• 산업기술연구
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• 제42권1호
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• pp.7-12
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• 2022

High nickel layered oxide cathodes are gaining increasing attention for lithium-ion batteries due to their higher energy density and lower cost compared to LiCoO₂. However, they suffer from the formation of residual lithium on the surface in the form of LiOH and Li₂CO₃ on exposure to ambient air. The residual lithium causes notorious issues, such as slurry gelation during electrode preparation and gas evolution during cell cycling. In this review, we investigate the residual lithium issues through its impact on cathode slurry instability based on deformed polyvinylidene fluoride (PVdF) as well as its formation and reduction mechanism in terms of inherently off-stoichiometric synthesis of high nickel cathodes. Additionally, new analysis method with anhydrous methanol was introduced to exclude Li⁺/H⁺ exchange effect during sample preparation with distilled water. We hope that this review would contribute to encouraging the academic efforts to consider practical aspects and mitigation in global high-energy-density lithium-ion battery manufacturers.

• 전기화학회지
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• 제2권1호
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• pp.5-12
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• 1999

PVA-전구체법을 사용하여, 리튬전지의 양극물질인 $Li_xNi_{1-y}Co_yO_2$의 다결정성 분말을 합성하였다. 합성된 분말을 양극물질로 사용하여 리튬이온전지를 제조하여 전지의 전기화학적 성질을 측정하였다. PVA와 금속이온간의 상대적 양, PVA의 농도 및 중합도, 열처리조건, 금속의 조성비 등 여러 다른 합성조건을 변화시키면서, 그러한 합성상의 조건 변화가 리튬이온전지의 전지특성과 어떠한 상호관계를 갖는지 조사하였다. 전지의 초기성능에 관한 한, PVA-전구체법으로 합성한 $Li_xNi_{1-y}Co_yO_2$의 경우, 최적의 조성은 x=1.0, y=0.26인 것으로 관찰되었다. PVA-전구체법으로 합성할 경우, 전구체에 남는 잔여탄소로 인해 형성되는 $Li_2CO_3$가 전지의 성능을 저하시키는 것으로 관찰되었다. 이를 제거하기 위해 건조 공기의 흐름 속에서 열처리를 하거나, 합성 후 2차 열처리 과정에서 $500^{\circ}C$의 온도에서 건조공기의 흐름을 유지하며 annealing 처리를 하는 것이 전지의 특성을 크게 개선하는 것으로 관찰되었다.

• 한국분말재료학회지
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• 제23권2호
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• pp.136-142
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• 2016

As precursors of cathode materials for lithium ion batteries, $Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$ powders are prepared in a continuously stirred tank reactor via a co-precipitation reaction between aqueous metal sulfates and NaOH in the presence of $NH_4OH$ in air or nitrogen ambient. Calcination of the precursors with $Li_2CO_3$ for 8 h at $1,000^{\circ}C$ in air produces dense spherical cathode materials. The precursors and final powders are characterized by X-ray diffraction (XRD), scanning electron microscopy, particle size analysis, tap density measurement, and thermal gravimetric analysis. The precursor powders obtained in air or nitrogen ambient show XRD patterns identified as $Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$. Regardless of the atmosphere, the final powders exhibit the XRD patterns of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ (NCM). The precursor powders obtained in air have larger particle size and lower tap density than those obtained in nitrogen ambient. NCM powders show similar tendencies in terms of particle size and tap density. Electrochemical characterization is performed after fabricating a coin cell using NCM as the cathode and Li metal as the anode. The NCM powders from the precursors obtained in air and those from the precursors obtained in nitrogen have similar initial charge/discharge capacities and cycle life. In conclusion, the powders co-precipitated in air can be utilized as precursor materials, replacing those synthesized in the presence of nitrogen injection, which is the usual industrial practice.

• Journal of Electrochemical Science and Technology
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• 제5권2호
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• pp.58-64
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• 2014

The surface of an ordered mesoporous silica (OMS) was functionalized using 1H,1H,2H,2H-perfluorooctyltrimethoxysilane at $20^{\circ}C$ and $60^{\circ}C$. It was shown that only elevated temperature allows lyophobic properties on the walls of OMS, eventually preventing pore flooding with nonaqueous electrolytes. The functionalized OMSs (OMS-F) were characterized with various techniques: wettability test, $N_2$ sorption measurement, high-resolution transmission electron microscopy (HR-TEM). Cathodes of $10mg/cm^2$ loading were prepared with a commercial Pt/C catalyst and polyvinylidene fluoride (PVDF, 2.5 wt.%) binder using a typical doctor blade method on a commercial gas diffusion layer (GDL) in the presence or in the absence of OMS-F additives. Subsequent discharge-charge curves were taken in a 1M LiTFSI-TEGDME electrolyte at 60oC in pure oxygen atmosphere. It was found that the discharge capacity was significantly affected by OMS-F: 5 wt.% of additive extended discharge capacity by a factor 1.5. On the other hand, a similar OMS material but synthesized at $20^{\circ}C$ did not show lyophobic properties and deteriorated cathode capacity.

• 공업화학
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• 제23권3호
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• pp.247-252
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• 2012

전기자동차, 하이브리드 자동차의 필요성과 스마트 IT 기기의 급속한 발전으로 인한 고용량 고출력 전지의 수요가 급증하고 있다. 현재 상용화 된 리튬이온전지는 기술적 문제에 의해 제한된 에너지 밀도만이 이용되고 있어서 보다 높은 에너지 밀도를 갖는 리튬-황 및 리튬-공기전지 개발이 주목 받고 있다. 새로운 Li 배터리 시스템의 양극물질인 황과 산소는 유사한 물리화학적 특성을 갖고 풍부한 자원 매장량으로 상용화가 어렵지 않을 것으로 전망한다. 따라서 본 총설에서는 리튬-황 및 리튬-공기 전지 시스템의 다공성 구조 양극개발, 양극과 전해질의 계면반응 최적화 및 높은 내구성이 있는 리튬음극 개발과 같은 공통 이슈를 해결하고자 하는 비전을 제시하고자 한다.

• 한국세라믹학회지
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• 제42권7호
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• pp.503-508
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• 2005

A simple and effective method for the synthesis of LiMn$_{2}$O$_{4}$ powder as a cathode material for lithium secondary battery is reported. Micrometer size LiMn$_{2}$O$_{4}$ was prepared by combustion synthesis technique employing initial mixture of l.l LiNO$_{3}$ -1.3Mn-0.7MnO$_{2}$-1NaCl composition. Parametric study of the combustion process including molar ratio of Mn/MnO$_{2}$ and NaCl concentration were carried out under air atmosphere. The combustion products obtained were additionally heat treated at the temperature 900$^{\circ}C$ and the washed by distilled water. The results of charging-discharging characteristics revealed that LiMn$_{2}$O$_{4}$ cell synthesized in the presence of NaCl had a high capacity and much better reversibility than one formed without NaCl An approximate chemical mechanism for LiMn$_{2}$O$_{4}$ formation is proposed.

• 대한전기학회논문지:전기물성ㆍ응용부문C
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• 제48권3호
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• pp.179-184
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• 1999

In the past ten years, $LiMn_2O_4$-based spinels have been extensively studied as positive electrode materials for lithium-ion batteries. To improve the cycle performance of spinel $LiMn_2O_4$ as the cathode of 4V class lithium secondary batteries, spinel phases $LiMn_2O_4$ were prepared at various temperatures ranging form 600-900$^{\cire}C$ in air. The results showed that charge.dischare capacity of $LiMn_2O_4$ varied at 1st temperature from $200^{\circ}C to 600^{\circ}C$ increase with increasing temperature. $LiMn_2O_4$ synthesized at 2nd temperature $750^{\circ}C$excellent charge.discharge capacity, efficiency and cyclability compared to the samplesynthesized different temperatures. The value of lst charge.discharge capacity was 121mAh/g, 118mAh/g, Also, the efficiency value was about 97%.

• 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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• 제15권3호
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• pp.198-205
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• 2012

리튬-공기전지 공기극으로서 탄소 상에 직접 수열합성법으로 망간산화물을 생성한 탄소지지 망간산화물 촉매를 합성하였다. 각 수열합성 조건에 따라서 만들어진 복합체에 대한 XRD, FE-SEM 분석을 통하여, 복합체의 결정구조, 형태, 크기 등을 확인하였는데 특히, 수열합성 온도 및 시간이 각각 $170^{\circ}C$, 12시간인 조건에서 만들어진 산화망간은 길이가 40-50 nm인 막대 모양을 갖는 것으로 나타났다. 합성된 복합체를 사용하여 만든 공기극과 리튬금속을 음극으로 하는 코인셀 형태의 리튬-공기전지를 만들어 전기화학적 특성을 조사한 결과 초기 방전 용량이 3,852 mAh/g으로 높았고 충 방전 횟수가 4회 정도 발현되었다.

• 전기화학회지
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• 제16권3호
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• pp.151-156
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• 2013

리튬이온 전지의 양극물질로써, 초임계 수열합성법을 이용해 만들어진 분말은 각각 $850^{\circ}C$와 $900^{\circ}C$ 공기 분위기에서 10시간씩 소성하여 $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$를 합성하였다. 온도를 조절함에 따라 합성된 분말은 어떠한 영향을 받는지 x-ray pattern, SEM-image, 물리적 특성과 전기화학적 거동을 관찰해 연구하였다. 그 결과, $900^{\circ}C$에서 열처리된 물질의 입자크기가 $850^{\circ}C$에서 열처리된 물질에 비해 더 큰 것으로 나타났고, 특히 초기 가역용량 163.84 mAh/g (0.1 C/2.0-4.3 V), 186.87 mAh/g (0.1 C/2.0-4.5 V)의 가역용량을 나타내면서 훌륭한 전기화학적 거동을 보였으며, 50th cycle에서도 91.49%(0.2 C/2.0-4.3 V)와 90.36%(0.2 C/2.0-4.5 V)의 높은 용량 유지율을 보였다.