• 한국재료학회지
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• 제32권4호
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• pp.210-215
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• 2022

Extensive research is being carried out on Ni-rich Li(Ni_xCo_yMn_1-x-y)O₂ (NCM) due to the growing demand for electric vehicles and reduced cost. In particular, Ni-rich Li(Ni_xCo_yMn_1-x-y-zAl_z)O₂ (NCMA) is attracting great attention as a promising candidate for the rapid development of Co-free but electrochemically more stable cathodes. Al, an inactive element in the structure, helps to improve structural stability and is also used as a doping element to improve cycle capability in Ni-rich NCM. In this study, NCMA was successfully synthesized with the desired composition by direct coprecipitation. Boron and tin were also used as dopants to improve the battery performance. Macro- and microstructures in the cathodes were examined by microscopy and X-ray diffraction. While Sn was not successfully doped into NCMA, boron could be doped into NCMA, leading to changes in its physicochemical properties. NCMA doped with boron revealed substantially improved electrochemical properties in terms of capacity retention and rate capability compared to the undoped NCMA.

• 한국세라믹학회지
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• 제40권5호
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• pp.401-404
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• 2003

LiN $i_{y}$M $n_{2-y}$ $O_4$were synthesized by calcining a mixture of LiOH, Mn $O_2$(CMD), and NiO at 40$0^{\circ}C$ for 10 h and then calcining at 85$0^{\circ}C$ for 48 h in air with intermediate grinding. The voltage vs. discharge capacity curves at a current density 300 $\mu$A/c $m^2$ between 3.5 V and 4.3 V showed two plateaus, but the plateaus became ambiguous as the y value increases. The sample with y=0.02 had the largest first discharge capacity, 118.1 mAh/g. As the value y increases from 0.02 up to 0.2, on the whole, the cycling performance became better. The LiN $i_{0.10}$M $n_{1.90}$ $O_4$sample had a relatively large first discharge capacity 95.0 mAh/g and showed an excellent cycling performance. The samples with larger lattice parameter have, in general, larger discharge capacities. The reduction curves in the cyclic voltammograms for the y=0.05-0.20 samples exhibit three peak showing that the reduction may proceed in three stages in these samples. For the samples with relatively large discharge capacity, the lattice destruction induced by strain causes the capacity fading of LiN $i_{y}$M $n_{2-y}$ $O_4$ with cycling.cling.ing.

• 전기화학회지
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• 제19권1호
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• pp.1-8
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• 2016

층상구조 삼성분계 $LiNi_{1-x-y}Co_xMn_yO_2$ 양극활물질을 4.3 V 이상 고전압으로 충전시키면 용량 증가를 기대할 수 있으나 기존 전해액의 산화안정성이 낮아 고전압 성능 구현에 제한이 있다. 본 연구에서는 설폰계 전해액 첨가제인 dimethyl sulfone (DMS), diethyl sulfone (DES), ethyl methyl sulfone (EMS)을 사용하여 $LiNi_{0.5}Co_{0.2}Mn_{0.3}O_2$ 양극의 고전압 특성을 향상시키고자 한다. 본 논문은 다양한 선형 sulfone계 첨가제가 포함된 전해액에서 3.0-4.6 V 전압범위에서 양극의 충방전 특성과 양극-전해액간 계면거동과 표면층 분석에 대한 내용으로 이루어져 있다. 특히 Dimethyl sulfone (DMS) 첨가제 사용시, 50 사이클 중 $198-173mAhg^{-1}$의 방전 용량과 87%의 용량유지율을 보여 기존 전해액 대비 상당히 향상된 충방전 안정성을 보였다. 표면조성 분광분석 결과, DMS 첨가제 사용시 양극에 안정한 표면보호층이 형성되고 금속 용출이 억제되어 고전압 충방전 특성이 향상되었음 알 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제34권1호
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• pp.89-94
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• 2013

Layered $Li_{1+x}(Mn_{0.4}Ni_{0.4}Fe_{0.2})_{1-x}O_2$ (0 < x < 0.3) solid solutions were synthesized using solgel method with adipic acid as chelating agent. Structural and electrochemical properties of the prepared powders were examined by means of X-ray diffraction, Scanning electron microscopy and galvanostatic charge/discharge cycling. All powders had a phase-pure layered structure with $R\bar{3}m$ space group. The morphological studies confirmed that the size of the particles increased at higher x content. The charge-discharge profiles of the solid solution against lithium using 1 M $LiPF_6$ in EC/DMC as electrolyte revealed that the discharge capacity increases with increasing lithium content at the 3a sites. Among the cells, $Li_{1.2}(Mn_{0.32}Ni_{0.32}Fe_{0.16})O_2$ (x = 0.2)/$Li^+$ exhibits a good electrochemical property with maximum initial capacity of 160 $mAhg^{-1}$ between 2-4.5 V at 0.1 $mAcm^{-2}$ current density and the capacity retention after 25 cycles was 92%. Whereas, the cell fabricated with x = 0.3 sample showed continuous capacity fading due to the formation of spinel like structure during the subsequent cycling. The preparation of solid solutions based on $LiNiO_2-LiFeO_2-Li_2MnO_3$ has improved the properties of its end members.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2007년도 하계학술대회 논문집 Vol.8
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• pp.46-46
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• 2007

There has been rapid progress in the portable electronics industry. which has led to a great increase for a demand of portable, lightweight power sources. Lithium 2'nd batteries have met these demand. and many studies on the cahtod materials for the lithium 2,nd batteries have been reported during the last decade. Possible candidates for the cathode materials for lithium 2,nd batteries are $LiCoO_2$, $LiNiO_2$, and $LiMn_2O_4$. Currently $LiCoO_2$ is widely used. but $LiMn_2O_4$ is an excellent alternative material in view of its several advantages such a low cost as well as the wasy availability of raw materials and environmental benignity. In this study, find the most suitable synthesis method that satisfied high capacitor and stability cycle character, etc in Li-Mn oxide for 2'nd batteries. And also made an experiment on doping the $LiMn_2O_4$ spinel with a small amount of metal ions has a remarkable effect on the electrochemical properties and characterics of powder, BET, PSA, Porosity, etc.

• Environmental Engineering Research
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• 제25권1호
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• pp.88-95
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• 2020

An investigation of rare metals recovery from LiNi_xCo_yMn_zO₂ cathode material of the end-of-life lithium-ion batteries is presented. To determine the influence of reductant on the leach process, the cathode material (containing Li 7.6%, Co 20.4%, Mn 19.4%, and Ni 19.3%) was leached in H₂SO₄ solutions either with or without H₂O₂. The optimal process parameters with respect to acid concentration, addition dosage of H₂O₂, temperature, and the leaching time were found to be 2.0 M H₂SO₄, 4 vol.% H₂O₂, 70℃, and 150 min, respectively. The yield of metal values in the leach liquor was > 99%. The leach liquor was subsequently treated by precipitation techniques to recover nickel as Ni(C₄H₇N₂O₂)₂ and lithium as Li₂CO₃ with stoichiometric ratios of 2:1 and 1.2:1 of dimethylglyoxime:Ni and Na₂CO₃:Li, respectively. Cobalt was recovered by solvent extraction following a 3-stage process using Na-Cyanex 272 at pH_eq ~5.0 with an organic-to-aqueous phase ratio (O/A) of 2/3. The loaded organic phase was stripped with 2.0 M H₂SO₄ at an O/A ratio of 8/1 to yield a solution of 114 g/L CoSO₄; finally recovered CoSO₄.xH₂O by crystallization. The process economics were analyzed and found to be viable with a margin of $476 per ton of the cathode material.

• 전기화학회지
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• 제10권3호
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• pp.184-189
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• 2007

전자 산업의 발전과 함께 휴대폰, 노트북, PDA등과 같은 휴대 정보 전자 기기의 고성능 에너지 공급원으로서 이차전지 산업의 중요성이 높아지고 있다. 이에 따라 리튬이차전지의 핵심부품인 양극재료의 고성능화 및 안전성 확보에 대해 많은 관심이 증대되고 있다. 현재 사용되고 있는 양극재료에는 $LiCoO_2,\;LiMn_2O_4,\;LiNi_xCo_yMn_zO_2,\;LiNi_xCo_yM_zO_2$ (M=Al, Zr, Mg 등) 등이 있으며, 그중 가장 대표적으로 사용되고 있는 물질은 $LiCoO_2$이다. 그러나 $LiCoO_2$가 가지고 있는 용량적 한계 및 안전성 문제로 인하여 $LiCoO_2$의 성능 개선 및 3성분계, 올리빈계와 같은 대체물질의 개발에 대한 연구가 활발히 진행중이다. 특히 산화물($M_xO_3$)을 이용한 활물질 표면처리와 같은 성능개선 및 안전성 확보연구는 국내 및 국외에서 활발히 진행되고 있다. 본 연구에서는 $LiCoO_2$의 표면처리 과정에서 불균일 코팅된 산화물의 탈리 및 이의 응집에 의한 침전물 생성 및 표면처리량의 증가에 따른 전지에서의 부작용에 대하여 분석하고, 이와 같은 문제점을 개선하기 위해 코팅량 조정 및 표면처리 공정의 혼합, 건조, 소성 조건 등과 같은 신공정에 대한 연구와 전기화학적 특성 고찰을 실시하였다.

• 한국분말재료학회지
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• 제23권4호
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• pp.287-296
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• 2016

$Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$ powders have been synthesized in a continuously stirred tank reactor via a co-precipitation reaction between aqueous metal sulfates and NaOH using $NH_4OH$ as a chelating agent. The co-precipitation temperature is varied in the range of $30-80^{\circ}C$. Calcination of the prepared precursors with $Li_2CO_3$ for 8 h at $1000^{\circ}C$ in air results in Li $Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ powders. Two kinds of obtained powders have been characterized by X-ray diffraction (XRD), scanning electron microscopy, particle size analyzer, and tap density measurements. The co-precipitation temperature does not differentiate the XRD patterns of precursors as well as their final powders. Precursor powders are spherical and dense, consisting of numerous acicular or flaky primary particles. The precursors obtained at 70 and $80^{\circ}C$ possess bigger primary particles having more irregular shapes than those at lower temperatures. This is related to the lower tap density measured for the former. The final powders show a similar tendency in terms of primary particle shape and tap density. Electrochemical characterization shows that the initial charge/discharge capacities and cycle life of final powders from the precursors obtained at 70 and $80^{\circ}C$ are inferior to those at $50^{\circ}C$. It is concluded that the optimum co-precipitation temperature is around $50^{\circ}C$.

• 한국분말재료학회지
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• 제26권1호
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• pp.49-57
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• 2019

Layered $LiNi_{0.83}Co_{0.11}Mn_{0.06}O_2$ cathode materials single- and dual-doped by the rare-earth elements Ce and Nd are successfully fabricated by using a coprecipitation-assisted solid-phase method. For comparison purposes, non-doping pristine $LiNi_{0.83}Co_{0.11}Mn_{0.06}O_2$ cathode material is also prepared using the same method. The crystal structure, morphology, and electrochemical performances are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) mapping, and electrochemical techniques. The XRD data demonstrates that all prepared samples maintain a typical ${\alpha}-NaFeO_2$-layered structure with the R-3m space group, and that the doped samples with Ce and/or Nd have lower cation mixing than that of pristine samples without doping. The results of SEM and EDS show that doped elements are uniformly distributed in all samples. The electrochemical performances of all doped samples are better than those of pristine samples without doping. In addition, the Ce/Nd dual-doped cathode material shows the best cycling performance and the least capacity loss. At a 10 C-rate, the electrodes of Ce/Nd dual-doped cathode material exhibit good capacity retention of 72.7, 58.5, and 45.2% after 100, 200, and 300 cycles, respectively, compared to those of pristine samples without doping (24.4, 11.1, and 8.0%).

• Bulletin of the Korean Chemical Society
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• 제34권9호
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• pp.2597-2603
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• 2013

The reactions of hydrated $CdCl_2$, $MnCl_2$, and $NiCl_2$ with 2,2'-bipyidine-3,3',6,6'-tetracarboxylic acid ($H_4bptc$) afforded the mononuclear [$Cd^{II}(H_2bptc)(H_2O)_3]{\cdot}H_2O$ (1), linear $\{[Cd(H_2bptc)(H_2O)]{\cdot}3H_2O\}_n$ (2), 3-D heterobimetallic $[NaCd(Hbptc)(H_2O)]$ (3), layer $[Mn(H_2bptc)(H_2O)]_n$ (4) and a dinuclear compound $[Ni_2(H_2bptc)-(H_2O)_2]{\cdot}6H_2O$ (5). These compounds have been characterized by elemental analysis, IR, and their structures have been determined by X-ray crystallography. The thermal stabilities of 1-3 were measured by thermogravimetric analysis (TGA) and their solid state luminescence properties together with the free ligand $H_4bptc$ were investigated at room temperature.