• 한국전기전자재료학회논문지
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• 제37권4호
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• pp.445-450
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• 2024

The expansion of lithium-ion battery usage beyond portable electronic devices to electric vehicles and energy storage systems is driven by their high energy density and favorable cycle characteristics. Enhancing the stability and performance of these batteries involves exploring solid electrolytes as alternatives to liquid ones. While sulfide-based solid electrolytes have received significant attention for commercialization, research on amorphous-phase glass solid electrolytes in oxide-based systems remains limited. Here, we investigate the glass transition temperatures and sintering behaviors by changing the molecular ratio of Li₂O/B₂O₃ in borate glass comprising Li₂O-B₂O₃-Al₂O₃ system. The glass transition temperature is decreasing as increasing the amount of Li₂O. When we sintered at 450℃, just above the glass transition temperature, the samples did not consolidate well, while the proper sintered samples could be obtained under the higher temperature. We successfully obtained the borate glass ceramics phases by melt-quenching method, and the sintering characteristics are investigated. Future studies could explore optimizing ion conductivity through refining processing conditions, adjusting the glass former-to-modifier ratio, and incorporating additional Li salt to enhance the ionic conductivity.

• 한국재료학회지
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• 제8권4호
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• pp.323-327
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• 1998

재충전이 가능한 Li/PEO-$LiClO_{4}$-PC/$LIMn_2O_4$구조의 전고상 전지를 제작하였다. $LIMn_2O_4$박막은 RF 마그네트론 스퍼터링 법으로 제작하였으며, $750^{\circ}C$ 부근에서의 급속열처리를 통하여 스피넬 상으로 결정화시킬 수 있었다. 상온 충.방전 시험을 행한 결과, 평균 전압 4V(vs. Li)의 평탄한 방전 전압과 우수한 재충전 능력을 나타내었다.

• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2003년도 전지기술심포지움
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• pp.153-168
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• 2003

Polymer electrolytes - solid polymeric membranes with dissolved salts - are being intensively studied for use in all-solid-state lithium-metal-polymer consumer electronic device. The low ionic conductivity at room temperature of existing polymer electrolytes, however, has seriously hindered the development of such batteries for many applications. The incorporation of salts molten at room temperature (room temperature ionic liquids or RTILs) into polymer electrolytes may be the necessary solution to overcoming the inherent ionic conductivity limitations of 'dry' polymer electrolytes.

• 한국세라믹학회지
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• 제53권6호
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• pp.712-718
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• 2016

In this study, we investigate the effect of the$Li_3BO_3$ additive on the densification and ionic conductivity of garnet-type $Li_7La_3Zr_2O_{12}$ solid electrolytes for all-solid-state lithium batteries. We analyze their densification behavior with the addition of $Li_3BO_3$ in the range of 2-10 wt.% by dilatometer measurements and isothermal sintering. Dilatometry analysis reveals that the sintering of $Li_7La_3Zr_2O_{12}-Li_3BO_3$ composites is characterized by two stages, resulting in two peaks, which show a significant dependence on the $Li_3BO_3$ additive content, in the shrinkage rate curves. Sintered density and total ion conductivity of the system increases with increasing $Li_3BO_3$ content. After sintering at $1100^{\circ}C$ for 8 h, the $Li_7La_3Zr_2O_{12}-8$ wt.% $Li_3BO_3$ composite shows a total ionic conductivity of $1.61{\times}10^{-5}Scm^{-1}$, while that of the pure $Li_7La_3Zr_2O_{12}$ is only $5.98{\times}10^{-6}Scm^{-1}$.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 1999년도 추계학술대회 논문집
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• pp.159-162
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• 1999

All solid state thin film micro-batteries consisting of lithium metal anode, an amorphous LiPON electrolyte and cathode of vanadium oxide have been fabricated and characterized, which were fabricated with cell structure of Li/LiPON/V$_2$O$\sub$5/Pt. The vanadium oxide thin films were formed by d.c. reactive sputtering on Pt current collector. After deposition of vanadium oxide films, in-situ growths of lithium phosphorus oxynitride film were conducted by r.f. sputtering of Li$_3$PO$_4$ target in mixture gas of N$_2$ and O$_2$. The pure metal lithium film was deposited by thermal evaporation on thin film LiPON electrolyte. The cell capacity was about 45${\mu}$Ah/$\textrm{cm}^2$ $\mu\textrm{m}$ after 200 cycle. No appreciable degradation of the cell capacity could be observed after 50 cycles .

• 공업화학
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• 제33권1호
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• pp.58-63
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• 2022

흑연은 낮은 탈/리튬화 전압, 372 mAh/g의 높은 이론 용량, 낮은 가격 및 긴 수명 특성을 가져 지난 30년 동안 리튬이 온전지 음극 재료로 활용되었다. 최근 무기 고체 재료로 구성되어 높은 안정성을 가지는 전고체 리튬이온전지는 전기자동차 및 차세대 에너지 저장 장치로 엄청난 주목을 받고 있지만, 전고체 리튬이온전지 시스템에 잘 구동되는 흑연 연구는 부족한 실정이다. 그래서 우리는 탄소재료 표면에 존재하여 저항층으로 작용하는 비정질 탄소를 흑연으로부터 제거하여 흑연의 전기전도도 향상을 통해 황화물계 전고체 전지 음극 흑연 재료의 성능 향상을 유도했다. 400, 500 및 600 ℃ 공기 열처리된 흑연의 X-ray diffraction (XRD) 분석 결과, (002) 피크 반치폭(FWHM)이 bare 흑연보다 줄어들어 열처리 후 흑연의 결정성이 향상됨을 보였다. 또한 열처리 후 흑연의 결정성이 증가할수록 방전 용량, 초기 쿨롱효율(ICE) 및 수명 특성이 증가함을 확인했다. 500 ℃ 공기 열처리 한 흑연의 경우 331.1 mAh/g 및 ICE 86.2%와 10사이클 수명 측정 후 92.7%의 높은 용량 유지율을 나타내었다.

• 전기화학회지
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• 제22권3호
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• pp.87-103
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• 2019

현재 상용화되어 있는 리튬이온전지에 사용하고 있는 비수계 유기 전해액은 가연성, 부식성, 고휘발성, 열적 불안정성 등의 단점 때문에 더욱 안전하고 장수명을 보이는 고체 전해질로 대체하는 연구가 진행되고 있으며, 이것은 전기자동차 및 에너지저장 시스템과 같은 중대형 이차전지에도 효율적으로 활용될 수 있다. 다양한 형태의 고체 전해질 중에서 현재 고분자 매트릭스에 활성 무기 충진재가 포함되어 있는 복합 고체 전해질이 고이온전도도와 전극과의 탁월한 계면접촉을 이루는데 가장 유리한 것으로 알려졌다. 본 총설에서는 우선 고체 전해질의 종류와 연혁에 관해 간단히 소개하고, 고분자 및 무기 충진재 (불활성 및 활성)로 구성되는 고체 고분자 전해질 및 무기 고체 전해질의 기본적 물성 및 전기화학적 특성을 개괄한다. 또한 이 소재들의 형상을 기준으로 입자형 (0D), 섬유형 (1D), 평판형 (2D), 입체형 (3D)의 형식으로 구성된 복합고체 전해질과 이에 따른 전고체 전지의 전기화학적 특성을 논의한다. 특히 리튬금속 음전극을 사용하는 전고체 전지에 있어서 양전극-전해질 계면, 음전극-전해질 계면, 입자간 계면의 특성에 관해 소개하고, 마지막으로 현재까지 보고된 관련 총설들을 참조하여 복합 고체 전해질 기술의 현재 요구조건 및 미래 전망을 알아본다.

• 한국재료학회지
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• 제34권4호
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• pp.185-193
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• 2024

In this study, NASICON-type Li_1+XGa_XTi_2-X(PO₄)₃ (x = 0.1, 0.3 and 0.4) solid-state electrolytes for all-solid-state batteries were synthesized through the sol-gel method. In addition, the influence on the ion conductivity of solid-state electrolytes when partially substituted for Ti⁴⁺ (0.61Å) site to Ga³⁺ (0.62Å) of trivalent cations was investigated. The obtained precursor was heat treated at 450 ℃, and a single crystalline phase of Li_1+XGa_XTi_2-X(PO₄)₃ systems was obtained at a calcination temperature above 650 ℃. Additionally, the calcinated powders were pelletized and sintered at temperatures from 800 ℃ to 1,000 ℃ at 100 ℃ intervals. The synthesized powder and sintered bodies of Li_1+XGa_XTi_2-X(PO₄)₃ were characterized using TG-DTA, XRD, XPS and FE-SEM. The ionic conduction properties as solid-state electrolytes were investigated by AC impedance. As a result, Li_1+XGa_XTi_2-X(PO₄)₃ was successfully produced in all cases. However, a GaPO₄ impurity was formed due to the high sintering temperatures and high Ga content. The crystallinity of Li_1+XGa_XTi_2-X(PO₄)₃ increased with the sintering temperature as evidenced by FE-SEM observations, which demonstrated that the edges of the larger cube-shaped grains become sharper with increases in the sintering temperature. In samples with high sintering temperatures at 1,000 ℃ and high Ga content above 0.3, coarsening of grains occurred. This resulted in the formation of many grain boundaries, leading to low sinterability. These two factors, the impurity and grain boundary, have an enormous impact on the properties of Li_1+XGa_XTi_2-X(PO₄)₃. The Li_1.3Ga_0.3Ti_1.7(PO₄)₃ pellet sintered at 900 ℃ was denser than those sintered at other conditions, showing the highest total ion conductivity of 7.66 × 10^-5 S/cm at room temperature. The total activation energy of Li-ion transport for the Li_1.3Ga_0.3Ti_1.7(PO₄)₃ solid-state electrolyte was estimated to be as low as 0.36 eV. Although the Li_1+XGa_XTi_2-X(PO₄)₃ sintered at 1,000 ℃ had a relatively high apparent density, it had less total ionic conductivity due to an increase in the grain-boundary resistance with coarse grains.

• Journal of Electrochemical Science and Technology
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• 제12권1호
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• pp.126-136
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• 2021

The electrochemical performance of all-solid-state cells (ASSCs) based on sulfide electrolytes is critically affected by the undesirable interfacial reactions between oxide cathodes and sulfide electrolytes because of the high reactivity of sulfide electrolytes. Based on the concept that the interfacial reactions are highly dependent on the type of sulfide electrolyte, the electrochemical properties of the ASSCs prepared using three types of sulfide electrolytes were observed and compared. The Li2MoO4-LiI coating layer was also introduced to suppress the interfacial reactions. The cells using argyrodite electrolyte exhibited a higher capacity and Coulombic efficiency than the cells using 75Li2S-22P2S5-3Li2SO4 and Li7P3S11 electrolytes, indicating that the argyrodite electrolyte is less reactive with cathodes than other electrolytes. Moreover, the introduction of Li2MoO4-LiI coating on the cathode surface significantly enhanced the electrochemical performance of ASSCs because of the protection of coating layer. Pulverization of argyrodite electrolyte is also effective in increasing the capacity of cells because the smaller size of electrolyte particles improved the contact stability between the cathode and the sulfide electrolyte. The cyclic performance of cells was also enhanced by pulverized electrolyte, which is also associated with improved contact stability at the cathode/electrolyte. These results show that the introduction of Li2MoO4-LiI coating and the use of pulverized sulfide electrolyte can exhibit a synergic effect of suppressed interfacial reaction by the coating layer and improved contact stability owing to the small particle size of electrolyte.

• 한국재료학회지
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• 제31권11호
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• pp.614-618
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• 2021

As the size of market for electric vehicles and energy storage systems grows, the demand for lithium-ion batteries (LIBs) is increasing. Currently, commercial LIBs are fabricated with liquid electrolytes, which have some safety issues such as low chemical stability, which can cause ignition of fire. As a substitute for liquid electrolytes, solid electrolytes are now being extensively studied. However, solid electrolytes have disadvantages of low ionic conductivity and high resistance at interface between electrode and electrolyte. In this study, Li₇La₃Zr₂O₁₂ (LLZO), one of the best ion conducting materials among oxide based solid electrolytes, is fabricated through RF-sputtering and various electrochemical properties are analyzed. Moreover, the electrochemical properties of LLZO are found to significantly improve with co-sputtered Li₂O. An all-solid thin film battery is fabricated by introducing a thin film solid electrolyte and an Li₄Ti₅O₁₂ (LTO) cathode; resulting electrochemical properties are also analyzed. The LLZO/Li₂O (60W) sample shows a very good performance in ionic conductivity of 7.3×10^-8 S/cm, with improvement in c-rate and stable cycle performance.