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.
본 연구는 대기 중 장기간 노출로 인해 열화된 Ni-rich NCM811(LiNi₀.₈Co₀.₁Mn₀.₁O₂) 양극 소재의 계면 저항 증가 및 전기화학적 성능 저하 문제를 해결하기 위해, 물리적 열처리 방법을 제안하였다. NCM811 양극 소재는 대기 중 수분 및 이산화탄소와의 반응에 의해 표면에 불순물이 형성되기 쉬우며, 이는 고체전해질과의 계면 저항을 증가시켜 전고 체전지 시스템에서의 성능 저하를 초래한다. 이러한 문제를 해결하기 위해, 열화된 NCM811 양극 소재를 O₂ 분위기 에서 열처리하여 표면의 불순물을 효과적으로 제거하고 양극 표면의 전도성을 향상시킴으로써, 양극-고체전해질 간의 계면 저항을 현저히 감소시키는 결과를 얻었다. SEM, XRD, ICP 분석을 통해 열화된 NCM811 양극 소재의 표면 특성 변화를 분석하였으며, 열처리 후 NCM811 소재의 계면 특성이 개선됨에 따라 전기화학적 성능 또한 상용 NCM811 소재와 유사한 수준으로 회복되는 것을 확인하였다. 특히, O₂ 분위기의 물리적 열처리 방법은 Ni-rich NCM811 양극 소재의 열화를 효과적으로 억제하고 고체전해질과의 계면 접촉을 개선하여, 황화물계 전고체전지의 전기화학적 성능 을 획기적으로 향상시킬 수 있는 유망한 기술임을 입증하였다. 이러한 결과는 전고체전지 상용화를 위한 핵심 전략으 로 적용될 수 있을 것으로 기대된다.
All-solid-state lithium batteries (ASSLBs) are receiving attention as a prospective next-generation secondary battery technology that can reduce the risk of commercial lithium-ion batteries by replacing flammable organic liquid electrolytes with non-flammable solid electrolytes. The practical application of ASSLBs requires developing robust solid electrolytes that possess ionic conductivity at room temperature on a par with that of organic liquids. These solid electrolytes must also be thermally and chemically stable, as well as compatible with electrode materials. Inorganic solid electrolytes, including oxide and sulfide-based compounds, are being studied as promising future candidates for ASSLBs due to their higher ionic conductivity and thermal stability than polymer electrolytes. Here, we present the challenges currently facing the development of oxide and sulfide-based solid electrolytes, as well as the research efforts underway aiming to resolve these challenges.
This study comprehensively investigates three types of graphite materials as potential anodes for potassium-ion batteries. Natural graphite, artificial carbon-coated graphite, and mesocarbon microbeads (MCMB) are examined for their structural characteristics and electrochemical performances. Structural analyses, including HRTEM, XRD, Raman spectroscopy, and laser particle size measurements, reveal distinct features in each graphite type. XRD spectra confirm that all graphites are composed of pure carbon, with high crystallinity and varying crystal sizes. Raman spectroscopy indicates differences in disorder levels, with artificial carbon-coated graphite exhibiting the highest disorder, attributed to its outer carbon coating. Ex-situ Raman and HRTEM techniques on the electrodes reveal their distinct electrochemical behaviors. MCMB stands out with superior stability and capacity retention during prolonged cycling, attributed to its unique spherical particle structure facilitating potassium-ion diffusion. The study suggests that MCMB holds promise for potassium-ion full batteries. In addition, artificial carbon-coated graphite, despite challenges in hindering potassium-ion diffusion, may find applications in commercial potassium-ion battery anodes with suitable coatings. The research contributes valuable insights into potassiumion battery anode materials, offering a significant extension to the current understanding of graphite-based electrode performance.
The electrochemical properties of a CFX cathode were improved by defluorination of the surface with a N2 plasma and using a silica wafer. Compared to the N2 plasma treatment alone, when the CFX and silica were reacted together, the C-F bonds were modified and the surface was etched efficiently, so defluorination was enhanced. An electrochemical analysis confirmed that Half-cells prepared by treating CFx and silica with nitrogen plasma exhibited a capacity of about 400 mAh/g at 5C. In addition, it was confirmed that the loss of charge transfer was reduced by up to 71% compared to that for pristine CFX. As shown by a GITT analysis, when the CFx and silica were treated with N2 plasma together, the ion conductivity gradually increased due to a decrease in the ion diffusion barriers and the formation of a carbon layer. Therefore, this is a simple and effective way to improve the conductivities of CFX cathode materials with the energy of a N2 plasma and the silica-fluorine reaction.
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.
In recent years, the energy storage sector has experienced a notable transition toward the use of organic electrodes. This shift is largely attributed to their superior energy density, cost-effectiveness, and eco-friendliness. However, there is a main drawback that the organic molecules oftentimes suffer shuttle phenomenon across the separator due to their high solubility in the organic electrolyte. In addition, the low electrical conductivity of organic materials is also detrimental, thereby requiring a large amount of carbon additives (up to 40 wt. %) in the electrode. In this perspective, addition of carbon additives with the desirable amount, which can prevent organic molecules from being dissolved into the liquid phase as well as provide the electrical conductivity. While N,Nʹ-dimethylphenazine (DMPZ) was investigated as a model material, we compared two carbon additives with different surface areas and functional groups. We carefully scrutinized the structural effect of carbon additives on the cycle-life performance of the organic electrode.
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.
Synthesis of extremely competent materials is of great interest in addressing the energy storage concerns. Manganese oxide nanowires ( MnO2 NWs) are prepared in situ with multiwall carbon nanotubes (MWCNT) and graphene oxide (GO) using a simple and effective hydrothermal method. Powder XRD, Raman and XPS analysis are utilized to examine the structural characteristics and chemical state of composites. The initial specific discharge capacity of pure MnO2 NWs, MnO2 NWs/ MWCNT and MnO2 NWs/rGO composites are 1225, 1589 and 1685 mAh/g, respectively. The MnO2 NWs/MWCNT and MnO2 NWs/rGO composites showed stable behavior with a specific capacity of 957 and 1108 mAh/g, respectively, after 60 cycles. Moreover, MnO2 NWs/rGO composite sustained a specific capacity of 784 mAh/g, even after 250 cycles at a current density of 1 A/g showing outstanding cycling stability.
N-doping content and configurations have a significant effect on the electrochemical performance of carbon anodes. Herein, we proposed a simple method to synthesize highly N self-doped chitosan-derived carbon with controllable N-doping types by introducing 2ZnCO3 ·3Zn(OH)2 into the precursor. The as-synthesized NC-CS/2ZnCO3·3Zn(OH)2 electrode exhibited more than twice the reversible capacity (518 mAh g− 1 after 100 cycles at 200 mA g− 1) compared to the NC-CS electrode, superior rate performance and outstanding cycling stability. The remarkable improvement should be mainly attributed to the increase of N-doping content (particularly the pyrrolic-N content), which provided more active sites and favored Li+ diffusion kinetics. This study develops a cost-effective and facile synthesis route to fabricate high-performance N self-doped carbon with tunable doping sites for rechargeable battery applications.
Aqueous Zn-ion batteries (ZIBs) are very attractive owing to their high safety and low cost. Among various cathode materials, organic materials-based electrodes incorporating various redox functional groups have gained significant attention in the field of ZIBs due to their benefits of a tunable structural design, facility, eco-friendly, and possibility of multivalent energy storage. Herein, we demonstrate the nanostructured organic active materials deposited onto the CNT networks (HyPT@ CNT) for flexible ZIBs. This HyPT nanorods were obtained reassemblying the herringbone structured 3,4,9,10-tetracarboxylic dianhydride through a hydrothermal process in the presence of acid. These HyPT@CNT hybrids were electronically conductive and redox active, as well as could be fabricated into a flexible electrode achieving flexibility from mechanical integrity of robust networked structure. The as-fabricated flexible ZIBs delivered the high capacity of 100 Ah g− 1 at a current density of 0.1 A g− 1 and long-term cycling performance exceeding 5000 cycles. Consequently, these electrochemical performances are associated with the redox reactivity of carbonyl groups as verified by spectroscopic and electrochemical characterizations and the hybridization of HyPT nanorods with CNT networks.
Liquid phase exfoliation of natural graphite is an industrially effective solution for graphene preparation. However, many countries have identified natural graphite as a strategic resource and restricted its mining. In this report, we used abundant and readily available needle coke (NC) as a graphene exfoliation precursor and sodium carboxymethyl cellulose (CMC) as a dispersant to prepare a sandwich structured conductive graphitized NC nanosheets (GNCNs) by liquid phase exfoliation, freeze-drying and high-temperature graphitization, in which a graphene layer is sandwiched between two thin CMC layers. CMC could increase the liquid absorption and retention ability of the conductive agent and improve the migration rate of lithium ions. The highly ordered graphene layer could accelerate the transmission of electrons. The GNCNs with 0.4 wt% CMC addition showed good rate performance (144.6 mAh g− 1 at 5 C) and high cycle stability (96.2% after 200 cycles at 1 C) for LiFePO4 (LFP) battery. The traditional Super-P (SP) conductive agent exhibited low-rate performance (113.9 mAh g− 1 at 5 C) and cycle performance (89.9% after 200 cycles at 1 C). This study offers a novel approach to selecting graphene precursors and has promising applications for conductive additives in high-performance LFP batteries.
In zinc-air batteries, the gel polymer electrolyte (GPE) is an important factor for improving performance. The rigid physical properties of polyvinyl alcohol reduce ionic conductivity, which degrades the performance of the batteries. Zinc acetate is an effective additive that can increase ionic conductivity by weakening the bonding structure of polyvinyl alcohol. In this study, polymer electrolytes were prepared by mixing polyvinyl alcohol and zinc acetate dihydride. The material properties of the prepared polymer electrolytes were analyzed by Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). Also, Electrochemical impedance spectroscopy was used to calculate ionic conductivity. The electrolyte resistances of GPE, 0.2 GPE, 0.4 GPE, and 0.6 GPE were 0.394, 0.338, 0.290, and 0.213 Ω, respectively. In addition, 0.6 GPE delivered 0.023 S/cm high ionic conductivity. Among all of the polymer electrolytes tested, 0.6 GPE showed enhanced cycle life performance and the highest specific discharge capacity of 11.73 mAh/cm2 at 10 mA. These results verified that 0.6 GPE improves the performance of zinc-air batteries.
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.