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The large volume change during lithiation/delithiation leads the silicon electrodes in lithium-ion batteries to severely degrade the mechanical performance and the silicon electrodes in lithium-ion batteries to further deteriorate electrochemical properties, which limits the commercial applications of silicon electrodes. After several year’s studies, the whole process of fracture for crystalline silicon anodes has been almost understood. However, the relationship between fracture behaviors and the lithiation depth has not been sufficiently studied. In this work, the in-situ observations of morphological changes (e.g., volume expansion, crack initiation, propagation, and debonding of lithiated silicon) during lithiation at the different current densities are reported for silicon micropillars fabricated by standard photolithography and a deep reactive ion etching process. Also, this work focuses on the relative depth of lithiation of silicon electrodes at the moment of crack initiation, which is one of the crucial parameters representing the utilization of active materials with no crack. The results show that the silicon micropillars are broken faster (i.e., crack initiation and pulverization in a shorter lithiation time) and more seriously at a large current density, exhibiting more prominent symmetry of morphology. However, the relative depths of lithiation at the different current densities have just a slight difference (i.e., 18%–22%), when cracks are initiated. Here in this work, a silicon micropillar fracture is confirmed by the optical observation, while the relative depth of lithiation is calculated according to the capacity data recorded by the charge/discharge battery test system. The small fluctuation of the relative depth of lithiation with the large wave of current density can be ascribed to the dominant role of local stress concentration caused by anisotropic volume change in fracture behavior, which is validated by the results obtained by the finite element model (i.e., the depth of lithiation predicted by numerical simulations is ～ 22.6%). Therefore, the relationship between fracture behavior and the lithiation kinetics is established, providing an effective strategy for estimating the utilization of active materials under crack-free operation. With the help of the theoretical mechanics model considering both volume change and concurrent movement of reaction front, the stress state in the lithiated silicon at the moment of crack initiation is given, showing the tensile hoop stress near the reaction front. Consequently, these results suggest that the fracture behaviors depend on the current density, but the position of crack initiation (i.e., the depth of lithiation with no crack) is unrelated to current density (at least in a relatively broad range) for large micron-sized crystalline silicon electrodes, thereby shedding light on the fracture mechanisms and the design of alloy anodes (e.g., size and structure) in lithium-ion batteries.
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Keywords:
- lithium-ion battery /
- silicon electrode /
- fracture behavior /
- current density
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图 1 在锂化过程中(111)单晶硅电极的衰减机制
Figure 1. Degradation mechanism of (111) single-crystalline silicon electrodes during lithiation.
图 2 (a) 自制电池装置示意图; (b) 光学观测平台
Figure 2. (a) Schematic diagram of a home-made battery cell; (b) experimental platform for the optical observation.
图 3 硅柱典型形貌FE-SEM图, 标尺为10 μm
Figure 3. Typical FE-SEM images of a micron-sized silicon pillar. Here, the scale bars are 10 μm.
图 5 不同电流密度下硅电极裂纹形成时对应的锂化时间和电压, 标尺为5 μm
Figure 5. Profile of voltage and lithiation time for crack initiation of silicon electrodes at different current density. Here, the scale bars are 5 μm.
图 6 (a) 不同电流密度下硅电极起裂时相对嵌锂深度; (b) 有限元模拟所得的应力云图; (c) 不同相边界移动速度下不同r/R (红色箭头标示)处径向应力分布
Figure 6. (a) Relative lithiation depth for crack initiation of silicon electrodes at different current density; (b) hoop stress contour of Si micropillars obtained by finite element method; (c) hoop stress along the radial direction at different moving velocity of phase interfaces.
图 7 硅基底锂化后形貌, 标尺为500 nm
Figure 7. Morphology of the silicon substrate after lithiation. Here, the scale bar is 500 nm.
图 8 (a) 锂化前硅柱圆截面示意图; (b) 锂化过程中硅柱圆界面示意图
Figure 8. Cross-section of a silicon micropillar: (a) Before lithiation; (b) during lithiation.
图 9 裂纹形成时硅电极在全锂化区域的受力示意图
Figure 9. Schematic diagram of stress state at the moment of crack initiation.
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[1] Kim U H, Ryu H H, Kim J H, Mücke R, Kaghazchi P, Yoon C S, Sun Y K 2019 Adv. Energy Mater. 9 1803902
Google Scholar
[2] Uxa D, Jerliu B, Hüger E, Dörrer L, Horisberger M, Stahn J, Schmidt H 2019 J. Phys. Chem. C 123 22027
Google Scholar
[3] Ryu J, Bok T, Kim S, Park S 2018 ChemNanoMat 4 319
Google Scholar
[4] Mukanova A, Jetybayeva A, Myung S, Kim S, Bakenov Z 2018 Mater. Today Energy 9 49
Google Scholar
[5] Li P, Zhao G, Zheng X, Xu X, Yao C, Sun W, Dou S X 2018 Energy Storage Mater. 15 422
Google Scholar
[6] Franco Gonzalez A, Yang N, Liu R 2017 J. Phys. Chem. C 121 27775
Google Scholar
[7] Zhang S 2017 npj Comput. Mater. 3 7
Google Scholar
[8] Jin Y, Zhu B, Lu Z, Liu N, Zhu J 2017 Adv. Energy Mater. 7 1700715
Google Scholar
[9] He Y, Yu X, Li G, Wang R, Li H, Wang Y, Gao H, Huang X 2012 J. Power Sources 216 131
Google Scholar
[10] Zhang X, Song W, Liu Z, Chen H, Li T, Wei Y, Fang D 2017 J. Mater. Chem. A 5 12793
Google Scholar
[11] Shi F, Song Z, Ross P N, Somorjai G A, Ritchie R O, Komvopoulos K 2016 Nat. Commun. 7 11886
Google Scholar
[12] Lee S W, Lee H, Ryu I, Nix W D, Gao H, Cui Y 2015 Nat. Commun. 6 7533
Google Scholar
[13] Lee S W, McDowell M T, Berla L A, Nix W D, Cui Y 2012 Proc. Natl. Acad. Sci. U.S.A. 109 4080
Google Scholar
[14] Pharr M, Zhao K, Wang X, Suo Z, Vlassak J J 2012 Nano Lett. 12 5039
Google Scholar
[15] McDowell M T, Ryu I, Lee S W, Wang C, Nix W D, Cui Y 2012 Adv. Mater. 24 6034
Google Scholar
[16] Ryu I, Choi J W, Cui Y, Nix W D 2011 J. Mech. Phys. Solids 59 1717
Google Scholar
[17] Lee S W, McDowell M T, Choi J W, Cui Y 2011 Nano Lett. 11 3034
Google Scholar
[18] Goldman J L, Long B R, Gewirth A A, Nuzzo R G 2011 Adv. Funct. Mater. 21 2412
Google Scholar
[19] Jia Z, Li T 2015 J. Power Sources 275 866
Google Scholar
[20] Zhao K, Pharr M, Wan Q, Wang W L, Kaxiras E, Vlassak J J, Suo Z 2012 J. Electrochem. Soc. 159 A238
Google Scholar
[21] Cui Z, Gao F, Qu J 2012 J. Mech. Phys. Solids 60 1280
Google Scholar
[22] Di Leo C V, Rejovitzky E, Anand L 2015 Int. J. Solids Struct. 67-68 283
Google Scholar
[23] 孙凤楠, 冯露, 卜家贺, 张静, 李林安, 王世斌 2019 68 120201
Google Scholar
Sun F N, Feng L, Bu J H, Zhang J, Li L A, Wang S B 2019 Acta Phys. Sin. 68 120201
Google Scholar
[24] 彭劼扬, 王家海, 沈斌, 张静, 李浩亮, 孙昊明 2019 68 090202
Google Scholar
Peng J Y, Wang J H, Shen B, Zhang J, Li H L, Sun H M 2019 Acta Phys. Sin. 68 090202
Google Scholar
[25] An Y, Wood B C, Ye J, Chiang Y, Wang Y M, Tang M, Jiang H 2015 Phys. Chem. Chem. Phys. 17 17718
Google Scholar
[26] Ryu I, Lee S W, Gao H, Cui Y, Nix W D 2014 J. Power Sources 255 274
Google Scholar
[27] Ye J C, An Y H, Heo T W, Biener M M, Nikolic R J, Tang M, Jiang H, Wang Y M 2014 J. Power Sources 248 447
Google Scholar
[28] Yang H, Fan F, Liang W, Guo X, Zhu T, Zhang S 2014 J. Mech. Phys. Solids 70 349
Google Scholar
[29] Tian R, Park S, King P J, Cunningham G, Coelho J, Nicolosi V, Coleman J N 2019 Nat. Commun. 10 1933
Google Scholar
[30] Pharr M, Suo Z, Vlassak J J 2014 J. Power Sources 270 569
Google Scholar
[31] Soni S K, Sheldon B W, Xiao X, Bower A F, Verbrugge M W 2012 J. Electrochem. Soc. 159 A1520
Google Scholar
[32] Boles S T, Thompson C V, Kraft O, Mönig R 2013 Appl. Phys. Lett. 103 263906
Google Scholar
[33] Berla L A, Lee S W, Cui Y, Nix W D 2015 J. Power Sources 273 41
Google Scholar
[34] Jia Z, Liu W K 2016 Appl. Phys. Lett. 109 163903
Google Scholar
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