탄소중립을 달성하기 위해 이산화탄소를 포집, 활용, 저장하는 CCUS (carbon capture, utilization, and storage) 기 술이 주목받고 있다. 본 연구에서는 광물 탄산화 공정을 통해 이산화탄소를 탄산염으로 고정하고, 이를 전이금속 탄산염 기반 리튬이온배터리 (LIB) 음극재로 적용하였다. CO2를 탄산염으로 고정후, 이를 이용해 FeCO3를 제작하고, rGO와 PVP와 복합 화하여 음극활물질에 적용하였다. rGO는 전기전도도를 높이고 입자의 응집을 방지해 부피 팽창을 완화했으며, PVP는 계면 활성제로서 입자 표면을 안정화하여 구조적 안정성을 강화하였다. FeCO3-PVP-rGO 복합체 기반한 음극재에 대한 전기화학 테스트를 진행한 결과, FeCO3/rGO 복합체는 1,620 mA/g의 전류 밀도에서 50 사이클 이후에도 400 mAh/g의 용량을 유지하 였다. 본 연구는 CO2를 고부가가치 배터리 소재로 전환하여 차세대 에너지 저장 기술에 기여할 가능성을 시사한다.
리튬이온전지는 친환경적이고 우수한 전지 성능덕분에 배터리 산업의 핵심으로 자리 잡았으며, 이에 따라 수요가 급증하고 있다. 그러나, 리튬이온전지의 수요증가는 리튬과 광물자원들의 공급문제를 초래하며, 수명이 다한 폐 리튬이온전지의 폐기방안이 아직 마련되지 않아 환경적 문제를 발생시킨다. 이러한 문제를 해결하기 위해 폐 리튬이온전지를 재활용하는 연구가 진행되고 있으며, 그 중에서도 폐 리튬이온전지에서 폐 양극 소재를 추출하여 재활용하는 다이렉트 리사이클링 연구가 주목받고 있다. 그러나, 폐 양극 소재는 오랜 충/방전으로 인해 구조적 붕괴(열화)가 발생한 상태로, 새로운 리튬이온전지에 적용을 위해서는 리튬이온전지 사용 전의 구조 즉, 층상구조로의 회복이 필요하다. 본 연구에서는 이를 위해 폐 양극 소재(LiNi0.6C0.2Mn0.2O2)가 열역학적으로 층상구조를 형성하는 온도를 분석하기 위해 700 ºC, 800 ºC, 900 ºC 범위에서 XRD를 통해 구조분석을 진행하였다. 폐 양극 소재는 700 ºC와 900 ºC 대비 800 ºC 열처리 시 1.44로 가장 높은 I003/I104 value를 보였다. 또한 800 ºC 열처리 시 0.1 C 기준 비 용량이 171.3 mAh/g으로 가장 높은 것을 확인하였다. 이를 통해 우리는 열역학적으로 층상구조를 형성하는 온도를 800 ºC로 도출하였으며 폐 양극 소재의 구조를 성공적으로 복원하였다.
환경오염을 제어하기 위한 청정에너지에 대한 수요 증가는 빠르게 증가하고 있습니다. 리튬 이온 배터리와 같은 충전식 배터리는 청정에너지의 우수한 원천이지만 높은 수요와 공급 불일치로 인해 리튬 금속이 빠르게 고갈되고 있습니다. 배터리 폐기물에서 귀금속을 회수하는 것은 환경오염 제어와 함께 가능한 해결책 중 하나입니다. 멤브레인 기반 분리 방법은 폐기물에서 리튬을 회수할 수 있는 매우 성공적인 상업적 공정입니다. 이 작업은 최근에 보고된 다양한 방법을 다룰 것이며 검토 형식으로 작성될 것입니다.
This study prepares highly porous carbon (c-fPI) for lithium-ion battery anode that starts from the synthesis of fluorinated polyimide (fPI) via a step polymerization, followed by carbonization. During the carbonization of fPI, the decomposition of fPI releases gases which are particularly from fluorine-containing moiety (–CF3) of fPI, creating well-defined microporous structure with small graphitic regions and a high specific surface area of 934.35 m2 g− 1. In particular, the graphitic region of c-fPI enables lithiation–delithiation processes and the high surface area can accommodate charges at electrolyte/electrode interface during charge–discharge, both of which contribute electrochemical performances. As a result, c-fPI shows high specific capacity of 248 mAh g− 1 at 25 mA g− 1, good rate-retention performance, and considerable cycle stability for at least 300 charge–discharge cycles. The concept of using a polymeric precursor (fPI), capable of forming considerable pores during carbonization is suitable for the use in various applications, particularly in energy storage systems, advancing materials science and energy technologies.
The lithium-ion battery has been utilized in various fields including energy storage system, portable electronic devices and electric vehicles due to their high energy and power densities, low self-discharge, and long cycle-life performances. However, despite of various research on electrode materials, there is a lack of research on developing of binder to replace conventional polymer-based binding materials. In this work, petroleum pitch (MP-50)/polymer (polyurethane, PU) composite binder for lithium-ion battery has fabricated not only to use as a binding material, but also to re-place conventional polymer-based binder. The MP-50/PU composite binder has also prepared to various ratios between petroleum pitch and polymer to optimize the physical and electro-chemical performance of the lithium-ion battery based on the MP-50/PU composite binder. The physical and electrochemical performances of the MP-50/PU composite binder-based lithium-ion battery were evaluated using a universal testing machine (UTM), charge/discharge test. As a result, lithium-ion battery based on the MP-50/PU composite (5:5, mass ratio) binder showed optimized performances with 1.53 gf mm− 1 of adhesion strength, 341 mAh g− 1 of specific discharge capacity and 99.5% of ICE value.
As the demand for lithium-ion batteries for electric vehicles is increasing, it is important to recover valuable metals from waste lithium-ion batteries. In this study, the effects of gas flow rate and hydrogen partial pressure on hydrogen reduction of NCM-based lithium-ion battery cathode materials were investigated. As the gas flow rate and hydrogen partial pressure increased, the weight loss rate increased significantly from the beginning of the reaction due to the reduction of NiO and CoO by hydrogen. At 700 °C and hydrogen partial pressure above 0.5 atm, Ni and Li2O were produced by hydrogen reduction. From the reduction product and Li recovery rate, the hydrogen reduction of NCM-based cathode materials was significantly affected by hydrogen partial pressure. The Li compounds recovered from the solution after water leaching of the reduction products were LiOH, LiOH·H2O, and Li2CO3, with about 0.02 wt% Al as an impurity.
최근 전기차 및 전력저장 시스템과 같은 대형 전지 시장의 성장으로 인해 리튬 이온 배터리에 대한 수요가 급증하 고 있다. 이에 따라 폐전지의 발생이 빠르게 증가할 것 으로 예상되며, 이에 대한 처리가 사회적 문제가 될 것 으로 예상된다. 폐전지 처리의 가장 효과적인 방법은 폐전지의 소재를 재활용하는 방법이다. 이 중 고가의 금속 물질로서, 재활용 시 경제성이 가장 높은 양극 소재 재활용 연구가 가장 활발히 이뤄지고 있다. 하지만 폐전지로부터 회수된 블 랙 파우더에는 도전재 및 바인더가 포함되어 있는데 양극 소재를 재활용하기 위해서는 이를 제거하는 공정이 필요하 다. 본 연구에서는 폐전지에서 추출된 폐양극 소재의 재활용을 위한 소재 전처리 연구를 제시한다. 열처리 및 화학 처리의 두 가지 전처리 공정을 사용하여 불순물을 제거하였고, 이에 따른 제거 정도를 SEM 분석을 통해 확인하였고, 불순물의 정량 분석을 TGA, EA 분석을 통해 확인하였으며, 전기화학 성능을 분석하였다.
Disposable masks manufactured in response to the COVID-19 pandemic have caused environmental problems due to improper disposal methods such as landfilling or incineration. To mitigate environmental pollution, we suggest a new process for recycling these disposable masks for ultimate application as a conductive material in lithium-ion batteries (LIBs). In our work, the masks were chemically processed via amine functionalization and sulfonation, followed by carbonization in a tube furnace in the Ar atmosphere. The residual weight percentages, as evaluated by thermogravimetric analysis (TGA), of the chemically modified masks were 30.6% (600 °C, C-600), 24.5% (750 °C, C-750), and 24.1% (900 °C, C-900), respectively, thereby demonstrating the possibility of using our proposed method to recycle masks intended for disposal. The electrochemical performance of the fabricated carbonized materials was assessed by fabricating silicon/graphite (20:80) anodes incorporating these materials as additives for use in LIBs. Using a coin-type half-cell system, cells with the aforementioned carbonized materials exhibited initial capacities of 553 mAh/g, 607 mAh/g, and 571 mAh/g, respectively, which are comparable to those of commercial Super P (591 mAh/g). Cell cycled at the rate of 0.33 C with C-600, C-750, and C-900 as additives demonstrated capacity retention of 53.2%, 47.4%, and 51.1%, respectively, compared with that of Super P (48.3%). In addition, when cycled at rates from 0.2 to 5 C, the cells with anodes containing the respective additives exhibited rate capabilities similar to those of Super P. These results might be attributable to the unique surface properties and morphologies of the carbonized materials derived from the new recycling procedure, such as the size and number of heteroatoms on the surface.
The complexation of silicon with carbon materials is considered an effective method for using silicon as an anode material for lithium-ion batteries. In the present study, carbon frameworks with a 3D porous structure were fabricated using metal–organic frameworks (MOFs), which have been drawing significant attention as a promising material in a wide range of applications. Subsequently, the fabricated carbon frameworks were subjected to CVD to obtain silicon-carbon complexes. These siliconcarbon complexes with a 3D porous structure exhibited excellent rate capability because they provided sufficient paths for Li-ion diffusion while facilitating contact with the electrolyte. In addition, unoccupied space within the silicon complex, combined with the stable structure of the carbon framework, allowed the volume expansion of silicon and the resultant stress to be more effectively accommodated, thereby reducing electrode expansion. The major findings of the present study demonstrate the applicability of MOF-based carbon frameworks as a material for silicon complex anodes.
The lithium ion battery has applied to various fields of energy storage systems such as electric vehicle and potable electronic devices in terms of high energy density and long-life cycle. Despite of various research on the electrode and electrolyte materials, there is a lack of research for investigating of the binding materials to replace polymer based binder. In this study, we have investigated petroleum pitch/polymer composite with various ratios between petroleum pitch and polymer in order to optimize the electrochemical and physical performance of the lithium-ion battery based on petroleum pitch/polymer composite binder. The electrochemical and physical performances of the petroleum pitch/polymer composite binder based lithium-ion battery were evaluated by using a charge/discharge test, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and universal testing machine (UTM). As a result, the petroleum pitch(MP-50)/polymer(PVDF) composite (5:5 wt % ratio) binder based lithium-ion battery showed 1.29 gf mm-1 of adhesion strength with 144 mAh g-1 of specific dis-charge capacity and 93.1 % of initial coulombic efficiency(ICE) value.
Highly safe lithium-ion batteries (LIBs) are required for large-scale applications such as electrical vehicles and energy storage systems. A highly stable cathode is essential for the development of safe LIBs. LiFePO4 is one of the most stable cathodes because of its stable structure and strong bonding between P and O. However, it has a lower energy density than lithium transition metal oxides. To investigate the high energy density of phosphate materials, vanadium phosphates were investigated. Vanadium enables multiple redox reactions as well as high redox potentials. LiVPO4O has two redox reactions (V5+/V4+/V3+) but low electrochemical activity. In this study, LiVPO4O is doped with fluorine to improve its electrochemical activity and increase its operational redox potential. With increasing fluorine content in LiVPO4O1-xFx, the local vanadium structure changed as the vanadium oxidation state changed. In addition, the operating potential increased with increasing fluorine content. Thus, it was confirmed that fluorine doping leads to a strong inductive effect and high operating voltage, which helps improve the energy density of the cathode materials.
Refined structured tin dioxide gets the amount of attraction because of its low cost and stability. The C@SnO2 nanospheres with mesoporous structures were produced using the hard template method in this work. The C@SnO2 is primarily gained attributed to the dehydration condensation of C6H12O6 and the hydrolysis of SnCl4 ·5H2O. The morphology of the C@SnO2 was analyzed by physical characterization and the diameter of the obtained C@SnO2 was around 138 nm. When C@SnO2 was applied to lithium-ion batteries as anode material, it performed outstanding electrochemical properties, with a capacity of 735 and 539 mA h g− 1 maintained at 1000 and 2000 mA g− 1, respectively. Furthermore, it exhibits favorable discharge/ charge cycle stability. This is probably because of the more chemically redox active sites provided by C@SnO2 nanocomposites and it also allows fast ion diffusion and electron migration.
In this study, we investigate the opportunity of using waste tire char as a cathode material for lithium-ion primary batteries (LPBs). The char obtained by carbonizing waste tires was washed with acid and thermally fluorinated to produce CFX. The structural and chemical properties of the char and CFX were analyzed to evaluate the effect of thermal fluorination. The carbon structure of the char was increasingly converted to CFX structure as the fluorination temperature increased. In addition, the manufactured CFX- based LPBs were evaluated through electrochemical analysis. The discharge capacity of the CFX reached a maximum of 800 mAh/g, which is comparable to that of CFX- based LPBs manufactured from other carbon sources. On the basis of these results, the use of waste tire char-based CFX as a cathode material for LPBs is presented as a new opportunity in the field of waste tire recycling.
전고체 전지는 전기 자동차의 안정성을 향상시키기 위해 기존의 리튬 이온 전지를 대체할 주요 후보로 간주되고 있 습니다. 그러나 전고체 전지에 사용되는 황화물계 고체 전해질은 산화 환원 안정성이 부족하며 양극복합전극과 표면 에서 부반응을 이르켜 문제를 야기시킵니다. 때문에 양극 표면 코팅법이 제안되었고 이는 충방전 사이클 안정성 및 속도 특성의 개선에 유용한 효과를 나타낼 수 있습니다. 본 논문에서는 결정학적 분석을 통하여 신규 Li-Zr-O 조성 탐색을 하였고, 다양한 양극 소재 코팅소재 후보군 중 리튬 이온 전도체인 Li6Zr2O7 구조가 매우 유망하다는 연구 결 과를 확인했습니다. 본 논문은 기존에 사용되는 LiNbO3, Li4Ti5O12가 아닌 새로운 다양한 구조 및 조성의 양극 코팅 소 재개발에 대한 필요성 및 가능성을 시사합니다.
With a rapid expansion in electric vehicles, a huge amount of the spent Li-ion batteries (LIBs) could be discharged in near future. And thus, the proper handling of the spent LIBs is essential to sustainable development in the industry of electrical vehicles. Among various approaches such as pyrometallurgy, hydrometallurgy, and direct recycling, the hydrometallurgical manner has gained interest in recycling the spent LIBs due to its high effectiveness in recycling raw materials (e.g., lithium, nickel, cobalt, and manganese). However, the hydrometallurgical process not only requires the use of large amounts of acids and water resources but also produces toxic gases and wastewater leading to environmental and economic problems, considering potential economic and environmental problems. Thus, this review aims to provide an overview of conventional and state-of-the-art hydrometallurgical processes to recover valuable metals from spent LIBs. First, we briefly introduce the basic principle and materials of LIBs. Then, we briefly introduce the operations and pros-and cons- of hydrometallurgical processes. Finally, this review proposes future research directions in hydrometallurgy, and its potential opportunities in the fundamental and practical challenges regarding its deployment going forward.
The inclusion of conductive carbon materials into lithium-ion batteries (LIBs) is essential for constructing an electrical network of electrodes. Considering the demand for cells in electric vehicles (e.g., higher energy density and lower cell cost), the replacement of the currently used carbon black with carbon nanotubes (CNTs) seems inevitable. This review discusses how CNTs can contribute to the development of advanced LIBs for EVs. First, the reason for choosing CNTs as a conducting agent for the cathode is discussed in terms of energy density. Second, the reinforcing effect of CNTs on the anode is described with respect to the choice of silicon as the active material. Third, the development of water-based cathode fabrication as well as dry electrode fabrication with aid of CNTs is discussed. Fourth, three technical hurdles, that is, the price, dispersion issue, and entrapped metal impurities, for widespread use of CNTs in LIBs are discussed.
본 연구는 코팅 방법을 활용한 단결정 양극 소재 연구로서 Ni-rich계 다결정 양극 소재로 부터 단결정 양극 소재를 합 성하여 사이클 구동 시 양극 소재의 안정성을 향상시키고자 한다. 양극 소재에 LixCoO2와 LixSnO3 를 각각 코팅하여 이차입자 내부 혹은 외부에 코팅층이 형성된 양극 소재를 합성한 후 이를 소결하여 단결정 형성에 대한 영향을 비교 하였다. 입자 외부에 LixSnO3가 코팅되어 열처리 된 Ni0.8Co0.1Mn0.1O2(NCM811)의 경우 코팅 처리 없이 열처리된 양극 소재 보다 개선된 수명특성을 보였으나, 단결정화가 이뤄지지 않았다. 입자 내부에 LixCoO2 코팅층이 형성된 NCM811 을 열처리 한 결과 이차입자 내부에 형성된 Co 코팅층이 결정화되어 50회 사이클 후 기준 단결정 양극 소재의 방전용 량인 117.34 mAh·g-1 대비 129.11 mAh·g-1의 높은 방전용량을 나타내었고, 형상제어를 통해 이성적인 단결정화가 이뤄 졌다. 본 연구는 다결정체인 Ni-rich 양극소재의 단결정화에 대한 유요한 통찰력을 제공할 것으로 예상한다.