Design and synthesis of SiO@SiO₂ core-shell anodes for enhanced performance in lithium-ion batteries

doi:10.21203/rs.3.rs-4845591/v1

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Design and synthesis of SiO@SiO₂ core-shell anodes for enhanced performance in lithium-ion batteries

https://doi.org/10.21203/rs.3.rs-4845591/v1

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The progress of energy storage technology crucially depends on the availability of high-performance lithium-ion batteries (LIBs). As a silicon-based composite material, silicon oxide (SiO) exhibits significant theoretical specific capacity and mitigates the volume expansion of pure silicon. However, poor electronic conductivity remains a significant issue, limiting the performance of LIBs. In this study, SiO@SiO₂ composites were synthesized by applying a silane coupling agent as the silicon source to coat silicon oxides onto the surface of micrometer-sized SiO particles using an in-situ coating technique within a liquid-phase system. This approach aims to address the problems of volume expansion and stability, thereby enhancing the performance of LIBs. The silicon oxide core provides high capacity, whereas the silica shell serves as a protective layer. The SiO₂ shell, with its greater rigidity compared to a carbon shell, better inhibits volume expansion, thereby extending the battery's service life. The results showed that when the mass of the silane coupling agent (SCA) was 15% of the mass of the SiO particles, the initial specific capacity of SiO@SiO₂-15 composites reached 2160.62 mAh·g^− 1, with the highest first coulombic efficiency (70.06%). Additionally, the composites exhibited the highest reversible capacity (1345.54 mAh·g^− 1) and a capacity retention of 62.28% after 100 cycles.

core-shell

composite materials

volume changes

cycle performance

lithium-ion battery anode

With the growing societal demand for energy, the need to develop efficient and eco-friendly energy storage systems has become increasingly urgent^[1–4]. Lithium-ion batteries have emerged as one of the most competitive and promising battery technologies, owing to their high energy density, low self-discharge rate, long cycle life, rapid charging capability, environmental friendliness, and broad range of applications.^[5–8]. However, conventional graphite anode materials have limitations in terms of their theoretical specific capacity (approximately 372 mAh·g^− 1)^[9] and cycling stability, rendering them inadequate to satisfy the increasing requirements of higher energy density. Therefore, the search for novel anode materials with high capacity and superior performance has become a central focus in lithium-ion battery development research.

Silicon (Si), as an anode material, possesses a high theoretical specific capacity (approximately 4200 mAh·g^− 1), indicating significant potential and broad prospects for enhancing battery performance and reducing costs^[10–15]. Despite the significant advantage of Si in increasing battery capacity, its considerable volume expansion (up to 300% or more)^[16–18] leads to structural fragmentation, causing pulverization of the electrode materials and rapid degradation of cycling stability^[19–23]. Silicon oxide (SiO), a silicon-based composite material, also boasts a high theoretical specific capacity (approximately 2000 mAh·g^− 1). Moreover, the irreversible reactions occurring in lithium-silicon alloys, coupled with the formation of a solid electrolyte interphase (SEI) film, lead to minimal capacity loss^{[24, 25]}. This results in SiO exhibiting a high initial coulombic efficiency, which helps enhance the battery's actual energy density. On the other hand, due to the presence of oxides, SiO can partially mitigate the volume expansion caused by pure silicon, thus improving the battery's electrochemical performance^[26–28]. However, the low conductivity of silicon oxide^[29] impedes electron transport within the electrode material, resulting in increased internal resistance and reduced charging and discharging efficiency of the battery^{[16, 30, 31]}. Therefore, researchers typically reduce particle size^[32], construct porous structures^{[33, 34]}, and apply carbon coatings^[35] to improve conductivity and increase the electrode reaction rate. These strategies significantly improve the performance and broaden the utilization of SiO in lithium-ion batteries.

Besides well-known carbon materials, oxides can enhance lithium storage performance by forming complexes with SiO^{[36, 37]}. Silane coupling agents (SCAs) are extensively used to modify silicon-based materials due to their ability to establish stable chemical bonds on the surfaces of inorganic substrates. This significantly improves both the dispersion and stability of the material at the interface^{[38, 39]}. Therefore, introducing a silane coupling agent to form a capping layer on SiO anode materials can limit and alleviate the volume expansion of SiO, thereby enhancing its electrochemical performance, particularly its lithium storage capability.

In this study, SiO composites coated with silane coupling agents (SiO@SiO₂) were prepared through in-situ coating combined with high-temperature sintering. The effects of varying amounts of silane coupling agents (SCAs) on the structure and morphology of the SiO anode material, as well as on the electrochemical performance of lithium-ion batteries, were researched.

2.1 Materials synthesis

SiO@SiO₂ composites were synthesized through insitu coating of SiO with precursors before high temperature sintering, as illustrated in Fig. 1.

First, dissolve 5 g of SiO and 0.05 g of cetyltrimethylammonium bromide (CTAB) in a 30 g mixture of water and ethanol. Stir the mixture at room temperature for 15 minutes. Adjust the pH of the SiO mixture by adding a small amount of ammonia and continue stirring until the pH reaches 10. Next, dissolve silane coupling agents (SCA) in the solution at concentrations of 2%, 5%, 10%, 15% and 20% relative to the mass of SiO, and stir at 60°C for 2 h. Transfer the mixture to a constant-temperature oven set at 80°C and keep it there for 12 h. Finally, calcine the prepared SiO-coated precursor powders in an argon atmosphere within a tube furnace at 900°C for 3 h. The composites with different amounts of SCA were labeled SiO@SiO₂-2, SiO@SiO₂-5, SiO@SiO₂-10, SiO@SiO₂-15 and SiO@SiO₂-20 after grinding.

2.2 Structure characterization

An X-ray diffractometer (XRD, D8, Bruker) utilizing Cu Kα radiation was employed to examine the internal phase composition of the material. The different valence states of the atoms were analyzed using X-ray photoelectron spectroscopy (XPS, ESCALAB 250xi, USA). Morphological features of the sample surface and microscopic characteristics of the material were observed with a scanning electron microscope (SEM, Quanta 200 FEG, USA). Transmission electron microscopy (TEM, JEM-2100, Japan) was employed to thoroughly investigate the composite distribution and the cladding structure of the SiO₂ and carbon layers.

2.3 Electrochemical characterization

The composite, binder (CMC + SBR) and conductive additive (SP) were combined in a mass ratio of 7:2:1. The viscosity of the slurry was adjusted by adding a small amount of deionized water. Subsequently, the paste was uniformly coated to the copper foil to achieve a coating thickness of 200 µm and then dried in a vacuum oven. A CR2025-type button cell was fabricated with lithium metal wafers as the counter electrode and an organic solution of LiPF₆/EC: DMC (1:1 by volume)/FEC (10% by mass fraction) as the electrolyte.

The electrochemical performance test was conducted on CR2025 button cell. Cycling performance was evaluated by first activating the cell and then discharging it at 750, 300 and 100 mA·g^− 1 while charging at 750 mA·g^− 1 current density. The battery was initially activated three times during the rate performance test and then charged and discharged 10 times each at current densities of 300, 750, 1500 and 300 mA·g^− 1. Cyclic voltammetry tests were performed to characterize the redox potentials of the materials using the CHI-660D electrochemical workstation. The starting voltage was the open-circuit voltage of the button cell, with a scanning range of 0.01-2 V and a scanning rate of 0.5 mV·s^− 1. To analyze the internal characteristics of the batteries, impedance tests were performed in the frequency range of 0.01 Hz to 10⁶ Hz.

As shown in Fig. 2(a), to analyze the effect of SCA concentration on the crystal structure and chemical composition, XRD analyses were performed on SiO@SiO₂-2, SiO@SiO₂-5, SiO@SiO₂-10, SiO@SiO₂-15 and SiO@SiO₂-20 composites. The SiO@SiO₂-2, SiO@SiO₂-5 and SiO@SiO₂-10 composites exhibit broad diffraction peaks at 20–30^°, corresponding to the amorphous SiOx phase. When the silane coupling agent concentration reached 15% (SiO@SiO₂-15), distinct diffraction peaks at 28.1^°, 46.9^° and 56.5^° appeared in the XRD pattern. According to the PDF card (PDF#27-1402), these peaks correspond to the (111), (220) and (311) crystal planes of silicon. Compared to SiO@SiO₂-20, the diffraction peaks of silicon were sharper, indicating increased crystallinity. This suggested that disproportionation reactions occur in certain silicon oxides, gradually transforming amorphous silicon into crystalline silicon ^[40].

Figure 2(b-e) showed the full XPS spectrum of the SiO@SiO₂-15 composite, including the fine spectra of Si 2p, O 1s and C 1s. There were distinct Si, O and C peaks in the full XPS spectrum (Fig. 2(b)) of the SiO@SiO₂-15 composite, which were attributed to the elements in the SiO material and the cladding layer. In Fig. 2(c-e), a split-peak fitting process was performed for the Si, C and O in the SiO@SiO₂-15 composite. From the XPS spectrum of Si (Fig. 2(c)), five subpeaks were clearly observed, reflecting the electronic binding energies of different spin states in the p-orbitals of elemental Si in various oxidation states. The carbothermal reduction of SiO₂ with amorphous C resulted in the reduction of Si to various valence states. The binding energies correspond to different oxidation states of Si: 103.9 eV for Si⁴⁺, 103.1 eV for Si³⁺, 102.2 eV for Si²⁺, 100.7 eV for Si¹⁺ and 99.8 eV for Si^0[41]. The peak at 533.1 eV in the O1s fine spectrum (Fig. 2(d)) indicated the presence of Si-O bonds within the structure. Similarly, in the C1s fine spectrum (Fig. 2(e)), the peak at 284.87 eV indicated the presence of C-C bonds, in other words, the presence of carbon phase in the composite. These results confirmed the inclusion of carbon and SiO₂ nanoparticles in the SiO₂ composites.

Figure 3 displayed the SEM different morphology of the SiO@SiO₂ composites prepared with different concentrations of the SCA.

The SiO particles in the SEM images (Fig. 3) were approximately 5 µm in size, irregularly shaped and uniformly distributed without agglomeration. As shown in Fig. 3(a) and 3(b), the particles were angular, with smooth and flat surfaces at higher magnification. This is due to the insufficient amount of silane coupling agent, resulting in a too-thin coating layer on the SiO particles, leaving some particles partially exposed. When the silane coupling agent was increased to 10% of the mass of SiO, the particle surfaces became rougher, as seen in Fig. 3(c). Upon local magnification, the SiO₂ layers were observed to encapsulate the particle surfaces completely, with the SiO particles entirely enclosed.

However, with excessive addition, the particles in Fig. 3(e) were encapsulated by a dense cladding layer, making it too thick. In Fig. 3(d), SiO₂ not only encapsulated the surface of the SiO particles but also grew through its own nucleation. In summary, the SiO@SiO₂-15 composite exhibited the best cladding effect. If the SiO₂ coating layer was too thin, the desired modification cannot be achieved. Although an excessively thick SiO₂ coating layer alleviated the volume expansion of the material, it adversely affected the electrochemical performance of the battery due to the poor electrical conductivity of SiO₂. SEM and TEM analyses confirmed that the SiO particles were encapsulated on the material surface by SiO₂ and C together^[42].

Figure 4 showed the TEM image of the SiO@SiO₂-15 composite selected for the best cladding effect.

The deeper shading represented regions with thicker particles, which were SiO particles, while the lighter shading indicates regions with thinner particles, which were the cladding layers. The surface of the particles displayed semicircular mixed microspheres of SiO₂ and C, resulting from the sintering process after the hydrolysis of the silane coupling agent, as corroborated by Fig. 3(d).

Fig. 4(b) illustrated the varying thicknesses of the cladding, showing that the overall cladding is effective with no exposed SiO particles. In summary, the SiO@SiO2-15 composite can completely encapsulate the SiO particles with a moderately thick encapsulation layer.

Figure 5(a) showed the 100-cycle performance of SiO@SiO₂-15. Figure 5(b) displayed the results of 100-cycle tests performed on five composites to investigate their cycling performance. The 100-cycle discharge specific capacities of SiO@SiO₂-2, SiO@SiO₂-5, SiO@SiO₂-10, SiO@SiO₂-15 and SiO@SiO₂-20 were 319.5945 mAh·g^-1, 940.21 mAh·g^-1, 1105.62 mAh·g^-1, 1345.54 mAh·g^-1 and 962.25 mAh·g^-1, respectively. The initial discharge specific capacities were 2251.39 mAh·g^-1, 2162.56 mAh·g^-1, 2199.74 mAh·g^-1, 2160.62 mAh·g^-1 and 2202.71 mAh·g^-1, respectively, and the initial coulombic efficiencies were 68.72%, 68.87%, 69.09%, 70.06% and 68.95%, respectively.

According to the comparison of the five materials, it was evident that with increasing addition of the SCA, the SiO₂ coating became thicker accordingly. This effectively inhibited the volume expansion of the SiO material during charge and discharge cycles, delayed the fragmentation of the host particles, slows rapid capacity decay, and ensured a higher capacity retention rate. Moreover, the complete and uniform SiO₂ cladding layer can protect the surface of SiO, effectively reducing direct connection between the SiO material and the electrolyte during charging and discharging. This enhancement led to improved first-time coulombic efficiency and cycling stability of the cell. Consequently, when the SiO₂ cladding layer was too thin, the contact between the SiO particles in the SiO@SiO₂ composites and the electrolyte resulted in an irreversible reaction of lithium ions, leading to low initial coulombic efficiency. Conversely, when the SiO₂ cladding layer was too thick, the conductivity of SiO@SiO₂ composites and the cycling performance of the battery were further reduced due to the poor electrical conductivity of SiO₂ itself.

Figure 5(c) displayed the initial charge/discharge curves of the five composites. The discharge plateaus occurring at 0.50 and 0.20 − 0.01 V during the first discharge represent the formation of the SEI film and the lithiation reaction of silicon, respectively. During the initial charging process, the delithiation reaction of silicon corresponds to the appearance of a charging plateau between 0.30 and 0.60 V, as indicated by the corresponding CV curve.

Figure 5(d) presented the rate performance test of the five SiO@SiO₂ composites, where the curves exhibited stepwise changes corresponding to variations in current density. The cycling performance showed varying degrees of decrease with increasing current density. At higher current densities (1C), the discharge specific capacities were 1163.70 mAh·g^-1, 1218.68 mAh·g^-1, 1270.58 mAh·g^-1, 1298.40 mAh·g^-1 and 1257.55 mAh·g^-1. After returning to 0.2 C, the capacity recoveries of the five composites were 80.75%, 91.48%, 93.85%, 96.56% and 95.34%, respectively. The difference in capacity recovery rates was due to the varying thicknesses of the SiO₂ coating, which results from the varying amounts of SCA added. The greater the mass of added silane, the denser and thicker the coating layer becomes, effectively protecting the SiO particles from crumbling and pulverization during high-rate charging and discharging, thus maintaining structural stability.

The peak changes during the charging/discharging of the five composites were shown in the CV curves in Fig. 6(a-e). The peaks around 0.005-0.3 V and 0.5–0.8 V indicated the alloying and dealloying reactions of lithium in the composites^[43]. Moreover, the broad absorption peaks appearing around 0.8 V indicated that the SiO@SiO₂ composite electrode reacts irreversibly with the electrolyte to form a passivation film (SEI) on the surface of the composite. After the second and third charging/discharging cycles, the peak areas gradually increase, indicating the activation of the electrode material and the establishment of a more complete conductive channel. In comparison, the reduction peak of SiO@SiO₂-15 (Fig. 6(d)) was not prominent around 0.8 V. This was attributed to the composite forming a thin and stable SEI film during the initial charge/discharge cycle, which effectively reduces interfacial impedance. Meanwhile, with increasing cycling time, the positions of oxidation and reduction peaks did not shift significantly, indicating good cycling stability and reversibility during the charging and discharging process. In summary, applying a thin carbon coating to the surface of SiO samples can mitigate defects induced by amorphous carbon, improve the conductivity of the electrode, and ensure interfacial stability.

Figure 6(f) showed the AC impedance (EIS) tests performed on the five composite materials. Each Nyquist curve exhibited a near-semicircular arc in the high-frequency region, with the diameter of the semicircle visually representing the charge transfer impedance^[44]. Additionally, there was a diagonal line in the low-frequency region that represents the diffusion impedance of lithium ions moving through the electrolyte of the electrode material during charging and discharging^[45]. The SiO@SiO₂-15 composite exhibited the smallest charge transfer impedance (249.3 Ω), but the diffusion impedance was relatively large (5.4 Ω), likely due to the insufficient penetration of the electrolyte into the electrode material. The magnitude of the charge transfer impedance depended on the state of the SiO₂ cladding layer. When the cladding was not homogeneous, the intercalation/deintercalation process can significantly hinder charge transfer due to the crushing of the electrode material. With the further increase of SiO₂ content, the interfacial stability between the electrode material and the electrolyte improves, enhancing the electrode's conductivity and, consequently, the battery's cycling performance. However, an excessively high SiO₂ content results in a larger specific surface area, causing an irreversible capacity increase and the formation of a thicker SEI film that obstructs lithium-ion diffusion. Therefore, an appropriate SiO₂ content can improve the interfacial stability between the electrode material and the electrolyte and increase the electronic conductivity of the electrode.

In summary, the silica cladding was regulated by controlling the amount of silane coupling agent added, enabling the examination of the microscopic morphology and electrochemical characteristics of the composites. This research focused on elucidating the role and mechanism of the silica shell in enhancing the performance of SiO anode materials. Compared to SiO feedstock, SiO@SiO₂-15 exhibited excellent electrical conductivity and structural stability when the silane coupling agent was added at 15% of the mass of the SiO particles. This improvement is primarily due to the core-shell structure. The SiO₂ shell, being more rigid than the carbon shell, effectively mitigates material pulverization during charge and discharge cycles, consequently enhancing electrical conductivity. The initial specific capacity of the SiO@SiO₂-15 composite reached 2160.62 mAh·g^− 1, with a first coulombic efficiency of 70.06%. Furthermore, the composite demonstrates excellent discharge capacity (1345.54 mAh·g^− 1) and cycling stability (62.28%) after 100 cycles. A reversible capacity of 2160.62 mAh·g^− 1 was achieved after 1 C charge/discharge, and a capacity recovery rate of 97.28% was observed upon returning to 0.2 C. In conclusion, the SiO@SiO₂ core-shell anode design offers a promising approach to enhance conductivity, improve ion transport efficiency, and boost the cycling performance of the material for next-generation energy storage systems.

Conflict of interest:

There are no conflicts of interest to declare.

Funding

for this work was supported by the Sub-Project of National key research and development program: Study on surface modification and electrical performance evaluation of recycled lithium metal anode materials (2023YFC3905904-03), Natural Science Basic Research Program of Shaanxi Province (2020JQ-679), (2021JM-370) and (2019JLM-36).

Author Contribution

Qian Li provided Funding acquisition and supervised the study.Shuoran Wang performed the experiments and wrote the original manuscript.Yan Wang reviewed and edited the manuscript.Na Huang, Changlin Li, and Wenpei Wang assisted with the experiments and performed the electrochemical performance tests.Xihong He, Jinjing Du, Hongzhou Ma and Yaqing Weng supervised the study.All authors discussed the results and commented on the manuscript.

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Design and synthesis of SiO@SiO₂ core-shell anodes for enhanced performance in lithium-ion batteries

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1 Introduction

2 Experimental

2.1 Materials synthesis

2.2 Structure characterization

2.3 Electrochemical characterization

3 Results and discussion

4 Conclusion

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