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Activity and Selectivity in the Electrochemical Reduction of CO2 at CuSnx Electrocatalysts Using a Zero-Gap Membrane Electrode Assembly 使用零间隙膜电极组件的 CuSnx 电催化剂在电化学还原 CO2 过程中的活性和选择性
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-28 DOI: 10.1149/1945-7111/ad6fd7
Monsuru Dauda, John Hendershot, Mustapha Bello, Junghyun Park, Alvaro Loaiza Orduz, Orhan Kizilkaya, Phillip Sprunger, Anthony Engler, Koffi Yao, Craig Plaisance, John Flake
In this study Cu, Sn, and bimetallic CuSnx nanoparticles were synthesized and evaluated as electrocatalysts for CO2 reduction using zero gap membrane electrode assemblies. Results show bimetallic electrocatalysts with Sn contents above 10% yield formate as a primary product with Faradaic Efficiencies near 70% at 350 mA cm−2. Cu-Snx electrocatalysts with less than 10% Sn yield CO at current densities below 350 mA cm−2 and relatively lower cell potentials. When the low-Sn content bimetallic electrocatalysts were evaluated in alkaline anolytes at 350 mA cm−2, ethanol was recorded as the primary product (FE = 48.5% at Ecell ≥ 3.0 V). We propose enhanced C2 activity and selectivity originate from Cu dimers adjacent to Sn atoms for bimetallic electrocatalyst with low-Sn content. The C2 active sites are lost when the surface Sn content exceeds 25%–38%.
本研究合成了铜、锡和双金属 CuSnx 纳米粒子,并将其作为使用零间隙膜电极组件进行二氧化碳还原的电催化剂进行了评估。结果表明,Sn 含量高于 10% 的双金属电催化剂在 350 mA cm-2 电流条件下,主要产物甲酸的法拉第效率接近 70%。锡含量低于 10%的铜锡双金属电催化剂在电流密度低于 350 mA cm-2 和电池电位相对较低的条件下产生 CO。在 350 mA cm-2 的碱性溶液中评估低锡含量的双金属电催化剂时,乙醇被记录为主要产物(Ecell ≥ 3.0 V 时 FE = 48.5%)。我们认为,C2 活性和选择性的增强源于低锡含量双金属电催化剂中与锡原子相邻的铜二聚体。当表面锡含量超过 25%-38% 时,C2 活性位点就会消失。
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引用次数: 0
The Effect of the Rare Earth Element Cerium on the Electrocrystallization and Microstructure of Nickel Electrodeposits in Industrial Electrolytes 稀土元素铈对工业电解液中镍电沉积物的电晶化和微观结构的影响
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-28 DOI: 10.1149/1945-7111/ad70da
Yang-Tao Xu, Yan-Hong Li, Yin Peng, Zhi-Qiang Zhong
To meet the industrial production needs for high-quality and precisely controllable structured high-end nickel foils, rare Earth compounds are added as additives in complex industrial electrolytes to improve the quality of the nickel deposition layer. This study investigates the effects of adding rare Earth compounds to the existing industrial production electrolytes (which already contain various organic and inorganic additives in a mixed acid solution) on the surface microstructure, cerium content, grain size, and crystal orientation of the nickel deposition layer. Using direct current electrodeposition, different concentrations of rare Earth compounds were added to the industrial electrolyte, and the cerium content, grain size, and crystal orientation were characterized. The results show that adding 0.8 g·l−1 CeCl3 accelerates the nucleation rate and shortens the nucleation relaxation time. The addition of rare Earth elements promotes multi-directional preferential growth, resulting in uniform and fine grain size, improved grain structure of the deposition layer, and reduced surface roughness of the nickel plating layer. Therefore, rare Earth elements can be used to regulate the structure, microstructure, and grain refinement of the nickel deposition layer without affecting its composition.
为满足工业生产对高质量、结构可精确控制的高端镍箔的需求,稀土化合物作为添加剂被添加到复杂的工业电解液中,以提高镍沉积层的质量。本研究探讨了在现有工业生产电解液(在混合酸溶液中已含有各种有机和无机添加剂)中添加稀土化合物对镍沉积层表面微观结构、铈含量、晶粒大小和晶体取向的影响。利用直流电沉积,在工业电解液中加入不同浓度的稀土化合物,对铈含量、晶粒大小和晶体取向进行了表征。结果表明,添加 0.8 g-l-1 CeCl3 可加快成核速度,缩短成核弛豫时间。稀土元素的加入促进了多向优先生长,使晶粒大小均匀且细小,改善了沉积层的晶粒结构,降低了镀镍层的表面粗糙度。因此,稀土元素可用于调节镍沉积层的结构、微观结构和晶粒细化,而不会影响其成分。
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引用次数: 0
Controlling Oxygen Vacancy Content by Varying Calcination Temperature to Enhance the Gas Sensing Performance of BiVO4 Material 通过改变煅烧温度控制氧空位含量以提高 BiVO4 材料的气体传感性能
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-28 DOI: 10.1149/1945-7111/ad6ef6
Si-Qi Jiao, Yu-Feng Liu, Xiao-Hong Zheng, Cheng Zhang, Xiao-Rui Wang
Compared to gas sensors based on single metal oxide, gas sensors based on binary metal oxide semiconductors (MOS) offer a rich variety of structural types and hold great potential for excellent selectivity. Inspired by this, we synthesized BiVO4 powder through a stepwise reaction combining calcination with hydrothermal bath and investigated the influence of different calcination temperatures on its gas sensitivity performance. Our study revealed that BiVO4-600 exhibited optimal TEA gas sensing behavior at 225 °C, showing high response values (Ra/Rg = 43.4) and fast response/recovery times (15 s/52 s). Additionally, the sensor displayed high stability, repeatability, and exceptional selectivity. Preliminary research indicates that calcination temperature induces changes in the oxygen vacancy content of BiVO4, thus affecting its sensing performance.
与基于单一金属氧化物的气体传感器相比,基于二元金属氧化物半导体(MOS)的气体传感器具有丰富的结构类型,在实现优异的选择性方面潜力巨大。受此启发,我们通过煅烧与水浴相结合的分步反应合成了 BiVO4 粉末,并研究了不同煅烧温度对其气体灵敏度性能的影响。研究结果表明,BiVO4-600 在 225 ℃ 时具有最佳的三乙醇胺气体传感性能,显示出高响应值(Ra/Rg = 43.4)和快速响应/恢复时间(15 秒/52 秒)。此外,该传感器还具有高稳定性、可重复性和优异的选择性。初步研究表明,煅烧温度会导致 BiVO4 的氧空位含量发生变化,从而影响其传感性能。
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引用次数: 0
Formation of Through-Hole Porous Anodic Aluminum Oxide Layer Locally with 3D Printed Solution Flow Type Microdroplet Cell 利用 3D 打印溶液流式微滴池在局部形成通孔多孔阳极氧化铝层
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-27 DOI: 10.1149/1945-7111/ad6fd6
Adane Adugna Ayalew, Xiaole Han, Yoganandan Govindaraj, Masatoshi Sakairi
In this study, a 3D-prinited solution-flow type microdroplet cell (SF-MDC) is employed as a new technique for the fabrication of porous anodic aluminum oxide (AAO) layer using oxalic acid electrolyte on aluminum. The surface morphology of the porous AAO film was characterized by a scanning electron microscope. The aim of this study was to fabricate a through-hole porous alumina layer in a single step anodizing process and to investigate the influence of anodized voltages and scanning speeds on the thickness and pore structure of alumina layer. The results showed that the pore diameter and interpore distance were directly proportional to the anodizing voltage. The thicknesses of formed AAO films were found to be 35.5, 50.7, and 81.6 μm at scanning speeds of 10, 5, and 2.5 μms−1, respectively. Through-hole porous AAO was successfully fabricated at room temperature without chemical etching. The SF-MDC fabrication technique is proposed as an environmentally attractive and suitable process for the fabrication of porous AAO layers.
本研究采用三维引射溶液流型微滴电池(SF-MDC)作为一种新技术,利用草酸电解液在铝上制造多孔阳极氧化铝(AAO)层。扫描电子显微镜对多孔 AAO 膜的表面形态进行了表征。本研究旨在通过一步阳极氧化工艺制作通孔多孔氧化铝层,并研究阳极氧化电压和扫描速度对氧化铝层厚度和孔结构的影响。结果表明,孔径和孔间距与阳极氧化电压成正比。在扫描速度为 10、5 和 2.5 μms-1 时,形成的 AAO 薄膜厚度分别为 35.5、50.7 和 81.6 μm。通孔多孔 AAO 无需化学蚀刻即可在室温下成功制备。SF-MDC制备技术是一种具有环境吸引力且适用于制备多孔 AAO 层的工艺。
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引用次数: 0
CoFe2O4 Nanoparticles on Bio-Based Polymer Derived Nitrogen Doped Carbon as Bifunctional Electrocatalyst for Li-Air Battery 生物基聚合物掺氮碳上的 CoFe2O4 纳米粒子作为锂空气电池的双功能电催化剂
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-27 DOI: 10.1149/1945-7111/ad69c9
Pirapath Arkasalerks, Amarshi Patra, Kottisa Sumala Patnaik, Koichi Higashimine, Noriyoshi Matsumi
Lithium-air batteries (LABs) are gaining attention as a promising energy storage solution. Their theoretical energy density of 3,505 Whkg−1 exceeds that of conventional lithium-ion batteries (500–800 Whkg−1). The commercial viability and widespread adoption of lithium-air batteries face challenges such as poor cycling stability, limited lifespan, and unresolved side reactions. In this study, we synthesized spinel CoFe2O4-decorated on bio-based poly(2,5-benzimidazole) derived N-doped carbon for electrocatalysts. Notably, strong metal-substrate interaction (SMSI) was observed through various characterizations. The bifunctional electrocatalytic activity and stability toward oxygen reduction reaction and oxygen evolution reaction were significantly enhanced by the SMSI, The LAB demonstrated a high discharge capacity of 18,356 mAhg−1 at a current density of 200 mAg−1, maintaining a remarkable discharge capacity of 1,000 mAhg−1 even at a high current density of 400 mAg−1 for 200 cycles. CoFe2O4-decorated on bio-derived ABPBI holds promise as a practical air-breathing electrode for high-capacity rechargeable LABs.
锂空气电池(LABs)作为一种前景广阔的储能解决方案正日益受到关注。其理论能量密度为 3,505 Whkg-1,超过了传统的锂离子电池(500-800 Whkg-1)。锂空气电池的商业可行性和广泛应用面临着各种挑战,如循环稳定性差、寿命有限以及副反应尚未解决。在本研究中,我们合成了装饰在生物基聚(2,5-苯并咪唑)衍生的掺杂 N 的碳上的尖晶石 CoFe2O4 作为电催化剂。值得注意的是,通过各种表征观察到了强烈的金属-基底相互作用(SMSI)。在 200 mAg-1 的电流密度下,LAB 的放电容量高达 18,356 mAhg-1,即使在 400 mAg-1 的高电流密度下循环 200 次,也能保持 1,000 mAhg-1 的显著放电容量。在生物萃取的 ABPBI 上装饰 CoFe2O4,有望成为高容量可充电 LAB 的实用呼吸空气电极。
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引用次数: 0
Enhanced Porous Electrode Theory Based Electrochemical Model for Higher Fidelity Modelling and Deciphering of the EIS Spectra 基于多孔电极理论的增强型电化学模型,用于更高保真建模和解密 EIS 光谱
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-27 DOI: 10.1149/1945-7111/ad6eb9
Igor Mele, Klemen Zelič, Marko Firm, Jože Moškon, Miran Gaberšček, Tomaž Katrašnik
Electrochemical impedance spectroscopy (EIS) is essential for non-invasive battery characterization. This paper addresses the challenge of adequate interpretation of EIS spectra, which are often complicated by overlapping internal phenomena occurring on similar time scales. We present, for the first time, a high-fidelity numerical time-domain electrochemical model that can virtually replicate experimental EIS spectra with three superimposed high-frequency semicircles, a transition to the diffusion tail at elevated imaginary values, and a tilted diffusion tail at low frequencies. These advanced features were made possible by extending state-of-the-art porous electrode model with innovative sub-models for the double layer phenomenon at the carbon black/electrolyte and metal Li-anode/electrolyte interfaces, and transport phenomena of charged species through the solid electrolyte interphase at the Li-anode interface. Additionally, we modelled the diffusion tail inclination by introducing representative active particles of varying sizes. Results from custom-made half-cells confirm the model’s ability to decipher EIS spectra more accurately compared to existing models. Moreover, innovative physics-based battery model that is capable of accurately modelling intra-cell phenomena can reveal internal states and physical parameters of batteries using measured EIS spectra. The model, therefore, also enables functionality of an advanced virtual sensor, which is an important diagnostics feature in next-generation battery management systems.
电化学阻抗光谱(EIS)对于非侵入式电池特性分析至关重要。本文探讨了如何充分解释 EIS 光谱的难题,因为在相似的时间尺度上发生的重叠内部现象通常会使 EIS 光谱变得复杂。我们首次提出了一种高保真数值时域电化学模型,该模型可以几乎复制实验 EIS 光谱,其中包括三个叠加的高频半圆、虚值升高时向扩散尾部的过渡以及低频时倾斜的扩散尾部。这些先进特性是通过扩展最先进的多孔电极模型实现的,该模型具有创新的子模型,可用于模拟炭黑/电解质和金属锂阳极/电解质界面的双层现象,以及带电物种通过锂阳极界面上的固体电解质相间层的传输现象。此外,我们还通过引入不同尺寸的代表性活性颗粒来模拟扩散尾部的倾斜度。定制半电池的结果证实,与现有模型相比,该模型能够更准确地解读 EIS 光谱。此外,基于物理学的创新电池模型能够准确模拟电池内部现象,利用测量的 EIS 光谱揭示电池的内部状态和物理参数。因此,该模型还能实现先进虚拟传感器的功能,而这正是下一代电池管理系统的重要诊断功能。
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引用次数: 0
Review—Advances in Rechargeable Lithium-Ion Batteries Utilizing Polyoxometalate-Functionalized Nanocarbon Materials 综述--利用聚氧化金属功能化纳米碳材料的可充电锂离子电池的研究进展
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-27 DOI: 10.1149/1945-7111/ad6b46
Samaneh Shahsavarifar, Morteza Rezapour, Mehdi Mehrpooya, Hermann Ehrlich, Teofil Jesionowski, Mohammad Reza Ganjali, Rafael Luque, Mehdi Rahimi-Nasrabadi
Polyoxometalates (POMs) are inorganic nanoclusters that consist of oxygen and transition metals. These nanoclusters serve as excellent precursors for creating electrode materials that contain transition metals. Additionally, the interaction between POMs and carbon substrates produces positive synergistic effects. There has been considerable attention on employing POMs and carbon nanostructures (for example carbon nanotubes, graphene, and mesoporous carbon) in composite materials for diverse purposes including catalysis, transformation, storage of energy, molecular detection, and electrical detection. By combining the reactive nature of POMs with the exceptional electrical properties of carbon nanostructures, highly desirable composite features can be achieved. This review delves into the extensive use of POM/nanocarbon materials for constructing rechargeable lithium-ion batteries, providing an in-depth analysis of the characteristics of POMs and the techniques employed for binding carbon.
聚氧化金属盐(POMs)是由氧和过渡金属组成的无机纳米团簇。这些纳米团簇是制造含有过渡金属的电极材料的绝佳前体。此外,POMs 与碳基底之间的相互作用会产生积极的协同效应。将 POM 和碳纳米结构(如碳纳米管、石墨烯和介孔碳)应用于催化、转化、储能、分子检测和电学检测等多种用途的复合材料已受到广泛关注。通过将聚甲醛的反应特性与碳纳米结构的优异电学特性相结合,可以实现非常理想的复合特性。本综述深入探讨了 POM/纳米碳材料在构建可充电锂离子电池中的广泛应用,深入分析了 POM 的特性以及结合碳所采用的技术。
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引用次数: 0
Influence of Potential and the Presence of Boric Acid on Pt1-xCox Alloy Electrodeposition and Magnetic Properties 电位和硼酸对 Pt1-xCox 合金电沉积和磁性能的影响
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-26 DOI: 10.1149/1945-7111/ad6b48
Eric D. Rus, Eduardo L. Corrêa, Cindi L. Dennis, Thomas P. Moffat
The effects of potential and the presence of B(OH)3 on Pt1-xCox alloy electrodeposition from aqueous chloride-based solutions on Ru substrates was investigated. Films deposited at potentials more reducing than −0.65 V vs SCE were hexagonal close packed and greater than 90% Co (mole basis), and films deposited at potentials more oxidizing than −0.65 V were face centered cubic and showed a monotonic decrease in cobalt content as the potential increased. The composition and structure-potential dependences were not strongly affected by the presence of B(OH)3. Structural change coincided with a distinct knee-like feature in the composition-potential relationship, along with a prominent narrow voltammetric peak associated with Co deposition, possibly related to nucleation and growth of the hcp phase. The presence of B(OH)3 produced a sharp minimum in both Coulombic efficiency and deposition rate at potentials near −0.65 V and almost entirely suppressed the voltammetric feature. This may be associated with a combination of B(OH)3-derived proton reduction and inhibition of metal deposition by adsorbed B(OH)3 or B(OH)3-derived species. The presence of B(OH)3 affected the magnetic behavior of films deposited at potentials more oxidizing than −0.55 V (i.e., those with compositions less than about 40% Co) only weakly, but resulted in generally smaller maximum magnetizations for films deposited at more reducing potentials, and notably a much lower magnetization for films deposited at −0.65 V.
研究了电位和 B(OH)3 的存在对 Pt1-xCox 合金在 Ru 基底上从氯化物水溶液中电沉积的影响。在相对于 SCE 的还原电位高于 -0.65 V 时沉积的薄膜为六方紧密堆积,钴含量超过 90%(摩尔基);而在相对于 SCE 的氧化电位高于 -0.65 V 时沉积的薄膜为面中心立方体,并且随着电位的升高,钴含量呈单调下降趋势。结构变化与成分-电位关系中明显的膝状特征以及与钴沉积有关的突出窄伏安峰相吻合,这可能与 hcp 相的成核和生长有关。在电位接近 -0.65 V 时,B(OH)3 的存在会使库仑效率和沉积速率急剧下降,并几乎完全抑制了伏安特性。这可能与 B(OH)3 衍生的质子还原以及吸附的 B(OH)3 或 B(OH)3 衍生物种对金属沉积的抑制作用有关。B(OH)3 的存在对在氧化性比 -0.55 V 更强的电位下沉积的薄膜(即钴含量低于 40% 的薄膜)的磁性行为影响较弱,但对在还原性更强的电位下沉积的薄膜的最大磁化率普遍较小,尤其是在 -0.65 V 下沉积的薄膜的磁化率更低。
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引用次数: 0
Bio-Based Materials for Electrochemical Detection of Bisphenol A 用于电化学检测双酚 A 的生物基材料
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-23 DOI: 10.1149/1945-7111/ad6eb8
Wassila Sefari, Ali Zazoua, Helim Rabiaa, Hafsa Korri-Youssoufi
Bisphenol A is a widely used endocrine disruptor known for its toxicity and prevalence in the environment. It contaminates drinking water, especially when plastic bottles are exposed to Sunlight. Rapid, on-site detection of BPA in drinking water is crucial for protecting human health and the environment. Herein, we developed an electrochemical sensor for detecting and monitoring bisphenol A in water bodies utilizing biobased materials. The device uses a biopolymeric membrane with agarose and gelified green tea tannins (GT/Agar). A sensitive part was made using this natural composite due to its high ability to attach bisphenol A to tannin monomers. Green tea tannins were purified and characterized through HPLC, FTIR, SEM, and AFM. The electrochemical activity of the GT-Agar/Au sensor is also evaluated by electrochemical impedance spectroscopy, cyclic voltammetry, square wave voltammetry and scan rate. Based on its redox signal under the optimal experimental conditions, this sensor has a detection range of 10−16 M to 10−4 M, a limit of detection of 1.52 to 10−17 M and very high selectivity. The proposed sensor successfully determined BPA levels from ultra-trace concentrations in bottled water samples, achieving satisfactory recovery rates. Compared to the results obtained using HPLC, it demonstrates high reliability.
双酚 A 是一种广泛使用的内分泌干扰物,以其毒性和在环境中的普遍存在而闻名。它污染饮用水,尤其是当塑料瓶暴露在阳光下时。快速现场检测饮用水中的双酚 A 对保护人类健康和环境至关重要。在此,我们利用生物基材料开发了一种用于检测和监测水体中双酚 A 的电化学传感器。该装置使用了含有琼脂糖和凝胶绿茶单宁(GT/Agar)的生物高分子膜。由于这种天然复合材料具有很强的将双酚 A 附着在单宁酸单体上的能力,因此使用这种天然复合材料制作了一个敏感部位。对绿茶单宁进行了纯化,并通过 HPLC、傅立叶变换红外光谱、扫描电镜和原子力显微镜对其进行了表征。还通过电化学阻抗谱、循环伏安法、方波伏安法和扫描速率评估了 GT-Agar/Au 传感器的电化学活性。根据其在最佳实验条件下的氧化还原信号,该传感器的检测范围为 10-16 M 至 10-4 M,检测限为 1.52 至 10-17 M,并具有极高的选择性。该传感器成功测定了瓶装水样品中超痕量浓度的双酚 A 含量,回收率令人满意。与使用高效液相色谱法得出的结果相比,它具有很高的可靠性。
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引用次数: 0
Effect of PVdF Distribution on Properties and Performance of Dry Spray-Coated Graphite Electrodes for Lithium-Ion Batteries for Electric Vehicle Applications PVdF 分布对电动汽车用锂离子电池干喷涂石墨电极特性和性能的影响
IF 3.9 4区 工程技术 Q2 ELECTROCHEMISTRY Pub Date : 2024-08-08 DOI: 10.1149/1945-7111/ad6936
J. Alberto Barreras-Uruchurtu, Nicolas Besnard, Clément Paul, Lauréline Marchal, Samuel Devisme and Bernard Lestriez
We used electrostatic dry spray-coating to fabricate graphite/PVdF anodes. We compared the morphological, mechanical, electrical, and electrochemical properties of electrodes fabricated with three different mixing times of dry electrode components. Quantitative and novel relationships between the PVdF distribution and the electrode properties were obtained. Our investigations suggest that our fabrication methods are viable alternatives for producing electrodes with comparable properties to those fabricated using traditional wet solvent-based methods. Overall, our work provides insights into new and promising methods for fabricating high-quality dry-sprayed electrodes (DSEs) with high mass loadings for use in a variety of electrochemical applications such as electric vehicles.
我们采用静电干喷涂法制造石墨/PVdF 阳极。我们比较了三种不同干法电极成分混合时间下制备的电极的形态、机械、电气和电化学性能。我们获得了 PVdF 分布与电极特性之间的新颖定量关系。我们的研究表明,我们的制造方法是生产电极的可行替代方法,其性能与使用传统湿溶剂方法制造的电极相当。总之,我们的工作为制造高质量、高负载的干喷涂电极(DSE)提供了新的、有前途的方法,可用于电动汽车等各种电化学应用。
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引用次数: 0
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