Solid State Ionics最新文献_第6页

Structural effects on oxygen vacancies and redox behavior in Mn-based perovskite oxides mn基钙钛矿氧化物中氧空位和氧化还原行为的结构影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-10-30 DOI: 10.1016/j.ssi.2025.117067

Vika Arzumanyan , Cijie Liu , Dawei Zhang , Wei Li , Jian Luo , Xingbo Liu , Yue Qi

A series of perovskite oxides

({Ln}_{2 / 3} A_{1 / 3}) Mn O_{3}

(Ln = La, Pr, Nd, Gd; A = Ba, Sr) was investigated to understand the effects of A-site cation size on oxygen vacancy formation. Quasirandom

(L n_{2 / 3} A_{1 / 3}) Mn O_{3}

mixed structures were generated using Alloy Theoretic Automated Toolkit (ATAT), followed by density functional theory (DFT) calculations. While mixing the orthorhombic

LnMn O_{3}

structures with the hexagonal AMnO₃ structures leads to lattices and global symmetries closer to cubic, the average volume generally increases with the average ionic size, and the local bond and angles exhibit more variations due to A-site mixing. DFT calculations and a statistical model were combined to predict oxygen reduction abilities. Thermogravimetric analysis (TGA) provided experimental validation of these predictions by measuring changes in oxygen non-stoichiometry (

Δδ

) under controlled conditions. Both indicated that larger A-site ionic size differences lead to greater

Δδ

, consistent with the larger variation in local structures, and enhanced redox capabilities. This combined computational-experimental approach highlights the importance of local structure variation, instead of average properties, in A-site cation engineering to optimize perovskite oxides for different devices relying on oxygen vacancy redox activity.

研究了一系列钙钛矿氧化物Ln2/3A1/3MnO3 (Ln = La, Pr, Nd, Gd; A = Ba, Sr)，以了解A位阳离子大小对氧空位形成的影响。利用Alloy theory Automated Toolkit （ATAT）生成准随机Ln2/3A1/3MnO3混合结构，并进行密度泛函理论（DFT）计算。当正交结构的LnMnO3与六方结构的AMnO3混合时，晶格和全局对称性更接近立方，平均体积一般随着平均离子尺寸的增加而增加，局域键和角度由于a位混合而表现出更多的变化。DFT计算和统计模型相结合来预测氧还原能力。热重分析（TGA）通过在受控条件下测量氧非化学计量学（Δδ）的变化，为这些预测提供了实验验证。两者都表明，较大的a位离子大小差异导致较大的Δδ，与较大的局部结构变化一致，并且增强了氧化还原能力。这种计算与实验相结合的方法强调了局部结构变化的重要性，而不是平均性质，在a位阳离子工程中，依靠氧空位氧化还原活性来优化不同器件的钙钛矿氧化物。

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引用次数: 0

Organic weak acid pretreatment enables surface-engineered Li-rich cathodes with suppressed voltage decay and enhanced kinetics 有机弱酸预处理使表面工程的富锂阴极具有抑制电压衰减和增强动力学

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-10-24 DOI: 10.1016/j.ssi.2025.117051

Jinhua Wu , Chao Han , Haijiao Yang , Zhonglei Zhao , Feifei Ling , Hang Zhao

Lithium-rich Mn-based layered oxides (LLOs) are regarded as promising cathodes owing to exceptional energy density and cost-effectiveness. Nevertheless, three primary drawbacks impede their commercialization: insufficient initial Coulombic efficiency (ICE), limited rate capability, and progressive voltage decay. In this study, the effects of pretreatment using an organic weak acid (tannic acid) and an inorganic strong acid (hydrochloric acid) on the structure, morphology, and electrochemical properties of Li_1.2Mn_0.6Ni_0.2O₂(LMNO) are systematically investigated. Acid pretreatment can cause the dissolution of Li₂O and hence increase electrodes ICE. Compared with the pristine LMNO (73.9 %), the ICE values of tannic acid-treated(LTA) and hydrochloric acid-treated (LHC) samples reach 82.6 % and 81.9 %, respectively. Unlike the severe structural damage caused by hydrochloric acid treatment, tannic acid pretreatment generates only nano-vacancy defects and a minor spinel phase on the LMNO surface. These modifications facilitate Li⁺ transport while suppressing capacity and voltage decay. As a result, the LTA sample exhibits superior rate capability (150 mAh g⁻¹ at 5C; 125 mAh g⁻¹ at 8C), good capacity retention (96.3 % after 100 cycles at 1C), and minimal voltage decay (1.24 mV per cycle). This work establishes organic weak acid pretreatment as a scalable strategy to simultaneously address ICE, rate capability, and voltage decay in LLOs.

富锂锰基层状氧化物（LLOs）由于其特殊的能量密度和成本效益而被认为是有前途的阴极。然而，三个主要的缺点阻碍了它们的商业化：初始库仑效率（ICE）不足，速率能力有限，电压逐渐衰减。本研究系统研究了有机弱酸（单宁酸）和无机强酸（盐酸）预处理对Li1.2Mn0.6Ni0.2O2（LMNO）结构、形貌和电化学性能的影响。酸预处理可以引起Li2O的溶解，从而增加电极的ICE。与原始LMNO（73.9%）相比，单宁酸处理（LTA）和盐酸处理（LHC）样品的ICE值分别达到82.6%和81.9%。与盐酸处理造成的严重结构损伤不同，单宁酸预处理只会在LMNO表面产生纳米空位缺陷和少量尖晶石相。这些修饰有利于Li+输运，同时抑制了容量和电压衰减。结果，LTA样品表现出优异的倍率性能（5C时150 mAh g - 1； 8C时125 mAh g - 1），良好的容量保持率（在1C下100次循环后96.3%）和最小的电压衰减（每循环1.24 mV）。这项工作建立了有机弱酸预处理作为一种可扩展的策略，可以同时解决LLOs中的ICE、速率能力和电压衰减问题。

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引用次数: 0

The doping factor approach in solid state ionics 固体离子学中的掺杂因子方法

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-10-23 DOI: 10.1016/j.ssi.2025.117068

Yoed Tsur, Rawan Halabi

The doping factor approach is a simple, sometimes a “back-of-the-envelope” method, to predict concentrations of native point defects upon doping with aliovalent dopants. The doping factor is defined as the ratio between the concentration of quasi-free electrons in the doped state and their concentration in a reference state, typically at the undoped state. In binary compounds, as long as the Boltzmann statistics hold, the neutrality equation becomes a polynomial equation for the doping factor. Once the doping factor is found, all the concentrations of the native point defects are readily determined. While other computational methods allow us to find those concentrations, it is beneficial for researchers to possess such a simple tool for calculating the resulting new concentrations. Furthermore, this method may be the only one available in cases with small deviations from stoichiometry. The method is explained and demonstrated using a simple case of magnesium oxide, as well as on intrinsic compound oxide semiconductors.

掺杂因子法是一种简单的方法，有时是一种“粗略”的方法，用于预测与共价掺杂剂掺杂后的天然点缺陷浓度。掺杂因子定义为掺杂态准自由电子的浓度与参考态（通常是未掺杂态）准自由电子的浓度之比。在二元化合物中，只要玻尔兹曼统计量成立，中性方程就成为掺杂因子的多项式方程。一旦发现掺杂因素，所有的原生点缺陷的浓度都很容易确定。虽然其他计算方法允许我们找到这些浓度，但对于研究人员来说，拥有这样一个简单的工具来计算产生的新浓度是有益的。此外，这种方法可能是在化学计量偏差很小的情况下唯一可用的方法。本文以氧化镁和本征化合物氧化物半导体为例，对该方法进行了说明和论证。

引用次数: 0

Quantifying protons in triple conducting perovskite-type oxides via laser-induced breakdown spectroscopy – A comparative validation approach 通过激光诱导击穿光谱定量三重导电钙钛矿型氧化物中的质子-一种比较验证方法

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-10-15 DOI: 10.1016/j.ssi.2025.117033

Melanie Maurer, Maximilian Weiss, Matthias Weil, Andreas Limbeck, Alexander Karl Opitz

Proton-conducting oxides are promising materials for renewable energy technologies - e.g. as electrolytes and electrodes in solid oxide cells or membranes for hydrogen purification. Particularly relevant for these applications are perovskites, which can accommodate high concentrations of protons in their crystal structure. However, quantifying the proton concentration is challenging under reducing conditions, OH uptake and oxygen loss occur simultaneously, causing compensating weight changes. Thus, attributing weight changes directly to OH uptake is not possible without complementary techniques for validation. Here, we focus on quantifying the proton concentration in the triple conducting perovskite-type oxide BaFe_0.85Y_0.15O_3–δ (BFY) under various oxidation and protonation states. To do so, we introduce an alternative analytical method, which is capable of direct proton detection in perovskites and well-suited for in-situ quantification: Laser-induced breakdown spectroscopy (LIBS). This technique analyses characteristic emissions from the plasma generated by UV-laser irradiation of the material. Validation of results involved gravimetry and Fourier-transform infrared spectroscopy (FT-IR). While gravimetry was used to determine the proton concentration under special experimental conditions, FT-IR spectroscopy was used to distinguish the protons – located in the perovskite structure in the form of

{(OH)}_{O}^{•}

point defects - from molecular water (e.g. at the surface). The results underscore the reliability of LIBS for the quantification of bulk protons in perovskite-type oxides, positioning it as a valuable alternative to conventional methods.

质子导电氧化物是可再生能源技术中很有前途的材料，例如用作固体氧化物电池或氢净化膜的电解质和电极。与这些应用特别相关的是钙钛矿，它可以在其晶体结构中容纳高浓度的质子。然而，在还原条件下，质子浓度的量化是具有挑战性的，OH的吸收和氧的损失同时发生，导致补偿重量的变化。因此，如果没有验证的补充技术，将体重变化直接归因于OH摄取是不可能的。本文研究了三导电钙钛矿型氧化物BaFe0.85Y0.15O3 -δ (BFY)在不同氧化和质子化状态下的质子浓度。为此，我们引入了一种替代分析方法，该方法能够直接检测钙钛矿中的质子，并且非常适合于原位定量：激光诱导击穿光谱（LIBS）。该技术分析了紫外激光照射材料产生的等离子体的特征发射。结果的验证涉及重力测量和傅里叶变换红外光谱（FT-IR）。在特殊实验条件下，用重力法测定质子浓度，用傅里叶变换红外光谱（FT-IR）区分质子（以OHO•点缺陷的形式位于钙钛矿结构中）和分子水（例如在表面）。结果强调了LIBS定量钙钛矿型氧化物中大块质子的可靠性，将其定位为传统方法的有价值的替代方法。

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引用次数: 0

Research on synthesis process and calcination reaction mechanism of porous LLZO with high specific surface area 高比表面积多孔LLZO的合成工艺及煅烧反应机理研究

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-11-26 DOI: 10.1016/j.ssi.2025.117086

Shengdong Tao , Jian Li , Yali Liu , Zulv Huang , Hui Fu , Guowen He , Kun Shen , Zheng Liu , Zhifang Yin

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO), a promising solid-state electrolyte due to its high ionic conductivity, wide electrochemical window, and stability against metallic lithium, has attracted significant attention in recent years. However, its practical application is severely limited by drawbacks, including insufficient mechanical flexibility, prolonged synthesis/calcination times and challenging process control. This study proposes a metal-organic framework (MOF)-mediated strategy for LLZO synthesis. Specifically, La-Zr-MOF was constructed via hydrothermal self-assembly in solution, leveraging the strong coordination of carboxylate ligands with La³⁺ and Zr⁴⁺ ions. Subsequent incorporation of a lithium salt yields an LLZO precursor with atomic-level homogeneous dispersion of La, Zr, and Li. Direct calcination of the precursor produced phase-pure LLZO in a single step. Through process optimization, employing polyethylene glycol-200 (PEG-200) as the MOF synthesis solvent, LiAc as the lithium source, and 20 mol% lithium excess, cubic-phase LLZO with a high specific surface area (144.76 m² g⁻¹) was successfully synthesized at a relatively low temperature (1000 °C) with a short holding time (5 h). Furthermore, the calcination mechanism of LLZO was elucidated by SEM, XRD, TEM, specific surface area analysis and pore size distribution analysis of samples calcined at different temperatures. This research provides a novel strategy for the low-temperature, rapid synthesis of high-surface-area cubic-phase LLZO.

石榴石型Li7La3Zr2O12 （LLZO）具有离子电导率高、电化学窗口宽、抗金属锂稳定性好等优点，近年来受到广泛关注。然而，它的实际应用受到一些缺点的严重限制，包括机械灵活性不足、合成/煅烧时间长和过程控制困难。本研究提出了一种金属有机框架（MOF）介导的LLZO合成策略。具体来说，利用羧酸配体与La3+和Zr4+离子的强配位，通过水热自组装在溶液中构建了La-Zr-MOF。随后加入锂盐产生具有原子水平均匀分散的La、Zr和Li的LLZO前驱体。前驱体直接煅烧一步制得相纯LLZO。通过工艺优化，以聚乙二醇-200 （PEG-200）为MOF合成溶剂，LiAc为锂源，过量锂量为20 mol%，在相对较低的温度（1000℃）和较短的保温时间（5 h）下成功合成了高比表面积（144.76 m2 g−1）的立方相LLZO。通过SEM、XRD、TEM、比表面积分析和不同温度下煅烧样品的孔径分布分析，阐明了LLZO的煅烧机理。本研究为低温、快速合成高比表面积的三相LLZO提供了一条新思路。

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引用次数: 0

Materials discovery through interpretation: An application to proton-conducting oxides 通过解释发现材料：在质子导电氧化物中的应用

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-10-27 DOI: 10.1016/j.ssi.2025.117054

Yoshihiro Yamazaki , Kota Tsujikawa , Junji Hyodo , Susumu Fujii

Machine learning has become a pivotal tool in materials discovery, but conventional data-driven models often behave as “black boxes” limited by the scope of their training data. In this perspective, we outline the current status of machine learning-driven materials discovery and present Materials Discovery through Interpretation (MDI), a framework that integrates scientific reasoning into the ML loop to enhance the reliability and impact of materials design. Instead of relying solely on statistical correlations, the MDI iteratively incorporates domain knowledge and insights from experimental and/or computational results such as phase formability and materials functionality into the predictive process. This interpretive strategy enables meaningful extrapolation even when underlying physics and chemical correlations remain poorly understood, guiding the identification of new candidate materials while simultaneously refining the models. Applied to proton-conducting oxides, MDI successfully identified previously unrecognized compounds, including those achieving conductivity above 0.01 Scm⁻¹ at 300 °C, a critical benchmark for fuel cell electrolytes, while providing clear rationales for their selection. By combining predictive power with interpretability, MDI offers a flexible pathway for accelerating materials innovation beyond the confines of existing data.

机器学习已经成为材料发现的关键工具，但传统的数据驱动模型往往表现得像“黑匣子”，受到其训练数据范围的限制。从这个角度来看，我们概述了机器学习驱动的材料发现的现状，并提出了通过解释发现材料（MDI），这是一个将科学推理集成到ML循环中的框架，以提高材料设计的可靠性和影响。MDI不再仅仅依赖于统计相关性，而是迭代地将领域知识和来自实验和/或计算结果的见解（如相成形性和材料功能）纳入预测过程。这种解释策略使得有意义的外推，即使在潜在的物理和化学相关性仍然知之甚少的情况下，指导新的候选材料的识别，同时改进模型。应用于质子导电氧化物，MDI成功识别了以前未被识别的化合物，包括那些在300°C（燃料电池电解质的关键基准）下电导率高于0.01 Scm−1的化合物，同时为它们的选择提供了明确的依据。通过将预测能力与可解释性相结合，MDI为加速材料创新提供了一种超越现有数据限制的灵活途径。

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引用次数: 0

A revised bond valence based approach to identify descriptor for correlated migration in superionic conductors 一种改进的基于键价的方法来识别超离子导体中相关迁移描述子

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-10-24 DOI: 10.1016/j.ssi.2025.117053

Bowei Pu , Zheyi Zou , Bing He , Fan Huang , Zuer Ye , Siqi Shi

Multi-ion correlated migration has become one of the critical features for superionic conductors (SICs). Finding a computable descriptor for correlated migration is a significant step for rational design of SICs. Here, we develop a revised bond valence based approach with the consideration of repulsive interactions between mobile ions to calculate Coulomb repulsion energy of crystal structure (E_c), which can quantify the correlated migration tendency. The SICs in which ion transport is governed by correlated migration are characterized by strong Coulomb repulsion energies, as seen in garnet-type Li₇La₃Zr₂O₁₂ (0.851 eV) and NASICON-type Na_3.15Zr₂Si_2.15P_0.85O₁₂ (0.898 eV). In contrast, the SICs with insignificant correlated migration exhibit much weaker Coulomb repulsion energies, exemplified by Li₃YCl₆ (0.441 eV) and Li₃YBr₆ (0.279 eV). Based on high-throughput calculations of 5226 Li-containing and 9363 Na-containing compounds, a threshold E_c of 0.7 eV is proposed to identify the SICs with significant correlated migration. These findings validate the effectiveness and universality of correlated migration descriptor, providing an efficient approach for the future design of superionic conductors.

多离子相关迁移已成为超离子导体的重要特征之一。为相关迁移寻找一个可计算的描述符是物理系统合理设计的重要一步。在此，我们提出了一种修正的基于键价的方法，考虑了移动离子之间的排斥相互作用来计算晶体结构的库仑排斥能（Ec），它可以量化相关的迁移趋势。离子输运受相关迁移控制的sic具有较强的库仑排斥能，如石榴石型Li7La3Zr2O12 （0.851 eV）和nasicon型Na3.15Zr2Si2.15P0.85O12 （0.898 eV）。相比之下，相关迁移不显著的无机硅的库仑排斥能要弱得多，如Li3YCl6 （0.441 eV）和Li3YBr6 （0.279 eV）。基于5226含锂化合物和9363含na化合物的高通量计算，提出了0.7 eV的阈值Ec来识别具有显著相关迁移的sic。这些发现验证了相关迁移描述符的有效性和通用性，为未来超离子导体的设计提供了一种有效的方法。

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引用次数: 0

Oxygen reduction reaction kinetics and H/D effects in electrodes in contact with proton-conducting electrolyte BaCe0.9Gd0.1O3-δ 质子导电电解质BaCe0.9Gd0.1O3-δ接触电极的氧还原反应动力学及H/D效应

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-10-22 DOI: 10.1016/j.ssi.2025.117065

E.P. Antonova , D.A. Osinkin

Solid oxides with proton conductivity have great potential for application in high-temperature electrochemical devices. These devices encompass fuel cells, electrolyzers, hydrogen sensors, and membrane reactors for the production of high-purity hydrogen. In order to ensure the efficient operation of these devices, active electrodes are required. In recent studies, complex oxides with triple proton/electron/oxygen conductivity have been identified as a promising solution. Concurrently, numerous studies have demonstrated that conventional mixed oxygen-ionic/electronic conductors (MIECs) with high electronic conductivity exhibit high efficiency in terms of their use as electrodes with proton-conducting electrolyte. In this study, we investigated the electrochemical behavior of the most popular electrode materials La_0.6Sr_0.4Fe_0.8Co_0.2O_3-δ, La₂NiO_4+δ and La_0.75Sr_0.2MnO_3±δ in contact with BaCe_0.9Gd_0.1O_3-δ electrolyte in terms of oxygen reduction kinetics. A feature of this study was the use of regular and heavy water (D₂O) for the humidification of the air when conducting impedance studies followed by analysis of impedance spectra by the method of distribution of relaxation times (DRT) with the subsequent determination of the stage of the oxygen reduction reaction in which the proton and/or water takes part. On the basis of the obtained results, oxygen adsorption, dissociation, and diffusion are proposed to be the rate-determining steps of the oxygen reduction reaction for La_0.6Sr_0.4Fe_0.8Co_0.2O_3-δ and La_0.75Sr_0.2MnO_3±δ electrodes.

具有质子导电性的固体氧化物在高温电化学器件中具有很大的应用潜力。这些装置包括燃料电池、电解槽、氢传感器和用于生产高纯度氢的膜反应器。为了保证这些器件的高效运行，需要有源电极。在最近的研究中，具有三重质子/电子/氧电导率的复合氧化物被认为是一种很有前途的解决方案。同时，大量研究表明，具有高电子导电性的传统混合氧离子/电子导体（MIECs）作为质子导电电解质的电极具有很高的效率。在本研究中，我们从氧还原动力学的角度研究了最常用的电极材料La0.6Sr0.4Fe0.8Co0.2O3-δ、La2NiO4+δ和La0.75Sr0.2MnO3±δ与BaCe0.9Gd0.1O3-δ电解质接触时的电化学行为。本研究的一个特点是在进行阻抗研究时使用常规水和重水（D2O）对空气进行加湿，然后通过松弛时间分布（DRT）方法分析阻抗谱，随后确定质子和/或水参与的氧还原反应的阶段。在此基础上，提出了la0.6 sr0.4 fe0.8 co0.3 2o3 -δ和La0.75Sr0.2MnO3±δ电极氧还原反应的速率决定步骤为氧吸附、解离和扩散。

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引用次数: 0

Polycarbonate-based polymer electrolytes for potassium batteries 钾电池用聚碳酸酯基聚合物电解质

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-11-12 DOI: 10.1016/j.ssi.2025.117069

Isabell Lee Johansson , Timofey I. Kolesnikov , Anna Khudyshkina , Ulf-Christian Rauska , Daniel Brandell , Jonas Mindemark , Guiomar Hernández , Fabian Jeschull

Polycarbonate-based solid polymer electrolytes (SPEs) are being intensively studied for use in all-solid-state batteries as a viable alternative to the commonly used poly(ethylene oxide)-based SPEs. Specifically, poly(trimethylene carbonate) (PTMC) and poly(ε-caprolactone–co–trimethylene carbonate) (P(CL-TMC)) as a well-performing copolymeric derivative represent two materials classes that so far have not been studied in potassium battery applications. Herein, we aim to close this knowledge gap by studying physical material properties of PTMC and P(CL-TMC) solid electrolytes with potassium bis(trifluoromethanesulfonyl)imide (KTFSI) as conductive salt and examine their electrochemical stability and characteristics in K-metal/K₂Fe[Fe(CN)₆] (KFF), as well as Fe[Fe(CN)₆/K₂Fe[Fe(CN)₆] cell configurations. While operation of polycarbonate-based solid-state potassium batteries at temperatures as low as 40 °C is feasible, comparatively low discharge capacities and capacity retention were observed in comparison to polyether-based systems. For the P(CL-TMC) material, rapid degradation through depolymerization processes in direct contact with potassium metal represents a major bottleneck. With this study, we set a starting point for further materials development in alternative polymer hosts for SPE applications in potassium batteries.

聚碳酸酯基固体聚合物电解质（spe）正被广泛研究用于全固态电池，作为常用的聚环氧乙烷基spe的可行替代品。具体来说，聚（三亚甲基碳酸酯）（PTMC）和聚（ε-己内酯-共三亚甲基碳酸酯）（P(CL-TMC)）作为一种性能良好的共聚衍生物，代表了迄今尚未在钾电池应用中研究的两类材料。本文旨在通过研究以二（三氟甲烷磺酰）亚胺钾（KTFSI）为导电盐的PTMC和P（CL-TMC）固体电解质的物理材料性质，以及它们在K-metal/K2Fe[Fe(CN)6] （KFF）和Fe[Fe(CN)6] /K2Fe[Fe(CN)6]电池构型中的电化学稳定性和特性，来弥补这一知识空白。虽然聚碳酸酯基固态钾电池在低至40°C的温度下运行是可行的，但与聚醚基电池相比，其放电容量和容量保持率相对较低。对于P（CL-TMC）材料来说，通过与金属钾直接接触的解聚过程进行快速降解是一个主要瓶颈。通过这项研究，我们为进一步开发用于钾电池中SPE应用的替代聚合物宿主材料奠定了起点。

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引用次数: 0

Electrical properties and conductivity mechanism for Ca2KH7(PO4)4·2H2O and Ca2(NH4)H7(PO4)4·2H2O Ca2KH7(PO4)4·2H2O和Ca2(NH4)H7(PO4)4·2H2O的电学性质及导电机理

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 Epub Date: 2025-11-10 DOI: 10.1016/j.ssi.2025.117070

K. Najkov , V. Koleva , V. Stefov , M. Pecovska Gjorgjevich

For the first time the acid salts Ca₂KH₇(PO₄)₄·2H₂O and Ca₂(NH₄)H₇(PO₄)₄·2H₂O are studied as potential proton conductors by complex impedance spectroscopy. Their electrical and dielectric properties, as well as conductivity are examined as a function of frequency (10 Hz–10 MHz) at various temperatures (293 K–363 K). The complex impedance spectra showed semicircle arcs depending on temperature indicating conductivity through grain boundaries with semiconducting behavior. It was found that for the two salts in the investigated temperature range the ac conductivity follows Joncher's power law and dc conductivity follows the Arrhenius behavior with activation energy 0.552 eV for Ca₂KH₇(PO₄)₄·2H₂O and 0.713 eV for Ca₂(NH₄)H₇(PO₄)₄·2H₂O. The results were confirmed with electric modulus analysis. The conductivity mechanism of the two compounds was also investigated and the experimental results were analyzed using various theoretical models. It has been established that the overlapping large polaron tunneling (OLPT) was the best model to explain the proton conduction of both acidic salts. Comparison of the conductivity with other phosphate proton conductors was made.

首次利用复阻抗谱技术研究了酸性盐Ca2KH7(PO4)4·2H2O和Ca2(NH4)H7(PO4)4·2H2O作为质子电位导体。在不同温度（293 K - 363 K）下，它们的电学和介电性能以及电导率作为频率（10 Hz-10 MHz）的函数进行了测试。复合阻抗谱随温度变化呈半圆弧，表明具有半导体行为的晶界电导率。结果表明，在研究温度范围内，两种盐的交流电导率服从Joncher幂定律，直流电导率服从Arrhenius行为，Ca2KH7(PO4)4·2H2O的活化能为0.552 eV, Ca2(NH4)H7(PO4)4·2H2O的活化能为0.713 eV。电模量分析证实了这一结果。研究了两种化合物的导电机理，并用各种理论模型对实验结果进行了分析。已经确定重叠大极化子隧穿（OLPT）是解释两种酸性盐的质子传导的最佳模型。并与其它磷酸盐质子导体的电导率进行了比较。

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引用次数: 0