• 한국분말재료학회지
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• 제25권4호
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• pp.296-301
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• 2018

In this study, an experiment is performed to recover the Li in $Li_2CO_3$ phase from the cathode active material NMC ($LiNiCoMnO_2$) in waste lithium ion batteries. Firstly, carbonation is performed to convert the LiNiO, LiCoO, and $Li_2MnO_3$ phases within the powder to $Li_2CO_3$ and NiO, CoO, and MnO. The carbonation for phase separation proceeds at a temperature range of $600^{\circ}C{\sim}800^{\circ}C$ in a $CO_2$ gas (300 cc/min) atmosphere. At $600{\sim}700^{\circ}C$, $Li_2CO_3$ and NiO, CoO, and MnO are not completely separated, while Li and other metallic compounds remain. At $800^{\circ}C$, we can confirm that LiNiO, LiCoO, and $Li_2MnO_3$ phases are separated into $Li_2CO_3$ and NiO, CoO, and MnO phases. After completing the phase separation, by using the solubility difference of $Li_2CO_3$ and NiO, CoO, and MnO, we set the ratio of solution (distilled water) to powder after carbonation as 30:1. Subsequently, water leaching is carried out. Then, the $Li_2CO_3$ within the solution melts and concentrates, while NiO, MnO, and CoO phases remain after filtering. Thus, $Li_2CO_3$ can be recovered.

• Korean Chemical Engineering Research
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• 제51권4호
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• pp.460-464
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• 2013

본 연구에서는 $LiMn_2O_4$ 제조에서 Mn 원료로 사용되는 CMD를 seed 첨가법을 사용하여 제조하고자 하였으며, Seed의 열처리 온도가 CMD 합성에 미치는 영향을 고찰하고, 그로부터 제조되는 $LiMn_2O_4$의 전기화학적 특성을 평가하고자 하였다. 제조한 시료의 물성평가는 X-선 회절 분석법(XRD), 주사전자현미경(SEM)을 통하여 실시하였다. 그 결과, $MnCO_3$를 $300^{\circ}C$ 이상의 온도에서 열처리하여 seed로 사용할 경우 ${\gamma}-MnO_2$ 상의 CMD가 얻어졌으며, 그 CMD를 LMO 제조에 사용할 경우 전기화학적 특성이 비교적 우수한 LMO가 얻어졌다.

• Bulletin of the Korean Chemical Society
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• 제34권9호
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• pp.2573-2576
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• 2013

Rate capability and cyclability of $LiMn_2O_4$ should be improved in order to use it as a cathode material of lithium-ion batteries for hybrid-electric-vehicles (HEV). To enhance the rate capability and cyclability of $LiMn_2O_4$, it was coated with $MnV_2O_6$ by a sol-gel method. A $V_2O_5$ sol was prepared by a melt-quenching method and the $LiMn_2O_4$ coated with the sol was heat-treated to obtain the $MnV_2O_6$ coating layer. Crystal structure and morphology of the samples were examined by X-ray diffraction, SEM and TEM. The electrochemical performances, including cyclability at $60^{\circ}C$, and rate capability of the bare and the coated $LiMn_2O_4$ were measured and compared. Overall, $MnV_2O_6$ coating on $LiMn_2O_4$ improves the cyclability at high temperature and rate capability at room temperature at the cost of discharge capacity. The improvement in cyclability at high temperature and the enhanced rate capability is believed to come from the reduced contact between the electrode, and electrolyte and higher electric conductivity of the coating layer. However, a dramatic decrease in discharge capacity would make it impractical to increase the coating amount above 3 wt %.

• 전기화학회지
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• 제14권3호
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• pp.131-137
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• 2011

[ $LiMn_2O_4$ ] $Mn^{2+}$이온 용출현상 연구를 위한 간단하고 신속한 전기화학적 $Mn^{2+}$이온 분석법을 정립하였다. 이 분석법은 완충용액에서 $Mn^{2+}$이온이 $Mn^{4+}(MnO_2)$로 산화되는 원리를 이용한다. 최적조건 (pH 8.9 0.04 M $NH_3-NH_4Cl$ 완충용액 및 glassy carbon 작업전극)에서, Linear sweep voltammetry(LSV) 측정에 대해 $5{\mu}M-100{\mu}M$ (0.275-5.5 ppm) $Mn^{2+}$이온 범위에서, differential pulse voltammetry (DPV) 측정에 대해 $0.2{\mu}M-10{\mu}M$ (0.011-0.55 ppm) 범위에서 선형적 응답 특성을 확인하였다. 또한, 측정용액에 리튬 이차전지용 전해액 ($LiPF_6$, EC, EMC)이 첨가할 경우, 첨가량에 비례하여 $Mn^{2+}$ 이온의 산화 전류 감소하였는데, 이러한 감소의 주요 원인은 EMC보다는 $LiPF_6$와 EC성분임을 확인하였다.

• 한국세라믹학회지
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• 제27권1호
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• pp.7-12
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• 1990

The influence of MnO2 on the sintering property and PTCR behavior of(Ba0.8Sr0.2)TiO2 has been investigated. And the densities, grain sizes and electrical resitivities of specimens were measured as a function of doping with Mn ion of varying concentration. The density and grain size of the sintered specimens were almost the same regardless of MnO2 addition up to 0.2mol% MnO2. But in the case of 0.25mol% MnO2 addition, abnormal grain growth was appeared. So the grain size distribution was wide and density decreased greatly. The room-temperature resistivity increased as Mn content increased and the temperature coefficient of resistivity was highest in the case of 0.15mol% MnO2 addition.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2980-2984
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• 2010

A new poly (vinyl chloride) (PVC) membrane electrode that is highly selective to $Mn^{+2}$ ions was prepared using N,N'-bis(2'-pyridinecarboxamide)-1,2-ethane ($bpenH_2$) as a suitable neutral carrier. This concentration range ($1.0{\times}10^{-5}$ to $1.0{\times}10^{-1}\;M$) with Nernstian slope of $29.3{\pm}0.5\;mV$ per decade. The detection limit and the response time of electrode were $8.0{\times}10^{-6}\;M$ and (${\leq}15\;s$) respectively. The membrane can be used for more than two months without observing any divergence. The electrodes exhibited excellent selectivity for $Mn^{+2}$ ion over other mono-, di- and trivalent cations. Selectivity coefficients were determined by the matched potential method (MPM). The electrode can be used in the pH range from 4.0 - 9.0. The isothermal coefficient of this electrode amounted to 0.00023 V/$^{\circ}C$. The stability constant (log $K_s$) of the $Mn^{+2}$ - $bpenH_2$ complex was determined at $25^{\circ}C$ by potentiometric titration in mixed aqueous solution. The proposed electrode was applied to the determination of $Mn^{+2}$ ions in real samples.

• 한국세라믹학회지
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• 제37권6호
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• pp.552-558
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• 2000

LiMn2O4 thin fiolm cathodes for Li-ion secondary battery were fabricated by r.f. magnetron sputtering technique. As-deposited films were amorphous. A spinel structure could not be obtained LiMn2O4 films by in-situ thermal annealing. After post thermal annealing over $700^{\circ}C$ in oxygen atmosphere, LiMn2O4 films prepared above 100 W r.f. power could be crystallized into a spinel structure. The electrochemical property of the LiMn2O4 film cathodes was tested in a Li/1 M LiClO4 in PC/LiMn2O4 cell. From cyclic voltammetry at scan rate of 2mV/sec of 2.5~4.5V, LiMn2O4 electrode prepared by post annealing at 75$0^{\circ}C$ showed good initial capacity. LiMn2O4 electrode prepared by post annealing at 80$0^{\circ}C$ showed the best crycling performance.

• 한국전기전자재료학회논문지
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• 제11권3호
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• pp.242-247
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• 1998

In this study, we have synthesized $ZnGa_2O_4$:Mn,X powder doped with Mn, MnO, $MnF_2$ and $MnCl_2$, low voltage green emitting phosphor, in vacuum atmosphere. From PL spectra, the intensity of the emission peak, the brightness with coactivator show that $ZnGa_2O_4$:Mn,Cl > $ZnGa_2O_4$:Mn,F > $ZnGa_2O_4$:Mn,O > $ZnGa_2O_4$:Mn. These improvement of the brightness are caused by the increase of the concentration of $Mn^{2+}$ ion. In case of $ZnGa_2O_4$:Mn,Cl and ZnGa$_2$O$_4$:Mn,F, the brightness is enhanced much more, which is owed to the decrease of defect of host material. For $ZnGa_2O_4$:Mn,Cl phosphor fabricated with optimized condition, the decay time becomes short from 30 ms of the $ZnGa_2O_4$:Mn and $ZnGa_2O_4$:Mn,O to 6 ms and the brightness of CL at 1 kV, 1 mA is 60 cd/$m^2$.

• 한국자기학회지
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• 제5권5호
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• pp.782-785
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• 1995

In this paper, $Mn^{2+}$ ion was doped in Y-Ba-Cu-O as an EPR probe. The following samples were prepared by conventional solid-state reaction method : $YBa_{2}Cu_{2.96}Mn_{0.04}O_{7-\delta}$ (MN-I), annealed $YBa_{2}Cu_{2.96}Mn_{0.04}O_{7-\delta}$ (AMN) and $YBa_{2}Cu_{2.94}Mn_{0.06}O_{7-\delta}$ (MN-II). AMN sample was obtained from MN-I by annealing for 1 hr under the Ar gas atmosphere at $600^{\circ}C$. X-band (~9.05 GHz) EPR spectra were measured from 103 K to room temperature by employing a JES-RE3X spectroscopy with a $TE_{0.11}$ cylindrical cavity and 100 kHz modulation frequency. In MN-I we have observed only the $Cu^{2+}$ signal. The fact that no $Mn^{2+}$ signal was observed, in spite of $Mn^{2+}$ being a very sensitive EPR probe, indicates that most likely isolated $Mn^{2+}$ ions don't exist in the MN-I sample. Most probably $Mn^{2+}$ ions in the MN-I sample interact antiferromagnetically and hence are EPR silent. The AMN spectra of at room temperature and 103 K indicate not only the $Cu^{2+}$ signal but also an extra signal, which increases with decreasing temperature. It is suggested that the extra signal originates from Mn ions that were antiferromagnetically coupled before the annealing process. In MN-II, from 103 K to room temperature, also, the extra signal was observed together with the $Cu^{2+}$ signal. The extra signal in MN-II, however, decreases with decreasing temperature and nearly disappears at 103 K. The signal originates from Mn ions in impurity phases that include $Mn^{2+}$ ions. We suppose that there exist at least two $Mn^{2+}$ doped phases in Y-Ba-Cu-O. The $Mn^{2+}$ signal of one phase is undectable at all temperature and that of another phase decreases with decreasing temperature and disappears around 103 K.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2016년도 추계학술대회 논문집
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• pp.97-97
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• 2016

Development of advanced Li-ion battery cells with high durability is critical for safe operation, especially in applications to electric vehicles and portable electronic devices. Understanding fundamental mechanism on the formation of a solid-electrolyte interphase (SEI) layer, which plays a substantial role in the electrochemical stability of the Li-ion battery, in a cathode was rarely reported unlike in an anode. Using first-principles density functional theory (DFT) calculations and ab-initio molecular dynamic (AIMD) simulations we demonstrate atomic-level process on the generation of the SEI layer at the interface of a carbonate-based electrolyte and a spinel $LiMn_2O_4$ cathode. To accomplish the object we calculate the energy band alignment between the work function of the cathode and frontier orbitals of the electrolyte. We figure out that a proton abstraction from the carbonate-based electrolyte is a critical step for the initiation of an SEI layer formation. Our results can provide a design concept for stable Li-ion batteries by optimizing electrolytes to form proper SEI layers.