• Clean Technology
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• v.27 no.2
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• pp.139-145
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• 2021

The purpose of this study is to recover valuable metals from spent batteries using a dry process. We focused on the effect of the smelting temperature on the composition of recovered solid and liquid products and collected gaseous products. After removal of the cover, the spent battery was left in NaCl solution and discharged. Then, the spent battery was made into a powder form through a crushing process. The smelting of the spent battery was performed in a tubular electric furnace in an oxygen atmosphere. For spent lithium-ion batteries, the recovery yield of the solid product was 80.1 wt% at a reaction temperature of 850 ℃, and the final product had 27.2 wt% of cobalt as well as other metals such as lithium, copper, and aluminum. Spent nickel-hydrogen batteries had a recovery yield of 99.2 wt% at a reaction temperature of 850 ℃ with about 37.6 wt% of nickel and other metals including iron. For spent nickel-cadmium batteries, the yield decreased to 65.4 wt% because of evaporation with increasing temperature. At 1050 ℃, the recovered metals were nickel (41 wt%) and cadmium (12.9 wt%). Benzene and toluene, which were not detected with the other secondary waste batteries, were detected in the gaseous product. The results of this study can be used as basic data for future research on the dry recycling process of spent secondary batteries.

• Resources Recycling
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• v.29 no.6
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• pp.27-34
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• 2020

In order to remove sulfate(SO42-) and purify the Li2CO3, dissolution and recrystallization of crude Li2CO3 using distilled water and HCl solution was performed. When Li2CO3 was dissolved using distilled water, the amount of dissolved Li2CO3(wt.%) increased as the solution temperature decrease and showed about 1.50 wt.% at 2.5℃. In addition, when Na2CO3 was added and the Li2CO3 solution was recrystallized, the recrystallization(%) increased with increasing temperature, resulting in a 49.00 % at 95 ℃. On the other hand, when Li2CO3 was dissolved using HCl solution, there was no effect of reaction temperature. As the concentration of HCl solution increased, the amount of dissolved Li2CO3(wt.%) increased, indicating 7.10 wt.% in 2.0 M HCl solution. When the LiCl solution was recrystallized by adding Na2CO3, it exhibited a recrystallization(%) of 86.10 % at a reaction temperature of 70 ℃, and showed a sulfate ion removal(%) of 96.50 % or more. Finally, more than 99.10 % of Na and more than 99.90 % of sulfate were removed from the recrystallized Li2CO3 powder through water washing, and purified Li2CO3 with a purity of 99.10 % could be recovered.

• Journal of the Korean Electrochemical Society
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• v.25 no.3
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• pp.95-104
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• 2022

The development of non-flammable all-solid-state batteries (ASSLBs) has become a hot topic due to the known drawbacks of commercial lithium-ion batteries. As the possibility of applying sulfide solid electrolytes (SSEs) for electric vehicle batteries increases, efforts for the low-cost mass-production are actively underway. Until now, most studies have used high-energy mechanical milling, which is easy to control composition and impurities and can reduce the process time. Through this, various SSEs that exceed the Li⁺ conductivity of liquid electrolytes have been reported, and expectations for the realization of ASSLBs are growing. However, the high-energy mechanical milling method has disadvantages in obtaining the same physical properties when mass-produced, and in controlling the particle size or shape, so that physical properties deteriorate during the full process. On the other hand, wet chemical synthesis technology, which has advantages in mass production and low price, is still in the initial exploration stage. In this technology, SSEs are mainly manufactured through producing a particle-type, solution-type, or mixed-type precursor, but a clear understanding of the reaction mechanism hasn't been made yet. In this review, wet chemical synthesis technologies for SSEs are summarized regarding the reaction mechanism between the raw materials in the solvent.

• Journal of the Korean Society of Safety
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• v.38 no.5
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• pp.8-14
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• 2023

Lithium ions can induce the thermal runaway phenomenon and lead to reignition due to electrical, mechanical, and environmental factors such as high temperature, smoke generation, explosions, or flames, which is extremely likely to create safety concerns. Therefore, one of the ways to improve the flame retardancy of the electrolyte is to use a flame-retardant additive. Comparing the associated characteristic value of existing substances with the required experimental value, it was found that these values were either considerably different or were not documented. It is vital to know a substance's combustion characteristic values, flash point, explosion limit, and autoignition temperature (AIT) as well as its combustion characteristics before using it. In this research, the flash point and AIT of materials were measured by mixing a highly volatile and flammable substance, diethyl carbonate (DEC), with flame-retardant dimethyl methylphosphonate (DMMP). The flash point of DEC, which is a pure substance, was 29℃, and that for DMMP was 65℃. Further, the lower explosion limit calculated using the measured flash point of DEC was 1.79 Vol.%, while that for DMMP was 0.79 Vol.%. The AIT was 410℃ and 390℃ for DEC and DMMP, respectively. In particular, since the AIT of DMMP has not been discussed in any previous study, it is necessary to ensure safety through experimental values. In this study, the experimental and regression analysis revealed that the average absolute deviation (ADD) for the flash point of the DEC+DMMP DEC+DMMP system is 0.58 sec and that the flash point tends to increase according to changes in the composition employed. It also revealed that the AAD for the AIT of the mixture was 3.17 sec and that the AIT tended to decrease and then increase based on changes in the composition.

• Journal of the Korean Electrochemical Society
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• v.14 no.4
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• pp.208-213
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• 2011

Solid polymer electrolytes using $BF_3LiMA$ as monomer were synthesized by usual one step radical polymerization in THF solvent. The effect of $BF_3LiMA$ concentration on ionic conductivity and electrochemical stability was investigated by AC impedance measurement and linear sweep voltammetry. As a result, the highest ionic conductivity reached $7.71{\times}10^{-6}S\;cm^{-1}$ at $25^{\circ}C$ was obtained in 12.9 wt% of $BF_3LiMA$ content. Further increase or decrease of $BF_3LiMA$ content result to decrease the ionic conductivity due to the brittle matrix properties in former case and the insufficient number of charge carrier in the latter case. Furthermore, since the counter-anion was immobilized in the self-doped solid polymer electrolytes, high electrochemical stability up to 6.0 V was observed even in $60^{\circ}C$.

• Journal of the Korean Electrochemical Society
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• v.17 no.1
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• pp.65-70
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• 2014

In this study, crosslinked poly(POEM-co-AMPSLi-co-GMA)s were prepared by epoxy coupling of GMA after radical copolymerization of AMPS, POEM and GMA followed by acid-base titration reaction between sulfonic acid of AMPS and $Li_2CO_3$. It was observed that the crystalline melting temperature of POEM was effected by mol% of components and shifted to lower value by lithiation of AMPS group. The ionic conductivity of crosslinked polymer electrolyte was decreased by addition of GMA but maintained over $1.0{\times}10^{-6}S\;cm^{-1}$ until 16 mol%. Particularly, the self-doped polymer electrolyte with 2 mol% of GMA showed its ionic conductivity as high as $4.08{\times}10^{-6}S\;cm^{-1}$ at room temperature and electrochemical stability up to 6 V. In addition, 0.11 MPa of modulus and 270% of elongation were obtained from the free standing film of crosslinked polymer electrolyte.

• Journal of the Korean Chemical Society
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• v.63 no.6
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• pp.446-452
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• 2019

We have developed a method that can leach Co, Mn, and Ni in the cathode active material safely using lactic acid. When cathode active material was leached by lactic acid, lactic acid showed the highest efficiency at 2 N than 1 N and above 4 N concentration. When the cathode active material was added incrementally into the solution of lactic acid, the maximum solubility was 30 g/L at 2 N concentration. Oxalic acid was added in the solution of lactic acid and it showed that rare metals represent the most economical recovery efficiency at 4 g/L. Based on this study, it was found that the optimal condition for recovery of rare metals from cathode active material is oxalic acid : cathode active material = 7 : 1 as a ratio of weight. In addition, it was observed that the precipitate produced by oxalic acid is a polynuclear crystalline material bonded with 3 components of Co, Ni, and Mn.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.18 no.6
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• pp.248-252
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• 2008

To get a fine $LiFePO_4$ powder with high electrical conductivity, the influences of doping of aliovalent elements(Cr+B and Cr+Al) on electrical conductivity and of heat treatment conditions on particle size of the doped powders were studied. Two kinds of the doped powders $LiFe_{0.965}Cr_{0.03}B_{0.005}PO_4$ and $LiFe_{0.065}Cr_{0.03}Al_{0.005}PO_4$ were synthesized using mechanochemical milling and subsequent heat treatment at $675{\sim}750^{\circ}C$ for $5{\sim}10\;h$. The doping enhanced grain growth and electrical conductivity. The electrical conductivity at $30^{\circ}C$ was $1{\times}10^{-8}S/cm$ in the doped with Cr and Al, and $5{\times}10^{-10}S/cm$ in the undoped one.

• Applied Chemistry for Engineering
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• v.27 no.4
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• pp.415-420
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• 2016

To enhance electrochemical performances of anode materials, the surface of coal tar pitch (CTP) was modified by incorporating heteroatoms through chemical treatment with phosphoric acid ($H_3PO_4$). The prepared anode materials with modified CTP was analyzed by XRD, FE-SEM and XPS. The electrochemical performances of modified CTP were investigated by constant current charge/discharge test, rate performance, cyclic voltammetry and impedance tests using the electrolyte of $LiPF_6$ dissolved in the mixed organic solvents (ethylene carbonate : dimethyl carbonate = 1 : 1 vol% + vinylene carbonate 3 wt%). The coin cell using modified CTP ($H_3PO_4/CTP$ = 3 : 100 in weight) has better initial capacity and initial efficiency (489 mAh/g, 82%) than those of other composition coin cells. Also, it was found that the capacity retention was 86% after 30 cycles and the rate capability was 87% at 2 C/0.1 C.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.06a
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• pp.462-462
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• 2009

$CeO_2$는 고체 산화물 연료전지 (SOFC, soild oxide fuel cell)의 전해질 재료와 CMP(Chemical Mechanical Polishing) 슬러리 재료, 자동차의 3원 촉매, gas sensor, UV absorbent등 여러 분야에서 사용되고 있다. 본 연구에서는 위의 활용범위 외에 $CeO_2$의 구조적 안정성과 빠른 $Ce^{3+}/Ce^{4+}$의 전환 특성을 이용하여 lithium ion battery의 anode 재료로서 전기화학적 특성을 알아보고자 실험을 실시하였다. $CeO_2$ 합성에 사용되는 전구체인 cerium carbonate의 형상 및 크기, 비표면적과 같은 물리화학적 특성이 $CeO_2$ 분말의 특성에 직접적인 영향을 주기 때문에 전구체의 합성 단계에서 입자의 특성을 조절하였다. 전구체 합성의 출발원료로 cerium nitrate hexahydrate 와 ammonium carbonate를 사용하였고 반응온도 및 농도 등을 변화시켜 입자의 형상 및 결정상을 fiber형태의 orthorombic $Ce_2O(CO_3)_2{\cdot}H_2O$와 구형의 hexagonal $CeCO_3OH$의 세리아 전구체를 합성하였다. 이를 $300^{\circ}C$에서 30분 동안 하소하여 전구체의 입자형상을 유지하는 cubic $CeO_2$를 합성하고 X-ray diffraction, FE-SEM, micropore physisorption analyzer 분석을 통하여 입자의 결정상과 형상, 비표면적 등을 비교 분석하고 $Li/CeO_2$ couple의 충,방전 용량과 수명특성을 비교 분석하여 $CeO_2$의 전기화학적 특성을 알아보았다.