The raw material selected for this research was Brazil chestnut shells (BCs), which were utilized to gain porous carbon as a positive electrode for lithium–sulfur batteries (LSBs). The effects of N/S co-doped on the electrochemical properties of porous carbon materials were studied using thiourea as nitrogen and sulfur sources. The experimental results indicate that the N/S co-doped carbon materials have a higher mesopore ratio than the undoped porous carbon materials. The porous carbon material NSPC-2 has a lotus-like structure with uniform pore distribution. The N and S doping contents are 2.5% and 5.4%. The prepared N/S co-doped porous carbon materials were combined with S, respectively, and three kinds of sulfur carbon composites were obtained. Among them, the composite NSPC-2/S can achieve the initial specific discharge capacity of 1018.6 mAh g− 1 at 0.2 C rate. At 1 C rate, the initial discharge capacity of the material is 730.6 mAh g− 1, and the coulomb efficiency is 98.6% and the capacity retention rate is 71.5% after 400 charge–discharge cycles.
The complexation of silicon with carbon materials is considered an effective method for using silicon as an anode material for lithium-ion batteries. In the present study, carbon frameworks with a 3D porous structure were fabricated using metal–organic frameworks (MOFs), which have been drawing significant attention as a promising material in a wide range of applications. Subsequently, the fabricated carbon frameworks were subjected to CVD to obtain silicon-carbon complexes. These siliconcarbon complexes with a 3D porous structure exhibited excellent rate capability because they provided sufficient paths for Li-ion diffusion while facilitating contact with the electrolyte. In addition, unoccupied space within the silicon complex, combined with the stable structure of the carbon framework, allowed the volume expansion of silicon and the resultant stress to be more effectively accommodated, thereby reducing electrode expansion. The major findings of the present study demonstrate the applicability of MOF-based carbon frameworks as a material for silicon complex anodes.
The potential use of cost-effective carbon anodes, as an alternative to expensive platinum, in the reduction of oxides within LiCl-Li2O molten salt at elevated cell potentials presents a promising avenue. However, this elevated potential gives rise to the generation of a complex mixture of anodic gases, including hazardous and corrosive species such as chlorine (Cl2), oxygen (O2), carbon monoxide (CO), and carbon dioxide (CO2). In this study, we investigate the influence of applied potential and salt composition on the composition of the generated gas mixture. Real-time gas analysis was conducted during the TiO reduction reaction in the molten salt at 650°C using a MAX-300-LG gas analyzer. Simultaneously, electronic signals, including current, potential, and salt composition, were monitored throughout the oxide reduction process. Additionally, XRD investigations were performed to verify the crystal structure of the resulting products. This research provides valuable insights into optimizing carbon anode-based reduction processes for improved efficiency and safety.
Refined structured tin dioxide gets the amount of attraction because of its low cost and stability. The C@SnO2 nanospheres with mesoporous structures were produced using the hard template method in this work. The C@SnO2 is primarily gained attributed to the dehydration condensation of C6H12O6 and the hydrolysis of SnCl4 ·5H2O. The morphology of the C@SnO2 was analyzed by physical characterization and the diameter of the obtained C@SnO2 was around 138 nm. When C@SnO2 was applied to lithium-ion batteries as anode material, it performed outstanding electrochemical properties, with a capacity of 735 and 539 mA h g− 1 maintained at 1000 and 2000 mA g− 1, respectively. Furthermore, it exhibits favorable discharge/ charge cycle stability. This is probably because of the more chemically redox active sites provided by C@SnO2 nanocomposites and it also allows fast ion diffusion and electron migration.
Transition metal chalcogenides are promising cathode materials for next-generation battery systems, particularly sodium-ion batteries. Ni3Co6S8-pitch-derived carbon composite microspheres with a yolk-shell structure (Ni3Co6S8@C-YS) were synthesized through a three-step process: spray pyrolysis, pitch coating, and post-heat treatment process. Ni3Co6S8@C-YS exhibited an impressive reversible capacity of 525.2 mA h g-1 at a current density of 0.5 A g-1 over 50 cycles when employed as an anode material for sodium-ion batteries. However, Ni3Co6S8 yolk shell nanopowder (Ni3Co6S8-YS) without pitch-derived carbon demonstrated a continuous decrease in capacity during charging and discharging. The superior sodium-ion storage properties of Ni3Co6S8@C-YS were attributed to the pitchderived carbon, which effectively adjusted the size and distribution of nanocrystals. The carbon-coated yolk-shell microspheres proposed here hold potential for various metal chalcogenide compounds and can be applied to various fields, including the energy storage field.
To develop a high capacity lithium secondary battery, a new approach to anode material synthesis is required, capable of producing an anode that exceeds the energy density limit of a carbon-based anode. This research synthesized carbon nano silicon composites as an anode material for a secondary battery using the RF thermal plasma method, which is an ecofriendly dry synthesis method. Prior to material synthesis, a silicon raw material was mixed at 10, 20, 30, 40, and 50 wt% based on the carbon raw material in a powder form, and the temperature change inside the reaction field depending on the applied plasma power was calculated. Information about the materials in the synthesized carbon nano silicon composites were confirmed through XRD analysis, showing carbon (86.7~52.6 %), silicon (7.2~36.2 %), and silicon carbide (6.1~11.2 %). Through FE-SEM analysis, it was confirmed that the silicon bonded to carbon was distributed at sizes of 100 nm or less. The bonding shape of the silicon nano particles bonded to carbon was observed through TEM analysis. The initial electrochemical charging/ discharging test for the 40 wt% silicon mixture showed excellent electrical characteristics of 1,517 mAh/g (91.9 %) and an irreversible capacity of 133 mAh/g (8.1 %).
Instead of using expensive platinum, carbon anodes could potentially be utilized in the process of reducing oxides in LiCl-Li2O molten salt at a high cell potential. However, this high potential leads to the generation of a mixture of anodic gases containing toxic and corrosive gases such as chlorine (Cl2), oxygen (O2), carbon monoxide (CO), and carbon dioxide (CO2). To better understand this gas mixture, we conducted real-time analyses of the gases generated on the carbon anode during the TiO reduction reaction in the molten salt at 650°C, using a MAX-300-LG gas analyzer. Our results indicate that the ratio of CO/O2/CO2/Cl2 in the gas mixture is significantly influenced by the composition of the salt, and that removing the sources of oxygen ions in the salt increases the likelihood of generating toxic and corrosive Cl2 gas.
Silicon oxide (SiOx) has been considered one of the most promising anode materials for lithium-ion batteries due to having a higher capacity than the commercial graphite anodes. However, its practical application is hampered by very large volume variations. In this work, pyrolysis fuel oil is the carbon coating precursor, and physical vapor deposition (PVD) is performed on SiOx at 200 and 400 °C (SiOx@C 200 and SiOx@C 400), followed by carbonization at 950 °C. SiOx@C 200 has a carbon coating layer with a thickness of ~ 20 nm and an amorphous structure, while that of SiOx@C 400 is approximately 10 nm thick and has a more semigraphitic structure. The carbon-coated SiOx anodes display better charge–discharge performance than the pristine SiOx anode. In particular, SiOx@C 200 shows the highest reversible capacity compared with the other samples at high C-rates (2.0 and 5.0 C). Moreover, SiOx@C 200 exhibits excellent cycling stability with a capacity retention of 90.2% after 80 cycles at 1.0 C. This result is ascribed to the suppressed volume expansion by the PFO carbon coating on SiOx after PVD.
The high level of lithium storage in synthetic porous carbons has necessitated the development of accurate models for estimating the specific capacity of carbon-based lithium-ion battery (LIB) anodes. To date, various models have been developed to estimate the storage capacity of lithium in carbonaceous materials. However, these models are complex and do not take into account the effect of porosity in their estimations. In this paper, a novel model is proposed to predict the specific capacity of porous carbon LIB anodes. For this purpose, a new factor is introduced, which is called normalized surface area. Considering this factor, the contribution of surface lithium storage can be added to the lithium stored in the bulk to have a better prediction. The novel model proposed in this study is able to estimate the lithium storage capacity of LIB anodes based on the porosity of porous carbons for the first time. Benefiting porosity value (specific surface area) makes the predictions quick, facile, and sensible for the scientists and experts designing LIBs using porous carbon anodes. The predicted capacities were compared with that of the literature reported by experimental works. The remarkable consistency of the measured and predicted capacities of the LIB anodes also confirms the validity of the approach and its reliability for further predictions.
The reaction between Li2CO3 and Cl2 was investigated to verify its occurrence during a carbon-anode-based oxide reduction (OR) process. The reaction temperature was identified as a key factor that determines the reaction rate and maximum conversion ratio. It was found that the reaction should be conducted at or above 500℃ to convert more than 90% of the Li2CO3 to LiCl. Experiments conducted at various total flow rate (Q) / initial sample weight (W i) ratios revealed that the reaction rate was controlled by the Cl2 mass transfer under the experimental conditions adopted in this work. A linear increase in the progress of reaction with an increase in Cl2 partial pressure (pCl2) was observed in the pCl2 region of 2.03–10.1 kPa for a constant Q of 100 mL∙min−1 and W i of 1.00 g. The results of this study indicate that the reaction between Li2CO3 and Cl2 is fast at 650℃ and the reaction is feasible during the OR process.
The corrosion behavior of Hastelloy C-276 was investigated to identify its applicability for carbon-anode-based oxide reduction (OR), in which Cl2 and O2 are simultaneously evolved at the anode. Under a 30 mL·min-1 Cl2 + 170 mL·min-1 Ar flow, the corrosion rate was less than 1 g·m-2·h-1 up to 500℃, whereas the rate increased exponentially from 500 to 700℃. The effects of the Cl2-O2 composition on the corrosion rate at flow rates of 30 mL·min-1 Cl2, 20 mL·min-1 Cl2 + 10 mL·min-1 O2, and 10 mL·min-1 Cl2 + 20 mL·min-1 O2 with a constant 170 mL·min-1 Ar flow rate at 600℃ was analyzed. Based on the data from an 8 h reaction, the fastest corrosion rate was observed for the 20 mL·min-1 Cl2 + 10 mL·min-1 O2 case, followed by 30 mL·min-1 Cl2 and 10 mL·min-1 Cl2 + 20 mL·min-1 O2. The effects of the chlorine flow rate on the corrosion rate were negligible within the 5–30 mL·min-1 range. A surface morphology analysis revealed the formation of vertical scratches in specimens that reacted under the Cl2-O2 mixed gas condition.
The corrosion behavior of the Inconel X-750 alloy was investigated for its potential application under a Cl2-O2 mixed gas flow in an Ar atmosphere. The corrosion rate was found to be negligible at temperatures up to 400℃ under a flow rate of 30 mL·min-1 Cl2 + 170 mL·min-1 Ar, whereas an exponential increase was observed in the corrosion rate at temperatures greater than 500℃. The suppression of the corrosion reaction due to the presence of O2 was verified experimentally at flow rates of 30 mL·min-1 Cl2 (4.96 g·m-2·h-1), 20 mL·min-1 Cl2 + 10 mL·min-1 O2 (2.02 g·m-2·h-1), and 10 mL·min-1 Cl2 + 20 mL·min-1 O2 (1.34 g·m-2·h-1) under a constant Ar flow rate of 170 mL·min-1 at 600℃ for 8 h. The surface morphology analysis results revealed that porous surfaces with tunnel-type holes were produced under the Cl2-O2 mixed-gas condition. Furthermore, the effects of the Cl2 flow rate on the corrosion rate were investigated, indicating that its impact was negligible within the range of 5–30 mL·min-1 Cl2 at 600℃.
Here, the stability of stainless steel 316 (SS-316) was investigated to identify its applicability in the oxide reduction process, as a component in related equipment, to produce a complicated gas mixture composed of O2 and Cl2 under an argon (Ar) atmosphere. The effects of the mixed gas composition were investigated at flow rates of 30 mL/min O2, 20 mL/min O2 + 10 mL/min Cl2, 10 mL/min O2 + 20 mL/ min Cl2, and 30 mL/min Cl2, each at 600℃, during a constant argon flow rate of 170 mL/min. It was found that the corrosion of SS-316 by the chlorine gas was suppressed by the presence of oxygen, while the reaction proceeded linearly with the reaction time regardless of gas composition. Surface observation results revealed an uneven surface with circular pits in the samples that were fed mixed gases. Thermodynamic calculations proposed the combination of Fe and Ni chlorination reactions as an explanation for this pit formation phenomenon. An exponential increase in the corrosion rate was observed with an increase in the reaction temperature in a range of 300 ~ 600℃ under a flow of 30 mL/min Cl2 + 170 mL/min Ar.
Free-standing electrodes of CuO nanorods in carbon nanotubes (CNTs) are developed by synthesizing porous CuO nanorods throughout CNT webs. The electrochemical performance of the free-standing electrodes is evaluated for their use in flexible lithium ion batteries (LIBs). The electrodes comprising CuO@CNT nanocomposites (NCs) were characterized by charge-discharge testing, cyclic voltammetry, and impedance measurement. These structures are capable of accommodating a high number of lithium ions as well as increasing stability; thus, an increase of capacity in long-term cycling and a good rate capability is achieved. We demonstrate a simple process of fabricating free-standing electrodes of CuO@ CNT NCs that can be utilized in flexible LIBs with high performance in terms of capacity and cycling stability.
In this study, several kinds of active carbons with high specific surface area and micro pore structure were prepared from the coconut shell charcoal using chemical activation method. The physical property of prepared active carbon was investigated by experimental variables such as activating chemical agents to char coal ratio, flow rate of inert gas and temperature. It was shown that chemical activation with KOH and NaOH was successfully able to make active carbons with high surface area of 1900~2500 m2/g and mean pore size of 1.85~2.32 nm. The coin cell using water-based binder in the electrolyte of LiPF6 dissolved in mixed organic solvents (EC:DMC:EMC=1:1:1 vol%) showed better capacity than that of oil-based binder. Also, it was found that the coin cell of water-based binder shows an improved cycling performance and coulombic efficiency.
The composite of porous silicon (Si) and amorphous carbon (C) is prepared by pyrolysis of a nano-porous Si + pitch mixture. The nano-porous Si is prepared by mechanical milling of magnesium powder with silicon monoxide (SiO) followed by removal of MgO with hydrochloric acid (etching process). The Brunauer-Emmett-Teller (BET) surface area of porous Si (64.52 m2g−1) is much higher than that before etching Si/MgO (4.28 m2g−1) which indicates pores are formed in Si after the etching process. Cycling stability is examined for the nano-porous Si + C composite and the result is compared with the composite of nonporous Si + C. The capacity retention of the former composite is 59.6% after 50 charge/discharge cycles while the latter shows only 28.0%. The pores of Si formed after the etching process is believed to accommodate large volumetric change of Si during charging and discharging process.