem
Li foil	Thickness: 450 μm	DoDoChem
CH₃CH₂OH	≥ 99.7%	General-Reagent
CH₃COCH₃	≥ 99.5%	Sinopharm Chemical Reagent

[1]	衡永丽, 谷振一, 郭晋芝, 吴兴隆. 水系锌离子电池用钒基正极材料的研究进展[J]. 物理化学学报, 2021, 37(3): 2005013 -0 .
[2]	吴晨, 周颖, 朱晓龙, 詹忞之, 杨汉西, 钱江锋. 锂金属电池用高浓度电解液体系研究进展[J]. 物理化学学报, 2021, 37(2): 2008044 -0 .
[3]	张云博, 林乔伟, 韩俊伟, 韩志远, 李曈, 康飞宇, 杨全红, 吕伟. 细菌纤维素衍生的三维碳集流体用于无枝晶的锂金属负极[J]. 物理化学学报, 2021, 37(2): 2008088 -0 .
[4]	钱华明, 李喜飞. 功能化固态电解质膜改性锂金属负极的研究进展[J]. 物理化学学报, 2021, 37(2): 2008092 -0 .
[5]	王志达, 冯元宬, 卢松涛, 王锐, 秦伟, 吴晓宏. 利用原位氟化保护层改善三维锡锂合金/碳纸负极贫电解液下性能[J]. 物理化学学报, 2021, 37(2): 2008082 -0 .
[6]	华广斌, 樊晏辰, 张千帆. 计算模拟在锂金属负极研究中的应用[J]. 物理化学学报, 2021, 37(2): 2008089 -0 .
[7]	康丹苗, NoamHart, 肖沐野, JohnP. Lemmon. 锂金属电池研究中对称电池的短路现象[J]. 物理化学学报, 2021, 37(2): 2008013 -0 .
[8]	刘凡凡, 张志文, 叶淑芬, 姚雨, 余彦. 锂金属负极的挑战与改善策略研究进展[J]. 物理化学学报, 2021, 37(1): 2006021 -0 .
[9]	孙宇恒, 高铭达, 李慧, 徐丽, 薛晴, 王欣然, 白莹, 吴川. 金属有机骨架材料在金属锂电池界面的应用[J]. 物理化学学报, 2021, 37(1): 2007048 -0 .
[10]	杨世杰, 徐向群, 程新兵, 王鑫萌, 陈金秀, 肖也, 袁洪, 刘鹤, 陈爱兵, 朱万诚, 黄佳琦, 张强. 柱状金属锂沉积物：电解液添加剂的影响[J]. 物理化学学报, 2021, 37(1): 2007058 -0 .
[11]	郑国瑞, 向宇轩, 杨勇. 中子深度剖析技术研究可充锂金属负极[J]. 物理化学学报, 2021, 37(1): 2008094 -0 .
[12]	秦金利, 任龙涛, 曹欣, 赵亚军, 许海军, 刘文, 孙晓明. 多孔泡沫铜和硫脲协同作用构筑无枝晶锂负极[J]. 物理化学学报, 2021, 37(1): 2009020 -0 .
[13]	王木钦, 彭哲, 林欢, 李振东, 刘健, 任重民, 何海勇, 王德宇. 一种有助于稳定锂金属循环的富氟化位点框架结构[J]. 物理化学学报, 2021, 37(1): 2007016 -0 .
[14]	李慧,刘双宇,袁天赐,王博,盛鹏,徐丽,赵广耀,白会涛,陈新,陈重学,曹余良. Na_0.44MnO₂在碱性溶液中的电化学机制[J]. 物理化学学报, 2020, 36(5): 1905027 -0 .
[15]	曾桂芳,刘以宁,顾春燕,张凯,安永灵,魏传亮,冯金奎,倪江锋. 不可燃氟代碳酸酯基钠离子电池电解液[J]. 物理化学学报, 2020, 36(5): 1905006 -0 .

锂金属负极的可逆性与沉积形貌的关联

Correlation between Li Plating Morphology and Reversibility of Li Metal Anode

RichHTML

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 46

相关文章 15

Metrics

本文评价

推荐阅读 0