• KEPCO Journal on Electric Power and Energy
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• 제6권4호
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• pp.461-466
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• 2020

There are many application fields of electrical energy storage such as load shifting, integration with renewables, frequency or voltage supports, and so on. Especially, the frequency regulation is needed to stabilize the electric power system, and there have to be more than 1 GW as power reserve in Korea. Ni-rich layered oxide cathode materials have been investigated as a cathode material for Li-ion batteries because of their higher discharge capacity and lower cost than lithium cobalt oxide. Nonetheless, most of them have been investigated using small coin cells, and therefore, there is a limit to understand the deterioration mode of Ni-rich layered oxides in commercial high energy Li-ion batteries. In this paper, the pouch-type 20 Ah-scale Li-ion full cells are fabricated using Ni-rich layered oxides as a cathode and graphite as an anode. Above all, two test conditions for the application of frequency regulation were established in order to examine the performances of cells. Then, the electrochemical performances of two types of Ni-rich layered oxides are compared, and the long-term performance and degradation mode of the cell using cathode material with high nickel contents among them were investigated in the frequency regulation conditions.

• Journal of Electrochemical Science and Technology
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• 제13권2호
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• pp.269-278
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• 2022

Utilization of high-voltage electrolyte additive(s) at a small fraction is a cost-effective strategy for a good solid electrolyte interphase (SEI) formation and performance improvement of a lithium-rich layered oxide-based high-energy lithium-ion cell by avoiding the occurrence of metal-dissolution that is one of the failure modes. To mitigate metal-dissolution, we explored fluorinated dual-additives of fluoroethylene carbonate (FEC) and di(2,2,2-trifluoroethyl)carbonate (DFDEC) for building-up of a good SEI in a 4.7 V full-cell that consists of high-capacity silicon-graphite composite (15 wt% Si/C/CF/C-graphite) anode and Li_1.13Mn_0.463Ni_0.203Co_0.203O₂ (LMNC) cathode. The full-cell including optimum fractions of dual-additives shows increased capacity to 228 mAhg^-1 at 0.2C and improved performance from the one in the base electrolyte. Surface analysis results find that the SEI stabilization of LMNC cathode induced by dual-additives leads to a suppression of soluble Mn²⁺-O formation at cathode surface, mitigating metal-dissolution event and crack formation as well as structural degradation. The SEI and structure of Si/C/CF/C-graphite anode is also stabilized by the effects of dual-additives, contributing to performance improvement. The data give insight into a basic understanding of cathode-electrolyte and anode-electrolyte interfacial processes and cathode-anode interaction that are critical factors affecting full-cell performance.

• 한국세라믹학회지
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• 제51권4호
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• pp.295-299
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• 2014

Electrical conductivities of complex perovskites, layered perovskite and Sr doped layered perovskite oxides were measured and analyzed for cathode materials of Intermediate Temperature-operating Solid Oxide Fuel Cells (IT-SOFCs). The electrical conductivities of $Sm_{1-x}Sr_xCoO_{3-\delta}$ (x = 0.3 and 0.7) exhibit a metal-insulator transition (MIT) behavior as a function of temperature. However, $Sm_{0.5}Sr_{0.5}CoO_{3-\delta}$ (SSC55) shows metallic conductivity characteristics and the maximum electrical conductivity value compared to the values of $Pr_{0.5}Sr_{0.5}CoO_{3-\delta}$ (PSC55) and $Nd_{0.5}Sr_{0.5}CoO_{3-\delta}$ (NSC55). The electrical conductivity of $SmBaCo_2O_{5+\delta}$ (SBCO) exhibits a MIT at about $250^{\circ}C$. The maximum conductivity is 570 S/cm at $200^{\circ}C$ and its value is higher than 170 S/cm over the whole temperature range tested. $SmBa_{0.5}Sr_{0.5}Co_2O_{5+\delta}$ (SBSCO), 0.5 mol% Sr and Ba substituted at the layered perovskite shows a typically metallic conductivity that is very similar to the behavior of the SSC55 cathode, and the maximum and minimum electrical conductivity in the SBSCO are 1280 S/cm at $50^{\circ}C$ and 280 S/cm at $900^{\circ}C$.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2006년도 추계학술대회
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• pp.368-371
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• 2006

[ $La_{0.8}Sr_{0.2}Co_{1-x}Mn_xO_3$ ] cathode as a high performance cathode on YSZ electrolyte was studied by analyzing impedance spectra. It was shown that cathode property of $La_{0.8}Sr_{0.2}Co_{1-x}Mn_xO_3$ is bet ter than that of$La_{0.8}Sr_{0.2}CoO_3$. At $700^{\circ}C$ in air environment, $La_{0.8}Sr_{0.2}Co_{0.4}Mn_{0.6}O_3$ cathode on CGO- layered YSZ electrolyte showed very low area specific resistance of $0.14{\Omega}cm^2$, which is low enough for intermediate-temperature sol id oxide fuel cells. This is because material properties of ionic conductivity and thermal expansion compatibility with electrolyte were optimized. Judging from activation energy and oxygen part i al pressure dependance of cathode property, it was noted that oxygen surface exchange kinetics is dominantly influential on cathode property in higher temperature region than $700^{\circ}C$ and oxygen self-diffusion in cathode material is more influential in lower temperature region.

• 공업화학
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• 제31권1호
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• pp.97-102
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• 2020

최근 리튬이차전지 양극 소재의 다양한 열화 메커니즘들이 밝혀지면서 이것을 제어하여 새로운 전기화학적 특성을 구현하고 기존 소재의 한계점을 극복하고자 하는 연구결과들이 많이 보고되고 있다. 특히, 리튬과잉산화물은 250 mA h g^-1 이상의 고 용량 차세대 리튬이차전지 양극 물질로 주목받고 있으나, 충방전 과정 중에 소재 특유의 원자 구조 열화로 인해 활용이 제한되고 있다. 본 연구는 0.4Li₂MnO₃_0.6LiNi_1/3Co_1/3Mn_1/3O₂ 리튬과잉소재의 충방전 과정 중에서 겪는 원자 구조 변화 과정을 분석하여 소재의 열화 과정을 밝히고 이를 개선하기 위한 연구 방향을 제시하고자 한다. 이를 위해, 원자 단위의 분해능을 갖는 전자투과현미경을 활용하여 충방전 중 원자 구조의 변화 과정을 분석하고 이러한 구조 변화가 소재의 전기화학적 특성에 어떠한 영향을 미치는지 밝히고자 하였다. 충전 과정 중에 발생한 다량의 리튬 빈자리로 인해 구조 불안정성이 일어났고, 이로 인해 전이 금속이 리튬 빈 자리로 이동하면서 구조 열화가 확인되었다. 결과적으로 이러한 구조 변이는 리튬과잉소재의 가장 큰 문제점인 방전 전압 강하 특성을 야기한다는 것을 알아내었다.

• Journal of Electrochemical Science and Technology
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• 제15권1호
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• pp.51-66
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• 2024

Modern society is making numerous efforts to reduce reliance on carbon-based energy systems. A notable solution in this transition is the adoption of lithium-ion batteries (LIBs) as potent energy sources, owing to their high energy and power densities. Driven by growing environmental challenges, the application scope of LIBs has expanded from their initial prevalence in portable electronic devices to include electric vehicles (EVs) and energy storage systems (ESSs). Accordingly, LIBs must exhibit long-lasting cyclability and high energy storage capacities to facilitate prolonged device usage, thereby offering a potential alternative to conventional sources like fossil fuels. Enhancing the durability of LIBs hinges on a comprehensive understanding of the reasons behind their performance decline. Therefore, comprehending the degradation mechanism, which includes detrimental chemical and mechanical phenomena in the components of LIBs, is an essential step in resolving cycle life issues. The LIB systems presently being commercialized and developed predominantly employ graphite anode and layered oxide cathode materials. A significant portion of the degradation process in LIB systems takes place during the electrochemical reactions involving these electrodes. In this review, we explore and organize the aging mechanisms of LIBs, especially those with graphite anodes and layered oxide cathodes.

• Journal of Industrial and Engineering Chemistry
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• 제68권
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• pp.180-186
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• 2018

We report the discovery of Li-rich $Li_{1+x}[(Ni_{0.225}Co_{0.15}Mn_{0.625})_{1-y}V_y]O_2$ as a cathode material for rechargeable lithium-ion batteries in which a small amount of tetravalent vanadium ($V^{4+}$) is selectively and completely incorporated into the manganese sites in the lattice structure. The unwanted oxidation of vanadium to form a $V_2O_5-like$ secondary phase during high-temperature crystallization is prevented by uniformly dispersing the vanadium ions in coprecipitated $[(Ni_{0.225}Co_{0.15}Mn_{0.625})_{1-y}V_y](OH)_2$ particles. Upon doping with $V^{4+}$ ions, the initial discharge capacity (>$275mA\;h\;g^{-1}$), capacity retention, and voltage decay characteristics of the Li-rich layered oxides are improved significantly in comparison with those of the conventional undoped counterpart.

• 한국분말재료학회지
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• 제24권2호
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• pp.87-95
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• 2017

Lithium silicate, a lithium-ion conducting ceramic, is coated on a layer-structured lithium nickel manganese oxide ($LiNi_{0.7}Mn_{0.3}O_2$). Residual lithium compounds ($Li_2CO_3$ and LiOH) on the surface of the cathode material and $SiO_2$ derived from tetraethylorthosilicate are used as lithium and silicon sources, respectively. Powder X-ray diffraction and scanning electron microscopy with energy-dispersive spectroscopy analyses show that lithium silicate is coated uniformly on the cathode particles. Charge and discharge tests of the samples show that the coating can enhance the rate capability and cycle life performance. The improvements are attributed to the reduced interfacial resistance originating from suppression of solid-electrolyte interface (SEI) formation and dissolution of Ni and Mn due to the coating. An X-ray photoelectron spectroscopy study of the cycled electrodes shows that nickel oxide and manganese oxide particles are formed on the surface of the electrode and that greater decomposition of the electrolyte occurs for the bare sample, which confirms the assumption that SEI formation and Ni and Mn dissolution can be reduced using the coating process.

• 전기화학회지
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• 제16권3호
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• pp.169-176
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• 2013

현재 이차전지에서 사용중인 양극활물질은 구조 안정성이 높은 층상구조(Layered Structure)의 리튬 금속 산화물(Solid State Lithium Oxide Compounds)이 주로 사용된다. 최근에는 리튬이차전지의 성능향상을 위해서 음극활물질과 전해질 사이의 계면뿐만 아니라, 양극활물질과 전해질 사이의 계면에 관한 연구가 활발히 진행되고 있으며, 이러한 계면의 연구를 위해서는 음극활물질 뿐만 아니라, 양극활물질의 표면에 관한 연구도 선행적으로 이루어져야 하는 상황이다. 대표적인 리튬금속 산화물질인 니켈산리튬($LiNiO_2$)과 코발트산리튬($LiCoO_2$)은 서로 매우 유사한 구조를 갖는 층상구조의 양극활물질이다. 코발트산리튬이 다양한 실험적, 이론적 연구가 진행된 반면에, 니켈산 리튬은 실험적 연구에 비해서 이론적 연구가 부족하다. 따라서, 본 연구에서는 니켈산리튬의 X-선 회절계 측정 결과(XRD data)에 나오는9개의 표면 방향을 범밀도함수이론(Density Functional Theory)을 이용하여 니켈산리튬 표면의 표면 에너지를 계산하였다. 니켈산리튬의 X-선 회절계 측정 결과(XRD data)에서는 (003), (104), (101), (110) 결정 등등이 순차적으로 주요하게 존재하는 것으로 확인되었다. 그러나 시뮬레이션을 이용한 각각의 표면 에너지 계산 결과, X-선 회절계 측정 결과와 다른 순서로 안정한 표면 에너지가 나타나는 결과를 얻었다. 따라서 에너지적으로 안정한 표면이자, X-선 회절계에서 주요하게 나타나는 (104)와 (101) 방향의 니켈산리튬 표면이 많이 노출되어 Li 이온의 충방전시 리튬의 삽입 탈리에 영향을 줄 것으로 예상된다.

• Journal of Electrochemical Science and Technology
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• 제2권3호
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• pp.180-185
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• 2011

The layered lithium-manganese oxide ($Li_2MnO_3$) as a cathode material of lithium ion secondary batteries was prepared and characterized the physico-chemical and electrochemical properties. The morphological and structural changes of MnO(OH) and $Li_2MnO_3$ are closely connected to the changes of electrochemical properties. The crystallinity of $Li_2MnO_3$ is enhanced as the annealing temperature increase, but its capacity is reduced due to the easier structural changes of less crystalline $Li_2MnO_3$ than highly crystalline one. Moreover, the addition of buffer material such as MnO(OH) into cathode causes to reduce the morphological and structural changes of layered $Li_2MnO_3$ and increase the discharge capacity and cycleability.