Solid State Ionics最新文献_第8页

Dopant synergy vs. competition in codoped Li7La3Zr2O12 garnet solid electrolytes 共掺杂Li7La3Zr2O12石榴石固体电解质中掺杂剂的协同与竞争

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-06 DOI: 10.1016/j.ssi.2025.117014

Ethan Anderson, Julie Cagnard, Rustam Z. Khaliullin, Eric McCalla

LLZO is typically singly doped with Ga or Ta to reach ionic conductivities over 1 mS/cm, and some recent studies have examined the potential conductivity benefits of codoping the material. However, to date codoped LLZO fails to out-perform singly doped LLZO in terms of conductivity, and no study has sufficiently explored the consequences on other necessary properties. We have previously screened 59 possible single dopants to determine their impact on these properties. No single dopant addresses all requirements, thus, here we explore triple doping. We choose Ga for high ionic conductivity and low electronic conductivity, Dy for high voltage stability, and Ti for low voltage stability. The benefits and tradeoffs of codoping are determined with 64 samples spanning the triple doping space. We find fundamental limitations to codoping. The high ionic conductivity of Ga-doped LLZO is lowered by the addition of the other dopants, though this is mitigated partly by increased Ga levels. Electronic conductivity, by contrast, shows that a critical level of Ga is needed to obtain low conductivities, and this is resilient to the other dopants such that codoping is effective here. By contrast, the high voltage stability is systematically limited by the poor performance of Ga, and Dy is not effective in overcoming this, but Ti alone does help the low voltage stability of the Ga containing materials. These fundamental limitations suggest that multilayer designs will likely be required for viable solid batteries.

LLZO通常单独掺杂Ga或Ta以达到超过1 mS/cm的离子电导率，最近的一些研究已经检测了共掺杂材料的潜在电导率效益。然而，迄今为止，共掺杂LLZO在电导率方面未能优于单掺杂LLZO，并且没有研究充分探讨对其他必要性质的影响。我们之前已经筛选了59种可能的单一掺杂剂来确定它们对这些特性的影响。没有一种掺杂剂能满足所有要求，因此，我们在这里探索三重掺杂。我们选择Ga具有高离子电导率和低电子电导率，Dy具有高电压稳定性，Ti具有低电压稳定性。共掺杂的好处和权衡是确定64个样品跨越三种掺杂空间。我们发现了共掺杂的基本限制。添加其他掺杂剂降低了Ga掺杂LLZO的高离子电导率，尽管这可以通过增加Ga水平部分地减轻。相比之下，电子电导率表明，获得低电导率需要临界水平的Ga，并且这对其他掺杂具有弹性，因此共掺杂在这里是有效的。相比之下，高电压稳定性系统地受到Ga性能差的限制，并且Dy不能有效地克服这一点，但单独使用Ti确实有助于含Ga材料的低电压稳定性。这些基本限制表明，可行的固体电池可能需要多层设计。

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引用次数: 0

Editorial for 24th International conference on Solid State Ionics (SSI-24) 第24届国际固体离子会议论文集（si -24）

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-05 DOI: 10.1016/j.ssi.2025.117012

John Kilner , Stephen J. Skinner , William C. Chueh

引用次数: 0

Interface issues for advanced all-solid-state batteries researched under Interface Ionics 界面离子学研究先进全固态电池的界面问题

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-04 DOI: 10.1016/j.ssi.2025.117013

Yasutoshi Iriyama, Takeshi Yajima, Norikazu Ishigaki

All-solid-state batteries are expected as next generation rechargeable batteries. The SSBs apply solid electrolyte and then several factors such as electrical, chemical, mechanical, and electrochemical factors around the interface influence on the charge-discharge performances of the SSBs. This paper briefly reviews interface issues for advanced all-solid-state batteries reearched under a project of Japan Society for the Promotion of Science (JSPS) named as Interface Ionics at 2019–2023. The topics is focused on interface issues arising at the interface bonding process and at the charging reactions. Also, some of the related other topics will be shortly introduced.

全固态电池有望成为下一代可充电电池。SSBs采用固体电解质，界面周围的电学、化学、力学和电化学等因素对SSBs的充放电性能有影响。本文简要回顾了日本科学促进会（JSPS） 2019-2023年“界面离子学”项目下研究的先进全固态电池的界面问题。主题集中在界面键合过程和充电反应中出现的界面问题。此外，还将简要介绍一些相关的其他主题。

引用次数: 0

Effect of hydration level on zinc electrolyte properties 水化水平对锌电解质性能的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-03 DOI: 10.1016/j.ssi.2025.117011

Alireza Mashayekhi

We study zinc (Zn) plating and stripping in zinc cells using various compositions of hydrated zinc chloride (ZnCl₂·nH₂O) electrolyte (n = 10, n = 2.33, n = 1.5) at temperatures from −10 °C to 40 °C. The effect of deposition temperature on nuclei size, nucleation density, and growth of deposited Zn metal is studied by ex-situ microscopy investigations. Lowering the deposition temperature leads to smaller nuclei, higher nucleation density, and smoother zinc growth, forming a dendrite-free electrode surface. Compact and smooth zinc deposits contribute to long-term stability. There is no change in overpotential for the cell at −10 °C for more than 400 h. Long-term Zn deposition in Zn/Cu cells achieves an average coulombic efficiency (CE) of 99.2 % in the last 50 cycles using ZnCl₂·10H₂O electrolyte. The performance of electrolytes is evaluated in zinc-ion batteries with (zinc hexacyanoferrate) ZnHCF cathodes. The electrochemical studies show that the capacity of our zinc-ion battery in molten hydrated electrolytes increases from 17 mAh g⁻¹ at −10 °C to 72 mAh g⁻¹ at 40 °C, using n = 10 and n = 1.5 compositions of molten ZnCl₂ electrolyte. Increasing the temperature to 40 °C yields a high capacity and long-life zinc-ion battery. This research advances understanding of temperature-dependent molten hydrated electrolyte systems for zinc batteries.

我们研究了锌电池中锌（Zn）的电镀和剥离，使用不同组成的水合氯化锌（ZnCl₂·nH₂O）电解质（n = 10, n = 2.33, n = 1.5），温度从- 10°C到40°C。采用非原位显微镜研究了沉积温度对锌金属核尺寸、成核密度和生长的影响。降低沉积温度可以使锌的核更小，成核密度更高，锌的生长更平滑，形成无枝晶的电极表面。致密光滑的锌矿有助于长期稳定。在−10°C下，电池的过电位在400小时内没有变化。在使用ZnCl₂·10H₂O电解质的情况下，锌/铜电池中的长期锌沉积在过去50个循环中达到了99.2%的平均库仑效率（CE）。在采用（六氰高铁锌）ZnHCF阴极的锌离子电池中，对电解质的性能进行了评价。电化学研究表明，在n = 10和n = 1.5的ZnCl 2溶液中，锌离子电池的容量从- 10°C时的17 mAh g−1增加到40°C时的72 mAh g−1。将温度提高到40°C可以得到高容量和长寿命的锌离子电池。这项研究促进了对锌电池温度依赖的熔融水合电解质系统的理解。

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引用次数: 0

Effect of iron‑phosphorus ratio on the structure and electrochemical performance of non-stoichiometric carbon-coated LiFePO4 cathode materials 铁磷比对非化学计量碳包覆LiFePO4正极材料结构和电化学性能的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-02 DOI: 10.1016/j.ssi.2025.117009

Zijun Fang , Guorong Hu , Ke Du , Zhongdong Peng , Quanjun Fu , Haifeng Wang , Xiyuan Jiang , Yanbing Cao

In this paper, non-stoichiometric LiFe_xPO₄/C (x = 0.965, 0.97, 0.975, 0.98) was prepared by high-temperature solid-phase method combined with spray drying. The effects of regulating Fe/P ratio on the crystal structure, morphology and electrochemical properties of LiFePO₄ cathode materials were studied. The structure and morphology of the synthesized materials were characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). The results show that the Fe/P ratio has a great influence on the lattice parameters, micro-stress and degree of antisite defects of LiFePO₄ in structure; it also affects the particle size and carbon layer quality in morphology. Therefore, among the four stoichiometric ratios in the experiment, LiFe_0.97PO₄/C has the most stable crystal structure and the best carbon layer quality, and exhibits the best electrochemical performance, with a discharge capacity of 159.23 mAh/g at a 0.1C rate, a discharge capacity of 122 mAh/g at a 5C rate, and a maximum lithium ion diffusion coefficient of 1.22 × 10⁻¹⁴ cm² s⁻¹.

本文采用高温固相法结合喷雾干燥法制备了非化学计量的LiFexPO4/C （x = 0.965, 0.97, 0.975, 0.98）。研究了铁磷比对LiFePO4正极材料晶体结构、形貌和电化学性能的影响。利用x射线衍射仪（XRD）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）对合成材料的结构和形貌进行了表征。结果表明：铁磷比对LiFePO4的晶格参数、微观应力和结构反位缺陷程度有较大影响；在形貌上也影响颗粒大小和碳层质量。因此，在实验的四种化学计量比中，LiFe0.97PO4/C具有最稳定的晶体结构和最佳的碳层质量，并表现出最佳的电化学性能，在0.1C倍率下放电容量为159.23 mAh/g，在5C倍率下放电容量为122 mAh/g，最大锂离子扩散系数为1.22 × 10−14 cm2 s−1。

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引用次数: 0

A mechanistic perspective of anion intercalation in graphite cathodes for dual-ion batteries 双离子电池负离子插入石墨负极的机理研究

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-02 DOI: 10.1016/j.ssi.2025.117010

Zexin Su , Yuanyuan Yang , Yuchen Zhang , Zheng Chen , Pengxian Han , Jingwen Zhao , Guanglei Cui

Graphite cathodes enable high-voltage dual-ion batteries (DIBs) through reversible anion intercalation. However, the molecular identity and dynamic evolution of intercalated anionic species, which critically govern the thermodynamic stability and electrochemical reversibility of this process, remain insufficiently understood. This Perspective synthesizes emerging evidence challenging the prevalent but oversimplified “naked anion” intercalation model, emphasizing how solvent co-intercalation potentially influences thermodynamic equilibria, interlayer anion transport kinetics, and charge storage mechanisms. The structural evolution of graphite during anion intercalation is also critically analyzed, with a focus on how interlayer spacing adjustments evolve during electrochemical cycling under solvent co-intercalation conditions. Furthermore, we present a systematic analysis of anion packing configurations within solvent-containing interlayers and their intrinsic link to theoretical capacity limits, offering new insights for optimizing intercalation efficiency. To advance the field, targeted research directions encompassing operando characterization of speciation dynamics, multiscale modeling of solvent co-intercalation pathways and mechanistic investigation into the origins of voltage hysteresis, are proposed to inform the rational design of next-generation high-performance DIB systems.

石墨阴极通过可逆的阴离子插入实现高压双离子电池（DIBs）。然而，对这一过程的热力学稳定性和电化学可逆性起关键作用的插层阴离子物种的分子特性和动态演化仍然知之甚少。本观点综合了挑战流行但过于简化的“裸阴离子”插层模型的新证据，强调了溶剂共插层如何潜在地影响热力学平衡、层间阴离子传输动力学和电荷存储机制。本文还分析了负离子插入过程中石墨的结构演变，重点研究了溶剂共插入条件下电化学循环过程中层间间距调整的变化。此外，我们还系统分析了含溶剂中间层中阴离子填充结构及其与理论容量限制的内在联系，为优化插层效率提供了新的见解。为了推动该领域的发展，提出了有针对性的研究方向，包括物种形成动力学的operando表征，溶剂共插层途径的多尺度建模以及电压滞后起源的机理研究，为下一代高性能DIB系统的合理设计提供信息。

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引用次数: 0

Non-filamentary three-terminal resistivity switch based on interface oxidation/reduction 基于界面氧化/还原的非丝状三端电阻率开关

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-08-30 DOI: 10.1016/j.ssi.2025.116999

Daniel Friedzon , Ellen Wachtel , Olga Brontvein , Anna Kossoy , Leonid Chernyak , David Ehre , Igor Lubomirsky

We present a three-terminal resistive switching device with a 20 mol% gadolinium-doped ceria (20GDC) thin film as the solid state electrolyte. The device features a top Ta-metal gate electrode and bottom Ta-metal source and drain electrodes, separated by a 1 mm gap filled with 20GDC. Its operation relies on the redox reaction of cerium, specifically the reduction of cerium (IV) to cerium (III) at the interface between the Ta-gate and the 20GDC electrolyte. Under positive gate bias, the Ta gate electrode undergoes oxidation, while cerium is reduced, forming a conductive layer between the source and drain electrodes. Applying a negative gate bias reverses this effect. To confirm that resistivity changes originate from interface redox reactions, we conducted cyclic voltammetry at 403 K. The results demonstrate that peak current is inversely proportional to the scan rate, a characteristic of reaction at a surface. Additionally, we demonstrated that sputtering a TaO_x blocking layer beneath the gate electrode suppresses resistive switching. While the resistance changes only by a factor of two, the proposed device operates near equilibrium, is simple to fabricate, and exhibits high robustness. These characteristics make the concept of interface oxidation/reduction appealing for further exploration.

提出了一种以20mol %掺钆铈（20GDC）薄膜为固态电解质的三端电阻开关器件。该器件具有顶部ta -金属栅极和底部ta -金属源极和漏极，中间间隔1mm，填充20GDC。它的运行依赖于铈的氧化还原反应，特别是在ta栅极和20GDC电解质之间的界面处，铈（IV）还原为铈（III）。在正栅极偏压下，Ta栅极被氧化，而铈被还原，在源极和漏极之间形成导电层。施加负栅极偏置可以逆转这种效应。为了证实电阻率的变化是由界面氧化还原反应引起的，我们在403 K下进行了循环伏安法。结果表明，峰值电流与扫描速率成反比，扫描速率是表面反应的一个特征。此外，我们证明了在栅极下溅射一个TaOx阻塞层可以抑制电阻开关。虽然电阻变化仅为两倍，但所提出的器件在接近平衡状态下工作，易于制造，并且具有高稳健性。这些特点使得界面氧化/还原的概念值得进一步探索。

{"title":"Non-filamentary three-terminal resistivity switch based on interface oxidation/reduction","authors":"Daniel Friedzon , Ellen Wachtel , Olga Brontvein , Anna Kossoy , Leonid Chernyak , David Ehre , Igor Lubomirsky","doi":"10.1016/j.ssi.2025.116999","DOIUrl":"10.1016/j.ssi.2025.116999","url":null,"abstract":"<div><div>We present a three-terminal resistive switching device with a 20 mol% gadolinium-doped ceria (20GDC) thin film as the solid state electrolyte. The device features a top Ta-metal gate electrode and bottom Ta-metal source and drain electrodes, separated by a 1 mm gap filled with 20GDC. Its operation relies on the redox reaction of cerium, specifically the reduction of cerium (IV) to cerium (III) at the interface between the Ta-gate and the 20GDC electrolyte. Under positive gate bias, the Ta gate electrode undergoes oxidation, while cerium is reduced, forming a conductive layer between the source and drain electrodes. Applying a negative gate bias reverses this effect. To confirm that resistivity changes originate from interface redox reactions, we conducted cyclic voltammetry at 403 K. The results demonstrate that peak current is inversely proportional to the scan rate, a characteristic of reaction at a surface. Additionally, we demonstrated that sputtering a TaO<sub>x</sub> blocking layer beneath the gate electrode suppresses resistive switching. While the resistance changes only by a factor of two, the proposed device operates near equilibrium, is simple to fabricate, and exhibits high robustness. These characteristics make the concept of interface oxidation/reduction appealing for further exploration.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 116999"},"PeriodicalIF":3.3,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144916925","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Guide for characterizing polymeric electrolytes in rechargeable solid-state Li and Na batteries 可充电固态锂和钠电池中聚合物电解质的表征指南

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-08-30 DOI: 10.1016/j.ssi.2025.116989

Miryam Fayena-Greenstein , Gayathri Peta , Hadas Alon-Yehezkel , Nagaprasad Reddy Samala , Ortal Breuer , Yuval Elias , Guoxiu Wang , Doron Aurbach

Solid polymer electrolytes (SPEs) present a promising alternative for rechargeable batteries with aprotic liquids. Although SPEs were extensively researched for several decades, recent studies have gained momentum in response to growing demand for safer battery options. While various electrochemical and spectral methods for characterizing polymeric electrolytes were proposed, a comprehensive guide to support future investigations appears lacking. Here, we propose a working protocol to derive parameters that characterize SPEs as crucial components of battery systems. An overview of various methods is provided, with particular emphasis on simple impedance measurements for extracting electrochemical parameters. We underscore the significance of considering the interfaces within the battery, specifically the electrolyte-anode and electrolyte-cathode interfaces. Post-mortem analysis is discussed along with the challenges it entails. A summary table detailing the extracted parameters, the corresponding characterization methods, and their applications is provided.

固体聚合物电解质（spe）是一种很有前途的非质子液体可充电电池替代品。尽管spe已经被广泛研究了几十年，但最近的研究获得了动力，以响应对更安全电池选择日益增长的需求。虽然提出了各种表征聚合物电解质的电化学和光谱方法，但缺乏支持未来研究的综合指南。在这里，我们提出了一个工作协议，以获得表征spe作为电池系统关键组件的参数。概述了各种方法，特别强调了提取电化学参数的简单阻抗测量。我们强调了考虑电池内部界面的重要性，特别是电解质-阳极和电解质-阴极界面。讨论了尸检分析及其带来的挑战。提供了一个汇总表，详细说明了提取的参数、相应的表征方法及其应用。

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引用次数: 0

The critical role of Al2O3, BaTiO3 and ZrO2 nanoceramic fillers in PVDF-HFP based composite polymer electrolytes for high performance lithium-metal batteries Al2O3、BaTiO3和ZrO2纳米陶瓷填料在高性能锂金属电池PVDF-HFP基复合聚合物电解质中的关键作用

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-08-29 DOI: 10.1016/j.ssi.2025.117008

Mononita Das , Kuntal Ghosh , Vijaya , Mir Wasim Raja

Lithium metal batteries (LMBs) can be the ultimate choice for future battery technologies since they use Lithium metal as anode, which offers high theoretical capacity (3860 mAh.g⁻¹) and lowest electrochemical potential (−3.04 V vs. SHE). However, their commercialization is limited by dendritic growth, interfacial instability, and safety risks associated with liquid electrolytes. In this work, composite solid polymer electrolytes (CSPEs) are developed by incorporating various (Al₂O₃, BaTiO₃, and ZrO₂) ceramic fillers into a PVDF-HFP/LiTFSI matrix via a scalable solution casting method. Among these, optimized 10 wt% ZrO₂-based CSPE (PLZ) delivers the highest room-temperature ionic conductivity (9.26 × 10⁻⁵ S cm⁻¹), excellent Li⁺ transference number (0.55), superior tensile strength (3.23 MPa), wide potential window (5.33 V), and good flame retardancy. Li/Li symmetric cells using PLZ showed stable lithium plating/stripping for more than 480 h at 0.10 mA.cm⁻² with a low overpotential of ∼7 mV. Electrochemical impedance spectroscopy and equivalent circuit fitting confirmed the lowest increase in interfacial resistance after cycling. Time-resolved distribution of relaxation time (DRT) and 2D contour analysis revealed that PLZ maintained stable SEI and charge-transfer resistances, while bare CSPEs showed growing interfacial instability during cycling. These improvements are attributed to Lewis acid-base interactions and surface charge effects that reduce crystallinity and promote Li⁺ mobility. Full-cell evaluations with LiFePO₄ and NMC111 cathodes demonstrated high discharge capacities and good cycling stability. Thus, this study offers a promising pathway for developing robust and safe CSPEs for next-generation solid-state LMBs.

锂金属电池（lmb）可以成为未来电池技术的最终选择，因为它们使用锂金属作为阳极，提供高理论容量（3860毫安时）。g−1)和最低电化学电位（−3.04 V vs. SHE）。然而，它们的商业化受到枝晶生长、界面不稳定性和与液体电解质相关的安全风险的限制。在这项工作中，通过可扩展的溶液铸造方法，将各种（Al2O3， BaTiO3和ZrO2）陶瓷填料掺入PVDF-HFP/LiTFSI基体中，开发了复合固体聚合物电解质（cspe）。其中，优化后的10 wt% zro2基CSPE （PLZ）具有最高的室温离子电导率（9.26 × 10−5 S cm−1）、优异的Li+转移数（0.55）、优异的抗拉强度（3.23 MPa）、宽电位窗（5.33 V）和良好的阻燃性。使用PLZ的Li/Li对称电池在0.10 mA.cm−2下具有低过电位~ 7 mV，可稳定镀锂/剥离超过480 h。电化学阻抗谱和等效电路拟合证实循环后界面电阻增幅最小。弛豫时间（DRT）的时间分辨分布和二维轮廓分析表明，PLZ保持稳定的SEI和电荷转移电阻，而裸cspe在循环过程中界面不稳定性增加。这些改进归功于路易斯酸碱相互作用和表面电荷效应，它们降低了结晶度，促进了Li+的迁移率。使用LiFePO4和NMC111阴极进行的全电池评估显示出高的放电容量和良好的循环稳定性。因此，该研究为下一代固态lmb开发稳健安全的cspe提供了一条有希望的途径。

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引用次数: 0

Return of the solid-state coulometric titration: A new hope to expand the p(O2) range 固态库仑滴定法的回归：扩大p（O2）范围的新希望

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-08-27 DOI: 10.1016/j.ssi.2025.117001

Stanislaus Breitwieser, Johannes Bock, Frederick Fechner, Jürgen Fleig, Andreas Nenning

The catalytic and electrochemical properties of many non-stoichiometric oxides are governed by their defect chemistry. Therefore, detailed knowledge of their oxygen non-stoichiometry under operating conditions is desired. For this, coulometric titration can offer a valuable tool that can have advantages in terms of required sample mass, accuracy and reachable p(O₂) range over other established techniques, such as thermogravimetric analysis (TGA). Here, we present a new design for an easy to fabricate miniature coulometric titration setup using materials selected for optimal electrode kinetics. The small chamber volume (0.03–0.05 ml), small sample mass (about 30 mg) and kinetically fast electrodes allow for a precise variation of the p(O₂) from 1 bar down to 10⁻³² bar at 625 °C. This is a much wider range than typically achievable under gas flow in TGA or with other titration setups described in the literature. A characterisation of the titration setup showed that residual errors in the defect chemistry of the investigated materials are in the range of 10⁻⁴ to 10⁻³ p.f.u. Exemplary measurements on CeO_2-δ and Sr_1-xTi_0.6Fe_0.4O_3-δ (STF) showcase how this wide p(O₂) range can not only be used to study oxygen non-stoichiometry at very reducing conditions and the p(O₂) at which vacancy ordering phenomena occur (for CeO_2-δ), but also detect and quantify small amounts of redox-active secondary phases (for STF).

许多非化学计量氧化物的催化和电化学性能是由它们的缺陷化学决定的。因此，需要在操作条件下详细了解它们的氧非化学计量学。为此，库伦滴定法可以提供一种有价值的工具，在所需的样品质量，精度和可达的p（O2）范围方面比其他既定技术（如热重分析（TGA））具有优势。在这里，我们提出了一种易于制造的微型库仑滴定装置的新设计，该装置使用了最佳电极动力学选择的材料。小腔体积（0.03-0.05 ml），小样品质量（约30 mg）和动态快速电极允许p（O2）在625°C下从1 bar到10 - 32 bar的精确变化。这比在TGA或文献中描述的其他滴定装置的气体流动下通常可实现的范围要宽得多。对滴定装置的表征表明，所研究材料的缺陷化学的残余误差在10−4到10−3 p.f.u之间。对CeO2-δ和Sr1-xTi0.6Fe0.4O3-δ (STF)的示例测量表明，这种宽的p（O2）范围不仅可以用于研究非常还原条件下的氧非化学计量学和空位有序现象发生的p(O2)（对于CeO2-δ），还可以检测和量化少量的氧化还原活性次级相（用于STF）。

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引用次数: 0