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固体氧化物燃料电池 8

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Localized high-concentration electrolytes for lithium metal batteries: progress and prospect

《化学科学与工程前沿（英文）》 2023年 第17卷 第10期   页码 1354-1371 doi: 10.1007/s11705-022-2286-4

摘要： With the increasing development of digital devices and electric vehicles, high energy-density rechargeable batteries are strongly required. As one of the most promising anode materials with an ultrahigh specific capacity and extremely low electrode potential, lithium metal is greatly considered an ideal candidate for next-generation battery systems. Nevertheless, limited Coulombic efficiency and potential safety risks severely hinder the practical applications of lithium metal batteries due to the inevitable growth of lithium dendrites and poor interface stability. Tremendous efforts have been explored to address these challenges, mainly focusing on the design of novel electrolytes. Here, we provide an overview of the recent developments of localized high-concentration electrolytes in lithium metal batteries. Firstly, the solvation structures and physicochemical properties of localized high-concentration electrolytes are analyzed. Then, the developments of localized high-concentration electrolytes to suppress the formation of dendritic lithium, broaden the voltage window of electrolytes, enhance safety, and render low-temperature operation for robust lithium metal batteries are discussed. Lastly, the remaining challenges and further possible research directions for localized high-concentration electrolytes are outlined, which can promisingly render the practical applications of lithium metal batteries.

关键词： high-concentration electrolyte     localized high-concentration electrolyte     lithium metal battery     solid electrolyte interphase     dendrite    

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Recent advances toward high voltage, EC-free electrolytes for graphite-based Li-ion battery

Tong Zhang, Elie Paillard

《化学科学与工程前沿（英文）》 2018年 第12卷 第3期   页码 577-591 doi: 10.1007/s11705-018-1758-z

摘要：

Lithium-ion batteries are a key technology in today’s world and improving their performances requires, in many cases, the use of cathodes operating above the anodic stability of state-of-the-art electrolytes based on ethylene carbonate (EC) mixtures. EC, however, is a crucial component of electrolytes, due to its excellent ability to allow graphite anode operation–also required for high energy density batteries–by stabilizing the electrode/electrolyte interface. In the last years, many alternative electrolytes, aiming at allowing high voltage battery operation, have been proposed. However, often, graphite electrode operation is not well demonstrated in these electrolytes. Thus, we review here the high voltage, EC-free alternative electrolytes, focusing on those allowing the steady operation of graphite anodes. This review covers electrolyte compositions, with the widespread use of additives, the change in main lithium salt, the effect of anion (or Li salt) concentration, but also reports on graphite protection strategies, by coatings or artificial solid electrolyte interphase (SEI) or by use of water-soluble binder for electrode processing as these can also enable the use of graphite in electrolytes with suboptimal intrinsic SEI formation ability.

关键词： lithium-ion     electrolyte     solid electrolyte interphase     additives     high voltage     graphite    

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A review on the development of electrolytes for lithium-based batteries for low temperature applications

《能源前沿（英文）》 2023年 第17卷 第1期   页码 43-71 doi: 10.1007/s11708-022-0853-5

摘要： The aerospace industry relies heavily on lithium-ion batteries in instrumentation such as satellites and land rovers. This equipment is exposed to extremely low temperatures in space or on the Martian surface. The extremely low temperatures affect the discharge characteristics of the battery and decrease its available working capacity. Various solvents, cosolvents, additives, and salts have been researched to fine tune the conductivity, solvation, and solid-electrolyte interface forming properties of the electrolytes. Several different resistive phenomena have been investigated to precisely determine the most limiting steps during charge and discharge at low temperatures. Longer mission lifespans as well as self-reliance on the chemistry are now highly desirable to allow low temperature performance rather than rely on external heating components. As Martian rovers are equipped with greater instrumentation and demands for greater energy storage rise, new materials also need to be adopted involving next generation lithium-ion chemistry to increase available capacity. With these objectives in mind, tailoring of the electrolyte with higher-capacity materials such as lithium metal and silicon anodes at low temperatures is of high priority. This review paper highlights the progression of electrolyte research for low temperature performance of lithium-ion batteries over the previous several decades.

关键词： electrolyte     lithium-ion     low temperature     aerospace     solid-electrolyte interface    

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固体氧化物燃料电池的电解质及电极材料的电导率研究方法

贺贝贝,潘 鑫,夏长荣

《中国工程科学》 2013年 第15卷 第2期   页码 57-65

摘要：

论述了晶体材料，重点是固体氧化物燃料电池组件的导电机理，介绍了影响电导率的几个因素。针对不同的电解质和电极材料，讨论了几种常用的测量电解质和电极总电导率、电子电导率以及离子电导率的方法，并指出在测量中需要注意的问题。

关键词： 导电机理     电解质     电极     电导率     固体氧化物燃料电池    

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Ion conduction path in composite solid electrolytes for lithium metal batteries: from polymer rich to

Zhouyu ZHANG, Hao CHEN, Zhenglin HU, Shoubin ZHOU, Lan ZHANG, Jiayan LUO

《能源前沿（英文）》 2022年 第16卷 第5期   页码 706-733 doi: 10.1007/s11708-022-0833-9

摘要： Solid-state electrolytes (SSEs) can address the safety issue of organic electrolyte in rechargeable lithium batteries. Unfortunately, neither polymer nor ceramic SSEs used alone can meet the demand although great progress has been made in the past few years. Composite solid electrolytes (CSEs) composed of flexible polymers and brittle but more conducting ceramics can take advantage of the individual system for solid-state lithium metal batteries (SSLMBs). CSEs can be largely divided into two categories by the mass fraction of the components: “polymer rich” (PR) and “ceramic rich” (CR) systems with different internal structures and electrochemical properties. This review provides a comprehensive and in-depth understanding of recent advances and limitations of both PR and CR electrolytes, with a special focus on the ion conduction path based on polymer-ceramic interaction mechanisms and structural designs of ceramic fillers/frameworks. In addition, it highlights the PR and CR which bring the leverage between the electrochemical property and the mechanical property. Moreover, it further prospects the possible route for future development of CSEs according to their rational design, which is expected to accelerate the practical application of SSLMBs.

关键词： composite solid electrolytes     active filler/framework     ion conduction path     interphase compatibility     multilayer design    

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低温固体氧化物燃料电池的复合电解质材料

谢富丞,王诚,毛宗强

《中国工程科学》 2013年 第15卷 第2期   页码 72-76

摘要：

固体氧化物燃料电池（SOFC）是一种高效、环保的发电装置。低温化是SOFC的主要发展方向。探索适合在低温（400~600 ℃）条件下操作的高性能电解质材料是SOFC低温化发展的关键。近年来，研究人员发展了新型的复合电解质材料，取得了较好的成果。本文综述了近年来低温SOFC复合电解质材料的研究进展，简要介绍了复合电解质材料的特点、类型和传导机理。

关键词： 低温SOFC     复合电解质     传导机理    

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Boosting the direct conversion of NHHCO electrolyte to syngas on Ag/Zn zeolitic imidazolate framework

《化学科学与工程前沿（英文）》 2023年 第17卷 第9期   页码 1196-1207 doi: 10.1007/s11705-022-2289-1

摘要： The electrochemical reduction of NH4HCO3 to syngas can bypass the high energy consumption of high-purity CO2 release and compression after the ammonia-based CO2 capture process. This technology has broad prospects in industrial applications and carbon neutrality. A zeolitic imidazolate framework-8 precursor was introduced with different Ag contents via colloid chemical synthesis. This material was carbonized at 1000 °C to obtain AgZn zeolitic imidazolate framework derived nitrogen carbon catalysts, which were used for the first time for boosting the direct conversion of NH4HCO3 electrolyte to syngas. The AgZn zeolitic imidazolate framework derived nitrogen carbon catalyst with a Ag/Zn ratio of 0.5:1 achieved the highest CO Faradaic efficiency of 52.0% with a current density of 1.15 mA·cm–2 at –0.5 V, a H2/CO ratio of 1–2 (–0.5 to –0.7 V), and a stable catalytic activity of more than 6 h. Its activity is comparable to that of the CO2-saturated NH4HCO3 electrolyte. The highly discrete Ag-Nx and Zn-Nx nodes may have combined catalytic effects in the catalysts synthesized by appropriate Ag doping and sufficient carbonization. These nodes could increase active sites of catalysts, which is conducive to the transport and adsorption of reactant CO2 and the stability of *COOH intermediate, thus can improve the selectivity and catalytic activity of CO.

关键词： Ag catalyst     zeolitic imidazolate framework     CO2 electroreduction     ammonium bicarbonate electrolyte     syngas    

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金属支撑型固体氧化物燃料电池研究进展

周永川,宋世栋,韩敏芳

《中国工程科学》 2013年 第15卷 第2期   页码 27-32

摘要：

随着固体氧化物燃料电池(SOFC)向中低温发展，使得金属材料用于SOFC的关键组件成为可能。金属支撑型SOFC（MS-SOFC）是以金属或合金作为燃料电池支撑体的结构。相对于其他支撑型SOFC，MS-SOFC具有更好的导电能力和导热能力、较高的机械强度以及较低的成本，所以引起了研究人员的广泛关注。目前，MS-SOFC的结构呈多样化发展，支撑体、电极和电解质的材料及其制备工艺也不尽相同。本文介绍了不同结构的MS-SOFC的研究现状，评述了它们各自的制备工艺和存在的问题，并提出了目前MS-SOFC亟需解决的问题。

关键词： 固体氧化物燃料电池     金属支撑型SOFC     薄膜电解质     热循环     快速启动    

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钠超离子导体型固体电解质的改性及其在钠离子电池中的应用 Article

张强强, 周权, 陆雅翔, 邵元骏, 戚钰若, 戚兴国, 钟贵明, 杨勇, 陈立泉, 胡勇胜

《工程（英文）》 2022年 第8卷 第1期   页码 170-180 doi: 10.1016/j.eng.2021.04.028

摘要：

固体电解质的低离子电导率及固体电解质与固态电极之间较差的界面可靠性是阻碍固态钠电池（SSSB）应用的两大紧迫挑战。本文采用简单的两步固相法合成了名义成分为Na3+2xZr2‒xMgxSi2PO12 的钠（Na）超离子导体（NASICON）型固体电解质，其中在25 ℃时Na3.3Zr1.85Mg0.15Si2PO12（x=0.15, NZSP-Mg0.15)表现出了3.54 mS∙cm‒1的最高离子电导率。通过深入研究，本文证实晶界成分在决定NASICON总离子电导率中起着至关重要的作用。此外，由于文献中缺乏关于NASICON是否能够提供足够的阳极电化学稳定性来实现高压固态钠电池的研究，我们首先使用了高压Na3(VOPO4)2F (NVOPF)正极来验证其与优化后的NZSP-Mg0.15固体电解质之间的兼容性。通过比较不同配置（低压阴极与高压阴极、液态电解质与固体电解质）电池的电化学性能，以及对循环后的NZSP-Mg0.15进行X射线光电子能谱（XPS）评估，结果表明，NASICON固体电解质在高电压下不够稳定，这证明了研究NASICON固体电解质和高压阴极之间界面的重要性。此外，通过将NZSP-Mg0.15 NASICON 粉末涂在聚乙烯（PE）隔膜（PE@NASICON）上，形成了2.42 A∙h 的碳|PE@NASICON|NaNi2/9Cu1/9Fe1/3Mn1/3O2 非水系钠离子电池，其具有出色的循环性能，在2000 周循环后容量保持率为88%，从而证明涂有NASICON型固体电解质的隔膜具有高可靠性。

关键词： 固态电解质     固态钠电池     NASICON     界面     隔膜     涂层    

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Effect of electrolyte concentration on the tribological performance of MAO coatings on aluminum alloys

Chao Wang, Jun Chen, Jihua He, Jing Jiang, Qinyong Zhang

《化学科学与工程前沿（英文）》 2020年 第14卷 第6期   页码 1065-1071 doi: 10.1007/s11705-019-1909-x

摘要： Micro-arc oxidation (MAO) is an efficient approach to improve the hardness, wear resistance, and other properties of aluminum alloys. In order to investigate the effect of the electrolyte concentration on the properties of MAO coatings for LY12 alloy, the voltage variation during the MAO process was recorded. The surface morphologies and phase compositions of the coatings produced with different electrolytes were investigated using scanning electron microscopy and X-ray diffraction, respectively. The roughness and thickness of the coatings were measured using a pocket roughness meter and an eddy-current thickness meter, respectively. The tribological performances of the coatings were investigated against GCr15 bearing steel on a ball-on-disc wear tester in open air. The results showed that with an increase in the Na SiO content, the working voltage of the MAO process decreased, the roughness and thickness of the coatings increased significantly, and the relative content of the -Al O phase decreased. With an increase in the KOH content, the working voltage decreased slightly, the roughness and thickness of the coatings increased slightly, and the α- and -Al O phase contents remained unchanged. The friction coefficient and wear rate of the coatings increased with an increase in the Na SiO and KOH concentrations. A decrease in the porosity and roughness and an increase in the α-Al O content of the coatings reduced their wear mass loss.

关键词： aluminum alloy     micro-arc oxidation     coating     electrolyte concentration     tribological performance    

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低碳钛、钒微合金钢中的相间析出

贾涛,魏娇,冯洁,张维娜,刘振宇,王国栋

《中国工程科学》 2014年 第16卷 第1期   页码 88-92

摘要：

针对目前较少关注的Ti-V微合金体系，在Formaster—FII 膨胀仪上进行奥氏体/铁素体两相区等温，在铁素体相变同时获得Ti、V复合相间析出。采用金相、透射电子显微镜对显微组织、尤其是相间析出形貌、及其与铁素体基体的位向关系进行了观察与分析。研究表明，650 ℃为静态等温相变的鼻温点，相间析出呈层状分布，具有平面和曲面两种形貌，相间析出碳化物与铁素体基体之间存在Baker-Nutting 取向关系。

关键词： Ti-V微合金钢     相间析出     等温相变     透射电子显微镜    

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Review of characterization and modeling of polymer electrolyte fuel cell catalyst layer: The blessing

Jun HUANG, Zhe LI, Jianbo ZHANG

《能源前沿（英文）》 2017年 第11卷 第3期   页码 334-364 doi: 10.1007/s11708-017-0490-6

摘要： Ionomer impregnation represents a milestone in the evolution of polymer electrolyte fuel cell (PEFC) catalyst layers. Ionomer acts as the binder, facilitates proton transport, and thereby drastically improves catalyst utilization and effectiveness. However, advanced morphological and functional characterizations have revealed that up to 60% of Pt nanoparticles can be trapped in the micropores of carbon support particles. Ionomer clusters and oxygen molecules can hardly enter into micropores, leading to low Pt utilization and effectiveness. Moreover, the ionomer thin-films covering Pt nanoparticles can cause significant mass transport loss especially at high current densities. Ionomer-free ultra-thin catalyst layers (UTCLs) emerge as a promising alternative to reduce Pt loading by improving catalyst utilization and effectiveness, while theoretical issues such as the proton conduction mechanism remain puzzling and practical issues such as the rather narrow operation window remain unsettled. At present, the development of PEFC catalyst layer has come to a crossroads: staying ionomer-impregnated or going ionomer-free. It is always beneficial to look back into the past when coming to a crossroads. This paper addresses the characterization and modeling of both the conventional ionomer-impregnated catalyst layer and the emerging ionomer-free UTCLs, featuring advances in characterizing microscale distributions of Pt particles, ionomer, support particles and unraveling their interactions; advances in fundamental understandings of proton conduction and flooding behaviors in ionomer-free UTCLs; advances in modeling of conventional catalyst layers and especially UTCLs; and discussions on high-impact research topics in characterizing and modeling of catalyst layers.

关键词： polymer electrolyte fuel cell     ultra-thin catalyst layer     electrostatic interactions     characterization and modeling     structure-property-performance relation     water management    

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Characterization and comparison of organic functional groups effects on electrolyte performance for vanadium

《化学科学与工程前沿（英文）》 2023年 第17卷 第9期   页码 1221-1230 doi: 10.1007/s11705-023-2298-8

摘要： The vanadium redox flow battery with a safe and capacity-controllable large-scale energy storage system offers a new method for the sustainability. In this case, acetic acid, methane sulfonic acid, sulfonic acid, amino methane sulfonic acid, and taurine are used to overcome the low electrolyte energy density and stability limitations, as well as to investigate the effects of various organic functional groups on the vanadium redox flow battery. When compared to the pristine electrolyte (0.22 Ah, 5.0 Wh·L–1, 85.0%), the results show that taurine has the advantage of maintaining vanadium ion concentrations, discharge capacity (1.43 Ah), energy density (33.9 Wh·L–1), and energy efficiency (90.5%) even after several cycles. The acetic acid electrolyte is more conducive to the low-temperature stability of the V(II) electrolyte (177 h at −25 °C) than pristine (82 h at −2 °C). The –SO3H group, specifically the coaction of the –NH2 and –SO3H groups, improves electrolyte stability. The –NH2 and –COOH additive groups improved conductivity and electrochemical activity.

关键词： vanadium redox flow battery     functional groups     organic additives     energy density     stability    

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Chemical composition and formation mechanisms in the cathode-electrolyte interface layer of lithium manganese

Sahithya REDDIVARI, Christian LASTOSKIE, Ruofei WU, Junliang ZHANG

《能源前沿（英文）》 2017年 第11卷 第3期   页码 365-373 doi: 10.1007/s11708-017-0500-8

摘要： Lithium manganese oxide (LiMn O ) is a principal cathode material for high power and high energy density electrochemical storage on account of its low cost, non-toxicity, and ease of preparation relative to other cathode materials. However, there are well-documented problems with capacity fade of lithium ion batteries containing LiMn O . Experimental observations indicate that the manganese content of the electrolyte increases as an electrochemical cell containing LiMn O ages, suggesting that active material loss by dissolution of divalent manganese from the LiMn O surface is the primary reason for reduced cell life in LiMn O batteries. To improve the retention of manganese in the active material, it is key to understand the reactions that occur at the cathode surface. Although a thin layer of electrolyte decomposition products is known to form at the cathode surface, the speciation and reaction mechanisms of Mn in this interface layer are not yet well understood. To bridge this knowledge gap, reactive force field (ReaxFF) based molecular dynamics was applied to investigate the reactions occurring at the LiMn O cathode surface and the mechanisms that lead to manganese dissolution. The ReaxFFMD simulations reveal that the cathode-electrolyte interface layer is composed of oxidation products of electrolyte solvent molecules including aldehydes, esters, alcohols, polycarbonates, and organic radicals. The oxidation reaction pathways for the electrolyte solvent molecules involve the formation of surface hydroxyl species that react with exposed manganese atoms on the cathode surface. The presence of hydrogen fluoride (HF) induces formation of inorganic metal fluorides and surface hydroxyl species. Reaction products predicted by ReaxFF-based MD are in agreement with experimentally identified cathode-electrolyte interface compounds. An overall cathode-electrolyte interface reaction scheme is proposed based on the molecular simulation results.

关键词： lithium manganese oxide batteries     reactive force field (ReaxFF)     cathode-electrolyte interface layer     molecular dynamics    

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下一代锂电池在能源化学工程方面的研究进展 Review

张学强, 赵辰孜, 黄佳琦, 张强

《工程（英文）》 2018年 第4卷 第6期   页码 831-847 doi: 10.1016/j.eng.2018.10.008

摘要：

锂离子电池（LIB）对当今人们的生活产生了深远的影响。然而由于插层化学本质上的限制，锂离子电池的能量密度已接近理论上限，难以满足人们在多方面日益增长的储能需求，如便携式电子设备、电动汽车和大规模储能。因此，下一代锂（Li）电池正在广泛研究中。其中，采用金属锂作为负极，插层或转化型材料作为正极的下一代锂电池是最受关注的体系，因其具有高能量密度和巨大的商业化潜力。近年来，随着材料和反应机理方面研究的深入以及技术手段的进步，锂电池取得了不断的发展。本文从下一代锂电池的电解液/ 电解质的设计出发，从能源化学工程的角度梳理锂离子电池、锂硫电池和锂空电池中的关键科学问题和研究进展，并阐述下一代锂电池未来的发展方向。下一代锂电池有望促进人类文明的可持续发展。

关键词： 锂离子电池     锂硫电池     锂空电池     锂金属     固态电池     电池化学     电解质    

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标题 作者 时间 类型 操作

Localized high-concentration electrolytes for lithium metal batteries: progress and prospect

期刊论文

Recent advances toward high voltage, EC-free electrolytes for graphite-based Li-ion battery

Tong Zhang, Elie Paillard

期刊论文

A review on the development of electrolytes for lithium-based batteries for low temperature applications

期刊论文

固体氧化物燃料电池的电解质及电极材料的电导率研究方法

贺贝贝,潘 鑫,夏长荣

期刊论文

Ion conduction path in composite solid electrolytes for lithium metal batteries: from polymer rich to

Zhouyu ZHANG, Hao CHEN, Zhenglin HU, Shoubin ZHOU, Lan ZHANG, Jiayan LUO

期刊论文

低温固体氧化物燃料电池的复合电解质材料

谢富丞,王诚,毛宗强

期刊论文

Boosting the direct conversion of NHHCO electrolyte to syngas on Ag/Zn zeolitic imidazolate framework

期刊论文

金属支撑型固体氧化物燃料电池研究进展

周永川,宋世栋,韩敏芳

期刊论文

钠超离子导体型固体电解质的改性及其在钠离子电池中的应用

张强强, 周权, 陆雅翔, 邵元骏, 戚钰若, 戚兴国, 钟贵明, 杨勇, 陈立泉, 胡勇胜

期刊论文

Effect of electrolyte concentration on the tribological performance of MAO coatings on aluminum alloys

Chao Wang, Jun Chen, Jihua He, Jing Jiang, Qinyong Zhang

期刊论文

低碳钛、钒微合金钢中的相间析出

贾涛,魏娇,冯洁,张维娜,刘振宇,王国栋

期刊论文

Review of characterization and modeling of polymer electrolyte fuel cell catalyst layer: The blessing

Jun HUANG, Zhe LI, Jianbo ZHANG

期刊论文

Characterization and comparison of organic functional groups effects on electrolyte performance for vanadium

期刊论文

Chemical composition and formation mechanisms in the cathode-electrolyte interface layer of lithium manganese

Sahithya REDDIVARI, Christian LASTOSKIE, Ruofei WU, Junliang ZHANG

期刊论文

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