• Journal of the Mineralogical Society of Korea
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• v.32 no.3
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• pp.213-222
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• 2019

Birnessite (birnessite, $7{\AA}$ manganate, ${\delta}-MnO_2$) is a major mineral comprising manganese nodule. Various synthetic methods have been studied and evaluated because it can be used as an ion exchange agent and a battery recharging material. However, it is difficult to obtain a single birnessite phase because it does not have a stoichiometric chemical composition. Feitknechtite (${\beta}-MnOOH$) is formed as an intermediate product during birnessite synthesis and in this study, the transition of this phase to birnessite was compared by using XRD and SEM. Two different methods, Feng et al. (2004) and Luo et al. (1998), based on redox reaction were used. It was possible to obtain the impurity-free birnessite for the sample aged 60 days at $27^{\circ}C$ by Feng et al. (2004) method and 3 days at $60^{\circ}C$ by Luo et al. (1998) method. The phase transition rate of the feitknechtite phase was slower in the case of $Mg^{2+}$ doped birnessite which was synthesized by Luo et al. (1998) method, and almost single phase almost single phase birnessite was identified at high temperature. Crystal surface and morphology also confirmed the difference between the samples synthesized by two methods.

• Journal of the Korean Electrochemical Society
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• v.25 no.4
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• pp.134-153
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• 2022

Regardless of a trade-off relationship between energy density and safety, it is essential to improve both properties for future lithium secondary batteries. Especially, to improve the energy density of batteries further, not only thickness but also weight of separators including ceramic coating layers should be reduced continuously apart from the development of high-capacity electrode active materials. For this purpose, an attempt to replace conventional slurry coating methods with a deposition one has attracted much attention for securing comparable thermal stability while minimizing the thickness and weight of ceramic coating layer in the separator. This review introduces state-of-the-art technology on ceramic-coated separators (CCSs) manufactured by the deposition method. There are three representative processes to form a ceramic coating layer as follows: chemical vapor deposition (CVD), atomic layer deposition (ALD), and physical vapor deposition (PVD). Herein, we summarized the principle and advantages/disadvantages of each deposition method. Furthermore, each CCS was analyzed and compared in terms of its mechanical and thermal properties, air permeability, ionic conductivity, and electrochemical performance.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.36 no.6
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• pp.638-646
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• 2023

Recently, active research has been conducted to enhance the power characteristics and thermal stability of lithium-ion batteries (LiBs) by modifying separators using a ceramic coating method. However, since the thermal properties and surface features of the separator vary depending on the characteristics of the ceramic powders applied to the separator, it is crucial to manufacture ceramic powders optimized for the separator's performance. In this study, we evaluated the characteristics of three types of α-alumina (A-1, A-2, and A-3) produced with varying dispersant contents and milling times, in addition to commercial α-alumina (AES-11). Subsequently, the optimized powders (A-3) were coated onto the separator using an aqueous binder for comparison with the characteristics of an AES-11 coated separator and an uncoated PE separator. The A-3 coated separator improved electrolyte wettability with a low contact angle (44.69°) and increased puncture strength (538 gf). Furthermore, it exhibited excellent thermal stability, with a shrinkage value of 5.64% when exposed to 140℃ for 1 hour, compared to the AES11 coated separator (6.09%) and the bare PE separator (69.64%).

• Resources Recycling
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• v.33 no.1
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• pp.58-68
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• 2024

Critical minerals such as nickel, cobalt and lithium, are known as materials for cathodic active materials of lithium ion batteries. The consumption of the minerals is expected to grow with increasing the demands of electric vehicles, resulting from carbon neutrality. Especially, the demand for LIB (lithium ion battery) recycling is expected to increase to meet the supply of nickel, cobalt and lithium for LIB. The recycling of EOL (end-of-life) LIB can be achieved by leaching EOL LIB using inorganic acid such as HCl, HNO₃ and H₂SO₄, which are regarded as hazardous materials. In the present study, the potential use of MSA (Methanesulfonic acid), as an alternative lixiviant replacing sulfuric acid was investigated. In addition, leaching behaviors of NCM black mass leaching with MSA was also investigated by studying various leaching factors such as chemical concentration, leaching time, pulp density (P/D) and temperatures. The leaching efficiency of nickel (Ni), cobalt (Co), lithium (Li), and manganese (Mn) from LIB was enhanced by increasing concentration of lixiviant and reductant, leaching time and temperature. The maximum leaching of the metals was above 99% at 80℃. In addition, MSA can replace sulfuric acid to recover Ni, Co, Li, Mn from NCM black mass.

• Korean Chemical Engineering Research
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• v.55 no.2
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• pp.242-246
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• 2017

The application of composite cathode materials including $LiFePO_4$ (lithium iron phosphate) of olivine crystal structure, which has high thermal stability, were investigated as alternatives for hybrid battery-capacitors with a $LiMn_2O_4$ (spinel crystal structure) cathode, which exhibits decreased performance at high temperatures due to Mn-dissolution. However, these composite cathode materials have been shown to have a reduction in capacity by conducting life cycle experiments in which a $LiFePO_4$/activated carbon cell was charged and discharged between 1.0 V and 2.3 V at two temperatures, $25^{\circ}C$ and $60^{\circ}C$, which caused a degradation of the anode due to the lowered voltage in the anode. To avoid the degradation of the anode, composite cathodes of $LiFePO_4/LiMn_2O_4$ (50:50 wt%), $LiFePO_4$/activated carbon (50:50 wt%) and $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ (50:50 wt%) were prepared and the life cycle experiments were conducted on these cells. The composite cathode including $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ of layered crystal structure showed stable voltage behavior. The discharge capacity retention ratio of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ was about twice as high as that of a $LiFePO_4/LiMn_2O_4$ cell at thermal stability experiment for a duration of 1,000 hours charged at 2.3 V and a temperature of $80^{\circ}C$.

• Clean Technology
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• v.24 no.1
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• pp.77-84
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• 2018

In this study, $Li_4Ti_5O_{12}$ anode materials for lithium ion battery were synthesized by dry ball-mill method. Polyvinyl chloride (PVC) as a carbon source was added to improve electrochemical properties. When the PVC was added after $Li_4Ti_5O_{12}$ formation, the spinel structure was well synthesized and it was confirmed by X-ray diffraction (XRD) experiments. When the carbon material was added before the synthesis and the heat treatment was performed, it was confirmed that a material having a different crystal structure was synthesized even when a small amount of carbon material was added. In the case of $Li_4Ti_5O_{12}$ without the carbon material, the electrical conductivity value was about $10{\mu}S\;m^{-1}$, which was very small and similar to that of the nonconductor. As the carbon was added, the electrical conductivity was greatly improved and increased up to 10,000 times. Electrochemical impedance spectroscopy (EIS) analysis showed that the size of semicircle corresponding to the resistance decreased with the carbon addition. This indicates that the resistance inside the electrode is reduced. According to the Cyclic voltammetry (CV) analysis, the potential difference between the oxidation peak and the reduction peak was reduced with carbon addition. This means that the rate of lithium ion insertion and deinsertion was increased. $Li_4Ti_5O_{12}$ with 9.5 wt% PVC added sample showed the best properties in rate capabilities of $180mA\;h\;g^{-1}$ at 0.2 C-rate, $165mA\;h\;g^{-1}$ at 0.5 C-rate, and $95.8mA\;h\;g^{-1}$ at 5 C-rate.

• Korean Chemical Engineering Research
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• v.60 no.2
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• pp.243-248
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• 2022

As the scope of use of portable and wearable electronic devices is expanding, the limitations of heavy and bulky solid-state batteries are being revealed. Given that, it is urgent to develop a small energy harvesting device that can partially share the role of a battery and the utilization of energy sources that are thrown away in daily life is becoming more important. Contact electrification, which generates electricity based on the coupling of the triboelectric effect and electrical induction when the two material surfaces are in contact and separated, can effectively harvest the physical and mechanical energy sources existing in the surrounding environment without going through a complicated intermediate process. Recently, the interest in the harvest and utilization of wind energy is growing since the wind is an infinitely ecofriendly energy source among the various environmental energy sources that exist in human surroundings. In this study, the optimization of the energy harvesting device for the effective harvest of wind energy based on the contact electrification was analyzed and then, the utilization strategy to maximize the utilization of the generated electricity was investigated. Natural wind based Fluttering TENG (NF-TENG) using fluttering film was developed, and design optimization was conducted. Moreover, the safe high voltage generation system was developed and a plan for application in the field requiring high voltage was proposed by highlighting the unique characteristics of TENG that generates low current and high voltage. In this respect, the result of this study demonstrates that a portable energy harvesting device based on the contact electrification shows great potential as a strategy to harvest wind energy thrown away in daily life and use it widely in fields requiring high voltage.

• Journal of the Korean Electrochemical Society
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• v.5 no.1
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• pp.30-38
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• 2002

Disordered carbon and boron-substituted disordered carbons $C_{l-x}B_x(x=0.05,\;0.10,\;0.20)$ were synthesized by Pyrolysis of LPG(liquid Propane gas)and $BCl_3$. Their electrochemical properties as anode materials for Li-ion secondary batteries were then investigated. When PVDF is added to the sample in a weight ratio 5 : 95, the disordered carbon with x=0.00 had the first discharge capacity 374 mAh/g. Its cycling performance was relatively good from the second cycle and it had the discharge capacity 258 mAh/g at the 10th cycle. When PVDF is added to the sample in a weight ratio 5 : 95, the sample with x=0.05 among the samples $C_{l-x}B_x(x=0.05,\;0.10,\;0.20)$ exhibited the largest first discharge capacity 860 mAh/g and discharge capacity 181 mAh/g at the 10th cycle. All the samples had similar cycling performances from the second cycle. The sample $C_{0.90}B_{0.10}$ showed the best electrochemical properties as a anode materials fur Li-ion secondary battery from the view points of the first discharge capacity(853 mAh/g when $10w1.\%$ PVDF is used), cycling performance, discharge capacity(400mAh/g at the 10th cycle when $10wt.\%$ PVDF is used). All the samples showed generally larger charge and discharge capacities when $10wt.\%$ PVDF ratter than $5wt.\%$ PVDF is used. The plateau region in the range of voltage lower than 1.25V becomes larger probably since the structure becomes less disordered by the addition of boron. When boron is added, the charge and discharge capacities decreased suddenly at the second cycle. This may be become only a part of Li are reversibly deintercalated and intercalated and a part of Li which are strongly combined with B are not deintercalated. The increases in charge and discharge capacities are considered to be resulted from the increase in the potential of Li in the boron-added carbons, caused by the strengthening of the chemical bond between the intercalated Li and the boron-carbon host since the boron acts as electron acceptor.

• Applied Chemistry for Engineering
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• v.23 no.2
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• pp.131-137
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• 2012

Polyaniline (PANI) and polypyrrole (Ppy) hollow sphere structures with controlled shell thicknesses can be easily synthesized than those of using a layer-by-layer method for cathode active material of lithium-ion batteries. Polystyrene (PS) core was synthesized by emulsion polymerization using an anion surfactant. The shell thicknesses of PANI and Ppy were controlled by amounts of aniline and pyrrole monomers. PS was removed by an organic solution. This structure increased in contact with an electrolyte and a specific capacity in lithium-ion batteries. But polymers have disadvantages such as the difficult control of molecular weights and low densities. These disadvantages were completed by controlled shell thicknesses. The amount of aniline monomer increased from 1.2, 2.4, 3.6, 4.8 to 6.0 mL, and the shell thicknesses were 30.2, 38.0, 42.2, 48.2, and 52.4 nm, respectively. And the amount of pyrrole monomer was 0.6, 1.2, 2.4 and 3.6 mL, the shell thicknesses were 16.0, 22.0, 27.0 and 34.0 nm, respectively. In the cathode materials with controlled shell thicknesses, shell thicknesses of the PANI hollow spheres were 30.2, 42.2, and 52.4 nm, and discharge specific capacities of after 10 cycle were ~18, ~29, and ~62 mAh/g, respectively. The shell thicknesses of the Ppy hollow spheres were 16.0, 22.0, 27.0 and 34.0 nm, and discharge specific capacities of after 15 cycle were ~15, ~36, ~56, and ~77 mAh/g, respectively. Thus, shell thicknesses of PANI and Ppy increased, the specific capacities increased.