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Aqueous multi-electron electrolyte for hybrid flow batteries with high energy and power densities 用于高能量和功率密度混合液流电池的多电子水溶液
IF 4.5 Q2 Energy Pub Date : 2020-08-01 DOI: 10.1016/j.powera.2020.100018
Qiuhong Wang, Walid A. Daoud

Flow battery is a promising energy storage technology for facilitating utilization of renewable resources. While new types of flow batteries have been explored toward high energy density, hampering the power density due to high electrolyte viscosity and sluggish reaction kinetics. Discovery of an aqueous electrolyte with multi-electron transfer reaction is thus favorable for both high energy and power densities due to its multiple charge stored at the same concentration. Both criteria are crucial to improve the flexibility of cell design and widen the application potential. Herein, bismuth is pioneered as negative electrolyte (negolyte) for hybrid flow battery owing to its three-electron reaction and the significantly increased solubility in methanesulfonic acid. In conjunction with cerium electrolyte, a volumetric energy density of 90 Wh L−1 is achieved and simultaneously a high power density of 295 mW cm−2 at 90% state-of-charge is demonstrated using low-cost carbon electrode. Furthermore, a high volumetric capacity of 120 Ah L−1 is reached via adopting graphite felt, which is 100% of the theoretical specific capacity of 1.5 M bismuth negolyte.

液流电池是一种很有前途的储能技术,可以促进可再生资源的利用。虽然新型液流电池正朝着高能量密度方向发展,但由于电解质粘度高,反应动力学缓慢,阻碍了功率密度的提高。具有多电子转移反应的水电解质的发现,由于其在相同浓度下存储了多个电荷,因此有利于高能量和功率密度。这两个标准对于提高电池设计的灵活性和扩大应用潜力至关重要。其中,铋因其三电子反应和在甲磺酸中的溶解度显著提高而被率先用作混合液流电池的负电解质(negolyte)。与铈电解质相结合,实现了90 Wh L−1的体积能量密度,同时证明了使用低成本碳电极在90%充电状态下的高功率密度为295 mW cm−2。此外,采用石墨毡可获得120 Ah L−1的高容量,是1.5 M无晶铋理论比容量的100%。
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引用次数: 4
In situ X-ray computational tomography measurement of single particle behavior of sulfide solid electrolyte under high-pressure compression 高压压缩下硫化物固体电解质单粒子行为的原位x射线计算机断层扫描测量
IF 4.5 Q2 Energy Pub Date : 2020-08-01 DOI: 10.1016/j.powera.2020.100019
M. Kodama, A. Ohashi, S. Hirai

High-pressure in situ X-ray computational tomography measurements of sulfide solid electrolyte were conducted to elucidate the behavior of a single particle. Chlorine in Li6PS5Cl solid electrolyte was replaced by iodine to obtain high-contrast X-ray computational tomography measurements, and the behavior of a single particle under high pressure was successfully visualized. The experimental results were statistically analyzed to extract the generalized behavior of a solid electrolyte particle. The results show that pressurization increased the contact area and sphericity of a solid electrolyte particle and suppressed the voids between and within the solid electrolyte particles, thereby enhancing ionic conductivity.

对硫化固体电解质进行了高压原位x射线计算机断层扫描测量,以阐明单个粒子的行为。用碘取代Li6PS5Cl固体电解质中的氯,获得高对比度x射线计算机断层扫描测量,并成功地可视化了高压下单个颗粒的行为。对实验结果进行统计分析,提取固体电解质颗粒的广义行为。结果表明,加压增加了固体电解质颗粒的接触面积和球形度,抑制了固体电解质颗粒之间和内部的空隙,从而提高了离子电导率。
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引用次数: 8
Cathode starvation as an accelerated conditioning procedure for perfluorosulfonic acid ionomer fuel cells 阴极饥饿作为全氟磺酸离聚体燃料电池的加速调理程序
IF 4.5 Q2 Energy Pub Date : 2020-06-01 DOI: 10.1016/j.powera.2020.100012
Emmanuel Balogun , Alejandro Oyarce Barnett , Steven Holdcroft

Freshly assembled proton exchange fuel cells (PEMFC) require conditioning to reach maximum power density. This process may last up to tens of hours and adds to the cost of commercial fuel cell technology. We present an accelerated conditioning procedure involving starving the cathode of oxidant. In single cells, this procedure conditions a membrane electrode assembly (MEA) within 40 min, without compromising durability. The performance and durability of MEAs conditioned using this technique are compared with US Department of Energy (DOE) and European Union (EU) harmonized protocols, and to an amperometric conditioning protocol. The time to reach peak power density using cathode starvation conditioning is <10% of the time required for DOE, EU, and amperometric protocols. Conditioned MEAs were subjected to accelerated degradation by cycling the cell voltage between 0.6 V and open-circuit voltage under low relative humidity. Degradation was found to be caused by loss of electrochemical surface area of the cathode, which in turn increases the charge transfer resistance of the MEA. MEAs conditioned using cathode starvation experienced only a 15% loss in performance; in contrast to 19, 17 and 17% losses in performance caused by the DOE, EU, and amperometric protocols, respectively.

新组装的质子交换燃料电池(PEMFC)需要调节以达到最大功率密度。这一过程可能持续长达数十小时,并增加了商业燃料电池技术的成本。我们提出了一种加速调节程序,包括饿死阴极的氧化剂。在单细胞中,该程序在40 min内调节膜电极组装(MEA),而不影响耐久性。使用该技术调节的mea的性能和耐久性与美国能源部(DOE)和欧盟(EU)协调协议以及安培调节协议进行了比较。使用阴极饥饿调节达到峰值功率密度的时间是DOE, EU和安培协议所需时间的10%。在低相对湿度条件下,通过将电池电压在0.6 V和开路电压之间循环,使条件化mea加速降解。降解是由阴极电化学表面积的损失引起的,这反过来又增加了MEA的电荷转移电阻。使用阴极饥饿条件的mea性能仅下降15%;相比之下,DOE、EU和安培方案分别造成了19%、17%和17%的性能损失。
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引用次数: 20
Atomic-scale studies of garnet-type Mg3Fe2Si3O12: Defect chemistry, diffusion and dopant properties 石榴石型Mg3Fe2Si3O12的原子尺度研究:缺陷化学、扩散和掺杂性能
IF 4.5 Q2 Energy Pub Date : 2020-06-01 DOI: 10.1016/j.powera.2020.100016
Navaratnarajah Kuganathan , Alexander Chroneos

Materials with low cost, environmentally benign, high structural stability and high Mg content are of considerable interest for the construction of rechargeable Mg-ion batteries. In the present study, atomistic simulations are used to provide insights into defect and diffusion properties of garnet type Mg3Fe2Si3O12. Calculations reveal that the Mg–Fe anti-site defect cluster (0.44 eV/defect) is the lowest energy intrinsic defect process. Three dimensional Mg-ion migration pathway with the activation energy of 2.19 eV suggests that Mg-ion diffusion in this material is slow. Favourable isovalent dopants are found to be Mn2+, Ga3+ and Ge4+ on the Mg, Fe and Si sites respectively. While the formation of Mg interstitials required for the capacity is facilitated by Al doping on the Si site, Mg vacancies needed for the vacancy assisted Mg-ion diffusion are enhanced by Ge doping on the Fe site. The electronic structures of favourable dopants are calculated and discussed using density functional theory.

低成本、环保、高结构稳定性和高镁含量的材料是构建可充电镁离子电池的重要研究方向。在本研究中,原子模拟被用于提供对石榴石型Mg3Fe2Si3O12的缺陷和扩散特性的见解。计算结果表明,Mg-Fe反位缺陷团簇(0.44 eV/defect)是能量最低的本构缺陷过程。三维mg离子迁移路径的活化能为2.19 eV,表明mg离子在该材料中的扩散较慢。在Mg、Fe和Si位点上,有利的同价掺杂剂分别是Mn2+、Ga3+和Ge4+。Al在Si位点上的掺杂促进了容量所需的Mg空位的形成,而Ge在Fe位点上的掺杂则增强了空位辅助Mg离子扩散所需的Mg空位。利用密度泛函理论对有利掺杂剂的电子结构进行了计算和讨论。
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引用次数: 2
Highly stable metal halide perovskite microcube anodes for lithium-air batteries 用于锂空气电池的高度稳定的金属卤化物钙钛矿微立方阳极
IF 4.5 Q2 Energy Pub Date : 2020-06-01 DOI: 10.1016/j.powera.2020.100015
Athanasia Kostopoulou , Dimitra Vernardou , Dimitra Makri , Konstantinos Brintakis , Kyriaki Savva , Emmanuel Stratakis

Metal halide perovskites have been recently proposed as hopeful materials for energy storage applications. Besides, the quite important electrochemical characteristics of these materials, all the perovskite-based anodes are synthesized at high temperatures (90–150 °C) and with reaction durations of the order of tens of hours. In this work, it has been particularly shown that the direct growth of all-inorganic, metal halide microcrystals free of ligands, provides high-performance and stable electrodes for Li-air batteries. We describe a very simple and rapid method to synthesize well-crystalline and ultra-stable, at both ambient and aqueous conditions, CsPbBr3 microcubes, exhibiting prominent electrochemical performance. In particular, it is shown that during the successive scans in which the Li-ions intercalate and deintercalate, the microcubes-based anodes showed a high specific capacity of 549 mAh·g−1 and operation durability up to 1500 cycles. The large interfacial area between the perovskite electroactive material and the electrolyte along with the increase of the active sites on the exposed microcubes facets favor the Li-ions intercalation. It is concluded that the anodes presented here demonstrate the best electrochemical features among the nano- and microparticulate lead halide perovskite anodes used for Li-air batteries, to date.

金属卤化物钙钛矿最近被提出作为储能应用的有希望的材料。此外,这些材料非常重要的电化学特性是,所有钙钛矿基阳极都是在高温(90-150 °C)下合成的,反应持续时间为数十小时。在这项工作中,已经特别表明,直接生长无配体的全无机金属卤化物微晶体,为锂-空气电池提供了高性能和稳定的电极。我们描述了一种非常简单和快速的方法来合成结晶良好和超稳定的CsPbBr3微立方体,在环境和水条件下都具有突出的电化学性能。特别是,在锂离子插入和脱插的连续扫描过程中,基于微立方的阳极显示出高达549 mAh·g−1的高比容量和高达1500次循环的工作耐久性。钙钛矿电活性材料与电解质之间的大界面面积以及暴露的微立方体表面活性位的增加有利于锂离子的插层。研究结果表明,在目前用于锂空气电池的纳米和微颗粒卤化铅钙钛矿阳极中,本文提出的阳极具有最好的电化学特性。
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引用次数: 17
Evaluation of counter and reference electrodes for the investigation of Ca battery materials 研究钙电池材料的反电极和参比电极的评价
IF 4.5 Q2 Energy Pub Date : 2020-04-01 DOI: 10.1016/j.powera.2020.100008
Xu Liu , Giuseppe Antonio Elia , Stefano Passerini

The growing needs for electrochemical storage systems are pushing the research community to explore alternatives to Li-ion technology. Ca-based chemistry is attracting more and more attention and expectation. However, the unsuitability of Ca metal as counter and reference electrodes limits the research activity on the topic. Herein we propose a simple electrochemical cell configuration employing activated carbon as counter and reference electrodes, which is suitable for positive electrode screening. The feasibility of this cell configuration has been confirmed by evaluating the electrochemical activity of bilayered-V2O5 in the Ca-ion system.

对电化学存储系统日益增长的需求正在推动研究界探索锂离子技术的替代品。钙基化学越来越受到人们的关注和期待。然而,金属钙作为计数电极和参比电极的不适用性限制了该课题的研究活动。本文提出了一种简单的电化学电池结构,采用活性炭作为对照电极和参比电极,适用于正极筛选。通过评价双层v2o5在钙离子体系中的电化学活性,证实了这种电池结构的可行性。
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引用次数: 10
Ni/NiFe2 dual-layer coating for SOFC steel interconnects application SOFC钢互连用Ni/NiFe2双层涂层
IF 4.5 Q2 Energy Pub Date : 2020-04-01 DOI: 10.1016/j.powera.2020.100011
Qingqing Zhao, Shujiang Geng, Xingye Gao, Gang Chen, Fuhui Wang

Ni/NiFe2 dual-layer coating is fabricated on SUS 430 stainless steel by magnetron sputtering for solid oxide fuel cells (SOFCs) interconnect application. Ni/NiFe2 coated steels are exposed to air at 800 °C for duration of up to 10 weeks in comparison with NiFe2 coated steels. Ni/NiFe2 coating is thermally converted to an oxide structure with an inner NiO layer and an outer NiFe2O4 spinel layer. NiO/NiFe2O4 oxide layer is more effective in blocking Cr migration and reducing oxidation rate during long-term exposure than a single NiFe2O4 layer converted from NiFe2 coating. Enhancements on oxidation resistance and Cr-blocking capability are attributed to NiO layer serving as a diffusion barrier between Cr2O3 and NiFe2O4.

采用磁控溅射技术在sus430不锈钢表面制备了Ni/NiFe2双层涂层,用于固体氧化物燃料电池(sofc)互连。与NiFe2涂层钢相比,Ni/NiFe2涂层钢暴露在800 °C的空气中持续时间长达10周。Ni/NiFe2涂层热转化为内部NiO层和外部NiFe2O4尖晶石层的氧化物结构。在长期暴露过程中,NiO/NiFe2O4氧化层比NiFe2涂层转化成单一NiFe2O4氧化层更有效地阻止Cr迁移和降低氧化速率。NiO层在Cr2O3和NiFe2O4之间起到了扩散屏障的作用,从而提高了材料的抗氧化性能和阻cr性能。
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引用次数: 11
A rapid mechanical durability test for reinforced fuel cell membranes 增强燃料电池膜的快速机械耐久性试验
IF 4.5 Q2 Energy Pub Date : 2020-04-01 DOI: 10.1016/j.powera.2020.100010
Alireza Sadeghi Alavijeh , Sandeep Bhattacharya , Owen Thomas , Carmen Chuy , Erik Kjeang

An in situ accelerated mechanical stress test (ΔP-AMST) that applies relative humidity (RH) cycling combined with a pressure differential (ΔP) at a high temperature is proposed to accelerate mechanical degradation in all types of reinforced membranes used in fuel cells and obtain mechanical failure in a relatively short time. For validation, ePTFE reinforced membranes are mechanically degraded by RH cycling accelerated by means of a ΔP applied from cathode to anode using a custom designed polycarbonate spacer. Reinforced membrane failure detected by ΔP loss is reached within ∼10 to 10,000 RH cycles using this method, depending on the level of applied ΔP. The ΔP-AMST protocol is hence demonstrated as a fast, economical in situ alternative compared to existing methods for evaluating the mechanical fatigue durability of advanced fuel cell membranes.

提出了一种在高温下应用相对湿度(RH)循环结合压差(ΔP)的原位加速机械应力测试(ΔP-AMST),以加速燃料电池中使用的所有类型的增强膜的机械降解,并在相对较短的时间内获得机械失效。为了验证,ePTFE增强膜通过使用定制设计的聚碳酸酯间隔剂从阴极到阳极施加ΔP,通过RH循环加速机械降解。通过ΔP损耗检测到的增强膜失效在使用该方法的~ 10至10,000 RH循环内达到,具体取决于施加的水平ΔP。因此,与现有的评估先进燃料电池膜机械疲劳耐久性的方法相比,ΔP-AMST方案被证明是一种快速、经济的原位替代方法。
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引用次数: 3
Efficiency analysis of 50 kWe SOFC systems fueled with biogas from waste water 以废水沼气为燃料的50kwe SOFC系统效率分析
IF 4.5 Q2 Energy Pub Date : 2020-04-01 DOI: 10.1016/j.powera.2020.100009
Hendrik Langnickel , Markus Rautanen , Marta Gandiglio , Massimo Santarelli , Tuomas Hakala , Marco Acri , Jari Kiviaho

Solid oxide fuel cell systems (SOFCs) are able to convert biogas from e.g. waste water plants highly efficiently into electricity and heat. An efficiency study of industrial sized solid oxide fuel cell systems installed at a waste water treatment plant is presented. The site consist of a biogas cleaning unit, two Convion C50 SOFC systems and a heat recovery section. The electric and total efficiencies of the systems are analyzed as a function of the electric net power output. The two systems achieved consistently high electric (50–55%) and total (80–90%) efficiencies in an electric net power output range between 25 kW and 55 kW. The study also shows that the high system efficiencies are independent of the CH4 content in the biogas. The results indicate that fuel cell systems are able to perform power modulation according to the power demand, while achieving constant high efficiencies. This is a clear benefit in comparison to micro turbines and combustion engines which are normally used for converting biogas into electricity and heat.

固体氧化物燃料电池系统(sofc)能够高效地将废水厂的沼气转化为电能和热能。介绍了工业规模固体氧化物燃料电池系统在污水处理厂的效率研究。该基地由一个沼气净化装置、两个Convion C50 SOFC系统和一个热回收部分组成。系统的电力效率和总效率作为净电力输出的函数进行了分析。这两个系统在25 kW和55 kW之间的净电力输出范围内实现了持续的高电力效率(50-55%)和总效率(80-90%)。研究还表明,系统的高效率与沼气中的CH4含量无关。结果表明,燃料电池系统能够根据功率需求进行功率调制,同时实现恒定的高效率。与通常用于将沼气转化为电能和热能的微型涡轮机和内燃机相比,这是一个明显的优势。
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引用次数: 17
Numerical simulation of mass transfer enhancement in liquid metal batteries by means of electro-vortex flow 电涡流增强液态金属电池传质的数值模拟
IF 4.5 Q2 Energy Pub Date : 2020-02-01 DOI: 10.1016/j.powera.2020.100004
Norbert Weber , Michael Nimtz , Paolo Personnettaz , Tom Weier , Donald Sadoway

Mass transfer is of paramount importance for an efficient operation of liquid metal batteries. We show for the first time that electrodynamically driven flow can indeed improve mixing of liquid electrodes, and reduces concentration polarisation substantially. Simulating the discharge of a realistic Li||Bi cell at 1 A/cm2, the corresponding overpotential reduces by up to 62%. Moreover, the formation of intermetallic phases is delayed, which improves capacity usage. Finally, we demonstrate that vertical magnetic fields – which are originating from external sources – change the flow structure entirely, and will homogenise the positive electrode even better.

传质对液态金属电池的高效运行至关重要。我们首次表明,电动力驱动的流动确实可以改善液体电极的混合,并大大减少浓度极化。模拟实际锂铋电池在1 a /cm2下的放电,相应的过电位降低高达62%。此外,延迟了金属间相的形成,提高了容量利用率。最后,我们证明了垂直磁场——来自外部源——完全改变了流动结构,并将更好地使正极均匀化。
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引用次数: 21
期刊
Journal of Power Sources Advances
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