• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2007.11a
• /
• pp.259-259
• /
• 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
• /
• v.57 no.6
• /
• pp.861-867
• /
• 2019

$Li_4Ti_5O_{12}$ is a promising next-generation anode material for lithium-ion batteries due to excellent cycle life, low irreversible capacity, and little volume expansion during charge-discharge process. However, it has poor charge capacity at high current density due to its low electrical conductivity. To improve this weakness, porous $Li_4Ti_5O_{12}$ was synthesized by sol-gel method with P123 as chelating agent. The physical characteristics of as-prepared sample was investigated by XRD, SEM, and BET analysis, and electrochemical properties were characterized by cycle performance test, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS). $Li_4Ti_5O_{12}$ synthesized by 0.01mol ratio of P123/Ti showed most unified particle size, high specific surface area, and relatively high porosity. EIS analysis showed that depressed semicircle size was remarkably reduced, which suggested resistance value in electrode was decreased. Capacity in rate performance showed 178 mAh/g at 0.2C, 170 mAh/g at 0.5C, 110 mA/h at 5C, and 90 mAh/g at 10C. Capacity retention also showed 99% after rate performance.

• Journal of the Korean Electrochemical Society
• /
• v.20 no.4
• /
• pp.67-74
• /
• 2017

Layered Ni-rich NCM cathode materials $Li[Ni_xCo_{(1-x)/2}Mn_{(1-x)/2}]O_2$ ($x{\geq}0.6$) have advantages of high energy density and cost competitive over $LiCoO_2$. The discharge capacity of NCM increases proportionally to the Ni contents. However, there is a problem that it is difficult to realize the stable electrochemical performance due to cation mixing. In this study, synthesis conditions for the layered Ni-rich NCMs are investigated to achieve deliver the ones having good electrochemical performances. Synthesis parameters are atmosphere, lithium source, synthesis time, synthesis temperature and Li/M (M=transition metal) ratio. The degree of cation mixing gets worse as the Ni content is increased from $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ (NCM6) to $Li[Ni_{0.8}Co_{0.1}Mn_{0.1}]O_2$ (NCM8). It is confirmed that higher level of cation mixing affects negatively on the electrochemical performance of NCMs. Optimum synthesis conditions are explored for NCMx (x=6, 7, 8) in order to reduce the cation mixing. Under optimized conditions for three representative NCMx, a high initial discharge capacity and a good cycle life are obtained for $180mAh{\cdot}g^{-1}$, 96.2% (50 cycle) in NCM6, $187mAh{\cdot}g^{-1}$, 94.7% (50 cycle) in NCM7, and $201mAh{\cdot}g^{-1}$, 92.7% (50 cycle) in NCM8, respectively.

• Clean Technology
• /
• v.24 no.1
• /
• pp.77-84
• /
• 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
• /
• v.8 no.2
• /
• pp.82-87
• /
• 2005

The cathode material, $LiNi_{0.5}Mn_{1.5}O_4$, for high voltage applications of Li-ion batteries exhibits impurity phases due to oxygen deficiency during the high temperature heat treatment. The impurity phase reduces the electrochemical properties of the electrode since the deficiency spinel structure disturbs the lithium ion intercalation and deintercalation. In this study, Cr-substituted $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4(0{\leq}x{\leq}0.05)$ powders are synthesized by a sol-gel method in order to reduce the amount of the impurity phases in the $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4$. Thermal analysis of the cathode material shows that the $LiNi_{0.5}Mn_{1.5}O_4$ without Cr substitution looses $2\%$ of its weight due to oxygen deficiency but the amount of weight loss is diminished when Cr is substituted. XRD analysis also supports the reduction of the impurity phases in the cathode after chromium substitution, suggesting that the improvement of the electrochemical properties such as the capacity retention and electrochemical stability are attributed to the low content of impurity phases in the Cr-substituted $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4.$

• Membrane Journal
• /
• v.33 no.4
• /
• pp.211-221
• /
• 2023

This study presents a comprehensive study on the synthesis and characterization of PVI-PGMA/LiTFSI polymeric membrane electrolytes and CxNy-C flexible electrodes for energy storage applications. The dual-functional PVI-PGMA copolymer exhibited excellent ionic conductivity, with the PVI-PGMA73/LiTFSI200 membrane electrolyte achieving the highest conductivity of 1.0 × 10^-3 S cm^-1. The electrochemical performance of the CxNy-C electrodes was systematically investigated, with C3N2-C demonstrating superior performance, achieving the highest specific capacitance of 958 F g^-1 and lowest charge transfer resistance (R_ct) due to its highly interconnected hybrid structure comprising nanowires and polyhedrons, along with binary Co/Ni oxides, which provided abundant redox-active sites and facilitated ion diffusion. The presence of a graphitic carbon shell further contributed to the enhanced electrochemical stability during charge-discharge cycles. These results highlight the potential of PVI-PGMA/LiTFSI polymeric membrane electrolytes and CxNy-C electrodes for advanced energy storage devices, such as supercapacitors and lithium-ion batteries, paving the way for further advancements in sustainable and high-performance energy storage technologies.

• Journal of the Korean Electrochemical Society
• /
• v.24 no.3
• /
• pp.65-75
• /
• 2021

Coin cell is a basic testing platform for battery research, discovering new materials and concepts, and contributing to fundamental research on next-generation batteries. Li metal batteries (LMBs) are promising since a high energy density (~500 Wh kg^-1) is deliverable far beyond Li-ion. However, Li dendrite-triggered volume fluctuation and high surface cause severe deterioration of performance. Given that such drawbacks are strongly dependent on the cell parameters and structure, such as the amount of electrolyte, Li thickness, and internal pressure, reliable Li metal coin cell testing is challenging. For the LMB-specialized coin cell testing platform, this study suggests the optimal coin cell structure that secures performance and reproducibility of LMBs under stringent conditions, such as lean electrolyte, high mass loading of NMC cathode, and thinner Li use. By controlling the cathode/anode (C/A) area ratio closer to 1.0, the inactive space was minimized, mitigating the cell degradation. The quantification and imaging of inner cell pressure elucidated that the uniformity of the pressure is a crucial matter to improving performance reliability. The LMB coin cells exhibit better cycling retention and reproducibility under higher (0.6 MPa → 2.13 MPa) and uniform (standard deviation: 0.43 → 0.16) stack pressure through the changes in internal parts and introducing a flexible polymer (PDMS) film.

• Journal of the Korean Electrochemical Society
• /
• v.24 no.3
• /
• pp.52-64
• /
• 2021

The effect of Fe and BO₃ doping on structure, thermal, and electrical properties of Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y (x = 0.2, 0.5)-based glass and glass ceramics was investigated. In addition, their crystallization behavior during sintering and ionic conductivity were also investigated in terms of sintering temperature. FT-IR and XPS results indicated that Fe²⁺ and Fe³⁺ ions in Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y glass worked as a network modifier (FeO₆ octahedra) and also as a network former (FeO₄ tetrahedra). In the case of the glass with low substitution of BO₃, boron formed (PB)O₄ network structure, while boron preferred BO₃ triangles or B₃O₃ boroxol rings with increasing the BO₃ content owing to boic oxide anomaly, which can result in an increased non-bridging oxygen. The glass transition temperature (GTT) and crystallization temperature (CT) was lowered as the BO₃ substitution was increased, while Fe²⁺ lowered the GTT and raised the CT. The ionic conductivity of Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y glass ceramics were 8.85×10^-4 and 1.38×10^-4S/cm for x = 0.2 and 0.5, respectively. The oxidation state of doped Fe and boric oxide anomaly were due to the enhanced lithium ion conductivity of glass ceramics.

• Journal of the Korean Electrochemical Society
• /
• v.15 no.4
• /
• pp.222-229
• /
• 2012

We studied the electrochemical phenomena and increase of capacity according to the polymer composite electrode of two different polymeric materials with different the voltage range and capacity. Polyaniline (PANI) with relatively high voltage and small capacity and poly [1,2] bis-thio[1,8]-naphthylidine (PTND) with slightly low voltage and large capacity were used as polymer composite electrode materials. After PTND was synthesized, PANI was synthesized on the surface of PTND. The synthesis and the fine structure were analyzed by FT-IR, XPS, FE-SEM, and FE-TEM. Charge/discharge capacity and cyclic voltammetry measurements were carried out for the electrochemical performance as a polymer cathode active material for lithium secondary batteries. The discharge capacities of PANI/PTND after 1,5, and 10 cycles at 1.3~4.0 V voltage range and room temperature 167 mAh/g, 90 mAh/g, and 81 mAh/g. When we compared with PANI (80, 67, and 62 mAh/g), the discharge capacity after 10 cycles was improved about 30%. After 50 cycles, the discharge capacity of PANI/PTND was 67 mAh/g.

• Journal of the Korean Electrochemical Society
• /
• v.19 no.3
• /
• pp.87-94
• /
• 2016

In order to improve performances of submicrometer-sized Si negative electrode which shows larger volumetric change than nano-sized Si, composite binders are introduced by blending between poly(phenanthrenequinone) (PPQ) conductive polymer binder and poly(acrylic acid) (PAA) having good adhesion strength due to its carboxyl functional group. Blending between PPQ and PAA shows an effect that the adhesion strength of the Si electrode with the composite conductive binder is greatly improved after blending and this makes its better stable cycle performance. Blending ratios between PPQ and PAA in this work are 2:1, 1:1, 1:2 (by weight) and the best capacity retention at 50th cycle is observed in the electrode with the blending ratio 2:1 (named QA21). This is because that PPQ plays a role of conductive carbon among the Si particles or between Si particles and Cu current collector and PAA binds effectively the particles and the current collector. According to this synergetic effect, the internal resistance of the Si electrode with the blending ratio 2:1 is the smallest value. In addition, the Si electrode with PPQ-PAA composite binder shows the better stable cycle performance than the electrode with conventional super-P conductive carbon (20 wt.%).