In situ growth of a carbon nanofiber/Si composite and its application in Li-ion storage

doi:10.1016/S1872-5805(08)60042-6

New Carbon Materials

Volume 24, Issue 2, June 2009, Pages 124-130

https://doi.org/10.1016/S1872-5805(08)60042-6 Get rights and content

Abstract

A CNF/Si composite was synthesized in situ by growing carbon nanofibers on the surface of silicon particles through catalytic chemical vapor deposition. Microstructures of the composites were characterized by scanning and transmission electron microscopy, and X-ray diffraction. Electrochemical measurements indicated that the composite showed higher reversible capacity (1 042 mAh/g) and better cyclability than did a CNF-Si mixture prepared by simple mechanical milling. A structural evolution mechanism is proposed to explain the superior electrochemical performance of the CNF/Si composite electrode in comparison with the CNF-Si mixture. Scanning electron microscopy and ac impedance analysis indicated that the electrochemical performance can be attributed to the good contact of the in situ grown carbon fiber with the silicon particles.

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Cited by (20)

Recent progress in the carbon-based frameworks for high specific capacity anodes/cathode in lithium/sodium ion batteries
2021, Xinxing Tan Cailiao/New Carbon Materials
Secondary-ion batteries, such as lithium-ion (LIBs) and sodium-ion batteries (SIBs), have become a hot research topic owing to their high safety and long cycling life. The electrode materials for LIB/SIBs need to be further developed to achieve high energy and power densities. Anode/cathode active materials based on their alloying/dealloying with lithium, such as the anode materials of silicon, phosphorus, germanium and tin, and the cathode material of sulfur, have a high specific capacity. However, their large volume changes during charging/discharging, the insulating nature of phosphorus and sulfur, as well as the shuttling of polysulfides in a battery with a sulfur cathode decrease their specific capacity and cycling performance. The formation of dendrites in anodes during the deposition/dissolution of Li and Na leads to severe safety issue and hinders their practical use. Carbon materials produced from abundant natural resources have a variety of structures and excellent conductivity making them suitable host frameworks for loading high specific capacity anode/cathode materials. Recent progress in this area is reviewed with a focus on the factors affecting their electrochemical performance as the hosts of active materials. It is found that the mass loading of the active materials and the energy density of the batteries can be enhanced by increasing the specific surface area and pore volume of the carbon frameworks. Large volume changes can be efficiently accommodated using high pore volume carbon frameworks and a moderate loading of the active material. Suppression of the shuttling of polysulfides and therefore a long cycling life can be achieved by increasing the number of binding sites and their binding affinity with polysulfides by surface modification of the carbon frameworks. Dendrite growth can be inhibited by a combination of a high specific surface area and appropriate interface modification. Rate performance can be improved by designing the pore structure to shorten Li⁺/Na⁺ diffusion paths and increasing the electrical conductivity of the carbon frameworks. DFT calculations and simulations can be used to design the structures of carbon frameworks and predict their electrochemical performance.
Synthesis and electrochemical performance of transition metal-coated carbon nanofibers as anode materials for lithium secondary batteries
2018, Journal of Industrial and Engineering Chemistry
Citation Excerpt :
Thus, they can be employed in electrodes of fuel cells, absorbents, and energy storage. Since physicochemical properties of carbon nanofibers such as diameter, presence of bonds, and number of layers can be selected by changing synthetic methods and conditions, carbon nanofibers might be promising materials to replace graphite-based anode active materials with structural limitation [11–18]. Since carbon-based anode materials have problems such as low charge/discharge capacity and low retention rate due to their high irreversible capacity, many studies are being actively conducted on transition metals as anode materials for lithium secondary batteries.
In this study, transition metal coated carbon nanofibers (CNFs) were synthesized and applied as anode materials of Li secondary batteries. CNFs/Ni foam was immersed into 0.01 M transition metal solutions after growing CNFs on Ni foam via chemical vapor deposition (CVD) method. Transition metal coated CNFs/Ni foam was dried in an oven at 80 °C. Morphologies, compositions, and crystal quality of CNFs-transition metal composites were characterized by scanning electron microscopy (SEM), Raman spectroscopy (Raman), and X-ray photoelectron spectroscopy (XPS), respectively. Electrochemical characteristics of CNFs-transition metal composites as anodes of Li secondary batteries were investigated using a three-electrode cell. Transition metal/CNFs/Ni foam was directly employed as a working electrode without any binder. Lithium foil was used as both counter and reference electrodes while 1 M LiClO₄ was employed as the electrolyte after it was dissolved in a mixture of propylene carbonate:ethylene carbonate (PC:EC) at 1:1 volume ratio. Galvanostatic charge/discharge cycling and cyclic voltammetry measurements were taken at room temperature using a battery tester. In particular, the capacity of the synthesized CNFs-Fe was improved compared to that of CNFs. After 30 cycles, the capacity of CNFs-Fe was increased by 78%. Among four transition metals of Fe, Cu, Co and Ni coated on carbon nanofibers, the retention rate of CNFs-Fe was the highest at 41%. The initial capacity of CNFs-Fe with 670 mAh/g was reduced to 275 mAh/g after 30 cycles.
Synthesis and electrochemical performance of transition metal-coated carbon nanofibers on ni foam as anode materials for lithium secondary batteries
2018, Carbon-Based Nanofillers and Their Rubber Nanocomposites: Carbon Nano-Objects
As a new generation of green rechargeable batteries, the lithium ion secondary battery has many advantages over other candidates, such as better portability, higher energy density, longer cycle life, and nonmemory effect, etc. It is widely used not only in the electronic products, small electric tools, aerospace instruments, and related industries, but also as one of the backup power supplies for electric vehicles, which attracts widespread concerns around the world. The electrode material is an important component of a lithium ion battery, and its research has been a crucial role as one of the key subsystems for the development of the lithium-ion battery. In this study, transition metal-coated carbon nanofibers (CNFs) were synthesized and applied as anode materials of Li secondary batteries. Carbon nanofibers/Ni foam was dipped into 0.01 M transition metal solutions after growing carbon nanofibers on Ni foam via the chemical vapor deposition (CVD) method. The transition metal-coated carbon nanofibers/Ni foam was dried in an oven at 80 °C. The morphologies, compositions, and crystal quality of carbon nanofibers/transition metal composites were characterized by scanning electron microscopy (SEM), Raman spectroscopy (Raman), and X-ray photoelectron spectroscopy (XPS). The electrochemical characteristics of carbon nanofiber/transition metal composites as anodes of Li secondary batteries were investigated using a three-electrode cell. The transition metals/carbon nanofibers/Ni foam was directly employed as a working electrode without any binder, and lithium foil was used as both the counter and reference electrodes. 1 M LiClO₄ was employed as the electrolyte and was dissolved in a mixture of propylene carbonate:ethylene carbonate (PC:EC) at a 1:1 volume ratio. The galvanostatic charge/discharge cycling and cyclic voltammetry measurements were taken at room temperature using a battery tester.
Synthesis and electrochemical performance of ruthenium oxide-coated carbon nanofibers as anode materials for lithium secondary batteries
2016, Applied Surface Science
Citation Excerpt :
The carbon nanofibers are carbon fibers with micro graphite crystal structures having excellent chemical stability, electrical conductivity, and high energy efficiency. Because they have a larger specific surface area than conventional carbon materials, they are expected to relatively easily react with ions as the anode material of Li secondary batteries [3–6,9–12]. However, the carbon-based anode material has some problems such as low charge/discharge capacity and efficiency because it has a high irreversible capacity.
In this study, ruthenium oxide (RuO₂) coated carbon nanofibers (CNFs) were synthesized and applied as anode materials of Li secondary batteries. The CNFs were grown on Ni foam via chemical vapor deposition (CVD) method after CNFs/Ni foam was put into the 0.01 M RuCl₃ solution. The ruthenium oxide-coated CNFs/Ni foam was dried in a dryer at 80 °C. The morphologies, compositions, and crystal quality of RuO₂/CNFs/Ni foam were characterized by SEM, EDS, XRD, Raman spectroscopy, and XPS. The electrochemical characteristics of RuO₂/CNFs/Ni foam as anode of Li secondary batteries were investigated using three-electrode cell. The RuO₂/CNFs/Ni foam was directly employed as a working electrode without any binder, and lithium foil was used as the counter and reference electrodes. LiClO₄ (1 M) was employed as electrolyte and dissolved in a mixture of propylene carbonate (PC): ethylene carbonate (EC) in a 1:1 volume ratio. The galvanostatic charge/discharge cycling and cyclic voltammetry measurements were carried out at room temperature by using a battery tester. In particular, synthesized RuO₂/CNFs/Ni foam showed the highest retention rate (47.4%). The initial capacity (494 mAh/g) was reduced to 234 mAh/g after 30 cycles.
Synthesis and electrochemical performance of mesoporous SiO<inf>2</inf>–carbon nanofibers composite as anode materials for lithium secondary batteries
2016, Materials Research Bulletin
Citation Excerpt :
Carbon-based materials currently used as the anode active materials of lithium secondary batteries have the maximum capacity of 372 mAh/g, which is theoretically low capacity and substantially lower than that of newly developed anode materials. New non-carbon (silicon or tin) based anode active materials are actively being developed for high capacity and high output for applications in middle- or large-sized lithium secondary batteries in the future [1–4,11–14]. Silicon (Si) is an attractive high capacity anode material owing to its highest theoretical capacity (4200 mAh/g).
In this study, carbon nanofibers (CNFs) and mesoporous SiO₂–carbon nanofibers composite were synthesized and applied as the anode materials in lithium secondary batteries. CNFs and mesoporous SiO₂–CNFs composite were grown via chemical vapor deposition method with iron-copper catalysts. Mesoporous SiO₂ materials were prepared by sol–gel method using tetraethylorthosilicate as the silica source and cetyltrimethylammoniumchloride as the template. Ethylene was used as the carbon source and passes into a quartz reactor of a tube furnace heated to 600 °C, and the temperature was maintained at 600 °C for 10 min to synthesize CNFs and mesoporous SiO₂–CNFs composite. The electrochemical characteristics of the as-prepared CNFs and mesoporous SiO₂–CNFs composite as the anode of lithium secondary batteries were investigated using a three-electrode cell. In particular, the mesoporous SiO₂–CNFs composites synthesized without binder after depositing mesoporous SiO₂ on Ni foam showed the highest charging and discharging capacity and retention rate. The initial capacity (2420 mAh/g) of mesoporous SiO₂–CNFs composites decreased to 2092 mAh/g after 30 cycles at a retention rate of 86.4%.
Preparation and electrochemical properties of novel silicon-carbon composite anode materials with a core-shell structure
2021, Xinxing Tan Cailiao/New Carbon Materials

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RESEARCH PAPERIn situ growth of a carbon nanofiber/Si composite and its application in Li-ion storage

Abstract

Journal of Power Sources

Electrochim Acta

J Power Sources

Electrochem Commun

Electrochem Commun

Electrochim Acta

Electrochim Acta

Electrochim Acta

J Power Sources

RESEARCH PAPER
In situ growth of a carbon nanofiber/Si composite and its application in Li-ion storage