• Journal of Electrochemical Science and Technology
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• 제14권4호
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• pp.361-368
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• 2023

In lithium-sulfur (Li-S) batteries, encapsulation of sulfur in activated carbon (AC) materials is a promising strategy for preventing the dissolution of lithium polysulfide into electrolytes and enhancing cycle life, because instead of solid-liquid-solid reactions, quasi-solid-state (QSS) reactions occur in the AC micropores. While a high weight fraction of sulfur in S/AC composites is essential for achieving a high energy density of Li-S cells, the deterioration mechanisms under such conditions are still unclear. In this study, we report the deterioration mechanisms during charge-discharge cycling when the discharge products overflow from the AC. Analysis using scanning electron microscopy and energy-dispersive X-ray spectrometry confirms that the sulfur in the S/AC composites migrates outside the AC as cycling progresses, and it is barely present in the AC after 20 cycles, which corresponds to the capacity decay of the cell. Impedance analysis clearly shows that the electrical resistance of the S/AC composite and the charge-transfer resistance of QSS reactions significantly increase as a result of sulfur migration. On the other hand, the charge-discharge cycling performance under limited-capacity conditions, where the discharge products are encapsulated inside the AC, is extremely stable. These results reveal the degradation mechanism of a Li-S cell with micro-porous carbon and provide crucial insights into the design of a S/AC composite cathode and its operating conditions needed to achieve stable cycling performance.

• Journal of Electrochemical Science and Technology
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• 제3권1호
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• pp.29-34
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• 2012

The structural changes of $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode material for lithium ion battery during the first charge was investigated in comparison with $Li_{1-x}Ni_{0.8}Co_{0.15}Al_{0.05}O_2$ using a synchrotron based in situ X-ray diffraction technique. The structural changes of these two cathode materials show similar trend during first charge: an expansion along the c-axis of the unit cell with contractions along the a- and b-axis during the early stage of charge and a major contraction along the c-axis with slight expansions along the a- and b-axis near the end of charge at high voltage limit. In $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode, however, the initial unit cell volume of H2 phase is bigger than that of H1 phase since the c-axis undergo large expansion while a- and b- axis shrink slightly. The change in the unit cell volume for $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ during charge is smaller than that of $Li_{1-x}Ni_{0.8}Co_{0.15}Al_{0.05}O_2$. This smaller change in unit cell volume may give the $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode material a better structural reversibility for a long cycling life.

• Journal of Electrochemical Science and Technology
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• 제13권4호
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• pp.472-478
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• 2022

Solar energy harvesting is practiced by various nations for the purpose of energy security and environment preservation in order to reduce overdependence on oil. Converting solar energy into electrical energy through Photovoltaic (PV) module can take place either in on-grid or off-grid applications. In recent time Lithium battery is exhibiting its presence in on-grid applications but its role in off-grid application is rarely discussed in the literature. The preliminary capacity and Peukert's study indicated that the battery quality is good and can be subjected for life cycle test. The capacity of the battery was 10.82 Ah at 1 A discharge current and the slope of 1.0117 in the Peukert's study indicated the reaction is very fast and independent on rate of discharge. In this study Lithium Iron Phosphate battery (LFP) after initial characterization was subjected to life cycle test which is specific to solar off-grid application as defined in IEC standard. The battery has delivered just 6 endurance units at room temperature before its capacity reached 75% of rated value. The low life of LFP battery in off-grid application is discussed based on State of Charge (SOC) operating window. The battery was operated both in high and low SOC's in off-grid application and both are detrimental to life of lithium battery. High SOC operation resulted in cell-to-cell variation and low SOC operation resulted in lithium plating on negative electrode. It is suggested that to make it more suitable for off-grid applications the battery by default has to be overdesigned by nearly 40% of its rated capacity.

• Journal of Power Electronics
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• 제13권4호
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• pp.516-527
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• 2013

This paper presents a new overall system for state-of-available-power (SoAP) prediction for a lithium-ion battery pack. The essential part of this method is based on an adaptive network architecture which utilizes both fuzzy model (FIS) and artificial neural network (ANN) into the framework of adaptive neuro-fuzzy inference system (ANFIS). While battery aging proceeds, the system is capable of delivering accurate power prediction not only for room temperature, but also at lower temperatures at which power prediction is most challenging. Due to design property of ANN, the network parameters are adapted on-line to the current battery states (state-of-charge (SoC), state-of-health (SoH), temperature). SoC is required as an input parameter to SoAP module and high accuracy is crucial for a reliable on-line adaptation. Therefore, a reasonable way to determine the battery state variables is proposed applying a combination of several partly different algorithms. Among other SoC boundary estimation methods, robust extended Kalman filter (REKF) for recalibration of amp hour counters was implemented. ANFIS then achieves the SoAP estimation by means of time forward voltage prognosis (TFVP) before a power pulse occurs. The trade-off between computational cost of batch-learning and accuracy during on-line adaptation was optimized resulting in a real-time system with TFVP absolute error less than 1%. The verification was performed on a software-in-the-loop test bench setup using a 53 Ah lithium-ion cell.

• 한국분말재료학회지
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• 제19권3호
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• pp.210-214
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• 2012

Mass production-capable $Li_2MnSiO_4$ powder was synthesized for use as cathode material in state-of-the-art lithium-ion batteries. These batteries are main powder sources for high tech-end digital electronic equipments and electric vehicles in the near future and they must possess high specific capacity and durable charge-discharge characteristics. Amorphous silicone was quite superior to crystalline one as starting material to fabricate silicone oxide with high reactivity between precursors of sol-gel type reaction intermediates. The amorphous silicone starting material also has beneficial effect of efficiently controlling secondary phases, most notably $Li_xSiO_x$. Lastly, carbon was coated on $Li_2MnSiO_4$ powders by using sucrose to afford some improved electrical conductivity. The carbon-coated $Li_2MnSiO_4$ cathode material was further characterized using SEM, XRD, and galvanostatic charge/discharge test method for morphological and electrochemical examinations. Coin cell was subject to 1.5-4.8 V at C/20, where 74 mAh/g was observed during primary discharge cycle.

• Bulletin of the Korean Chemical Society
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• 제19권1호
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• pp.39-44
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• 1998

$LiCoO_2$ powder was synthesized in an aqueous solution by a sol-gel method and used as a cathode active material for a lithium ion rechargeable battery. The layered $LiCoO_2$ powders were prepared by igniting in air for 12 hrs at 600 ℃ $(600-LiCoO_2)$ and 850 ℃ $(850-LiCoO_2)$. The structure of the $LiCoO_2$ powder was assigned to the space group R bar 3 m (lattice parameters a=2.814 Å and c=14.04Å). The SEM pictures of $600-LiCoO_2$ revealed homogeneous and fine particles of about 1 μm in diameter. Cyclic voltammograms (CVs) of $600-LiCoO_2$ electrode displayed a set of redox peaks at 3.80/4.05 V due to the intercalation/deintercalation of the lithium ions into/out of the $LiCoO_2$ structure. CVs for the $850-LiCoO_2$ electrode had a major set of redox peaks at 3.88/4.13 V, and two small set of redox peaks at 4.18/4.42 V and 4.05/4.25 V due to phase transitions. The initial charge-discharge capacity was 156-132 mAh/g for the $600-LiCoO_2$ electrode and 158-131 mAh/g for the $850-LiCoO_2$ electrode at the current density of 0.2 mA/cm2. The cycleability of the cell consisting of the $600-LiCoO_2$ electrode was better than that of the $850-LiCoO_2$. The diffusion coefficient of the $Li^+$ ion in the $600-LiCoO_2$ electrode was calculated as $4.6{\times}10^{-8}\; cm^2/sec$.

• 전기화학회지
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• 제14권2호
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• pp.117-124
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• 2011

We demonstrate a new surface modification of high-voltage lithium cobalt oxide ($LiCoO_2$) cathode active materials for lithium-ion batteries. This approach is based on exploitation of a polarity-tuned gel polymer electrolyte (GPE) coating. Herein, two contrast polymers having different polarity are chosen: polyimide (PI) synthesized from thermally curing 4-component (pyromellitic dianhydride/biphenyl dianhydride/phenylenediamine/oxydianiline) polyamic acid (as a polar GPE) and ethylene-vinyl acetate copolymer (EVA) containing 12 wt% vinyl acetate repeating unit (as a less polar GPE). The strong affinity of polyamic acid for $LiCoO_2$ allows the resulting PI coating layer to present a highly-continuous surface film of nanometer thickness. On the other hand, the less polar EVA coating layer is poorly deposited onto the $LiCoO_2$, resulting in a locally agglomerated morphology with relatively high thickness. Based on the characterization of GPE coating layers, their structural difference on the electrochemical performance and thermal stability of high-voltage (herein, 4.4 V) $LiCoO_2$ is thoroughly investigated. In comparison to the EVA coating layer, the PI coating layer is effective in preventing the direct exposure of $LiCoO_2$ to liquid electrolyte, which thus plays a viable role in improving the high-voltage cell performance and mitigating the interfacial exothermic reaction between the charged $LiCoO_2$ and liquid electrolytes.

• 반도체디스플레이기술학회지
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• 제22권1호
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• pp.28-32
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• 2023

Recently, the use of stable lithium nanostructures as substrates and electrodes for secondary batteries can be a fundamental alternative to the development of next-generation system semiconductor devices. However, lithium structures pose safety concerns by severely limiting battery life due to the growth of Li dendrites during rapid charge/discharge cycles. Also, enabling long cyclability of high-voltage oxide cathodes is a persistent challenge for all-solid-state batteries, largely because of their poor interfacial stabilities against oxide solid electrolytes. For the development of next-generation system semiconductor devices, solid electrolyte nanostructures, which are used in high-density micro-energy storage devices and avoid the instability of liquid electrolytes, can be promising alternatives for next-generation batteries. Nevertheless, poor lithium ion conductivity and structural defects at room temperature have been pointed out as limitations. In this study, a low-dimensional Graphene Oxide (GO) structure was applied to demonstrate stable operation characteristics based on Li+ ion conductivity and excellent electrochemical performance. The low-dimensional structure of GO-based solid electrolytes can provide an important strategy for stable scalable solid-state power system semiconductor applications at room temperature. The device using uncoated bare NCA delivers a low capacity of 89 mA h g-1, while the cell using GO-coated NCA delivers a high capacity of 158 mA h g−1 and a low polarization. A full Li GO-based device was fabricated to demonstrate the practicality of the modified Li structure using the Li-GO heterointerface. This study promises that the lowdimensional structure of Li-GO can be an effective approach for the stabilization of solid-state power system semiconductor architectures.

• 한국산학기술학회논문지
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• 제19권3호
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• pp.14-20
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• 2018

전기자동차는 가솔린 자동차와는 달리 배출가스가 없어 친환경 차량을 대표하지만, 장착된 축전지에 충전된 전기로 구동되기 때문에, 1회 충전으로 갈 수 있는 거리가 전지의 에너지 밀도에 의해 좌우된다. 따라서 높은 에너지 밀도를 갖는 리튬이온 전지가 전기자동차용 전지로 유력한 후보이다. 리튬이온 전지의 효율을 지배하는 중요한 구성품은 전극이므로 전극 제조공정은 리튬이온 전지 전체 생산 공정에서 중요한 역할을 한다. 특히 전극의 제조 공정 중 코팅 공정은 성능에 큰 영향을 미치는 매우 중요한 공정이다. 본 논문에서는 전극 제조에서 코팅 공법의 효율성 및 생산성 증대를 위한 혁신적인 공정을 제안하고, 장비 설계 방법 및 개발 결과에 대하여 기술하였다. 구체적으로, 극판 핵심 코팅 품질 25% Upgrade 기술, 제품 고출력/고용량화 에 따른 조립 마진 감소 대응 가능 기술, 그리고 제품 용량 품질 및 조립 공정 수율 향상 기술들에 대한 설계 절차 및 개발방법을 제시하였다. 결과로 리튬이온 배터리의 셀의 제품 수명 개선 효과를 확보 하였다. 기존의 코팅 공정과 비교할 때 양극 용량 유지 위해 Target Loading Level 유지, 산포를 향상시켰다(${\pm}0.4{\rightarrow}{\pm}0.3mg/cm^2r$감소).

• 자원리싸이클링
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• 제28권6호
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• pp.79-86
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• 2019

최근, 전기차 증가에 따른 리튬 전지의 사용량 증가로 리튬 가격 증가 및 폐리튬전지 발생량이 증가하고 있다. 이러한 이유로 폐리튬전지 내 리튬 회수에 대한 연구가 진행되고있다. 본 연구에서는 폐전기차 셀분말의 열처리 조건에 따른 선택적 리튬 침출에 관한 연구를 진행하였다. 셀 분말(LiNi_xCo_yMn_zO₂, LiCoO₂)로부터 선택적 리튬 침출을 위해서는 환원을 통한 상변화 및 분리가 필요하다. 폐전기차 셀분말 내 탄소는 고온에서 산소와 반응하여 환원제 역할을 한다. 적정 온도를 알고자 대기/질소 분위기에서 TG-DSC 분석 및 550 ~ 850 ℃ 열처리 후, XRD 분석을 하였다. 열처리 된 분말은 ICP 분석을 위해 D.I water에서 1:10 비율로 침출 후 분석하였다. XRD 분석결과, 700 ℃에서 Li₂CO₃ 피크가 확인되었다. 850 ℃ 열처리 시 Li₂O의 피크가 확인되었는데, 이는 Li₂CO₃가 723 ℃ 이상의 온도에서 Li₂O와 CO₂로 분해되었기 때문이다. 또한 Li₂O와 Al₂O₃와 반응으로 LiAlO₂가 확인되었다. 850 ℃에서 열처리 시 Li 침출율이 낮아졌는데 이는 LiAlO₂가 D.I water에서 침출하지 않기 때문으로 판단된다. 리튬 침출율의 경우 열처리의 조건에 따라 달라지며, 질소 분위기 중 700 ℃로 열처리 시 약 45 %의 리튬침출이 확인되었다. 침출 용액을 고-액분리 후증발농축하여 XRD 분석을 실시한 결과, Li₂CO₃의 피크를 확인하였다.