Solid State Ionics最新文献

{"title":"Quantitative determination of charge trapped at grain boundaries in ionic conductors by impedance spectroscopy","authors":"Sangtae Kim ,&nbsp;Sergey Khodorov ,&nbsp;Leonid Chernyak ,&nbsp;Thomas Defferriere ,&nbsp;Harry Tuller ,&nbsp;Igor Lubomirsky","doi":"10.1016/j.ssi.2024.116706","DOIUrl":"10.1016/j.ssi.2024.116706","url":null,"abstract":"<div><div>We propose a method for determining the density of space charge trapped at grain boundaries in polycrystalline solid state ionic conductors. The method is an extension of the earlier proposed Linear Diffusion Model (LDM) that relies on the impedance spectra-derived current-voltage characteristics of grain boundaries. The utility of the extended LDM version is demonstrated to successfully and nondestructively obtain values for the space charge density trapped at the grain boundaries in a variety of oxygen ion conductors including Sr-doped LaGaO₃, Y-doped CeO₂, and Gd-doped CeO₂, and proton conductors including Sr-doped LaNbO₃ and Y-doped BaZrO₃. For all cases, the density of the space charge trapped at the grain boundaries was &lt;0.2C/m², corresponding to a fraction of electron charge per unit cell. The proposed technique, while it lacks the ability to determine the thickness of the grain boundary core when much smaller than the Debye length, it can be used to distinguish between space charge vs insulating layer contributions to the grain boundary resistance.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116706"},"PeriodicalIF":3.0,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142357885","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":"Enhancement in conductivity by K2O in MgO-V2O5 glass-ceramic for solid- state battery application","authors":"Vimi Dua,&nbsp;K. Singh","doi":"10.1016/j.ssi.2024.116707","DOIUrl":"10.1016/j.ssi.2024.116707","url":null,"abstract":"<div><div>Composition of 75V₂O₅-(25-x) MgO-(x) K₂O (x = 6, 9, 12, and 15 mol%) are synthesized by melt quench technique. All the as quenched samples either formed the glasses or glass ceramic as confirmed by differential scanning calorimeter (DSC) and X-ray diffraction (XRD). The DSC curves exhibited the two glass transition temperatures (T_g), two crystallization temperatures (T_c)_, and with two melting temperatures (T_m) which could be related to the presence of two distinct glass in the present samples. The K₂O content increases the devitrification tendency of as quenched samples and formed the crystalline phases i.e. K₃VO₄ along with glassy phase in higher concentration of K₂O. X-ray photoelectron spectroscopy (XPS) is confirmed that the vanadium exhibit two oxidation states V⁴⁺ / V⁵⁺. The highest ratio of V⁴⁺/V⁵⁺ is found in (x = 15) sample which exhibited the highest conductivity i.e. 1.3 × 10⁻³ S/cm at 250 °C. It is two orders higher than the (x = 6) sample at 250 °C. The high conducting glass ceramics can be used as cathode in all solid state battery and fuel cells.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116707"},"PeriodicalIF":3.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326966","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":"Crystal structure, electronic conductivity and oxygen exchange kinetics of high-entropy perovskites La0.2Pr0.2Nd0.2Sm0.2Sr0.2Co1-xFexO3-δ (x = 0, 0.5, 1)","authors":"Patrick Pretschuh,&nbsp;Andreas Egger,&nbsp;Edith Bucher","doi":"10.1016/j.ssi.2024.116705","DOIUrl":"10.1016/j.ssi.2024.116705","url":null,"abstract":"<div><div>High-entropy perovskites (HEPs) are attracting increasing attention as air electrode materials for solid oxide cells (SOCs). In this work, three different HEPs from the series La_0.2Pr_0.2Nd_0.2Sm_0.2Sr_0.2Co_1-xFe_xO_3-δ (x = 0, 0.5, 1) are synthesized using the citric acid-ethylenediaminetetraacetate (EDTA) method. X-ray diffraction analysis finds crystal structures with the orthorhombic space group 62 (<em>Pnma</em>) at room temperature. The lattice distortion increases with increased Fe-substitution at the B-site. The electrical conductivity (<em>σ</em>_e) is determined at temperatures from 600 to 850 °C and oxygen partial pressures (<em>p</em>O₂) between 0.001 and 0.15 bar. For the pure cobaltate, <em>σ</em>_e is 1469 S cm⁻¹ at 800 °C and 0.15 bar <em>p</em>O₂. The conductivity is significantly reduced with Fe-doping, reaching 87 S cm⁻¹ for the pure ferrate at 800 °C. The chemical oxygen surface exchange coefficient (<em>k</em>_chem) and the chemical oxygen diffusion coefficient (<em>D</em>_chem) are determined by the electrical conductivity relaxation technique. <em>D</em>_chem is found to be quite independent of B-site doping and <em>p</em>O₂, with values of approx. 5 × 10⁻⁶ cm² s⁻¹ at 800 °C. In contrast, <em>k</em>_chem is strongly influenced by the B-site composition, which results in an increase of more than one order of magnitude from the ferrate (3.4 × 10⁻⁵ cm s⁻¹) to the cobaltate (7.7 × 10⁻⁴ cm s⁻¹) at 800 °C and 0.001 bar <em>p</em>O₂. This clearly demonstrates the beneficial effects of Co on the electronic conductivity as well as on the catalytic activity for the oxygen surface exchange reaction.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116705"},"PeriodicalIF":3.0,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319467","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":"Quantitative assessment of enhanced performance of Ru-loaded direct ammonia proton ceramic fuel cells","authors":"Koki Kitabayashi ,&nbsp;Junji Hyodo ,&nbsp;Nai Shi ,&nbsp;Yoshihiro Yamazaki","doi":"10.1016/j.ssi.2024.116701","DOIUrl":"10.1016/j.ssi.2024.116701","url":null,"abstract":"<div><p>Liquid ammonia is an attractive candidate for use as a hydrogen carrier because of its high volumetric density. The successful development of direct ammonia proton-conducting ceramic fuel cells (PCFCs) operating at intermediate temperatures can be seamlessly integrated into the current infrastructure without the need for investing in hydrogen gas pipelines and storage facilities. However, the low power output of PCFCs using ammonia fuel hinders their practical applications. In this study, we systematically investigated the ammonia conversion ratio and rate, maximum power density, open-circuit voltage, and ohmic and polarization resistances of PCFCs (Ni-BaCe_0.7Zr_0.1Y_0.1Yb_0.1O_3−δ |BaCe_0.7Zr_0.1Y_0.1Yb_0.1O_3−δ| PrBaCo₂O_5+δ) for ammonia and hydrogen fuels at intermediate temperatures of 500–650 °C and quantitatively assessed the impact of Ru catalyst loading on the electrochemical performance of direct ammonia PCFC. Ru loading improved the maximum power density of the direct ammonia PCFC from 100 to 149 mWcm⁻² at 500 °C. Combined analysis of gas chromatography and AC impedance spectroscopy revealed that Ru catalysts improved the internal ammonia reforming rate by a factor of 1.9 at 500 °C and reduced polarization resistance by a factor of 1.4 at 500 °C. All results consistently support that the enhanced maximum power density of the direct ammonia PCFC is predominantly attributed to the improved electrochemical reaction kinetics at the electrode/electrolyte/gas interface.</p></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116701"},"PeriodicalIF":3.0,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271362","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":"Synthesis and temperature dependence of the crystal structure of proton conductor BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb1711) by combined neutron and X-ray diffraction","authors":"Lozane Hamze ,&nbsp;Emmanuelle Suard ,&nbsp;Olivier Joubert ,&nbsp;Eric Quarez","doi":"10.1016/j.ssi.2024.116682","DOIUrl":"10.1016/j.ssi.2024.116682","url":null,"abstract":"<div><p>BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ is a widely studied proton conductor for solid oxide fuel cells but its structure has not been examined in detail. In this study, we synthesized a pure, well-crystallized BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ powder via a glycine-nitrate process. Using Rietveld analysis on X-ray and neutron diffraction powder patterns collected both at room temperature and at elevated temperatures, we investigate the crystal structure of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ. At room temperature, the sample exhibits <em>I</em>4<em>/mcm</em> tetragonal symmetry, with cell parameters of a = 6.14911(7) Å and c = 8.87903(14) Å. The structure of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ can be described by a distortion of the ideal cubic perovskite (<em>a</em>_<em>p</em>), resulting from the cooperative tilt of the (Zr,Ce,Y,Yb)O₆ octahedra along the [001]_p axis (tilt system <em>a</em>⁰<em>a</em>⁰c⁻). Within the octahedra, it consists of a disordered arrangement of Zr, Ce, Y, and Yb atoms with an average distance (Zr,Ce,Y,Yb)-O of 2.219 Å. At around 650 °C, BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ undergoes a phase transition to the primitive cubic structure <em>Pm</em><span><math><mover><mn>3</mn><mo>¯</mo></mover></math></span><em>m</em>. This transition is characterized by a progressive decrease in the tilt angle, indicating a continuous phase transition, and is tricritical in nature.</p><p>Crystallographic data for BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ obtained from neutron data have been deposited at the Cambridge Crystallographic Data Centre, CSD 2341244 (room temperature) and CSD 2341246–2341252 (100 to 700 °C).</p></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116682"},"PeriodicalIF":3.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271361","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":"Effect of doping with iron and cations deficiency in the high conductive electrolyte La0.8Sr0.2Ga0.8Mg0.2O3–δ on oxygen exchange kinetics","authors":"Natalia Porotnikova ,&nbsp;Anna Khodimchuk ,&nbsp;Egor Gordeev ,&nbsp;Denis Osinkin","doi":"10.1016/j.ssi.2024.116704","DOIUrl":"10.1016/j.ssi.2024.116704","url":null,"abstract":"<div><p>The oxygen isotope exchange method was used to investigate the kinetics of the interaction between gaseous oxygen and LaGaO₃-based oxides in a temperature range of 650 to 850 °C, with an oxygen pressure of 10 mbar. The stable isotopes of ¹⁸O/¹⁶O were used as labelled ions. The temperature dependencies of the heterogeneous oxygen exchange rate (<em>r</em>_<em>H</em>), the oxygen dissociative adsorption rate (<em>r</em>_<em>a</em>), the oxygen incorporation rate (<em>r</em>_<em>i</em>), and the oxygen diffusion coefficient (<em>D</em>) were determined. A comparative analysis of the <em>r</em>_<em>H</em> and <em>D</em> values for La_0.8Sr_0.2Ga_0.8Mg_0.2O_3–δ was carried out with a view to identifying any similarities or differences when compared with the literature data on oxides with similar compositions. The effect of <span><math><msubsup><mi>Fe</mi><mi>Ga</mi><mo>′</mo></msubsup></math></span> doping and the creation of an A-sublattice deficiency on the kinetic characteristics were investigated using the (La_0.8Sr_0.2)_0.98Ga_0.7Fe_0.1Mg_0.2O_3–δ oxide as a case example. Correlations between the rate-determining step of oxygen exchange and the modification of the oxide composition were identified.</p></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116704"},"PeriodicalIF":3.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142241385","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":"Lithium tracer diffusion in ion-beam sputtered nano-crystalline and amorphous LiNi0.33Mn0.33Co0.33O2 films","authors":"Erwin Hüger ,&nbsp;Harald Schmidt","doi":"10.1016/j.ssi.2024.116702","DOIUrl":"10.1016/j.ssi.2024.116702","url":null,"abstract":"<div><p>The LiNi_0.33Mn_0.33Co_0.33O₂ compound is a cathode material for Li-ion batteries. Li diffusion in this material directly influences charging/discharging times, power densities, maximum capacities, stress formation and possible side reactions. In the present study, Li tracer self-diffusion is investigated on ion-beam sputtered films after deposition (amorphous) and after crystallization at 700 °C. For the experiments, ⁷Li isotope enriched films with about 1.5 μm thickness were combined with a 50–90 nm thick ⁶Li tracer layer with the same chemical composition. Afterwards, the films were diffusion annealed between 100 and 300 °C. For analysis secondary ion mass spectrometry in depth profile mode was applied. The diffusivities of the crystalline films are identical to those of sintered bulk samples within error limits as known from literature and show an activation enthalpy of diffusion about 0.9 eV. In contrast, the diffusivities of the amorphous films are about one order of magnitude lower at 100 °C due to a higher activation enthalpy of diffusion of 1.1 eV. We attribute this higher activation enthalpy to a hindered diffusion in the amorphous state of the two-dimensional ion conductor.</p></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116702"},"PeriodicalIF":3.0,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0167273824002509/pdfft?md5=24a71192781b06644d20889466bfcea5&pid=1-s2.0-S0167273824002509-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142241384","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}

{"title":"Fabricating self-standing argyrodite electrolyte sheets containing SiO2 fibers for all-solid-state batteries","authors":"Reiko Matsuda,&nbsp;Irine Yunhafita Malya,&nbsp;Takuya Matsushita,&nbsp;Kazuhiro Hikima,&nbsp;Atsunori Matsuda","doi":"10.1016/j.ssi.2024.116684","DOIUrl":"10.1016/j.ssi.2024.116684","url":null,"abstract":"<div><p>Due to their high ionic conductivities, sulfide-based solid electrolytes (SEs)—such as argyrodite Li₆PS₅Cl—are good candidates for all-solid-state lithium-ion batteries (ASSLIBs). For adequate energy density, the thinner SE layers of ASSLIBs, the better, but it must also be durable to avoid short circuits. Using SiO₂ fibers in the SE layer as a support, we used a liquid process to produce all-inorganic, self-standing-sheet argyrodite-SEs with a thickness of approximately 60 μm, without resorting to organofluorine compounds such as polytetrafluoroethylene (PTFE) or polyvinylidene difluoride (PVDF). The ionic conductivity of a sheet containing 20 % SiO₂ fibers was 4.2 × 10⁻⁴ S cm⁻¹ at 25 °C. We also prepared graphite composites as anodes using argyrodite SE containing SiO₂ fibers. In addition, we fabricated ASSLIB cells using these SE sheets, Ni_1/3Mn_1/3Co_1/3O₂-composite positive, and graphite-composite negative electrodes and evaluated their charge–discharge characteristics.</p></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116684"},"PeriodicalIF":3.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142167712","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":"Structure and properties of proton exchange layers in lithium niobate-tantalate solid solutions","authors":"A.V. Sosunov ,&nbsp;I.V. Petukhov ,&nbsp;A.R. Kornilicyn ,&nbsp;А.А. Mololkin ,&nbsp;E.A. Komarnitskaya ,&nbsp;N.Yu. Tabachkova ,&nbsp;М. Kuneva","doi":"10.1016/j.ssi.2024.116692","DOIUrl":"10.1016/j.ssi.2024.116692","url":null,"abstract":"<div><p>New optical materials, in particular mixed lithium niobate-tantalate (LNT) solid solutions, are promising for application in photonics and microelectronics. Proton exchange is one of the widely used methods for producing low-contrast optical waveguides. The structure and properties of the proton exchange layers in <em>X</em>- and <em>Z</em>-cut samples were systematically studied using various structural and integrated optical methods. Direct proton exchange leads to the formation of a waveguide layer with a step-like refractive index profile. The waveguide-substrate boundary is clear (not blurred). At this boundary, the parameters of the crystal lattice change abruptly. Proton exchange leads to with the formation of deformation twins and surface damage of the LNT crystal structure. Indices and geometric parameters of surface damage were determined. The results of phase analysis of the samples indicate the presence of <em>β</em>-phases with high degrees of deformation of the crystal lattice. The calculated kinetic parameters of proton diffusion in LNT are significantly lower than for lithium niobate crystals, which is due to both the tantalum impurity and the greater disorder of the crystal lattice, and this leads to a decrease in the increment of the refractive index. The results provide a physical basis of diffuse process and design and fabrication of proton exchange waveguides in mixed LNT solid solutions.</p></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116692"},"PeriodicalIF":3.0,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142150668","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":"Cu-doped ring-shaped Fe2O3 as high-capacity and high-rate anode for lithium-ion batteries","authors":"Weizu Du ,&nbsp;Penglin Zhang ,&nbsp;Xiujuan Chen ,&nbsp;Junfeng Ke ,&nbsp;Kangkang Chang","doi":"10.1016/j.ssi.2024.116688","DOIUrl":"10.1016/j.ssi.2024.116688","url":null,"abstract":"<div><p>In this paper, ring-shaped Fe₂O₃ anode materials were modified by using ion doping. Ring-shaped Fe₂O₃ anode materials doped with different concentrations of Cu were prepared by hydrothermal method. The overall morphology of ring-shaped Fe₂O₃ did not change after Cu doped while the lattice deformation led to the generation of more oxygen vacancies and thus enhanced the lithium storage capacity. The Cu doped ring-shaped Fe₂O₃ showed excellent cycling and multiplicity performance, and the Fe₂O₃ material with 3 % Cu doped had the best electrochemical performance, with a specific capacity of 862.6 mAh g⁻¹ after 100 cycles at a current density of 0.1C and a better multiplicity performance. The experimental results indicated that the electrochemical performance of Fe₂O₃ anode materials can be effectively improved by ion doping.</p></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116688"},"PeriodicalIF":3.0,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142150666","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}