Solid State Ionics最新文献_第8页

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 : 2025-11-01 Epub Date: 2025-09-05 DOI: 10.1016/j.ssi.2025.117012

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

引用次数: 0

Influence of Germanium oxide nanoparticles on the electrical conductivity of Li-ion conducting NaCMC/PVA nanocomposite films 氧化锗纳米颗粒对锂离子导电NaCMC/PVA纳米复合膜电导率的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-01 Epub Date: 2025-09-09 DOI: 10.1016/j.ssi.2025.117015

Seshan T.N , Vipin Cyriac , Demappa T , Ismayil

This study examines the influence of GeO₂ nanoparticles (NPs) on the ionic conductivity and structural properties of NaCMC/PVA/LiBr-based solid polymer electrolytes synthesized via solution casting technique. XRD analysis revealed enhanced amorphous character with increasing GeO₂ content. FTIR spectra confirmed interactions between GeO₂ NPs and the polymer-salt matrix. SEM and EDX analyses were used to investigate morphology and elemental composition. UV–Vis spectroscopy showed a redshift in absorption edge and a bandgap reduction from 5.70 to 5.50 eV with GeO₂ addition. Impedance spectroscopy (100 Hz - 5 MHz) indicated improved ionic conductivity, following Jonscher's universal power law, with a maximum value of (1.13 ± 0.02) × 10⁻⁵ S cm⁻¹ at 5 wt% GeO₂. LSV confirmed electrochemical stability up to 2.7 V. Dielectric studies revealed an increase in permittivity due to interfacial polarization. Transference number measurement evaluates the relative contributions of ionic and electronic charge carriers in solid polymer electrolytes using polarization technique. These results highlight the potential of GeO₂-dispersed NaCMC/PVA/LiBr films for energy storage applications.

本研究考察了纳米GeO2对溶液铸造法制备的NaCMC/PVA/ lib基固体聚合物电解质的离子电导率和结构性能的影响。XRD分析表明，随着GeO2含量的增加，非晶态特性增强。FTIR光谱证实了GeO2 NPs与聚合物盐基质之间的相互作用。SEM和EDX分析研究了其形貌和元素组成。紫外可见光谱显示，添加GeO2后，吸收边红移，带隙从5.70 eV减小到5.50 eV。阻抗谱（100 Hz - 5 MHz）表明离子电导率提高，符合Jonscher的通用幂定律，在5 wt%的GeO2下，最大值为（1.13±0.02）× 10−5 S cm−1。LSV确认电化学稳定性高达2.7 V。介电研究表明，由于界面极化，介电常数增加。转移数测量是利用极化技术评价固体聚合物电解质中离子载流子和电子载流子的相对贡献。这些结果突出了geo2分散NaCMC/PVA/LiBr薄膜在储能应用中的潜力。

{"title":"Influence of Germanium oxide nanoparticles on the electrical conductivity of Li-ion conducting NaCMC/PVA nanocomposite films","authors":"Seshan T.N , Vipin Cyriac , Demappa T , Ismayil","doi":"10.1016/j.ssi.2025.117015","DOIUrl":"10.1016/j.ssi.2025.117015","url":null,"abstract":"<div><div>This study examines the influence of GeO2 nanoparticles (NPs) on the ionic conductivity and structural properties of NaCMC/PVA/LiBr-based solid polymer electrolytes synthesized via solution casting technique. XRD analysis revealed enhanced amorphous character with increasing GeO2 content. FTIR spectra confirmed interactions between GeO2 NPs and the polymer-salt matrix. SEM and EDX analyses were used to investigate morphology and elemental composition. UV–Vis spectroscopy showed a redshift in absorption edge and a bandgap reduction from 5.70 to 5.50 eV with GeO2 addition. Impedance spectroscopy (100 Hz - 5 MHz) indicated improved ionic conductivity, following Jonscher's universal power law, with a maximum value of (1.13 ± 0.02) × 10−5 S cm−1 at 5 wt% GeO2. LSV confirmed electrochemical stability up to 2.7 V. Dielectric studies revealed an increase in permittivity due to interfacial polarization. Transference number measurement evaluates the relative contributions of ionic and electronic charge carriers in solid polymer electrolytes using polarization technique. These results highlight the potential of GeO2-dispersed NaCMC/PVA/LiBr films for energy storage applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"431 ","pages":"Article 117015"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020852","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

Separating grain vs. grain boundary conductivity in Li2OHCl antiperovskite solid electrolytes during and after synthesis Li2OHCl反钙钛矿固体电解质合成过程中与合成后晶粒分离与晶界电导率的关系

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-01 Epub Date: 2025-10-07 DOI: 10.1016/j.ssi.2025.117038

Kai-Wei Lan , Mebatsion S. Gebre , Beniamin Zahiri , Paul V. Braun , Daniel P. Shoemaker , Nicola H. Perry

Oxychloride antiperovskite Li conductors represent compelling candidates for battery solid electrolytes (SEs), owing to their stability vs. Li and ductility. However, the influence of synthesis route and resulting microstructure on transport behavior remains incompletely studied. We prepared Li₂OHCl in 3 ways: a) cold-pressing of solid-state-synthesized orthorhombic and cubic Li₂OHCl powders, b) sintering of these powders into pellets, and c) reactive sintering of high-energy ball-milled LiCl and LiOH reagents. We studied the impedance spectra for route a) at 25 °C, for route b) from ∼25–270 °C, and for route c) during the reactive sintering process to form the cubic phase, coupled to in-situ XRD. Cold-pressed powders typically exhibited a single impedance arc, while ex-situ sintered pellets exhibited an offset resistance with lower activation energy (∼0.44–0.48 eV) >60 °C and an arc with higher activation energy (∼0.6–1.2 eV). With increasing temperature, the offset feature increasingly dominated the impedance spectra, and its associated conductivity (1.9 × 10⁻³ Scm⁻¹) was in good agreement with the total conductivity magnitude (1.3 × 10⁻³ Scm⁻¹) and activation energy (0.42 eV) measured during reactive sintering of reagents once the cubic phase was obtained (>160 °C). Spectra were simulated using the brick layer model corresponding to the microstructure observed by SEM and varied specific conductivities and permittivities. Based on the above results, we attribute the offset feature to grains and the arc to blocking grain boundaries. A signature of possible proton transport in adsorbed H₂O layers was observed in non-Arrhenius behavior below ∼60 °C, rendering separation of grain and grain boundary Li transport challenging at room temperature.

氯氧反钙钛矿锂导体由于其相对于锂的稳定性和延展性而成为电池固体电解质（SEs）的令人信服的候选者。然而，合成路线和合成后的微观结构对输运行为的影响尚未得到充分的研究。我们采用三种方法制备Li2OHCl: a)冷压固态合成的正交和立方Li2OHCl粉末，b)将这些粉末烧结成球团，c)高能球磨LiCl和LiOH试剂的反应烧结。我们研究了路线a)在25°C时的阻抗谱，路线b)在~ 25 - 270°C时的阻抗谱，以及路线C)在反应烧结过程中形成立方相的阻抗谱，并与原位XRD相结合。冷压粉末通常表现为单阻抗电弧，而非原位烧结颗粒表现为具有较低活化能（~ 0.44-0.48 eV） >；60°C的偏移电阻和具有较高活化能（~ 0.6-1.2 eV）的电弧。随着温度的升高，偏置特征在阻抗谱中占主导地位，其相关的电导率（1.9 × 10−3 Scm−1）与获得立方相（>160°C）时反应烧结时测量的总电导率（1.3 × 10−3 Scm−1）和活化能（0.42 eV）吻合良好。采用与SEM观察到的微观结构相对应的砖层模型模拟了光谱，并改变了比电导率和介电常数。基于上述结果，我们将偏移特征归因于晶粒，将圆弧归因于阻挡晶界。在~ 60℃以下，在非arrhenius行为中观察到吸附H2O层中可能的质子输运特征，这使得在室温下晶粒和晶界Li输运的分离变得困难。

{"title":"Separating grain vs. grain boundary conductivity in Li2OHCl antiperovskite solid electrolytes during and after synthesis","authors":"Kai-Wei Lan , Mebatsion S. Gebre , Beniamin Zahiri , Paul V. Braun , Daniel P. Shoemaker , Nicola H. Perry","doi":"10.1016/j.ssi.2025.117038","DOIUrl":"10.1016/j.ssi.2025.117038","url":null,"abstract":"<div><div>Oxychloride antiperovskite Li conductors represent compelling candidates for battery solid electrolytes (SEs), owing to their stability vs. Li and ductility. However, the influence of synthesis route and resulting microstructure on transport behavior remains incompletely studied. We prepared Li2OHCl in 3 ways: a) cold-pressing of solid-state-synthesized orthorhombic and cubic Li2OHCl powders, b) sintering of these powders into pellets, and c) reactive sintering of high-energy ball-milled LiCl and LiOH reagents. We studied the impedance spectra for route a) at 25 °C, for route b) from ∼25–270 °C, and for route c) during the reactive sintering process to form the cubic phase, coupled to in-situ XRD. Cold-pressed powders typically exhibited a single impedance arc, while ex-situ sintered pellets exhibited an offset resistance with lower activation energy (∼0.44–0.48 eV) >60 °C and an arc with higher activation energy (∼0.6–1.2 eV). With increasing temperature, the offset feature increasingly dominated the impedance spectra, and its associated conductivity (1.9 × 10−3 Scm−1) was in good agreement with the total conductivity magnitude (1.3 × 10−3 Scm−1) and activation energy (0.42 eV) measured during reactive sintering of reagents once the cubic phase was obtained (>160 °C). Spectra were simulated using the brick layer model corresponding to the microstructure observed by SEM and varied specific conductivities and permittivities. Based on the above results, we attribute the offset feature to grains and the arc to blocking grain boundaries. A signature of possible proton transport in adsorbed H2O layers was observed in non-Arrhenius behavior below ∼60 °C, rendering separation of grain and grain boundary Li transport challenging at room temperature.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"431 ","pages":"Article 117038"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262984","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

Synergy-electrode based on micron-sized LiNi0.5Mn0.3Co0.2O2/LiFePO4 particles with bimodal size distribution 基于微米级双峰尺寸分布的LiNi0.5Mn0.3Co0.2O2/LiFePO4粒子的协同电极

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-01 Epub Date: 2025-08-21 DOI: 10.1016/j.ssi.2025.117000

Oncu Akyildiz , Ezgi Yılmaz

We investigated the electrochemical behavior of binary blend cathodes made by mixing micro-spheres of LiNi_0.5Mn_0.3Co_0.2O₂ and smaller micro-platelets of LiFePO₄ in different proportions (10–40 wt%). Results show that the discharge profiles of the blended electrodes at 0.1C are predictable through a model based on the weighted averages of specific differential capacities of pristine electrodes. However, at high C-rates (>1C), the blended electrode contains 20 wt% LiFePO₄ (coined as the synergy-electrode) shows significantly higher discharge capacity and better capacity retention (observed up to the 100th cycle) than other electrodes. The synergy is rationalized using cyclic voltammetry and electrochemical impedance spectroscopy, indicating the facilitation of the charge-discharge reactions, reduction of both the bulk and the charge-transfer resistances, and higher Li diffusion coefficients observed for the synergy-electrode.

研究了以不同比例（10-40 wt%）混合LiNi0.5Mn0.3Co0.2O2微球和较小的LiFePO4微片制成的二元共混阴极的电化学行为。结果表明，基于原始电极比差容量加权平均的模型可以预测混合电极在0.1C下的放电曲线。然而，在高倍率（>1C）下，混合电极含有20wt %的LiFePO4（称为协同电极），与其他电极相比，显示出更高的放电容量和更好的容量保持能力（观察到100次循环）。利用循环伏安法和电化学阻抗谱对协同作用进行了合理化分析，表明协同电极的充放电反应更容易，体积电阻和电荷转移电阻都降低了，并且观察到更高的Li扩散系数。

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 : 2025-11-01 Epub 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。

{"title":"Effect of hydration level on zinc electrolyte properties","authors":"Alireza Mashayekhi","doi":"10.1016/j.ssi.2025.117011","DOIUrl":"10.1016/j.ssi.2025.117011","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 117011"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144932595","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

Self-rectifying hysteresis with dynamic conductance modulation in amorphous-nanocrystalline lanthanum nickelate based memristive devices 非晶纳米镍酸镧基忆阻器件中动态电导调制的自整流磁滞

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-01 Epub Date: 2025-10-06 DOI: 10.1016/j.ssi.2025.117039

Aleksandra Koroleva , Dmitry Kuzmichev , Laetitia Rapenne , Hervé Roussel , Carmen Jiménez , Christoph Schlueter , Céline Ternon , Elena-Ioana Vatajelu , Mónica Burriel

In this work, an investigation of the structural properties of the lanthanum nickelate (LNO) films grown by metal-organic chemical vapor deposition (MOCVD) at 450 °C as well as the memristive properties of the TiN/LNO/Pt devices based on the back-end-of-the-line-compatible LNO films is carried out. We show that the films deposited at 450 °C consist of incipient nanocrystals of the La₂NiO_4+δ phase randomly distributed within the amorphous matrix. This peculiar nanostructure gives rise to the self-rectifying double-pinched hysteresis effect in TiN/LNO/Pt devices. In addition, the device demonstrates area dependence of the resistance in the high and low resistance states, which together with the absence of a forming process indicates nonfilamentary resistive switching, based on space charge accumulation under applied bias. The memory window can be increased through the application of a higher voltage amplitude or subsequent sweeps at constant voltage, which indicates the ability of the device for dynamic conductance modulation. Overall, self-selective and forming-free nonfilamentary TiN/LNO/Pt devices can be integrated in neuromorphic arrays without the additional selector, which allows for increased integration density.

在这项工作中，研究了在450°C下由金属有机化学气相沉积（MOCVD）生长的镍酸镧（LNO）薄膜的结构性能以及基于后端相容LNO薄膜的TiN/LNO/Pt器件的记忆性。结果表明，在450°C下沉积的薄膜由La2NiO4+δ相的纳米晶组成，这些纳米晶随机分布在非晶基体中。这种特殊的纳米结构在TiN/LNO/Pt器件中产生了自整流双箝位迟滞效应。此外，该器件在高电阻和低电阻状态下显示出电阻的面积依赖性，加上没有形成过程，表明基于施加偏压下的空间电荷积累的非丝状电阻开关。存储器窗口可以通过施加更高的电压幅值或随后的恒电压扫描来增加，这表明该器件具有动态电导调制的能力。总的来说，自选择和无形成的非丝状TiN/LNO/Pt器件可以集成在神经形态阵列中，而无需额外的选择器，这可以增加集成密度。

{"title":"Self-rectifying hysteresis with dynamic conductance modulation in amorphous-nanocrystalline lanthanum nickelate based memristive devices","authors":"Aleksandra Koroleva , Dmitry Kuzmichev , Laetitia Rapenne , Hervé Roussel , Carmen Jiménez , Christoph Schlueter , Céline Ternon , Elena-Ioana Vatajelu , Mónica Burriel","doi":"10.1016/j.ssi.2025.117039","DOIUrl":"10.1016/j.ssi.2025.117039","url":null,"abstract":"<div><div>In this work, an investigation of the structural properties of the lanthanum nickelate (LNO) films grown by metal-organic chemical vapor deposition (MOCVD) at 450 °C as well as the memristive properties of the TiN/LNO/Pt devices based on the back-end-of-the-line-compatible LNO films is carried out. We show that the films deposited at 450 °C consist of incipient nanocrystals of the La2NiO4+δ phase randomly distributed within the amorphous matrix. This peculiar nanostructure gives rise to the self-rectifying double-pinched hysteresis effect in TiN/LNO/Pt devices. In addition, the device demonstrates area dependence of the resistance in the high and low resistance states, which together with the absence of a forming process indicates nonfilamentary resistive switching, based on space charge accumulation under applied bias. The memory window can be increased through the application of a higher voltage amplitude or subsequent sweeps at constant voltage, which indicates the ability of the device for dynamic conductance modulation. Overall, self-selective and forming-free nonfilamentary TiN/LNO/Pt devices can be integrated in neuromorphic arrays without the additional selector, which allows for increased integration density.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"431 ","pages":"Article 117039"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263034","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

Optimization of Ba0.5Sr0.5Co0.8Fe0.2O3-δ-BaCe0.7Zr0.1Y0.1Yb0.1O3-δ composite electrodes: Influence of component ratio and current collector Ba0.5Sr0.5Co0.8Fe0.2O3-δ- bace0.7 zr0.1 y0.1 yb0.1 o3 -δ复合电极的优化：组分比和集流器的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-01 Epub Date: 2025-09-30 DOI: 10.1016/j.ssi.2025.117035

Kristina Fedorova , Egor Gordeev , Olga Seliverstova , Ekaterina Antonova

Composite Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ-BaCe_0.7Zr_0.1Y_0.1Yb_0.1O_3-δ electrodes were studied as promising cathodes for application in electrochemical devices based on a proton-conducting electrolyte. Electrochemical activity of electrodes with different ratio of components was investigated by impedance spectroscopy in the oxygen-containing atmospheres, humidified with H₂O and D₂O. The optimal ratio of components in the electrode was found to be 80/20 wt% Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ/BaCe_0.7Zr_0.1Y_0.1Yb_0.1O_3-δ. The polarization resistance of the electrode of such a composition is 0.8 Ohm*cm² at 650 °C in a H₂O-humidified air atmosphere. The use of a current collector made it possible to reduce the polarization resistance to 0.5 Ohm*cm² under the same conditions. For all investigated compositions and conditions, the H/D isotope effect in the electrode response was detected. The influence of the ratio of the electrode components and the current collector on the mechanism of the electrode reaction is discussed.

研究了复合电极Ba0.5Sr0.5Co0.8Fe0.2O3-δ- bace0.7 zr0.1 y0.1 yb0.1 o3 -δ在质子导电电解质电化学器件中的应用前景。采用阻抗谱法研究了不同组分比例的电极在含氧气氛中，用H2O和D2O加湿后的电化学活性。电极中各组分的最佳配比为80/20 wt% Ba0.5Sr0.5Co0.8Fe0.2O3-δ/BaCe0.7Zr0.1Y0.1Yb0.1O3-δ。这种组合物的电极在650℃的水湿空气环境中极化电阻为0.8欧姆*cm2。在相同条件下，使用集流器可以将极化电阻降低到0.5欧姆*平方厘米。对于所有研究的成分和条件，H/D同位素效应在电极响应中被检测到。讨论了电极组分与集流器配比对电极反应机理的影响。

{"title":"Optimization of Ba0.5Sr0.5Co0.8Fe0.2O3-δ-BaCe0.7Zr0.1Y0.1Yb0.1O3-δ composite electrodes: Influence of component ratio and current collector","authors":"Kristina Fedorova , Egor Gordeev , Olga Seliverstova , Ekaterina Antonova","doi":"10.1016/j.ssi.2025.117035","DOIUrl":"10.1016/j.ssi.2025.117035","url":null,"abstract":"<div><div>Composite Ba0.5Sr0.5Co0.8Fe0.2O3-δ-BaCe0.7Zr0.1Y0.1Yb0.1O3-δ electrodes were studied as promising cathodes for application in electrochemical devices based on a proton-conducting electrolyte. Electrochemical activity of electrodes with different ratio of components was investigated by impedance spectroscopy in the oxygen-containing atmospheres, humidified with H2O and D2O. The optimal ratio of components in the electrode was found to be 80/20 wt% Ba0.5Sr0.5Co0.8Fe0.2O3-δ/BaCe0.7Zr0.1Y0.1Yb0.1O3-δ. The polarization resistance of the electrode of such a composition is 0.8 Ohm*cm2 at 650 °C in a H2O-humidified air atmosphere. The use of a current collector made it possible to reduce the polarization resistance to 0.5 Ohm*cm2 under the same conditions. For all investigated compositions and conditions, the H/D isotope effect in the electrode response was detected. The influence of the ratio of the electrode components and the current collector on the mechanism of the electrode reaction is discussed.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"431 ","pages":"Article 117035"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217518","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

The extraction of hopping frequencies of mobile fluorine ions in the superionic conductor Ba0.5La0.5F2.5 from electrical modulus spectroscopy data 利用电模谱数据提取超离子导体Ba0.5La0.5F2.5中可移动氟离子的跳频

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-01 Epub Date: 2025-09-07 DOI: 10.1016/j.ssi.2025.117017

N.I. Sorokin

The spectra of the complex electrical modulus M*(ν) = M ^/+iM ^// for a single crystal of the superionic conductor Ba_0.5La_0.5F_2.5 with a fluorite-type structure (sp. gr.

Fm \bar{3} m

) were studied in the frequency range of 10⁻¹–10⁷ Hz at temperatures of 210–407 K. The diagrams of the complex modulus M ^/(ν), M ^//(ν) take the Cole-Cole form and are characterized by the presence of a distribution of relaxation times of mobile ion carriers. On the frequency dependences of the imaginary part of the complex modulus M ^//(ν), the relaxation peaks are observed, caused by hopping rates of mobile interstitial fluorine ions (charge carriers). Based on the temperature change in the position of relaxation maxima, calculations were made of the activation enthalpy ΔH_h and the average frequency ν_h of carrier jumps. The calculated values of ΔH_h and ν_h are in satisfactory agreement with the results obtained by the Almond-West method for this crystal. Within the framework of the crystallophysical model, the carrier mobility μ_mob and mobile ion concentration n_mob were calculated. Research using the method of modular spectroscopy is of undoubted interest for the further search and creation of fluorine-conducting solid electrolytes.

在210 ~ 407 K的频率范围内，研究了具有荧光型结构的超离子导体Ba0.5La0.5F2.5 （sp. gr. Fm3¯M）单晶的复电模量M*(ν) = M /+iM //的光谱。复模量M /(ν)和M //(ν)的图采用Cole-Cole形式，其特征是存在一个移动离子载流子的弛豫时间分布。在复模量M //(ν)虚部的频率依赖上，观察到由移动间隙氟离子（载流子）的跳变率引起的弛豫峰。根据弛豫最大值位置的温度变化，计算了活化焓ΔHh和载流子跳变的平均频率νh。该晶体的ΔHh和νh的计算值与Almond-West法的计算结果吻合得很好。在晶体物理模型的框架内，计算了载流子迁移率μmob和迁移离子浓度nmob。使用模光谱方法的研究无疑对进一步寻找和创造氟导电固体电解质具有重要意义。

{"title":"The extraction of hopping frequencies of mobile fluorine ions in the superionic conductor Ba0.5La0.5F2.5 from electrical modulus spectroscopy data","authors":"N.I. Sorokin","doi":"10.1016/j.ssi.2025.117017","DOIUrl":"10.1016/j.ssi.2025.117017","url":null,"abstract":"<div><div>The spectra of the complex electrical modulus M*(ν) = M /+iM // for a single crystal of the superionic conductor Ba0.5La0.5F2.5 with a fluorite-type structure (sp. gr. <math><mi>Fm</mi><mover><mn>3</mn><mo>¯</mo></mover><mi>m</mi></math>) were studied in the frequency range of 10−1–107 Hz at temperatures of 210–407 K. The diagrams of the complex modulus M /(ν), M //(ν) take the Cole-Cole form and are characterized by the presence of a distribution of relaxation times of mobile ion carriers. On the frequency dependences of the imaginary part of the complex modulus M //(ν), the relaxation peaks are observed, caused by hopping rates of mobile interstitial fluorine ions (charge carriers). Based on the temperature change in the position of relaxation maxima, calculations were made of the activation enthalpy ΔHh and the average frequency νh of carrier jumps. The calculated values of ΔHh and νh are in satisfactory agreement with the results obtained by the Almond-West method for this crystal. Within the framework of the crystallophysical model, the carrier mobility μmob and mobile ion concentration nmob were calculated. Research using the method of modular spectroscopy is of undoubted interest for the further search and creation of fluorine-conducting solid electrolytes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"431 ","pages":"Article 117017"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007565","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

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 : 2025-11-01 Epub 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。

{"title":"Effect of iron‑phosphorus ratio on the structure and electrochemical performance of non-stoichiometric carbon-coated LiFePO4 cathode materials","authors":"Zijun Fang , Guorong Hu , Ke Du , Zhongdong Peng , Quanjun Fu , Haifeng Wang , Xiyuan Jiang , Yanbing Cao","doi":"10.1016/j.ssi.2025.117009","DOIUrl":"10.1016/j.ssi.2025.117009","url":null,"abstract":"<div><div>In this paper, non-stoichiometric LiFexPO4/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, LiFe0.97PO4/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.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 117009"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144926044","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

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 : 2025-11-01 Epub 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。

{"title":"The critical role of Al2O3, BaTiO3 and ZrO2 nanoceramic fillers in PVDF-HFP based composite polymer electrolytes for high performance lithium-metal batteries","authors":"Mononita Das , Kuntal Ghosh , Vijaya , Mir Wasim Raja","doi":"10.1016/j.ssi.2025.117008","DOIUrl":"10.1016/j.ssi.2025.117008","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 117008"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913477","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