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Electrochemical behavior of deoxidation titanium scrap process by induced overpotential molten salt electrolyte 诱导过电位熔盐电解液脱氧废钛工艺的电化学行为
IF 4.7 3区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-07-17 DOI: 10.1016/j.elecom.2024.107780

This study investigates the deoxidation process of low-grade titanium scrap through molten salt electrolysis induced by overpotential. The research focuses on understanding the efficiency and mechanisms involved in the deoxidation of titanium scrap, utilizing induced overpotential as a key parameter. The analysis includes a detailed examination of the molten salt deoxidation process, with emphasis on electrochemical reactions and overall performance. The findings contribute valuable insights into the application of induced overpotential in enhancing the deoxidation of low-grade titanium scrap through molten salt electrolysis. This research contributes to the optimization of titanium recycling processes, with potential implications for sustainable and resource-efficient metallurgical practices. The induction of overvoltage phenomena was intentionally introduced to achieve an oxygen separation efficiency beyond thermodynamic limits. Furthermore, the correlation between electrochemical factors, formation electrode potential, and oxygen removal efficiency was elucidated. The initial titanium scraps, characterized by an oxygen concentration of 5500 ppm and a purity of 98.2 %, underwent a significant enhancement in characteristics, reaching 1850 ppm of oxygen concentration and 98.97 % purity after the first electrolysis process. In summary, this study presents a comprehensive approach to the separation and purification of titanium from low-grade scraps, by molten salt electrolysis.

本研究探讨了通过过电位诱导熔盐电解低级钛废料的脱氧过程。研究重点是利用诱导过电位作为关键参数,了解钛废料脱氧过程的效率和机理。分析包括对熔盐脱氧过程的详细检查,重点是电化学反应和整体性能。研究结果为诱导过电位在通过熔盐电解增强低级钛废料脱氧过程中的应用提供了宝贵的见解。这项研究有助于优化钛回收工艺,对可持续和资源节约型冶金实践具有潜在影响。为了实现超出热力学极限的氧气分离效率,特意引入了过电压现象。此外,还阐明了电化学因素、形成电极电位和除氧效率之间的相关性。初始钛渣的氧浓度为 5500 ppm,纯度为 98.2%,经过第一次电解过程后,钛渣的特性显著增强,氧浓度达到 1850 ppm,纯度达到 98.97%。总之,本研究提出了一种通过熔盐电解从低级废料中分离和提纯钛的综合方法。
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引用次数: 0
Conductive disposable screen-printed graphene oxide-molybdenum disulfide electrode for electrochemical sensing applications 用于电化学传感应用的导电性一次性丝网印刷氧化石墨烯-二硫化钼电极
IF 4.7 3区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-07-17 DOI: 10.1016/j.elecom.2024.107778

In this work, a new and convenient fabrication process for screen-printed reduced graphene oxide-molybdenum disulfide electrode (SPrGO-MoS2E) was proposed. Reduced graphene oxide-molybdenum disulfide (rGO-MoS2) composite was hydrothermally synthesized and then dispersed in deionized water and ethanol with a ratio of 2:3 (v/v) to form a conductive suspension. The suspension was then blended with carbon paste at a ratio of 0.1:9.9 (g/g) to obtain a screen-printable rGO-MoS2 conductive ink. An electrochemical sensing electrode was formed by screening this conductive ink onto a polyethylene terephthalate substrate. The characteristics of this electrode were investigated by scanning electron microscopy, energy-dispersive X-ray spectrometry, X-ray diffractometry, Raman spectroscopy, and electrochemical impedance spectroscopy. Overall, the conductive suspension comprising the rGO-MoS2 composite showed higher electrochemical sensing performance compared with electrodes containing only rGO or MoS2. Cyclic voltammetry revealed that the SPrGO-MoS2 electrode exhibited excellent electrochemical sensing performance toward several electroactive species, namely, potassium hexacyanoferrate (III) ([Fe(CN6)]3−/4−), nicotinamide adenine dinucleotide (NAD+/NADH), and hydrogen peroxide (H2O2) dissolved in 0.1 M PBS (pH 7.4). The limits of detection for [Fe(CN6)]3−/4−, NAD+/NADH, and H2O2 were 0.34, 0.25, and 1.36 μM, respectively. In addition, the reproducibility, repeatability, and stability determined from the relative standard deviations (RSDs, n = 7) of these analytes were less than 12.1 %, 8.6 %, and 7.4 %, respectively. Therefore, the ready-to-use SPrGO-MoS2E could be an alternative material for advanced chemical and biological sensing applications.

本研究提出了一种新型便捷的丝网印刷还原氧化石墨烯-二硫化钼电极(SPrGO-MoS2E)制造工艺。还原氧化石墨烯-二硫化钼(rGO-MoS2)复合材料通过水热法合成,然后以 2:3 (v/v) 的比例分散在去离子水和乙醇中,形成导电悬浮液。然后按 0.1:9.9 (g/g) 的比例将悬浮液与碳浆混合,得到可丝网印刷的 rGO-MoS2 导电墨水。通过在聚对苯二甲酸乙二醇酯基底上丝网印刷这种导电墨水,形成了电化学传感电极。扫描电子显微镜、能量色散 X 射线光谱仪、X 射线衍射仪、拉曼光谱和电化学阻抗光谱仪对该电极的特性进行了研究。总体而言,与仅含有 rGO 或 MoS2 的电极相比,由 rGO-MoS2 复合材料组成的导电悬浮液显示出更高的电化学传感性能。循环伏安法显示,SPrGO-MoS2 电极对几种电活性物质(即溶于 0.1 M PBS(pH 7.4)的六氰基铁酸钾(III)([Fe(CN6)]3-/4-)、烟酰胺腺嘌呤二核苷酸(NAD+/NADH)和过氧化氢(H2O2))具有优异的电化学传感性能。Fe(CN6)]3-/4-、NAD+/NADH 和 H2O2 的检测限分别为 0.34、0.25 和 1.36 μM。此外,根据这些分析物的相对标准偏差(RSD,n = 7)确定的重现性、重复性和稳定性分别小于 12.1%、8.6% 和 7.4%。因此,即用型 SPrGO-MoS2E 可以作为先进化学和生物传感应用的替代材料。
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引用次数: 0
An electrothermal coupling model for estimating the internal temperature of lithium-ion battery based on microthermal resistance method 基于微热阻法估算锂离子电池内部温度的电热耦合模型
IF 4.7 3区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-07-14 DOI: 10.1016/j.elecom.2024.107776

In the current study, the CN-CD30V10A battery tester, K-type temperature sensor, and RS485 are utilized to perform charging and discharging tests on the Panasonic 21,700 lithium-ion battery at various rates. The voltage and temperature changes are measured in real-time, with the data transmitted to the computer via RS485. Then a micro-thermal resistance method is proposed to calculate the equivalent thermal resistance of the cell core along the axial positive and negative poles, as well as along the radial outer circumference surface under anisotropic conditions. Based on the experimental results and the equivalent thermal resistance, an electrothermal coupling model is established for battery internal temperature estimation, taking into account anisotropy and temperature effects on heat transfer. Through the integration of the model and externally measured temperature, the internal temperature is accurately estimated. Moreover, the proposed model (Root-Mean-Square Error, RMSE=0.329) exhibits a significant improvement in accuracy compared to equivalent circuit model (RMSE=1.08), extended Kalman filter (RMSE=0.95), network extended Kalman filter (RMSE=0.58), and neural network unscented Kalman filter (RMSE=0.61). Specifically, the model achieves an approximately 76 % to 228 % reduction in RMSE compared to these methods.

在当前的研究中,利用 CN-CD30V10A 电池测试仪、K 型温度传感器和 RS485,对松下 21,700 锂离子电池进行了不同速率的充电和放电测试。电压和温度变化是实时测量的,数据通过 RS485 传输到计算机。然后提出了一种微热阻方法,用于计算各向异性条件下电池芯沿轴向正负极以及沿径向外圆周表面的等效热阻。根据实验结果和等效热阻,考虑到各向异性和温度对热传导的影响,建立了用于电池内部温度估算的电热耦合模型。通过对模型和外部测量温度进行整合,可以准确估算出内部温度。此外,与等效电路模型(RMSE=1.08)、扩展卡尔曼滤波器(RMSE=0.95)、网络扩展卡尔曼滤波器(RMSE=0.58)和神经网络非特征卡尔曼滤波器(RMSE=0.61)相比,所提出的模型(均方根误差,RMSE=0.329)在精度上有显著提高。具体来说,与这些方法相比,该模型的 RMSE 降低了约 76% 至 228%。
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引用次数: 0
Application of voltammetry as a technique to monitor cathodic protection performance of steel in simulated soil solution 应用伏安法监测模拟土壤溶液中钢铁的阴极保护性能
IF 4.7 3区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-07-14 DOI: 10.1016/j.elecom.2024.107777

Cathodic protection (CP) in combination with organic coating is applied as a secondary technique to mitigate corrosion of buried steel in an effort to prolong the lifespan of the buried steel pipeline. This study was aimed at developing and applying an adequate technique for monitoring the electrochemical behaviour of buried steel in the presence of CP. A modified voltammetry procedure was applied on carbon steel immersed in simulated soil solution for four days under open circuit potential (OCP) before applying CP for further ten days. Electrochemical impedance spectroscopy (EIS) was also applied at various time intervals to investigate the electrochemistry at the steel/solution interface. The voltammetry experiments revealed that the corrosion rate peaked at 680 µm/yr after three days of being subjected to OCP and then decreased to 411 µm/yr on day four as a result of a passive layer development on the steel surface. The corrosion rate was reduced from 411 µm/yr to 8 µm/yr as result of CP application before fluctuating between 21 and 40 µm/yr. The examination of steel surface via x-ray diffraction revealed the presence of calcareous deposit which resulted due to the application of cathodic protection.

阴极保护(CP)与有机涂层相结合,是减轻埋地钢管腐蚀的辅助技术,目的是延长埋地钢管的使用寿命。本研究旨在开发和应用一种适当的技术,用于监测埋地钢管在 CP 存在下的电化学行为。在开路电位(OCP)下,将碳钢浸入模拟土壤溶液中四天,然后再施加氯化石蜡十天。此外,还在不同的时间间隔内使用电化学阻抗谱(EIS)来研究钢/溶液界面的电化学。伏安法实验显示,在使用 OCP 三天后,腐蚀速率达到峰值 680 微米/年,然后由于钢表面被动层的形成,腐蚀速率在第四天下降到 411 微米/年。使用氯化石蜡后,腐蚀速度从 411 微米/年降低到 8 微米/年,然后在 21 至 40 微米/年之间波动。通过 X 射线衍射对钢材表面进行的检查显示,由于采用了阴极保护,钢材表面出现了钙质沉积物。
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引用次数: 0
Constructing high-performance micro fuel electrodes for reversible proton ceramic electrochemical cells 为可逆质子陶瓷电化学电池构建高性能微型燃料电极
IF 4.7 3区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-07-06 DOI: 10.1016/j.elecom.2024.107775
Yeqing Ling, Feifan Huang, Bin Wang, Tao Li

Reversible proton ceramic electrochemical cells (R-PCECs) are of great interest as efficient energy conversion device. Optimization of structural design can enhance the mechanical properties and gas transport of the cells, resulting in improved electrochemical performance. In this study, we developed a 7-channel micro-monolithic R-PCEC for the first time, with uniform channel distribution and smaller gas diffusion pathway length using phase inversion/extrusion technique. The assembled cell with Ni-BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (Ni-BZCYYb, fuel electrode support) | BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb, electrolyte) | PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF, air electrode) structure showed a peak power density of 0.94 W cm−2 at 700 °C in fuel cell mode and electrolysis current density of 2.17 A cm−2 at 700 °C with an operating voltage of 1.3 V. Additionally, electrochemical impedance spectroscopy (EIS) further indicated that the diffusive polarization of the structured cell was effectively reduced compared to single-channel counterpart.

可逆质子陶瓷电化学电池(R-PCECs)作为一种高效的能量转换装置备受关注。优化结构设计可以提高电池的机械性能和气体传输性能,从而改善电化学性能。在这项研究中,我们利用相反转/挤压技术首次开发出了一种 7 通道微单片 R-PCEC 电池,其通道分布均匀,气体扩散通道长度较小。组装好的电池由 Ni-BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (Ni-BZCYYb,燃料电极支撑) | BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb,电解质) | PrBa0.5Sr0.5Co1.5Fe0.5O5+δ(PBSCF,空气电极)结构的燃料电池在 700 °C 时的峰值功率密度为 0.94 W cm-2,在 700 °C 时的电解电流密度为 2.此外,电化学阻抗谱(EIS)进一步表明,与单通道电池相比,结构电池的扩散极化有效降低。
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引用次数: 0
Carbon nanotubes decorated with bimetallic PtCo nanoparticles for sensitive detection of uric acid 装饰有双金属铂钴纳米粒子的碳纳米管用于灵敏检测尿酸
IF 4.7 3区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-07-02 DOI: 10.1016/j.elecom.2024.107774
Shun Lu , Shouqin Xiang , Chuan Wang , Hong Liu

Common methods based on enzymatic approaches for uric acid (UA) have potential issues such as limited detection range, low linearity, and susceptibility to interference. Our study focuses on enhancing the sensitivity and selectivity of detecting UA by decorating carbon nanotubes (CNTs) with bimetallic platinum-cobalt nanoparticles (PtCo/CNTs) using an adsorbing-thermal reducing method for electrochemical analysis. Physical characterizations are employed to confirm its structural and element compositions. Then, an electrochemical biosensor based on screen printed electrode (SPE) modified with PtCo/CNTs was constructed for UA determination. PtCo/CNTs modified SPE (PtCo/CNTs@SPE) demonstrates significant electrochemical activity and selectivity toward UA detection due to the synergistic effect between PtCo nanoparticles and CNTs, and the excellent electrical conductivity. Under optimized conditions, the current response of UA at the PtCo/CNTs@SPE presented linear dependence on the concentration, ranging from 0.1 µM to 3000.0 µM with a low limit of detection of 0.05 µM. In addition, the selectivity, stability, and practical applications of the as-prepared sensor are also explored.

基于酶法检测尿酸(UA)的常见方法存在一些潜在问题,如检测范围有限、线性度低、易受干扰等。我们的研究重点是利用吸附-热还原法将碳纳米管(CNTs)与双金属铂钴纳米粒子(PtCo/CNTs)装饰在一起进行电化学分析,从而提高检测尿酸的灵敏度和选择性。物理特性分析确认了其结构和元素组成。然后,构建了一种基于铂钴/碳纳米管修饰的丝网印刷电极(SPE)的电化学生物传感器,用于测定 UA。铂钴/碳纳米管修饰的丝网印刷电极(PtCo/CNTs@SPE)由于铂钴纳米颗粒与碳纳米管之间的协同效应和优异的导电性,对UA的检测具有显著的电化学活性和选择性。在优化条件下,PtCo/CNTs@SPE 上的 UA 电流响应与浓度呈线性关系,从 0.1 µM 到 3000.0 µM,检测限低至 0.05 µM。此外,还探讨了制备的传感器的选择性、稳定性和实际应用。
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引用次数: 0
Determining phase-transition temperatures of molten salt mixtures through microsecond-scale staircase voltammetry 通过微秒级阶梯伏安法确定熔盐混合物的相变温度
IF 4.7 3区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-06-29 DOI: 10.1016/j.elecom.2024.107773
Hwakyeung Jeong , Tae-Hyeong Kim , Han Lim Cha , Sang Ho Lim , Jong-Yun Kim

Determining the phase-transition temperature is crucial in the design of molten salt reactors, as operational temperatures need to be established considering the safety margins related to the thermodynamic stability of the molten salt system. This study introduces a novel approach to determine the phase-transition temperature based on rapid electrical conductivity measurements using a microsecond-scale staircase voltammetry technique. The phase-transition temperature is determined near distinct points where the electrical conductivity abruptly changes, indicating phase transitions. The phase-transition temperatures of three LiCl–KCl molten salt systems, determined using the proposed approach based on electrical conductivity measurements, are with relative errors less than 3% compared with reported phase transition data based on conventional thermal analysis techniques.

确定相变温度对于熔盐反应堆的设计至关重要,因为在确定运行温度时需要考虑与熔盐系统热力学稳定性相关的安全系数。本研究介绍了一种基于微秒级阶梯伏安法技术的快速电导率测量来确定相变温度的新方法。相变温度是在电导率突然变化的明显点附近测定的,这些点表明了相变。与基于传统热分析技术的相变数据相比,使用基于电导率测量的拟议方法测定的三种锂盐-氯化钾熔盐体系的相变温度的相对误差小于 3%。
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引用次数: 0
Operando X-ray radiography of liquid water distribution in 100 mm polymer electrolyte fuel cell channels 对 100 毫米聚合物电解质燃料电池通道中的液态水分布进行 X 射线操作成像
IF 4.7 3区 工程技术 Q1 Chemistry Pub Date : 2024-06-18 DOI: 10.1016/j.elecom.2024.107772
Akihiko Kato , Satoshi Yamaguchi , Wataru Yoshimune , Kazuhisa Isegawa , Masashi Maeda , Daisuke Hayashi , Takahisa Suzuki , Satoru Kato

Preventing the accumulation of water in the gas diffusion layer (GDL) proves effective in enhancing the performance of polymer electrolyte fuel cells (PEFCs). To understand the water transport phenomena in GDLs and channels of PEFCs, cell hardware for operando synchrotron X-ray radiography was developed with a 100 mm channel length, facilitating the separate quantification of liquid water in the cathode and anode GDLs. The presence of liquid water in the cathode and anode GDLs was confirmed during operation with a supply of dry gas in a counter-flow configuration. Furthermore, the amount of liquid water in the cathode and anode GDLs increased toward the cathode inlet, while the amount of water in the cathode and anode channel regions increased toward each outlet. The liquid water distribution in the GDLs along the channel direction can be attributed to water transport from cathode to anode (back-diffusion), decreasing toward the anode outlet. Therefore, conducting radiography experiments aligned parallel to the GDLs and perpendicular to the channel could provide valuable insights for a more comprehensive understanding of water transport in cells.

事实证明,防止水在气体扩散层(GDL)中积聚可有效提高聚合物电解质燃料电池(PEFC)的性能。为了了解 PEFC 的气体扩散层和通道中的水传输现象,我们开发了通道长度为 100 毫米的用于操作同步辐射 X 射线成像的电池硬件,便于对阴极和阳极气体扩散层中的液态水进行单独量化。阴极和阳极 GDL 中液态水的存在已在以逆流配置供应干燥气体的运行过程中得到证实。此外,阴极和阳极 GDL 中的液态水量向阴极入口方向增加,而阴极和阳极通道区域中的水量则向每个出口方向增加。GDL 中的液态水沿通道方向的分布可归因于水从阴极向阳极的传输(反向扩散),而向阳极出口方向的分布则有所减少。因此,进行平行于 GDLs 并垂直于通道的射线照相实验可为更全面地了解细胞中的水传输提供有价值的见解。
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引用次数: 0
Real-time and operando observation of intermediates on TiO2 photoelectrocatalysis by soft X-ray absorption spectroscopy 利用软 X 射线吸收光谱对 TiO2 光电催化中间产物进行实时和操作观察
IF 5.4 3区 工程技术 Q1 Chemistry Pub Date : 2024-06-08 DOI: 10.1016/j.elecom.2024.107771
Kaoruho Sakata , Kenta Amemiya

The oxygen evolution reaction (OER) on the TiO2 surface at the solid–liquid interface was observed in real-time and operando using fluorescence-yield X-ray absorption spectroscopy (XAS) in the soft X-ray region. The OER was observed during a potential sweep with UV light on or off, focusing on the oxygen K-edge XAS. Although conventional XAS measurements require long measurement times, the spectra during the reaction were obtained every 3 s in the present experiment via wavelength-dispersive XAS technique. An increase in the X-ray absorption intensity at approximately 533.8 eV was observed during the potential sweep only with UV light on. The observed spectral change is discussed in relation to the reaction mechanism of the OER. The present technique can be applied to a wide range of analyses of (photo-) electrocatalysis and electrochemical reactions at solid–liquid interfaces to observe their products and intermediates during the reaction.

利用软 X 射线区域的荧光-产率 X 射线吸收光谱(XAS)实时观察了固液界面 TiO2 表面的氧进化反应(OER)。在紫外光开启或关闭的电位扫描过程中观察了 OER,重点是氧 K 边 XAS。虽然传统的 XAS 测量需要较长的测量时间,但在本实验中,通过波长色散 XAS 技术,每隔 3 秒就能获得反应过程中的光谱。在电位扫描过程中,只有在紫外光下才能观察到约 533.8 eV 处的 X 射线吸收强度增加。观察到的光谱变化与 OER 的反应机制有关。本技术可广泛应用于固液界面(光)电催化和电化学反应的分析,以观察反应过程中的产物和中间产物。
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引用次数: 0
Enhanced electrochemical performance of molten salt synthesized V2CTx MXene@VOx composite in Zn ion aqueous electrolytes 增强熔盐合成的 V2CTx MXene@VOx 复合材料在锌离子水溶液电解质中的电化学性能
IF 5.4 3区 工程技术 Q1 Chemistry Pub Date : 2024-06-06 DOI: 10.1016/j.elecom.2024.107770
Jinru Wen , Hongyan Dan , Chunyang Li , Chunlong Dai , Zifeng Lin

The development of MXenes using Lewis acidic salts for etching (MS-MXenes) in molten salts presents a novel, fluorine-free method attracting considerable interest. However, the behavior of various MS-MXenes and their derivatives in aqueous environments remains largely unexplored. Particularly, vanadium-based MXenes demonstrate intriguing properties in Zn ion aqueous electrolytes. Herein, a fluorine-free V2CTx MXene@VOx is synthesized by molten salt etching under an argon atmosphere. The electrochemical properties of V2CTx@VOx are tested in various aqueous electrolytes, including Zn(TFSI)2, ZnSO4, ZnBr2, ZnAc2, and ZnCl2 solutions. The V2CTx@VOx shows high redox capacities in all these Zn ion electrolytes, with the peak performance observed in 1 M ZnBr2, achieving a maximum capacity of 172 mAh g−1 at 1 mV s−1. This performance rivals that of V2CTx MXene prepared through wet-chemical methods. These results underscore the potential of MS-MXenes materials in aqueous energy storage applications.

在熔盐中使用路易斯酸盐进行蚀刻(MS-MXenes)的 MXenes 的开发是一种新颖的无氟方法,引起了人们的极大兴趣。然而,各种 MS-MXenes 及其衍生物在水环境中的行为在很大程度上仍未得到探索。特别是,钒基 MXenes 在锌离子水性电解质中表现出了耐人寻味的特性。本文在氩气环境下通过熔盐蚀刻合成了无氟 V2CTx MXene@VOx。测试了 V2CTx@VOx 在各种水电解质(包括 Zn(TFSI)2、ZnSO4、ZnBr2、ZnAc2 和 ZnCl2 溶液)中的电化学特性。V2CTx@VOx 在所有这些锌离子电解质中都显示出很高的氧化还原容量,在 1 M ZnBr2 中达到峰值,在 1 mV s-1 时的最大容量为 172 mAh g-1。这一性能可与通过湿化学方法制备的 V2CTx MXene 相媲美。这些结果凸显了 MS-MXenes 材料在水性储能应用中的潜力。
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引用次数: 0
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Electrochemistry Communications
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