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Lithiation Behavior of Coaxial Hollow Nanocables of Carbon−Silicon Composite Tianyi Ma,†,§ Hanying Xu,†,§ Xiangnan Yu,† Huiyu Li,‡ Wenguang Zhang,‡ Xiaolu Cheng,† Wentao Zhu,† and Xinping Qiu*,† †
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Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China ‡ Institute of Tsinghua University Hebei, Beijing 100084, China S Supporting Information *
ABSTRACT: A design of coaxial hollow nanocables of carbon nanotubes and silicon composite (CNTs@Silicon) was presented, and the lithiation/delithiation behavior was investigated. The FIB-SEM studies demonstrated hollow structured silicon tends to expand inward and shrink outward during lithiation/delithiation, which reveal the mechanism of inhibitive effect of the excessive growth of solid−electrolyte interface by hollow structured silicon. The as-prepared coaxial hollow nanocables demonstrate an impressive reversible specific capacity of 1150 mAh g−1 over 500 cycles, giving an average Coulombic efficiency of >99.9%. The electrochemical impedance spectroscopy and differential scanning calorimetry confirmed the SEI film excessive growth is prevented. KEYWORDS: hollow structured silicon, carbon nanotubes, solid−electrolyte interface confinement, high Coulombic efficiency, Li-ion battery
L
sources, leading to low Coulombic efficiency and capacity fading in real batteries.19,20 Some strategies have been proposed to improve the Coulombic efficiency of silicon anodes, such as anode prelithiation21,22 and isolation of silicon from electrolyte with a coating layer.23−30 However, it is still difficult to enhance the Coulombic efficiency up to 99.9%. Some hollow structured silicon materials presented high Coulombic efficiency.31−34 Our group prepared hollow structured silicon with high Coulombic efficiency, and we found that hollow structured silicon can inhibit the excessive growth of SEI, which was confirmed by characterization of SEI with electrochemical impedance spectroscopy (EIS) and differential scanning calorimetry (DSC) method.35,36 However, the mechanism is still not clear. In principle, surface expansion of silicon caused by volume change is the root cause of the excessive growth of SEI. Due to the inner/outer surface of hollow structured silicon having a different curvature radius, the lithiation/delithiation behavior of it will be anisotropy.37 However, it is hard to study the lithiation/delithiation behavior by the as-prepared hollow structured silicon due to its irregular morphology and low conductivity.36 Here, we fabricated coaxial hollow nanocables of CNTs@Silicon (HNCSi) and used them as model materials for elucidation of SEI growth
ithium ion batteries (LIBs), widely used in portable electronic devices and electric vehicles, have become increasingly important products for human life. In order to satisfy the requirement of energy density higher than 300 Wh kg−1, replacement of graphite with high-capacity anode materials remains a significant challenge.1−3 Among all the candidates, silicon shows the highest theoretical capacity of 3580 mAh g−1.4,5 However, due to the large volume variation (300%) of lithiation/delithiation reaction, silicon anode suffers from several critical problems including pulverization of silicon particles, unstable of electrode, and excessive growth of solid− electrolyte interface (SEI).6−9 To alleviate the problems of silicon anode, various strategies have been adopted. Nanosized silicon has been proofed to prevent crack and fracture on the particle scale owing to the lower mechanical stress of nanostructured silicon materials during lithiation reaction.10−12 On the other hand, porous silicon and its composites are designed to accommodate or buffer the large volume expansion upon lithiation.13−17 Combined with these strategies, the silicon anode demonstrated significant improvement of cycle performance in Li-half cells. However, these silicon materials are less successful in real Liion batteries due to the excessive growth of SEI. Because of the low Young’s moduli (0−3 GPa), SEI cannot endure the large volume variation of silicon, thus continuous cracks and reconstructs due to the exposure of silicon with electrolyte.18 The excessive growth of SEI consumes electrolyte and Li © XXXX American Chemical Society
Received: November 26, 2018 Accepted: January 16, 2019 Published: January 16, 2019 A
DOI: 10.1021/acsnano.8b08962 ACS Nano XXXX, XXX, XXX−XXX
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cable is ca. 115 nm. The thickness of Si nanotubes (SiNTs), outer sheath of the cables, is about 20 nm. The SEM image of HNCSi is shown in Figure 1e. It appears that the surface of SiNTs is smooth and uniform, and the hollow structure of cables and MWCNTs inside can also be easily distinguished from the crevasse of silicon sheath. Raman spectra of HNCSi and MWCNTs are illustrated in Figure 2a. Peaks at the wavenumbers of 155, 474, and 400 cm−1 correspond to amorphous silicon vibration modes, indicating the amorphous phase of Si.38 The peaks at the wavenumber of 1310 and 1595 cm−1 for HNCSi and MWCNTs correspond to the vibration modes of MWCNTs, indicating the synthesis of HNCSi did not damage the structure of MWCNTs.39 Content of silicon was analyzed by TGA, as supplied in Figure S1. The weight decrease in the lowtemperature region is mainly due to the oxidation of MWCNTs, and the further weight increase in the high temperature region is caused by the oxidation of silicon to SiO2. According to the TGA results, the Si content was calculated to be ca. 70 wt %. The high content of Si is due to the low mass density of MWCNTs, which can give a high gravimetric capacity for HNCSi. Since nanostructured silicon materials are easily oxidized in air during the samples transfer,40,41 we use X-ray photoelectron spectroscopy (XPS) to analyze the valence of silicon in HNCSi. The XPS result of Si 2p orbital is shown Figure 2b. The first main 3/2−1/2 doublet peak, located at 99.1−99.7 eV, corresponds to Si0. Peaks located at 100.8 and 103.4 eV correspond to SiOx (mainly Si2O and SiO2), indicating the partly oxidized surface of HNCSi. To get more evidence, we conducted the time-of-flight secondary ion mass spectrometry (TOF-SIMS) to characterize the composition of SiOx in depth, as shown in Figure 2c,d. The intensity of O+ and SiO+ is related to the compositional variation of SiOx in depth, which decreases to 1/5 of their original intensity after 2 nm of sputtering and then gradually decreases to negligible. Combining the results of XPS and TOF-SIMS, we can conclude that the SiOx layer on the surface of HNCSi is very thin (1150 mAh g−1 after 500 cycles and an average Columbic efficiency of >99.9%.
RESULTS AND DISCUSSION HNCSi was prepared by a template scarification method, as schematically illustrated in Figure 1a. We used commercialized
Figure 1. (a) Schematic diagram of the preparation of HNCSi. (b) TEM image of MWCNTs. (c) TEM image of MWCNT@SiO2 composite. (d) HRTEM image of HNCSi. (e) SEM image of HNCSi.
MWCNTs as an inner wire due to their high conductivity and great mechanical strength. Their average diameter is about 30 nm (Figure 1b). SiO2 was uniformly coated on the surface of MWCNTs with the hydrolysis reaction of tetraethyl orthosilicate (TEOS). Here, the SiO2 layer acts not only as a substrate for Si deposition but also as a removable template for the formation of the hollow structure. The thickness of SiO2 can be easily tuned by monitoring the reaction time. It can be seen from Figure 1c that SiO2 was homogeneously coated onto the surface of MWCNTs, the diameter of MWCNT@SiO2 is about 60 nm. Silicon was deposited on the surface of SiO2 by a CVD method. The thickness of the silicon layer can be tailored by controlling the CVD time. After the SiO2 template was etched away with hydrofluoric acid, coaxial hollow nanocables of CNTs@Silicon were formed, which can be observed from the HRTEM image in Figure 1d. The outer diameter of this B
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Figure 2. (a) Raman analysis of HNCSi and MWCNT. (b) XPS analysis (Si 2p) of HNCSi. TOF-SIMS depth profiles of (c) SiO+ and (d) O+ in HNCSi.
Figure 3. Lithiation/delithiation behavior study of HNCSi by FIB-SEM. (a) Cross section of HNCSi anode before battery cycle. SiNTs and MWCNTs can be observed clearly. (b) Cross section of first lithiated HNCSi. SiNTs expand inward with lithiation; most of the hollow structure was occupied. (c) Cross section of first delithiated HNCSi. SiNTs shrink to its original morphology. (d) Cross section of lithiated HNCSi after 10 cycles.
The observation of HNCSi by FIB-SEM shows the almost unchanged outer diameter and the periodic variation of inner diameter during lithiation/delithiation, which reveal the mechanism of SEI confinement by hollow structured silicon. More clearly, inner surfaces of SiNTs expand inward upon lithiation, shrink outward upon delithiation, and recover to its original structure. Outer surface of SiNTs remain stable, thus
only a thin SEI layer will growth on it. Moreover, due to the limited volume of hollow structure, lithiated SiNTs and MWCNTs will occupy most of the space, thus minimizing the SEI excessive growth due to the inner surface variation. The electrochemical performances of HNCSi anode are measured by galvanostatic charge/discharge tests, and mass loading of electrodes is controlled among 1.9−2.0 mg cm−2. C
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Figure 4. Electrochemical performance of HNCSi. (a) Charge and discharge profiles of HNCSi of first and second cycles. (b) Plots of differential capacity of HNCSi in different cycles. (c) Rate performance of HNCSi at different current densities from 0.2 A g−1 to 2 A g−1. (d) Half-cell discharge capacity and Coulombic efficiency of HNCSi.
1152 mA h g−1 after 500 cycles and gives an average Coulombic efficiency of up to 99.9%, which is higher than values of reported silicon anodes.46,47 To get more evidence of the structural stability of HNCSi during long cycles, the electrode of HNCSi after 500 cycles is removed and rinsed with dimethyl carbonate and acetic acid (2 wt %) to remove the SEI film. TEM image of the cycled HNCSi is shown in Figure 5a. The Si sheath can be observed clearly without fracture or crack, and inside MWCNTs (strong contrast areas) can also be distinguished, which confirms the high structural stability of HNCSi. To further investigate the evolution of SEI in HNCSi anode, EIS after different cycles were collected. In detail, the threeelectrode cell was assembled with HNCSi as work electrode and lithium foil as both counter and reference electrode. Figure 5b shows the Nyquist plots for different cycles. The semicircle in the midfrequency region corresponds to interfacial impedance, including charge transfer and SEI growth between HNCSi and electrolyte. The impedance tail in the lowfrequency region can be attributed to the bulk diffusional effects.48 We adopted a equivalent circuit, which is inserted in Figure 5b to calculate Rsur. Fitting results of Rsur are illustrated in Figure 5c. The increasing of Rsur in HNCSi electrode at initial 10 cycles is due to the SEI formation, and Rsur maintains at ca. 60 Ω in subsequent cycles, indicating the excessive growth of SEI is inhibited. For comparison, we also collected EIS results of the nanosilicon particle (50 nm) anode. The continuously increasing of Rsur nanoparticle anode indicates that the excessive growth of SEI cannot be confined. To get direct evidence of the mass of SEI growth in HNCSi electrode, differential scanning calorimetry (DSC) was conducted. In detail, HNCSi half-cells after different cycles were discharged to 0.01 V and stabilized for 2 h. Then the cells were disassembled, and electrode materials were scratched from the current collector and sealed into high-pressure stainless steel crucibles for DSC testing. Figure 5d shows the DSC curves of
Table 1. Diameter Variation of HNCSi during Lithiation/ Delithiation
initial HNCSi first lithiation first delithiation 10th lithiation
outer diameter of SiNT (nm)
inner diameter of SiNT (nm)
outer diameter of MWCNT (nm)
115
64
27
116
40
30
114
62
30
117
42
29
Figure 4a shows the initial charge−discharge profiles of HNCSi at current density of 200 mA g−1. Due to the Si sheath contributing most of the capacity, the charge−discharge curves are similar to typical lithiation reaction of amorphous silicon.42,43 The long flat plateau during the first discharge corresponds to irreversible reactions, including formation of SEI. The specific capacity of the first discharge and charge is 1934 mAh g−1 and 1514 mAh g−1, respectively, corresponding to a Coulombic efficiency of 78.3%. Furthermore, Coulombic efficiency of the second cycle reaches to 95.3%. Figure 4b shows the differential capacity curves after different cycles.44 Cathodic peaks at 0.04 V correspond to the Li-alloy reaction of silicon, and anodic peaks at 0.29 and 0.49 V correspond to the dealloy reaction of LixSi,45 which confirm the lithiation/ delithiation reaction of amorphous silicon in HNCSi. Figure 5c shows the rate stability. By increasing the current density from 0.2 A g−1 to 2 A g−1, specific capacity of HNCSi is maintained above 700 mAh g−1. After current density recovers to 0.2 A g−1, 1370 mAh g−1 of the capacity can be obtained. Figure 4d shows the discharge capacity and Coulombic efficiency in galvanostatic tests, and the calculation of specific capacity is based on the total mass of HNCSi. The current density is settled at 200 mA g−1 in the first three cycles and 600 mA g−1 in the subsequent cycles. Reversible discharge capacity retains D
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Figure 5. (a) TEM images of HNCSi after 500 cycles, and electrolyte and SEI have been removed. (b) Nyquist diagrams of HNCSi electrode with different cycles. (c) The evolution of the resistance of the Rsur. (d) DSC curves of HNCSi with different cycles. commercialized MWCNTs was dispersed into a mixed solution of deionized water (50 mL), ethanol (50 mL), and ammonia (4 mL). Then 6 mL of TEOS was added into the mixed solution with stirring at room temperature for 30 min. The MWCNT@SiO2 composite was collected and washed by deionized water for several times. We used the CVD method to coat Si onto the SiO2 layer. In detail, the CVD reaction was carried out in a horizontal tube furnace at gradient temperatures of 480−440 °C. A mixed gas of high-purity 5 wt % SiH4 and 95 wt % Ar gas was introduced at a flow rate of 100 sccm for 2 h. Reductive atmosphere (mixture of 5% H2 and 95% Ar gas) was adopted to prevent silicon from oxidation before and after the CVD reaction. The thickness of the Si layer can be controlled by CVD time. The CVD products were further etched with hydrofluoric acid (5 wt %) for 2 h to remove silica template. The final product was collected by centrifugation, washed with ethanol for several times, and then dried in a vacuum at 60 °C overnight. Structural Characterization. Morphologies of the samples were observed on transmission electron microscopy (JEOL model JEM2011), high-resolution transmission electron microscopy (HRTEM, JEM-2011F), and scanning electron microscopy (ZEISS Merlin). Raman spectra were recorded on a RamanMicro300 (PerkinElmer). X-ray photoelectron spectroscopy (XPS) measurements were conducted on a PHI Quantera SXM spectrometer equipped with a focused and monochromatized Al Kα radiation, and the binding energy scale was calibrated using the C 1s peak at 284.8 eV. Time of flight secondary ion mass spectrometry (TOF-SIMS) was performed with the use of TOF.SIMS 5 (ION-TOF), and sputtering rate was controlled to be ∼0.3 nm s−1.The thermal gravimetric analysis (TGA) was performed using a METTLER TOLEDO TGA instrument of STAR system in the temperature range of 30−1000 °C with a scanning rate of 10 °C min−1, then kept at 1000 °C for 1 h. The cross sections of HNCSi during lithiation/delithiation were obtained and observed on focus an ion beam scanning electron microscopy (FIBSEM, ZEISS Auriga). The differential scanning calorimetry (DSC) test was performed by METTLER TOLEDO DSC instrument of STAR system, temperature range of 30−300 °C with a scanning rate of 5 °C min−1. Electrochemical Measurements. The electrodes for electrochemical tests were prepared by coating slurries containing the HNCSi (60 wt %), carbon black (20 wt %), and poly(acrylic acid) (PAA as binder, 20 wt %) on copper foil. 2025-Type coin cells were
lithiated HNCSi after different cycles. The exothermic peak between 60 and 80 °C is associated with the decomposition reaction between SEI,49,50 and the area of the exothermic peaks is proportional to the mass of SEI. After 10, 20, 30, and 50 cycles, the areas of the exothermic are 0.62, 0.63, 0.68, and 0.68 J, respectively. The little exothermic change indicates that the mass of SEI does not increase much during cycles, confirming the inhibitive effect of HNCSi against SEI excessive growth.
CONCLUSIONS In conclusion, we demonstrated a hollow structured onedimension silicon−carbon nanotube to study the lithiation/ delithiation behavior of hollow structured nanosilicon materials. FIB-SEM studies demonstrated that hollow structured silicon tends to expand inward and shrink outward during lithiation/delithiation, where the little change of the outer diameter makes SEI stable. Used as anode of LIBs, the as-prepared HNCSi delivers a high initial specific capacity of >1900 mAh g−1 and a reversible specific capacity of >1150 mAh g−1 over 500 cycles with an average Coulombic efficiency higher than 99.9%. We combined EIS and DSC to evaluate the evolution of SEI, confirming that HNCSi can inhibit the SEI excessive growth during repeated lithiation/delithiation. Instead of surface coating to separate silicon from electrolyte, hollow structured silicon can retard SEI growth and prolong cycle life of silicon anodes. EXPERIMENTAL SECTION Materials Preparation. Coaxial hollow nanocables of CNTs@ Silicon (HNCSi) were prepared by a template scarification method, where we first coated a layer of SiO2 onto the surface of multiwall carbon nanotubes (MWCNTs) to obtain MWCNT@SiO2 composite, and then a layer of silicon was further coated onto SiO2 by a CVD method. The SiO2 layer was used as template, which was removed with HF acid. MWCNT@SiO2 composite was prepared by the hydrolysis reaction of tetraethyl orthosilicate (TEOS). In detail, 0.1 g E
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assembled with lithium foil as the counter electrode. A non-aqueous solution of ethylene carbonate/dimethyl carbonate/ethylmethyl carbonate (EC/DMC/EMC) with a volume ratio of 1:1:1 and 1 M LiPF6 (Guotai-Huarong New Chemical Materials Co., Ltd.) was used as electrolyte. Charge/discharge cycling tests were carried out on a Neware battery test system. The potential was controlled in the range of 0 and 1.2 V vs Li/Li+. The current density of 200 mA g−1 was used for the first three cycles and 600 mA g−1 for the subsequence cycles. The specific capacity was calculated based on the mass of HNCSi. EIS were collected on a PARSTAT 2273 electrochemical workstation with a three-electrode cell (EL-CELL, ECC-REF model), where Li foil was used as reference electrode and counter electrode, respectively. Electrochemical AC potential was controlled by applied voltage of 5.0 mV over a frequency range of 105−0.01 Hz. Before each EIS test, the electrodes were discharged to 0.01 V and stabilized at open circuit for 2 h. All cells were assembled in an Ar-filled glovebox.
ASSOCIATED CONTENT S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.8b08962. TGA curve of HNCSi under air; nitrogen sorption isotherms of HNCSi and the corresponding pore size distributions (PDF)
AUTHOR INFORMATION Corresponding Author
*E-mail:
[email protected]. ORCID
Huiyu Li: 0000-0003-2462-1170 Xinping Qiu: 0000-0001-5291-7943 Author Contributions §
These authors contributed equally to this paper.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS The authors appreciate financial supports from National Key Project on Basic Research (2015CB251104), China-US Electric Vehicle Project (S2016G9004), and Natural Science Foundation of China (U1664256). REFERENCES (1) Goodenough, J. B.; Kim, Y. Challenges for Rechargeable Li Batteries. Chem. Mater. 2010, 22, 587−603. (2) Tarascon, J. M.; Armand, M. Issues and Challenges Facing Rechargeable Lithium Batteries. Nature 2001, 414, 359−367. (3) Billaud, J.; Bouville, F.; Magrini, T.; Villevieille, C.; Studart, A. R. Magnetically Aligned Graphite Electrodes for High-Rate Performance Li-Ion Batteries. Nat. Energy 2016, 1, 16097. (4) Jin, N.; Su, Z.; Yue, N.; Song, H.; Chen, X.; Zhou, J. SiliconBased Anode Materials for Lithium-Ion Batteries. Prog. Chem. 2015, 27, 1275−1290. (5) Su, X.; Wu, Q.; Li, J.; Xiao, X.; Lott, A.; Lu, W.; Sheldon, B. W.; Wu, J. Silicon-Based Nanomaterials for Lithium-Ion Batteries: A Review. Adv. Energy Mater. 2014, 4, 1300882. (6) McDowell, M. T.; Lee, S. W.; Nix, W. D.; Cui, Y. 25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium-Ion Batteries. Adv. Mater. 2013, 25, 4966−4984. (7) Wu, H.; Cui, Y. Designing Nanostructured Si Anodes for High Energy Lithium Ion Batteries. Nano Today 2012, 7, 414−429. (8) He, Y.; Yu, X.; et al. Shape Evolution of Patterned Amorphous and Polycrystalline Silicon Microarray Thin Film Electrodes Caused F
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DOI: 10.1021/acsnano.8b08962 ACS Nano XXXX, XXX, XXX−XXX
