Silicon alloys are considered promising anode active materials to replace Li-ion batteries by graphite powder, because they have a relatively high capacity of up to 4200 mAh/g, and are environmentally friendly and inexpensive ECO-materials. However, its poor charge/discharge properties, induced by cracking during cycles, constitute their most serious problem as anode electrode. In order to solve these problems, Si-Ge-Al alloys with porous structure are designed as anode alloy powders, to improve cycling stability. The alloys are melt-spun to obtain the rapidly solidified ribbons, and then ball-milled to make fine powders. The powders are etched using 1 M HCl solution, which gives the powders a porous structure by removing the element Al. Subsequently, in this study, the microstructures and the characteristics of the etched powders are evaluated for application as anode materials. As a result, the etched porous powder shows better electrochemical properties than as-milled Si-Ge-Al powder.

Lithium ion battery are one of representative rechargeable batteries with high energy density, tiny memory effect, and low self-discharge and composed of anode, cathode, electrolyte, and membrane separator. The importance of membrane separator has been improved further as electric vehicle market increases rapidly. The conventional membrane separators are based on polyolefin (e.g., polyethylene and/or polypropylene). In case of lithium ion battery with a high capacity, polyolefin membrane separators are suffering from low thermal resistance and easy short-circuit formation leading to overheating. For these reasons, in this study, gel polymers are in-situ synthesized in electrolytes used as solvent, which are located in pores of polyolefin separators to obtain gel polymer electrolyte-polyolefin reinforced membranes.

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.

리튬이온 이차전지는 리튬이온이 이동하면서 전기화학적 충방전사이클을 완성하는 에너지변환장치를 의미한다. 리튬이온 이차전지는 높은 에너지밀도와 낮은 자가방전률, 상대적으로 긴 수명주기 등 다양한 장점을 갖는다. 최근 전기차 수 요증가는 고용량 리튬이온 이차전지 개발을 촉진하고 있으나 음극에서의 dendrite 형성으로 인한 전기적 단락 현상과 전지 폭 발 문제와 같은 심각한 안전문제를 야기한다. 또한, 리튬이온 이차전지 구동시 상승된 온도에서 폴리올레핀계열(예 : 폴리에 틸렌과 폴리프로필렌) 격리막의 열수축 문제가 발생한다. 이와 같이 낮은 열 안정성은 리튬이온 이차전지의 성능과 수명의 감소로 이어진다. 본 연구에서는 폴리올레핀계열 함침격리막 제조를 위한 중요한 소재로서 술폰화 폴리아릴렌에테르술폰 랜 덤 공중합체를 사용하였으며, 제조된 격리막을 이용하여 dendrite 형성과 관련된 금속이온 흡착 능력과 리튬이온전도성, 열적 내구성이 평가되었다.

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.

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 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.

The electrochemical properties of cells assembled with the LiNiO2 (LNO) recycled from cathode materialsof waste lithium secondary batteries (Li[Ni,Co,Mn]O2), were evaluated in this study. The leaching, neutralization andsolvent extraction process were applied to produce high-purity NiSO4 solution from waste lithium secondary batteries.High-purity NiO powder was then fabricated by the heat-treatment and mixing of the NiSO4 solution and H2C2O4.Finally, LiNiO2 as a cathode material for lithium ion secondary batteries was synthesized by heat treatment and mixingof the NiO and Li2CO3 powders. We assembled the cells using the LiNiO2 powders and evaluated the electrochemicalproperties. Subsequently, we evaluated the recycling possibility of the cathode materials for waste lithium secondary bat-tery using the processes applied in this work.

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.

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.

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.

Expanded graphites were used as anode materials of high power Li-ion secondary battery. The expanded graphite was prepared by mixing the graphite with HClO4 as a intercalation agents and KMnO4 as a oxidizing agents. The physical and electrochemical properties of prepared expanded graphites through the variation of process variables such as contents of intercalation agent and oxidizing agent, and heat treatment temperature were analyzed for determination of optimal conditions as the anode of high power Li-ion secondary battery. After examing the electrochemical properties of expanded graphites at the different preparing conditions, the optimal conditions of expanded graphite were selected as 8 wt.% of oxidizing agent, 400 g of intercalation agent for 20 g of natural graphite, and heat treatment at 1000℃. The sample showed the improved charge/discharge characteristics such as 432 mAh/g of initial reversible capacity, 88% of discharge rate capability at 10 C-rate, and 24 mAh/g of charge capacity at 10 C-rate. However, the expanded graphite had the problems of potential plateaus like natural graphite and lower initial efficiency than the natural graphite.

One of the greatest challenges for our society is providing powerful electrochemical energy conversion and storage devices. Rechargeable lithium-ion batteries and fuel cells are among the most promising candidates in terms of energy and power density. As the starting material, TiCl4·YCl3 solution and dispersing agent (HCP) were mixed and synthesized using ammonia as the precipitation agent, in order to prepare the nano size Y doped spherical TiO2 precursor. Then, the Li4Ti5O12 was synthesized using solid state reaction method through the stoichiometric mixture of Y doped spherical TiO2 precursor and LiOH. The Ti mole increased the concentration of the spherical particle size due to the addition of HPC with a similar particle size distribution in a well in which Li4Ti5O12 spherical particles could be obtained. The optimal synthesis conditions and the molar ratio of the Ti 0.05 mol reaction at 50˚C for 30 minutes and at 850˚C for 6 hours heat treatment time were optimized. Li4Ti5O12 was prepared by the above conditions as a working electrode after generating the Coin cell; then, electrochemical properties were evaluated when the voltage range of 1.5V was flat, the initial capacity was 141 mAh/g, and cycle retention rate was 86%; also, redox reactions between 1.5 and 1.7V, which arose from the insertion and deintercalation of 0.005 mole of Y doping is not a case of doping because the C-rate characteristics were significantly better.

A porous nickel-tin nano-dendritic electrode, for use as the anode in a rechargeable lithium battery, has been prepared by using an electrochemical deposition process. The adjustment of the complexing agent content in the deposition bath enabled the nickel-tin alloys to have specific stoichiometries while the amount of acid, as a dynamic template for micro-porous structure, was limited to a certain amount to prevent its undesirable side reaction with the complexing agent. The ratios of nickel to tin in the electro-deposits were nearly identical to the ratios of nickel ion to tin ion in the deposition bath; the particle changed from spherical to dendritic shape according to the tin content in the deposits. The nickel to tin ratio and the dendritic structure were quite uniform throughout the thickness of the deposits. The resulting nickel-tin alloy was reversibly lithiated and delithiated as an anode in rechargeable lithium battery. Furthermore, the resulting anode showed much more stable cycling performance up to 50 cycles, as compared to that resulting from dense electro-deposit with the same atomic composition and from tin electrodeposit with a similar porous structure. From the results, it is expected that highly-porous nickel-tin alloys presented in this work could provide a promising option for the high performance anode materials for rechargeable lithium batteries.

다공성 Poly(propylene) 분리막의 지지 하에 전해질 용액 (EC/DEC 1 : 1 혼합물 내의 LiPF6 1 M 용액) 내에서 DEGDMA [Di(ethylene glycol) dimethacrylate]의 70℃ 열중합을 통하여 겔 고분자 전해질(GPE)막이 합성 되었다. 합성된 겔 고분자 전해질막의 이온전도도 및 전기화학적 안정성은 AC 임피던스법 및 CV (cyclic voltametry)법에 의하여 측정 평가하였다. 겔 고분자를 전해질로, 그리고 양극 및 음극으로는 각각 LiMi0.8Co0.2O2 및 graphite로 이용하여 리튬이온전지(LIB)도 제작하였다. 열중합을 통하여 리튬 이온전지에 적합한 이온전도도(10 -3 S/cm 이상) 및 전기화학적 안정성을 보이면서 자체적인 성상을 유지하는 겔 고분자 전해질막을 얻을 수 있었다. 단량체 함량 5%의 전구체로 제작한 겔 고분자 전지는 단량체 함량이 7.0% 및 10.0%인 경우에 비하여 우수한 고율 및 충-방전 효율을 보였다.