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Sep 13, 2018 - ABSTRACT: A porous silicon and carbon composite (PSi/. C) with granadilla-like structure as an anode material for lithium-ion batteries...
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Cite This: ACS Appl. Mater. Interfaces 2018, 10, 34283−34290

Facile and Scalable Approach To Fabricate Granadilla-like PorousStructured Silicon-Based Anode for Lithium Ion Batteries Peng Guan,†,∥ Jianjiang Li,†,‡,∥ Taige Lu,† Tong Guan,† Zhaoli Ma,† Zhi Peng,*,† Xiaoyi Zhu,*,† and Lei Zhang*,§

ACS Appl. Mater. Interfaces 2018.10:34283-34290. Downloaded from pubs.acs.org by KAOHSIUNG MEDICAL UNIV on 10/10/18. For personal use only.

†

School of Material Science and Engineering, School of Environmental Science and Engineering, Chemical Experimental Teaching Center, School of Chemical Science and Engineering, The Microcomposite Materials Key Lab of Shandong Province, Qingdao University, No. 308, Ningxia Road, Qingdao 266071, P. R. China ‡ Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, Shanghai 200240, P. R. China § Centre for Clean Environment and Energy, Griffith University, Gold Coast Campus, Gold Coast, Queensland 4222, Australia S Supporting Information *

ABSTRACT: A porous silicon and carbon composite (PSi/ C) with granadilla-like structure as an anode material for lithium-ion batteries has been easily fabricated by spray drying and subsequent pyrolysis treatments. For the PSi/C, yolk− shell-structured Si/C nanobeads are equably distributed inside the porous carbon framework. The key point of this work is the combination of the advantages of both the yolk−shell structure and porous structure in one system. The void space inside the yolk−shell Si/C nanobeads and the interconnected three-dimensional porous carbon frameworks can effectively enhance the cyclic stability and conductivity of this composite. As expected, PSi/C with 15.4% silicon content exhibited a specific capacity as high as 1357.43 mAh g−1 and retained 933.62 mAh g−1 beyond 100 cycles at 100 mA g−1. Moreover, it showed a reversible specific capacity as high as 610.38 mAh g−1 at 1000 mA g−1, even after 3000 cycles. KEYWORDS: granadilla-like structure, silicon, yolk−shell, anode, lithium-ion batteries

1. INTRODUCTION Compared with different energy storage systems, the commercialized lithium-ion batteries (LIBs) are very successful because of their suitable working potential, large capacity density, long-term cyclic life, and environmental friendliness.1−3 Silicon (Si) with a large range of sources has received remarkable attention as an anode for LIBs on account of its relatively low stable plateau potential (∼0.4 V vs Li/Li+) and specific theoretical capacity as high as 4200 mAh g−1.4−6 Nevertheless, the huge volumetric changes of Si anode in the charge and discharge process lead to structural pulverization and consequently result in poor cycling life.7,8 Furthermore, the lower electrical conductivity of Si causes electrode polarization, which also confines its practical use. 9,10 Tremendous endeavors have been directed toward improving the stability of the Si anode by using nanosized silicon, including Si nanowires, porous nanosilicon, and coating Si with a conductive agent, such as carbon, Ag, or a conducting polymer.11,12 Among them, well-designed nanosized silicon/ carbon (Si/C) composites with special core−shell, yolk−shell, and porous structures have been reported and exhibit good electrochemical performance.13−15 A sufficient and welldemarcated internal void space between the Si nanoparticles © 2018 American Chemical Society

(NPs) inside and the outer carbon shell is necessary to maintain structural integrity, resulting in the unparalleled yolk−shell structure.16−18 The outer carbon shell can limit the formation of solid−electrolyte interface (SEI) films, and the void space inside alleviates the volumetric expansion of Si.19−22 Besides, the novelly introduced porous structure provides an effective and fast electron-transfer network for Si, enabling a better Li ion diffusion rate and good cyclic stability.23−26 Various methods have been applied, such as high-energy ball milling, solution polymerization, soft or hard templating, chemical vapor deposition, spray drying, and pyrolysis, to synthesize Si/C composites with the above-mentioned promising structures.27−30 Li et al. prepared Si/C microspheres with core−shell structure, the capacity of which is about 900 mAh g−1 beyond 30 cycles by spray drying in combination with surface coating.13 Liang et al. produced a porous and conductive framework-structured Si/C microsphere via electrostatic spraying and following high-temperature process. The microspheres maintained a capacity as high as 1325 mAh g−1 Received: July 20, 2018 Accepted: September 13, 2018 Published: September 13, 2018 34283

DOI: 10.1021/acsami.8b12071 ACS Appl. Mater. Interfaces 2018, 10, 34283−34290

Research Article

ACS Applied Materials & Interfaces Scheme 1. Schematic Illustration of the Preparation of the Granadilla-like PSi/C Composite

Figure 1. XRD patterns (a), Raman spectra (b), and TGA curves (c) of Si NPs, PSi/C-800, PSi/C-400, and Si/C-400, and (d) the X-ray photoelectron spectroscopy (XPS) high-resolution spectrum of Si 2p in PSi/C-400 (d).

with a capacity retention rate of about 87% after 60 cycles.31 Cui’s group fabricated a pomegranate-like Si-based electrode through a bottom-up microemulsion approach using silica as the template, which showed an excellent cyclic life (maintaining 1160 mAh g−1 with a capacity retention as high as 97% beyond 1000 cycles).2 Zhang et al. developed a granadilla-like Si/C composite by using CaCO3 as the template and subsequent carbon deposition, which exhibited a reversible capacity of approximately 1100 mAh g−1 even after 200 cycles, with a capacity retention of 82.65%.19 The electrochemical improvements of these Si/C composites with novel and unique structural designs are quite notable and encouraging.

Herein, we introduce a scalable method to fabricate a granadilla-like yolk−shell-structured porous silicon/carbon (PSi/C) composite (as shown in Scheme 1). These PSi/C microspheres are first prefabricated via the spray-drying technique using a slurry made up of silica-coated Si NPs (SiO2/Si NPs) and poly(vinylpyrrolidone) (PVP). During the spray-drying process at a relatively high temperature, the PVP molecules can be cross-linked to form a coating shell on the outer surface of every single SiO2/Si NP nanobead (PVP/ SiO2/Si NPs). At the same time, an interconnected PVP framework with a microsized spherical morphology can also be generated due to the precarbonization of PVP. The SiO2/Si NPs nanobeads are uniformly distributed inside the PVP 34284

DOI: 10.1021/acsami.8b12071 ACS Appl. Mater. Interfaces 2018, 10, 34283−34290

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ACS Applied Materials & Interfaces

Figure 2. SEM images of Si NP precursor powders (a), SiO2/Si NPs with PVP after spray drying (PVP/SiO2/Si-400) (b), a single PVP/SiO2/Si400 microsphere (c), and PVP/SiO2/Si-400 microspheres after HF etching (PSi/C-400) (d), a single PSi/C-400 microsphere (e), the enlarged holes on the surface of the microsphere (f), and elemental mapping of PSi/C-400 (g).

cycles. Apart from the significantly improved performance, the facile synthetic strategy makes this composite prospective for wholesale production of good-performance Si-based anode materials for LIBs.

framework. After washing with diluted hydrofluoric acid (HF) and subsequent high-temperature carbonization, the silica sacrificial coating layer is removed, and a void space is formed in situ between the inner Si NPs and the outer carbon shell, resulting in the unique yolk−shell Si/C nanobeads. More importantly, due to the pyrolysis of the PVP framework at high temperature, abundant pore-size-controlled micropores can be generated on the entire microsphere outer surface as well as on the carbon framework inside, leading to a special porous structure. Compared with all of the previously reported yolk− shell-structured Si/C composites, the tunable micropores distributed in the carbon framework along with the facile and scalable fabrication method are the main advantages of this composite. Unlike the traditional simple yolk−shell, core− shell, or porous Si/C structures, the unique PSi/C composite proposed in this work inherits the predominate advantages of these three different structures. The void space between the inner Si NPs and the outer carbon shell can effectively buffer the expansion and contraction of Si NPs. The porous carbon framework provides more active Li+ storage sites and adequate electrical conductivity, while enhancing the mechanical strength and facilitating fast ion diffusion.32−34 As a result, excellent electrochemical performance is obtained for the PSi/ C composite, which is ascribed to this particular structure. The designed PSi/C delivered excellent cyclic stability with a capacity of 933.62 mAh g−1 at 100 mA g−1 even after 100 cycles. Excitingly, outstanding cyclic stability was obtained even when the current density was increased to 1000 mA g−1. It could reach a notable capacity of 610.38 mAh g−1 after 3000

2. RESULTS AND DISCUSSION The X-ray diffraction (XRD) patterns of PSi/C-800, PSi/C400, Si/C-400, and Si NPs are displayed in Figure 1a. All of the diffraction peaks centered at 2θ values of 28.4, 47.0, and 55.8° are assigned to the (111), (220), and (311) planes of the Si phase, respectively. In addition, a wide peak at approximately 25° corresponds to the (002) plane of carbon, indicating the low degree of graphitization of the amorphous carbon derived from the PVP pyrolysis during the carbonization process. Figure 1b exhibits the Raman spectra of PSi/C-800, PSi/C400, and Si NPs. The intense peak at approximately 500 cm−1 is associated with the spectrum of Si NPs. The two peaks at about 1358 and 1583 cm−1 correspond to the D (disordered carbon) band and G (graphitic carbon) band, respectively. The calculated peak intensity ratios (ID/IG) for PSi/C-800, PSi/C400, and Si/C-400 are 1.11, 1.06, and 1.08, respectively, suggesting that PSi/C-400 has higher graphitization than PSi/ C-800 and Si/C-400, in accordance with the results of the above XRD analysis. The mass ratio of Si NPs in the Si/C composite was determined by thermogravimetric analysis (TGA). Figure 1c shows the TGA curves of PSi/C-800, PSi/ C-400, Si/C-400, and Si NPs in air. We can observe that the oxidization of Si NPs starts slowly above 600 °C and becomes rapid above 700 °C. For the PSi/C composites, the weight loss 34285

DOI: 10.1021/acsami.8b12071 ACS Appl. Mater. Interfaces 2018, 10, 34283−34290

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ACS Applied Materials & Interfaces

Figure 3. TEM and HRTEM images of PSi/C-400 before (a, b) and after HF etching (c, d).

Figure 4. Electrochemical properties: cyclic voltammograms for the first three cycles of PSi/C-400 (a), the initial discharge−charge curves of PSi/ C-800, PSi/C-400, and Si/C-400 (b), cycling performances of PSi/C-800, PSi/C-400, and Si/C-800 at 100 mA g−1 (c), and the rate performances of PSi/C-800, PSi/C-400, and Si/C-400 at different current densities (d). 34286

DOI: 10.1021/acsami.8b12071 ACS Appl. Mater. Interfaces 2018, 10, 34283−34290

Research Article

ACS Applied Materials & Interfaces derived from carbon combustion started at around 500 °C and ended at about 750 °C. Thus, the content of silicon in PSi/C400, PSi/C-800, and Si/C-400 can be roughly calculated to be around 15.4, 20.8, and 50.1%, respectively. X-ray photoelectron spectroscopy (XPS) measurements indicate that the elemental compositions on the surface of PSi/C-400 and valence states of PSi/C-400 are Si 2p, C 1s, and O 1s (Figure S1). The XPS spectrum of Si 2p in Figure 1d can be divided into two positions: 99.8 eV for Si−Si and 102.9 eV for Si−O. Figure 2a shows an scanning electron microscopy (SEM) image of Si NPs. It can be observed that Si NPs are about 80 nm. Figure 2b shows the SEM image of the PVP/SiO2/Si microspheres after spray drying. Great spherical morphology with a homogeneous size distribution ranging from 3 to 5 μm could be obviously seen. The enlarged view of PVP/SiO2/Si microspheres in Figure 2c shows that these microspheres are endowed with smooth surfaces. After the subsequent hightemperature carbonization and diluted HF washing, it can be seen that the spherical morphology is well maintained (Figure 2d), and abundant pores with a diameter of 5−10 nm can be seen on the surfaces of these microspheres (Figure 2e,f), which are attributed to the pyrolysis of the PVP framework at high temperature. Energy-dispersive X-ray spectroscopy (EDS) mapping is employed to test the distribution of the elements. Figure 2g shows that the Si and C elements are homogeneously dispersed within the microsphere. Figure S2 presents SEM images of PSi/C-800, which has a higher Si content than PSi/C-400. PSi/C-800 exhibits a similar spherical morphology after the spray-drying process. After the following HF washing process, however, the spherical morphology was mostly destroyed due to the weak carbon framework. In addition, Figure S3 shows that the Si/C-400, which was prepared without the SiO2 coating on the surfaces of the Si NPs, also has a similar spherical morphology. Table S1 shows the Brunauer−Emmett−Teller (BET) results of PSi/C-800, PSi/C-400, and Si/C-400, respectively. The surface areas of the three samples were 278.25, 197.49, and 66.16 m2 g−1, respectively. What is noteworthy is that, compared with PSi/C-400, an increased amount of microspheres in PSi/C-800 are partially destroyed after pyrolysis and HF etching due to its weak carbon interconnections. The N2 adsorption−desorption isotherms and pore size distributions of PSi/C-400, PSi/C-800, and Si/C-400 are displayed in Figure S4a, respectively. The isotherm of PSi/C-400 with a relative pressure ranging from 0 to 1.0 is different from those of PSi/C-800 and Si/C-400, which have a relative pressure ranging from 0.7 to 1.0. Meanwhile, Figure S4b demonstrates that the PSi/C composite has a diverse pore structure (below 10 nm), which includes a sequence of micro- and mesopores. These multiple pores facilitate the electrolyte to penetrate into PSi/C composite and shorten the diffusion paths from Li ions to Si NPs.27−29 Furthermore, the particular porous structure can provide buffer space for the expansion of Si NPs and offer free channels for electrolyte penetration to increase the electroactive areas, resulting in their better electrochemical performance.30−32 Transmission electron microscopy (TEM) and highresolution TEM (HRTEM) images of PSi/C composite before and after HF etching are shown in Figure 3. Figure 3a contains a TEM image of PSi/C before HF etching. We can notice that the interior Si/C nanobeads of about 100 nm have a doubleshell structure. The Si core inside is well encapsulated by the

inner SiO2 shell and the outer carbon framework, resulting in a double-shell structure. The thickness of the inner SiO2 shell is about 10 nm (Figure 3b). In addition, the d-spacing of 0.31 nm is attributed to the (111) planes of Si NPs.33−35 After the HF washing treatment, the silica sacrificial coating layer is removed and the in situ void space (about 10 nm in depth) appears between the Si NPs inside and the outer carbon layer, leading to the unique yolk−shell structure (Figure 3c,d). Figure 4a shows the cyclic voltammetry (CV) curve of PSi/ C-400 for the first three cycles. In the first discharge process, the broad peak between 0.3 and 0.8 V could be ascribed to the irreversible formation of the SEI layer, which vanishes in the following cycles, owing to the irreversible formation of an SEI film.36,37 The peak situated at around 0.18 V is attributed to the reversible lithiation of Si. Similarly, the peaks located at 0.34 and 0.55 V are attributed to the delithiation process of Si.38 In the subsequent cycles, no obvious shift was observed, manifesting good cyclic performance in the subsequent cycles. The slight shift of the peaks could be ascribed to the phase transitions.31,39 Figure 4b shows the initial charge−discharge curves of PSi/C-800, PSi/C-400, and Si/C-400 at 100 mA g−1. The flat and long voltage plateau below 0.2 V indicates that the lithium ions are embedded in carbon and Si.40,41 The discharge and charge capacity of the three composites were 1414.12 and 1049.65 mAh g−1 for PSi/C-800, 1357.47 and 1078.84 mAh g−1 for PSi/C-400, and 1511.14 and 1069.07 mAh g−1 for Si/ C-400, respectively. Therefore, their initial Coulombic efficiencies are 74.2, 79.4, and 70.8%, respectively. To some degree, the irreversible capacity of the first cycle is attributed to the formation of the SEI film at around 0.3−0.7 V.42,43 The cycling performances presented in Figure 4c show that the charge capacities of PSi/C-800, PSi/C-400, and Si/C-400 are 718.16, 933.62 (the areal capacity is about 1.19 mAh cm−2), and 487.65 mAh g−1 at 100 mA g−1 beyond 100 cycles, respectively. As a result, the capacity retention of these samples is about 68.4, 86.5, and 45.6%, respectively, suggesting that PSi/C-400 has better cycling stability than PSi/C-800 and Si/ C-400. Compared with PSi/C-800 and Si/C-400, PSi/C-400 can absorb the volumetric changes of Si NPs better due to its lower silicon content and increased void space inside, leading to improved structure stability. We also demonstrate the electrochemical performance of the porous carbon without Si in Figure S5, which is consistent with previous published reports.44−46 For the full LIBs, our prepared PSi/C-400 and the commercial LiNi0.5Co0.2Mn0.3O2 (NCM523) were employed as the anode and cathode, respectively. The full-cell electrochemical performance is shown in Figure S6. We can see that the first charge and discharge capacities of the battery are 205.17 and 145.02 mAh g−1, respectively, and the reversible capacity remains 105.7 mAh g−1 at 100 mA g−1 after 100 cycles. Figure 4d illustrates the rate performances of PSi/C800, PSi/C-400, and Si/C-400 at different current densities. As expected, PSi/C-400 exhibits the best rate performance even at higher current densities. The reversible charge capacity of PSi/ C-400 is 522.10 mAh g−1 at 2000 mA g−1, and 96.7% capacity retention even after 20 cycles under such a high current density. A reversible capacity of 942.3 mAh g−1 was retained while the testing current density was recovered to 100 mA g−1, which means that fast Li ion insertion and extraction does not destroy its electrode integrity. The long-term cyclic performance of PSi/C-400 at 1000 mA g−1 is demonstrated in Figure S7. The reversible capacity is well retained at 610.32 mAh g−1 (the areal capacity is 0.78 mAh cm−2) even after 3000 cycles, 34287

DOI: 10.1021/acsami.8b12071 ACS Appl. Mater. Interfaces 2018, 10, 34283−34290

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ACS Applied Materials & Interfaces maintaining a capacity of 65.9%. After cycling, a good structural integrity of PSi/C-400 is maintained (Figure S8). The electrochemical impedance plots of PSi/C-400, PSi/C800, and Si/C-400 are displayed in Figure S9. The size of the semicircles follows the sequence of PSi/C-400 < PSi/C-800 < Si/C-400, suggesting that PSi/C-400 has the minimum resistance to transfer Li ions and the maximal electrical conductivity, with both contributing to the superior LIB performance. Furthermore, a comparison between this novel PSi/C-400 electrode and other recently published similar porous Si/C composites is shown in Table S2. Obviously, PSi/ C-400 exhibits the best cycling stability and has comparable capacity at higher current densities, demonstrating its promising structural design. The combination of void space inside the yolk−shell Si/C nanobeads and the abundant nanopores, which are uniformly distributed on the threedimensional carbon frameworks in PSi/C-400, are of benefit to the outstanding cyclic stability and superior rate performance of PSi/C-400.

300X) at 15 kV and a transmission electron microscope (TEM; EKYS-261) were applied to characterize the morphologies of samples. 4.3. Electrochemical Measurements. The working anode was prepared by grinding the active materials, acetylene black, and poly(vinylidene fluoride) in a mass ratio of 8:1:1 with Nmethylpyrrolidone as a solvent to form a homogeneous suspension, which was then cast onto copper foil as the current collector. The foils were then transferred to a vacuum oven and dried at 110 °C for 24 h. The foils were cut into disks with diameter of 1 cm and then transferred to an argon-filled glove box with oxygen and water contents less than 0.1 ppm. The mass loading was 1.27 mg cm−2. CR2016 coin-type cells were assembled in the glove box by using a porous polypropylene-containing liquid electrolyte to separate the working anode with a lithium wafer counter electrode. The liquid electrolyte was 1 mol L−1 LiPF6 in a mixture of ethylene carbonate and dimethyl carbonate (1:1, v/v). The charge and discharge tests were conducted via a CT2001A battery tester in the voltage range between 0 and 2 V at 100, 200, 500, 1000, and 2000 mAh g−1. Electrochemical impedance spectroscopy measurements and CV measurements were carried out via CHI-760 electrochemical workstation.

3. CONCLUSIONS In summary, a facile spray-drying process was employed to prepare a granadilla-like porous-structured Si/C anode for LIBs. The yolk−shell Si/C nanobeads are uniformly distributed in the porous carbon framework. As a result, the yolk−shell and porous structures are effectively combined together in one system with benefits to its cyclic stability and good rate performance. The porous Si/C composite with 15.4% Si content shows the best electrochemical performance due to its successful design, such as its well-defined void space and strong carbon interconnections. Even at 1000 mAh g−1, the capacity of PSi/C-400 still can be well maintained at 610.38 mAh g−1 after 3000 cycles. Furthermore, the facile and scalable fabrication method makes this porous Si/C composite promising as an anode material for next-generation LIBs.

S Supporting Information *

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ASSOCIATED CONTENT

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b12071. XPS data, SEM images of PSi/C-800 and PSi/C-400, N2 adsorption−desorption isotherms and pore size distributions of PSi/C-400, PSi/C-800, and Si/C-400, electrochemical performance of the porous carbon without Si, full cell performance of using PSi/C-400 as anode, long-term cyclic performance of PSi/C-400 at 1000 mA g−1, SEM and TEM images of PSi/C-400 after cycling test, electrochemical impedance plots of PSi/C400, PSi/C-800, and Si/C-400 (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: lei.zhang@griffith.edu.au (L.Z.). *E-mail: [email protected] (Z. P.). *E-mail: [email protected] (X. Z.).

4. EXPERIMENTAL SECTION 4.1. Materials Synthesis. In this work, 600 mg commercial Si NPs (∼80 nm, 99.99%, ST-nano, Shanghai, China) were coated with an SiO2 layer using tetraethoxysilane (AR, Sinopharm) to obtain SiO2/Si NPs. In a typical synthesis, 400 mg SiO2/Si and 800 mg PVP were mixed with 500 mL deionized water and stirred to form a homogeneous suspension for 5 h. Then, the suspension was introduced into a spray dryer to create the precursor PVP/SiO2/Si400 microspheres, which were then carbonized at 900 °C in argon atmosphere for 2 h to obtain C/SiO2/Si-400 powders. Finally, the SiO2 sacrificial layer inside the C/SiO2/Si-400 was removed with dilute hydrofluoric acid solution, followed by centrifugation and ethanol washing four times, and ultimately drying in a vacuum oven. The final composite was denoted as PSi/C-400. When using 800 mg SiO2/Si without changing the preparation conditions, the obtained composite was called PSi/C-800. For comparison, Si/C-400 was prepared under the same conditions as described without the SiO2 coating treatment. 4.2. Characterization. The phases and crystallinity of composites were characterized via X-ray diffraction (XRD; DX-2007) using Cu Kα radiation (λ = 1.5418 Å). Thermogravimetric analysis (TG209F3) was performed at a heating rate of 10 °C min−1 under air flow. The Brunauer−Emmett−Teller (BET) testing was conducted via a Micromeritics ASAP-2020M nitrogen adsorption apparatus to measure the surface areas and pore size distributions of the samples. Raman spectroscopy (JobinYvon HR800) was conducted to confirm the formation of carbon. A scanning electron microscope (SEM; JSM5600LV) with an energy-dispersive X-ray spectrometer (EDS; IE

ORCID

Lei Zhang: 0000-0003-3766-4882 Author Contributions ∥

P.G. and Dr J.L. contributed equally to this work.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is financially supported by the National Natural Science Foundation of China (No. 51503109), Qingdao Applied Basic Research Project (16-5-1-85-jch), and China Postdoctoral Science Foundation Funded Project (No. 2016M600522).

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DOI: 10.1021/acsami.8b12071 ACS Appl. Mater. Interfaces 2018, 10, 34283−34290