• 전기화학회지
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• 제9권2호
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• pp.64-69
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• 2006

초음파분무열분해법과 한 단계의 후열처리로 이차상이 없는 Al이 첨가된 $Li(Ni_{1/3}Co_{1/3}Mn_{1/3-x}Al_x)O_2$ (x=0.0, 0.005, 0.01. 0.05) 리튬이차전지용 양극활물질을 합성하였다. 합성된 분말은 Al의 첨가량이 많아짐에 따라서 $I_{003}/I_{104}$ 비는 감소하고 입자가 커지는 경향을 보였다. 상온에서 전류밀도 1C의 rate로 $3.0\sim4.5V$ 범위에서 충방전 시험한 결과, Al 치환량이 0.5와 1.0 at%에서는 초기용량이 180과 $184mAhg^{-1}$으로 치환하지 않았을 때의 $182mAhg^{-1}$과 차이가 없었으며, 싸이클 특성도 치환하지 않은 것과 0.5, 1.0 at% 치환한 조성에서 각각 81, 77, 81%의 방전용량이 유지되었다. 그러나 $3.0\sim4.6V$에서는 치환효과가 확실하게 나타나서, 50 싸이클 후의 치환하지 않은 것의 방전용량은 초기용량의 30%가지 감소한데 비하여 Al을 0.5 at% 치환한 것은 70%를 유지하였다. 치환에 의한 싸이클 특성 향상은 XPS 분석 결과 Al 치환이 $Mn^{3+}$의 양을 감소시켰기 때문인 것으로 사료되었다.

• Bulletin of the Korean Chemical Society
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• 제30권11호
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• pp.2584-2588
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• 2009

The effect of $LaF_3$ coating on the structural and electrochemical properties of $Li[Ni_{0.3}Co_{0.4}Mn_{0.3}]O_{2}$ cathodes was investigated using XRD, SEM, TEM, and a cycler. The coating layer consisted of nano-sized particles attached nonuniformly to the surface of pristine powder. Despite the surface coating treatment, phase difference by $LaF_3$ coating was not detected. The discharge capacities of coated electrodes were a little lower than that of pristine sample at a 1 C rate. However, as the C rate increases, the capacity retention of the coated sample becomes obviously superior to that of the pristine sample. The cyclic performances of the electrodes in the voltage range of 4.8 $\sim$ 3.0 V were also improved by the surface coating. Such enhancement is attributed to the presence of the $LaF_3$ coating layer, which effectively suppressd the reaction between electrodes and electrolytes on the surface of the $Li[Ni_{0.3}Co_{0.4}Mn_{0.3}]O_{2}$ electrode.

• 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.

• 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 $50^{\circ}C$.

• 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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2006년도 영호남 합동 학술대회 및 춘계학술대회 논문집 센서 박막 기술교육
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• pp.113-116
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• 2006

자발착화 연소반응법 (Glycine Nitrate Process)을 응용한 초음파분무열분해장치를 이용하여 이차전지의 양극재료인 Ni치환형 $LiMn_2O-4$ 분말을 합성하였고, 각각의 하소온도에 따른 분말의 특성을 평가하였다. 전구용액은 산화제로 $Mn(NO_3)_2{\cdot}6H_20$EX>, $LiNO_3$, $Ni(NO_3)_2{\cdot}6H_20$를 사용하였고, 자발착화 에너지를 공급하기 위한 연료로는 glycine를 사용하였다. 분말의 결정상을 확인하기 위해 X-선 회절 시험을 시행하였으며, 각각의 조성별로 ICP측정결과 여러 조성들($LiNi_xNm_{2-x}O_4\;0{\leq}x{\leq]0.5$) 중 $LiNi_{0.3}Nm_{1.7}O_4$의 분말이 비교적 우수한 특성을 나타내었지만, 전기화학적 특성 평가 결과 이론용량값에 미치지 못하는 용량값을 나타내었다. 이것은 분말 합성 시 미량의 미 반응된 유기물들이 분말 표면에 피복되어 전기적 성질을 변화시키고 있기 때문임을 확인하였다. 이러한 특성을 개선하고자 추가적으로 하소 공정을 실시하여 전지의 성능를 평가 하였다. 분말의 미세구조와 형태, 크기, 전기 화학적 특성을 관찰하여 하소 전 후의 분말을 비교하였다.

• Bulletin of the Korean Chemical Society
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• 제31권2호
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• pp.355-359
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• 2010

A $Li[Co_{1/3}Ni_{1/3}Mn_{1/3}]O_2$ cathode was modified by applying a $ZrF_x$ coating. The surface-modified cathodes were characterized by XRD, SEM, EDS, TEM techniques. XRD patterns of $ZrF_x$-coated $Li[Co_{1/3}Ni_{1/3}Mn_{1/3}]O_2$ revealed that the coating did not affect the crystal structure of the parent powder. SEM and TEM images showed that $ZrF_x$ nano-particles were formed as a coating layer, and EDS data confirmed that $ZrF_x$ distributed uniformly on the surface the powder. Capacity retention of coated samples at high C rates was superior to that of pristine sample. However, as the coating concentration increases beyond the optimum concentration, the rate capability was deteriorated. Whereas, as the increase of coating concentration to 2.0 wt %, the cyclic performances of the electrodes under the severe conditions (high cut-off voltage, 4.8 V, and high measurement temperature, $55^{\circ}C$) were improved considerably.

• Bulletin of the Korean Chemical Society
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• 제25권4호
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• pp.511-516
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• 2004

A Li$[Co_{0.17}Li_{0.28}Mn_{0.55}]O_2$ cathode compound was prepared by a simple combustion method. The X-ray diffraction pattern showed that this compound could be classified as ${\alpha} -NaFeO_2$ structure type with the lattice constants of a = 2.8405(9) ${\AA}$ and c = 14.228(4) ${\AA}$. According to XANES analysis, the oxidation state of Mn and Co ions in the compound were 4+ and 3+, respectively. During the first charge process, the irreversible voltage plateau at around 4.65 V was observed. The similar voltage-plateau was observed in the initial charge profile of other solid solution series between $Li_2MnO_3\;and\;LiMnO_2$ (M=Ni, Cr...). The first discharge capacity was 187 mAh/g and the second discharge capacity increased to 204 mAh/g. As the increase of cycling number, one smooth discharge profile was converted to two distinct sub-plateaus and the discharge capacity was slowly decreased. From the Co and Mn K-edge XANES spectra measured at different cyclic process, it can be concluded that irreversible transformation of phase is occurred during continuous cycling process.

• Bulletin of the Korean Chemical Society
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• 제35권9호
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• pp.2684-2688
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• 2014

Two two-dimensional cyanide- and phenoxo-bridged heterometallic M(II)-Mn(III) (M = Ni, Pd) coordination polymers $\{[Mn(saltmen)]_4[Ni(CN)_4]\}(ClO_4)_2{\cdot}CH_3OH{\cdot}H_2O$ (1) and $\{[Mn(saltmen)]_4[Pd(CN)_4]\}(ClO_4)_2{\cdot}CH_3CN{\cdot}H_2O$ (2) ($saltmen^{2-}$ = N,N'-(1,1,2,2-tetramethylethylene)bis(salicylideneaminato)dianion) have been obtained by using $K_2[M(CN)_4]$ as building blocks and a salen-tpye Schiff-base manganese(III) compound as assembling segment. Single X-ray analysis reveals their isostrutural cyanide-bridged $MMn_4$ pentanuclear cationic structure. The four Schiff base manganese units of the pentanuclear entity are self-complementary through the phenoxo oxygen atoms from the neighboring complex, therefore forming cyanide- and phenoxo-bridged 2D sheet-like structure. Investigation over magnetic susceptibilities reveals the overall ferromagnetic coupling between the adjacent Mn(III) ions bridged by the phenoxo oxygen atoms with J = 2.13 and $2.21cm^{-1}$ for complexes 1 and 2, respectively.

• 자원리싸이클링
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• 제21권5호
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• pp.79-87
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• 2012

리튬이온전지의 대형화와 범용화에 따라 경제성과 안정성 관점에서 정극재료의 개발은 중요한 과제로 대두되고 있다. 18650 원통형 전지의 에너지 밀도는 발매 초기인 1991년 230Wh/l에서 2005년 2배 이상의 500Wh/l로 증가하였으며, 제품 대부분의 에너지용량은 450~500 Wh/l, 150~190Wh/kg이고 안전성, 제조비 절감 및 장 수명을 중점적으로 개발하고 있다. $LiCoO_2$ 정극활물질 중의 Co가 고가이므로 Co 사용량을 줄이면서 에너지 용량을 향상시키기 위하여 $LiMn_2O_4$, $LiCo_{1/3}N_{i1/3}Mn_{1/3}O_2$, $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$, $LiFePO_4$-C복합체 (167 mA/g)등이 개발되고 있다. 전동자전거용 전지는 출력밀도 500 Wh/kg, 전동공구용 1,500Wh/kg, EV나 PHEV용으로는 4,000~5,000Wh/kg의 대용량 출력밀도를 요구하고 있으므로 배터리 소재의 성능을 향상시키려고 많은 연구가 진행되고 있다. 최근 Graphene-sulfur 복합체정극활물질 600 Ah/kg, 2차전지용 분자클러스터(molecular cluster) 320 Ah/kg 등의 새로운 정극활물질이 연구 개발되고 있으므로 실용화가 기대된다.