• Journal of the Korean Electrochemical Society
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• v.10 no.1
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• pp.20-24
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• 2007

Lithium ion secondary battery has been applied widely to portable devices, and has been studied for application to high power electric cell system such as power tool or hybrid electronic vehicle. The structure change of the electrodes materials occur when lithium ions move between electrodes. Neutron or X-rays can analyze the structure of electrode. The advantage of X-rays is convenient in test. However X-rays is scattered by electron cloud in atoms. Therefore, The elucidation for correct position of lithium is difficult with X-rays because lithium has small atomic weight. Neutron analysis techniques could solve this problem. In this review, We wish to discuss about structure analysis and the principle of structural characterization method using neutron beam source.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.11a
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• pp.510-510
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• 2007

Titanate nanotube(TNT)는 높은 비표면적과 우수한 물리화학적 특성을 가지고 있어 광촉매, 수소 저장재료, 태양전지용 전극재료 등에 적용되고 있다. 또한, 티타네이트 나노튜브는 전자 이동이 원활한 구조적 특징을 가지고 있어 리듐 이차전지용 호스트 재료로서 많은 연구가 진행 중이다. 이에 본 연구에서는 저온균일침전법으로 제조한 루틸상 $TiO_2$ 분말에 Lithium chloride를 1~10wt%를 동시에 첨가한 후 10M의 sodium hydroxide 수용액 내에서 수열합성하여 리튬이 도핑된 티타네이트 나노튜브를 제조하였다. 제조된 분말의 입자형상 및 크기는 전자주사 현미경을 이용하여 관찰하였으며, X-선 회절분석을 이용하여 리튬 첨가에 따른 결정상 변화를 관찰하였다. 또한 리튬이 도핑된 티타네이트 나노튜브의 전기화학적 특성 평가를 위해 양극 활물질 : 도전제 : 바인더를 75 : 20 : 5의 비율로 혼합한 후 coin cell을 제조하였고, potentiostat를 이용하여 용량 측정 및 cycle 특성을 실시하였다. 수열 합성법에 의해 형성된 입자는 직경 10nm, 길이 수 ${\mu}m$로 관찰되었으며, X-선 회절 시험 결과 LiO와 같은 이차상은 발견되지 않았다. 측정된 coin cell의 용량은 240mAh/g을 나타내었으나, 싸이클 특성이 빠르게 저하됨을 확인할 수 있었다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.11a
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• pp.259-259
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• 2007

층상구조의 전이금속 산화물($LiMO_2$, M=Co, Ni, Mn)은 리튬이차전지용 양극재료로 활발한 연구가 진행되고 있다. 차세대 리튬이차전지 시스템의 개발 및 고성능화를 위해서는 전지의 용량을 결정하는 핵심 부품인 양극재료의 고용량화 및 고안정화는 필수 불가결하다. 따라서 본 연구에서는 상업적으로 큰 장점이 있는 고상반응 공정을 이용하여 리튬이차전지용 양극소재를 제조하고, 소재의 전기화학적, 구조적인 특성을 평가하였으며, 다음과 같은 주제를 가지고 연구를 진행하였다. $LiCoO_2$ 양극재료는 리튬이온전지로 널리 사용되고 있다. 높은 에너지 밀도의 리튬이온전지를 얻기 위해서는 $LiCoO_2$ 양극재료가 고용량화 및 고밀도화를 가져야 한다. 여기서 $LiCoO_2$ 분말이 irregular particle morphology를 가지면 tap density가 $2.2-2.4gcm^{-3}$로 에너지 밀도가 낮으나, 구형 $LiCoO_2$의 정극재료는 tap density가 $2.6-2.8gcm^{-3}$로 상대적으로 energy density가 높아지는 효과가 있다. 구형 $LiCoO_2$ 양극재료를 합성하기 위해서는 chelating agent를 이용한 "controlled crystallization" 침전법을 사용하여 합성한 구형 코발트 수화물을 사용하고 있다. "controlled crystallization" 침전법에서 사용되는 chelating agent로는 주로 ammonia가 이용되고 있다. 본 연구에서는 chelating agent로 ethylene diamine을 사용하여 sodium hydroxides를 precipitation으로 침전 반응하여 구형 코발트 수화물을 합성하였다. 상기 방법으로 합성된 코발트 수화물과 리튬 수화물($LiOH{\cdot}H_2O$-고순도화학(高殉道化學))을 사용하여 고상법을 통하여 $LiCoO_2$를 합성하였다. 제조된 분말의 결정구조와 전기화학적 특성분석은 X-선 회절분석 및 리트벨트 구조정산, 그리고 충/방전 싸이클링을 수행하였으며, 분말의 미세구조 변화를 SEM을 이용하여 분석하였다.

• Korean Chemical Engineering Research
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• v.59 no.1
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• pp.42-48
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• 2021

Zn and Al added LiNi0.85Co0.15O2 cathode materials were synthesized to improve electrochemical properties and thermal stability using a solid-state route. Crystal structure, particle size and surface shape of the synthesized cathode materials was measured using XRD (X-ray diffraction) and SEM (scanning electron microscopy). CV (cyclic voltammetry), first charge-discharge profiles, rate capability, and cycle life were measured using battery cycler (Maccor, series 4000). Strong binding energy of Al-O bond enhanced structure stability of cathode material. Electrochemical properties were improved by preventing cation mixing between Li+ and Ni2+. Large ion radius of Zn+ increased lattice parameter of NC cathode material, which meant unit-cell volume was expanded. NCZA25 showed 80% of capacity retention at 0.5 C-rate during 100 cycles, which was 12% higher than that of NC cathode. The discharge capacity of NCZA25 showed 104 mAh/g at 5 C-rate. NCZA25 achieved 36 mAh/g more capacity than that of NC cathod. NCZA25 cathode material showed excellent rate capability and cycling performance.

• Clean Technology
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• v.24 no.1
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• pp.77-84
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• 2018

In this study, $Li_4Ti_5O_{12}$ anode materials for lithium ion battery were synthesized by dry ball-mill method. Polyvinyl chloride (PVC) as a carbon source was added to improve electrochemical properties. When the PVC was added after $Li_4Ti_5O_{12}$ formation, the spinel structure was well synthesized and it was confirmed by X-ray diffraction (XRD) experiments. When the carbon material was added before the synthesis and the heat treatment was performed, it was confirmed that a material having a different crystal structure was synthesized even when a small amount of carbon material was added. In the case of $Li_4Ti_5O_{12}$ without the carbon material, the electrical conductivity value was about $10{\mu}S\;m^{-1}$, which was very small and similar to that of the nonconductor. As the carbon was added, the electrical conductivity was greatly improved and increased up to 10,000 times. Electrochemical impedance spectroscopy (EIS) analysis showed that the size of semicircle corresponding to the resistance decreased with the carbon addition. This indicates that the resistance inside the electrode is reduced. According to the Cyclic voltammetry (CV) analysis, the potential difference between the oxidation peak and the reduction peak was reduced with carbon addition. This means that the rate of lithium ion insertion and deinsertion was increased. $Li_4Ti_5O_{12}$ with 9.5 wt% PVC added sample showed the best properties in rate capabilities of $180mA\;h\;g^{-1}$ at 0.2 C-rate, $165mA\;h\;g^{-1}$ at 0.5 C-rate, and $95.8mA\;h\;g^{-1}$ at 5 C-rate.

• Journal of the Korean Electrochemical Society
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• v.17 no.4
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• pp.222-228
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• 2014

Ni-rich system $Li[Ni_{1-x-y}Co_xMn_y]O_2$ of lithium secondary battery cathode material keep a high discharge capacity. However, by the Ni content increases, there is a problem that the electrochemical properties and stability of the structure are reduced. In order to solve these problems, research for positive ion doping is performed. The one of the cathode material, barium-doped $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01), was synthesized by the precursor, $Ni_{0.6}Co_{0.1}Mn_{0.3}(OH)_2$, from the co-precipitation method. The barium doped materials have studied the structural and electrochemical properties. The analysis of structural properties, results of X-ray diffraction analysis, and those results confirmed the change of the lattice from the binding energy in the structure by barium doping. Increased stability of the layered structure was observed by $I_{(006)}+I_{(102)}/I_{(101)}$(R-factor) ratio decrease. we expected that the electrochemical characteristics are improved. 23 mAh/g discharge capacity of barium-doped $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01) electrode is higher than discharge capacity of $Li[Ni_{0.6}Co_{0.1}Mn_{0.3}]O_2$ due to decrease overvoltage. And, through the structural stability was confirmed that improved the cycle characteristics. We caused a reduction in charge transfer resistance between the electrolyte and the electrode was confirmed that the C-rate characteristics are improved.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.22 no.2
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• pp.789-793
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• 2021

A lithium secondary battery is the most promising candidate for future energy storage devices. On the other hand, the battery capacity decreases gradually due to the small amount of water and decomposition of the salts during the charging and discharging process, which deteriorates at high temperatures. Many researchers focused on increasing the cycling performance, but there have been few studies on the fundamental problem that removes water and HF molecules. In this study, silane molecules that are capable of absorbing water and HF molecules are introduced to the separator. Firstly, silica-coated amino-silane (APTES, 3-aminopropyltriethoxysilane) was synthesized, then the silica reacted with epoxy-silane, GPTMS ((3-glycidyloxypropyl)trimethoxysilane). A ceramic-coated separator was fabricated using the silane-coated silica, which is coated on porous polyethylene substrates. FT-IR spectroscopy and TEM analysis were performed to examine the chemical composition and the shape of the silane-coated silica. SEM was performed to confirm the ceramic layers. LMO half cells were fabricated to evaluate the cycling performance at 60 ℃. The cells equipped with a GPTMS-silica separator showed stable cycling performance, suggesting that it would be a solution for improving the cycling performance of the Li-ion batteries at high temperatures.

• Journal of the Korean Electrochemical Society
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• v.24 no.2
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• pp.28-33
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• 2021

Many researchers have increased the loading level of electrodes to improve the energy density of secondary batteries. In this study, high-loading NCM523 (LiNi_0.5Co_0.2Mn_0.3O₂) positive electrode is manufactured using a polytetrafluoroethylene (PTFE) binder, not the conventional polyvinylidene fluoride (PVdF) binder, which has been commonly used in lithium-ion batteries. Through the kneading process using PTFE suspension, not the conventional slurry process using PVdF solution in N-methyl-2-pyrrolidinone (NMP), thick electrodes with high loading are easily manufactured. When the PTFE and PVdF-based electrodes are prepared at a loading level of 5.0 mAh/cm², respectively, the PTFE-based electrode shows better cycle performance and rate capability than those of PVdF-based electrodes. The electrode manufactured by the kneading process using a PTFE binder has high electrode porosity due to insufficient roll-press, but the porosity can be lowered by high temperature roll-press over 120℃. However, there is no significant difference in cycle performance according to the roll press temperature. In addition, the cycle performance of the high loading electrode is slightly improved by increasing the content of the conductive material. Overall, the PTFE binder can improve the performance of the high loading electrode, but additional solutions will be needed.

• Journal of the Korean Electrochemical Society
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• v.17 no.1
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• pp.7-12
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• 2014

There is increasing demand on the reducing the weight and the volume of the major components in lithium secondary battery to improve energy density. Separator not only provides pathway for lithium ion movement but also prevents direct contact between anode and cathode. Herein we fabricated polyethylene separator by varying biaxial stretching ratio to obtain membrane thickness of 16, 12, and $9{\mu}m$. Mechanical and thermal properties of the separator with different thickness were investigated. Also rate capability and charge-discharge cycle property up to 500 cycles were studied using coin type full-cell with $LiCoO_2$ and graphite as a cathode and an anode, respectively. All the cells using separator with different thickness demonstrated excellent capacity retention after 500cycles (around 80%). Considering the rate capability, cell using separator with thickness of $9{\mu}m$ showed best performance. Interestingly, separator thickness of $9{\mu}m$ was more resistant to heat contraction compared to that of $16{\mu}m$ separator.

• Journal of the Korean Electrochemical Society
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• v.26 no.1
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• pp.11-18
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• 2023

As the use of lithium-ion secondary batteries is rapidly increasing due to the rapid growth of the electric vehicle market, the disposal and recycling of spent batteries after use has been raised as a serious problem. Since stored energy must be removed in order to recycle the spent batteries, an effective discharging process is required. In this study, graphite and NCM622 were used as active materials to manufacture coin-type half cells and full cells, and the electrochemical behavior occurring during overdischarge was analyzed. When the positive and negative electrodes are overdischarged respectively using a half-cell, a conversion reaction in which transition metal oxide is reduced to metal occurs first in the positive electrode, and a side reaction in which Cu, the current collector, is corroded following decomposition of the SEI film occurs in the negative electrode. In addition, a side reaction during overdischarge is difficult to occur because a large polarization at the initial stage is required. When the full cell is overdischarged, the cell reaches 0 V and the overdischarge ends with almost no side reaction due to this large polarization. However, if the full cell whose capacity is degraded due to the cycle is overdischarged, corrosion of the Cu current collector occurs in the negative electrode. Therefore, cycled cell requires an appropriate treatment process because its electrochemical behavior during overdischarge is different from that of a fresh cell.