The oxygen exchange with the gas phase, thermal expansion, and electrical transport properties of a multi-cationic perovskite LaMn0.2Fe0.2Co0.2Ni0.2Cu0.2O3–δ and its four-cation derivatives have been investigated. The B-sublattice content was found to impact the crystal structure, expansion, and oxygen release with temperature, as well as the electrical properties. The oxides exhibit predominantly p-type semiconducting behavior, with activation energies ranging from 0.04 to 0.26 eV. The optimal compound of LaFe0.25Co0.25Ni0.25Cu0.25O3–δ was selected based on the cobination of the highest oxygen nonstiochiometry with maximum electrical conductivity, which reaches almost 500 S/cm at 750 °C. The symmetrical cell on LSGM supporting electrolyte has a polarization resistance of 0.12 Ω cm2 at 800 °C and an activation energy of 152 kJ/mol. The obtained characteristic was found to be better than one for the five-cation perovskite, casting doubt on the advantages of applying the high-entropy materials concept to the development of solid oxide fuel cells.
研究了多阳离子包晶石 LaMn0.2Fe0.2Co0.2Ni0.2Cu0.2O3-δ 及其四阳离子衍生物与气相的氧交换、热膨胀和电传输特性。研究发现，B 子晶格含量会影响晶体结构、膨胀、氧随温度的释放以及电学特性。这些氧化物主要表现出 p 型半导体行为，活化能在 0.04 至 0.26 eV 之间。LaFe0.25Co0.25Ni0.25Cu0.25O3-δ 的最佳化合物是在 750 °C 时达到近 500 S/cm 的最高电导率和最高氧不稳定度的基础上选出的。以 LSGM 为支撑电解质的对称电池在 800 °C 时的极化电阻为 0.12 Ω cm2，活化能为 152 kJ/mol。所获得的特性优于五阳离子包晶石的特性，这使人们对应用高熵材料概念开发固体氧化物燃料电池的优势产生了怀疑。
{"title":"Impact of multi-cationic B-sublattice upon crystal structure, transport and electrochemical properties of perovskite oxides LaBO3","authors":"A.M. Shalamova , A.D. Koryakov , E.P. Antonova , D.A. Osinkin , A.Yu. Suntsov","doi":"10.1016/j.ssi.2024.116729","DOIUrl":"10.1016/j.ssi.2024.116729","url":null,"abstract":"<div><div>The oxygen exchange with the gas phase, thermal expansion, and electrical transport properties of a multi-cationic perovskite LaMn<sub>0.2</sub>Fe<sub>0.2</sub>Co<sub>0.2</sub>Ni<sub>0.2</sub>Cu<sub>0.2</sub>O<sub>3–δ</sub> and its four-cation derivatives have been investigated. The B-sublattice content was found to impact the crystal structure, expansion, and oxygen release with temperature, as well as the electrical properties. The oxides exhibit predominantly p-type semiconducting behavior, with activation energies ranging from 0.04 to 0.26 eV. The optimal compound of LaFe<sub>0.25</sub>Co<sub>0.25</sub>Ni<sub>0.25</sub>Cu<sub>0.25</sub>O<sub>3–δ</sub> was selected based on the cobination of the highest oxygen nonstiochiometry with maximum electrical conductivity, which reaches almost 500 S/cm at 750 °C. The symmetrical cell on LSGM supporting electrolyte has a polarization resistance of 0.12 Ω cm<sup>2</sup> at 800 °C and an activation energy of 152 kJ/mol. The obtained characteristic was found to be better than one for the five-cation perovskite, casting doubt on the advantages of applying the high-entropy materials concept to the development of solid oxide fuel cells.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116729"},"PeriodicalIF":3.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560662","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}
Based on the high entropy theory, Fe, Mn, and Ni elements are doped into the transition metal Co sites in the LiCoO2 cathode structure. Two high entropy oxide cathode structures, namely the LiTMuniformO2 model and the LiTMnon-uniformO2 model, are constructed based on whether the distribution of transition metal elements is uniform. The crystal structure parameters, mechanical performance parameters, anisotropy index, and stress-strain performance of two high entropy models are calculated using first principles calculation method, and the structural stability is analyzed from a mechanical perspective. The effects of lithium-ion deintercalation on the crystal structure, mechanical properties, and stress-strain properties of two structures during the charging and discharging processes are studied. The research results indicate that the synergistic effect of multiple transition metal atoms is beneficial for improving the stability and mechanical properties of the cathode structure. The study of mechanical properties during delithiation process shows that as the degree of lithium removal increases, the Young's modulus of the material continues to decrease, while plasticity and toughness first increase and then decrease. Compared with non-uniform model, uniform model has better mechanical properties and cycle stability. The stress-strain performance of the LiTMuniformO2 model is superior to that of the LiTMnonuniformO2 model, and it can resist the influence of internal stress during battery cycling. This work provides some theoretical guidance for studying cathode materials with excellent mechanical properties and high energy density.
根据高熵理论，在钴酸锂阴极结构中的过渡金属 Co 位上掺入了 Fe、Mn 和 Ni 元素。根据过渡金属元素的分布是否均匀，构建了两种高熵氧化物阴极结构，即 LiTMuniformO2 模型和 LiTMnon-uniformO2 模型。利用第一性原理计算方法计算了两种高熵模型的晶体结构参数、力学性能参数、各向异性指数和应力应变性能，并从力学角度分析了结构的稳定性。研究了充放电过程中锂离子脱插对两种结构的晶体结构、力学性能和应力应变性能的影响。研究结果表明，多个过渡金属原子的协同效应有利于提高正极结构的稳定性和机械性能。对脱锂过程中力学性能的研究表明，随着脱锂程度的增加，材料的杨氏模量持续降低，而塑性和韧性先增加后降低。与非均匀模型相比，均匀模型具有更好的力学性能和循环稳定性。LiTMuniformO2 模型的应力-应变性能优于 LiTMnonuniformO2 模型，并能抵抗电池循环过程中内应力的影响。这项工作为研究具有优异机械性能和高能量密度的正极材料提供了一些理论指导。
{"title":"Mechanical properties of high entropy layered cathode structures","authors":"Junbo Zhang , Xiqi Zhang , Nini Qian , Bingbing Chen , Jianqiu Zhou","doi":"10.1016/j.ssi.2024.116726","DOIUrl":"10.1016/j.ssi.2024.116726","url":null,"abstract":"<div><div>Based on the high entropy theory, Fe, Mn, and Ni elements are doped into the transition metal Co sites in the LiCoO<sub>2</sub> cathode structure. Two high entropy oxide cathode structures, namely the LiTM<sub>uniform</sub>O<sub>2</sub> model and the LiTM<sub>non-uniform</sub>O<sub>2</sub> model, are constructed based on whether the distribution of transition metal elements is uniform. The crystal structure parameters, mechanical performance parameters, anisotropy index, and stress-strain performance of two high entropy models are calculated using first principles calculation method, and the structural stability is analyzed from a mechanical perspective. The effects of lithium-ion deintercalation on the crystal structure, mechanical properties, and stress-strain properties of two structures during the charging and discharging processes are studied. The research results indicate that the synergistic effect of multiple transition metal atoms is beneficial for improving the stability and mechanical properties of the cathode structure. The study of mechanical properties during delithiation process shows that as the degree of lithium removal increases, the Young's modulus of the material continues to decrease, while plasticity and toughness first increase and then decrease. Compared with non-uniform model, uniform model has better mechanical properties and cycle stability. The stress-strain performance of the LiTM<sub>uniform</sub>O<sub>2</sub> model is superior to that of the LiTM<sub>nonuniform</sub>O<sub>2</sub> model, and it can resist the influence of internal stress during battery cycling. This work provides some theoretical guidance for studying cathode materials with excellent mechanical properties and high energy density.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116726"},"PeriodicalIF":3.0,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533608","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}
Pub Date : 2024-10-28DOI: 10.1016/j.ssi.2024.116728
Onur Ozturk , Doruk Dogu
Ammonia is one of the most used chemicals in the world. It is commonly synthesized by the Haber-Bosch process which requires high temperature (450–500 °C) and pressure (up to 300 bar). This process is thermodynamically limited and causes environmental problems due to CO2 emissions caused by the production of H2 required by this process from fossil fuels. Electrocatalytic processes using oxide and proton-conducting electrolytes are gaining interest for ammonia production to overcome these limitations. Although both methods overcome many of the problems associated with the Haber-Bosch process, due to strong NN triple bonds selectivity towards ammonia decreases. This is because the reaction occurs on the same side of the membrane electrode assembly, namely the cathode electrode, where nitrogen is fed in the gas phase and nitrogen bonds should be broken to react with hydrogen ions readily available on the electrolyte surface. Since NN bond cleavage requires very high energy, hydrogen ions generally recombine to form H2 before the nitrogen can be ionized. Nitride conducting electrolytes can be an answer to this problem because in their use nitrogen ionization and ammonia synthesis reactions occur at different electrodes and nitrogen is fed to the reaction site in the ionic form which is more active for the reaction. This study focuses on two alternative methods for the production of nitride conducting solid electrolytes by nitridation of 8 % Yttria Stabilized Zirconia (8YSZ). Two different methods for nitridation were studied: gas phase powder nitridation and electrochemical nitridation of YSZ electrolytes. This study shows that although gas phase nitridation of YSZ powders at high temperatures under nitrogen is not efficient, electrochemical nitridation of YSZ electrolytes is a highly promising method to produce nitride conducting electrolytes.
{"title":"Comparison between gas phase and electrochemical nitridation of 8YSZ under nitrogen atmosphere to produce nitride conducting solid electrolytes","authors":"Onur Ozturk , Doruk Dogu","doi":"10.1016/j.ssi.2024.116728","DOIUrl":"10.1016/j.ssi.2024.116728","url":null,"abstract":"<div><div>Ammonia is one of the most used chemicals in the world. It is commonly synthesized by the Haber-Bosch process which requires high temperature (450–500 °C) and pressure (up to 300 bar). This process is thermodynamically limited and causes environmental problems due to CO<sub>2</sub> emissions caused by the production of H<sub>2</sub> required by this process from fossil fuels. Electrocatalytic processes using oxide and proton-conducting electrolytes are gaining interest for ammonia production to overcome these limitations. Although both methods overcome many of the problems associated with the Haber-Bosch process, due to strong N<img>N triple bonds selectivity towards ammonia decreases. This is because the reaction occurs on the same side of the membrane electrode assembly, namely the cathode electrode, where nitrogen is fed in the gas phase and nitrogen bonds should be broken to react with hydrogen ions readily available on the electrolyte surface. Since N<img>N bond cleavage requires very high energy, hydrogen ions generally recombine to form H<sub>2</sub> before the nitrogen can be ionized. Nitride conducting electrolytes can be an answer to this problem because in their use nitrogen ionization and ammonia synthesis reactions occur at different electrodes and nitrogen is fed to the reaction site in the ionic form which is more active for the reaction. This study focuses on two alternative methods for the production of nitride conducting solid electrolytes by nitridation of 8 % Yttria Stabilized Zirconia (8YSZ). Two different methods for nitridation were studied: gas phase powder nitridation and electrochemical nitridation of YSZ electrolytes. This study shows that although gas phase nitridation of YSZ powders at high temperatures under nitrogen is not efficient, electrochemical nitridation of YSZ electrolytes is a highly promising method to produce nitride conducting electrolytes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116728"},"PeriodicalIF":3.0,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533610","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}
Pub Date : 2024-10-25DOI: 10.1016/j.ssi.2024.116722
Yibei Wang , Biao Wang , Dongchao Qiu , Bingbing Niu , Chunling Lu
The protonic ceramic fuel cells (PCFCs) exhibits a remarkable high-energy conversion efficiency and significant application potential at low temperatures. In this context, the layered ternary lithium-ion batteries (LIB) material, LiNixCoyMn1-x-yO2 (LNCM), is explored as a potential cathode for PCFCs. Utilizing density functional theory (DFT) calculations, we have conducted a comprehensive analysis of oxygen vacancies, hydration energy, density of states, and other pertinent properties to evaluate these ternary materials. Both theoretical and experimental findings suggest that LiNi0.5Co0.2Mn0.3O2 (LNCM523) may offer the optimal performance as a PCFCs cathode. Notably, after calcination in air at 700 °C for 100 h, LNCM523 displayed no phase transition or the emergence of new phases. The impedance of LNCM523, measured on a BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) electrolyte, is 0.225 Ω cm2 at 650 °C. At this temperature, the peak power density of the single cell reaches 355 mW cm−2. Moreover, during a 100-h stability test conducted at 550 °C, the output performance of the single cell remained unaltered. In electrolysis mode, at 650 °C and 1.3 V, the current density for electrolysis water attained 1.75 A cm−2. Based on these promising results, LNCM emerges as a viable cathode candidate for PCFCs.
质子陶瓷燃料电池（PCFC）在低温条件下具有显著的高能量转换效率和巨大的应用潜力。在此背景下，我们探索了层状三元锂离子电池（LIB）材料 LiNixCoyMn1-x-yO2（LNCM）作为 PCFCs 潜在阴极的可能性。利用密度泛函理论（DFT）计算，我们对氧空位、水合能、状态密度和其他相关特性进行了全面分析，以评估这些三元材料。理论和实验结果都表明，LiNi0.5Co0.2Mn0.3O2（LNCM523）作为 PCFCs 阴极可能具有最佳性能。值得注意的是，在 700 °C 的空气中煅烧 100 小时后，LNCM523 没有出现相变或新相的出现。在 BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) 电解质上测量的 LNCM523 阻抗在 650 °C 时为 0.225 Ω cm2。在此温度下，单电池的峰值功率密度达到 355 mW cm-2。此外，在 550 °C 下进行的 100 小时稳定性测试中，单电池的输出性能保持不变。在电解模式下，温度为 650 ℃、电压为 1.3 V 时，电解水的电流密度达到 1.75 A cm-2。基于这些良好的结果，LNCM 成为 PCFCs 的一种可行的阴极候选材料。
{"title":"Comprehensive study on lithium-ion battery cathode LiNixCoyMn1-x-yO2 as an air electrode for protonic ceramic fuel cells","authors":"Yibei Wang , Biao Wang , Dongchao Qiu , Bingbing Niu , Chunling Lu","doi":"10.1016/j.ssi.2024.116722","DOIUrl":"10.1016/j.ssi.2024.116722","url":null,"abstract":"<div><div>The protonic ceramic fuel cells (PCFCs) exhibits a remarkable high-energy conversion efficiency and significant application potential at low temperatures. In this context, the layered ternary lithium-ion batteries (LIB) material, LiNi<sub><em>x</em></sub>Co<sub>y</sub>Mn<sub>1-x-y</sub>O<sub>2</sub> (LNCM), is explored as a potential cathode for PCFCs. Utilizing density functional theory (DFT) calculations, we have conducted a comprehensive analysis of oxygen vacancies, hydration energy, density of states, and other pertinent properties to evaluate these ternary materials. Both theoretical and experimental findings suggest that LiNi<sub>0.5</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub>O<sub>2</sub> (LNCM523) may offer the optimal performance as a PCFCs cathode. Notably, after calcination in air at 700 °C for 100 h, LNCM523 displayed no phase transition or the emergence of new phases. The impedance of LNCM523, measured on a BaZr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3-δ</sub> (BZCYYb) electrolyte, is 0.225 Ω cm<sup>2</sup> at 650 °C. At this temperature, the peak power density of the single cell reaches 355 mW cm<sup>−2</sup>. Moreover, during a 100-h stability test conducted at 550 °C, the output performance of the single cell remained unaltered. In electrolysis mode, at 650 °C and 1.3 V, the current density for electrolysis water attained 1.75 A cm<sup>−2</sup>. Based on these promising results, LNCM emerges as a viable cathode candidate for PCFCs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116722"},"PeriodicalIF":3.0,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533609","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}
Pub Date : 2024-10-24DOI: 10.1016/j.ssi.2024.116721
Xuelei Li , Weibo Yang , Yinzhou Wang , Liu Tonggang
Ultra-high‑nickel layered oxide cathodes are extensively explored in lithium-ion battery research owing to their high specific capacity. However, the rapid decline in discharge specific capacity considerably limits their long-term performance. The choice of lithium precursors is crucial in enhancing both the structural and cycle stability of these batteries, yet this aspect has not been adequately addressed in existing studies. In this study, Li2O, LiOH, and Li2CO3 were used as lithium precursors to synthesize LiNi0.92Co0.04Mn0.04O2 (NCM92) cathodes. We compare the structure and electrochemical properties of NCM92 cathode materials prepared with these three lithium precursors, examining a lithium residual layer on the surface of three NCM92 and thus inferring the varying amounts of Li incorporation into the bulk lattice. Our findings highlight the effect of lithium precursors on the rapid degradation of NCM92's discharge capacity. Notably, the NCM92–Li2O cathode demonstrates a higher discharge specific capacity and superior capacity retention after 100 cycles compared to cathodes synthesized with LiOH and Li2CO3. This study provides valuable insights and guidance for further research on ultra-high‑nickel layered oxide cathode materials.
{"title":"Electrochemical performance of ultra-high‑nickel layered oxide cathode synthesized using different lithium sources","authors":"Xuelei Li , Weibo Yang , Yinzhou Wang , Liu Tonggang","doi":"10.1016/j.ssi.2024.116721","DOIUrl":"10.1016/j.ssi.2024.116721","url":null,"abstract":"<div><div>Ultra-high‑nickel layered oxide cathodes are extensively explored in lithium-ion battery research owing to their high specific capacity. However, the rapid decline in discharge specific capacity considerably limits their long-term performance. The choice of lithium precursors is crucial in enhancing both the structural and cycle stability of these batteries, yet this aspect has not been adequately addressed in existing studies. In this study, Li<sub>2</sub>O, LiOH, and Li<sub>2</sub>CO<sub>3</sub> were used as lithium precursors to synthesize LiNi<sub>0.92</sub>Co<sub>0.04</sub>Mn<sub>0.04</sub>O<sub>2</sub> (NCM92) cathodes. We compare the structure and electrochemical properties of NCM92 cathode materials prepared with these three lithium precursors, examining a lithium residual layer on the surface of three NCM92 and thus inferring the varying amounts of Li incorporation into the bulk lattice. Our findings highlight the effect of lithium precursors on the rapid degradation of NCM92's discharge capacity. Notably, the NCM92–Li<sub>2</sub>O cathode demonstrates a higher discharge specific capacity and superior capacity retention after 100 cycles compared to cathodes synthesized with LiOH and Li<sub>2</sub>CO<sub>3</sub>. This study provides valuable insights and guidance for further research on ultra-high‑nickel layered oxide cathode materials.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116721"},"PeriodicalIF":3.0,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533607","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}
La0.1Sr0.9TiO3 (LST) perovskite has been studied as anode material for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC) applications. LST powders were synthesized by two chemical methods, one employed hexamethylenetetramine (HMTA) as a complexing agent while the other utilized ethylenediaminetetraacetic acid (EDTA). These approaches yielded different microstructures as evidenced by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and N2 adsorption/desorption isotherms studies. The effect of the microstructure on the electrochemical behavior of the obtained electrodes was studied by Electrochemical Impedance Spectroscopy (EIS) by varying the hydrogen partial pressure and the temperature. In addition, the evolution of specific area resistance with the hydrogen partial pressure allowed the identification of the reaction mechanism. The results of EIS were studied by electrical equivalent circuit (EEC) and distribution of relaxation times (DRT). The results suggest that the hydrogen oxidation reaction (HOR) limiting step for both samples is controlled by hydrogen dissociative-adsorption at the surface. The hydrogen adsorption is faster at the electrode formed by smaller nanoparticles, in which the activation energy decreases and the rate coefficient changes.
{"title":"Study of La0.1Sr0.9TiO3 electrochemical response as anode for SOFC and its relation with microstructure","authors":"Ernesto Tagarelli , Jesús Vega-Castillo , Mariela Ortiz , Horacio Troiani , Corina M. Chanquía , Alejandra Montenegro-Hernández","doi":"10.1016/j.ssi.2024.116719","DOIUrl":"10.1016/j.ssi.2024.116719","url":null,"abstract":"<div><div>La<sub>0.1</sub>Sr<sub>0.9</sub>TiO<sub>3</sub> (LST) perovskite has been studied as anode material for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC) applications. LST powders were synthesized by two chemical methods, one employed hexamethylenetetramine (HMTA) as a complexing agent while the other utilized ethylenediaminetetraacetic acid (EDTA). These approaches yielded different microstructures as evidenced by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and N<sub>2</sub> adsorption/desorption isotherms studies. The effect of the microstructure on the electrochemical behavior of the obtained electrodes was studied by Electrochemical Impedance Spectroscopy (EIS) by varying the hydrogen partial pressure and the temperature. In addition, the evolution of specific area resistance with the hydrogen partial pressure allowed the identification of the reaction mechanism. The results of EIS were studied by electrical equivalent circuit (EEC) and distribution of relaxation times (DRT). The results suggest that the hydrogen oxidation reaction (HOR) limiting step for both samples is controlled by hydrogen dissociative-adsorption at the surface. The hydrogen adsorption is faster at the electrode formed by smaller nanoparticles, in which the activation energy decreases and the rate coefficient changes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116719"},"PeriodicalIF":3.0,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533011","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}
Pub Date : 2024-10-23DOI: 10.1016/j.ssi.2024.116720
Yuliya A. Fadeeva, Liudmila E. Shmukler, Liubov P. Safonova
Fuel cells (FC) with proton exchange membranes (PEMs) are seen as an alternative energy source due to their efficiency, power density, low emissions, and reliable energy supply. Proton exchange membranes based on polybenzimidazole have shown potential for operating at high and medium temperatures to enhance FCs performance. New composite membranes made from m-PBI and diethylammonium mesylate [DEAH/MsO] ionic liquid were prepared trough a solution casting method. Silica nanopowder (SiO2) was used as an inorganic filler at varying concentrations (0.5–20 wt%). The ionic liquid content in the membranes ranged from 1 to 2.5 mol per mole of PBI monomer units. Our study is focused on the thermal properties, such as thermal stability and phase transition temperatures, morphology, conductivity, and electrochemical stability of the membranes. The influence of the inorganic filler on these properties was also discussed.
{"title":"Ionic liquid/polybenzimidazole/SiO2 composite membranes for medium temperature operating","authors":"Yuliya A. Fadeeva, Liudmila E. Shmukler, Liubov P. Safonova","doi":"10.1016/j.ssi.2024.116720","DOIUrl":"10.1016/j.ssi.2024.116720","url":null,"abstract":"<div><div>Fuel cells (FC) with proton exchange membranes (PEMs) are seen as an alternative energy source due to their efficiency, power density, low emissions, and reliable energy supply. Proton exchange membranes based on polybenzimidazole have shown potential for operating at high and medium temperatures to enhance FCs performance. New composite membranes made from <em>m</em>-PBI and diethylammonium mesylate [DEAH/MsO] ionic liquid were prepared trough a solution casting method. Silica nanopowder (SiO<sub>2</sub>) was used as an inorganic filler at varying concentrations (0.5–20 wt%). The ionic liquid content in the membranes ranged from 1 to 2.5 mol per mole of PBI monomer units. Our study is focused on the thermal properties, such as thermal stability and phase transition temperatures, morphology, conductivity, and electrochemical stability of the membranes. The influence of the inorganic filler on these properties was also discussed.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116720"},"PeriodicalIF":3.0,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533501","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}
Pub Date : 2024-10-17DOI: 10.1016/j.ssi.2024.116710
D.N. Karimov, N.I. Sorokin
The single crystals with the composition La1−y(Sm3+1−xSm2+x)yF3−xy (y = 0.04) were grown from melt by the vertical Bridgman technique. A part of the Sm3+ doping ions in LaF3 matrix is reduced to the Sm2+oxidation state due to interaction with carbon during the growth process. The crystals were studied by X-ray diffraction analysis, optical and impedance spectroscopy. The Sm-doped crystals LaF3 are single-phase, retaining the tysonite-type structure (sp. gr. P-3c1) and demonstrate a bipolar electrical conductivity mechanism. Both the ionic conductivity σi = 4.7 × 10−5 S/cm caused by heterovalent substitutions of La3+ for Sm2+ and the comparable electronic conductivity σe = 3 × 10−5 S/cm due to the variable oxidation states Sm2+/Sm3+ ions were detected for the grown crystals. The discovered mixed ionic-electronic conductivity of La0.96Sm3+0.004Sm2+0.036F2.964 crystals opens up a new direction for the practical application of the tysonite-type fluorides as a component of electrode materials for fluorine-ion current sources.
{"title":"Mixed-valence Sm-doped LaF3 crystals as ion-electron conductors: Crystal growth and impedance characterization","authors":"D.N. Karimov, N.I. Sorokin","doi":"10.1016/j.ssi.2024.116710","DOIUrl":"10.1016/j.ssi.2024.116710","url":null,"abstract":"<div><div>The single crystals with the composition La<sub>1−<em>y</em></sub>(Sm<sup>3+</sup><sub>1−<em>x</em></sub>Sm<sup>2+</sup><sub><em>x</em></sub>)<sub><em>y</em></sub>F<sub>3−<em>xy</em></sub> <span><math><mi>L</mi><msub><mi>a</mi><mrow><mn>1</mn><mo>−</mo><mi>y</mi></mrow></msub><msub><mfenced><mrow><mi>S</mi><msubsup><mi>m</mi><mrow><mn>1</mn><mo>−</mo><mi>x</mi></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><mi>S</mi><msubsup><mi>m</mi><mi>x</mi><mrow><mn>2</mn><mo>+</mo></mrow></msubsup></mrow></mfenced><mi>y</mi></msub><msub><mi>F</mi><mrow><mn>3</mn><mo>−</mo><mi>xy</mi></mrow></msub></math></span>(<em>y</em> = 0.04) were grown from melt by the vertical Bridgman technique. A part of the Sm<sup>3+</sup> doping ions in LaF<sub>3</sub> matrix is reduced to the Sm<sup>2+</sup> <em>oxidation</em> state due to interaction with carbon during the growth process. The crystals were studied by X-ray diffraction analysis, optical and impedance spectroscopy. The Sm-doped crystals LaF<sub>3</sub> are single-phase, retaining the tysonite-type structure (sp. gr. <em>P-3c1</em><span><math><mi>P</mi><mover><mn>3</mn><mo>̄</mo></mover><mi>c</mi><mn>1</mn></math></span>) and demonstrate a bipolar electrical conductivity mechanism. Both the ionic conductivity σ<sub>i</sub> = 4.7 × 10<sup>−5</sup> S/cm caused by heterovalent substitutions of La<sup>3+</sup> for Sm<sup>2+</sup> and the comparable electronic conductivity σ<sub>e</sub> = 3 × 10<sup>−5</sup> S/cm due to the variable <em>oxidation states</em> Sm<sup>2+</sup>/Sm<sup>3+</sup> ions were detected for the grown crystals. The discovered mixed ionic-electronic conductivity of La<sub>0.96</sub>Sm<sup>3+</sup><sub>0.004</sub>Sm<sup>2+</sup><sub>0.036</sub>F<sub>2.964</sub> crystals opens up a new direction for the practical application of the tysonite-type fluorides as a component of electrode materials for fluorine-ion current sources.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116710"},"PeriodicalIF":3.0,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445251","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}
Pub Date : 2024-10-16DOI: 10.1016/j.ssi.2024.116718
Jingxiu Tian , Li-ang Zhu , Hongshun Miao , Xiangxin Li , Yan Liu
O3-NaNi1/3Fe1/3Mn1/3O2 (NaNFM) materials are susceptible to complex phase transitions during electrical cycling leading to poor structural, capacity retention and multiplicity properties. These drawbacks hinder the application of NaNFM in sodium-ion batteries. Here, Mg2+ with larger ionic radius was used to dope its transition metal layer Ni site. The effects of Mg2+ doped NaNFM crystal structure and transition metal valence states on its electrochemical properties were investigated by XRD, SEM, and XPS. The capacity retention of NaNMFM-0.02 (84.05 %) was higher than that of NaNFM (73 %) after 200 cycles of the material at 5C. In addition, NaNMFM-0.02 achieved a first discharge specific capacity of 146.5 mAh/g at high voltage. Based on structural and electrochemical analyses, this improvement is attributed to the fact that magnesium acts as a “pillar” to stabilize the crystal structure of NaNFM, while magnesium doping reduces the Jahn-Teller effect. As a result, the material has better electrochemical properties.
{"title":"Effect of the position of Mg replacing Ni on O3-NaNi1/3Fe1/3Mn1/3O2 on the structural stability of cathode materials","authors":"Jingxiu Tian , Li-ang Zhu , Hongshun Miao , Xiangxin Li , Yan Liu","doi":"10.1016/j.ssi.2024.116718","DOIUrl":"10.1016/j.ssi.2024.116718","url":null,"abstract":"<div><div>O3-NaNi<sub>1/3</sub>Fe<sub>1/3</sub>Mn<sub>1/3</sub>O<sub>2</sub> (NaNFM) materials are susceptible to complex phase transitions during electrical cycling leading to poor structural, capacity retention and multiplicity properties. These drawbacks hinder the application of NaNFM in sodium-ion batteries. Here, Mg<sup>2+</sup> with larger ionic radius was used to dope its transition metal layer Ni site. The effects of Mg<sup>2+</sup> doped NaNFM crystal structure and transition metal valence states on its electrochemical properties were investigated by XRD, SEM, and XPS. The capacity retention of NaNMFM-0.02 (84.05 %) was higher than that of NaNFM (73 %) after 200 cycles of the material at 5C. In addition, NaNMFM-0.02 achieved a first discharge specific capacity of 146.5 mAh/g at high voltage. Based on structural and electrochemical analyses, this improvement is attributed to the fact that magnesium acts as a “pillar” to stabilize the crystal structure of NaNFM, while magnesium doping reduces the Jahn-Teller effect. As a result, the material has better electrochemical properties.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116718"},"PeriodicalIF":3.0,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142441521","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}
Pub Date : 2024-10-16DOI: 10.1016/j.ssi.2024.116711
Tianxin Zhao, Lulu Wang, Yang Zhang, Fan Zhang, Jilin Wang
A series of anion exchange membranes (AEMs) with highly ion conductivity suitable for practical application in fuel cells were prepared in this paper. Polysulfone (PSf) was used as backbone to prepare chloromethylation polysulfone (CMPSf). Then the synthesized CMPSf was blended with tetramethyldiaminopropane (TMPDA) and polyethylene glycol (PEG 400), to construct interpenetrating polymer networks with hydrogen-bonding conduction sites. In this paper the chemical structure of the AEM is confirmed by nuclear magnetic resonance spectrum (1H NMR) spectroscopy and fourier transform infrared spectroscopy (FT-IR). The morphologies of synthesized membranes in this paper are investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The electrochemical and physical properties of AEMs are tested comprising water uptake (WU), ion exchange capacity (IEC), alkaline stability, thermal stability and mechanical stability. The introduction of hydrogen-bonding networks enhanced the OH− conductivity of the membranes (from 37.03 mS·cm−1 of QAPSf-PEG0% to 104.67 mS·cm−1 of QAPSf-PEG30%). The interpenetrating polymer networks make the membranes have good mechanical property (tensile strengh is 19.61 MPa, elongation at break is 20.30 %) and anti-swelling properties (29.3 %, 80 °C). Due to the introduction of hydrogen-bonding conduction networks, the alkaline stability of the AEMs can be enhanced by reducing the modification of the polysulfone backbone. Thus, even after soaking in 6 mol·L−1 KOH solution for 30 days, the retained OH− conductivity of QAPSf-PEG30% still reached 92.0 %. At the same time, the addition of PEG leads to the increased water uptake, so that the OH− ions could be better transported. And the single cell performance of QAPSf-PEG30% was also revealed that the power density increases significantly from 323.35 mW·cm−2 at 60 °C to 514.8 mW·cm−2 at 80 °C as the temperature increases. Overall, QAPSf-PEG30% exhibits promising development potential in the fuel cells.
{"title":"High conductivity of a fuel cell through a hydrogen bond network within an interpenetrating anion exchange membrane","authors":"Tianxin Zhao, Lulu Wang, Yang Zhang, Fan Zhang, Jilin Wang","doi":"10.1016/j.ssi.2024.116711","DOIUrl":"10.1016/j.ssi.2024.116711","url":null,"abstract":"<div><div>A series of anion exchange membranes (AEMs) with highly ion conductivity suitable for practical application in fuel cells were prepared in this paper. Polysulfone (PSf) was used as backbone to prepare chloromethylation polysulfone (CMPSf). Then the synthesized CMPSf was blended with tetramethyldiaminopropane (TMPDA) and polyethylene glycol (PEG 400), to construct interpenetrating polymer networks with hydrogen-bonding conduction sites. In this paper the chemical structure of the AEM is confirmed by nuclear magnetic resonance spectrum (<sup>1</sup>H NMR) spectroscopy and fourier transform infrared spectroscopy (FT-IR). The morphologies of synthesized membranes in this paper are investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The electrochemical and physical properties of AEMs are tested comprising water uptake (WU), ion exchange capacity (IEC), alkaline stability, thermal stability and mechanical stability. The introduction of hydrogen-bonding networks enhanced the OH<sup>−</sup> conductivity of the membranes (from 37.03 mS·cm<sup>−1</sup> of QAPSf-PEG<sub>0%</sub> to 104.67 mS·cm<sup>−1</sup> of QAPSf-PEG<sub>30%</sub>). The interpenetrating polymer networks make the membranes have good mechanical property (tensile strengh is 19.61 MPa, elongation at break is 20.30 %) and anti-swelling properties (29.3 %, 80 °C). Due to the introduction of hydrogen-bonding conduction networks, the alkaline stability of the AEMs can be enhanced by reducing the modification of the polysulfone backbone. Thus, even after soaking in 6 mol·L<sup>−1</sup> KOH solution for 30 days, the retained OH<sup>−</sup> conductivity of QAPSf-PEG<sub>3</sub><sub>0%</sub> still reached 92.0 %. At the same time, the addition of PEG leads to the increased water uptake, so that the OH<sup>−</sup> ions could be better transported. And the single cell performance of QAPSf-PEG<sub>30%</sub> was also revealed that the power density increases significantly from 323.35 mW·cm<sup>−2</sup> at 60 °C to 514.8 mW·cm<sup>−2</sup> at 80 °C as the temperature increases. Overall, QAPSf-PEG<sub>30%</sub> exhibits promising development potential in the fuel cells.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116711"},"PeriodicalIF":3.0,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142441523","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号