Solid State Ionics最新文献_第5页

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 : 2025-10-22 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

Dielectric and conductivity studies of Tb-doped zinc orthotitanate nanomaterials for next-generation electronics and energy storage 新一代电子和储能用掺杂tb的正钛酸锌纳米材料的介电和电导率研究

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-21 DOI: 10.1016/j.ssi.2025.117048

K.M. Girish , R. Lavanya , M.V. Hemantha Reddy , G.R. Rajath , B.N. Deepak Kumar , S.C. Prashantha

Zn₂TiO₄ nanomaterials doped with Terbium were synthesized via a combustion route using oxalyl dihydrazide (ODH) as fuel. The crystalline nature and morphology were confirmed by Powder X-ray diffraction (PXRD), and Scanning Electron Microscopy (SEM) techniques. Optical studies and the nature of liberated organics were conducted through Diffuse Reflectance Spectroscopy (DRS), and Fourier Transform Infrared (FTIR)spectroscopy techniques. Conductivity and Dielectric studies were carried out for the prepared materials and optimized. Dielectric spectra revealed distinct relaxation behaviors at high and low frequencies. Highest dielectric constant was noticed for the 5 mol% Tb-doped Zn₂TiO₄ compared to other compositions. Dielectric plots exhibit a clear merging beyond a certain frequency, and their behavior changes significantly at higher frequencies which can be attributed to the release of space charge and the consequent reduction in the material's barrier properties. The frequency dependence of AC conductivity Tb³⁺ (1–7 mol%): Zn₂TiO₄ nanoparticles follows Jonscher's power law. All the results suggest that the Tb³⁺-doped Zn₂TiO₄ material is potentially suitable for electronics and energy storage applications.

以草酰二肼（ODH）为燃料，通过燃烧途径合成了掺铽纳米Zn2TiO4。通过粉末x射线衍射（PXRD）和扫描电子显微镜（SEM）技术对晶体性质和形貌进行了表征。通过漫反射光谱（DRS）和傅里叶变换红外（FTIR）光谱技术进行光学研究和释放有机物的性质。对制备的材料进行了电导率和介电性能的研究并进行了优化。介质谱在高、低频表现出明显的弛豫行为。与其他组合物相比，5mol % tb掺杂Zn₂TiO₄的介电常数最高。介电图在超过一定频率时表现出明显的合并，其行为在较高频率时发生显著变化，这可归因于空间电荷的释放和随之而来的材料势垒特性的降低。Tb3+ (1 - 7mol %): Zn2TiO4纳米粒子的交流电导率与频率的关系遵循Jonscher幂定律。这些结果表明，Tb3+掺杂的Zn2TiO4材料具有潜在的电子和储能应用潜力。

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引用次数: 0

Hydrogen conductivity and anisotropy of ionic conductivity of LiB3O5 crystals LiB3O5晶体的氢电导率和离子电导率的各向异性

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-21 DOI: 10.1016/j.ssi.2025.117046

Mikhail N. Palatnikov, Vladimir A. Sandler, Nikolay V. Sidorov, Olga V. Palatnikova

The defect structure of LBO crystals of different orientations has been studied. Various types of macro-, meso- and micro-defects have been discovered in the crystal structure. Optical microscopy studies revealed the greatest defects in z-oriented LBO crystalline samples. Dendrite fractal structures have spontaneously formed on the surface of LBO samples. Features of the structures indicate internal stresses in the crystalline plates upper layers, and crystal defects. The anisotropy of ionic conductivity of LiB₃O₅ (LBO) crystals containing H⁺ cations as a technological impurity has been studied. A pronounced effect of high-temperature annealing of LBO crystals on the dielectric properties and conductivity features has been found. The obtained results explain some contradictions in the literature data on the phase states, conductivity character and pyroelectric properties of LBO crystals. The contributions of intrinsic (Li⁺) and impurity (H⁺) conductivity have been separated in LBO samples of x, z orientation with small values of intrinsic conductivity, and their temperature dependences have been obtained. The transition temperatures from impurity to intrinsic conductivity with the corresponding increase in the activation enthalpy for x, y, z cuts of LBO crystals have been established. It has been shown that in LBO crystal technology it is desirable to reduce the concentration of doping H⁺ cations.

研究了不同取向LBO晶体的缺陷结构。在晶体结构中发现了各种宏观、中观和微观缺陷。光学显微镜研究揭示了z取向LBO晶体样品中最大的缺陷。LBO样品表面自发形成了枝晶分形结构。这些结构的特征表明了晶片上层的内应力和晶体缺陷。研究了含氢离子为工艺杂质的li3o5 （LBO）晶体离子电导率的各向异性。高温退火对LBO晶体的介电性能和电导率有显著影响。所得结果解释了LBO晶体的相态、电导率和热释电性质等方面的文献数据中存在的矛盾。在x、z两种取向的LBO样品中，本征电导率（Li+）和杂质电导率（H+）的贡献被分离出来，其本征电导率值较小，并得到了它们的温度依赖关系。确定了LBO晶体x、y、z切割从杂质到本征电导率的转变温度和相应的激活焓的增加。研究表明，在LBO晶体技术中，降低掺杂H+阳离子的浓度是可取的。

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引用次数: 0

Understanding interfacial reactions and electrochemical performance of MoS2 cathodes with laponite-based solid polymer electrolytes 了解二硫化钼阴极与钙钛矿基固体聚合物电解质的界面反应和电化学性能

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-18 DOI: 10.1016/j.ssi.2025.117052

Sneha Mandal , Catherine Tom , Subbiah Alwarappan , Ravi Kumar Pujala , Surendra K. Martha , Vijayamohanan K. Pillai

Solid-state batteries have recently attracted unprecedented interest as potentially safe and stable high-energy storage systems for niche applications. However, modulating the mobility of cations is a challenge, which limits the ionic conductivity and hinders further development of practical devices using these solid electrolytes. The electrode/electrolyte interface is critical in determining the ion transport mechanism, cycle life, and energy storage efficiency in secondary batteries. Here, we report some exciting results on a novel composite polymer electrolyte comprising laponite and nanocellulose, which expands the interlayer gap by ∼2 Å, facilitating a high transference number of 0.84, with a robust electrochemical stability window of 2.7–4.8 V with Na metal. Coupling this electrolyte with few-layer MoS₂ nanosheet cathodes exhibiting expansion along the (001) direction and in-plane compression, we demonstrate charge-discharge with an initial capacity of 17 mAh g⁻¹. FT-IR and Raman analyses reveal hydroxyl groups of cellulose interfere with cathode interface stability, contributing to capacity degradation, while promoting robust anode interface formation. These findings elucidate interfacial reactions impacting performance and suggest that tailored electrode or electrolyte modifications could improve cycling stability in solid-state Na batteries employing laponite-based polymer electrolytes and MoS₂ cathodes.

固态电池作为一种潜在的安全稳定的高能存储系统，最近引起了人们前所未有的兴趣。然而，调节阳离子的迁移率是一个挑战，它限制了离子的电导率，并阻碍了使用这些固体电解质的实用设备的进一步发展。电极/电解质界面是决定二次电池离子传输机制、循环寿命和能量存储效率的关键。在这里，我们报告了一种由拉脱土和纳米纤维素组成的新型复合聚合物电解质的一些令人兴奋的结果，该电解质将层间间隙扩大了~ 2 Å，促进了0.84的高转移数，具有2.7-4.8 V的强大电化学稳定窗口。将这种电解质与具有沿（001）方向膨胀和面内压缩的少层MoS2纳米片阴极耦合，我们展示了初始容量为17 mAh g−1的充放电。FT-IR和拉曼分析显示纤维素的羟基干扰阴极界面的稳定性，导致容量下降，同时促进阳极界面的形成。这些发现阐明了界面反应对性能的影响，并表明定制电极或电解质修饰可以提高采用lapoite基聚合物电解质和MoS2阴极的固态Na电池的循环稳定性。

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引用次数: 0

Effect of LiNbO3 surface dry-coating on the air stability of Ga-doped LLZO solid electrolytes LiNbO3表面干涂对掺ga LLZO固体电解质空气稳定性的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-18 DOI: 10.1016/j.ssi.2025.117056

Hyein Song , Young-Woong Song , Hyochan Lee , Jinsub Lim , Jieun Ryu , Yoojeong Noh , Sung-Won Kang , Seung Heon Lee , Jin Geon Yang , Jaekook Kim , Min-Young Kim

Oxide-based garnet-type Li₇La₃Zr₂O₁₂ (LLZO) solid electrolytes (SEs) have attracted significant attention as promising candidates for next-generation all-solid-state batteries (ASSBs) with high ionic conductivity of 1 × 10⁻³–10⁻⁴ S cm⁻¹. However, LLZO is prone to surface degradation upon exposure to H₂O and CO₂ in the air, leading to the formation of Li₂CO₃ impurities. This not only reduces the ionic conductivity but also increases interfacial resistance with the electrode, ultimately impairing the electrochemical and mechanical performance of the cell. In this study, we investigated and compared the air stability of LiNbO₃-coated Ga-LLZO and the pristine Ga-LLZO. According to the Accelerated Durability Test (ADT), the formation of Li₂CO₃ on the surface of LiNbO₃-coated Ga-LLZO pellets was suppressed compared to the pristine Ga-LLZO. The total ionic conductivity of the pristine Ga-LLZO was 3.90 × 10⁻⁴ S cm⁻¹, while the LiNbO₃-coated Ga-LLZO was 9.17 × 10⁻⁴ S cm⁻¹. Therefore, the ionic conductivity maintenance rates after ADT were 79 % for the LiNbO₃-coated Ga-LLZO, compared to only 23 % for the pristine Ga-LLZO. These results demonstrate that surface coating of Ga-LLZO particles with LiNbO₃ effectively suppresses air degradation reactions and significantly contributes to long-term ionic conductivity maintenance and improved air stability.

氧化基石榴石型Li7La3Zr2O12 （LLZO）固体电解质（SEs）具有1 × 10−3-10−4 S cm−1的高离子电导率，作为下一代全固态电池（assb）的有希望的候选者受到了广泛的关注。然而，LLZO暴露在空气中的H2O和CO2中容易发生表面降解，导致Li2CO3杂质的形成。这不仅降低了离子电导率，还增加了与电极的界面电阻，最终损害了电池的电化学和机械性能。在这项研究中，我们研究并比较了linbo3涂层的Ga-LLZO和原始Ga-LLZO的空气稳定性。通过加速耐久性试验（ADT），与原始Ga-LLZO相比，linbo3涂层的Ga-LLZO球团表面Li2CO3的形成受到抑制。原始Ga-LLZO的总离子电导率为3.90 × 10−4 S cm−1，而涂覆linbo3的Ga-LLZO的总离子电导率为9.17 × 10−4 S cm−1。因此，经过ADT处理后，linbo3涂层的Ga-LLZO的离子电导率维持率为79%，而原始Ga-LLZO的离子电导率仅为23%。这些结果表明，在Ga-LLZO颗粒表面涂覆LiNbO3可以有效抑制空气降解反应，并显著有助于长期维持离子电导率和提高空气稳定性。

{"title":"Effect of LiNbO3 surface dry-coating on the air stability of Ga-doped LLZO solid electrolytes","authors":"Hyein Song , Young-Woong Song , Hyochan Lee , Jinsub Lim , Jieun Ryu , Yoojeong Noh , Sung-Won Kang , Seung Heon Lee , Jin Geon Yang , Jaekook Kim , Min-Young Kim","doi":"10.1016/j.ssi.2025.117056","DOIUrl":"10.1016/j.ssi.2025.117056","url":null,"abstract":"<div><div>Oxide-based garnet-type Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> (LLZO) solid electrolytes (SEs) have attracted significant attention as promising candidates for next-generation all-solid-state batteries (ASSBs) with high ionic conductivity of 1 × 10<sup>−3</sup>–10<sup>−4</sup> S cm<sup>−1</sup>. However, LLZO is prone to surface degradation upon exposure to H<sub>2</sub>O and CO<sub>2</sub> in the air, leading to the formation of Li<sub>2</sub>CO<sub>3</sub> impurities. This not only reduces the ionic conductivity but also increases interfacial resistance with the electrode, ultimately impairing the electrochemical and mechanical performance of the cell. In this study, we investigated and compared the air stability of LiNbO<sub>3</sub>-coated Ga-LLZO and the pristine Ga-LLZO. According to the Accelerated Durability Test (ADT), the formation of Li<sub>2</sub>CO<sub>3</sub> on the surface of LiNbO<sub>3</sub>-coated Ga-LLZO pellets was suppressed compared to the pristine Ga-LLZO. The total ionic conductivity of the pristine Ga-LLZO was 3.90 × 10<sup>−4</sup> S cm<sup>−1</sup>, while the LiNbO<sub>3</sub>-coated Ga-LLZO was 9.17 × 10<sup>−4</sup> S cm<sup>−1</sup>. Therefore, the ionic conductivity maintenance rates after ADT were 79 % for the LiNbO<sub>3</sub>-coated Ga-LLZO, compared to only 23 % for the pristine Ga-LLZO. These results demonstrate that surface coating of Ga-LLZO particles with LiNbO<sub>3</sub> effectively suppresses air degradation reactions and significantly contributes to long-term ionic conductivity maintenance and improved air stability.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117056"},"PeriodicalIF":3.3,"publicationDate":"2025-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145322995","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

Synthesis of LiFePO4 cathode materials from amorphous FePO4 precursor: Effects of Li/P molar ratio on crystal defect formation and electrochemical performance 非晶FePO4前驱体合成LiFePO4正极材料：Li/P摩尔比对晶体缺陷形成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 : 2025-10-17 DOI: 10.1016/j.ssi.2025.117050

Yongsheng Chen , Siman Yang , Jianbin Zheng , Mingwei Hu , Mingdeng Wei , Peixun Xiong

As an excellent cathode material, lithium iron phosphate (LiFePO₄) has been widely used in commercial lithium-ion batteries (LIBs). However, the impact of synthetic conditions on LiFePO₄ cathode derived from amorphous iron phosphate (FePO₄) remains underexplored. In the present study, the effects of Li/P molar ratio on the crystallinity and electrochemical properties of LiFePO₄ were investigated in detail using FePO₄ as a precursor. When the Li/P molar ratio in LiFePO₄ was approximately 1, the material exhibited an excellent long-term cycling stability with a high capacity retention of 97 % after 500 cycles. In addition, multiple characterizations demonstrate that the higher molar ratio of the Li/P resulted in the higher concentration of defects in LiFePO₄ crystals, which not only reduced the reversible capacity but also compromised the structural stability, leading to a poor cyclic stability and quick capacity degradation. Therefore, such a work could provide a scientific insight for rational design and synthesis of high-performance LiFePO₄ cathodes from amorphous FePO₄ precursor.

磷酸铁锂（LiFePO4）作为一种优良的正极材料，已广泛应用于商用锂离子电池（LIBs）中。然而，合成条件对非晶态磷酸铁（FePO4）制备的LiFePO4阴极的影响尚不清楚。本文以FePO4为前驱体，研究了Li/P摩尔比对LiFePO4结晶度和电化学性能的影响。当LiFePO4中Li/P摩尔比约为1时，材料表现出优异的长期循环稳定性，500次循环后容量保持率高达97%。此外，多重表征表明，较高的Li/P摩尔比会导致LiFePO4晶体中缺陷浓度的增加，这不仅降低了LiFePO4的可逆容量，而且影响了LiFePO4的结构稳定性，导致其循环稳定性差，容量退化快。因此，该工作为合理设计和合成非晶FePO4前驱体的高性能LiFePO4阴极提供了科学的见解。

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引用次数: 0

Highly conductive Na5YSi4O12 ceramic solid electrolyte by controlling Na deficiency in the precursors 通过控制前驱体钠缺乏制备高导电性Na5YSi4O12陶瓷固体电解质

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-16 DOI: 10.1016/j.ssi.2025.117049

Yoshiki Yasuda, Genta Tateno, Tomohiro Tojo, Ryoji Inada

Na₅YSi₄O₁₂ (NYSO) is known as a fast sodium-ion conductive oxide with both high ionic conductivity above 1 mS cm⁻¹ at room temperature and excellent electrochemical stability against sodium metal anode, making it promising for solid-state sodium battery application. In this study, we investigated the influence of non-stoichiometry in the precursor composition on the crystal phase, microstructure and ionic conducting property of NYSO. It is found that NYSO prepared from the precursor with slight sodium-deficient composition showed the highest total (bulk + grain boundary) conductivity of 2.8 mS cm⁻¹ at room temperature, which is superior to NYSO with stoichiometric precursor composition (∼ 1 mS cm⁻¹). Although excess Na deficiency in the precursor results in the formation of Na₃YSi₃O₉ phase, it does not influence so much on the sinterability and grain-boundary resistance of NYSO. Mitigation of Na₉YSi₆O₁₈ phase formation during the fabrication is very important for the densification and reduction of grain-boundary resistance in NYSO ceramic electrolyte.

Na5YSi4O12 （NYSO）是一种快速的钠离子导电氧化物，在室温下具有高于1ms cm - 1的高离子电导率，并且对钠金属阳极具有良好的电化学稳定性，使其在固态钠电池中的应用前景广阔。在本研究中，我们研究了前驱体组成中的非化学计量对NYSO晶体相、微观结构和离子导电性能的影响。研究发现，由微缺钠前驱体制备的NYSO在室温下表现出最高的总电导率（体积+晶界），为2.8 mS cm−1，优于由化学测量前驱体组成的NYSO （~ 1 mS cm−1）。虽然前驱体中过量的Na缺乏导致了Na3YSi3O9相的形成，但对NYSO的烧结性能和晶界电阻影响不大。在制备过程中减缓Na9YSi6O18相的形成对于NYSO陶瓷电解质的致密化和降低晶界电阻非常重要。

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引用次数: 0

Direct electrochemical ammonia synthesis from water and air via solid-state protonic electrochemical cells – A critical review 通过固态质子电化学电池从水和空气中直接电化学合成氨

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-15 DOI: 10.1016/j.ssi.2025.117042

Jonathan Perry, Jafar Zanganeh, Behdad Moghtaderi

Solid-state protonic electrochemical cells (SSPECs) are gaining attention as a technology that has great potential for sustainable ammonia (NH₃) synthesis, energy storage, and power generation, while providing seamless integration with renewable energy thereby offering a pathway towards a low-carbon economy. However, challenges remain in achieving industrially relevant NH₃ production rates and overall energy efficiencies required for commercial applications. Key barriers are outlined, including the thermodynamically favoured hydrogen evolution reaction (HER) at the cathode, which limits selectivity and lowers efficiencies. Recent advancements are highlighted including the importance of rational catalyst design, often focusing on functionalisation or defect-engineered sites, and integrated systems optimisation. In particular, co-fed electrochemical nitrogen reduction (eNRR) presents a strategy for enhancing NH₃ yields, while plasma-assisted processes also show promise in increasing both NH₃ production rates and selectivity. Furthermore, the lack of consistent ammonia detection methods has been outlined as a critical variable in comparative performance evaluation, which significantly impacts robust benchmarking of new catalyst and system designs. Despite these current limitations, SSPECs present a compelling opportunity for converting renewable electricity into liquid fuels, with significant potential for scaling solid-state protonic eNRR.

固态质子电化学电池（SSPECs）在合成氨（NH₃）、能源储存、发电等方面具有巨大潜力，而且与可再生能源无缝结合，为低碳经济提供了途径，因此备受关注。然而，在实现商业应用所需的工业相关的NH₃生产率和整体能源效率方面仍然存在挑战。概述了关键的障碍，包括热力学上有利的阴极析氢反应（HER），它限制了选择性和降低了效率。最近的进展包括合理催化剂设计的重要性，通常侧重于功能化或缺陷工程位点，以及集成系统优化。特别是，共馈电化学氮还原（eNRR）提出了一种提高NH3产率的策略，而等离子体辅助工艺也显示出提高NH₃产率和选择性的希望。此外，缺乏一致的氨检测方法已被概述为比较性能评估的关键变量，这将显著影响新催化剂和系统设计的稳健基准。尽管目前存在这些限制，但SSPECs为将可再生电力转化为液体燃料提供了一个引人注目的机会，具有扩大固态质子eNRR的巨大潜力。

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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 : 2025-10-15 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

Influence of succinonitrile on structural, thermal, electrochemical and optical properties of sodium-ion conducting PVdF-HFP based gel polymer electrolyte membranes 丁二腈对钠离子导电PVdF-HFP基凝胶聚合物电解质膜结构、热、电化学和光学性能的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-14 DOI: 10.1016/j.ssi.2025.117045

Vishalkumar Oli , M. Initha , Vaishali Madhani , Kalappa Prashantha , Neeladri Das , Sujeet Kumar Chaurasia , Kuldeep Mishra , Rahul Gera , Jehova Jire L. Hmar , Deepak Kumar

A novel sodium (Na)-ion conducting gel polymer electrolyte composed of poly(vinylidine-fluoride-co-hexafluoropropylene) (PVdF-HFP) complexed with sodium tetrafluoro-borate (NaBF₄) and ethylene carbonate (EC)-propylene carbonate (PC) as a co-solvent, coupled via differing fractions of a non-ionic plastic crystal succinonitrile (SN) are developed and studied. X-ray diffraction and Fourier transform infra-red studies identifies significant structural alterations in terms of reduced crystallinity and the interactions among the polymeric components on incorporation of SN. The thermogravimetric and differential scanning calorimetry investigations indicate that the synthesized electrolytes experience a weight reduction of less than 5 % up to 100 °C and maintain the gel stage up to 125 °C, respectively. The elevated polarity and rotational disorder of the SN molecules in the plastic-crystalline phase facilitate the improvement of ionic conductivity in the PVdF-HFP/EC-PC/NaBF₄ complex system, achieving an optimal RT ionic conductivity of about 4.55 × 10⁻³ S cm⁻¹ with the incorporation of 50 wt% of SN with purely ionic character. The working voltage range for the optimized electrolyte specimen was 4.9 V. The UV–Vis studies demonstrate the enhancement in absorbance and the reduction of the optical band gap by adding SN up to 50 wt%. The experimental results of the contact angle indicated an improvement in hydrophobicity with higher concentrations of SN across the PVdF-HFP matrix. The operational attributes for the SN-incorporated polymeric system suggest their possible use as electrolytes in electrochemical energy storage applications.

研究了以聚偏乙烯-氟-共六氟丙烯（PVdF-HFP）与四氟硼酸钠（NaBF4）和碳酸乙烯(EC)-碳酸丙烯（PC）为共溶剂，通过不同馏分的非离子塑料晶体丁二腈（SN）偶联的新型钠离子导电凝胶聚合物电解质。x射线衍射和傅里叶变换红外研究发现，SN加入后，聚合物的结晶度降低，聚合物组分之间的相互作用发生了显著的结构变化。热重法和差示扫描量热法研究表明，合成的电解质在100°C时重量减轻不到5%，在125°C时保持凝胶状态。在PVdF-HFP/EC-PC/NaBF4复合体系中，SN分子的极性和旋转无序性的提高促进了离子电导率的提高，当纯离子性质的SN加入量为50%时，其RT离子电导率约为4.55 × 10−3 S cm−1。优化后电解质试样的工作电压范围为4.9 V。紫外-可见研究表明，当SN添加到50%时，吸光度增强，光学带隙减小。接触角实验结果表明，随着SN浓度的增加，PVdF-HFP基质的疏水性得到改善。sn掺杂聚合物体系的操作特性表明它们可能在电化学储能应用中用作电解质。

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