• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.598-598
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• 2012

Rechargeable lithium-ion batteries have been considered the most attractive power sources for mobile electronic devices. Although graphite is widely used as the anode material for commercial lithium-ion batteries, it cannot fulfill the requirement for higher storage capacity because of its insufficient theoretical capacity of 372 mAh/g. For the sake of replacing graphite, Sn-based materials have been extensively investigated as anode materials because they can have much higher theoretical capacities (994 mAh/g for Sn, 875 mAh/g for SnO, 783 mAh/g for $SnO_2$). However, these materials generate huge volume expansion and shrinkage during $Li^+$ intercalation and de-intercalation and result in the pulverization and cracking of the contact between anode materials and current collector. Therefore, there have been significant efforts of avoiding these drawbacks by using nanostructures. In this study, we present the CVD growth of SnO branched nanostructures on Cu current collector without any binder, using a combinatorial system of the vapor transport method and resistance heating technique. The growth mechanism of SnO branched nanostructures is introduced. The SnO nanostructures are evaluated as an anode for lithium-ion battery. Remarkably, they exhibited very high discharge capacities, over 520mAh/g and good coulombic efficiency up to 50 cylces.

• Korean Chemical Engineering Research
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• v.60 no.3
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• pp.327-333
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• 2022

In this study, silicon/carbon nanotube/carbon (Si/CNT/C) composites for anode were prepared to improve the volume expansion of silicon used as a high-capacity anode material. Si/CNT were prepared by electrostatic attraction of the positively charged Si and negatively charged CNT and then hydrothermal synthesis was performed to obtain the spherical Si/CNT/C composites. Poly(vinylidene fluoride) (PVDF), polyacrylic acid (PAA), and styrene butadiene rubber (SBR) were used as binders for electrode preparation, and coin cell was assembled using 1.0 M LiPF₆ (EC:DMC:EMC = 1:1:1 vol%) electrolyte and fluoroethylene carbonate (FEC) additive. The physical properties of Si/CNT/C anode materials were analyzed using SEM, EDS, XRD and TGA, and the electrochemical performances of lithium-ion batteries were investigated by charge-discharge cycle, rate performance, dQ/dV and electrochemical impedance spectroscopy tests. Also, it was confirmed that both capacity and rate performance were significantly improved using the PAA/SBR binder and 10 wt% FEC-added electrolyte. It is found that Si/CNT/C have the reversible capacity of 914 mAh/g, the capacity retention ratio of 83% during 50 cycles and the rate performance of 70% in 2 C/0.1 C.

• Journal of Adhesion and Interface
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• v.24 no.1
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• pp.9-16
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• 2023

Silicon has been studied as an anode material for next-generation lithium ion batteries due to its high theoretical electrochemical capacity. However, the extreme volume change during the lithiation/delithiation and the inherently low electronic conductivity of silicon hamper the practical application of silicon anodes. Conductive polymer binders are effective means to solve these problems, and it has been reported that the performance of the silicon anode can be greatly improved through the proper molecular design of the conductive polymer binders. In this paper, representative recent studies on conductive polymer binders for silicon anodes will be introduced, and through this, binder design strategies to overcome the limitations of silicon anodes will be explored.

• Resources Recycling
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• v.32 no.6
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• pp.25-33
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• 2023

With the growth of the battery industry, a rapid increase in the production and usage of lithium-ion batteries is expected, and in line with this, much interest and effort is being paid to recycle waste batteries, including production scrap. Although much effort has been made to recycle cathode material, much attention has begun to recycle anode material to secure the supply chain of critical minerals and improve recycling rates. The proximate analysis that measures the content of coal can be used to analyze graphite in anode material, but it cannot accurately analyze due to the interaction between the components of the black mass. Therefore, in this study, thermogravimetric analysis of each component of black mass was measured as the temperature increased up to 950℃ in an oxygen atmosphere. As a result, in the case of cathode material, no change in mass was measured other than a mass reduction of about 5% due to oxidation of the binder and conductive material. In the case of anode material, except for a mass reduction of about 2% due to the binder, all mass reduction were due to the graphite(fixed carbon). In addition, metal conductors (Al, Cu) were oxidized and their mass increased as the temperature increased. Thermal analysis results of mixed samples of cathode/anode show similar results to the predictive values that can be calculated through each cathode and anode analysis results.

• Applied Chemistry for Engineering
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• v.29 no.6
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• pp.696-702
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• 2018

Recently, the current thermal battery technology needs new materials for electrodes in the power and energy density to meet various space and defense requirements. In this paper, to replace the pellet type Li(Si) anode having limitations of the formability and capacity, electrochemical properties of the lithium anode with high density for thermal batteries were investigated. The lithium anode (Li 17, 15, 13 wt%) was fabricated by mixing the molten lithium and iron powder used as a binder to hold the molten lithium at $500^{\circ}C$. The single cell with 13 wt% lithium showed a stable performance. The 2.06 V (OCV) of the lithium anode was significantly improved compared to 1.93 V (OCV) of the Li(Si) anode. Specific capacities during the first phase of the lithium anode and Li(Si) were 1,632 and $1,181As{\cdot}g^{-1}$, respectively. As a result of the thermal battery performance test at both room and high temperatures, the voltage and operating time of lithium anode thermal batteries were superior to those of using Li(Si) anode thermal batteries. The power and energy densities of Li anode thermal batteries were also remarkably improved.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.32 no.2
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• pp.165-173
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• 2019

Lithium anodes (13, 15, 17, and 20 wt% Li) were fabricated by mixing molten lithium and iron powder, which was used as a binder to hold the molten lithium, at about $500^{\circ}C$ (discharge temp.). In this study, the effect of applied pressure and lithium content on the discharge properties of a thermal battery's single cell was investigated. A single cell using a Li anode with a lithium content of less than 15 wt% presented reliable performance without any abrupt voltage drop resulting from molten lithium leakage under an applied pressure of less than $6kgf/cm^2$. Furthermore, it was confirmed that even when the solid electrolyte is thinner, the Li anode of the single cell normally discharges well without a deterioration in performance. The Li anode of the single cell presented a significantly improved open-circuit voltage of 2.06 V, compared to that of a Li-Si anode (1.93 V). The cut-off voltage and specific capacity were 1.83 V and $1,380As\;g^{-1}$ (Li anode), and 1.72 V and $1,364As\;g^{-1}$ (Li-Si anode). Additionally, the Li anode exhibited a stable and flat discharge curve until 1.83 V because of the absence of phase change phenomena of Li metal and a subsequent rapid voltage drop below 1.83 V due to the complete depletion of Li at the end state of discharge. On the other hand, the voltage of the Li-Si anode cell decreased in steps, $1.93V{\rightarrow}1.72V(Li_{13}Si_4{\rightarrow}Li_7Si_3){\rightarrow}1.65V(Li_7Si_3{\rightarrow}Li_{12}Si_7)$, according to the Li-Si phase changes during the discharge reaction. The energy density of the Li anode cell was $807.1Wh\;l^{-1}$, which was about 50% higher than that of the Li-Si cell ($522.2Wh\;l^{-1}$).

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.145-148
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• 2011

The thermal behavior of lithiated Si anodes has been investigated using differential scanning calorimetry (DSC). In particular, the effect of Si particle size on the thermal stability of a fully lithiated Si electrode was investigated. For DSC measurements, a lithiated Si anode was heated in a hermetically sealed high-pressure pan with a polyvinylidene fluoride (PVDF) binder and a 1 M $LiPF_6$ solution in an ethylene carbonate (EC)-diethyl carbonate (DEC) mixture. The thermal evolution around $140^{\circ}C$ increases with lithiation and with decreasing particle size; this phenomenon is attributed to the thermal decomposition of the solid electrolyte interface (SEI) film. Exothermic peaks, following a broad peak at around $140^{\circ}C$, shift to a lower temperature with a decrease in particle size, indicating that the thermal stability of the lithiated Si electrode strongly depends on the Si particle size.

• Journal of Powder Materials
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• v.24 no.5
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• pp.364-369
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• 2017

Ceramic powder, such as MgO, is added as a binder to prepare the green compacts of molten salts of an electrolyte for a thermal battery. Despite the addition of a binder, when the thickness of the electrolyte decreases to improve the battery performance, the problem with the unintentional short circuit between the anode and cathode still remains. To improve the current powder molding method, a new type of electrolyte separator with porous MgO preforms is prepared and characteristics of the thermal battery are evaluated. A Spherical PMMA polymer powder is added as a pore-forming agent in the MgO powder, and an organic binder is used to prepare slurry appropriate for tape casting. A porous MgO preform with $300{\mu}m$ thickness is prepared through a binder burnout and sintering process. The particle size of the starting MgO powder has an effect, not on the porosity of the porous MgO preform, but on the battery characteristics. The porosity of the porous MgO preforms is controlled from 60 to 75% using a pore-forming agent. The batteries prepared using various porosities of preforms show a performance equal to or higher than that of the pellet-shaped battery prepared by the conventional powder molding method.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1199-1204
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• 2013

Nanocomposites consisting of Sn nanoparticles and graphene oxide (GO) were electrophoretically deposited onto Cu current collectors that was used for anodes in Li ion batteries (LIBs). In order to optimize the electrochemical performance of nanocomposites as an anode material by controlling the oxygen functionality, the GO was subjected to $O_3$ treatment prior to electrophoretic deposition (EPD). During thermal reduction of the GO in the nanocomposites, the Sn nanoparticles were reduced in size, along with the formation of SnO and/or $SnO_2$ at a small fraction, relying on the oxygen functionalities of the GO. The variation in the duration of time for the $O_3$ irradiation resulted in a small change in total oxygen content, but in a significantly different fraction of each functional group in the GO, which influenced the Sn nanoparticle size and the amount of SnO (and/or $SnO_2$). As a result, the EPD films prepared with the GO that possessed the least amount of carboxylic groups (made by treating GO in an $O_3$ environment for 3 h) showed the best performance, when compared with the nanocomposites composed of untreated GO or GO that was $O_3$-treated for a duration of less than 3 h.

• Journal of Industrial and Engineering Chemistry
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• v.68
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• pp.161-167
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• 2018

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 $80^{\circ}C$. 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 $LiClO_4$ 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.