Operando Nanomechanical Mapping of Silicon Thin Film Electrode during the First Lithiation and Delithiation Investigated By Bimodal Atomic Force Microscopy
Authors: Putra Ridwan Pratama , Matsushita Kyosuke , Ohnishi Tsuyoshi , Masuda Takuya 
Published: September 2023

Si is emerging as one of the most prospective anode materials for all-solid-state Li-ion batteries due to its extremely high theoretical capacity density of 4200 mAh g-1 and relatively negative potential for lithiation/delithiation. Towards its widespread use, controlling severe volume expansion/contraction during lithiation/delithiation is a challenge because it may cause cracking, fracture, and pulverization that negatively influence the cycle performance and rate capability of the cells [1]. Such mechanical event is induced by the change in the lattice structure due to the formation of LixSi and successive increasing/decreasing of Li content x in LixSi [2].
Bimodal atomic force microscopy (AFM) offers quantitative mapping of nanoscale mechanical property, simultaneously with surface topography imaging [3]. Our group previously applied this technique to the cross-section of a composite electrode consist of active materials, binders, conductive additives, and deposited electrolyte solution and successfully demonstrated nanomechanical mapping [4]. Here, we develop an operando bimodal AFM system to track Young’s modulus changes of electrode materials in an all-solid-state battery configuration during the lithiation and delithiation reactions in real-time.
A cell in a Cu/Si/LLZT/In/Li configuration was fabricated as follows; a 3 µm-thick Si thin-film and a 100 nm-thick Cu layer were sputter-deposited on one side of Li6.6La3Zr1.6Ta0.4O12 (LLZT) solid electrolyte, an In layer was sputter-deposited on the other side of LLZT, the Cu/Si/LLZT/In sample was milled with an Ar-ion beam to yield a flat and smooth cross-section suitable for AFM analysis, and then a 50 µm-thick Li metal foil was combined with the pre-coated In thin layer. Operando nanomechanical mapping was performed by mounting the cross-section-exposed cell in the custom-made sample holder coupled with a potentiostat for bias applications, in an Ar-filled glove box to prevent any atmospheric influences.
Electrochemical lithiation and delithiation were carried out within a potential window of 0.01-1.20 V vs. Li/Li+. Electrochemical characterization indicated that the capacities of the Si electrode for the first lithiation and delithiation are 3300 and 1833 mAh g-1, respectively. These capacities are equal to the formation of Li3.46Si after the first lithiation of the pristine Si and Li1.54Si after the successive delithiation from Li3.46Si. Throughout the lithiation, the averaged Young’s modulus of Si electrode decreased due to the formation of LixSi and increase in the Li content x in LixSi. In the initial stage of lithiation, it drastically decreased because LixSi was formed by the lithiation of pristine Si. Then, it moderately decreased with increasing Li content x in LixSi. Unfortunately, the Young’s modulus maps were only recorded until the formation of Li1.54Si because the successive delithiation was not completed possibly due to the phase transformation of crystalline LixSi to amorphous LixSi [5], which may cause a significant mechanical strain inside the thin film. The measured Young’s modulus values were consistent with those obtained by first principle calculation [6]. Further details are given at the presentation.

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