• 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.

• 대한기계학회논문집B
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• 제37권4호
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• pp.313-322
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• 2013

배터리는 최근 여러 분야에서 중요한 에너지원 역할을 하고 있는데, 사용 중 충방전을 거듭하면 용량이 점차 저하되며 초기 대비 80% 이하로 떨어지면 고장으로 간주되므로, 이를 예측하기 위한 수명 예측 기법이 활발히 개발되고 있다. 본 연구에서는 사용중인 배터리에 대해 충전곡선 기울기를 이용하여 배터리의 용량을 평가하고 이를 바탕으로 잔존수명을 예측하는 새로운 방법을 제안하였다. 이 과정에서 발생하는 여러 불확실성을 고려하기 위해 베이지안 접근법에 기반한 파티클 필터 방법을 활용하였고 그 결과 잔존수명을 확률분포로 구하였다. 개발된 방법을 미국 NASA Ames 연구소와 본 연구실에서 직접 수행한 배터리 충방전 시험 데이터에 대해 각각 적용한 결과 충전곡선 기울기가 용량 열화를 잘 나타내며 파티클 필터로 예측된 잔존수명 신뢰구간은 실제 수명을 잘 포함함을 확인할 수 있었다.

• Journal of Electrochemical Science and Technology
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• 제2권3호
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• pp.146-151
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• 2011

The formation of Li-Si-O phases, $Li_4SiO_4$ and $Li_2SiO_3$ from the starting materials SiO and $Li_2O$ are analyzed using Vienna Ab-initio Simulation (VASP) package and the total energies of Li-Si-O compounds are evaluated using Projector Augmented Wave (PAW) method and correlated the structural characteristics of the binary system SiO-$Li_2O$ with experimental data from electrochemical method. Despite $Li_2SiO_3$ becomes stable phase by virtue of lowest formation energy calculated through VASP, the experimental method shows presence of $Li_4SiO_4$ as the only product formed when SiO and $Li_2O$ reacts during slow heating to reach $550^{\circ}C$ and found no evidence for the formation of $Li_2SiO_3$. Also, higher density of $Li_4SiO_4$(2.42 g $ml^{-1}$) compared to the compositional mixture $1SiO_2-2Li_2O$ (2.226 g $ml^{-1}$) and better cycle capacity observed through experiment proves that $Li_4SiO_4$ as the most stable anode supported by better cycleabilityfor lithium ion battery remains as paradox from the point of view of VASP calculations.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.5-5
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• 2011

The research and development of hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV) and electric vehicle (EV) are intensified due to the energy crisis and environmental concerns. In order to meet the challenging requirements of powering HEV, PHEV and EV, the current lithium battery technology needs to be significantly improved in terms of the cost, safety, power and energy density, as well as the calendar and cycle life. One new technology being developed is the utilization of composite cathode by mixing two different types of insertion compounds [e.g., spinel $LiMn_2O_4$ and layered $LiMO_2$ (M=Ni, Co, and Mn)]. Recently, some studies on mixing two different types of cathode materials to make a composite cathode have been reported, which were aimed at reducing cost and improving self-discharge. Numata et al. reported that when stored in a sealed can together with electrolyte at $80^{\circ}C$ for 10 days, the concentrations of both HF and $Mn^{2+}$ were lower in the can containing $LiMn_2O_4$ blended with $LiNi_{0.8}Co_{0.2}O_2$ than that containing $LiMn_2O_4$ only. That reports clearly showed that this blending technique can prevent the decline in capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and related structural phase transitions for these composite cathodes. In this presentation, we will report our in situ x-ray diffraction studies on this mixed composite cathode material during charge-discharge cycling. The mixed cathodes were incorporated into in situ XRD cells with a Li foil anode, a Celgard separator, and a 1M $LiPF_6$ electrolyte in a 1 : 1 EC : DMC solvent (LP 30 from EM Industries, Inc.). For in situ XRD cell, Mylar windows were used as has been described in detail elsewhere. All of these in situ XRD spectra were collected on beam line X18A at National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory using two different detectors. One is a conventional scintillation detector with data collection at 0.02 degree in two theta angle for each step. The other is a wide angle position sensitive detector (PSD). The wavelengths used were 1.1950 ${\AA}$ for the scintillation detector and 0.9999 A for the PSD. The newly installed PSD at beam line X18A of NSLS can collect XRD patterns as short as a few minutes covering $90^{\circ}$ of two theta angles simultaneously with good signal to noise ratio. It significantly reduced the data collection time for each scan, giving us a great advantage in studying the phase transition in real time. The two theta angles of all the XRD spectra presented in this paper have been recalculated and converted to corresponding angles for ${\lambda}=1.54\;{\AA}$, which is the wavelength of conventional x-ray tube source with Cu-$k{\alpha}$ radiation, for easy comparison with data in other literatures. The structural changes of the composite cathode made by mixing spinel $LiMn_2O_4$ and layered $Li-Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ in 1 : 1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ~5.2 V vs. $Li/Li^+$, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component only. When the cell voltage reaches at ~4.0 V vs. $Li/Li^+$, lithium extraction from the spinel $LiMn_2O_4$ component starts and becomes the major contributor for the cell capacity due to the higher rate capability of $LiMn_2O_4$. When the voltage passed 4.3 V, the major structural changes are from the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, while the $LiMn_2O_4$ component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel $LiMn_2O_4$ component, with much less changes in the layered $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research. More detailed discussion will be presented at the meeting.

• 한국수소및신에너지학회논문집
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• 제32권6호
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• pp.592-611
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• 2021

In this study a rarely available high-throughput cycling data set of 124 commercial lithium iron phosphate/graphite cells cycled under fast-charging conditions, with widely varying cycle lives ranging from 150 to 2,300 cycles including in-cycle temperature and per-cycle IR measurements. We worked out own Python codes which reproduced the various data plots and machine learning approaches for cycle life prediction using early cycles and more details not presented in the article and the supplementary information. Particularly, we applied regularized ridge, lasso and elastic net linear regression models using features extracted from capacity fade curves, discharge voltage curves, and other data such as internal resistance and cell can temperature. We found that due to the limitation in the quantity and quality of the data from costly and lengthy battery testing a careful hyperparameter tuning may be required and that model features need to be extracted based on the domain knowledge.

• 전기전자학회논문지
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• 제23권1호
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• pp.1-8
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• 2019

본 논문에서는 18650 원통형 NCA 리튬이온 배터리로 구성된 고출력 직렬 배터리로 다양한 C-rate의 전기적 특성을 테스트한다. 테스트를 통해 추출한 14S1P 배터리 팩의 방전 용량 데이터와 4S1P 배터리 팩의 EV cycle 데이터를 통해 C-rate의 변화에 따른 전기적 특성을 분석한다. 분석을 통해 얻은 데이터를 기반으로 C-rate에 따른 방전용량 실험의 셀 간 전압 편차와 EV cycle 실험의 셀 간 전압 편차를 다중선형회귀 모델로 추정하여 선형적인 특징을 가진 데이터와 비선형적인 특징을 가진 데이터에 대한 각각의 추정성능을 검증한다. 모델의 추정성능을 검증하기 위해 추정 데이터와 실제 데이터의 RMSE를 구해 알고리즘의 정확성을 평가한다. 논문의 결과는 14S1P 배터리 팩의 방전 용량의 셀 간 전압 불균형과 4S1P 배터리 팩의 EV cycle의 셀 간 전압 불균형 중 선형적인 데이터인 방전 용량의 셀 간 불균형 데이터의 추정 성능이 더 뛰어난 것을 검증하는데 기여한다.

• Journal of Electrochemical Science and Technology
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• 제3권4호
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• pp.172-177
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• 2012

Mo-doped $LiFePO_4$ was synthesized via co-precipitation method using sucrose as the carbon source. Structure, surface morphology, and the electrochemical properties of the synthesized olivine compounds were investigated using Rietveld refinement of X-ray diffraction data (XRD), scanning electron microscopy (SEM), and electrochemical charge-ischarge tests. Spherical morphology with the particle size of ${\sim}8{\mu}m$ authenticated the enhanced tap density and volumetric energy density of the synthesized materials. Charge-discharge behavior of $LiFePO_4$ and Mo-doped $LiFePO_4$ cells demonstrated a specific capacity of 130 and 145 mAh $g^{-1}$, respectively. Mo-doped $LiFePO_4$ cells exhibited an excellent discharge capacity at 96 mAh $g^{-1}$ at 7 C-rate.

• 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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• 제33권2호
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• pp.608-612
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• 2012

We investigated the cycling behavior of $Li_4Ti_5O_{12}$ electrode in a cross-linked gel polymer electrolyte based on non-flammable ionic liquid consisting of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide and vinylene carbonate. The $Li_4Ti_5O_{12}$ electrodes in ionic liquid-based gel polymer electrolytes exhibited reversible cycling behavior with good capacity retention. Cycling data and electrochemical impedance spectroscopy analyses revealed that the optimum content of the cross-linking agent necessary to ensure both acceptable initial discharge capacity and good capacity retention was about 8 wt %.

• 한국화재소방학회논문지
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• 제34권1호
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• pp.66-71
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• 2020

리튬-이온 배터리를 폐기하는 방법으로 흔히 사용되고 있는 염수를 이용한 방전 방법은 자칫 화재로 이어질 개연성이 있음에도 불구하고 배터리의 염수 방전 과정의 화재 위험성에 대한 연구는 많지 않다. 본 연구에서는 리튬-이온 배터리 중 휴대폰 배터리를 대상으로 하여 염수에 배터리를 담가 방전 시킬 때 방전특성과 발열에 의한 화재 발생 가능성을 확인하고자 염수농도와 배터리의 개수를 변화시킨 여러 조건에서 실험을 수행하였다. 각 조건에서 방전전압 및 배터리의 발열온도를 측정하여 방전 과정 및 발열에 의한 화재 위험성을 예측하였다. 실험 결과로는, 염수농도가 높을수록 휴대폰 배터리의 방전이 더 잘 되었으며, 발열온도 또한 높게 측정 되었고, 염수에 침수된 배터리 1개의 발열온도보다 중첩된 배터리의 발열온도가 더 높게 측정되었다. 또한, 배터리의 가장 높은 발열이 발생하는 부분은 (+),(-)전극에서 발생하는 것을 알 수 있었다.