향후 우리 사회의 혁신적 변화를 가져올 휴대용 전자기기, 전기자동차 및 스마트 그리드 에너지 저장장치 등의 비약적인 발전에 따라, 그 전원으로서 리튬이차전지에 대한 관심이 더욱 증대하고 있다. 본 총설에서는, 리튬이차전지 핵심 소재 중 하나인 분리막에 대해 기공 구조 및 물리화학적 물성 관점에서 고찰하고, 이와 함께 최신 연구 동향을 소개하고자 한다. 리튬이차전지 분리막은 양극과 음극 사이에 위치하는 다공성 막으로서, 두 전극 간의 전기적 단락을 방지하고, 이온의 흐름을 가능하게 하는 기능을 갖는다. 분리막 자체는 전지 내 전기화학 반응에는 직접적으로 참여하지 않으나, 앞서 언급한 기능들에 의해 전지 성능 및 안전성에 큰 영향을 끼친다. 최근 들어, 이러한 분리막의 기본 특성 이외에, 전지 안전성 강화 및 금속 이온 흡착 등을 비롯한 다양한 기능 부여를 위한 노력들이 활발히 진행되고 있다. 본 총설에서는 현재 상업화된 폴리올 레핀 분리막에 대한 이해를 토대로, 개질 폴리올레핀 분리막, 부직포 분리막, 세라믹 복합 분리막 및 화학 활성 분리막 등으 로 대표되는 최신 분리막 기술들을, 차세대 전지 개발 방향과 관련 지어 기술하고자 한다.

The characteristics of aqueous lithium recovery by ion exchange were studied using three commercial cation exchange resins: CMP28 (porous type strong acid exchange resin), SCR-B (gel type strong acid exchange resin) and WK60L (porous type weak acid exchange resin). CMP28 was the most effective material for aqueous lithium recovery; its performance was even enhanced by modifying the cation with K+. A comparison to Na+ and H+ form resins demonstrated that the performance enhancement is reciprocally related to the electronegativity of the cation form. Further kinetic and equilibrium isotherm studies with the K+ form CMP28 showed that aqueous lithium recovery by ion exchange was well fitted with the pseudo-second-order rate equation and the Langmuir isotherm. The maximum ion exchange capacity of aqueous lithium recovery was found to be 14.28 mg/g and the optimal pH was in the region of 4-10.

Nitrogen-atom doped graphene oxide was considered to prevent the dissolution of polysulfide and to guarantee the enhanced redox reaction of sulfur for good cycle performance of lithium sulfur cells. In this study, we used urea as a nitrogen source due to its low cost and easy preparation. To find the optimum urea content, we tested three different ratios of urea to graphene oxide. The morphology of the composites was examined by field emission scanning electron microscope. Functional groups and bonding characterization were measured by X-ray photoelectron spectroscopy. Electrochemical properties were characterized by cyclic voltammetry in an organic electrolyte solution. Compared with thermally reduced graphene/sulfur (S) composite, nitrogen-doped graphene/S composites showed higher electroactivity and more stable capacity retention.

Lithium-ion batteries (LIBs) are rapidly improving in capacity and life cycle characteristics to meet the requirements of a wide range of applications, such as portable electronics, electric vehicles, and micro- or nanoelectromechanical systems. Recently, atomic layer deposition (ALD), one of the vapor deposition methods, has been explored to expand the capability of LIBs by producing near-atomically flat and uniform coatings on the shell of nanostructured electrodes and membranes for conventional LIBs. In this paper, we introduce various ALD coatings on the anode, cathode, and separator materials to protect them and improve their electrochemical and thermomechanical stability. In addition, we discuss the effects of ALD coatings on the three-dimensional structuring and conduction layer through activation of electrochemical reactions and facilitation of fluent charge collection.

We have investigated the crystallization mechanism of the lithium disilicate (Li2O-2SiO2, LSO) glass particles with different sizes by isothermal and non-isothermal processes. The LSO glass was fabricated by rapid quenching of melt. X-ray diffraction and differential scanning calorimetry measurements were performed. Different crystallization models of Johnson- Mehl-Avrami, modified Ozawa and Arrhenius were adopted to analyze the thermal measurements. The activation energy E and the Avrami exponent n, which describe a crystallization mechanism, were obtained for three different glass particle sizes. Values of E and n for the glass particle with size under 45 μm, 75~106 μm, and 125~150 μm, were 2.28 eV, 2.21 eV, 2.19 eV, and ~1.5 for the isothermal process, respectively. Those values for the non-isothermal process were 2.4 eV, 2.3 eV, 2.2 eV, and ~1.3, for the isothermal process, respectively. The obtained values of the crystallization parameters indicate that the crystallization occurs through the decreasing nucleation rate with a diffusion controlled growth, irrespective to the particle sizes. It is also concluded that the smaller glass particles require the higher heat absorption to be crystallized.

In this study, several kinds of active carbons with high specific surface area and micro pore structure were prepared from the coconut shell charcoal using chemical activation method. The physical property of prepared active carbon was investigated by experimental variables such as activating chemical agents to char coal ratio, flow rate of inert gas and temperature. It was shown that chemical activation with KOH and NaOH was successfully able to make active carbons with high surface area of 1900~2500 m2/g and mean pore size of 1.85~2.32 nm. The coin cell using water-based binder in the electrolyte of LiPF6 dissolved in mixed organic solvents (EC:DMC:EMC=1:1:1 vol%) showed better capacity than that of oil-based binder. Also, it was found that the coin cell of water-based binder shows an improved cycling performance and coulombic efficiency.

The microstructures and cyclic voltammograms of Al-Si/C nano-composites were investigated as the anode of lithium ion batteries. Al-Si nanoparticles were prepared by the arc-discharge method. Al-Si/C nanoparticles were obtained by coated Al-Si nanoparticles with the precursor of glucose (C6H12O6) as carbon source. It was indicated that the post carbon coating treatment can reduce Al2O3 film on Al-Si particles, and new phase Al4C3 formed in the process can activate the inactivated materials of electrode in a certain extent.

In order to prepare anode materials for high power lithium ion secondary batteries, carbon composites were fabricated with a mixture of petroleum pitch and coke (PC) and a mixture of petroleum pitch, coke, and natural graphite (PCNG). Although natural graphite has a good reversible capacity, it has disadvantages of a sharp decrease in capacity during high rate charging and potential plateaus. This may cause difficulties in perceiving the capacity variations as a function of electrical potential. The coke anodes have advantages without potential plateaus and a high rate capability, but they have a low reversible capacity. With PC anode composites, the petroleum pitch/cokes mixture at 1:4 with heat treatment at 1000 oC (PC14-1000C) showed relatively high electrochemical properties. With PC-NG anode composites, the proper graphite contents were determined at 10~30 wt.%. The composites with a given content of natural graphite and remaining content of various petroleum pitch/cokes mixtures at 1:4~4:1 mass ratios were heated at 800~1200 oC. By increasing the content of petroleum pitch, reversible capacity increased, but a high rate capability decreased. For a given composition of carbonaceous composite, the discharge rate capability improved but the reversible capacity decreased with an increase in heat treatment temperature. The carbonaceous composites fabricated with a mixture of 30 wt.% natural graphite and 70 wt.% petroleum pitch/cokes mixture at 1:4 mass ratio and heat treated at 1000 oC showed relatively high electrochemical properties, of which the reversible capacity, initial efficiency, discharge rate capability (retention of discharge capacity in 10 C/0.2 C), and charge capacity at 5 C were 330 mAh/g, 79 %, 80 %, and 60 mAh/g, respectively.

The composite of porous silicon (Si) and amorphous carbon (C) is prepared by pyrolysis of a nano-porous Si + pitch mixture. The nano-porous Si is prepared by mechanical milling of magnesium powder with silicon monoxide (SiO) followed by removal of MgO with hydrochloric acid (etching process). The Brunauer-Emmett-Teller (BET) surface area of porous Si (64.52 m2g−1) is much higher than that before etching Si/MgO (4.28 m2g−1) which indicates pores are formed in Si after the etching process. Cycling stability is examined for the nano-porous Si + C composite and the result is compared with the composite of nonporous Si + C. The capacity retention of the former composite is 59.6% after 50 charge/discharge cycles while the latter shows only 28.0%. The pores of Si formed after the etching process is believed to accommodate large volumetric change of Si during charging and discharging process.

본 연구는 냉각코일과 리튬브로마이드 수용액을 활용 하여 유리 chamber 내 냉각 및 제습 실험을 수행하였다. 냉각수 온도별 냉각 효과와 리튬브로마이드 수용액의 제습량을 확인하였으며, 이를 동시에 적용하여 실험을 수행하였다. 냉각수 온도별 냉각 실험은 279K, 286K, 293K에서 각각 19K, 13K, 10K 가량 감소되는 경향을 보였다. 냉각수 온도가 낮을수록 높은 냉각 성능을 보였으며, 여름철 상하수도 온도인 293K의 물로도 충분히 작물이 생육하기 좋은 온실 내부온도를 유지할 수 있다고 판단되었다. 또한 리튬브로마이드 수용액을 활용한 제습 실험에서는 약 80%의 외부 습도가 리튬브로마이드 수용액과 결합하여 약 50%로 감소되어 약 30%의 제습량을 보였으며, 이는 시설 내 제습 시스템의 적용에 적합한 물질로 판단된다. 냉각코일과 리튬브로마이드 수용액을 동시에 적용한 실험에서 약 9K의 온도 강하, 15%의 제습량을 나타냈으며, 리튬브로마이드 수용액이 수증기를 흡수하는 과정에서 반응열이 발생하는 것을 확인하였다. 또한, 시뮬레이션을 통해 냉각 실험 결과와 대비 비교 한 결과 약 299.7K의 내부 온도를 보여 일치하는 것을 확인하였다. 수분의 제습과정을 거치면서 농도가 낮아진 리튬브로 마이드 수용액(희용액)은 수집탱크로 모아 재생부로 이송되어 가열, 수분을 증발시켜 농용액으로 전환된 후 열 교환을 거쳐 냉각되어 다시 제습시스템으로 공급되는 시스템을 적용하면 일정량의 리튬브로마이드 수용액만으로 온실 제습을 할 수 있을 것으로 판단된다. 본 실험을 통해 냉각 및 제습이 동시에 가능하다는 것을 확인하였으며, 리튬브로마이드 수용액을 활용하여 실제 온실에 적용된다면 기존 온실에서 사용하고 있는 냉방 및 제습 방법에 비해 에너지 절감을 통한 경제적 효과를 얻을 수 있을 것으로 판단된다. 향후, 제습 부분은 시뮬레이션을 통한 분석 및 실험결과와 대비 검증이 요구되고, Lab scale의 제습 시스템에 서 Farm scale의 온실 규모로 확장하여, 추가 변수에 대한 제습 및 냉각 연구가 수행되어야 할 것이다.

Silicon-carbon composite was prepared by the magnesiothermic reduction of mesoporous silica and subsequent impregnation with a carbon precursor. This was applied for use as an anode material for high-performance lithium-ion batteries. Well-ordered mesoporous silica(SBA-15) was employed as a starting material for the mesoporous silicon, and sucrose was used as a carbon source. It was found that complete removal of by-products (Mg2Si and Mg2SiO4) formed by side reactions of silica and magnesium during the magnesiothermic reduction, was a crucial factor for successful formation of mesoporous silicon. Successful formation of the silicon-carbon composite was well confirmed by appropriate characterization tools (e.g., N2 adsorption-desorption, small-angle X-ray scattering, X-ray diffraction, and thermogravimetric analyses). A lithium-ion battery was fabricated using the prepared silicon-carbon composite as the anode, and lithium foil as the counter-electrode. Electrochemical analysis revealed that the silicon-carbon composite showed better cycling stability than graphite, when used as the anode in the lithium-ion battery. This improvement could be due to the fact that carbon efficiently suppressed the change in volume of the silicon material caused by the charge-discharge cycle. This indicates that silicon-carbon composite, prepared via the magnesiothermic reduction and impregnation methods, could be an efficient anode material for lithium ion batteries.

Due to their morphology, electrochemical stability, and function as a conducting carbon matrix, graphene nanosheets (GNS) have been studied for their potential roles in improving the performance of sulfur cathodes. In this study, a GNS/sulfur (GNS/S) composite was prepared using the infiltration method with organic solvent. The structure, morphology and crystallinity of the composites were examined using scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The electrochemical properties were also characterized using cyclic voltammetry (CV). The CV data revealed that the GNS/S composites exhibited enhanced specific-current density and ~10% higher capacity, in comparison with the S-containing, activated-carbon samples. The composite electrode also showed better cycling performance for multiple charge/discharge cycles. The improvement in the capacity and cycling stability of the GNS/S composite electrode is probably related to the fact that the graphene in the composite improves conductivity and that the graphene is well dispersed in the composites.

Cathode materials and their precursors are prepared with transition metal solutions recycled from the thewaste lithium-ion batteries containing NCM (nickel-cobalt-manganese) cathodes by a H2 and C-reduction process. Therecycled transition metal sulfate solutions are used in a co-precipitation process in a CSTR reactor to obtain the tran-sition metal hydroxide. The NCM cathode materials (Ni:Mn:Co=5:3:2) are prepared from the transition metal hydroxideby calcining with lithium carbonate. X-ray diffraction and scanning electron microscopy analyses show that the cathodematerial has a layered structure and particle size of about 10 µm. The cathode materials also exhibited a capacity ofabout 160 mAh/g with a retention rate of 93~96% after 100 cycles.

Tungsten oxide films were prepared by an electrochemical deposition method for use as the anode in rechargeable lithium batteries. Continuous potentiostatic deposition of the film led to numerous cracks of the deposits while pulsed deposition significantly suppressed crack generation and film delamination. In particular, a crack-free dense tungsten oxide film with a thickness of ca. 210 nm was successfully created by pulsed deposition. The thickness of tungsten oxide was linearly proportional to deposition time. Compositional and structural analyses revealed that the as-prepared deposit was amorphous tungsten oxide and the heat treatment transformed it into crystalline triclinic tungsten oxide. Both the as-prepared and heat-treated samples reacted reversibly with lithium as the anode for rechargeable lithium batteries. Typical peaks for the conversion processes of tungsten oxides were observed in cyclic voltammograms, and the reversibility of the heat-treated sample exceeded that of the as-prepared one. Consistently, the cycling stability of the heat-treated sample proved to be much better than that of the as-prepared one in a galvanostatic charge/discharge experiment. These results demonstrate the feasibility of using electrolytic tungsten oxide films as the anode in rechargeable lithium batteries. However, further works are still needed to make a dense film with higher thickness and improved cycling stability for its practical use.

ZnO nanoparticles in the size range from 5 to 15 nm were prepared by zinc-lithium-acetate system. The morphologies and structures of ZnO were characterized by TEM, XRD and FT-IR spectra. UV-visible results shows that the absorption of ZnO nanoparticles is blue shifted with decrease in particles size. Furthermore, photoluminescence spectra of the ZnO nanoparticles were also investigated. The ZnO nanoparticles have strong visible-emission intensity and their intensities depend upon size of ZnO nanoparticles.

The electrolytic reduction of a spent oxide fuel involves liberation of the oxygen in a molten LiCl electrolyte, which is a chemically aggressive environment that is too crosive for typical structural materials. Therefore, it is essential to choose the optimum material for the process equipment for handling a molten salt. In this study, the corrosion behavior of pyro-carbon made by CVD was investigated in a molten LiCl-Li2O salt under an oxidation atmosphere at 650˚C and 750˚C for 72 hours. Pyro-carbon showed no chemical reactions with the molten salt because of its low wettability between pyro-carbon and the molten salt. As a result of XRD analysis, pyro-carbon exposed to the molten salt showed pure graphite after corrosion tests. As a result of TGA, whereas the coated layer by CVD showed high anti-oxidation, the non-coated layer showed relatively low anti-oxidation. The stable phases in the reactions were C(S), Li2CO3(S), LiCl(l), Li2O at 650˚C and C(S), LiCl(l), Li2O(S) at 750˚C. Li2CO(S) was decomposed at 750˚C into Li2O(S) and CO2(g).

nanotubes were successfully synthesized using an electrospinning technique followed by calcination in air. The nanotubes were the single phase nature of and consisted of approximately 14 nm nanocrystals. SEM and TEM characterizations demonstrated that uniform hollow fibers with an average outer diameter of around 124 nm and wall thickness of around 25 nm were successfully obtained. As anode materials for lithium ion batteries, the nanotubes exhibited excellent cyclability and reversible capacity of up to 25 cycles at as compared to nanoparticles with a capacity of . Such excellent performance of the nanotube was related to the one-dimensional hollow structure which acted as a buffer zone during the volume contraction and expansion of Sn.

Mass production-capable 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 . Lastly, carbon was coated on powders by using sucrose to afford some improved electrical conductivity. The carbon-coated 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.