Pub Date : 2025-09-02DOI: 10.1016/j.ssi.2025.117010
Zexin Su , Yuanyuan Yang , Yuchen Zhang , Zheng Chen , Pengxian Han , Jingwen Zhao , Guanglei Cui
Graphite cathodes enable high-voltage dual-ion batteries (DIBs) through reversible anion intercalation. However, the molecular identity and dynamic evolution of intercalated anionic species, which critically govern the thermodynamic stability and electrochemical reversibility of this process, remain insufficiently understood. This Perspective synthesizes emerging evidence challenging the prevalent but oversimplified “naked anion” intercalation model, emphasizing how solvent co-intercalation potentially influences thermodynamic equilibria, interlayer anion transport kinetics, and charge storage mechanisms. The structural evolution of graphite during anion intercalation is also critically analyzed, with a focus on how interlayer spacing adjustments evolve during electrochemical cycling under solvent co-intercalation conditions. Furthermore, we present a systematic analysis of anion packing configurations within solvent-containing interlayers and their intrinsic link to theoretical capacity limits, offering new insights for optimizing intercalation efficiency. To advance the field, targeted research directions encompassing operando characterization of speciation dynamics, multiscale modeling of solvent co-intercalation pathways and mechanistic investigation into the origins of voltage hysteresis, are proposed to inform the rational design of next-generation high-performance DIB systems.
{"title":"A mechanistic perspective of anion intercalation in graphite cathodes for dual-ion batteries","authors":"Zexin Su , Yuanyuan Yang , Yuchen Zhang , Zheng Chen , Pengxian Han , Jingwen Zhao , Guanglei Cui","doi":"10.1016/j.ssi.2025.117010","DOIUrl":"10.1016/j.ssi.2025.117010","url":null,"abstract":"<div><div>Graphite cathodes enable high-voltage dual-ion batteries (DIBs) through reversible anion intercalation. However, the molecular identity and dynamic evolution of intercalated anionic species, which critically govern the thermodynamic stability and electrochemical reversibility of this process, remain insufficiently understood. This Perspective synthesizes emerging evidence challenging the prevalent but oversimplified “naked anion” intercalation model, emphasizing how solvent co-intercalation potentially influences thermodynamic equilibria, interlayer anion transport kinetics, and charge storage mechanisms. The structural evolution of graphite during anion intercalation is also critically analyzed, with a focus on how interlayer spacing adjustments evolve during electrochemical cycling under solvent co-intercalation conditions. Furthermore, we present a systematic analysis of anion packing configurations within solvent-containing interlayers and their intrinsic link to theoretical capacity limits, offering new insights for optimizing intercalation efficiency. To advance the field, targeted research directions encompassing operando characterization of speciation dynamics, multiscale modeling of solvent co-intercalation pathways and mechanistic investigation into the origins of voltage hysteresis, are proposed to inform the rational design of next-generation high-performance DIB systems.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 117010"},"PeriodicalIF":3.3,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144926043","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 : 2025-08-30DOI: 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":"2025-08-30","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}
Solid polymer electrolytes (SPEs) present a promising alternative for rechargeable batteries with aprotic liquids. Although SPEs were extensively researched for several decades, recent studies have gained momentum in response to growing demand for safer battery options. While various electrochemical and spectral methods for characterizing polymeric electrolytes were proposed, a comprehensive guide to support future investigations appears lacking. Here, we propose a working protocol to derive parameters that characterize SPEs as crucial components of battery systems. An overview of various methods is provided, with particular emphasis on simple impedance measurements for extracting electrochemical parameters. We underscore the significance of considering the interfaces within the battery, specifically the electrolyte-anode and electrolyte-cathode interfaces. Post-mortem analysis is discussed along with the challenges it entails. A summary table detailing the extracted parameters, the corresponding characterization methods, and their applications is provided.
{"title":"Guide for characterizing polymeric electrolytes in rechargeable solid-state Li and Na batteries","authors":"Miryam Fayena-Greenstein , Gayathri Peta , Hadas Alon-Yehezkel , Nagaprasad Reddy Samala , Ortal Breuer , Yuval Elias , Guoxiu Wang , Doron Aurbach","doi":"10.1016/j.ssi.2025.116989","DOIUrl":"10.1016/j.ssi.2025.116989","url":null,"abstract":"<div><div>Solid polymer electrolytes (SPEs) present a promising alternative for rechargeable batteries with aprotic liquids. Although SPEs were extensively researched for several decades, recent studies have gained momentum in response to growing demand for safer battery options. While various electrochemical and spectral methods for characterizing polymeric electrolytes were proposed, a comprehensive guide to support future investigations appears lacking. Here, we propose a working protocol to derive parameters that characterize SPEs as crucial components of battery systems. An overview of various methods is provided, with particular emphasis on simple impedance measurements for extracting electrochemical parameters. We underscore the significance of considering the interfaces within the battery, specifically the electrolyte-anode and electrolyte-cathode interfaces. <em>Post-mortem</em> analysis is discussed along with the challenges it entails. A summary table detailing the extracted parameters, the corresponding characterization methods, and their applications is provided.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 116989"},"PeriodicalIF":3.3,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144916924","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 : 2025-08-29DOI: 10.1016/j.ssi.2025.117008
Mononita Das , Kuntal Ghosh , Vijaya , Mir Wasim Raja
Lithium metal batteries (LMBs) can be the ultimate choice for future battery technologies since they use Lithium metal as anode, which offers high theoretical capacity (3860 mAh.g−1) and lowest electrochemical potential (−3.04 V vs. SHE). However, their commercialization is limited by dendritic growth, interfacial instability, and safety risks associated with liquid electrolytes. In this work, composite solid polymer electrolytes (CSPEs) are developed by incorporating various (Al2O3, BaTiO3, and ZrO2) ceramic fillers into a PVDF-HFP/LiTFSI matrix via a scalable solution casting method. Among these, optimized 10 wt% ZrO2-based CSPE (PLZ) delivers the highest room-temperature ionic conductivity (9.26 × 10−5 S cm−1), excellent Li+ transference number (0.55), superior tensile strength (3.23 MPa), wide potential window (5.33 V), and good flame retardancy. Li/Li symmetric cells using PLZ showed stable lithium plating/stripping for more than 480 h at 0.10 mA.cm−2 with a low overpotential of ∼7 mV. Electrochemical impedance spectroscopy and equivalent circuit fitting confirmed the lowest increase in interfacial resistance after cycling. Time-resolved distribution of relaxation time (DRT) and 2D contour analysis revealed that PLZ maintained stable SEI and charge-transfer resistances, while bare CSPEs showed growing interfacial instability during cycling. These improvements are attributed to Lewis acid-base interactions and surface charge effects that reduce crystallinity and promote Li+ mobility. Full-cell evaluations with LiFePO4 and NMC111 cathodes demonstrated high discharge capacities and good cycling stability. Thus, this study offers a promising pathway for developing robust and safe CSPEs for next-generation solid-state LMBs.
锂金属电池（lmb）可以成为未来电池技术的最终选择，因为它们使用锂金属作为阳极，提供高理论容量（3860毫安时）。g−1)和最低电化学电位（−3.04 V vs. SHE）。然而，它们的商业化受到枝晶生长、界面不稳定性和与液体电解质相关的安全风险的限制。在这项工作中，通过可扩展的溶液铸造方法，将各种（Al2O3， BaTiO3和ZrO2）陶瓷填料掺入PVDF-HFP/LiTFSI基体中，开发了复合固体聚合物电解质（cspe）。其中，优化后的10 wt% zro2基CSPE （PLZ）具有最高的室温离子电导率（9.26 × 10−5 S cm−1）、优异的Li+转移数（0.55）、优异的抗拉强度（3.23 MPa）、宽电位窗（5.33 V）和良好的阻燃性。使用PLZ的Li/Li对称电池在0.10 mA.cm−2下具有低过电位~ 7 mV，可稳定镀锂/剥离超过480 h。电化学阻抗谱和等效电路拟合证实循环后界面电阻增幅最小。弛豫时间（DRT）的时间分辨分布和二维轮廓分析表明，PLZ保持稳定的SEI和电荷转移电阻，而裸cspe在循环过程中界面不稳定性增加。这些改进归功于路易斯酸碱相互作用和表面电荷效应，它们降低了结晶度，促进了Li+的迁移率。使用LiFePO4和NMC111阴极进行的全电池评估显示出高的放电容量和良好的循环稳定性。因此，该研究为下一代固态lmb开发稳健安全的cspe提供了一条有希望的途径。
{"title":"The critical role of Al2O3, BaTiO3 and ZrO2 nanoceramic fillers in PVDF-HFP based composite polymer electrolytes for high performance lithium-metal batteries","authors":"Mononita Das , Kuntal Ghosh , Vijaya , Mir Wasim Raja","doi":"10.1016/j.ssi.2025.117008","DOIUrl":"10.1016/j.ssi.2025.117008","url":null,"abstract":"<div><div>Lithium metal batteries (LMBs) can be the ultimate choice for future battery technologies since they use Lithium metal as anode, which offers high theoretical capacity (3860 mAh.g<sup>−1</sup>) and lowest electrochemical potential (−3.04 V vs. SHE). However, their commercialization is limited by dendritic growth, interfacial instability, and safety risks associated with liquid electrolytes. In this work, composite solid polymer electrolytes (CSPEs) are developed by incorporating various (Al<sub>2</sub>O<sub>3</sub>, BaTiO<sub>3</sub>, and ZrO<sub>2</sub>) ceramic fillers into a PVDF-HFP/LiTFSI matrix via a scalable solution casting method. Among these, optimized 10 wt% ZrO<sub>2</sub>-based CSPE (PLZ) delivers the highest room-temperature ionic conductivity (9.26 × 10<sup>−5</sup> S cm<sup>−1</sup>), excellent Li<sup>+</sup> transference number (0.55), superior tensile strength (3.23 MPa), wide potential window (5.33 V), and good flame retardancy. Li/Li symmetric cells using PLZ showed stable lithium plating/stripping for more than 480 h at 0.10 mA.cm<sup>−2</sup> with a low overpotential of ∼7 mV. Electrochemical impedance spectroscopy and equivalent circuit fitting confirmed the lowest increase in interfacial resistance after cycling. Time-resolved distribution of relaxation time (DRT) and 2D contour analysis revealed that PLZ maintained stable SEI and charge-transfer resistances, while bare CSPEs showed growing interfacial instability during cycling. These improvements are attributed to Lewis acid-base interactions and surface charge effects that reduce crystallinity and promote Li<sup>+</sup> mobility. Full-cell evaluations with LiFePO<sub>4</sub> and NMC111 cathodes demonstrated high discharge capacities and good cycling stability. Thus, this study offers a promising pathway for developing robust and safe CSPEs for next-generation solid-state LMBs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 117008"},"PeriodicalIF":3.3,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913477","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 : 2025-08-27DOI: 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":"2025-08-27","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":"2025-08-27","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 : 2025-08-26DOI: 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":"2025-08-26","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 : 2025-08-22DOI: 10.1016/j.ssi.2025.116996
Alessandro Raffaele Ferrari, Diego Stucchi, Tommaso Caielli, Raziyeh Akbari, Ivan Claudio Pellini, Carlo Antonini, Piercarlo Mustarelli
The main requirement for the development of Anion Exchange Membranes Fuel Cells (AEMFCs) and Water Electrolyzers (AEMFEs) on an industrial scale is the improvement of Anion Exchange Membranes performance. Besides good ionic conductivity, dimensional stability and mechanical properties in the wet state, the main challenge to be overcome is the improvement of AEMs chemical resistance in harsh alkaline environment. Poly(aryl piperidinium)s are among the most promising AEMs in terms of conductivity, mechanical properties, and chemical stability. Here we report the fabrication and physico-chemical characterization of composite AEMs based on poly(biphenyl piperidinium) (PBP) with the addition of zirconium oxide as a filler to improve membrane properties, including anionic conductivity, water uptake and alkali resistance. The optimal ZrO2 filler content was found to be 5 wt% of dry polymer mass. Compared to plain PBP, composite membranes exhibit increased hydroxide conductivity (from 75 to 116 mS cm−1 at 80 °C), reduced water uptake (from 427 % to 278 % at 80 °C) and swelling ratio (from 85 to 62 % at 80 °C), and a limited reduction (41 %) of cationic groups after ageing in KOH 1 M for 500 h at 80 °C. We demonstrate that ZrO2 filler hinders Hoffman elimination reaction on the piperidinium ring.
阴离子交换膜燃料电池（aemfc）和水电解槽（AEMFEs）产业化发展的主要要求是提高阴离子交换膜的性能。除了在湿态下具有良好的离子电导率、尺寸稳定性和力学性能外，需要克服的主要挑战是提高AEMs在恶劣碱性环境下的耐化学性。在电导率、机械性能和化学稳定性方面，聚芳基胡椒啶是最有前途的AEMs之一。本文报道了基于聚联苯哌啶（PBP）的复合AEMs的制备和物理化学表征，并添加氧化锆作为填料来改善膜的性能，包括阴离子导电性、吸水性和耐碱性。ZrO2填料的最佳含量为干聚合物质量的5 wt%。与普通PBP相比，复合膜表现出更高的氢氧化物导电性（在80°C时从75到116 mS cm−1），降低的吸水率（在80°C时从427%到278%）和溶胀率（在80°C时从85%到62%），并且在80°C下KOH 1 M中老化500小时后阳离子基团的有限减少（41%）。我们证明了ZrO2填料阻碍了哌啶环上的霍夫曼消去反应。
{"title":"Composite anion exchange membranes based on poly(biphenyl piperidinium) / ZrO2","authors":"Alessandro Raffaele Ferrari, Diego Stucchi, Tommaso Caielli, Raziyeh Akbari, Ivan Claudio Pellini, Carlo Antonini, Piercarlo Mustarelli","doi":"10.1016/j.ssi.2025.116996","DOIUrl":"10.1016/j.ssi.2025.116996","url":null,"abstract":"<div><div>The main requirement for the development of Anion Exchange Membranes Fuel Cells (AEMFCs) and Water Electrolyzers (AEMFEs) on an industrial scale is the improvement of Anion Exchange Membranes performance. Besides good ionic conductivity, dimensional stability and mechanical properties in the wet state, the main challenge to be overcome is the improvement of AEMs chemical resistance in harsh alkaline environment. Poly(aryl piperidinium)s are among the most promising AEMs in terms of conductivity, mechanical properties, and chemical stability. Here we report the fabrication and physico-chemical characterization of composite AEMs based on poly(biphenyl piperidinium) (PBP) with the addition of zirconium oxide as a filler to improve membrane properties, including anionic conductivity, water uptake and alkali resistance. The optimal ZrO<sub>2</sub> filler content was found to be 5 wt% of dry polymer mass. Compared to plain PBP, composite membranes exhibit increased hydroxide conductivity (from 75 to 116 mS cm<sup>−1</sup> at 80 °C), reduced water uptake (from 427 % to 278 % at 80 °C) and swelling ratio (from 85 to 62 % at 80 °C), and a limited reduction (41 %) of cationic groups after ageing in KOH 1 M for 500 h at 80 °C. We demonstrate that ZrO<sub>2</sub> filler hinders Hoffman elimination reaction on the piperidinium ring.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 116996"},"PeriodicalIF":3.3,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144890524","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 : 2025-08-22DOI: 10.1016/j.ssi.2025.116998
Han-Ill Yoo
All the mass/charge transport properties of a material with, e.g., single-type ions (i) and electrons (e) as mobile charged components may be documented exhaustively and succinctly in terms of a coupling coefficient matrix L of the Onsagerian causality as
,
where Jk and ηk stand for the flux and electrochemical potential, respectively, of the mobile charged-component k(=i,e), and T the absolute temperature. Due to the Onsager reciprocity and the L-matrix transformation rule,
,
where is the transported entropy of k, the sum of its partial entropy, and entropy-of-transport, or
{"title":"Transient-state methods to determine all the mass/charge transport properties of a material","authors":"Han-Ill Yoo","doi":"10.1016/j.ssi.2025.116998","DOIUrl":"10.1016/j.ssi.2025.116998","url":null,"abstract":"<div><div>All the mass/charge transport properties of a material with, e.g., single-type ions (i) and electrons (e) as mobile charged components may be documented exhaustively and succinctly in terms of a coupling coefficient matrix L of the Onsagerian causality as</div><div><span><math><mfenced><mtable><mtr><mtd><msub><mi>J</mi><mi>i</mi></msub></mtd></mtr><mtr><mtd><msub><mi>J</mi><mi>e</mi></msub></mtd></mtr></mtable></mfenced><mo>=</mo><mfenced><mtable><mtr><mtd><msub><mi>L</mi><mi>ii</mi></msub></mtd><mtd><msub><mi>L</mi><mi>ie</mi></msub></mtd><mtd><msub><mi>L</mi><mi>iT</mi></msub></mtd></mtr><mtr><mtd><msub><mi>L</mi><mi>ei</mi></msub></mtd><mtd><msub><mi>L</mi><mi>ee</mi></msub></mtd><mtd><msub><mi>L</mi><mi>eT</mi></msub></mtd></mtr></mtable></mfenced><mfenced><mtable><mtr><mtd><mo>−</mo><mo>∇</mo><msub><mi>η</mi><mi>i</mi></msub></mtd></mtr><mtr><mtd><mo>−</mo><mo>∇</mo><msub><mi>η</mi><mi>e</mi></msub></mtd></mtr><mtr><mtd><mo>−</mo><mo>∇</mo><mi>T</mi></mtd></mtr></mtable></mfenced></math></span>,</div><div>where J<sub>k</sub> and η<sub>k</sub> stand for the flux and electrochemical potential, respectively, of the mobile charged-component k(=i,e), and T the absolute temperature. Due to the Onsager reciprocity and the L-matrix transformation rule,</div><div><span><math><msub><mi>L</mi><mi>ie</mi></msub><mo>=</mo><msub><mi>L</mi><mi>ei</mi></msub><mo>;</mo><mspace></mspace><mfenced><mtable><mtr><mtd><msub><mi>L</mi><mi>iT</mi></msub></mtd></mtr><mtr><mtd><msub><mi>L</mi><mi>eT</mi></msub></mtd></mtr></mtable></mfenced><mo>=</mo><mfenced><mtable><mtr><mtd><msub><mi>L</mi><mi>ii</mi></msub></mtd><mtd><msub><mi>L</mi><mi>ie</mi></msub></mtd></mtr><mtr><mtd><msub><mi>L</mi><mi>ei</mi></msub></mtd><mtd><msub><mi>L</mi><mi>ee</mi></msub></mtd></mtr></mtable></mfenced><mfenced><mtable><mtr><mtd><msub><mover><mover><mi>S</mi><mo>̄</mo></mover><mo>̄</mo></mover><mi>i</mi></msub></mtd></mtr><mtr><mtd><msub><mover><mover><mi>S</mi><mo>̄</mo></mover><mo>̄</mo></mover><mi>e</mi></msub></mtd></mtr></mtable></mfenced></math></span>,</div><div>where <span><math><msub><mover><mover><mi>S</mi><mo>̄</mo></mover><mo>̄</mo></mover><mi>k</mi></msub></math></span>is the transported entropy of k, the sum of its partial entropy, <span><math><msub><mover><mi>S</mi><mo>̄</mo></mover><mi>k</mi></msub><mspace></mspace></math></span>and entropy-of-transport, <span><math><msubsup><mi>S</mi><mi>k</mi><mo>∗</mo></msubsup></math></span> or<span><span><span><math><msub><mover><mover><mi>S</mi><mo>̄</mo></mover><mo>̄</mo></mover><mi>k</mi></msub><mo>≡</mo><msub><mover><mi>S</mi><mo>̄</mo></mover><mi>k</mi></msub><mo>+</mo><msubsup><mi>S</mi><mi>k</mi><mo>∗</mo></msubsup><mo>;</mo><mspace></mspace><msubsup><mi>S</mi><mi>k</mi><mo>∗</mo></msubsup><mo>≡</mo><mfrac><msubsup><mi>q</mi><mi>k</mi><mo>∗</mo></msubsup><mi>T</mi></mfrac></math></span></span></span></div><div>with <span><math><msubsup><mi>q</mi><mi>k</mi><mo>∗</mo></msubsup></math></span> being the reduced heat-of-","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 116998"},"PeriodicalIF":3.3,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144890523","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 : 2025-08-21DOI: 10.1016/j.ssi.2025.117000
Oncu Akyildiz , Ezgi Yılmaz
We investigated the electrochemical behavior of binary blend cathodes made by mixing micro-spheres of LiNi0.5Mn0.3Co0.2O2 and smaller micro-platelets of LiFePO4 in different proportions (10–40 wt%). Results show that the discharge profiles of the blended electrodes at 0.1C are predictable through a model based on the weighted averages of specific differential capacities of pristine electrodes. However, at high C-rates (>1C), the blended electrode contains 20 wt% LiFePO4 (coined as the synergy-electrode) shows significantly higher discharge capacity and better capacity retention (observed up to the 100th cycle) than other electrodes. The synergy is rationalized using cyclic voltammetry and electrochemical impedance spectroscopy, indicating the facilitation of the charge-discharge reactions, reduction of both the bulk and the charge-transfer resistances, and higher Li diffusion coefficients observed for the synergy-electrode.
{"title":"Synergy-electrode based on micron-sized LiNi0.5Mn0.3Co0.2O2/LiFePO4 particles with bimodal size distribution","authors":"Oncu Akyildiz , Ezgi Yılmaz","doi":"10.1016/j.ssi.2025.117000","DOIUrl":"10.1016/j.ssi.2025.117000","url":null,"abstract":"<div><div>We investigated the electrochemical behavior of binary blend cathodes made by mixing micro-spheres of LiNi<sub>0.5</sub>Mn<sub>0.3</sub>Co<sub>0.2</sub>O<sub>2</sub> and smaller micro-platelets of LiFePO<sub>4</sub> in different proportions (10–40 wt%). Results show that the discharge profiles of the blended electrodes at 0.1C are predictable through a model based on the weighted averages of specific differential capacities of pristine electrodes. However, at high C-rates (>1C), the blended electrode contains 20 wt% LiFePO<sub>4</sub> (coined as the synergy-electrode) shows significantly higher discharge capacity and better capacity retention (observed up to the 100th cycle) than other electrodes. The synergy is rationalized using cyclic voltammetry and electrochemical impedance spectroscopy, indicating the facilitation of the charge-discharge reactions, reduction of both the bulk and the charge-transfer resistances, and higher Li diffusion coefficients observed for the synergy-electrode.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"430 ","pages":"Article 117000"},"PeriodicalIF":3.3,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144885429","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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