In Situ Atomic Force Microscopic Studies of Single Tin Nanoparticle

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In Situ Atomic Force Microscopic Studies of Single Tin Nanoparticle: Sodiation and Desodiation in Liquid Electrolyte Mo Han, Chenbo Zhu, Qing Zhao, Chengcheng Chen, Zhanliang Tao, Wei Xie, Fangyi Cheng,* and Jun Chen Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) and State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China W Web-Enhanced Feature * S Supporting Information *

ABSTRACT: Probing electrodes at a nanometer scale is challenging but desirable to reveal the structural evolution of materials in electrochemical reactions. Herein, we present an atomic force microscopic method for an in situ analysis of a single Sn nanoparticle during sodiation and desodiation, which is conducted in an aprotic liquid electrolyte akin to a real electrochemical environment of the Na-ion cells. The morphological evolution of different-sized single Sn nanoparticle is visualized during the charge/discharge cycles by using a homemade planar electrode. All of the Sn nanoparticles exhibit a dramatic initial volume expansion of about 420% after sodiation to Na15Sn4. Interestingly, we find that the smaller Sn nanoparticles show a lower rate of irreversible volume change and a better shape maintenance than the larger ones after desodiation. This finding suggests the importance of downsizing in improving the mechanical stability and the cycling performance of the Sn-based anodes in sodium-ion batteries. KEYWORDS: atomic force microscopy, tin, single nanoparticle, sodium-ion batteries, irreversible volume change

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INTRODUCTION As one of the most promising anode materials in the sodiumion batteries (SIBs),1−8 Sn is cheap and safe with a high capacity (847 mAh g−1 for Na15Sn4).9−13 However, Sn suffers from a theoretical volume variation of 420% when fully sodiated in the alloying process.14 The large volume expansion causes cracks and pulverization after cycling, resulting in an electrical disconnection between Sn and current collector, which, in turn, leads to a rapid fading of the capacity.15−17 To accommodate the volume expansion and suppress the fracture of Sn anode, extensive researches have been focused on fabricating nanosized Sn-based materials, including Sn-based nanoalloys,18−20 three-dimensional (3D) array of Sn nanorods,21 Sn/C nanocomposites,22,23 and so on. It is therefore of fundamental importance to understand how the particle size influences the cycling performance. An in situ characterization technique is urgently required to investigate the size-dependent morphological evolution of Sn nanoparticles in the charge/ discharge cycles. In the past few years, in situ techniques have brought significant progress in the electrochemical researches.24−32 Huang and co-workers reported the structural changes and the phase transformations of Sn nanoparticles (size between 100 and 300 nm) during fast electrochemical sodiation using in situ transmission electron microscopy (TEM).14 More recently, Lee’s group explored the influence of electrically resistive Zintl ions in Na−Sn batteries using an in situ-focused ion-beam system.33 Previous studies indicate that the sodiation of Sn is © XXXX American Chemical Society

complex, which could be influenced by the particle size, test environment, and even charging rates. The in situ studies mentioned above were performed in all of the solid-state systems. Because sodium-ion batteries usually work in a liquid electrolyte, characterization of the corresponding solid−liquid interface is required to study the morphological evolution and the interfacial properties of Sn sodiation/desodiation under the real working conditions of batteries. Atomic force microscopy (AFM) is a useful analytical technique to adapt liquid testing environment as in real cells. Moreover, AFM is nondestructive and can provide a wide range of spatial resolutions from nanoto micrometer.34−37 When AFM is coupled with a potentiostat or galvanostat, the electrochemical reaction of the electrode materials occurs like in operating cells. Important surface changes of electrode, including morphological evolution,38−40 interfacial mechanisms,41,42 and solid−electrolyte interphase (SEI) formation,43−48 can be visualized during the in situ AFM scan in working conditions. In this article, we report an in situ AFM study of a single Sn nanoparticle sodiation and desodiation in a liquid electrolyte. By combining the voltammetry technique with the in situ AFM system on a rationally designed planar electrode, the volume change of Sn nanoparticles with different sizes is characterized at different potentials during the electrochemical reaction. As Received: June 21, 2017 Accepted: August 3, 2017

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DOI: 10.1021/acsami.7b08870 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces

anodes with low melting point. The whole electrochemical testing system includes a single Sn particle planar electrode, a sodium electrode, and an AFM probe (Figure 1b). Figure S3 shows the photograph of the in situ setup designed for the AFM measurement in liquid environment, where the sodium counter-electrode and the AFM probe are fixed and immersed in the electrolyte, whereas the Sn electrode moves through the transparent holder for data collection. By using an o-ring and two tubes for electrolyte filling, the liquid electrolyte (NaClO4ethylene carbonate/propylene carbonate (EC/PC)) is sealed inside the holder and the in situ cell can keep working for several days. Figure 2a shows the morphological evolution of a single 180 nm Sn nanoparticle (Figure S4) in the first cycle of sodiation and desodiation. To investigate the evolution of Sn nanoparticles at different potentials, linear sweep voltammetry is used in combination with potentiostatic method during the electrochemical testing.40 According to the cyclic voltammograms (CV) curve of the Sn nanoparticles (Figure 2b), potentiostatic holds at 0.50, 0.30, 0.15, and 0.01 V during the sodiation process and 0.24, 0.58, 0.71, 0.83, and 2.00 V during the desodiation process are selected for the measurement (a video of continuous sodiation/desodiation process can be found in Supporting Movie 1). The anode is held for 6 h under each potential to complete the Sn expansion and contraction. Representative electrochemical curves at different potentials from the potentiostatic method are shown in Figure S5. In the sodiation process, swelling of Sn starts below 0.50 V and the maximum is observed between 0.15 and 0.01 V. After full sodiation, the nanoparticle is converted to Na15Sn4 with a (220) interplanar distance of 0.46 nm (Figure S6). Meanwhile, some byproducts show up on the Au film, which can be attributed to the decomposition of the electrolyte.44 During the desodiation process, the particle contracts stably with the increase in potential. The morphology does not change drastically above 0.83 V and the particle cannot return to the original size after full charging. Figure 2c plots the volume change rate versus the applied potential in the first cycle. The volume change is calculated by using the analysis software based on the integral calculation and the details can be found in the Supporting Information. Data of volume change are reported as the average values with error bars displayed in the figures. There is also an unavoidable tipbroadening effect of the AFM imaging,50 which, however, does not influence the calculations of volume change rate, considering the sizes of Sn and the tip radius (Figure S7). At the end of the sodiation process, Sn particle reaches a volume expansion of 427%, which is close to the theoretical volume change (420%) when it is fully sodiated to Na15Sn4. The Sn nanoparticle maintained an irreversible volume expansion of 207% after desodiation. To deduct the contribution of SEI to the volume change, force spectroscopy is applied to provide quantitative measurements on the SEI thickness covered on the nanoparticle. Principles of detecting SEI thickness using force curve method of AFM have been reported in previous researches.38 Representative force−displacement curve (Figure S8a) was taken from the desodiated Sn nanoparticle. The force started to increase when the AFM probe tip contacted with the soft SEI. Upon interacting with the hard Sn particle, the force started to increase linearly. The distance between the fitted hard interaction distance and the surface of SEI was calculated to be the thickness of SEI. The distribution of SEI thickness (Figure S8b) covered on the particle is in a range of 0.5−4.5

expected, all of the Sn nanoparticles (70−330 nm) investigated by the AFM reach a theoretical volume expansion of about 420% after sodiation. Interestingly, we find in the desodiation process that the irreversible volume change of nanoparticles is strongly size dependent, indicating the vital role of size controlling in the design of the Sn-based electrode materials.

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RESULTS AND DISCUSSION Figure 1 shows schematically the preparation of planar anode and in situ AFM setup for a single Sn nanoparticle

Figure 1. (a) Preparation schematics of a single Sn nanoparticle planar anode. (b) Schematic of the planar microscale battery analyzed by AFM in a liquid electrolyte for in situ measurements. (c) The photograph of Sn nanoparticle planar anode. (d) SEM image of single Sn nanoparticle on planar anode.

characterization. In contrast to the complicated electrode fabrication techniques like electron beam lithography in previous studies, we use a simple spray painting method to prepare the planar electrode (Figure 1a). No binder or conductive carbon was used in the electrode. The Au film was first deposited as a current collector on a silica substrate by magnetron sputtering. The as-deposited film was flat, dense, and about 300 nm thick (Figure S1). Then, Sn nanoparticles with a high phase purity and a particle size of 50−400 nm (Figure S2) were firmly supported on the Au film using the spray painting49 method. The particles were ultrasonically dispersed in ethanol, and the suspension of single particle was sprayed homogeneously on the Au film using an air brush. Finally, the planar anode was calcined in Ar to fix the Sn nanoparticles tightly on the current collector. The photograph of Sn electrode (Figure 1c) and the scanning electron microscopy (SEM) images of Sn nanoparticles assembled on the Au film (Figures 1d and S2c) show that different-sized single Sn nanoparticle can be well dispersed and fixed on the planar Au film in a single-layer form. This simple method of fabricating planar electrode realizes the testing of a single particle on the electrode without the binder or carbon, which could also be applied to prepare other metal nanoparticle B


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Figure 2. (a) In situ 3D AFM images of one Sn nanoparticle taken at selected electrochemical potentials during sodiation and desodiation in the first cycle. (b) Representative CV curve of Sn nanoparticles in the first cycle at a sweep rate of 0.1 mV/s. (c) Volume changes of the Sn nanoparticle taken at the selected electrochemical potentials.

nm and the average value is 2.13 nm. Compared with the particle size of Sn (180 nm), the contribution of SEI to the volume expansion is relatively small (∼2.3%) and could be ignored. This phenomenon of irreversible volume change is in agreement with the observation on other alloy-type anodes by using in situ TEM.51−53 It is probably caused by the following reasons: (1) nanoscale pores formed inside the particles during the dealloying process;51,54 and (2) the diffusion-controlled trapping of alkali metal in Sn particles, which causes limited dealloying and thus contributes to partial irreversible volume change.55 The volume change of Sn nanoparticles with various sizes (80, 100, 120, 180, 200, 230, 260, and 330 nm) was characterized after initial sodiation and desodiation. Figure 3 shows the relationship between the volume change and the pristine particle size. The corresponding 3D AFM images and the cross-section analysis of particles are displayed in Figures S9 and S10, respectively. Regardless of the particle size, all of the Sn nanoparticles swell dramatically after being fully sodiated, with similar expansion ratios close to the theoretical value (420%). However, after desodiation, the irreversible volume change exhibits a continuously ascending tendency with an increase in the particle size. The 80 nm Sn shows the lowest irreversible change rate of 190%. For the particles with sizes 100, 120, and 200 nm, the volume contracts to 200, 202, and 233%, respectively. The Sn nanoparticles above 200 nm bear much larger irreversible volume change. The irreversible

Figure 3. In situ AFM measurements of a series of Sn nanoparticle during sodiation and desodiation in the first cycle. Volume change of Sn nanoparticles of 80, 100, 120, 200, 230, 260, and 330 nm after sodiation and desodiation.

volume of 230, 260, and 330 nm particles increases to 278, 288, and 320%, respectively. As no separation of all of Sn particles from Au film was observed (Figure S9), these irreversible volume changes do not result from the electrical disconnection between particles and current collector. Therefore, decreasing the particle size significantly improves the volume recovery of Sn nanoparticle on first desodiation, which may exert a profound effect on the cycling performance in the following cycles. C


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Figure 4. In situ AFM measurements of selected Sn nanoparticles during sodiation and desodiation in cycles. Three-dimensional AFM images and the corresponding volume change of particles of 70 (a, b) and 240 nm (c, d).

during the five cycles (Figure S12b). The unstable shape maintenance of the larger Sn nanoparticle indicates that more trapped sodium or more nanovoids have been formed in the structure. This continuous morphology change of a larger Sn particle would cause a structure fracture and worsen the electrochemical performance in real batteries. Electrochemical measurement of coin-type half cells was also carried out to verify the difference in the cycling performance between Sn nanoparticles with large and small sizes. The Sn nanoparticles tested here are synthesized by a surfactantassisted method (details of preparation are described in the Supporting Information). The synthesized Sn nanoparticles show a high phase purity (Figure S13) and a homogeneous morphology with mean sizes of 75 and 260 nm (Figure 5a,b), respectively. The galvanostatic charge/discharge profiles (Figure 5c,d) and the cycling performance (Figure 5e,f) of these two Sn materials exhibit distinct trends in the first five cycles. The 75 nm Sn nanoparticles deliver higher capacity with a better capacity retention, which is due to the better shape maintenance as observed by the AFM. However, the larger Sn shows a faster fading capacity and a lower Coulombic efficiency. Therefore, it can be concluded that the mechanical stability and cyclability of Sn can be improved significantly by merely downsizing. Confining ultrasmall Sn in an elastic matrix can be expected to further enhance the electrode performance.

The morphological evolution of representative small (70 nm) and large (240 nm) Sn particles (Figure S11) was further investigated during the first five cycles. Particles below 70 nm had also been tested, whereas the coverage of byproducts and the continuous scanning of probe influenced the normal testing of small particles below 70 nm. Figure 4a,b shows the 3D images and the corresponding volume change of the 70 nm Sn particle. There is apparent contrast on the right of the particle during electrochemical testing, which might originate from the byproducts of the decomposition of the electrolyte.44 The first sodiation results in a volume expansion of 422%, which returns to 190% after desodiation. Similar volume changes are found in the next four cycles. The average thickness of SEI (Figure S12a) increased from 1.90 to 3 nm during the cycles, and the contribution of SEI to the irreversible volume variation changed slightly from 5.6 to 8.5%. In addition, the particle shape remains stable, indicating that the irreversible volume change might originate from the nanoscale pores formed in the previous desodiation and partially accommodate the expansion in the following sodiation process. Similar phenomenon has also been reported in the case of depotassiation from Sn.54 For the larger particle (240 nm), the mechanical stability is largely declined after several cycles of discharge and charge. As shown in Figure 4c,d, the volume expansion is 430% in the first cycle and continuously increases subsequently. After the fifth sodiation process, the volume change rate reaches as high as 520%, and the shape of the particle starts to change. The thickness of SEI and its contribution to the volume also keeps increasing slightly D


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Figure 5. SEM images, particle size distribution histogram (inset), galvanostatic charge/discharge profiles (in the potential window of 0.01−2 V vs Na+/Na), and cycling performance of synthesized Sn nanoparticles of 75 nm (a, c, e) and 260 nm (b, d, f). Scale bar: 100 nm.

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CONCLUSIONS

behavior also indicates the importance of size and interface controlling in the design of alloy-based electrode materials undergoing large volume variation during cycling.

In summary, we have used AFM to analyze the sodiation and desodiation processes of single Sn nanoparticle directly in liquid electrolyte. Our results indicate that the volume expansion of Sn nanoparticles is always ∼420% after the first full sodiation, whereas the volume change in desodiation is strongly size dependent. Interestingly, compared with the larger Sn nanoparticles, the smaller ones show a lower irreversible volume change rate and a better shape maintenance after the desodiation process. Decreasing the particle size significantly enhances the mechanical stability and thus the cycling performance of Sn nanoparticles. This finding provides new insights into what is happening to Sn anode on charging and discharging. A mechanistic understanding of the size-dependent

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b08870. Detailed experimental procedures and additional materials characterization (PDF) W Web-Enhanced Features *

Continuous sodiation/desodiation process (Movie 1) E


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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Fangyi Cheng: 0000-0002-9400-1500 Jun Chen: 0000-0001-8604-9689 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by MOST (2016YFA0202500); NSFC (21231005); and MOE (B12015, 113016A, and IRT13R30).

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REFERENCES

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In Situ Atomic Force Microscopic Studies of Single Tin Nanoparticle

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