Abstract
Lithium metal is considered the ultimate anode material for future rechargeable batteries1,2, but the development of Li metal-based rechargeable batteries has achieved only limited success due to uncontrollable Li dendrite growth3,4,5,6,7. In a broad class of all-solid-state Li batteries, one approach to suppress Li dendrite growth has been the use of mechanically stiff solid electrolytes8,9. However, Li dendrites still grow through them10,11. Resolving this issue requires a fundamental understanding of the growth and associated electro-chemo-mechanical behaviour of Li dendrites. Here, we report in situ growth observation and stress measurement of individual Li whiskers, the primary Li dendrite morphologies12. We combine an atomic force microscope with an environmental transmission electron microscope in a novel experimental set-up. At room temperature, a submicrometre whisker grows under an applied voltage (overpotential) against the atomic force microscope tip, generating a growth stress up to 130 MPa; this value is substantially higher than the stresses previously reported for bulk13 and micrometre-sized Li14. The measured yield strength of Li whiskers under pure mechanical loading reaches as high as 244 MPa. Our results provide quantitative benchmarks for the design of Li dendrite growth suppression strategies in all-solid-state batteries.
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Acknowledgements
This work was financially supported by the National Key Research and Development Programme of China (nos. 2018YFB0104300, 2017YFB0702001), Beijing Natural Science Foundation of China-Haidian Special Project (L182065), the National Natural Science Foundation of China (nos. 51971245, 51772262, 21406191, 21935009, 11575154, 21777177, 51971194), Natural Science Foundation of Hebei Province (no. B2018203297), Hebei One Hundred Talent Programme (grant no. 4570028), Youth Top-notch Talent Support Programme of Higher Education in Hebei Province (no. BJ2016053) and High-Level Talents Research Programme of the Yanshan University (nos. 00500021502, 005000201). We thank Z. Shan, Y. Wang, P. Li, H. Yang and C. Li for their support with the compression experiments.
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L.Z., T.Y. and C.D. conceived the experiment. Q.L., Yushu Tang and J.Z. performed ETEM measurements. Y.S., P.J. and H.L. fabricated the AFM device. L.G., J.C. and H.Y. fabricated the carbon nanotube. Z.W., Y.L., H.S., X.L. and Q.D. conducted mechanical measurements. B.W. and T.C. performed computational modelling. Q.P., T.S., Yo Tang, S.Z., T.Z. and J.H. supervised the project. L.Z., T.Z. and J.H. wrote the paper. All authors discussed the results and commented on the manuscript.
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Supplementary information
Supplementary Information
Supplementary methods and discussion, Videos 1–19 and Figs. 1–34.
Supplementary Video 1
An in situ TEM movie showing the growth of a Li whisker (corresponding to Fig. 1d). As a negative potential was applied to the CNT against Li, a single Li spheroid started to nucleate at the contact point between the CNT and the Li2CO3 on the surface of the Li metal and then grew along the CNT, pushing the AFM cantilever upward. As the Li ball grew to about 1.26 μm in size, a whisker emerged underneath the ball which pushed the AFM cantilever up, thus generating the axially compressive stress in the whisker. When the whisker reached 4.08 μm in length, it collapsed due to the compression by the AFM tip. The attachment of a CNT to the AFM tip rendered controllable whisker nucleation. The movie was recorded at 5 frames per second in the bright field (BF) mode, and played at 97× speed (during ball generation) and 49× speed (during Li whisker generation).
Supplementary Video 2
An in situ TEM movie showing the growth of a Li whisker (corresponding to Supplementary Fig. 3). The Li whisker grows directly underneath the AFM cantilever without the prior formation of Li balls. The movie was recorded at 5 frames per second in BF mode, and played at 5× speed.
Supplementary Video 3
A Li whisker grows directly underneath the AFM cantilever (corresponding to Supplementary Fig. 4). A Li ball grows before the growth of a whisker. The movie was recorded at 5 frames per second in BF mode, and played at 212× speed (during ball generation) and 157× speed (during Li whisker generation).
Supplementary Video 4
A Li whisker grows directly underneath the AFM cantilever (corresponding to Supplementary Fig. 5). The movie was recorded at 5 frames per second in the BF mode, and played at 61× speed (during ball generation) and 44× speed (during Li whisker generation).
Supplementary Video 5
An in situ TEM movie showing the growth of a Li whisker underneath the AFM cantilever (corresponding to Supplementary Fig. 6). The whisker buckles after reaching a length of 1.90 μm. The movie was recorded at 5 frames per second in BF mode, and played at 13× speed (during ball generation) and 10× speed (during Li whisker generation).
Supplementary Video 6
An in situ TEM movie showing the growth of a Li whisker underneath the AFM cantilever (corresponding to Supplementary Fig. 7). The movie was recorded at 5 frames per second in BF mode, and played at 8× speed.
Supplementary Video 7
An in situ TEM movie showing the growth of a Li whisker underneath the AFM cantilever (corresponding to Supplementary Fig. 8). The movie was recorded at 5 frames per second in BF mode, and played at 184× speed.
Supplementary Video 8
An in situ TEM movie showing the growth of a Li whisker with <001> orientation (corresponding to Supplementary Fig. 12). A Li ball forms before the whisker growth. The movie was recorded at 5 frames per second in BF mode, and played at 188×speed (during ball generation) and 156× speed (during Li whisker generation).
Supplementary Video 9
An in situ TEM movie showing the growth of a Li whisker with <112> orientation (corresponding to Supplementary Fig. 13). The movie was recorded at 5 frames per second in BF mode, and played at 15× speed.
Supplementary Video 10
An in situ TEM movie showing the growth of a Li whisker with <110> orientation (corresponding to Supplementary Fig. 14). The movie was recorded at 5 frames per second in BF mode, and played at 31× speed (during ball generation) and 22× speed (during Li whisker generation).
Supplementary Video 11
An in situ TEM movie showing the growth of a Li whisker with <111> orientation (corresponding to Supplementary Fig. 15). The movie was recorded at 5 frames per second in BF mode, and played at 51× speed.
Supplementary Video 12
An in situ TEM movie showing the growth of a Li ball at the CNT and Li2CO3 contact point (corresponding to Supplementary Fig. 16). The movie was recorded at 5 frames per second in BF mode, and played at 201× speed.
Supplementary Video 13
An in situ TEM movie showing the generation of a Li whisker (corresponding to Fig. 2a). A faceted Li nanocrystal formed before the formation of a Li whisker. The movie was recorded at 5 frames per second in BF mode, and played at 46× speed (during ball generation) and 25× speed (during Li whisker generation).
Supplementary Video 14
An in situ TEM movie showing the growth of a Li whisker. To explore the relationship between the applied voltage and the growth stress, the potential was ramped up after the Li whisker ceased its growth (corresponding to Supplementary Fig. 18), which stimulated further whisker growth. The movie was recorded at 5 frames per second in BF mode, and played at 24× speed.
Supplementary Video 15
An in situ TEM movie showing the growth of a Li whisker. To explore the relationship between the applied voltage and the growth stress, the potential was ramped up after the Li whisker ceased its growth, which stimulated further whisker growth (corresponding to Supplementary Fig. 19). The movie was recorded at 5 frames per second in BF mode, and played at 18× speed.
Supplementary Video 16
An in situ TEM movie showing the growth of a Li whisker. To explore the relationship between the applied voltage and the growth stress, the potential was ramped up after the Li whisker ceased its growth (corresponding to Supplementary Fig. 2c). The movie was recorded at 5 frames per second in BF mode, and played at 25× speed.
Supplementary Video 17
Assessing the mechanical properties of a Li whisker by in situ compression (corresponding to Supplementary Fig. 22). After its growth, the whisker was pushed up against the AFM cantilever, causing the whisker to deform. The movie was recorded at 5 frames per second in BF mode, and played at 14× speed.
Supplementary Video 18
In situ growth followed by in situ compression of a Li whisker. (corresponding to Supplementary Fig. 23). The whisker was manipulated to contact the AFM tip, causing growth of a secondary whisker over the old one at the bottom, pushing up against the AFM tip under bias. The movie was recorded at 5 frames per second in BF mode, and played at 48× speed.
Supplementary Video 19
Assessing the mechanical properties of a Li whisker by in situ compression (corresponding to Supplementary Fig. 26). After its growth, the whisker was pushed up against the AFM cantilever, causing the whisker to deform. The movie was recorded at 5 frames per second in BF mode, and played at 18× speed.
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Zhang, L., Yang, T., Du, C. et al. Lithium whisker growth and stress generation in an in situ atomic force microscope–environmental transmission electron microscope set-up. Nat. Nanotechnol. 15, 94–98 (2020). https://doi.org/10.1038/s41565-019-0604-x
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DOI: https://doi.org/10.1038/s41565-019-0604-x
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