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Three-Dimensional Printing, an Emerging Advanced Technique in Electrochemical Energy Storage and Conversion 三维打印——电化学能量存储与转换的新兴先进技术
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-11-06 DOI: 10.3390/batteries9110546
Shu Zhang, Shuyue Xue, Yaohui Wang, Gufei Zhang, Nayab Arif, Peng Li, Yu-Jia Zeng
Three-dimensional (3D) printing, as an advanced additive manufacturing technique, is emerging as a promising material-processing approach in the electrical energy storage and conversion field, e.g., electrocatalysis, secondary batteries and supercapacitors. Compared to traditional manufacturing techniques, 3D printing allows for more the precise control of electrochemical energy storage behaviors in delicately printed structures and reasonably designed porosity. Through 3D printing, it is possible to deeply analyze charge migration and catalytic behavior in electrocatalysis, enhance the energy density, cycle stability and safety of battery components, and revolutionize the way we design high-performance supercapacitors. Over the past few years, a significant amount of work has been completed on 3D printing to explore various high-performance energy-related materials. Although impressive strides have been made, challenges still exist and need to be overcome in order to meet the ever-increasing demand. In this review, the recent research progress and applications of 3D-printed electrocatalysis materials, battery components and supercapacitors are systematically presented. Perspectives on the prospects for this exciting field are also proposed with applicable discussion and analysis.
三维打印作为一种先进的增材制造技术,在电催化、二次电池和超级电容器等电能存储和转换领域正成为一种有前途的材料加工方法。与传统制造技术相比,3D打印可以更精确地控制精细打印结构和合理设计孔隙度的电化学储能行为。通过3D打印,可以深入分析电催化中的电荷迁移和催化行为,提高电池组件的能量密度、循环稳定性和安全性,并彻底改变我们设计高性能超级电容器的方式。在过去的几年里,人们已经完成了大量的3D打印工作,以探索各种高性能的能源相关材料。虽然取得了令人印象深刻的进展,但仍然存在挑战,需要克服这些挑战,以满足日益增长的需求。本文系统介绍了3d打印电催化材料、电池部件和超级电容器的最新研究进展和应用。对这一激动人心的领域的前景提出了展望,并进行了相应的讨论和分析。
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引用次数: 0
Ion-Selective Membranes Fabricated Using Finely Controlled Swelling of Non-Ionic Fluoropolymer for Redox Flow Batteries 精细控制非离子含氟聚合物溶胀制备氧化还原液流电池用离子选择膜
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-11-06 DOI: 10.3390/batteries9110545
Fengjing Jiang, Rui Xue
Ion-selective membranes based on non-ionic polymers are promising for redox flow batteries due to their superior chemical stability and low cost. In this work, a poly(vinylidene fluoride) (PVDF) ion-selective membrane is successfully prepared using a solvent-controlled swelling method, where Nafion is used as a channel-forming promoter. The influences of Nafion on the channel formation of the membranes are studied. The results indicate that the addition of Nafion resin can greatly promote the formation of ion-conducting channels in the PVDF matrix. The obtained membranes show well-controlled proton conductivity and proton/vanadium selectivity. A battery test on a vanadium redox flow single cell is successfully performed. The energy efficiency of the cell equipped with the PVDF-based ion-selective membrane reaches 81.7% at a current density of 60 mA cm−2 and possesses excellent cycling stability and suppressed self-discharge after modification with Nafion.
基于非离子聚合物的离子选择膜因其优异的化学稳定性和低廉的成本在氧化还原液流电池中具有广阔的应用前景。在这项工作中,使用溶剂控制膨胀法成功制备了聚偏氟乙烯(PVDF)离子选择性膜,其中使用Nafion作为通道形成促进剂。研究了钠离子对膜通道形成的影响。结果表明,Nafion树脂的加入能极大地促进PVDF基体中离子导电通道的形成。所得膜具有良好控制的质子电导率和质子/钒选择性。成功地进行了钒氧化还原流单体电池的电池试验。在电流密度为60 mA cm−2的情况下,pvdf基离子选择膜的电池能量效率达到81.7%,并且经过Nafion修饰后具有良好的循环稳定性和抑制自放电。
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引用次数: 0
Hybrid Estimation Method for the State of Charge of Lithium Batteries Using a Temporal Convolutional Network and XGBoost 基于时间卷积网络和XGBoost的锂电池充电状态混合估计方法
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-11-05 DOI: 10.3390/batteries9110544
Jong-Hyun Lee, In-Soo Lee
Lithium batteries have recently attracted significant attention as highly promising energy storage devices within the secondary battery industry. However, it is important to note that they may pose safety risks, including the potential for explosions during use. Therefore, achieving stable and safe utilization of these batteries necessitates accurate state-of-charge (SOC) estimation. In this study, we propose a hybrid model combining temporal convolutional network (TCN) and eXtreme gradient boosting (XGBoost) to investigate the nonlinear and evolving characteristics of batteries. The primary goal is to enhance SOC estimation performance by leveraging TCN’s long-effective memory capabilities and XGBoost’s robust generalization abilities. We conducted experiments using datasets from NASA, Oxford, and a vehicle simulator to validate the model’s performance. Additionally, we compared the performance of our model with that of a multilayer neural network, long short-term memory, gated recurrent unit, XGBoost, and TCN. The experimental results confirm that our proposed TCN–XGBoost hybrid model outperforms the other models in SOC estimation across all datasets.
近年来,锂电池作为一种极具潜力的储能设备在二次电池产业中备受关注。然而,重要的是要注意它们可能会带来安全风险,包括在使用过程中可能发生爆炸。因此,要实现这些电池的稳定和安全使用,就需要准确的荷电状态(SOC)估计。在这项研究中,我们提出了一个结合时间卷积网络(TCN)和极限梯度提升(XGBoost)的混合模型来研究电池的非线性和进化特性。主要目标是通过利用TCN的长期有效内存能力和XGBoost的强大泛化能力来提高SOC估计性能。我们使用来自NASA、牛津大学的数据集和车辆模拟器进行了实验,以验证模型的性能。此外,我们还将模型的性能与多层神经网络、长短期记忆、门控循环单元、XGBoost和TCN的性能进行了比较。实验结果证实,我们提出的TCN-XGBoost混合模型在所有数据集上的SOC估计都优于其他模型。
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引用次数: 0
Co-Sintering of Li1.3Al0.3Ti1.7(PO4)3 and LiFePO4 in Tape-Casted Composite Cathodes for Oxide Solid-State Batteries Li1.3Al0.3Ti1.7(PO4)3和LiFePO4在带铸复合阴极中的共烧结研究
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-11-02 DOI: 10.3390/batteries9110543
Jean Philippe Beaupain, Katja Waetzig, Henry Auer, Nicolas Zapp, Kristian Nikolowski, Mareike Partsch, Mihails Kusnezoff, Alexander Michaelis
Solid-state batteries (SSBs) with Li-ion conductive electrolytes made from polymers, thiophosphates (sulfides) or oxides instead of liquid electrolytes have different challenges in material development and manufacturing. For oxide-based SSBs, the co-sintering of a composite cathode is one of the main challenges. High process temperatures cause undesired decomposition reactions of the active material and the solid electrolyte. The formed phases inhibit the high energy and power density of ceramic SSBs. Therefore, the selection of suitable material combinations as well as the reduction of the sintering temperatures are crucial milestones in the development of ceramic SSBs. In this work, the co-sintering behavior of Li1.3Al0.3Ti1.7(PO4)3 (LATP) as a solid electrolyte with Li-ion conductivity of ≥0.38 mS/cm and LiFePO4 with a C-coating (LFP) as a Li-ion storage material (active material) is investigated. The shrinkage behavior, crystallographic analysis and microstructural changes during co-sintering at temperatures between 650 and 850 °C are characterized in a simplified model system by mixing, pressing and sintering the LATP and LFP and compared with tape-casted composite cathodes (d = 55 µm). The tape-casted and sintered composite cathodes were infiltrated by liquid electrolyte as well as polyethylene oxide (PEO) electrolyte and electrochemically characterized as half cells against a Li metal anode. The results indicate the formation of reaction layers between LATP and LFP during co-sintering. At Ts > 750 °C, the rhombohedral LATP phase is transformed into an orthorhombic Li1.3+xAl0.3−yFex+yTi1.7−x(PO4)3 (LAFTP) phase. During co-sintering, Fe3+ diffuses into the LATP phase and partially occupies the Al3+ and Ti4+ sites of the NASICON structure. The formation of this LAFTP leads to significant changes in the electrochemical properties of the infiltrated composite tapes. Nevertheless, a high specific capacity of 134 mAh g−1 is measured by infiltrating the sintered composite tapes with liquid electrolytes. Additionally, infiltration with a PEO electrolyte leads to a capacity of 125 mAh g−1. Therefore, the material combination of LATP and LFP is a promising approach to realize sintered ceramic SSBs.
由聚合物、硫代磷酸盐(硫化物)或氧化物代替液体电解质制成的锂离子导电电解质的固态电池(SSBs)在材料开发和制造方面面临着不同的挑战。对于氧化物基固态电池,复合阴极的共烧结是主要挑战之一。较高的工艺温度会导致活性物质和固体电解质发生不希望发生的分解反应。形成的相抑制了陶瓷ssb的高能量和功率密度。因此,选择合适的材料组合以及降低烧结温度是陶瓷ssb发展的关键里程碑。本文研究了Li1.3Al0.3Ti1.7(PO4)3 (LATP)作为锂离子电导率≥0.38 mS/cm的固体电解质和含c涂层的LiFePO4 (LFP)作为锂离子存储材料(活性材料)的共烧结行为。通过混合、压制和烧结LATP和LFP,并与带铸复合阴极(d = 55µm)进行比较,在一个简化的模型系统中表征了在650 ~ 850℃共烧结过程中的收缩行为、晶体学分析和显微组织变化。采用液态电解质和聚氧聚乙烯(PEO)电解质对带铸和烧结复合阴极进行浸渍,并在锂金属阳极上进行了电化学表征。结果表明,在共烧结过程中,LATP和LFP之间形成了反应层。在Ts >750℃时,斜方面体LATP相转变为正交Li1.3+xAl0.3−yFex+yTi1.7−x(PO4)3 (LAFTP)相。在共烧结过程中,Fe3+扩散到LATP相中,部分占据了NASICON结构的Al3+和Ti4+位点。这种LAFTP的形成导致渗透复合带的电化学性能发生显著变化。然而,通过将液体电解质渗透到烧结的复合带中,可以测量到134 mAh g−1的高比容量。此外,PEO电解质的渗透可使电池容量达到125 mAh g−1。因此,LATP和LFP的材料组合是实现烧结陶瓷ssb的一种很有前途的方法。
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引用次数: 0
Assessment of Health Indicators to Detect the Aging State of Commercial Second-Life Lithium-Ion Battery Cells through Basic Electrochemical Cycling 基础电化学循环检测商用二次寿命锂离子电池老化状态的健康指标评估
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-11-01 DOI: 10.3390/batteries9110542
Emanuele Michelini, Patrick Höschele, Syed Muhammad Abbas, Christian Ellersdorfer, Jörg Moser
Upon reaching certain limits, electric vehicle batteries are replaced and may find a second life in various applications. However, the state of such batteries in terms of aging and safety remains uncertain when they enter the second-life market. The aging mechanisms within these batteries involve a combination of processes, impacting their safety and performance. Presently, direct health indicators (HIs) like state of health (SOH) and internal resistance increase are utilized to assess battery aging, but they do not always provide accurate indications of the battery’s health state. This study focuses on analyzing various HIs obtained through a basic charging–discharging cycle and assessing their sensitivity to aging. Commercial 50 Ah pouch cells with different aging histories were tested, and the HIs were evaluated. Thirteen HIs out of 31 proved to be highly aging-sensitive, and thus good indicators. Namely, SOH upon charging and discharging, Coulombic efficiency, constant current discharge time, voltage relaxation profile trend, voltage–charge area upon discharging, hysteresis open circuit voltage HIs, and temperature difference between the tabs upon charging. The findings offer valuable insights for developing robust qualification algorithms and reliable battery health monitoring systems for second-life batteries, ensuring safe and efficient battery operation in diverse second-life applications.
在达到一定限度后,电动汽车电池被更换,并可能在各种应用中找到第二次生命。然而,当这些电池进入二次使用市场时,它们在老化和安全性方面的状况仍不明朗。这些电池的老化机制涉及一系列过程,影响其安全性和性能。目前,使用健康状态(SOH)和内阻增加等直接健康指标(HIs)来评估电池老化,但它们并不总是提供准确的电池健康状态指示。本研究的重点是分析通过一个基本充放电循环得到的各种HIs,并评估其对老化的敏感性。对不同老化历史的商用50 Ah袋细胞进行测试,并对HIs进行评估。31个HIs中有13个被证明是高度衰老敏感的,因此是很好的指标。即充放电时的SOH、库仑效率、恒流放电时间、电压弛豫曲线趋势、放电时的电压充电面积、滞后开路电压HIs、充电时片间温度差。研究结果为开发可靠的二次寿命电池鉴定算法和可靠的电池健康监测系统提供了有价值的见解,确保电池在各种二次寿命应用中安全高效地运行。
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引用次数: 0
Mechanical and Optical Characterization of Lithium-Ion Battery Cell Components/Cross-Ply Lamination Effect 锂离子电池组件的机械和光学特性/交叉层压效应
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-11-01 DOI: 10.3390/batteries9110541
David Sypeck, Feng Zhu, Jie Deng, Chulheung Bae
Excessive mechanical loading of lithium-ion batteries can impair performance and safety. Their ability to resist loads depends upon the properties of the materials they are made from and how they are constructed and loaded. Here, prismatic lithium-ion battery cell components were mechanically and optically characterized to examine details of material morphology, construction, and mechanical loading response. Tensile tests were conducted on the cell case enclosure, anodes, cathodes, and separators. Compression tests on stacks of anodes, cathodes, separators, and jellyrolls were made from them. Substantially differing behaviors were observed amongst all components tested. An optical examination of the anodes, cathodes, and separators revealed homogeneities, anisotropies, and defects. Substantial texturing was present parallel to the winding direction. When highly compressed, jellyrolls develop well-defined V-shaped cracks aligned parallel to the texturing. Like many laminates, altering the lay-up construction affects jellyroll mechanical performance. To demonstrate, a cross-ply jellyroll was fabricated by rotating every other complete component set (cathode/separator/anode/separator), reassembling, and compressing. A distinctly different fracture pattern and increased compressive strength were observed.
锂离子电池的机械负荷过大会影响其性能和安全性。它们抵抗载荷的能力取决于制造它们的材料的特性以及它们是如何构造和加载的。在这里,对棱柱形锂离子电池组件进行了机械和光学表征,以检查材料形态、结构和机械负载响应的细节。对电池外壳、阳极、阴极和隔板进行了拉伸试验。用它们对成堆的阳极、阴极、分离器和软糖进行了压缩试验。在所有被测试的成分中观察到的行为有很大的不同。对阳极、阴极和隔膜进行光学检查,发现其均质性、各向异性和缺陷。大量纹理与缠绕方向平行。当受到高度压缩时,果冻卷会产生与纹理平行的明确的v形裂纹。像许多层压板一样,改变铺层结构会影响果冻卷的机械性能。为了证明这一点,通过旋转所有其他完整的组件组(阴极/分离器/阳极/分离器),重组和压缩来制造交叉层jellyroll。观察到明显不同的断裂模式和增加的抗压强度。
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引用次数: 0
Online State-of-Health Estimation for Fast-Charging Lithium-Ion Batteries Based on a Transformer–Long Short-Term Memory Neural Network 基于变压器-长短期记忆神经网络的快充锂离子电池在线健康状态估计
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-10-31 DOI: 10.3390/batteries9110539
Yuqian Fan, Yi Li, Jifei Zhao, Linbing Wang, Chong Yan, Xiaoying Wu, Pingchuan Zhang, Jianping Wang, Guohong Gao, Liangliang Wei
With the rapid development of machine learning and cloud computing, deep learning methods based on big data have been widely applied in the assessment of lithium-ion battery health status. However, enhancing the accuracy and robustness of assessment models remains a challenge. This study introduces an innovative T-LSTM prediction network. Initially, a one-dimensional convolutional neural network (1DCNN) is employed to effectively extract local and global features from raw battery data, providing enriched inputs for subsequent networks. Subsequently, LSTM and transformer models are ingeniously combined to fully utilize their unique advantages in sequence modeling, further enhancing the accurate prediction of battery health status. Experiments were conducted using both proprietary and open-source datasets, and the results validated the accuracy and robustness of the proposed method. The experimental results on the proprietary dataset show that the T-LSTM-based estimation method exhibits excellent performance in various evaluation metrics, with MSE, RMSE, MAE, MAPE, and MAXE values of 0.43, 0.66, 0.53, 0.58, and 1.65, respectively. The performance improved by 30–50% compared to that of the other models. The method demonstrated superior performance in comparative experiments, offering novel insights for optimizing intelligent battery management and maintenance strategies.
随着机器学习和云计算的快速发展,基于大数据的深度学习方法在锂离子电池健康状态评估中得到了广泛的应用。然而,提高评估模型的准确性和鲁棒性仍然是一个挑战。本文介绍了一种创新的T-LSTM预测网络。首先,采用一维卷积神经网络(1DCNN)从原始电池数据中有效提取局部和全局特征,为后续网络提供丰富的输入。随后,将LSTM与变压器模型巧妙结合,充分发挥其在序列建模方面的独特优势,进一步提高了对电池健康状态的准确预测。在专有和开源数据集上进行了实验,结果验证了该方法的准确性和鲁棒性。在专有数据集上的实验结果表明,基于t - lstm的估计方法在各种评价指标上都表现出优异的性能,MSE、RMSE、MAE、MAPE和MAXE的值分别为0.43、0.66、0.53、0.58和1.65。与其他型号相比,性能提高了30-50%。该方法在对比实验中表现出优异的性能,为优化智能电池管理和维护策略提供了新的见解。
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引用次数: 0
Arcing in Li-Ion Batteries 锂离子电池中的电弧
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-10-31 DOI: 10.3390/batteries9110540
Theo Ledinski, Andrey W. Golubkov, Oskar Schweighofer, Simon Erker
Lithium-Ion battery cells and automotive battery systems are constantly improving as a result of the rising popularity of electric vehicles. With higher energy densities of the cells, the risks in case of failure rise as well. In the worst case, a fast exothermic reaction known as thermal runaway can occur. During thermal runaway, the cell can emit around 66% of its mass as gas and particles. An experimental setup was designed and showed that the gas-particle-vent of a cell going through thermal runaway can cause electric breakthroughs. These breakthroughs could start electric arcing in the battery system, which could lead to additional damages such as burning through the casing or igniting the vent gas, making the damage more severe and difficult to control. Uncontrollable battery fires must be prevented. The emitted gas was analyzed and the ejected particles were examined to discuss the potential causes of the breakthroughs.
随着电动汽车的日益普及,锂离子电池和汽车电池系统也在不断改进。电池的能量密度越高,发生故障的风险也就越大。在最坏的情况下,会发生被称为热失控的快速放热反应。在热失控过程中,电池可以释放出大约66%的气体和粒子。设计了一个实验装置,并证明了电池热失控时的气-颗粒出口会引起电突破。这些突破可能会在电池系统中产生电弧,这可能会导致额外的损害,如烧毁外壳或点燃排气口,使损害更加严重,难以控制。必须防止不可控的电池火灾。分析了产生的气体和喷出的粒子,探讨了产生突破的可能原因。
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引用次数: 1
Performance Analysis of the Liquid Cooling System for Lithium-Ion Batteries According to Cooling Plate Parameters 基于冷却板参数的锂离子电池液冷系统性能分析
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-10-30 DOI: 10.3390/batteries9110538
Nayoung You, Jeonggyun Ham, Donghyeon Shin, Honghyun Cho
In this study, the effects of battery thermal management (BTM), pumping power, and heat transfer rate were compared and analyzed under different operating conditions and cooling configurations for the liquid cooling plate of a lithium-ion battery. The results elucidated that when the flow rate in the cooling plate increased from 2 to 6 L/min, the average temperature of the battery module decreased from 53.8 to 50.7 °C, but the pumping power increased from 0.036 to 0.808 W. In addition, an increase in the width of the cooling channel and number of channels resulted in a decrease in the average temperature of the battery module and a reduction in the pumping power. The most influential variable for the temperature control of the battery was an increase in the flow rate. In addition, according to the results of the orthogonal analysis, an increase in the number of cooling plate channels resulted in the best cooling performance and reduced pumping power. Based on this, a cooling plate with six channels was applied to both the top and bottom parts, and the top and bottom cooling showed sufficient cooling performance in maintaining the average temperature of the battery module below 45 °C.
本研究对比分析了锂离子电池液冷板在不同工况和冷却配置下对电池热管理(BTM)、泵送功率和换热速率的影响。结果表明,当冷却板内流量从2 L/min增加到6 L/min时,电池组件的平均温度从53.8℃下降到50.7℃,而泵送功率从0.036 W增加到0.808 W。此外,增加冷却通道的宽度和通道的数量,导致电池模块的平均温度降低,泵送功率降低。对电池温度控制影响最大的变量是流量的增加。此外,根据正交分析结果,冷却板通道数量的增加导致冷却性能最佳,泵浦功率降低。在此基础上,在顶部和底部均采用了六通道冷却板,顶部和底部冷却具有足够的冷却性能,可以将电池模块的平均温度保持在45℃以下。
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引用次数: 0
Microwave-Assisted Recovery of Spent LiCoO2 Battery from the Corresponding Black Mass 微波辅助回收废LiCoO2电池相应黑质量
4区 化学 Q2 ELECTROCHEMISTRY Pub Date : 2023-10-28 DOI: 10.3390/batteries9110536
Matteo Scaglia, Antonella Cornelio, Alessandra Zanoletti, Daniele La Corte, Giada Biava, Ivano Alessandri, Angelo Forestan, Catya Alba, Laura Eleonora Depero, Elza Bontempi
The literature indicates that utilizing pyrometallurgical methods for processing spent LiCoO2 (LCO) batteries can lead to cobalt recovery in the forms of Co3O4, CoO, and Co, while lithium can be retrieved as Li2O or Li2CO3. However, the technology’s high energy consumption has also been noted as a challenge in this recovery process. Recently, an innovative and sustainable approach using microwave (MW) radiation has been proposed as an alternative to traditional pyrometallurgical methods for treating used lithium-ion batteries (LiBs). This method aims to address the shortcomings of the conventional approach. In this study, the treatment of the black mass (BM) from spent LCO batteries is explored for the first time using MW–materials interaction under an air atmosphere. The research reveals that the process can trigger carbothermic reactions. However, MW makes the BM so reactive that it causes rapid heating of the sample in a few minutes, also posing a fire risk. This paper presents and discusses the benefits and potential hazards associated with this novel technology for the recovery of spent LCO batteries and gives information about real samples of BM. The work opens the possibility of using a microwave for raw material recovery in spent LIBs, allowing to obtain rapid and more efficient reactions.
文献表明,利用火法对废LiCoO2 (LCO)电池进行处理,钴可以以Co3O4、CoO和Co的形式回收,锂可以以Li2O或Li2CO3的形式回收。然而,该技术的高能耗也被认为是该回收过程中的一个挑战。最近,人们提出了一种利用微波(MW)辐射的创新和可持续的方法来替代传统的火法冶金方法来处理废旧锂离子电池(LiBs)。这种方法旨在解决传统方法的缺点。在这项研究中,首次探索了在空气气氛下利用mw -材料相互作用处理废LCO电池的黑质量(BM)。研究表明,这一过程可以引发碳热反应。然而,MW使BM如此活跃,它导致样品在几分钟内迅速加热,也构成火灾风险。本文介绍并讨论了这种回收废旧LCO电池的新技术的好处和潜在危险,并提供了有关BM实际样品的信息。这项工作开启了使用微波对废lib进行原料回收的可能性,允许获得快速和更有效的反应。
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引用次数: 0
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Batteries
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