Pub Date : 2026-04-01Epub Date: 2026-02-11DOI: 10.1016/j.ssi.2026.117151
Tatsumi Ishihara , Fumitake Kanehara , Shotaro Kuramitsu , Jun Tae Song , Motonori Watanabe , Miki Inada
Fluoride ion battery is now expecting as a high energy density rechargeable battery which is alternative to Li ion rechargeable battery. For realizing all solid-state concept, fast fluoride ion conductor with wide electrochemical windows is required. In this study, fluoride ion conductivity in doped ASn2F5 (A = Na, K, Rb, Cs) were measured and it was found that reasonably high fluoride ion conductivity was achieved on Rb0.9Li0.1Sn2F5 which is layered structure and contained intrinsic fluoride vacancy. Transport number of fluoride ion in this Rb0.9Li0.1Sn2F5 was also measured with fluoride concentration cell, Pb/sample/BiF3 and the estimated transport number of fluoride ion was higher than 90% of theoretical one. For further analysis of fluoride ion conductivity in Rb0.9Li0.1Sn2F5, electrochemical pumping of fluoride ion was measured on the symmetrical cell consisting of BiF3/BiF3 over 48 h and the amount of fluoride transported was reasonably agreed with the coulomb number through the sample. Linear scan voltammetry (LSV) shows the electrochemical stability windows of Rb0.9Li0.1Sn2F5 was close to ca.3 V.
{"title":"Fluoride ion conductivity in Li doped ASn2F5 (A = Na, K, Rb, Cs)","authors":"Tatsumi Ishihara , Fumitake Kanehara , Shotaro Kuramitsu , Jun Tae Song , Motonori Watanabe , Miki Inada","doi":"10.1016/j.ssi.2026.117151","DOIUrl":"10.1016/j.ssi.2026.117151","url":null,"abstract":"<div><div>Fluoride ion battery is now expecting as a high energy density rechargeable battery which is alternative to Li ion rechargeable battery. For realizing all solid-state concept, fast fluoride ion conductor with wide electrochemical windows is required. In this study, fluoride ion conductivity in doped ASn<sub>2</sub>F<sub>5</sub> (A = Na, K, Rb, Cs) were measured and it was found that reasonably high fluoride ion conductivity was achieved on Rb<sub>0.9</sub>Li<sub>0.1</sub>Sn<sub>2</sub>F<sub>5</sub> which is layered structure and contained intrinsic fluoride vacancy. Transport number of fluoride ion in this Rb<sub>0.9</sub>Li<sub>0.1</sub>Sn<sub>2</sub>F<sub>5</sub> was also measured with fluoride concentration cell, Pb/sample/BiF<sub>3</sub> and the estimated transport number of fluoride ion was higher than 90% of theoretical one. For further analysis of fluoride ion conductivity in Rb<sub>0.9</sub>Li<sub>0.1</sub>Sn<sub>2</sub>F<sub>5</sub>, electrochemical pumping of fluoride ion was measured on the symmetrical cell consisting of BiF<sub>3</sub>/BiF<sub>3</sub> over 48 h and the amount of fluoride transported was reasonably agreed with the coulomb number through the sample. Linear scan voltammetry (LSV) shows the electrochemical stability windows of Rb<sub>0.9</sub>Li<sub>0.1</sub>Sn<sub>2</sub>F<sub>5</sub> was close to ca.3 V.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"438 ","pages":"Article 117151"},"PeriodicalIF":3.3,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172297","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 : 2026-04-01Epub Date: 2026-02-09DOI: 10.1016/j.ssi.2026.117155
Zhen Ma, Runqing Yao, Dongmei Liu, Longrong Yao, Changyun Li, Xuliang Zhao, Yang Li
The tape-casting process has been widely used for the fabrication of solid electrolyte thin films. To further investigate the impact of this forming process on the performance of solid electrolytes, this study examines the key process parameters and optimization strategies involved in the tape-casting preparation of LLZTO solid electrolytes. A systematic investigation was conducted on the effects of solvent systems, dispersants, binder-plasticizer ratios, ball milling time, and degassing methods on the properties of the tape-casting slurry. The rheological and thixotropic properties of the slurry were optimized, and by combining a mother powder covering sintering method, lithium volatilization was effectively suppressed. The results indicate that under a sintering condition of 1250 °C, the relative density of the electrolyte pellet reached 94.3%, with an ionic conductivity of 1.02 × 10−4 S/cm. The assembled all-solid-state battery exhibited a capacity retention of approximately 82% after 180 cycles at a 1C rate, demonstrating excellent electrochemical performance and cycling stability.
{"title":"Research on casting technology and properties of LLZTO solid electrolytes","authors":"Zhen Ma, Runqing Yao, Dongmei Liu, Longrong Yao, Changyun Li, Xuliang Zhao, Yang Li","doi":"10.1016/j.ssi.2026.117155","DOIUrl":"10.1016/j.ssi.2026.117155","url":null,"abstract":"<div><div>The tape-casting process has been widely used for the fabrication of solid electrolyte thin films. To further investigate the impact of this forming process on the performance of solid electrolytes, this study examines the key process parameters and optimization strategies involved in the tape-casting preparation of LLZTO solid electrolytes. A systematic investigation was conducted on the effects of solvent systems, dispersants, binder-plasticizer ratios, ball milling time, and degassing methods on the properties of the tape-casting slurry. The rheological and thixotropic properties of the slurry were optimized, and by combining a mother powder covering sintering method, lithium volatilization was effectively suppressed. The results indicate that under a sintering condition of 1250 °C, the relative density of the electrolyte pellet reached 94.3%, with an ionic conductivity of 1.02 × 10<sup>−4</sup> S/cm. The assembled all-solid-state battery exhibited a capacity retention of approximately 82% after 180 cycles at a 1C rate, demonstrating excellent electrochemical performance and cycling stability.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"438 ","pages":"Article 117155"},"PeriodicalIF":3.3,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172324","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 : 2026-04-01Epub Date: 2026-02-04DOI: 10.1016/j.ssi.2026.117142
Ning Han, Yang Liu, Ying Chen, Hongyan Yan
Fe2AlB2 has emerged as a research hotspot due to its high damage tolerance and magnetocaloric effect, serving as a representative MAB-phase ceramic. Addressing the stringent storage and reaction environment requirements associated with using Al powder as raw material in Fe2AlB2 preparation, this study employs a molten salt electrochemical method using FeB and Al2O3 as raw materials. Analysis of the reaction mechanism reveals that electrochemical reduction of Al2O3 occurs first, followed by mutual diffusion of Al and FeB to form Fe2AlB2. The reduction of Al2O3 primarily occurs during the initial stage and influences the formation of Fe2AlB2 due to the rapid progression of the electrochemical reaction. Characterization and performance studies of the synthesized Fe2AlB2 demonstrate the acquisition of a layered structure and Fe2AlB2 powder with certain electrochemical properties.
{"title":"Research on the preparation of Fe2AlB2 MAB phase by molten salt electrochemical method and its electrochemical performance","authors":"Ning Han, Yang Liu, Ying Chen, Hongyan Yan","doi":"10.1016/j.ssi.2026.117142","DOIUrl":"10.1016/j.ssi.2026.117142","url":null,"abstract":"<div><div>Fe<sub>2</sub>AlB<sub>2</sub> has emerged as a research hotspot due to its high damage tolerance and magnetocaloric effect, serving as a representative MAB-phase ceramic. Addressing the stringent storage and reaction environment requirements associated with using Al powder as raw material in Fe<sub>2</sub>AlB<sub>2</sub> preparation, this study employs a molten salt electrochemical method using FeB and Al<sub>2</sub>O<sub>3</sub> as raw materials. Analysis of the reaction mechanism reveals that electrochemical reduction of Al<sub>2</sub>O<sub>3</sub> occurs first, followed by mutual diffusion of Al and FeB to form Fe<sub>2</sub>AlB<sub>2</sub>. The reduction of Al<sub>2</sub>O<sub>3</sub> primarily occurs during the initial stage and influences the formation of Fe<sub>2</sub>AlB<sub>2</sub> due to the rapid progression of the electrochemical reaction. Characterization and performance studies of the synthesized Fe<sub>2</sub>AlB<sub>2</sub> demonstrate the acquisition of a layered structure and Fe<sub>2</sub>AlB<sub>2</sub> powder with certain electrochemical properties.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"438 ","pages":"Article 117142"},"PeriodicalIF":3.3,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116712","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 : 2026-04-01Epub Date: 2026-02-10DOI: 10.1016/j.ssi.2026.117153
Nikita A. Afimchenko, Aleksandr A. Shubin, Igor L. Zilberberg, Alexander P. Nemudry
The “O−” state in the ABO3 perovskites has been discussed for decades to explain high oxygen ionic conductivity in some perovskites. Although the electron states of oxygen ion with low electron density have indeed been detected using the O1s X-ray photoelectron spectroscopy (XPS) in many perovskites, the structure (atomic or molecular) of “O−” remains uncertain. On base of the plane-wave DFT modeling in the present work the mysterious “O−” state has been assigned to the oxygen of peroxo group which forms via the association of two “O−” species on the surface and possibly at the grain boundary of the polycrystalline samples. Such effects is suggested to take place primarily for the perovskites possessing negative charge-transfer gap and so being able for spontaneous electron holes formation in the oxygen valence band. The appearance of these holes reveals itself in (1) the inverted t2g-eg crystal-field splitting of the d(Fe) states, and (2) the “3+” oxidation state for all iron ions. To model peroxo-like species there has been chosen the strontium ferrite SrFeO3-δ. DFT modeling shows that each OO association forms the peroxide ion which traps two electron holes making them localized and detectible via the density of states. Simultaneously, the OO association is accompanied by the drop of the number of states at the Fermi level due to the disruption of conducting Fe-O-Fe bridges.
几十年来，人们一直在讨论ABO3钙钛矿中的“O -”态，以解释某些钙钛矿中氧离子电导率高的原因。虽然利用O1s x射线光电子能谱（XPS）确实在许多钙钛矿中检测到低电子密度的氧离子的电子态，但“O -”的原子或分子结构仍然不确定。在平面波DFT模型的基础上，我们将神秘的“O -”态分配给了多晶样品表面和可能在晶界上由两种“O -”缔合形成的过氧基团氧。这种效应主要发生在具有负电荷转移隙的钙钛矿，因此能够在氧价带中自发形成电子空穴。这些空穴的出现体现在(1)d（Fe）态的反t2g-eg晶体场分裂和(2)所有铁离子的“3+”氧化态。为了模拟过氧类物质，我们选择了锶铁氧体SrFeO3-δ。DFT模型表明，每个OO缔合形成过氧化离子，过氧化离子捕获两个电子空穴，使它们定位并通过态密度可检测到。同时，由于Fe-O-Fe电桥的破坏，o - o - fe的关联伴随着费米能级态数的下降。
{"title":"Unraveling the “O−” electron state in perovskites on the example of SrFeO3 by means of plane-wave DFT","authors":"Nikita A. Afimchenko, Aleksandr A. Shubin, Igor L. Zilberberg, Alexander P. Nemudry","doi":"10.1016/j.ssi.2026.117153","DOIUrl":"10.1016/j.ssi.2026.117153","url":null,"abstract":"<div><div>The “O<sup>−</sup>” state in the ABO<sub>3</sub> perovskites has been discussed for decades to explain high oxygen ionic conductivity in some perovskites. Although the electron states of oxygen ion with low electron density have indeed been detected using the O1s X-ray photoelectron spectroscopy (XPS) in many perovskites, the structure (atomic or molecular) of “O<sup>−</sup>” remains uncertain. On base of the plane-wave DFT modeling in the present work the mysterious “O<sup>−</sup>” state has been assigned to the oxygen of peroxo group which forms via the association of two “O<sup>−</sup>” species on the surface and possibly at the grain boundary of the polycrystalline samples. Such effects is suggested to take place primarily for the perovskites possessing negative charge-transfer gap and so being able for spontaneous electron holes formation in the oxygen valence band. The appearance of these holes reveals itself in (1) the inverted t<sub>2g</sub>-e<sub>g</sub> crystal-field splitting of the <em>d</em>(Fe) states, and (2) the “3+” oxidation state for all iron ions. To model peroxo-like species there has been chosen the strontium ferrite SrFeO<sub>3-δ</sub>. DFT modeling shows that each O<img>O association forms the peroxide ion which traps two electron holes making them localized and detectible via the density of states. Simultaneously, the O<img>O association is accompanied by the drop of the number of states at the Fermi level due to the disruption of conducting Fe-O-Fe bridges.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"438 ","pages":"Article 117153"},"PeriodicalIF":3.3,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172323","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 : 2026-04-01Epub Date: 2026-02-11DOI: 10.1016/j.ssi.2026.117150
Daniel Freidzon , Ellen Wachtel , Anna Kossoy , Hagai Cohen , Ayelet Vilan , David Ehre , Isaac Abrahams , Igor Lubomirsky
Proton conductors are essential for a wide range of applications including solid oxide fuel cells, sensors and resistivity switches. However, commonly used proton-conducting materials such as Nafion, doped barium zirconate, and cesium dihydrogen phosphate suffer from significant limitations - including poor long-term stability and microfabrication compatibility. Recent work has shown that bulk La2Ce2O7 (LCO50) ceramics hydrate in moist environments and exhibit increased conductivity at temperatures below 473 K. In this work, we investigate the hydration behavior of magnetron-sputtered LCO50 thin films. We demonstrate that water can be incorporated into the crystal lattice, leading to an approximately fivefold increase at 363 K in the total conductivity of the as-deposited film. Extrapolating the exponential temperature dependence to room temperature, yields an approximately 103 fold conductivity enhancement, in agreement with values derived from XPS/CREM. To confirm that the total conductivity of the hydrated film is at least partially protonic, and to demonstrate that LCO50 can function as a mixed ion conductor, we demonstrate its use as the electrolyte in a layered tungsten oxide electrochromic device.
{"title":"Increasing the electrical conductivity of La2Ce2O7 thin films by hydration","authors":"Daniel Freidzon , Ellen Wachtel , Anna Kossoy , Hagai Cohen , Ayelet Vilan , David Ehre , Isaac Abrahams , Igor Lubomirsky","doi":"10.1016/j.ssi.2026.117150","DOIUrl":"10.1016/j.ssi.2026.117150","url":null,"abstract":"<div><div>Proton conductors are essential for a wide range of applications including solid oxide fuel cells, sensors and resistivity switches. However, commonly used proton-conducting materials such as Nafion, doped barium zirconate, and cesium dihydrogen phosphate suffer from significant limitations - including poor long-term stability and microfabrication compatibility. Recent work has shown that bulk La<sub>2</sub>Ce<sub>2</sub>O<sub>7</sub> (LCO50) ceramics hydrate in moist environments and exhibit increased conductivity at temperatures below 473 K. In this work, we investigate the hydration behavior of magnetron-sputtered LCO50 thin films. We demonstrate that water can be incorporated into the crystal lattice, leading to an approximately fivefold increase at 363 K in the total conductivity of the as-deposited film. Extrapolating the exponential temperature dependence to room temperature, yields an approximately 10<sup>3</sup> fold conductivity enhancement, in agreement with values derived from XPS/CREM. To confirm that the total conductivity of the hydrated film is at least partially protonic, and to demonstrate that LCO50 can function as a mixed ion conductor, we demonstrate its use as the electrolyte in a layered tungsten oxide electrochromic device.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"438 ","pages":"Article 117150"},"PeriodicalIF":3.3,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172296","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 : 2026-04-01Epub Date: 2026-02-11DOI: 10.1016/j.ssi.2026.117152
S. Neitzel-Grieshammer , M. Martin
Defect interactions play a crucial role for thermodynamics and kinetics in Solid State Ionics. They strongly affect both the thermodynamics of defect formation in a solid and the mobility of defects and ions. This applies in particular to oxides with relatively high defect concentrations, which are nowadays used in many technical applications such as sensors, electrolysers, solid oxide fuel cells etc. As examples for this class of oxides, we consider ceria as prototype mixed ionic-electronic conductor, doped ceria as prototype oxygen ion conductor, and doped barium zirconate as prototype proton conductor. Here we summarize our years of computational work in which we applied density functional theory (DFT) in combination with Metropolis Monte Carlo simulations (MMC) and kinetic Monte Carlo simulations (KMC) to investigate the defect chemistry and ion transport in these prototype oxides.
{"title":"The crucial role of defect interactions for thermodynamics and kinetics in solid state Ionics","authors":"S. Neitzel-Grieshammer , M. Martin","doi":"10.1016/j.ssi.2026.117152","DOIUrl":"10.1016/j.ssi.2026.117152","url":null,"abstract":"<div><div>Defect interactions play a crucial role for thermodynamics and kinetics in Solid State Ionics. They strongly affect both the thermodynamics of defect formation in a solid and the mobility of defects and ions. This applies in particular to oxides with relatively high defect concentrations, which are nowadays used in many technical applications such as sensors, electrolysers, solid oxide fuel cells etc. As examples for this class of oxides, we consider ceria as prototype mixed ionic-electronic conductor, doped ceria as prototype oxygen ion conductor, and doped barium zirconate as prototype proton conductor. Here we summarize our years of computational work in which we applied density functional theory (DFT) in combination with Metropolis Monte Carlo simulations (MMC) and kinetic Monte Carlo simulations (KMC) to investigate the defect chemistry and ion transport in these prototype oxides.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"438 ","pages":"Article 117152"},"PeriodicalIF":3.3,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172295","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 : 2026-04-01Epub Date: 2026-02-12DOI: 10.1016/j.ssi.2026.117160
Fei Han, Qinan Zhou, Yan Liu, Bi Xu, Zhijian Zhang, Hongxue Li, Yuanyuan Wang, Tianyu Liu, Haochen Shi
The development of cathodes that exhibit high oxygen catalytic activity represents a critical focus in the field of solid oxide fuel cells (SOFCs). This study characterizes La2Ni1-xBixO4+δ (LN1-xBxO x = 0–0.05) perovskite-like layered oxide and evaluates it as a potential cathode material for SOFCs. The results show that when Bi3+ ion with larger radii is introduced into the Ni-site, the tolerance factor of the material decreased and the free unit-cell volume increased, which enhances the oxygen ion conductivity of the material. The iodometric titration results further confirm that the increase in Bi3+ content leads to an increase in the δ value, indicating a higher interstitial oxygen content in the material. The interstitial oxygen can easier be released in the crystal lattice which form oxygen vacancies and promote oxygen catalytic activity. Additionally, the sample with x = 0.04 exhibits optimal porosity and particle size, resulting in an expanded triple-phase boundaries (TPBs). The process of reduction of oxygen atoms at the TPBs is accelerated after doping. The LNB0.04O/SDC/LNB0.04O symmetrical cell has the minimum polarization resistance (Rp) and the maximum power density at the same test temperature. These results suggest that the addition of Bi ions effectively boosts the electrochemical properties of the cathode materials.
具有高氧催化活性的阴极的开发是固体氧化物燃料电池（sofc）领域的一个关键焦点。本研究表征了La2Ni1-xBixO4+δ (LN1-xBxO x = 0-0.05)钙钛矿样层状氧化物，并评价其作为sofc的潜在正极材料。结果表明：在ni位点引入半径较大的Bi3+离子后，材料的容差系数降低，自由单元胞体积增大，提高了材料的氧离子电导率；碘量滴定结果进一步证实，Bi3+含量的增加导致δ值的增加，表明材料中间隙氧含量增加。间隙氧更容易在晶格中释放，形成氧空位，提高氧催化活性。此外，当x = 0.04时，样品具有最佳的孔隙率和粒径，从而扩大了三相边界（TPBs）。掺杂后，tpb上氧原子的还原过程加快。在相同测试温度下，lnb0.040 o /SDC/ lnb0.040 o对称电池具有最小的极化电阻（Rp）和最大的功率密度。这些结果表明，Bi离子的加入有效地提高了正极材料的电化学性能。
{"title":"Electrochemical performance of bismuth doping La2NiO4+δ for SOFCs cathode","authors":"Fei Han, Qinan Zhou, Yan Liu, Bi Xu, Zhijian Zhang, Hongxue Li, Yuanyuan Wang, Tianyu Liu, Haochen Shi","doi":"10.1016/j.ssi.2026.117160","DOIUrl":"10.1016/j.ssi.2026.117160","url":null,"abstract":"<div><div>The development of cathodes that exhibit high oxygen catalytic activity represents a critical focus in the field of solid oxide fuel cells (SOFCs). This study characterizes La<sub>2</sub>Ni<sub>1-x</sub>Bi<sub>x</sub>O<sub>4+δ</sub> (LN<sub>1-x</sub>B<sub>x</sub>O x = 0–0.05) perovskite-like layered oxide and evaluates it as a potential cathode material for SOFCs. The results show that when Bi<sup>3+</sup> ion with larger radii is introduced into the Ni-site, the tolerance factor of the material decreased and the free unit-cell volume increased, which enhances the oxygen ion conductivity of the material. The iodometric titration results further confirm that the increase in Bi<sup>3+</sup> content leads to an increase in the δ value, indicating a higher interstitial oxygen content in the material. The interstitial oxygen can easier be released in the crystal lattice which form oxygen vacancies and promote oxygen catalytic activity. Additionally, the sample with x = 0.04 exhibits optimal porosity and particle size, resulting in an expanded triple-phase boundaries (TPBs). The process of reduction of oxygen atoms at the TPBs is accelerated after doping. The LNB<sub>0.04</sub>O/SDC/LNB<sub>0.04</sub>O symmetrical cell has the minimum polarization resistance (<em>Rp</em>) and the maximum power density at the same test temperature. These results suggest that the addition of Bi ions effectively boosts the electrochemical properties of the cathode materials.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"438 ","pages":"Article 117160"},"PeriodicalIF":3.3,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172294","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 : 2026-04-01Epub Date: 2026-02-13DOI: 10.1016/j.ssi.2026.117156
Yage Wang , Rui Wang , Yu Shen , Tao Huan , Jingxin Lu
The interfacial instability between sulfide-based solid electrolytes (SSEs) and sodium metal anodes significantly hinders the development of all-solid-state sodium batteries. Therefore, the design of solid electrolytes combining high ionic conductivity and excellent interfacial stability is of critical importance for advancing their practical application. To address the poor interfacial compatibility of Na3SbS4 (NSS) electrolyte with sodium metal, this study proposes a modification strategy via synergistic anion-cation co-doping. Using CaO as the doping source, a series of solid electrolytes with the composition Na3-2xCaxSbS4-xOx (x = 0.025–0.1) were successfully synthesized through high-energy ball milling followed by heat treatment. The effects of CaO dual doping on the crystal structure, ion transport behavior, and electrochemical stability of the materials were systematically investigated. It was found that the introduction of Ca2+ optimizes bulk ionic conductivity by generating sodium vacancies, while the incorporation of O2− induces the formation of a highly ion-conductive passivation layer at the electrolyte/sodium metal interface. These effects work synergistically to enhance the overall performance of the material. The results demonstrate that multi-element doping is a viable strategy for simultaneously regulating the bulk and interfacial properties of sulfide electrolytes, providing experimental support for the development of high-performance all-solid-state sodium batteries.
{"title":"High-performance solid-state electrolytes via synergistic ion interaction","authors":"Yage Wang , Rui Wang , Yu Shen , Tao Huan , Jingxin Lu","doi":"10.1016/j.ssi.2026.117156","DOIUrl":"10.1016/j.ssi.2026.117156","url":null,"abstract":"<div><div>The interfacial instability between sulfide-based solid electrolytes (SSEs) and sodium metal anodes significantly hinders the development of all-solid-state sodium batteries. Therefore, the design of solid electrolytes combining high ionic conductivity and excellent interfacial stability is of critical importance for advancing their practical application. To address the poor interfacial compatibility of Na<sub>3</sub>SbS<sub>4</sub> (NSS) electrolyte with sodium metal, this study proposes a modification strategy via synergistic anion-cation co-doping. Using CaO as the doping source, a series of solid electrolytes with the composition Na<sub>3-2x</sub>Ca<sub>x</sub>SbS<sub>4-x</sub>O<sub>x</sub> (x = 0.025–0.1) were successfully synthesized through high-energy ball milling followed by heat treatment. The effects of Ca<img>O dual doping on the crystal structure, ion transport behavior, and electrochemical stability of the materials were systematically investigated. It was found that the introduction of Ca<sup>2+</sup> optimizes bulk ionic conductivity by generating sodium vacancies, while the incorporation of O<sup>2−</sup> induces the formation of a highly ion-conductive passivation layer at the electrolyte/sodium metal interface. These effects work synergistically to enhance the overall performance of the material. The results demonstrate that multi-element doping is a viable strategy for simultaneously regulating the bulk and interfacial properties of sulfide electrolytes, providing experimental support for the development of high-performance all-solid-state sodium batteries.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"438 ","pages":"Article 117156"},"PeriodicalIF":3.3,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172293","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 : 2026-03-15Epub Date: 2026-01-29DOI: 10.1016/j.ssi.2026.117139
Qianhui Fu , Mingzhu Gao , Shaoyang Dai , Peng Liu , Yanfei Hua , Ya Yao , Zhongfa Cheng , Zhongmin Wang , Jianqiu Deng
Pitch with low cost and high carbon yield serves as an ideal precursor for high-performance hard carbon anodes in sodium-ion batteries. While air pre-oxidation is critical for promoting pitch crosslinking during hard carbon preparation, low-softening-point pitch suffers from inefficient oxidative crosslinking, often resulting in soft carbon with narrow interlayer spacing. Herein, we propose a biomass skeleton-loaded catalyst strategy to suppress the melt rearrangement of pitch through physical confinement by the biomass skeleton and SbCl3-catalyzed deep crosslinking. Notably, the in-situ generated antimony nanoparticles during the pyrolysis process can serve as an active component to enhance sodium storage performance and eliminate the need for subsequent pickling procedures. The resultant hard carbon/antimony composite exhibits superior electrochemical performance, delivering a high reversible capacity of 275.5 mAh g−1 at 30 mA g−1 with 82.7% capacity retention after 100 cycles. Remarkably, it maintains 158.5 mAh g−1 after 2000 cycles at 1 A g−1, demonstrating exceptional high-rate cyclability. FTIR and XPS analyses reveal that SbCl3 catalysis modulates the type and concentration of oxygen-containing functional groups on the carbon surface, creating abundant active sites for reversible sodium-ion adsorption.
低成本、高产碳率的沥青是钠离子电池中高性能硬碳阳极的理想前驱体。在硬碳制备过程中，空气预氧化是促进沥青交联的关键，但低软化点沥青的氧化交联效率低，往往导致软碳层间距窄。在此，我们提出了一种生物质骨架负载催化剂策略，通过生物质骨架和sbcl3催化的深度交联的物理约束来抑制沥青的熔体重排。值得注意的是，在热解过程中原位生成的纳米锑可以作为一种活性成分，提高钠的储存性能，并消除后续酸洗过程的需要。所得硬碳/锑复合材料表现出优异的电化学性能，在30 mA g - 1下提供275.5 mAh g - 1的高可逆容量，100次循环后容量保持率为82.7%。值得注意的是，它在1 A g−1下循环2000次后保持158.5 mAh g−1，表现出卓越的高速率循环能力。FTIR和XPS分析表明，SbCl3的催化作用调节了碳表面含氧官能团的类型和浓度，为钠离子的可逆吸附创造了丰富的活性位点。
{"title":"Catalytic synthesis of closed packed antimony-incorporated hard carbon composites for enhanced sodium storage","authors":"Qianhui Fu , Mingzhu Gao , Shaoyang Dai , Peng Liu , Yanfei Hua , Ya Yao , Zhongfa Cheng , Zhongmin Wang , Jianqiu Deng","doi":"10.1016/j.ssi.2026.117139","DOIUrl":"10.1016/j.ssi.2026.117139","url":null,"abstract":"<div><div>Pitch with low cost and high carbon yield serves as an ideal precursor for high-performance hard carbon anodes in sodium-ion batteries. While air pre-oxidation is critical for promoting pitch crosslinking during hard carbon preparation, low-softening-point pitch suffers from inefficient oxidative crosslinking, often resulting in soft carbon with narrow interlayer spacing. Herein, we propose a biomass skeleton-loaded catalyst strategy to suppress the melt rearrangement of pitch through physical confinement by the biomass skeleton and SbCl<sub>3</sub>-catalyzed deep crosslinking. Notably, the in-situ generated antimony nanoparticles during the pyrolysis process can serve as an active component to enhance sodium storage performance and eliminate the need for subsequent pickling procedures. The resultant hard carbon/antimony composite exhibits superior electrochemical performance, delivering a high reversible capacity of 275.5 mAh g<sup>−1</sup> at 30 mA g<sup>−1</sup> with 82.7% capacity retention after 100 cycles. Remarkably, it maintains 158.5 mAh g<sup>−1</sup> after 2000 cycles at 1 A g<sup>−1</sup>, demonstrating exceptional high-rate cyclability. FTIR and XPS analyses reveal that SbCl<sub>3</sub> catalysis modulates the type and concentration of oxygen-containing functional groups on the carbon surface, creating abundant active sites for reversible sodium-ion adsorption.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"437 ","pages":"Article 117139"},"PeriodicalIF":3.3,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076258","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 : 2026-03-15Epub Date: 2026-02-03DOI: 10.1016/j.ssi.2026.117140
Changyong Mo , Weiqi Liang , Ning Xu , Guanjie Li , Youhao Liao , Weishan Li
The application of gel polymer electrolyte (GPE) is currently the most effective strategy to address the safety issues associated with high-energy-density lithium metal batteries (LMBs). However, traditional poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP))-based GPE demonstrates poor interfacial compatibility with lithium anode, limiting its further application in LMBs. To solve this issue, [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium (SBMA) is chemically grafted onto P(VdF-HFP) polymer matrix. As an amphoteric polymer, PSBMA guids the uniform decomposition of lithium, thus avoiding the formation of lithium dendrites. Compared with pure P(VdF-HFP), the grafted membrane illustrates the improved wettability with liquid electrolyte, as evidenced by a reduction in the contact angle of 23.04°. Additionally, the Li+-ion transference number enhances from 0.68 to 0.76. Due to the increased fracture stress of 129.4 MPa and the ionic conductivity at room temperature of 1.96 × 10−3 S cm−1, the grafted GPE assembled Li||Li symmetrical cell presents a stable cycling time exceeding 2000 h at a current density of 0.5 mA cm−2. Furthermore, the discharge capacity of LiNi0.8Co0.15Al0.05O2/Li cell with grafted GPE retains 78% of initial capacity after 100 cycles at 1C rate within a voltage of 3 V to 4.5 V, compared with that of 74% for pure P(VdF-HFP) based GPE. Therefore, the developed grafting GPE, which is compatible with electrode has shown great potential for application in LMBs.
凝胶聚合物电解质（GPE）的应用是目前解决高能量密度锂金属电池（lmb）安全问题的最有效策略。然而，传统的聚偏氟乙烯-六氟丙烯（P(VdF-HFP)）基GPE与锂阳极的界面相容性较差，限制了其在LMBs中的进一步应用。为了解决这一问题，将[2-（甲基丙烯氧基）乙基]二甲基-（3-磺基丙基）铵（SBMA）化学接枝到P（VdF-HFP）聚合物基体上。作为两性聚合物，PSBMA引导锂的均匀分解，从而避免了锂枝晶的形成。与纯P（VdF-HFP）相比，接枝膜与液体电解质的润湿性得到了改善，接触角降低了23.04°。Li+-离子转移数由0.68增加到0.76。由于断裂应力增加到129.4 MPa，室温离子电导率为1.96 × 10−3 S cm−1，接枝GPE组装的Li||锂对称电池在0.5 mA cm−2电流密度下的稳定循环时间超过2000 h。此外，接枝GPE的LiNi0.8Co0.15Al0.05O2/Li电池在3 V ~ 4.5 V电压下，以1C倍率循环100次后，放电容量仍保持78%的初始容量，而纯P(VdF-HFP) GPE的放电容量为74%。因此，所开发的与电极兼容的接枝GPE在lmb中具有很大的应用潜力。
{"title":"Interface-compatible P(VdF-HFP)-graft-PSBMA based gel polymer electrolyte for high-voltage lithium metal batteries","authors":"Changyong Mo , Weiqi Liang , Ning Xu , Guanjie Li , Youhao Liao , Weishan Li","doi":"10.1016/j.ssi.2026.117140","DOIUrl":"10.1016/j.ssi.2026.117140","url":null,"abstract":"<div><div>The application of gel polymer electrolyte (GPE) is currently the most effective strategy to address the safety issues associated with high-energy-density lithium metal batteries (LMBs). However, traditional poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP))-based GPE demonstrates poor interfacial compatibility with lithium anode, limiting its further application in LMBs. To solve this issue, [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium (SBMA) is chemically grafted onto P(VdF-HFP) polymer matrix. As an amphoteric polymer, PSBMA guids the uniform decomposition of lithium, thus avoiding the formation of lithium dendrites. Compared with pure P(VdF-HFP), the grafted membrane illustrates the improved wettability with liquid electrolyte, as evidenced by a reduction in the contact angle of 23.04°. Additionally, the Li<sup>+</sup>-ion transference number enhances from 0.68 to 0.76. Due to the increased fracture stress of 129.4 MPa and the ionic conductivity at room temperature of 1.96 × 10<sup>−3</sup> S cm<sup>−1</sup>, the grafted GPE assembled Li||Li symmetrical cell presents a stable cycling time exceeding 2000 h at a current density of 0.5 mA cm<sup>−2</sup>. Furthermore, the discharge capacity of LiNi<sub>0.8</sub>Co<sub>0.15</sub>Al<sub>0.05</sub>O<sub>2</sub>/Li cell with grafted GPE retains 78% of initial capacity after 100 cycles at 1C rate within a voltage of 3 V to 4.5 V, compared with that of 74% for pure P(VdF-HFP) based GPE. Therefore, the developed grafting GPE, which is compatible with electrode has shown great potential for application in LMBs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"437 ","pages":"Article 117140"},"PeriodicalIF":3.3,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171166","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}
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