Pub Date : 2025-12-01Epub Date: 2025-10-10DOI: 10.1016/j.ssi.2025.117037
Qianlong Ji, Natalia A. Melnikova, Oleg V. Glumov, Igor V. Murin
Fluorite-structure solid solutions with ultrahigh fluoride ion mobility are widely recognized as promising solid electrolytes for applications in solid-state electrochemical devices like fluoride ion batteries (FIBs). Herein, solid solutions in the PbF2-CaF2-KF system were prepared by mechanochemical synthesis. The structure and morphology of the synthesized solid solutions are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The fluoride ion conductivity of the samples is investigated by the electrochemical impedance spectroscopy (EIS). The results show that the fluorite-structure solid electrolyte β-Pb0.75Ca0.2K0.05F1.95 with high ionic conductivity (1.46 × 10−3 S/cm at 20 °C) can be obtained combined with brief low-temperature heat treatment.
{"title":"Highly conductive solid electrolytes in the PbF2-CaF2-KF system: mechanochemical synthesis, electrical properties, microstructure and stability","authors":"Qianlong Ji, Natalia A. Melnikova, Oleg V. Glumov, Igor V. Murin","doi":"10.1016/j.ssi.2025.117037","DOIUrl":"10.1016/j.ssi.2025.117037","url":null,"abstract":"<div><div>Fluorite-structure solid solutions with ultrahigh fluoride ion mobility are widely recognized as promising solid electrolytes for applications in solid-state electrochemical devices like fluoride ion batteries (FIBs). Herein, solid solutions in the PbF<sub>2</sub>-CaF<sub>2</sub>-KF system were prepared by mechanochemical synthesis. The structure and morphology of the synthesized solid solutions are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The fluoride ion conductivity of the samples is investigated by the electrochemical impedance spectroscopy (EIS). The results show that the fluorite-structure solid electrolyte β-Pb<sub>0.75</sub>Ca<sub>0.2</sub>K<sub>0.05</sub>F<sub>1.95</sub> with high ionic conductivity (1.46 × 10<sup>−3</sup> S/cm at 20 °C) can be obtained combined with brief low-temperature heat treatment.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117037"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145248004","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 : 2025-12-01Epub Date: 2025-10-24DOI: 10.1016/j.ssi.2025.117066
B. Jeevanantham , D. Vignesh , M.K. Shobana
Lithium-ion batteries (LIBs) with LiNixMnyCozO2 (NMC) cathodes are a promising contender due to their high energy density and cost-effectiveness. The excellent performance metrics of the NMC cathode make it an attractive candidate for electric vehicles. With the high capacity and good cycling of NMC, it also causes cationic disorder, transition metal dissolution, and parasitic side reactions. Doping and coating effectively mitigate these effects, helping to minimize irreversible capacity loss. Metal-oxide coating not only covers the cathode surface but also aids in structural stabilization. X-ray diffraction confirms the layered structure and reduces cation disorder. The I(003)/I(104) ratio increases as the NMC gets modified. XPS measurements validate the oxidation state and the reduction of carbonate content post-modification. The thermoelectric response verifies that NMC-LA exhibits superior electronic conductivity and thermoelectric performance compared to other electrodes. The cathode coating effectively minimizes cation mixing, enhances structural stability, and boosts electronic conductivity.
{"title":"High nickel-rich layered oxide: The intrinsic role of cation substitution and metal-oxide coating in tuning cationic mixing and enhancing electronic conductivity","authors":"B. Jeevanantham , D. Vignesh , M.K. Shobana","doi":"10.1016/j.ssi.2025.117066","DOIUrl":"10.1016/j.ssi.2025.117066","url":null,"abstract":"<div><div>Lithium-ion batteries (LIBs) with LiNi<sub>x</sub>Mn<sub>y</sub>Co<sub>z</sub>O<sub>2</sub> (NMC) cathodes are a promising contender due to their high energy density and cost-effectiveness. The excellent performance metrics of the NMC cathode make it an attractive candidate for electric vehicles. With the high capacity and good cycling of NMC, it also causes cationic disorder, transition metal dissolution, and parasitic side reactions. Doping and coating effectively mitigate these effects, helping to minimize irreversible capacity loss. Metal-oxide coating not only covers the cathode surface but also aids in structural stabilization. X-ray diffraction confirms the layered structure and reduces cation disorder. The I(003)/I(104) ratio increases as the NMC gets modified. XPS measurements validate the oxidation state and the reduction of carbonate content post-modification. The thermoelectric response verifies that NMC-LA exhibits superior electronic conductivity and thermoelectric performance compared to other electrodes. The cathode coating effectively minimizes cation mixing, enhances structural stability, and boosts electronic conductivity.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117066"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360233","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 : 2025-12-01Epub Date: 2025-10-30DOI: 10.1016/j.ssi.2025.117047
Peng Dong , Jing Luo , Zhe Zhu , Xiangzhi Zeng
Understanding the electrochemical and mechanical behavior of single cathode particles is essential for advancing lithium-ion battery performance. This study combines nanoscale characterization and computational modeling to investigate the voltage-dependent responses of Li[Ni0.885Co0.1Al0.015]O2 (NCA) particles. Experimental measurements using conductive atomic force microscopy (CAFM) and electrochemical strain microscopy (ESM) under varying voltages were supported by a reconstructed two-dimensional realistic particle and an electrochemical-mechanical coupled model with anisotropic diffusion. Simulation results revealed that higher applied voltages increase the chemical potential for Li+ diffusion, enhancing ion transport and current response in CAFM, while stress gradients between the core and surface of particles lead to significant deformation observed in ESM. This work demonstrates the critical role of local electro-chemo-mechanical coupling in single-particle behavior and provides a microstructure-based interpretation of nanoscale phenomena.
{"title":"Current and deformation in the single Li[Ni0.885 Co0.1 Al0.015]O2 nanoparticle studied by phase field simulation","authors":"Peng Dong , Jing Luo , Zhe Zhu , Xiangzhi Zeng","doi":"10.1016/j.ssi.2025.117047","DOIUrl":"10.1016/j.ssi.2025.117047","url":null,"abstract":"<div><div>Understanding the electrochemical and mechanical behavior of single cathode particles is essential for advancing lithium-ion battery performance. This study combines nanoscale characterization and computational modeling to investigate the voltage-dependent responses of Li[Ni<sub>0.885</sub>Co<sub>0.1</sub>Al<sub>0.015</sub>]O<sub>2</sub> (NCA) particles. Experimental measurements using conductive atomic force microscopy (CAFM) and electrochemical strain microscopy (ESM) under varying voltages were supported by a reconstructed two-dimensional realistic particle and an electrochemical-mechanical coupled model with anisotropic diffusion. Simulation results revealed that higher applied voltages increase the chemical potential for Li<sup>+</sup> diffusion, enhancing ion transport and current response in CAFM, while stress gradients between the core and surface of particles lead to significant deformation observed in ESM. This work demonstrates the critical role of local electro-chemo-mechanical coupling in single-particle behavior and provides a microstructure-based interpretation of nanoscale phenomena.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117047"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145413869","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 : 2025-11-01Epub Date: 2025-09-23DOI: 10.1016/j.ssi.2025.117029
Zhenhong Tian , Li-ang Zhu , Jingxiu Tian , Hongshun Miao , Yinghui Jiang , Rongkang Tan , Xiangxin Li , Yan Liu
A trace Ti/Mg co-doped Na0.8Ni0.35Mn0.48Ti0.12Mg0.05O2 (TiMg-NNM) cathode was synthesized, where Ti ions are located in the transition metal layers and Mg ions are incorporated into the sodium layers. The co-doping expands the Na-layer spacing within the layered structure, thereby lowering the diffusion barrier for Na-ions. Structural stability is significantly enhanced due to the robust TiO bond and the pillar-like effect of Mg ions, which also helps to minimize surface side reactions with the electrolyte. The merits endow a high reversible capacity of TiMg-NNM cathode with 130.5 mAh/g at 1C, the 85.8 % capacity retention rate at 100 cycles at 1C, much greater than 35.6 % of NNM. The synergistic effect of P2 and O3 phases was strengthened by the doping of Mg and Ti, so that the obtained NNMMT had high electrochemical stability. The research offers a practical approach and fresh perspectives for designing high-performance layered oxide cathode materials with improved structural and interfacial stability for SIBs.
{"title":"Study on the structure and electrochemical properties of double-doped regulated P2/O3 cophasic sodium-ion batteries","authors":"Zhenhong Tian , Li-ang Zhu , Jingxiu Tian , Hongshun Miao , Yinghui Jiang , Rongkang Tan , Xiangxin Li , Yan Liu","doi":"10.1016/j.ssi.2025.117029","DOIUrl":"10.1016/j.ssi.2025.117029","url":null,"abstract":"<div><div>A trace Ti/Mg co-doped Na<sub>0.8</sub>Ni<sub>0.35</sub>Mn<sub>0.48</sub>Ti<sub>0.12</sub>Mg<sub>0.05</sub>O<sub>2</sub> (TiMg-NNM) cathode was synthesized, where Ti ions are located in the transition metal layers and Mg ions are incorporated into the sodium layers. The co-doping expands the Na-layer spacing within the layered structure, thereby lowering the diffusion barrier for Na-ions. Structural stability is significantly enhanced due to the robust Ti<img>O bond and the pillar-like effect of Mg ions, which also helps to minimize surface side reactions with the electrolyte. The merits endow a high reversible capacity of TiMg-NNM cathode with 130.5 mAh/g at 1C, the 85.8 % capacity retention rate at 100 cycles at 1C, much greater than 35.6 % of NNM. The synergistic effect of P2 and O3 phases was strengthened by the doping of Mg and Ti, so that the obtained NNMMT had high electrochemical stability. The research offers a practical approach and fresh perspectives for designing high-performance layered oxide cathode materials with improved structural and interfacial stability for SIBs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"431 ","pages":"Article 117029"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145119332","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 : 2025-11-01Epub Date: 2025-08-27DOI: 10.1016/j.ssi.2025.117001
Stanislaus Breitwieser, Johannes Bock, Frederick Fechner, Jürgen Fleig, Andreas Nenning
The catalytic and electrochemical properties of many non-stoichiometric oxides are governed by their defect chemistry. Therefore, detailed knowledge of their oxygen non-stoichiometry under operating conditions is desired. For this, coulometric titration can offer a valuable tool that can have advantages in terms of required sample mass, accuracy and reachable p(O2) range over other established techniques, such as thermogravimetric analysis (TGA). Here, we present a new design for an easy to fabricate miniature coulometric titration setup using materials selected for optimal electrode kinetics. The small chamber volume (0.03–0.05 ml), small sample mass (about 30 mg) and kinetically fast electrodes allow for a precise variation of the p(O2) from 1 bar down to 10−32 bar at 625 °C. This is a much wider range than typically achievable under gas flow in TGA or with other titration setups described in the literature. A characterisation of the titration setup showed that residual errors in the defect chemistry of the investigated materials are in the range of 10−4 to 10−3 p.f.u. Exemplary measurements on CeO2-δ and Sr1-xTi0.6Fe0.4O3-δ (STF) showcase how this wide p(O2) range can not only be used to study oxygen non-stoichiometry at very reducing conditions and the p(O2) at which vacancy ordering phenomena occur (for CeO2-δ), but also detect and quantify small amounts of redox-active secondary phases (for STF).
{"title":"Return of the solid-state coulometric titration: A new hope to expand the p(O2) range","authors":"Stanislaus Breitwieser, Johannes Bock, Frederick Fechner, Jürgen Fleig, Andreas Nenning","doi":"10.1016/j.ssi.2025.117001","DOIUrl":"10.1016/j.ssi.2025.117001","url":null,"abstract":"<div><div>The catalytic and electrochemical properties of many non-stoichiometric oxides are governed by their defect chemistry. Therefore, detailed knowledge of their oxygen non-stoichiometry under operating conditions is desired. For this, coulometric titration can offer a valuable tool that can have advantages in terms of required sample mass, accuracy and reachable p(O<sub>2</sub>) range over other established techniques, such as thermogravimetric analysis (TGA). Here, we present a new design for an easy to fabricate miniature coulometric titration setup using materials selected for optimal electrode kinetics. The small chamber volume (0.03–0.05 ml), small sample mass (about 30 mg) and kinetically fast electrodes allow for a precise variation of the p(O<sub>2</sub>) from 1 bar down to 10<sup>−32</sup> bar at 625 °C. This is a much wider range than typically achievable under gas flow in TGA or with other titration setups described in the literature. A characterisation of the titration setup showed that residual errors in the defect chemistry of the investigated materials are in the range of 10<sup>−4</sup> to 10<sup>−3</sup> p.f.u. Exemplary measurements on CeO<sub>2-δ</sub> and Sr<sub>1-x</sub>Ti<sub>0.6</sub>Fe<sub>0.4</sub>O<sub>3-δ</sub> (STF) showcase how this wide p(O<sub>2</sub>) range can not only be used to study oxygen non-stoichiometry at very reducing conditions and the p(O<sub>2</sub>) at which vacancy ordering phenomena occur (for CeO<sub>2-δ</sub>), but also detect and quantify small amounts of redox-active secondary phases (for STF).</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 117001"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144903315","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}
Al is known as a unique element to enhance the stability of Sc2O3-stabilized ZrO2 (ScSZ); however, understanding the Al state in the material is insufficient for the mechanism to be understood. In this study, the states and roles of Al in the ScSZ-based materials are elucidated by 27Al NMR spectroscopy, DFT calculations, and detailed structural analysis concerning cubicity. The 27Al NMR and DFT calculations reveal that Al substitutes Zr sites as 6-, 7- and 8-coordinated states in ScSZ even though the ionic radius of Al is much smaller than that of Zr. The formation of 6-coordinated Al with two oxygen vacancies in its vicinity indicates oxygen vacancies are preferentially located around the smaller cations. The local structure revealed by DFT calculations suggests that the coordination polyhedron of 7- and 8-coordinated Al is effectively 4-coordinated Al. The 27Al NMR results also support this unique local structure. The results of this study show that manipulating the Al state is a key step in stabilizing Sc2O3-stabilized ZrO2 and help to clarify the suppression mechanism of the degradation of conductivity.
{"title":"Four and six-coordinated Al in a fluorite-type structure: A key to the stabilization of Sc2O3-stabilized ZrO2","authors":"Itaru Oikawa , Akihiro Fujimaki , Akihiro Ishii , Fuminori Tamazaki , Hiroshi Okamoto , Hitoshi Takamura","doi":"10.1016/j.ssi.2025.116997","DOIUrl":"10.1016/j.ssi.2025.116997","url":null,"abstract":"<div><div>Al is known as a unique element to enhance the stability of Sc<sub>2</sub>O<sub>3</sub>-stabilized ZrO<sub>2</sub> (ScSZ); however, understanding the Al state in the material is insufficient for the mechanism to be understood. In this study, the states and roles of Al in the ScSZ-based materials are elucidated by <sup>27</sup>Al NMR spectroscopy, DFT calculations, and detailed structural analysis concerning cubicity. The <sup>27</sup>Al NMR and DFT calculations reveal that Al substitutes Zr sites as 6-, 7- and 8-coordinated states in ScSZ even though the ionic radius of Al is much smaller than that of Zr. The formation of 6-coordinated Al with two oxygen vacancies in its vicinity indicates oxygen vacancies are preferentially located around the smaller cations. The local structure revealed by DFT calculations suggests that the coordination polyhedron of 7- and 8-coordinated Al is effectively 4-coordinated Al. The <sup>27</sup>Al NMR results also support this unique local structure. The results of this study show that manipulating the Al state is a key step in stabilizing Sc<sub>2</sub>O<sub>3</sub>-stabilized ZrO<sub>2</sub> and help to clarify the suppression mechanism of the degradation of conductivity.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 116997"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144903316","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 : 2025-11-01Epub Date: 2025-09-17DOI: 10.1016/j.ssi.2025.117018
A. Gouder , B.V. Lotsch
Optoionics has recently emerged at the intersection of optoelectronics and solid state ionics, triggered by fundamental work on light-induced ionic conductivity enhancement in methylammonium lead iodide (MAPI). This perspective traces the evolution of optoionics from early 20th century studies on photoionics to contemporary research, elucidating the semantic nuances and historical development of light–ion interactions. We follow the first observations such as copper photoionization and subsequent conceptual extensions such as molecular photoionics and photo-ionic cells, leading on to the current definition and understanding of optoionics. We then proceed to apply this understanding on light–ion interactions in carbon nitrides, distinguishing between intrinsic and extrinsic optoionic effects depending on whether one or more distinct phases are involved. This nuanced understanding is essential for the design of optoionic devices that exploit light–ion interactions to couple light harvesting and electrochemical energy storage. Finally, we provide an outlook on emerging optoionic devices at the intersection of energy conversion and storage and discuss smart circuit elements that integrate optoionic principles for advanced technological applications.
{"title":"Optoionics – Controlling ions with light","authors":"A. Gouder , B.V. Lotsch","doi":"10.1016/j.ssi.2025.117018","DOIUrl":"10.1016/j.ssi.2025.117018","url":null,"abstract":"<div><div>Optoionics has recently emerged at the intersection of optoelectronics and solid state ionics, triggered by fundamental work on light-induced ionic conductivity enhancement in methylammonium lead iodide (MAPI). This perspective traces the evolution of optoionics from early 20th century studies on photoionics to contemporary research, elucidating the semantic nuances and historical development of light–ion interactions. We follow the first observations such as copper photoionization and subsequent conceptual extensions such as molecular photoionics and photo-ionic cells, leading on to the current definition and understanding of optoionics. We then proceed to apply this understanding on light–ion interactions in carbon nitrides, distinguishing between intrinsic and extrinsic optoionic effects depending on whether one or more distinct phases are involved. This nuanced understanding is essential for the design of optoionic devices that exploit light–ion interactions to couple light harvesting and electrochemical energy storage. Finally, we provide an outlook on emerging optoionic devices at the intersection of energy conversion and storage and discuss smart circuit elements that integrate optoionic principles for advanced technological applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"431 ","pages":"Article 117018"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145107092","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 : 2025-11-01Epub Date: 2025-08-30DOI: 10.1016/j.ssi.2025.116999
Daniel Friedzon , Ellen Wachtel , Olga Brontvein , Anna Kossoy , Leonid Chernyak , David Ehre , Igor Lubomirsky
We present a three-terminal resistive switching device with a 20 mol% gadolinium-doped ceria (20GDC) thin film as the solid state electrolyte. The device features a top Ta-metal gate electrode and bottom Ta-metal source and drain electrodes, separated by a 1 mm gap filled with 20GDC. Its operation relies on the redox reaction of cerium, specifically the reduction of cerium (IV) to cerium (III) at the interface between the Ta-gate and the 20GDC electrolyte. Under positive gate bias, the Ta gate electrode undergoes oxidation, while cerium is reduced, forming a conductive layer between the source and drain electrodes. Applying a negative gate bias reverses this effect. To confirm that resistivity changes originate from interface redox reactions, we conducted cyclic voltammetry at 403 K. The results demonstrate that peak current is inversely proportional to the scan rate, a characteristic of reaction at a surface. Additionally, we demonstrated that sputtering a TaOx blocking layer beneath the gate electrode suppresses resistive switching. While the resistance changes only by a factor of two, the proposed device operates near equilibrium, is simple to fabricate, and exhibits high robustness. These characteristics make the concept of interface oxidation/reduction appealing for further exploration.
{"title":"Non-filamentary three-terminal resistivity switch based on interface oxidation/reduction","authors":"Daniel Friedzon , Ellen Wachtel , Olga Brontvein , Anna Kossoy , Leonid Chernyak , David Ehre , Igor Lubomirsky","doi":"10.1016/j.ssi.2025.116999","DOIUrl":"10.1016/j.ssi.2025.116999","url":null,"abstract":"<div><div>We present a three-terminal resistive switching device with a 20 mol% gadolinium-doped ceria (20GDC) thin film as the solid state electrolyte. The device features a top Ta-metal gate electrode and bottom Ta-metal source and drain electrodes, separated by a 1 mm gap filled with 20GDC. Its operation relies on the redox reaction of cerium, specifically the reduction of cerium (IV) to cerium (III) at the interface between the Ta-gate and the 20GDC electrolyte. Under positive gate bias, the Ta gate electrode undergoes oxidation, while cerium is reduced, forming a conductive layer between the source and drain electrodes. Applying a negative gate bias reverses this effect. To confirm that resistivity changes originate from interface redox reactions, we conducted cyclic voltammetry at 403 K. The results demonstrate that peak current is inversely proportional to the scan rate, a characteristic of reaction at a surface. Additionally, we demonstrated that sputtering a TaO<sub>x</sub> blocking layer beneath the gate electrode suppresses resistive switching. While the resistance changes only by a factor of two, the proposed device operates near equilibrium, is simple to fabricate, and exhibits high robustness. These characteristics make the concept of interface oxidation/reduction appealing for further exploration.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 116999"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144916925","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 : 2025-11-01Epub Date: 2025-08-26DOI: 10.1016/j.ssi.2025.116995
Kazuya Terabe , Takashi Tsuchiya , Tohru Tsuruoka , Hirofumi Tanaka , Ilia Valov , James K. Gimzewski , Tsuyoshi Hasegawa
Today's scientific and technological growth relies on rapid advances in electronic information technologies. Semiconductor devices such as transistors are essential to these technologies, and they are constantly being improved by being made smaller and more integrated. However, there is a concern that these improvements may slow down in the near future. Thus, creating new types of devices that can overcome the problems and/or enhance the capabilities of traditional semiconductor devices has become an important challenge. In particular, solid-state ionic devices can potentially meet this challenge. In this review, we describe the design of such devices using ionic nanoarchitectonics techniques that locally control ion conduction and electrochemical behavior in ion conductors and mixed conductors. In addition, we describe solid-state ionic devices developed for electronic information technology as well as the electrical, magnetic, optical, and brain-inspired neuromorphic functionalities of these devices.
{"title":"Ionic nanoarchitectonics for electronic information devices","authors":"Kazuya Terabe , Takashi Tsuchiya , Tohru Tsuruoka , Hirofumi Tanaka , Ilia Valov , James K. Gimzewski , Tsuyoshi Hasegawa","doi":"10.1016/j.ssi.2025.116995","DOIUrl":"10.1016/j.ssi.2025.116995","url":null,"abstract":"<div><div>Today's scientific and technological growth relies on rapid advances in electronic information technologies. Semiconductor devices such as transistors are essential to these technologies, and they are constantly being improved by being made smaller and more integrated. However, there is a concern that these improvements may slow down in the near future. Thus, creating new types of devices that can overcome the problems and/or enhance the capabilities of traditional semiconductor devices has become an important challenge. In particular, solid-state ionic devices can potentially meet this challenge. In this review, we describe the design of such devices using ionic nanoarchitectonics techniques that locally control ion conduction and electrochemical behavior in ion conductors and mixed conductors. In addition, we describe solid-state ionic devices developed for electronic information technology as well as the electrical, magnetic, optical, and brain-inspired neuromorphic functionalities of these devices.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 116995"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144902521","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 : 2025-11-01Epub Date: 2025-09-25DOI: 10.1016/j.ssi.2025.117028
Koichiro Fukuda, Aya Miyasawa, Daisuke Urushihara, Toru Asaka
The potential for Ca2+ conduction along the 〈001〉 and 〈110〉 directions in the melilite structure type compound Ca2Ga2SiO7 (space group P21m) has been elucidated through the utilization of the bond valence energy landscape method. The randomly grain-oriented polycrystal exhibited an increase in bulk conductivity for Ca2+ (σbulk) from 6.24 × 10−10 S cm−1 at 573 K to 2.09 × 10−5 S cm−1 at 1073 K, with an activation energy of 1.146(10) eV. The transference number at 1073 K was 0.982. The σbulk-value of Ca2Ga2SiO7 at each temperature from 673 to 1073 K was intermediate between those of the grossite structure type compounds CaGa4O7 and CaAl4O7, while the σbulk-value of the NASICON-type compound (Ca0.05Hf0.9)4/3.9Nb(PO4)3 at each temperature from 573 to 873 K was superior to those of these three compounds. The total conductivity for Ca2+ of Ca2Ga2SiO7 was more than 12.4 times larger than that of the NASICON-type compound CaZr4(PO4)6 at each temperature from 923 to 1073 K.
{"title":"Ca2+ conduction in melilite structure type compound Ca2Ga2SiO7","authors":"Koichiro Fukuda, Aya Miyasawa, Daisuke Urushihara, Toru Asaka","doi":"10.1016/j.ssi.2025.117028","DOIUrl":"10.1016/j.ssi.2025.117028","url":null,"abstract":"<div><div>The potential for Ca<sup>2+</sup> conduction along the 〈001〉 and 〈110〉 directions in the melilite structure type compound Ca<sub>2</sub>Ga<sub>2</sub>SiO<sub>7</sub> (space group <em>P</em><span><math><mover><mn>4</mn><mo>¯</mo></mover></math></span>2<sub>1</sub><em>m</em>) has been elucidated through the utilization of the bond valence energy landscape method. The randomly grain-oriented polycrystal exhibited an increase in bulk conductivity for Ca<sup>2+</sup> (<em>σ</em><sub>bulk</sub>) from 6.24 × 10<sup>−10</sup> S cm<sup>−1</sup> at 573 K to 2.09 × 10<sup>−5</sup> S cm<sup>−1</sup> at 1073 K, with an activation energy of 1.146(10) eV. The transference number at 1073 K was 0.982. The <em>σ</em><sub>bulk</sub>-value of Ca<sub>2</sub>Ga<sub>2</sub>SiO<sub>7</sub> at each temperature from 673 to 1073 K was intermediate between those of the grossite structure type compounds CaGa<sub>4</sub>O<sub>7</sub> and CaAl<sub>4</sub>O<sub>7</sub>, while the <em>σ</em><sub>bulk</sub>-value of the NASICON-type compound (Ca<sub>0.05</sub>Hf<sub>0.9</sub>)<sub>4/3.9</sub>Nb(PO<sub>4</sub>)<sub>3</sub> at each temperature from 573 to 873 K was superior to those of these three compounds. The total conductivity for Ca<sup>2+</sup> of Ca<sub>2</sub>Ga<sub>2</sub>SiO<sub>7</sub> was more than 12.4 times larger than that of the NASICON-type compound CaZr<sub>4</sub>(PO<sub>4</sub>)<sub>6</sub> at each temperature from 923 to 1073 K.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"431 ","pages":"Article 117028"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145155779","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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