Solid State Ionics最新文献

{"title":"Cation disorder and lithium conductivity in mechanochemically synthesized chloride solid electrolytes","authors":"Raül Artal ,&nbsp;Henrik Lyder Andersen ,&nbsp;Rafael Del Olmo ,&nbsp;Irune Villaluenga ,&nbsp;Isabel Sobrados ,&nbsp;Virginia Diez-Gómez ,&nbsp;Javier Gainza ,&nbsp;María Teresa Fernández-Diaz ,&nbsp;José Antonio Alonso ,&nbsp;Ricardo Jimenez ,&nbsp;Ainara Aguadero","doi":"10.1016/j.ssi.2025.116952","DOIUrl":"10.1016/j.ssi.2025.116952","url":null,"abstract":"<div><div>Developing fast, stable, and scalable Li conductors is crucial for advancing all-solid-state batteries (ASSBs). Here, we present a rapid, one-hour mechanochemical synthesis of chloride electrolytes Li₂B_xCl₄ (B = Zn, Mg, Zr and x = 1 and 2/3) <em>via</em> high-energy ball milling (HEBM), achieving the targeted spinel phase without the need for any annealing steps. In Li₂ZnCl₄ electrochemical impedance spectroscopy reveals an unexpected, reversible low-temperature ionic transition at ∼75 °C, leading to a dramatic increase in total Li⁺ conductivity, from 2.95·10⁻⁹ S·cm⁻¹ at 25 °C to an extrapolated room temperature conductivity of 3.24·10⁻⁵ S·cm⁻¹ following heating to 125 °C. To elucidate the structural origins of this transition, we employ neutron powder diffraction (NPD), variable-temperature powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), and ⁶Li MAS NMR spectroscopy. We explore the stabilization of the high conducting phase <em>via</em> the introduction of host cation vacancies and therefore increasing the Li/B ratio based on the spinel-related compounds, Li₂Zn_1/3Zr_1/3Cl₄ and Li₂Mg_1/3Zr_1/3Cl₄, synthesized <em>via</em> the same one-hour mechanochemical approach. Rietveld refinement of NPD data reveals a monoclinic lattice distortion and cation disorder in both compounds, which open new Li conduction pathways. In both materials, 2–4 orders of magnitude increase of conductivity is achieved by aliovalent Zr⁴⁺-substitution compared to the undoped counterparts Li₂ZnCl₄ and Li₂MgCl₄, leading to maximum bulk conductivities up to 10⁻⁴ S·cm⁻¹ at room temperature. Notably, the investigated chloride-based solid electrolytes consist of non-critical elements and exhibit high thermal stability up to at least 190 °C which can be key for easy scalable processing. These results highlight the potential of spinel-based chloride electrolytes as candidates for next-generation solid-state battery applications, combining rapid and scalable synthesis with promising ionic transport properties.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116952"},"PeriodicalIF":3.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144572787","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}

{"title":"Kinetic Monte Carlo simulation of proton conductivity in Y-doped barium cerate","authors":"Giulia Winterhoff ,&nbsp;Steffen Neitzel-Grieshammer","doi":"10.1016/j.ssi.2025.116953","DOIUrl":"10.1016/j.ssi.2025.116953","url":null,"abstract":"<div><div>Barium cerate provides high protonic conductivity when doped with trivalent ions such as yttrium. Insights into the details of proton migration can be obtained by density functional theory, providing information about proton-dopant interactions and migration barriers. In this work, we give a summarizing overview of calculated energy parameters from the literature. These parameters are applied in kinetic Monte Carlo simulations to estimate the activation energy of proton conduction in Y-doped barium cerate. While the simulated values are lower than the experimental values, they are close to previously reported simulation results on Gd-doped barium cerate.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116953"},"PeriodicalIF":3.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144572786","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}

{"title":"High specific capacity O3-NaNi₁/₃Fe₁/₃Mn₁/₃O₂ cathode material for sodium-ion batteries","authors":"Jiatai Wang ,&nbsp;Hongyun Liu ,&nbsp;Yan Tan ,&nbsp;Chao Fan ,&nbsp;Yuanyuan Li ,&nbsp;Jiting Li ,&nbsp;Xuchao Zhang ,&nbsp;Yansheng Rong ,&nbsp;Jian Li","doi":"10.1016/j.ssi.2025.116958","DOIUrl":"10.1016/j.ssi.2025.116958","url":null,"abstract":"<div><div>Sodium-ion batteries (SIBs) have emerged as a promising alternative to lithium-ion batteries (LIBs) due to the abundance of sodium resources and lower material costs. O3-type layered oxides, particularly nickel‑manganese-based materials have a stable crystal structure. The preparation method of sodium-ion battery cathode materials is particularly crucial for their electrochemical performance. The conventional coprecipitation method imposes relatively stringent requirements regarding the concentrations of precipitants and complexing agents, as well as the inflow rate and pH control. Herein, the precursor of NaNi_1/3Fe_1/3Mn_1/3O₂ is prepared by the homogeneous co-precipitation, and the di-n-butylamine is used as the precipitant. Then O3-type NaNi₁_/₃Fe₁_/₃Mn₁_/₃O₂ cathode material is obtained at calcination temperatures ranging from 800 °C to 900 °C. The sample calcined at 850 °C, exhibits lower Mn³⁺ content, which effectively suppresses the Jahn-Teller effect. Electrochemical tests demonstrates that at 0.1C and 1.5–4.3 V the initial discharge capacity of NNFM-850 is 155.11 mAh/g. The initial discharge capacity of NNFM-850 at 1C is 105.09 mAh/g and retained 79.35 % capacity after 100 cycles.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116958"},"PeriodicalIF":3.0,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144550058","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}

{"title":"Synergistic effects of halloysite nanotubes in electrospun PVDF-HFP separator for advanced sodium ion battery","authors":"Akash Kankane ,&nbsp;Dhirendra Kumar Rai ,&nbsp;S. Janakiraman","doi":"10.1016/j.ssi.2025.116947","DOIUrl":"10.1016/j.ssi.2025.116947","url":null,"abstract":"<div><div>Sodium-ion batteries (SIBs) emerge as a sustainable option for energy storage, standing out as a cost-effective and resource-abundant substitute to lithium-ion batteries (LIBs). However, the development of sustainable SIBs necessitates the innovation of separator materials capable of enhancing battery efficiency and safety. This research highlights the fabrication and characterization of a novel separator made up of polyvinylidene fluoride-<em>co</em>-hexafluoropropylene (PVDF-HFP) filled with halloysite nanotubes (HNTs) via the electrospinning technique for SIBs application. The electrospun composite separator was systematically fabricated and comprehensively characterized to investigate its morphological, electrochemical, thermal and mechanical properties. Field emission scanning electron microscopy (FESEM) analysis revealed a well-dispersed HNTs network within the PVDF-HFP matrix, resulting in a fibrous structure with enhanced mechanical strength (23.6 MPa). Electrochemical performance was evaluated through electrochemical impedance spectroscopy (EIS) and cyclic charge-discharge (GCD). The halloysite filled PVDF-HFP separator demonstrated higher ion conductivity (2.11 mS cm⁻¹) and electrochemical stability at ambient temperature, leading to enhanced battery performance, including higher specific capacity (171 mA h g⁻¹) at 0.1C-rate. Thermal stability studies confirmed the improved thermal resistance of the composite separator, crucial for maintaining structural integrity under high temperatures. The incorporation of HNTs into the structure of PVDF-HFP contributes to the development of robust and efficient separators for SIBs, facilitating the development of sustainable and scalable energy storage.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116947"},"PeriodicalIF":3.0,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144549722","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}

{"title":"Carrier transport in sulfur cathodes of all-solid-state lithium-sulfur batteries: Challenges, strategies, and characterizations","authors":"Haoyue Zhong ,&nbsp;Changbao Zhu","doi":"10.1016/j.ssi.2025.116945","DOIUrl":"10.1016/j.ssi.2025.116945","url":null,"abstract":"<div><div>All-solid-state lithium‑sulfur batteries (ASSLSBs) have emerged as promising candidates for next-generation energy storage systems due to their high energy density, excellent safety, and low cost. However, the inherently low electronic and ionic conductivity of sulfur, as well as inadequate solid-solid interfacial contact, leads to sluggish electrochemical reaction kinetics, severely impacting the electrochemical performance of ASSLSBs. To address these challenges, various modification strategies have been developed, focusing on improving charge carrier transport to enhance electrochemical activity and stability of the sulfur cathode. Here, we present a comprehensive review of the key electronic and ionic transport limitations in the sulfur cathode of ASSLSBs, along with the modification strategies and advanced characterization techniques. Finally, we highlight future research directions for the development of sulfur cathodes in realizing high-performance ASSLSBs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116945"},"PeriodicalIF":3.0,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144562844","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}

{"title":"Aluminum ion doped vanadium oxides as highly stable cathodes for aqueous zinc ion batteries","authors":"Yulia D. Salnikova,&nbsp;Mikhail A. Kamenskii,&nbsp;Elena G. Tolstopyatova,&nbsp;Veniamin V. Kondratiev","doi":"10.1016/j.ssi.2025.116946","DOIUrl":"10.1016/j.ssi.2025.116946","url":null,"abstract":"<div><div>In this work, Al³⁺- doped nanosized layered vanadium oxides (Al_xV₂O₅) with different Al:V ratios have been synthesized by hydrothermal method. The morphology and structure of the obtained compounds were characterized by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Thin layers of Al-doped vanadium oxide agglomerated in the form of “nanoflowers”. The presence of Al³⁺ in the layered structure of the vanadium oxide Al_xV₂O₅ with expanded interlayer distance was confirmed. The electrochemical properties of the obtained cathode materials were investigated in coin-type zinc-ion battery cells with a zinc anode in an aqueous solution of 3 M ZnSO₄ by cyclic voltammetry and galvanostatic charge/discharge. The initial capacity of the cathodes depended on the aluminum content (<em>x</em>-values). The highest initial capacity of 383 mAh·g⁻¹ at a current density of 1.0 A·g⁻¹ was observed for Al_0.060V₂O₅, which degraded faster due to the lower content of Al³⁺ ions, and the capacity retention was 89 % of the initial value. Al_0.072V₂O₅ had the lowest initial discharge capacity (196 mAh·g⁻¹), but was the most stable with a capacity retention of 98 % (192 mAh·g⁻¹ after 100 cycles) and 96 % (189 mAh·g⁻¹ after 300 cycles). Except for the first cycle, the coulombic efficiency of all cathodes is close to 100 %, confirming the perfect reversibility of the charge/discharge process.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116946"},"PeriodicalIF":3.0,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144562843","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}

{"title":"Change of electrochemical potential and entropy of Li around an edge dislocation in solid electrolytes","authors":"Kyuichi Yasui,&nbsp;Koichi Hamamoto","doi":"10.1016/j.ssi.2025.116950","DOIUrl":"10.1016/j.ssi.2025.116950","url":null,"abstract":"<div><div>The equations of the electrochemical potential and entropy of Li atoms near an edge dislocation inside solid electrolytes are derived. Although a stress field becomes complex in the presence of many dislocations in polycrystalline materials, the equations are still valid and the qualitative conclusions are robust at least for lower dislocation density than about <span><math><msup><mn>10</mn><mn>16</mn></msup></math></span> <span><math><msup><mi>m</mi><mrow><mo>−</mo><mn>2</mn></mrow></msup></math></span>. As the modified electrochemical potential of <span><math><msup><mi>Li</mi><mo>+</mo></msup></math></span> ions in a stress field is spatially uniform at equilibrium in solid electrolytes due to the high mobility of <span><math><msup><mi>Li</mi><mo>+</mo></msup></math></span> ions, the spatial variations of the entropies associated with the stress and electric-potential field are obtained. From the increase in the local entropy by a positively charged dislocation, the concentration of Frenkel pairs of <span><math><msup><mi>Li</mi><mo>+</mo></msup></math></span> interstitials and vacancies is derived, which could be considerably higher near the dislocation. It could be the reason for higher ionic conductivity along a dislocation. It is suggested that a dislocation should be positively charged in an ionic conductor of positive ions in the absence of impurities. When the dilation due to <span><math><msup><mi>Li</mi><mo>+</mo></msup></math></span> interstitials is relatively large, reduction or oxidation of the solid electrolyte may possibly occur near a dislocation although considerable diffusion of atoms and electrons is necessary for it.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116950"},"PeriodicalIF":3.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144549720","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}

{"title":"Garnet solid electrolytes: Material design, microstructural engineering, and pathways to high-energy density solid-state lithium batteries","authors":"Xin Chen ,&nbsp;Ning Zhao ,&nbsp;Zhiqing Jia ,&nbsp;Xiangxin Guo","doi":"10.1016/j.ssi.2025.116943","DOIUrl":"10.1016/j.ssi.2025.116943","url":null,"abstract":"<div><div>Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) solid electrolytes have been identified as potential candidates for high-energy solid-state lithium batteries due to their distinguished ionic conductivity, wide-ranging electrochemical stability, and compatibility with lithium metal. This review provides a systematic examination of the structure-property relationships of LLZO, with a specific focus on the pivotal role of grain boundary engineering in improving ionic conductivity. Advanced doping strategies, encompassing single/multi-ion substitution and anion-cation co-doping, are evaluated for their impact on stabilizing the cubic phase and optimizing lithium vacancy distribution. Innovations in sintering techniques and LLZO film fabrication methods are emphasized for their contributions to achieving high ionic conductivity and ultrathin thickness. Moreover, the design of ultrathin flexible organic-inorganic composite electrolytes is discussed to tackle challenges associated with mechanical brittleness and industrialization. The critical evaluations of ionic conductivity enhancement, ultrathin electrolyte fabrication strategies, and scalability challenges provide insightful references for the advancement of LLZO-based solid-state batteries toward high energy density and industrial practicality.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116943"},"PeriodicalIF":3.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144549723","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}

{"title":"Key design considerations for blended electrodes in Li-ion batteries","authors":"D. Chatzogiannakis ,&nbsp;O. Arcelus ,&nbsp;E. Ayerbe ,&nbsp;P. Ghorbanzade ,&nbsp;B. Ricci ,&nbsp;I. de Meatza ,&nbsp;M. Casas-Cabanas ,&nbsp;M. Rosa Palacin","doi":"10.1016/j.ssi.2025.116942","DOIUrl":"10.1016/j.ssi.2025.116942","url":null,"abstract":"<div><div>Blended electrodes, containing two or more active materials, are already a key part of commercial battery cells, especially ones used in EVs. Yet, surprisingly, research on them at a fundamental level remains limited. This work aims to shed light on their unique characteristics, discuss how best to study them, and offer practical guidelines for designing them effectively. A particular emphasis is placed in specific cell designs to study them, such as the decoupled blend cell. This allows the study of each material separately within the same system, helping to assess effective rates. Beyond experimental techniques, this work also touches on modeling approaches for blended electrodes aiming at predicting performance, fine-tune material combinations, and accelerate the development of better electrode formulations. By combining all these strategies, a deeper understanding of blended electrodes should be achieved, ultimately enabling improving battery performance, longevity, and efficiency. Given their growing role in commercial energy storage, continued research is essential to unlock their full potential and push battery technology forward.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116942"},"PeriodicalIF":3.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514186","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}

{"title":"Current-overpotential relationships from electrochemical impedance spectroscopy (EIS) under DC bias – A tutorial exercise applied to a Pt||YSZ electrode","authors":"Stine Roen ,&nbsp;Ragnar Strandbakke ,&nbsp;Truls Norby","doi":"10.1016/j.ssi.2025.116939","DOIUrl":"10.1016/j.ssi.2025.116939","url":null,"abstract":"<div><div>Electrochemical impedance spectroscopy (EIS) of electrode polarisation offers the possibility to delineate overpotentials into ohmic, charge transfer kinetic, and transport and other mass transfer contributions, commonly applied and interpreted under open circuit conditions. It is sometimes also applied under DC bias, as it in principle then can provide information about net anodic or cathodic processes. However, the impedances so obtained are seldomly converted to overpotentials and therefore remain as qualitative indicators only. Here, we tutorially derive formalism of converting resistances from EIS under DC bias properly into overpotential contributions to the total overpotential, allowing identification of their origins from their dependencies on the current. We illustrate the methodology by generated model current-voltage curves and then apply it to an experimental data set for a Pt electrode on an yttria-stabilised zirconia (YSZ) oxide ion conducting electrolyte. The result reveals that a dominating electrode polarisation easily taken to reflect mass transfer in fact behaves like a second charge transfer step following Butler-Volmer kinetics, allowing us to hypothesise a new model for the O₂,Pt||YSZ electrode. Our tutorial exercise is applicable to both liquid- and solid-state electrochemistry and should apply equally also to EIS under DC bias of any types of junctions.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"428 ","pages":"Article 116939"},"PeriodicalIF":3.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144513635","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}