In this study, carbon coating was carried out by physical vapor deposition (PVD) on SiOx surfaces to investigate the effect of the deposited carbon layer on the performance of lithium-ion batteries as a function of the asphaltene content of petroleum residues. The petroleum residue was separated into asphaltene-free petroleum residue (ASF) and asphaltene-based petroleum residue (AS) containing 12.54% asphaltene by a solvent extraction method, and the components were analyzed. The deposited carbon coating layer became thinner, with the thickness decreasing from 15.4 to 8.1 nm, as the asphaltene content of the petroleum residue increased, and a highly crystalline layer was obtained. In particular, the SiOx electrode carbon-coated with AS exhibited excellent cycling performance with an initial efficiency of 85.5% and a capacity retention rate of 94.1% after 100 cycles at a current density of 1.0 C. This is because the carbon layer with enhanced crystallinity had sufficient thickness to alleviate the volume expansion of SiOx, resulting in stable SEI layer formation and enhanced structural stability. In addition, the SiOx electrode exhibited the lowest resistance with a low impedance of 23.35 Ω, attributed to the crystalline carbon layer that enhanced electrical conductivity and the mobility of Li ions. This study demonstrated that increasing the asphaltene content of petroleum residues is the simplest strategy for preparing SiOx@C anode materials with thin, crystalline carbon layers and excellent electrochemical performance with high efficiency and high rate performance.
In this study, ester co-solvents and fluoroethylene carbonate (FEC) were used as low-temperature electrolyte additives to improve the formation of the solid electrolyte interface (SEI) on graphite anodes in lithium-ion batteries (LIBs). Four ester co-solvents, namely methyl acetate (MA), ethyl acetate, methyl propionate, and ethyl propionate, were mixed with 1.0 M LiPF6 ethylene carbonate:diethyl carbonate:dimethyl carbonate (1:1:1 by vol%) as the base electrolyte (BE). Different concentrations were used to compare the electrochemical performance of the LiCoO2/ graphite full cells. Among various ester co-solvents, the cell employing BE mixed with 30 vol% MA (BE/MA30) achieved the highest discharge capacity at − 20 °C. In contrast, mixing esters with low-molecular-weight degraded the cell performance owing to the unstable SEI formation on the graphite anodes. Therefore, FEC was added to BE/MA30 (BE/MA30-FEC5) to form a stable SEI layer on the graphite anode surface. The LiCoO2/ graphite cell using BE/MA30-FEC5 exhibited an excellent capacity of 127.3 mAh g− 1 at − 20 °C with a capacity retention of 80.6% after 100 cycles owing to the synergistic effect of MA and formation of a stable and uniform inorganic SEI layer by FEC decomposition reaction. The low-temperature electrolyte designed in this study may provide new guidelines for resolving low-temperature issues related to LIBs, graphite anodes, and SEI layers.
To improve the lithium-ion battery performance and stability, a conducting polymer, which can simultaneously serve as both a conductive additive and a binder, is introduced into the anode. Water-soluble polyaniline:polystyrene sulfonate (PANI:PSS) can be successfully prepared through chemical oxidative polymerization, and their chemical/mechanical properties are adjusted by varying the molecular weight of PSS. As a conductive additive, the PANI with a conjugated double bond structure is introduced between active materials or between the active material and the current collector to provide fast and short electrical pathways. As a binder, the PSS prevents short circuits through strong π‒π stacking interaction with active material, and it exhibits superior adhesion to the current collector, thereby ensuring the maintenance of stable mechanical properties, even under high-speed charging/discharging conditions. Based on the synergistic effect of the intrinsic properties of PANI and PSS, it is confirmed that the anode with PANI:PSS introduced as a binder has about 1.8 times higher bonding strength (0.4 kgf/20 mm) compared to conventional binders. Moreover, since active materials can be additionally added in place of the generally added conductive additives, the total cell capacity increased by about 12.0%, and improved stability is shown with a capacity retention rate of 99.3% even after 200 cycles at a current rate of 0.2 C.
With the emergence of the new energy field, the demand for high-performance lithium-ion batteries (LIBs) and green energy storage devices is growing with each passing day. Carbon nanotubes (CNTs) exhibit tremendous potential in application due to superior electrical and mechanical properties, and the excellent lithium insertion properties make it possible to be LIBs anode materials. Based on the lithium insertion mechanism of CNTs, this paper systematically and categorically reviewed the design strategies of CNTs-based composites as LIBs anode materials, and summarized in detail the enhancement effect of CNTs fillers on various anode materials. More importantly, the superiorities and limitations of various anode materials for LIBs were evaluated. Finally, the research direction and current challenges of the industrial application of CNTs in LIBs were prospected.
Silicon-based anode materials have attracted significant interest because of their advantages, including high theoretical specific capacity (~4,200 mAh/g), low working potential (0.4 V vs Li/Li+), and abundant sources. However, their significant initial capacity loss and large volume changes during cycling impede the application of silicon-based anodes in lithium-ion batteries. In this work, we propose a silicon oxide (SiOx) anode material for lithium-ion batteries produced with a magnesio-thermic reduction (MTR) process adopting Boryeong mud as a starting material. Boryeong mud contains various minerals such as clinochlore [(Mg,Fe)6(Si,Al)4O10(OH)8], anorthite (CaAl2Si2O8), illite [K0.7Al2(Si,Al)4O10(OH)2], and quartz (SiO2). The MTR process with Boryeong mud generates a mixture of amorphous silicon oxides (SiOx and SiO2), and magnesium aluminate which helps to alleviate the volume expansion of the electrode during charge/discharge. To observe the effects of these oxides, we conducted various analyses including X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-Transformation infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET) and cyclic voltammetry (CV) galvanic cell testing. The amorphous SiO2 and MgAl2O4 suppressed the volume expansion of the silicon-based anode, and excellent cycle performance was achieved as a result.
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.
Mesocrystals are macroscopic structures formed by the assembly of nanoparticles that possess distinct surface structures and collective properties when compared to traditional crystalline materials. Various growth mechanisms and their unique features have promise as material design tools for diverse potential applications. This paper presents a straightforward method for metal–organic coordination-based mesocrystals using nickel ions and terephthalic acid. The coordinative compound between Ni2+ and terephthalic acid drives the particle-mediated growth mechanism, resulting in the mesocrystal formation through a mesoscale assembly. Subsequent carbonization converts mesocrystals to multidirectional interconnected graphite nanospheres along the macroscopic framework while preserving the original structure of the Ni-terephthalic acid mesocrystal. Comprehensive investigations demonstrate that multi-oriented edge sites and high crystallinity with larger interlayer spacing facilitate lithium ion transport and continuous intercalation. The resulting graphitic superparticle electrodes show superior rate capability (128.6 mAh g− 1 at 5 A g− 1) and stable cycle stability (0.052% of capacity decay per cycle), certifying it as an advanced anode material for lithium-ion batteries.
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.