Editorial Feature

Flexible Technique for Synthesis of Silicon Nanowires on Carbon Cloth for Li-Ion Battery Applications

Si has emerged as a possible candidate for next-generation Li-ion battery anodes due to its better theoretical gravimetric capacity than graphite. Additionally, Si in nanowire (NW) form is better able to handle the unfavorable impacts of volume expansion and contraction during cycling, as well as the resulting loss of current collector contact.

Flexible Technique for Synthesis of Silicon Nanowires on Carbon Cloth for Li-Ion Battery Applications

Image Credit: Love Employee/Shutterstock.com

SiNWs may also be generated directly from the electrode current collector, eliminating the requirement for inert electrode materials. However, there are still issues with Si NW manufacture and scalability, particularly when using complicated and expensive chemical vapor deposition (CVD) equipment.

Another barrier to wide-scale use of directly-grown NW anodes is the low mass loadings (usually <0.5 mg/cm2) and associated areal capacities obtainable by traditional synthetic techniques. Due to their enhanced nucleation sites for Si NW development, high surface area (HSA) current collectors provide a promising solution to this problem, allowing for greater mass loadings.

Si NWs grown on flexible HSA carbon substrates had previously been shown to be more suitable for wearable electronics or flexible devices, with the carbon cloth (CC) having the extra benefit of storing additional charge.

The creation of a woven Si/C fabric with weight loadings of 13.75 mg/cm2 and areal capacities of 14.3 mAh/cm2 is a more recent development on flexible Si-based anodes. Microscrolled, carbon-coated Si nanoparticles were fixed on conductive carbon nanotubes and then restricted in cellulose carbon rolls as an alternative strategy to generate flexible Si-based anodes.

Although good cycling stability over 800 cycles was observed, production of the active substance required long processing times (>48 hours) and high temperatures (700 °C).

For HSA CC substrates, researchers describe a Si NW synthesis technique in a new study published in Material Today Energy The method combines the advantages of the previously described growing system, which is a simple glassware-based system that uses liquid Si precursors at low temperatures (460 °C) and ambient pressures, with solvent-free/CVD conditions that are ideal for Si NW growth on CC.

When compared to NWs grown on planar substrates, the CC substrate guarantees that the anodes are flexible and allow for a larger mass loading. Higher areal capacities (2.0 mAh/cm2 on CC versus 0.3 mAh/cm2 on SS), as well as consistent cycling performance and high rate capabilities, result from this.

Methodology

Fluorochem provided phenylsilane (PS, 97%) and kept it in an Ar-filled glovebox. To enhance the surface area, stainless steel (SS, 316) foil with a thickness of 0.1 mm was roughened with sandpaper. Reactions were carried out in a Pyrex 100 mL round-bottomed flask with a long neck. Before being placed in the flask, the growth substrates were placed in a custom-made holder. A water condenser connected the flask to a Schlenk line arrangement.

Two electrode coin cell (CR2032) type cells were assembled in an Ar-filled glovebox to test electrochemical performance. Si NWs on an SS (or CC) current collector, Li foil as the counter and reference electrode, and a Celgard separator made up the cells.

On a Hitachi SU-70 system based between 5 and 20 kV, a scanning electron microscopy (SEM) investigation was done. The NWs were sonicated from the growing substrate before being drop cast onto a lacy carbon TEM grid for transmission electron microscopy (TEM) examination.

Results

Figures 1a and b show the Si NW synthetic method, which is a modification of the previously disclosed SVG NW growing procedure. In the reaction chamber, the technique allows for huge growth substrates (Figure 1c). CC is also very flexible, with no visible Si NW delamination when twisted or bent (Figure 1d).

a) Schematic illustration representing glassware based CVD growth of Si NWs. (b) Schematic description of Si NW growth on CC. c) Optical photograph showing SiNW (matt yellow) coverage on CC (black) with bare CC anode and SiNW@CC anode (inset). d) Images showing the flexible nature of the SiNW@CC substrates.

Figure 1. a) Schematic illustration representing glassware based CVD growth of Si NWs. (b) Schematic description of Si NW growth on CC. c) Optical photograph showing SiNW (matt yellow) coverage on CC (black) with bare CC anode and SiNW@CC anode (inset). d) Images showing the flexible nature of the SiNW@CC substrates. Image Credit: Storan, et al., 2022

CC was used as an HSA conductive current collector substrate with the optimal Si NW growth conditions (460 °C, 20 minutes) (Figure 2a-c). The fibrous structure of CC is shown via SEM examination (Figure 2a). With Sn seeds, SEM exhibited dense coverage of all fibers on the substrate (Figure 2b). The high density of Si NWs formed on the CC fibers was found by post-synthesis SEM examination (Figure 2c).

Si NWs are so densely packed that the individual carbon fibers’ surfaces are no longer visible. A seeded NW was discovered using TEM and STEM analysis (Figure 2d), with EDS mapping revealing a Sn (purple) seed with a Si (yellow) body (Figure 2e).

Schematic and SEM images of a) bare CC, b) Sn coated CC and c) SiNW coated CC. d) TEM and e) STEM image of a Sn seeded SiNW with corresponding Sn and Si EDS elemental maps.

Figure 2. Schematic and SEM images of a) bare CC, b) Sn coated CC and c) SiNW coated CC. d) TEM and e) STEM image of a Sn seeded SiNW with corresponding Sn and Si EDS elemental maps. Image Credit: Storan, et al., 2022

In a 1 M LiPF6 in EC/DEC + 10 wt.% FEC at a current density of 200 mA/g, 1.1 mg Si/cm2 anodes were cycled in the voltage range of 0.01-1 V vs Li/Li+ (Figure 3a). The voltage profile study clearly shows negligible capacity decline after 200 cycles, demonstrating this high capacity retention (Figure 3b).

Figure 3c shows cyclic voltammograms (CVs) of bare CC and Si NW coated CC (SiNW@CC), which revealed that the SiNW@CC CV had more peaks than the bare CC-CV. Figure 3d shows that at 200 mA/g, areal capacities of 2.0 mAh/cm2 were attained in a rate capability test (RCT).

a) Columbic efficiency, charge and discharge areal capacities of SiNW@CC anode cycled at 200 mA/g, showing stable cycling performance and high Columbic efficiency. b) Voltage profile of SiNW@CC showing excellent capacity retention after 200 cycles. c) CV plots of bare CC (black) and SiNW@CC (purple) scanned at 0.025 mV s-1 between 0.01-1 V d) Rate capability testing of SiNW@CC anode showing the relationship between current density and achievable areal capacity. e) Voltage profiles of rate capability testing of SiNW@CC showing the decreasing capacity with increasing current density with good recovery when current density is returned to 200 mA/g.

Figure 3. a) Columbic efficiency, charge and discharge areal capacities of SiNW@CC anode cycled at 200 mA/g, showing stable cycling performance and high Columbic efficiency. b) Voltage profile of SiNW@CC showing excellent capacity retention after 200 cycles. c) CV plots of bare CC (black) and SiNW@CC (purple) scanned at 0.025 mV s-1 between 0.01-1 V d) Rate capability testing of SiNW@CC anode showing the relationship between current density and achievable areal capacity. e) Voltage profiles of rate capability testing of SiNW@CC showing the decreasing capacity with increasing current density with good recovery when current density is returned to 200 mA/g. Image Credit: Storan, et al., 2022

After the first and 50th cycles of the SiNW@CC-based battery, electrochemical impedance spectroscopy (EIS) study was performed (Figure 4a). After the first and 50th cycles, the corresponding RS stayed the same, whereas RSEI reduced from 64.8 Ohm to 31.1 Ohm and Rct decreased from 198.10 Ohm to 110.1 Ohm, respectively (Figure 4b).

The production of porous interconnected and mesh-like Si was also confirmed by post-mortem SEM examination (Figure 4c, d).

a) Nyquest plot of SiNW@CC cell after 1 cycle and 50 cycles. b) Bar chart revealing the difference in RSEI and RCT after the 1st and 50th cycles. c) And d) SEM images showing the porous amorphous Si ligament-like structure after 50 cycles.

Figure 4. a) Nyquest plot of SiNW@CC cell after 1 cycle and 50 cycles. b) Bar chart revealing the difference in RSEI and RCT after the 1st and 50th cycles. c) And d) SEM images showing the porous amorphous Si ligament-like structure after 50 cycles. Image Credit: Storan, et al., 2022

The mesh exhibits good adhesion to the CC substrate, as evidenced by the fact that it is still adhering to it after 50 cycles with no symptoms of delamination from the CC current collector. The evidence of porosity network creation during cycling is further supported by post-mortem TEM examination.

Conclusion

Finally, researchers have shown that SiNW@CC can develop to be used as Li-ion battery anodes. In comparison to existing state-of-the-art CVD technologies, which employ greater temperatures, lower pressures, and longer reaction times, the growth conditions are appealing. Si NWs grown on CC have excellent charge and discharge capacities (>2mAh/cm2), excellent rate capability performance, and steady cycling capacity retention of 80% after 200 cycles.

This study demonstrated a practical approach for the quick and easy synthesis of Si NWs on CC for Li-ion battery applications.

Journal Reference:

Storan, D., Ahad, S. A., Forde, R., Kilian, S., Adegoke, T. E., Kennedy, T., Geaney, H. and Ryan, K. M. (2022) Silicon Nanowire Growth on Carbon Cloth for Flexible Li-ion Battery Anodes. Materials Today Energy. Available Online: https://www.sciencedirect.com/science/article/pii/S2468606922000880.

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Megan Craig

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Megan Craig

Megan graduated from The University of Manchester with a B.Sc. in Genetics, and decided to pursue an M.Sc. in Science and Health Communication due to her passion for learning about and sharing scientific innovations. During her time at AZoNetwork, Megan has interviewed key Thought Leaders across several scientific, medical and engineering sectors and attended prominent exhibitions worldwide.

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