RegisterSign in
ViewPDF
- Access throughyour institution
Article preview
- Abstract
- Introduction
- Section snippets
- References (59)
- Recommended articles (6)
Journal of Alloys and Compounds
Available online 6 January 2023
, 168743
In Press, Journal Pre-proof
What are Journal Pre-proof articles?Author links open overlay panel
Abstract
Developing an effective structure for the silicon-carbon composite that promotes electric-ionic conductivity and reduces the volume change is a key issue for Si-based anode. In this study, spherical granules comprising silicon nanoparticles (Si-NPs) grafted with nitrogen-doped carbon nanotubes (Si-NCNTs) are fabricated via spray drying followed by catalytic chemical vapor deposition (CCVD). The initial discharge and charge capacities of the Si-NCNTs are 2,457 and 1,820mAh g−1, respectively. The Si-NCNTs shows a capacity retention of 57% after 200 cycles as well as improved rate capability when compared to the Si-NPs and commercial CNTs composites (Si-CNTs) fabricated via spray drying alone. The Li+ ion-diffusion-coefficient (DLi+) of the Si-NCNTs is approximately ~three times larger than that of the Si-CNTs at critical lithiation potential. The NCNTs that form the interconnections between Si-NPs play the role of electrically conductive buffers that could accommodate the volume change produced and favor Li+ ion transport.
Introduction
The conventional lithium-ion batteries (LIBs) comprising lithium transition metal oxide and graphite as cathode and anode based on intercalation reactions, respectively, are reaching their limit of energy density [1], [2], [3]. Therefore, numerous efforts have been made to achieve a breakthrough in overcoming limitations with regard to energy density by combining these materials with anode materials that can form alloys [4], [5], [6], [7], [8]. Among these anode materials, silicon (Si) which has a high theoretical capacity (close to 4,000mAh g−1) is a promising candidate as an alternative to graphite used in the conventional anode of LIBs. However, Si generally suffers from intrinsic drawbacks such as low electrical conductivity and significant volume changes during alloying and dealloying with Li, which results in the pulverization and swelling-induced deformation of the electrodes [9], [10], [11], [12], [13].
The co-utilization of carbonaceous materials and Si has been considered the most suitable approach for the conventional LIBs to achieve high energy density with Si [14], [15], [16]. Much research has been conducted on the preparation of the Si/carbon composite using highly electrically conductive crystalline carbon such as graphite, graphitic carbon, graphene, and carbon nanotubes (CNTs) [16], [17], [18], [19], [20], [21]; various methods have also been used to prepare the composite [13], [15], [17], [22], [23]. The spray drying process is widely applied to produce Si/carbon composite particles because the process is simple and continuous as well as capable of producing spherical particles which could have high tap density [24], [25], [26], [27], [28]. In addition, since the graphene and CNTs are flexible, spherical Si/CNTs or Si/graphene composites can be prepared through the spray drying process [29], [30], [31], [32], [33]. However, it is difficult to effectively achieve high degrees of dispersion and contact between carbonaceous materials and silicon due to the density difference between silicon and carbonaceous materials [34].
Among the carbonaceous materials, CNTs have many advantages due to their high electrical conductivity, mechanical flexibility and chemical stability [35], [36], [37]. Low-dimensional structured materials, such as CNT, have been developed for improved electrochemical properties [38], [39]. The low dimensional structures have shown fast electron transfer and shortened lithium diffusion pathway due to their large surface area. Park et al. prepared the Si/CNT/C composite using the spray drying process. To improve contact between Si and CNTs, amorphous carbon was introduced in the Si/CNT composite [20]. However, low electrical conductivity could hinder Li+ ion and electron transport across the amorphous carbon created from sucrose. Han et al. used copper silicide as a mechanical matrix to integrate Si and CNTs using the spray drying process followed by high-temperature carbonization processes [40]. Copper silicide successfully contributed to improving cycling stability owing to its good mechanical strength. However, the undesirable capacity loss brought about by the electrochemically inactive copper silicide, and its insufficient dispersion among Si and CNTs remained unsolved. When it comes to fabricating Si/CNTs composite materials, it is important to avoid contact among Si particles which would induces local volumetric deformation during lithiation and delithiation. CNTs connecting every single Si particle could play the role of a buffer preventing volume expansion, and additionally could contribute to a better rate performance through its superior electrical conductivity. Furthermore, substitutional doping of nitrogen in the lattice of CNT is known to increase the rate capabilities by contributing free electrons to the conduction band [41].
In this study, Si aggregates with the catalyst uniformly distributed for the growth of nitrogen-doped CNTs (NCNTs) were first fabricated via the spray drying method. Next, the aggregates were post-treated by the catalytic chemical vapor deposition (CCVD) method where the NCNTs produced are dispersed in the composite as the electrical bridges, to form silicon nanoparticles grafted with nitrogen-doped carbon nanotubes (Si-NCNTs). The structure and properties of the carbonaceous materials converted from various carbon sources are very important in electrochemical fields [42], [43]. In this study, the NCNTs were grown on the internal and external surfaces of the Si aggregates using the CHx and NHx gases formed by the decomposition of dicyandiamide. The Li-ion cell applied with the Si-NCNTs showed highly improved capacity retention (57% after 200 cycles) and rate capability (48% at 3Ag−1) compared to Si-CNTs (under 50% within 31 cycles and 22.5% at 3Ag−1, respectively).
Section snippets
Sample preparation
The Si-NCNTs powders were fabricated via the spray drying process followed by CCVD (Fig. S1). The precursor solution was prepared by dissolving 0.01M nickel nitrate hexahydrate (Samchun, 98%) in 200mL of distilled water, the reduced phase of which serves as a seed for the growth of NCNTs. 1g of silicon nanoparticles (NanoAmor, ~100nm) were then dispersed in the solution with vigorous stirring by a magnetic stirrer at a rotating speed of 600rpm to assist their wetting and dispersion. The
Results and discussions
The mechanism of formation of the Si-NCNTs composite synthesized by the spray drying and post-treatment is illustrated in Scheme 1. In the first step, as the spray solution passes through the tip of the twin-fluid atomizer of the spray dryer, the compressed air induces it to split into droplets and travel through the cylindrical drying chamber; the cruising droplets which contain silicon nanoparticles and dissolved nickel nitrate undergo volume precipitation and desiccation. The drying of the
Conclusions
In this study, spherical granules comprising silicon nanoparticles grafted with nitrogen-doped carbon nanotubes are fabricated via spray drying followed by CCVD. The nitrogen-doped CNTs are highly dispersed in the composite and connect every single primary Si particle, providing sufficient electrical contact to the Si particle and buffer for the volumetric expansion of Si. The Li+ ion cells with Si-NCNTs showed high reversible capacity (1,820mAh g−1) as well as superior capacity retention (57%
CRediT authorship contribution statement
Hyemin Kim; Conceptualization, Data curation, Methodology, Investigation. Seongmin Shin; Methodology, Investigation. Dae Soo Jung; Data curation, writing, Jung Hyun Kim; Supervision, Writing – review & editing
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
ACKNOWLEDGEMENTS
This work was supported by the “Policy R&D program” funded by the Korea Institute of Ceramic Engineering and Technology, Republic of Korea (KPP21008). This work was supported by the Technology Innovation Program (20009985) funded by the Ministry of Trade, Industry & Energy.
References (59)
- N. Ding et al.Determination of the diffusion coefficient of lithium ions in nano-Si
Solid State Ion
(2009)
- X. Li et al.High concentration nitrogen doped carbon nanotube anodes with superior Li+ storage performance for lithium rechargeable battery application
J. Power Sources
(2012)
- C.-d Kim et al.Effect of NH3 gas ratio on the formation of nitrogen-doped carbon nanotubes using thermal chemical vapor deposition
Mater. Chem. Phys.
(2016)
- Y.J. Oh et al.Highly efficient hierarchical multiroom-structured molybdenum carbide/carbon composite microspheres grafted with nickel-nanoparticle-embedded nitrogen-doped carbon nanotubes as air electrode for lithium-oxygen batteries
Chem. Eng. J
(2018)
- Q. Kong et al.Influence of multiply modified FeCu-montmorillonite on fire safety and mechanical performances of epoxy resin nanocomposites
Thermochim. Acta
(2022)
- Y. Bie et al.Porous microspherical silicon composite anode material for lithium ion battery
Electrochim. Acta
(2015)
- X. Jia et al.Building flexible Li4Ti5O12/CNT lithium-ion battery anodes with superior rate performance and ultralong cycling stability
Nano Energy
(2014)
- D. Lee et al.Controlled swelling behavior and stable cycling of silicon/graphite granular composite for high energy density in lithium ion batteries
J. Power Sources
(2020)
- Q. Pan et al.Micro-sized spherical [emailprotected]@graphene prepared by spray drying as anode material for lithium-ion batteries
J. Alloys Compd
(2017)
- L. Wu et al.High tap-density and high performance LiFePO4/C cathode material synthesized by the combined sol spray-drying and liquid nitrogen quenching method
Mater. Lett.
(2012)
Electrochim. Acta
(2012)
J. Power Sources
(2019)
J. Power Sources
(2018)
J. Power Sources
(2020)
Chem. Eng. J
(2019)
J. Energy Chem
(2018)
Nano Energy
(2019)
Energy Storage Mater
(2021)
Energy Storage Mater
(2021)
A reflection on lithium-ion battery cathode chemistry
Nat. Commun.
(2020)
Electrode Degradation in Lithium-Ion Batteries
ACS Nano
(2020)
Considering Critical Factors of Silicon/Graphite Anode Materials for Practical High-Energy Lithium-Ion Battery Applications
Energy Fuels
(2020)
A Mapping of the Physical and Electrochemical Properties of Composite Lithium‐Ion Batteries Anodes Made from Graphite, Sn, and Si
Batter. Supercaps
(2020)
Graphite/nano-Sn composite anode materials for lithium-ion batteries, Energy Storage
Sci. Technol
(2021)
Alloying Germanium Nanowire Anodes Dramatically Outperform Graphite Anodes in Full-Cell Chemistries over a Wide Temperature Range
ACS Appl. Energy Mater
(2021)
Integration of Graphite and Silicon Anodes for the Commercialization of High‐Energy Lithium‐Ion Batteries
Angew. Chem. Int. Ed.
(2020)
Challenges and Recent Progress on Silicon‐Based Anode Materials for Next‐Generation Lithium‐Ion Batteries
Small Struct
(2021)
Review on Carbon and Silicon Based Materials as Anode Materials for Lithium Ion Batteries
J. New Mat. Electrochem. Systems
(2010)
Confronting the Challenges of Next‐Generation Silicon Anode‐Based Lithium‐Ion Batteries: Role of Designer Electrolyte Additives and Polymeric Binders
ChemSusChem
(2019)
Cited by (0)
Recommended articles (6)
Research article
The TOPSIS method to identify the optimal machining condition with reduced particle emission during machining of the Al-Si based 1%SiC reinforced nanocomposite materialMaterials Today: Proceedings, 2022
The machining was done following the Taguchi’s L9 orthogonal array. The work - piece was Al-Si based silicon carbide nanoparticle reinforced nanocomposite material. The objective of the present study is to identify the machining condition such that the emission of the particle during the machining of the nanocomposite is minimized. The health problem arises due to the emission of the particle during the machining of the nanocomposite. The machining was performed on the lathe by using the Tungaloy made carbide tool insert. The speed (v), feed (f) and depth of cut (DOC, d) were the machining parameters. The chip reduction coefficient (CRC) and surface roughness (Ra) were the measured output responses. The scanning electron microscopy was performed for the chip surfaces. The TOPSIS (Technique for order preference by similarity to ideal solution) method was applied to optimize the machining parameters. The method is very effective to optimize the machining parameters. The analysis of variance (ANOVA) was done to find out the influential parameters for CRC and Ra minimization. The optimal solution was found for v=122.02m/min, feed=0.06mm/rev., and d=1.5mm. The optimal solution was validated with a qualitative assessment. This ensured the novelty of the work. The studies on chip types, machined surfaces etc. further indicated that the TOPSIS method was very effective in identifying the optimal parameters with reduced particle emission.
Research article
Experimental investigation of cutting conditions in turning of Al-MMCMaterials Today: Proceedings, 2022
Machining of Aluminium Metal Matrix Composite (Al-MMC) is one of the challenging tasks due to its properties. Prediction of optimum machining conditions by systematic way is a difficult task which can be used for improve the performance of machining as well as sustainability assessment. In this investigation, turning operation is performed on Al-MMC using different machining conditions such as dry condition, wet condition and solid lubrication. Taguchi L9 orthogonal matrix is considered for performing the experiments. Cutting speed, feed rate and depth of cut are considered as input parameters. Output parameter considered is machined surface roughness. Taguchi procedure is adopted for finding optimum process parameters and its significance. The result revealed that solid lubrication is provided better surface finish than dry and wet conditions. It is observed that lower value of surface roughness by reducing the frictional coefficient in solid lubrication than dry and wet conditions. This work is used to find out the suitable machining conditions by statistical approach.
Research article
RF plasma treatment of shallow ion-implanted layers of germaniumMaterials Science in Semiconductor Processing, Volume 42, Part 2, 2016, pp. 204-209
RF plasma annealing (RFPA) and rapid thermal annealing (RTA) of high-dose implanted n-type and p-type amorphized Ge layers have been studied by Raman scattering spectroscopy and X-ray diffraction techniques. It is shown that recrystallization of n-Ge implanted by ions requires higher RTA temperatures and power density of RFPA as compared to p-Ge implanted by P+ ions with the same dose. The RFPA has been performed at considerably lower temperatures than RTA and resulted in the formation of a sharp interface between the implanted and underlying Ge layers both for ion implantation and P+ ions implantation.
Research article
EditorialProcedia CIRP, Volume 43, 2016, p. 2
Research article
Effect of electron-beam treatment on the structure and properties of (B + Cr) film deposited on a high-entropy alloy AlCrFeCoNiMaterials Letters, Volume 335, 2023, Article 133704
The B + Cr film with a thickness of ∼ 1 µm was deposited by plasma-assisted RF sputtering on AlCrFeCoNi HEA of non-equiatomic composition prepared by WAAM. The subsequent treatment included electron beam irradiation of the surface with parameters as follows: energy density Es=(20–40) J/cm2, pulse duration 200 µs, frequency 0.3 s−1, number of pulses 3. It has been proved that microhardness increases by 2 times and wear resistance – by 5 times, whereas friction coefficient decreases by 1.3 times at an energy density Es = 20 J/cm2. High-speed crystallization of the surface layer leads to the formation of a cellular structure with cell sizes (150–200) nm. The increase in strength and tribological properties effected by electron beam treatment has been interpreted with the three factors in view: (1) the decreasing cell size, (2) formation of chromium and aluminum oxyborides, (3) formation of a HEA crystal lattice incorporating solid solution of boron.
Research article
PrefaceProcedia Manufacturing, Volume 10, 2017, pp. vii-viii
© 2023 Published by Elsevier B.V.
FAQs
How carbon nanotubes are synthesized by catalytic chemical vapor deposition? ›
In the synthesis of CNTs by CVD, catalyst is deposited on substrate and then nucleation of catalyst is carried via chemical etching (as ammonia) or thermal annealing. The pre-prepared supported material is then placed in a tabular reactor for growth process.
How would you prepare carbon nanotubes CNTs using chemical vapor deposition CVD technique and discuss in detail? ›The synthesis of CNTs (single- or multiple-walled) by CVD involves the catalytic decomposition of a carbon pre- cursor (e.g., CO, hydrocarbons, or alcohol) on nanostruc- tured transition metal catalyst like Co, Ni, or Fe. Typical CVD temperatures vary between 600 and 1000 °C.
How are carbon nanotubes fabricated? ›Carbon nanotubes for thin film transistors are usually synthesized by thermal CVD or plasma-enhanced chemical vapor deposition (PECVD). Floating catalyst chemical vapor deposition (FCCVD) is also an alternative for CNT growth.
What is catalyzed chemical vapor deposition? ›Catalytic chemical vapor deposition (CCVD) is another efficient and low-cost method for the mass production of highly pure carbon nanotubes (CNTs). In this process, CNTs are produced by the catalytic de- composition of hydrocarbon vapors.
What is chemical Vapour deposition method for synthesis of nanotubes? ›The chemical vapor deposition method is to cleave a carbon atom-containing gas continuously flowing through the catalyst nanoparticle to generate carbon atoms and then generate CNTs on the surface of the catalyst or the substrate.
What is CVD method for carbon nanotubes? ›CVD is the most widely used method for the production of carbon nanotubes. For this purpose, the metal nanoparticles are mixed with a catalyst support such as MgO or Al2O3 to increase the surface area for higher yield of the catalytic reaction of the carbon feedstock with the metal particles.
Which method uses catalyst for the synthesis of CNT? ›Catalytic chemical vapor deposition (CCVD) has become the standard technique for CNT synthesis.
Is the most common method for fabricating nanotubes? ›- CVD is the most popular technique used to form CNTs due to its distinct advantages over the other techniques. ...
- The nature of the catalyst used by different research groups to obtain different products in the fabrication process has been varied.
- 3.1. Physical state of the catalyst. The first effort to observe the carbon filament growth process in-situ was made by Baker et al. ...
- 3.2. Mode of carbon diffusion. ...
- 3.3. Chemical state of the catalyst.
But catalytic chemical vapor deposition (CCVD) is currently the standard technique for the synthesis of carbon nanotubes. This technique allows CNTs to expand on different of materials and involves the chemical breakdown of a hydrocarbon on a substrate.
Which material is suitable for fabrication of carbon nanotube field effect transistor? ›
CNT-FET was fabricated through conventional photolithography method and drop coating CNT between two electrodes Au/Ti on the silicon dioxide/silicon substrate.
How single walled carbon nanotubes are synthesized? ›The synthesis of bulk amounts of high quality single-walled carbon nanotubes (SWNTs) is accomplished by optimizing the chemical compositions and textural properties of the catalyst material used in the chemical vapor deposition (CVD) of methane.
What are the steps of CVD process? ›The main steps that occur in a typical CVD process can be summarized as follows [14]: (1) transport of reacting gaseous species to the surface of a substrate, (2) adsorption of the species on that surface, (3) heterogeneous surface reaction catalyzed by the surface of the substrate, (4) surface diffusion of the species ...
What are the advantages of chemical Vapour deposition method? ›Some of the advantages of CVD are production of uniform film with low porosity, high purity, and stability. However, it has some disadvantages also, as it requires highly expensive instrumentation and emits toxic gaseous by-products during reaction.
What are the three types of catalyst in chemical reaction? ›Catalysts can be categorized as homogeneous, heterogeneous, or enzymatic. Homogeneous catalysts exist in the same phase as the reactants, whereas heterogeneous catalysts exist in a different phase than the reactants.
What happens in chemical Vapour deposition? ›Chemical Vapor Deposition (CVD) is a process in which the substrate is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired thin film deposit.
Which chemical methods are used to synthesize nano materials? ›Two main approaches are used for the synthesis of nanomaterials (Fig. 1): top-down approaches and bottom-up approaches.
How many methods are used to prepare carbon nanotubes? ›The production of carbon nanotubes can be done by plasma based synthesis method or arc discharge evaporation method, laser ablation method, thermal synthesis process, chemical vapor deposition and by plasma-enhanced chemical vapor deposition.
What are the three types of carbon nanotubes? ›These three types of CNTs are armchair carbon nanotubes, zigzag carbon nanotubes, and chiral carbon nanotubes. The difference in these types of carbon nanotubes are created depending on how the graphite is “rolled up” during its creation process.
Why is it preferred to use carbon nanotubes as catalysts in chemical industries? ›The exceptional physical properties of carbon nanotubes (CNTs) such as large specific surface areas, excellent electron conductivity incorporated with the good chemical inertness, and relatively high oxidation stability makes it a promising support material for heterogeneous catalysis.
Which method is best for synthesis of nanoparticles? ›
Chemical reduction is an effective wet-chemical method for making zero-valent nanoparticles based on chemical-reducing aqueous salts of metals, such as silver nitrate (AgNO3) in the case of synthesis of silver nanoparticles, for instance.
Which type of catalyst is used in catalytic reactions? ›Catalytic converters contain transition metal catalysts embedded on a solid phase support. The solid-phase catalyst comes into contact with gases from the car's exhaust stream, increasing the rate of reactions to form less toxic products from pollutants in the exhaust stream such as carbon monoxide and unburnt fuel.
What is the correct method for synthesis of nanoparticles? ›The Polyol method is a chemical method for the synthesis of nanoparticles. This method uses nonaqueous liquid (polyol) as a solvent and reducing agent. The nonaqueous solvents that are used in this method have an advantage of minimizing surface oxidation and agglomeration.
Which method is widely used for fabrication of nanostructures? ›Several methods are used to fabricate nanostructures using the top-down approach such as photolithography, scanning lithography, laser machining, soft lithography, nanocontact printing, nanosphere lithography, colloidal lithography, scanning probe lithography, ion implantation, diffusion, deposition.
Are carbon nanotubes easy to make? ›Arc Method
"The carbon arc discharge method, initially used for producing C60 fullerenes, is the most common and perhaps easiest way to produce CNTs, as it is rather simple.
Presence of impurities, non-uniformity in morphology and structure, large surface area (leads to protein opsonization), hydrophobicity, insolubility and tendency of CNTs to bundle together are some obstacles for their nano-medical applications.
Which method is best in terms of yield to form carbon nano tubes? ›One of the best techniques for the production of CNTs is chemical vapor deposition (CVD). There are different CVD techniques such as catalytic chemical vapor deposition either thermal [33] and water assisted [6], plasma enhanced oxygen assisted CVD [34, 35, 36] or hot filament CVD (HFCVD) [37].
What are the two methods of synthesis? ›The four most adopted methods of synthesis of single crystals are solid-state, hydrothermal, slow evaporation at room temperature, and flux methods.
How do carbon nanoparticles synthesis? ›Synthesis of CNPs
About 1.0 g of soot was taken in 200 ml of concentrated nitric acid in 250 ml R.B. flask. The mass was sonicated for 15 min and then heated at 85°C on an oil bath with continuous stirring for 12 h. After this, the reaction mass was cooled to room temperature and diluted to its double mass by DI water.