Solid State Ionics最新文献_第3页

Na+ self-diffusion and ionic transport in sodium β″-alumina

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-03-01 DOI: 10.1016/j.ssi.2025.116809

Sarah Lunghammer, H. Martin R. Wilkening

{"title":"Na+ self-diffusion and ionic transport in sodium β″-alumina","authors":"Sarah Lunghammer, H. Martin R. Wilkening","doi":"10.1016/j.ssi.2025.116809","DOIUrl":"10.1016/j.ssi.2025.116809","url":null,"abstract":"<div><div>Fast ion transport is crucial for solid materials to serve as electrolytes, with only a few classes achieving the high ionic conductivity needed for practical use. The discovery of fast ion transport in Na β″-alumina not only introduced a groundbreaking class of materials but also marked the advent of the research field now known as solid-state ionics. Since the early 1980s, Na β″-alumina has been widely recognized as a solid electrolyte for high-temperature sodium-based batteries, such as Na‑sulfur batteries. Despite numerous studies on the diffusion and transport properties of layer-structured Na β″-alumina, a comprehensive investigation combining conductivity and nuclear magnetic resonance (NMR) to study both short-range and long-range ion dynamics has been lacking. In this work, we used a commercially available, highly sintered Na β″-alumina sample to explore Na+ dynamics in detail through GHz conductivity spectroscopy and 23Na nuclear spin relaxation. The two methods provide a rather consistent picture of ion transport. While long-range Na+ transport, reaching a conductivity of 4 mS cm−1 at ambient temperature, is governed by an activation energy of 0.3 eV, short-range motions sense a barrier of 0.13 eV. The Arrhenius pre-factor obtained from characteristic electric relaxation frequencies is consist with that determined from diffusion-induced longitudinal NMR spin-lattice relaxation rates if analyzed with a modified BPP (Bloembergen, Purcell, Pound) spectral density function.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"422 ","pages":"Article 116809"},"PeriodicalIF":3.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Harnessing ion migration in halide perovskites: Implication and applications

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-03-01 DOI: 10.1016/j.ssi.2025.116816

Sungwoo Park , Hyeon-Ji Lee , Ho Won Jang

引用次数: 0

What limits the rate of thermally activated self-discharge of nickel oxyhydroxide electrodes?

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-02-27 DOI: 10.1016/j.ssi.2025.116815

Elena S. Davydova , Yossi Halpern , Anna Breytus , Avner Rothschild

{"title":"What limits the rate of thermally activated self-discharge of nickel oxyhydroxide electrodes?","authors":"Elena S. Davydova , Yossi Halpern , Anna Breytus , Avner Rothschild","doi":"10.1016/j.ssi.2025.116815","DOIUrl":"10.1016/j.ssi.2025.116815","url":null,"abstract":"<div><div>Nickel (oxy)hydroxide electrodes are widely used in alkaline batteries and water electrolyzers. Their operation involves reversible phase transformations (Ni(OH)2 + OH− <math><mo>⇌</mo></math> NiOOH + H2O + e−) upon charge and discharge at potentials below the onset of oxygen evolution; electrocatalytic oxygen evolution reaction (OER, 4OH− → O2 + 2H2O + 4e−) at higher potentials; and spontaneous chemical self-discharge (4NiOOH + 2H2O → 4Ni(OH)2 + O2) that is accelerated at elevated temperatures. This work studied compositional and microstructural changes in nickel-boride-based electrodes during cold (room temperature) charge and hot (95 °C) self-discharge cycles that enable decoupled membraneless water electrolysis. Pristine electrodes comprised agglomerates of equiaxed nickel boride nanoparticles that transformed into boron-depleted Ni(OH)2 platelets upon chemical aging and electrochemical activation treatments followed by operation in cold charge and hot self-discharge cycles. Cyclic operation in alternating cold and hot alkaline electrolytes resulted in crystallization and growth of mosaic hexagonal plates that seem to have been formed by detachment of small platelets from the agglomerates and oriented reattachment onto the edges of the growing plates. Concomitant with the plate growth, the self-discharge kinetics (at 95 °C) decreased from one cycle to another whilst the OER kinetics (at room temperature) slightly enhanced. This observation suggests that bulk processes involving solid-state diffusion and phase transformation limit the rate of thermally activated self-discharge rather than OER. This finding sheds new light on the mechanism of the self-discharge reaction that limits the performance of alkaline batteries and decoupled alkaline water electrolyzers.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"422 ","pages":"Article 116815"},"PeriodicalIF":3.0,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143508012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Investigation of structural, dielectric, and AC conductivity response in potassium-based polymer electrolytes: Tailoring PEO-PVDF blends for enhanced performance

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-02-26 DOI: 10.1016/j.ssi.2025.116811

Venkata Ramana Jeedi , Kiran Kumar Ganta , Rayudu Katuri , N. Kundana , Malla Reddy Yalla , Anji Reddy Polu , Firdaus Mohamad Hamzah

{"title":"Investigation of structural, dielectric, and AC conductivity response in potassium-based polymer electrolytes: Tailoring PEO-PVDF blends for enhanced performance","authors":"Venkata Ramana Jeedi , Kiran Kumar Ganta , Rayudu Katuri , N. Kundana , Malla Reddy Yalla , Anji Reddy Polu , Firdaus Mohamad Hamzah","doi":"10.1016/j.ssi.2025.116811","DOIUrl":"10.1016/j.ssi.2025.116811","url":null,"abstract":"<div><div>Polymer electrolyte membranes comprising Poly(ethylene Oxide) and Poly(vinylidene Fluoride) blends complexed with KNO3 were developed using the solution casting technique by varying the polymers. These systems were extensively characterized through X-Ray Diffractogram, Fourier Transform Infrared, and SEM to analyze their complexation behavior, functional groups, and morphology. The ionic conductivity and electrical characteristics were investigated via impedance spectroscopy over a frequency up to 10 MHz. Dielectric properties, including the dielectric constant (ε'), dielectric loss (ε\"), relaxation time (τ), and modulus (M' and M\"), were also examined. The AC conductivity profile revealed a frequency-independent plateau, indicating ion migration as the primary contributor to conductivity. The 80PEO:20PVDF composition exhibited the highest ionic conductivity (1.60 × 10−4 S.cm−1) and the least activation energy, attributed to efficient ion dissociation and structural reorganization due to the interactions between PEO and PVDF molecules.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"422 ","pages":"Article 116811"},"PeriodicalIF":3.0,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143488822","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

Enhanced oxygen reduction reaction activity of Ca doping CoFe2O4 as cathodes for solid oxide fuel cells

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-02-26 DOI: 10.1016/j.ssi.2025.116812

Fangjie Liu, Zhengqi Su, Haizhao Li, Qingjie Wang, Xin Wang, Weiwei Shang, Bin Xu

{"title":"Enhanced oxygen reduction reaction activity of Ca doping CoFe2O4 as cathodes for solid oxide fuel cells","authors":"Fangjie Liu, Zhengqi Su, Haizhao Li, Qingjie Wang, Xin Wang, Weiwei Shang, Bin Xu","doi":"10.1016/j.ssi.2025.116812","DOIUrl":"10.1016/j.ssi.2025.116812","url":null,"abstract":"<div><div>CoFe2O4 (CFO) was identified as one of the potential cathode materials for solid oxide fuel cells (SOFCs). However, optimization was required due to limitations of electrochemical performance. Here effects of Ca doping on CFO were investigated for the oxygen reduction reaction (ORR) properties. Co1-xCaxFe2O4 (CCxFO, x = 0, 0.2 (CC2FO), 0.4 (CC4FO)) were synthesized with sol-gel method. Oxygen vacancy concentration was increased by Ca doping enhancing the electrochemical performance of CFO. At 750 °C, the polarization resistance (Rp) of CC4FO was 1.04 Ω·cm2, which was 1.09 Ω·cm2 lower than that of CFO (2.13 Ω·cm2). The electronic conductivity value (σ) of CC4FO was 0.614 at 750 °C and the activation energy (Ea) of CC4FO was 102.81 kJ/mol. The results indicated that improvements in the ORR activity of the CFO spinel material were mainly attributed to an increase in oxygen vacancy concentration and oxygen surface exchange rate due to Ca doping, CC4FO showed promising potential as SOFC cathode.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"422 ","pages":"Article 116812"},"PeriodicalIF":3.0,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143508011","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

Low-dimensional Li+ ion dynamics in the lithiated Buckminster fullerene Li4C60 锂化巴克明斯特富勒烯 Li4C60 中的低维 Li+ 离子动力学

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-02-24 DOI: 10.1016/j.ssi.2025.116805

Bernhard Gadermaier , H. Martin R. Wilkening

{"title":"Low-dimensional Li+ ion dynamics in the lithiated Buckminster fullerene Li4C60","authors":"Bernhard Gadermaier , H. Martin R. Wilkening","doi":"10.1016/j.ssi.2025.116805","DOIUrl":"10.1016/j.ssi.2025.116805","url":null,"abstract":"<div><div>Lithiated Buckminster fullerene (Li4C60) has recently been identified as a fast Li+ ion conductor. Here, we present a comprehensive NMR-based analysis of 7Li dynamics in Li4C60. Our findings indicate that long-range lithium hopping is to be characterized by an activation energy of 0.26 eV. At 378 K, the Li+ jump rate turned out to be in the order of 109 s−1, which translates into Einstein-Smoluchowski diffusion coefficients D ranging from ca. 2 to 5 × 10−7 cm2 s−1, depending on the jump distance chosen (3.6–5 Å) to convert the jump rate into D. The corresponding Arrhenius pre-factor reaches 3 × 1012 s−1 and lies in the range of typical phonon frequencies. Comparing our relaxation rates with those presented in the literature earlier suggests low-dimensional Li+ diffusion in Li4C60. For short-range or localized Li+ jump processes, presumably governed by motional correlation effects, we find much lower activation energies ranging from 0.08 eV to 0.17 eV.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116805"},"PeriodicalIF":3.0,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143474564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The unique properties of the monomolecular surface layer of reduced ceria

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-02-15 DOI: 10.1016/j.ssi.2025.116807

Ilan Riess

{"title":"The unique properties of the monomolecular surface layer of reduced ceria","authors":"Ilan Riess","doi":"10.1016/j.ssi.2025.116807","DOIUrl":"10.1016/j.ssi.2025.116807","url":null,"abstract":"<div><div>Experimental results of the defect concentrations in highly reduced, monomolecular surface layer of ceria-based oxides, are discussed. The data is XPS vs. oxygen pressure relations of reduced Pr0.1Ce0.9O2.-x (PCO), CeO2-x and Sm0.2Ce0.8O1.9-x (SDC). In PCO the analysis predicts that the surface layer is negatively charged and the concentration of Pr3+ ions is higher than in the bulk. A double layer exists between the surface layer and the bulk. In CeO2 and SDC the concentration of Ce3+ ions and oxygen vacancies in the surface is higher than in the bulk. The surface is neutral. The analysis predicts that the surface layer is metallic, i.e. the electrons on Ce3+ are delocalized and not localized small polarons. The bulk is a semiconductor. The Ce3+ ions are randomly distributed on the Ce sublattice and not in the boundary of oxygen vacancies. The latter are doubly ionized vacancies <math><msup><msub><mtext>V</mtext><mtext>O</mtext></msub><mrow><mo>•</mo><mo>•</mo></mrow></msup></math>despite the presence of a high concentration of quasi free electrons. It is also predicted that the surface of ceria or SDC has a phase diagram of temperature vs. oxygen vacancy concentration, at T > 450 °C, like that of ceria bulk or SDC bulk, respectively. Further, the phase diagram of SDC bulk (and surface) is like that of ceria bulk shifted to a higher oxygen vacancy concentration and doping has no other effect at elevated temperature. Both in ceria and SDC the difference between the surface and the corresponding bulk is only in the oxygen pressure at which a level of reduction is reached, with the surface more easily being reduced than the bulk.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116807"},"PeriodicalIF":3.0,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143420359","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanistic insights into oxygen reduction reaction on metal/perovskite catalysts: Interfacial interactions and reaction pathways

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-02-15 DOI: 10.1016/j.ssi.2025.116808

Wenhao Li , Vadym Drozd , Md Shariful Islam Sozal , Meng Li , Zhe Cheng

{"title":"Mechanistic insights into oxygen reduction reaction on metal/perovskite catalysts: Interfacial interactions and reaction pathways","authors":"Wenhao Li , Vadym Drozd , Md Shariful Islam Sozal , Meng Li , Zhe Cheng","doi":"10.1016/j.ssi.2025.116808","DOIUrl":"10.1016/j.ssi.2025.116808","url":null,"abstract":"<div><div>The oxygen reduction reaction (ORR) is a critical process in energy conversion systems, influencing the efficiency and performance of various devices such as fuel cells, batteries, and electrolyzers. Perovskite-supported metal materials (metal/perovskite) offer several advantages as ORR electrocatalysts, including strong metal-support interactions, oxygen vacancy formation in the perovskite lattice, and synergistic triple-phase boundary (TPB) activity at the interface. Despite their significance, the mechanistic understanding of ORR on metal/perovskite catalysts remains incomplete, particularly at metal/perovskite interfaces. This study investigates ORR on BaZrO3 (BZO) perovskite-supported metal clusters (Pt or Ag) using density functional theory (DFT) to unravel critical insights into charge redistribution at the metal/BZO interface. Energy profiles for elemental steps along two different ORR pathways—oxygen adsorption on the metal cluster surface and direct oxygen adsorption at the TPB—were calculated to explore the effects of different active sites. The results provide a deeper understanding of ORR on metal/perovskite catalysts, emphasizing the role of interfacial interactions and pathway-dependent reaction mechanisms. This work paves the way for guiding the design of high-performance electrocatalysts for ORR in terms of composition, interface design, and local environment modification for a broad range of energy applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116808"},"PeriodicalIF":3.0,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143420426","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

Highly ordered Li(Ni0.6Ti0.2Co0.2)O2 (NTC622) cathode material made by all-dry synthesis

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-02-11 DOI: 10.1016/j.ssi.2025.116806

Macgregor F. Macintosh , P. Popli , Andrew George , M.N. Obrovac

引用次数: 0

Structural analysis of the LiCoO2 cathodes/garnet-type Li6.5La3Zr1.5Ta0.5O12 solid electrolyte interface

IF 3 4区材料科学

Solid State Ionics Pub Date : 2025-02-10 DOI: 10.1016/j.ssi.2025.116804

K. Niitsu , F. Ichihara , S. Miyoshi , M. Ode , K. Mitsuishi , T. Masuda , K. Takada

{"title":"Structural analysis of the LiCoO2 cathodes/garnet-type Li6.5La3Zr1.5Ta0.5O12 solid electrolyte interface","authors":"K. Niitsu , F. Ichihara , S. Miyoshi , M. Ode , K. Mitsuishi , T. Masuda , K. Takada","doi":"10.1016/j.ssi.2025.116804","DOIUrl":"10.1016/j.ssi.2025.116804","url":null,"abstract":"<div><div>The sinterability of oxide cathode LiCoO2 and garnet-type solid electrolyte Li7-xLa3Zr2-xTaxO12 (x = 0.5) at 980 and 1080 °C has been studied using an integrated suite of scanning transmission electron microscopy and spectroscopic techniques, with a particular focus on the LiCoO2/Li7-xLa3Zr2-xTaxO12 interfaces. Whereas the densification hardly progresses and the interdiffusion is limited to the vicinity of the interface at 980 °C, dramatic densification can be achieved at 1080 °C at the expense of severe interfacial modification. The structural, chemical, and electronic characteristics of the interphases are systematically investigated. Two kinds of interphases are formed: one has a disordered LiCoO2 structure, thickly forming in contact with LiCoO2, and the other has a structural and chemical character similar to Li7-xLa3Zr2-xTaxO12, thinly forming in contact with Li7-xLa3Zr2-xTaxO12. The former is assumed to play a vital role in the densification of the pellet. Analysis using energy-dispersive spectroscopy and electron energy loss spectroscopy reveals that the disordered LiCoO2 interphase is somewhat depleted of Li and contaminated with La, Zr, and Ta. These properties are considered less favorable for achieving undisturbed ionic conductivity.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116804"},"PeriodicalIF":3.0,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377493","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