Synthesis of SiO x Nano-Powders Using a Microwave Plasma Torch at Atmospheric Pressure

The silicon oxide nano-powders (SiOx-NPs) were obtained in an atmospheric microwave plasma torch using a gas-phase silicon tetrachloride (SiCl4) with N2 and H2. The gas-phase SiCl4 was injected with H2 gas into the microwave plasma torch generated by N2 and air swirl gas, and then the dark brown powders were deposited on the inner wall of a quartz tube. The sample was analyzed by an X-ray photoelectron spectroscopy (XPS), a scanning electron microscope (SEM), an energy dispersive spectrometer (EDS), and an X-ray diffraction (XRD). The average size and oxidation x values of synthesized SiOx-NPs were approximately 230 nm and 0.91, respectively. Furthermore, the volumetric charge capacity is 1127 mAh/g and has 89.2% retention after 100 cycles.


Introduction
Nanostructures have attracted considerable attention in many research fields due to their unique low-dimensional quantum size effects, interesting geometry, and potential applications in nanotechnology.Silicon oxide nanopowders (SiO x -NPs) in particular have generated a great deal of interest for their outstanding semiconducting, mechanical, and optical properties, all of which enable them to be used as coating materials, sensitive sensors, protective layers, and blue-light-emitting diodes.These future applications, however, impose more challenging standards for a range of cell perspectives, including energy density, power performance, cycle life, and safety.While issues in these parameters need to be addressed in parallel, the simultaneous improvement of the energy density and cycle life is more critical [1]- [3].Of late, there has been a focus on SiO x -NPs (x ≈ 1) due its high charge/discharge efficiency and capacity as an alternative material to carbonaceous materials among secondary cell anode materials [4]- [7].SiO x -NPs are usually synthesized using chemical reaction routes which are often complex and offer a relatively small production yield [8] [9].The adsorptive capabilities of nano-scaled SiO x will exceed those of conventional SiO x .In this context, we report a simple synthetic method of preparing SiO x -NPs, making use of an atmospheric microwave plasma torch.

Experiment
Figure 1 shows the experimental setup for the preparation of SiO x -NPs with the microwave plasma torch.The design and operation of the atmospheric microwave plasma torch are briefly summarized here for completeness, although they have been reported in detail in our previous literatures [10]- [13].As shown in Figure 1, the microwave energy is supplied to the flowing gas at atmospheric pressure by a microwave generator, and efficient power transfer is achieved through a matching network, which basically consists of an auto-matcher, a matcher controller, and an isolator, namely, the microwave radiation generated from the magnetron passes through the circulator and the auto-matcher, is guided through a tapered waveguide, and enters the discharge tube made of a fused quartz.The center axis of the quartz dielectric tube, with an outer diameter of approximately 30 mm and a thickness of 2 mm, is located one-quarter wavelength from the short end of the waveguide and is perpendicular to the wide waveguide walls.The electric field induced by the microwave radiation in the quartz tube can be maximized by adjusting the auto-matcher.Additionally, the reflected power adjusted with the auto-matcher is less than 1% of the forward power.This produces a plasma torch with a high temperature and a high plasma density.The microwave plasma torch provides a highly unusual and reactive chemical environment at high temperatures.For example, the air microwave plasma torch produces plasma with a high temperature of ~6000 K and a high plasma density of ~10 13 /cm 3 [14].
All the gas flows in Figure 1 were controlled by mass flow controllers (MFCs).The silicon source in our experiment was silicon tetrachloride (SiCl 4 ), which has a high vapor pressure, low activation energy, and low cost.The properties mentioned above may be suitable for a plasma-enhanced gas-phase synthesis method at atmospheric pressure.SiCl 4 is handled in a glove box with a non-moisture atmosphere, and a bottle for SiCl 4 bubbling has to be packed well because of a moisture-sensitive reagent.SiCl 4 (99.9%,Aldrich) in the liquid solution is directly bubbled by argon gas and is axially injected with hydrogen gas through the Teflon tube, as shown in Figure 1, which guides a mixture of bubbled SiCl 4 and hydrogen gas into the center of the plasma flame.As shown in Figure 1, SiCl 4 in liquid solution and the inlet line of axial gases were maintained at about 65˚C by making use of automatic-controlled heaters.Nitrogen and air as swirl gas enter the microwave plasma torch via four small holes in the tangential direction of the inner surface of the quartz tube, not shown in Figure 1, and hydrogen as an additive gas was used for partial oxidation of silicon oxide formed from the decomposition and reduction of SiCl 4 .The SiO x -NPs were synthesized by 20 lpm of N 2 and 0.5 lpm air as swirl gases and 10 lpm of N 2 gas with 10 lpm of H 2 gas for SiCl 4 carrier and then SiCl 4 liquid pre-cursor of approximately 1 ml per minute (ml/min) were injected into the microwave plasma torch operated at 2 kW power.Furthermore, the swirl gases of N 2 were injected before sampling to cool down because as-produced SiO x -NPs had avoided oxidation under high temperature conditions.Once the synthesis of SiO x -NPs starts by passing through the plasma flame, a red-brownish light, like a flash, emits from the torch flame, not shown in this paper.All the samples were taken from deposits inside the quartz tube.The SiO x sample colors were strongly dependent on their valence states and became brighter when x increased.When the x value was 1.18, the color was brown, whereas it was almost white at an x value of 1.83 [15].Additionally, the size distribution of synthesized SiO x -NPs was analyzed using an SEM image (insert image) and the average size was approximately 230 nm, as shown in Figure 2(b).Figure 2(c) illustrates the EDS analysis data in the form of spectra, where the peaks corresponding to the elements Si, O, and carbon appear to be dominant, as seen in the spectra, and the data listed in Table 1 show a small amount of carbon.It is believed that the trace of carbon in the spectrum was detected due to the atmospheric pressure synthesis process and during the sampling of SiO x -NPs.For this reason, the carbon spectra were detected by EDS analysis.Hence, the synthesized SiO x -NPs were examined by performing an EDS analysis.To determine the valence state of the Si in the SiO x in synthesized SiO x , an X-ray Photoelectron Spectroscopy (XPS) analysis was conducted.

Results and Discussion
Figure 3(a) shows the Si-2p binging energy spectra of Si in the SiO x from the X-ray photoelectron spectroscopy (XPS).The analysis condition of XPS (AXIS Ultra DLD, Kratos Inc.) was a monochromatic Al Kα (1486.6 eV, 150W).The measured band of the Si-2p binding energy was divided into five sub bands: Si (99.8 eV), SiO 0.5 (100.7 eV), SiO 1.0 (101.5 eV), SiO 1.5 (102.5 eV), and SiO 2.0 (103.5 eV).The x value was calculated using the following equation [16]: where, x is the valence state of the Si in the SiO x , and a, b, c, d, and e represent the intensity of the Si-2p binding of the Si, SiO 0.5 , SiO 1.0 , SiO 1.5 , and SiO 2.0 , respectively.The normalized intensities for calculating the x values are 0.53 of Si, 0.12 of SiO 0.5 , 0.37 of SiO 1.0 , 0.77 of SiO 1.5 , and 0.32 of SiO 2.0 , respectively.In this context, the x value of synthesized SiO x was 0.91.Additionally, a comparison with the X-ray diffraction (XRD) pattern of synthesized SiO

Conclusion
The microwave plasma torch method has been developed to synthesize SiO x -NPs.The high-temperature microwave plasma flame evaporated the SiCl 4 pre-cursor and produced SiO x -NPs through the cooling of Si atoms in the downstream direction of nitrogen and air plasma torch.The SiO x -NPs can easily be obtained by making use of the microwave plasma torch, although the synthetic approach reported here is not finely controlled.The x value and average size of the synthesized SiO x were 0.91 and approximately 230 nm, respectively.The volumetric charge capacity is 1127 mAh/g and 89.2% retention after 100 cycles.This method may be suitable for direct continuous preparation and mass production of SiO x -NPs by adding a collection chamber, such as filtration apparatus.This work might provide the synthesis for controlling the x-value in SiO x -NPs by oxygen content.

Figure 1 .
Figure 1.The presentation of the synthetic system of SiO x -NPs with the atmospheric microwave plasma torch.

Figure 2
Figure 2 depicts the graph of the size distribution bars with an inert scanning electron micro-scope (SEM) image, and energy dispersive spectrometer (EDS) spectra of synthesized SiO x -NPs.The photo image of Figure 2(a) is the synthesized SiO x -NPs by the microwave plasma torch.Kim et al. reported different colors of SiO x powders in terms of oxide x values.The SiO x sample colors were strongly dependent on their valence states and became brighter when x increased.When the x value was 1.18, the color was brown, whereas it was almost white at an x value of 1.83[15].Additionally, the size distribution of synthesized SiO x -NPs was analyzed using an SEM image (insert image) and the average size was approximately 230 nm, as shown in Figure2(b).Figure2(c) illustrates the EDS analysis data in the form of spectra, where the peaks corresponding to the elements Si, O, and carbon appear to be dominant, as seen in the spectra, and the data listed in Table1show a small amount of carbon.It is believed that the trace of carbon in the spectrum was detected due to the atmospheric pressure synthesis process and during the sampling of SiO x -NPs.For this reason, the carbon spectra were detected by EDS analysis.Hence, the synthesized SiO x -NPs were examined by performing an EDS analysis.To determine the valence state of the Si in the SiO x in synthesized SiO x , an X-ray Photoelectron Spectroscopy (XPS) analysis was conducted.Figure3(a) shows the Si-2p binging energy spectra of Si in the SiO x from the X-ray photoelectron spectroscopy (XPS).The analysis condition of XPS (AXIS Ultra DLD, Kratos Inc.) was a monochromatic Al Kα (1486.6 eV, 150W).The measured band of the Si-2p binding energy was divided into five sub bands: Si (99.8 eV), SiO 0.5 (100.7 eV), SiO 1.0 (101.5 eV), SiO 1.5 (102.5 eV), and SiO 2.0 (103.5 eV).The x value was calculated using the following equation[16]:

x and commercial SiO 2
NPs are shown in Figure 3(b).The commercial SiO 2 NPs were prepared

Figure 2 .Figure 3 .
Figure 2. (a) Photo, (b) size distribution bars with insert SEM image, and (c) spectra data from EDS of synthesized SiO x -NPs.

Figure 4
shows the volumetric charge (delithiation) capacity of the anodes using the Ref.Si and synthesized SiO x -NPs as a function of cycle number and Coulomb efficiency at a 0.2 C rate between 0.01 and 1.5 V in a coin-type half-cell.The Ref. Si-NPs (average size of approximately 200 nm) showed before and after 100 cycles of charge/discharge capacity at 2343 mAh/g and 511 mAh/g, respectively.The Ref. Si-NPs showed that the highest first charge/discharge capacity faded out quickly with the increase in the number of cycles.Therefore, the retention

Figure 4 .
Figure 4. Cycle performances of the anodes using by the Ref.Si and synthesized SiO x -NPs.ratio of Ref. Si-NPs is only 21.8%.However, the synthesized SiO x -NPs demonstrated very stable cycle performance.The synthesized SiO x -NPs showed before and after 100 cycles charge/discharge capacity at 1264 mAh/g and 1127 mAh/g, respectively.Therefore, the retention rate is 89.2% after 100 charge/discharge cycles.These results were due to the large portion of Li-based oxides such as Li 2 O and Li 4 SiO 4 on the nano-particles.Li 2 O and Li 4 SiO 4 are inactive to an electrical field, but they can serve as a buffer to the expansion of Si during the lithiation process.These buffers can result in good cycle performance from the next cycle [15] [18] [19].

Table 1 .
Spectrum data from EDS analysis of synthesized SiO x -NPs.