Pub Date : 2026-02-01Epub Date: 2025-12-07DOI: 10.1016/j.ssi.2025.117098
Ivan Nikulin, Tatiana Nikulicheva, Vitaly Vyazmin, Oleg Ivanov, Nikita Anosov, Olga Telpova
CaSO4-based citrogypsum was used to prepare bulk samples of calcium sulfate hemihydrate (CaSO4·0.5H2O). To alter composition and improve conductivity, the samples were treated at 95 °C in 85 wt% orthophosphoric acid for 1 to 15 min. Within <1 min, CaSO4·0.5H2O transforms into CaSO4·2H2O. At longer times, partial dehydration converts part of the CaSO4·2H2O. back into CaSO4·0.5H2O, yielding a two-phase mixture. Acid treatment induces cation (2H+ ↔ Ca2+) and anion ((HPO4)2− ↔ (SO4)2−) exchange, producing a transition from insulating to solid-electrolyte behavior. Weakly bound H+ ions, incorporated either by Ca2+ substitution or via (HPO4)2− residues, act as mobile charge carriers and enable proton conductivity. Residues that release protons convert to (PO4)3− groups, which can be displaced in an alternating field, generating ionic polarization and relaxation currents. The combined effects of H+ mobility and (PO4)3− polarization produce two arcs in AC impedance spectra. Conductivity parameters extracted with the Cole model strongly depend on sample composition.
{"title":"Crossover from insulating into solid electrolyte behavior in bulk CaSO4⋅0.5H2O material due to ion exchange processes induced by high-temperature treatment with orthophosphoric acid","authors":"Ivan Nikulin, Tatiana Nikulicheva, Vitaly Vyazmin, Oleg Ivanov, Nikita Anosov, Olga Telpova","doi":"10.1016/j.ssi.2025.117098","DOIUrl":"10.1016/j.ssi.2025.117098","url":null,"abstract":"<div><div>CaSO<sub>4</sub>-based citrogypsum was used to prepare bulk samples of calcium sulfate hemihydrate (CaSO<sub>4</sub>·0.5H<sub>2</sub>O). To alter composition and improve conductivity, the samples were treated at 95 °C in 85 wt% orthophosphoric acid for 1 to 15 min. Within <1 min, CaSO<sub>4</sub>·0.5H<sub>2</sub>O transforms into CaSO<sub>4</sub>·2H<sub>2</sub>O. At longer times, partial dehydration converts part of the CaSO<sub>4</sub>·2H<sub>2</sub>O. back into CaSO<sub>4</sub>·0.5H<sub>2</sub>O, yielding a two-phase mixture. Acid treatment induces cation (2H<sup>+</sup> ↔ Ca<sup>2+</sup>) and anion ((HPO<sub>4</sub>)<sup>2−</sup> ↔ (SO<sub>4</sub>)<sup>2−</sup>) exchange, producing a transition from insulating to solid-electrolyte behavior. Weakly bound H<sup>+</sup> ions, incorporated either by Ca<sup>2+</sup> substitution or via (HPO<sub>4</sub>)<sup>2−</sup> residues, act as mobile charge carriers and enable proton conductivity. Residues that release protons convert to (PO<sub>4</sub>)<sup>3−</sup> groups, which can be displaced in an alternating field, generating ionic polarization and relaxation currents. The combined effects of H<sup>+</sup> mobility and (PO<sub>4</sub>)<sup>3−</sup> polarization produce two arcs in AC impedance spectra. Conductivity parameters extracted with the Cole model strongly depend on sample composition.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"434 ","pages":"Article 117098"},"PeriodicalIF":3.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748358","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}
The possibility of synthesizing highly conductive thin-film composite polymer membranes based on cesium dihydrogen phosphate and poly(vinylidene fluoride-co-hexafluoropropylene) [p(VDF-HFP)] with a reduced polymer additive content (mass fraction of 17 %) has been demonstrated. A uniform distribution of salt particles within the polymer matrix, with an average size of approximately 260 nm, was achieved using bead milling. The crystallite sizes determined by scanning electron microscopy and X-ray diffraction are in good agreement. The investigated composite polymer electrolytes exhibit high proton conductivity (∼5 mS·cm−1) in the medium-temperature range (220–250 °C), making them promising for application in novel medium-temperature fuel cells.
{"title":"Influence of synthesis method on particles size of cesium dihydrogen phosphate for promising thin-film proton-conducting membranes CsH2PO4-p(VDF-HFP)","authors":"Y.E. Kungurtsev, I.N. Bagryantseva, V.G. Ponomareva","doi":"10.1016/j.ssi.2025.117102","DOIUrl":"10.1016/j.ssi.2025.117102","url":null,"abstract":"<div><div>The possibility of synthesizing highly conductive thin-film composite polymer membranes based on cesium dihydrogen phosphate and poly(vinylidene fluoride-<em>co</em>-hexafluoropropylene) [p(VDF-HFP)] with a reduced polymer additive content (mass fraction of 17 %) has been demonstrated. A uniform distribution of salt particles within the polymer matrix, with an average size of approximately 260 nm, was achieved using bead milling. The crystallite sizes determined by scanning electron microscopy and X-ray diffraction are in good agreement. The investigated composite polymer electrolytes exhibit high proton conductivity (∼5 mS·cm<sup>−1</sup>) in the medium-temperature range (220–250 °C), making them promising for application in novel medium-temperature fuel cells.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"434 ","pages":"Article 117102"},"PeriodicalIF":3.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797676","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 : 2026-02-01Epub Date: 2025-12-08DOI: 10.1016/j.ssi.2025.117084
Or Ben Zion , Isaac Abrahams , Ellen Wachtel , Xiao-Dong Zhang , Xin Guo , Igor Lubomirsky , David Ehre
Conventional methods for hydrating bulk ceramic samples at relatively low pressures (<5 atm of water steam) often fail to achieve significant hydration because of kinetic barriers and mechanical failures, the latter primarily due to inhomogeneous lattice expansion accompanying hydration. We propose a small, high-pressure chamber that can reach tens of atm of steam pressure without the necessity of operating a high-pressure/high temperature autoclave or pressure vessel. The chamber takes advantage of the dehydration of CoSO₄·7H₂O powder to stabilize water partial pressure up to 100 atm. This facilitates effective hydration at moderate temperatures, producing crack free pellets under reproducible conditions. Using La0.45Ce0.55O1.775 ceramics (LCO45) as a test case, we demonstrate that hydration in the chamber with atm produces at least ten times more water incorporation than hydration with 1 atm steam (38.5 % vs 3.7 % of oxygen vacancies filled) at the same temperature, 673 K, while requiring approximately one-tenth of the time (5 h vs 48 h). X-ray powder diffraction reveals an expansion of 0.43 % in the fluorite lattice parameter of LCO45 ceramics hydrated in the chamber. Chamber hydration increased conductivity in the temperature range 383–463 K by ca. two orders of magnitude compared to the dry pellet, the increase attributable to proton conductivity. The hydration protocol described below does not allow independent setting of temperature and pressure; however, due to its simplicity and economic accessibility, it may provide a viable method for achieving a high degree of hydration in ceramic samples while, at the same time, preserving their mechanical integrity.
在相对较低的压力下（<；5 大气压的水蒸气）水化大块陶瓷样品的传统方法往往由于动力学障碍和机械故障而无法实现显著的水化，后者主要是由于水化过程中不均匀的晶格膨胀。我们提出了一种小型高压室，可以达到数十atm的蒸汽压力，而无需操作高压/高温高压灭菌器或压力容器。该室利用CoSO₄·7h2o粉体的脱水作用，将水分压稳定在100 atm以下。这有利于在中等温度下有效的水化，在可重复的条件下生产无裂纹的颗粒。使用La0.45Ce0.55O1.775陶瓷（LCO45）作为测试案例，我们证明了在相同温度（673 K）下，PH2O≈56 atm的水化室中，水化产生的水掺入量至少是1 atm水化室的十倍（38.5 % vs 3.7 %的氧空位填充），而所需的时间约为十分之一（5 h vs 48 h）。x射线粉末衍射结果表明，水化LCO45陶瓷的萤石晶格参数膨胀了0.43 %。在383-463 K温度范围内，与干燥球团相比，腔室水化提高了大约两个数量级的电导率，这是由于质子电导率的增加。下面描述的水化方案不允许独立设置温度和压力；然而，由于其简单性和经济可及性，它可能提供一种可行的方法来实现陶瓷样品的高度水化，同时保持其机械完整性。
{"title":"A hydration chamber for La-doped ceria ceramics with crystal hydrate-stabilized water vapor pressure","authors":"Or Ben Zion , Isaac Abrahams , Ellen Wachtel , Xiao-Dong Zhang , Xin Guo , Igor Lubomirsky , David Ehre","doi":"10.1016/j.ssi.2025.117084","DOIUrl":"10.1016/j.ssi.2025.117084","url":null,"abstract":"<div><div>Conventional methods for hydrating bulk ceramic samples at relatively low pressures (<5 atm of water steam) often fail to achieve significant hydration because of kinetic barriers and mechanical failures, the latter primarily due to inhomogeneous lattice expansion accompanying hydration. We propose a small, high-pressure chamber that can reach tens of atm of steam pressure without the necessity of operating a high-pressure/high temperature autoclave or pressure vessel. The chamber takes advantage of the dehydration of CoSO₄·7H₂O powder to stabilize water partial pressure up to 100 atm. This facilitates effective hydration at moderate temperatures, producing crack free pellets under reproducible conditions. Using La<sub>0.45</sub>Ce<sub>0.55</sub>O<sub>1.775</sub> ceramics (LCO45) as a test case, we demonstrate that hydration in the chamber with <span><math><msub><mi>P</mi><mrow><msub><mi>H</mi><mn>2</mn></msub><mi>O</mi></mrow></msub><mo>≈</mo><mn>56</mn></math></span> atm produces at least ten times more water incorporation than hydration with 1 atm steam (38.5 % vs 3.7 % of oxygen vacancies filled) at the same temperature, 673 K, while requiring approximately one-tenth of the time (5 h vs 48 h). X-ray powder diffraction reveals an expansion of 0.43 % in the fluorite lattice parameter of LCO45 ceramics hydrated in the chamber. Chamber hydration increased conductivity in the temperature range 383–463 K by ca. two orders of magnitude compared to the dry pellet, the increase attributable to proton conductivity. The hydration protocol described below does not allow independent setting of temperature and pressure; however, due to its simplicity and economic accessibility, it may provide a viable method for achieving a high degree of hydration in ceramic samples while, at the same time, preserving their mechanical integrity.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"434 ","pages":"Article 117084"},"PeriodicalIF":3.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748357","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: 2025-10-13DOI: 10.1016/j.ssi.2025.117043
Joshua Budde, Ingo Bardenhagen, Julian Schwenzel
This study investigates the ionic conductivity of a mixture comprising 2-adamantanone and lithium bis(trifluoromethanesulfonyl)imide, with focus on the impact of temperature and residual tetrahydrofuran. Previous investigations have shown that the plastic crystal 2-adamantanone, when paired with lithium bis(trifluoromethanesulfonyl)imide, exhibits an ionic conductivity of 1.2 × 10−4 S cm−1 and a considerable oxidation potential of 5.1 V. Nonetheless, the influence of any residual processing solvent on the ionic conductivity is not yet fully understood. The Design of Experiments methodology was utilized to analyze a broad spectrum of potential compositions of 2-adamantanone, lithium bis(trifluoromethanesulfonyl)imide, and tetrahydrofuran. We measured the ionic conductivity of the samples using electrochemical impedance spectroscopy and conducted structural studies via differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction and solid-state NMR. Our findings indicate that the leftover amount of THF enhances ionic conductivity more strongly than the molarity. Moreover, compared to crystallization from the solvent, ionic conductivity increases by over an order of magnitude following recrystallization from the melt. We suggest that the residual solvent is integrated into the crystal structure of the 2-adamantanone, thereby increasing the free volume and facilitating lithium-ion transport. At elevated temperatures, the optimized formulation transforms from a solid to a wax-like consistency, functioning as a solid electrolyte with a high ionic conductivity of 2.6 × 10−4 S cm−1 at room temperature, making it a promising candidate for electrolyte applications.
本研究考察了2-金刚烷酮和锂二（三氟甲烷磺酰）亚胺混合物的离子电导率，重点研究了温度和残余四氢呋喃的影响。先前的研究表明，塑料晶体2-金刚烷酮与双（三氟甲烷磺酰）亚胺锂配对时，离子电导率为1.2 × 10−4 S cm−1，氧化电位为5.1 V。然而，任何残留的加工溶剂对离子电导率的影响尚不完全清楚。利用实验设计方法分析了2-金刚烷酮、锂二（三氟甲烷磺酰基）亚胺和四氢呋喃的广谱潜在成分。我们使用电化学阻抗谱测量了样品的离子电导率，并通过差示扫描量热法、傅里叶变换红外光谱、x射线衍射和固态核磁共振进行了结构研究。我们的研究结果表明，剩余的THF量比摩尔浓度更能增强离子电导率。此外，与溶剂结晶相比，熔体再结晶后离子电导率增加了一个数量级以上。我们认为残留的溶剂被整合到2-金刚烷酮的晶体结构中，从而增加了自由体积，促进了锂离子的传输。在高温下，优化的配方从固体转变为蜡状稠度，在室温下具有2.6 × 10−4 S cm−1的高离子电导率的固体电解质，使其成为电解质应用的有希望的候选者。
{"title":"Conductivity of 2-adamantanone with lithium bis(trifluoromethanesulfonyl)imide: Impact of residual solvent and temperature","authors":"Joshua Budde, Ingo Bardenhagen, Julian Schwenzel","doi":"10.1016/j.ssi.2025.117043","DOIUrl":"10.1016/j.ssi.2025.117043","url":null,"abstract":"<div><div>This study investigates the ionic conductivity of a mixture comprising 2-adamantanone and lithium bis(trifluoromethanesulfonyl)imide, with focus on the impact of temperature and residual tetrahydrofuran. Previous investigations have shown that the plastic crystal 2-adamantanone, when paired with lithium bis(trifluoromethanesulfonyl)imide, exhibits an ionic conductivity of 1.2 × 10<sup>−4</sup> S cm<sup>−1</sup> and a considerable oxidation potential of 5.1 V. Nonetheless, the influence of any residual processing solvent on the ionic conductivity is not yet fully understood. The Design of Experiments methodology was utilized to analyze a broad spectrum of potential compositions of 2-adamantanone, lithium bis(trifluoromethanesulfonyl)imide, and tetrahydrofuran. We measured the ionic conductivity of the samples using electrochemical impedance spectroscopy and conducted structural studies via differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction and solid-state NMR. Our findings indicate that the leftover amount of THF enhances ionic conductivity more strongly than the molarity. Moreover, compared to crystallization from the solvent, ionic conductivity increases by over an order of magnitude following recrystallization from the melt. We suggest that the residual solvent is integrated into the crystal structure of the 2-adamantanone, thereby increasing the free volume and facilitating lithium-ion transport. At elevated temperatures, the optimized formulation transforms from a solid to a wax-like consistency, functioning as a solid electrolyte with a high ionic conductivity of 2.6 × 10<sup>−4</sup> S cm<sup>−1</sup> at room temperature, making it a promising candidate for electrolyte applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117043"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145322999","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}
Polymer-based electrolytes have emerged as the most viable component for various electrochemical applications, including batteries, fuel cells, and supercapacitors, due to their unique combination of properties, such as competitive ionic conductivity, a high electrochemical stability window, and superior adhesion at the electrolyte/electrode interface with mechanical flexibility. To obtain the most suitable electrolyte system, these electrolyte systems have undergone through various structural and compositional modifications. There are different classes of polymer electrolytes. Understanding the ion-transport mechanisms in these complex materials is essential for optimizing their performance. This study offers a thorough examination of several models suggested for ion conduction in polymer electrolytes. The classical approaches, such as the vehicular and segmental motion models, as well as more recent theories, including the Vogel-Tammann-Fulcher (VTF) model, dynamic bond percolation, and hopping mechanisms, are discussed in detail. Emphasis is given to the interplay between polymer segmental motion and ion transport, the role of ion–polymer interactions, the role of different fillers and plasticizers, and the influence of structural heterogeneity on conduction pathways. This work also highlights the strengths and limitations of the ion conduction models.
{"title":"Insights into ion transport in polymer electrolytes: Classifications, models and mechanisms","authors":"Maitri Patel , Kuldeep Mishra , J.J. Chaudhari , Vaishali Madhani , Jehova Jire L. Hmar , Ashwani Kumar , Neeladri Das , Deepak Kumar","doi":"10.1016/j.ssi.2025.117083","DOIUrl":"10.1016/j.ssi.2025.117083","url":null,"abstract":"<div><div>Polymer-based electrolytes have emerged as the most viable component for various electrochemical applications, including batteries, fuel cells, and supercapacitors, due to their unique combination of properties, such as competitive ionic conductivity, a high electrochemical stability window, and superior adhesion at the electrolyte/electrode interface with mechanical flexibility. To obtain the most suitable electrolyte system, these electrolyte systems have undergone through various structural and compositional modifications. There are different classes of polymer electrolytes. Understanding the ion-transport mechanisms in these complex materials is essential for optimizing their performance. This study offers a thorough examination of several models suggested for ion conduction in polymer electrolytes. The classical approaches, such as the vehicular and segmental motion models, as well as more recent theories, including the Vogel-Tammann-Fulcher (VTF) model, dynamic bond percolation, and hopping mechanisms, are discussed in detail. Emphasis is given to the interplay between polymer segmental motion and ion transport, the role of ion–polymer interactions, the role of different fillers and plasticizers, and the influence of structural heterogeneity on conduction pathways. This work also highlights the strengths and limitations of the ion conduction models.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"433 ","pages":"Article 117083"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145578273","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: 2025-10-18DOI: 10.1016/j.ssi.2025.117052
Sneha Mandal , Catherine Tom , Subbiah Alwarappan , Ravi Kumar Pujala , Surendra K. Martha , Vijayamohanan K. Pillai
Solid-state batteries have recently attracted unprecedented interest as potentially safe and stable high-energy storage systems for niche applications. However, modulating the mobility of cations is a challenge, which limits the ionic conductivity and hinders further development of practical devices using these solid electrolytes. The electrode/electrolyte interface is critical in determining the ion transport mechanism, cycle life, and energy storage efficiency in secondary batteries. Here, we report some exciting results on a novel composite polymer electrolyte comprising laponite and nanocellulose, which expands the interlayer gap by ∼2 Å, facilitating a high transference number of 0.84, with a robust electrochemical stability window of 2.7–4.8 V with Na metal. Coupling this electrolyte with few-layer MoS2 nanosheet cathodes exhibiting expansion along the (001) direction and in-plane compression, we demonstrate charge-discharge with an initial capacity of 17 mAh g−1. FT-IR and Raman analyses reveal hydroxyl groups of cellulose interfere with cathode interface stability, contributing to capacity degradation, while promoting robust anode interface formation. These findings elucidate interfacial reactions impacting performance and suggest that tailored electrode or electrolyte modifications could improve cycling stability in solid-state Na batteries employing laponite-based polymer electrolytes and MoS2 cathodes.
固态电池作为一种潜在的安全稳定的高能存储系统，最近引起了人们前所未有的兴趣。然而，调节阳离子的迁移率是一个挑战，它限制了离子的电导率，并阻碍了使用这些固体电解质的实用设备的进一步发展。电极/电解质界面是决定二次电池离子传输机制、循环寿命和能量存储效率的关键。在这里，我们报告了一种由拉脱土和纳米纤维素组成的新型复合聚合物电解质的一些令人兴奋的结果，该电解质将层间间隙扩大了~ 2 Å，促进了0.84的高转移数，具有2.7-4.8 V的强大电化学稳定窗口。将这种电解质与具有沿（001）方向膨胀和面内压缩的少层MoS2纳米片阴极耦合，我们展示了初始容量为17 mAh g−1的充放电。FT-IR和拉曼分析显示纤维素的羟基干扰阴极界面的稳定性，导致容量下降，同时促进阳极界面的形成。这些发现阐明了界面反应对性能的影响，并表明定制电极或电解质修饰可以提高采用lapoite基聚合物电解质和MoS2阴极的固态Na电池的循环稳定性。
{"title":"Understanding interfacial reactions and electrochemical performance of MoS2 cathodes with laponite-based solid polymer electrolytes","authors":"Sneha Mandal , Catherine Tom , Subbiah Alwarappan , Ravi Kumar Pujala , Surendra K. Martha , Vijayamohanan K. Pillai","doi":"10.1016/j.ssi.2025.117052","DOIUrl":"10.1016/j.ssi.2025.117052","url":null,"abstract":"<div><div>Solid-state batteries have recently attracted unprecedented interest as potentially safe and stable high-energy storage systems for niche applications. However, modulating the mobility of cations is a challenge, which limits the ionic conductivity and hinders further development of practical devices using these solid electrolytes. The electrode/electrolyte interface is critical in determining the ion transport mechanism, cycle life, and energy storage efficiency in secondary batteries. Here, we report some exciting results on a novel composite polymer electrolyte comprising laponite and nanocellulose, which expands the interlayer gap by ∼2 Å, facilitating a high transference number of 0.84, with a robust electrochemical stability window of 2.7–4.8 V with Na metal. Coupling this electrolyte with few-layer MoS<sub>2</sub> nanosheet cathodes exhibiting expansion along the (001) direction and in-plane compression, we demonstrate charge-discharge with an initial capacity of 17 mAh g<sup>−1</sup>. FT-IR and Raman analyses reveal hydroxyl groups of cellulose interfere with cathode interface stability, contributing to capacity degradation, while promoting robust anode interface formation. These findings elucidate interfacial reactions impacting performance and suggest that tailored electrode or electrolyte modifications could improve cycling stability in solid-state Na batteries employing laponite-based polymer electrolytes and MoS<sub>2</sub> cathodes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117052"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145322996","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}
Zn2TiO4 nanomaterials doped with Terbium were synthesized via a combustion route using oxalyl dihydrazide (ODH) as fuel. The crystalline nature and morphology were confirmed by Powder X-ray diffraction (PXRD), and Scanning Electron Microscopy (SEM) techniques. Optical studies and the nature of liberated organics were conducted through Diffuse Reflectance Spectroscopy (DRS), and Fourier Transform Infrared (FTIR)spectroscopy techniques. Conductivity and Dielectric studies were carried out for the prepared materials and optimized. Dielectric spectra revealed distinct relaxation behaviors at high and low frequencies. Highest dielectric constant was noticed for the 5 mol% Tb-doped Zn₂TiO₄ compared to other compositions. Dielectric plots exhibit a clear merging beyond a certain frequency, and their behavior changes significantly at higher frequencies which can be attributed to the release of space charge and the consequent reduction in the material's barrier properties. The frequency dependence of AC conductivity Tb3+ (1–7 mol%): Zn2TiO4 nanoparticles follows Jonscher's power law. All the results suggest that the Tb3+-doped Zn2TiO4 material is potentially suitable for electronics and energy storage applications.
{"title":"Dielectric and conductivity studies of Tb-doped zinc orthotitanate nanomaterials for next-generation electronics and energy storage","authors":"K.M. Girish , R. Lavanya , M.V. Hemantha Reddy , G.R. Rajath , B.N. Deepak Kumar , S.C. Prashantha","doi":"10.1016/j.ssi.2025.117048","DOIUrl":"10.1016/j.ssi.2025.117048","url":null,"abstract":"<div><div>Zn<sub>2</sub>TiO<sub>4</sub> nanomaterials doped with Terbium were synthesized via a combustion route using oxalyl dihydrazide (ODH) as fuel. The crystalline nature and morphology were confirmed by Powder X-ray diffraction (PXRD), and Scanning Electron Microscopy (SEM) techniques. Optical studies and the nature of liberated organics were conducted through Diffuse Reflectance Spectroscopy (DRS), and Fourier Transform Infrared (FTIR)spectroscopy techniques. Conductivity and Dielectric studies were carried out for the prepared materials and optimized. Dielectric spectra revealed distinct relaxation behaviors at high and low frequencies. Highest dielectric constant was noticed for the 5 mol% Tb-doped Zn₂TiO₄ compared to other compositions. Dielectric plots exhibit a clear merging beyond a certain frequency, and their behavior changes significantly at higher frequencies which can be attributed to the release of space charge and the consequent reduction in the material's barrier properties. The frequency dependence of AC conductivity Tb<sup>3+</sup> (1–7 mol%): Zn<sub>2</sub>TiO<sub>4</sub> nanoparticles follows Jonscher's power law. All the results suggest that the Tb<sup>3+</sup>-doped Zn<sub>2</sub>TiO<sub>4</sub> material is potentially suitable for electronics and energy storage applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117048"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360228","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.2025.117055
Chunzhi Du , Ruitai Liu , Rui Zhou , Hao Wu , Zhiwei Sang , Yunteng Jiang
As the cornerstone of next-generation energy storage technology characterized by high safety and high energy density, the development of all-solid-state lithium batteries relies critically on the advancement of high-performance composite solid electrolytes (CSEs). In this study, LATP inorganic fillers were incorporated into a PEO/PLA/LiTFSI matrix for the first time to fabricate a novel organic–inorganic composite solid electrolyte (CSE) membrane. Using this membrane, an all-solid-state graphite anode battery with an LFP│CSE│C (graphite) configuration was assembled. The CSE film containing 15 wt% LATP demonstrated superior overall performance, exhibiting a room-temperature ionic conductivity of 1.6 × 10−4 S/cm. This represents an enhancement of approximately five orders of magnitude compared to the pure PEO/PLA/LiTFSI solid polymer electrolyte. At 60 °C, the ionic conductivity reached 9.6 × 10−2 S/cm, reflecting a 600 % improvement over its room-temperature value. The electrolyte exhibited an electrochemical stability window of 4.8 V and an ion transference number of 0.7. After 100 cycles, the battery demonstrated excellent cycling durability at 0.2C and 60 °C, retaining 96.5 % of its initial capacity—a 10 % improvement in capacity retention—with a Coulombic efficiency of 99.56 %. The PEO/PLA/LiTFSI/LATP composite solid electrolyte (CSE) represents a promising flexible electrolyte system for all-solid-state lithium batteries, offering a viable strategy for advancing the development of current all-solid-state lithium batteries with graphite anodes.
{"title":"PEO/PLA-based high-temperature organic-inorganic composite solid electrolyte for all-solid-state graphite anode Lithium batteries","authors":"Chunzhi Du , Ruitai Liu , Rui Zhou , Hao Wu , Zhiwei Sang , Yunteng Jiang","doi":"10.1016/j.ssi.2025.117055","DOIUrl":"10.1016/j.ssi.2025.117055","url":null,"abstract":"<div><div>As the cornerstone of next-generation energy storage technology characterized by high safety and high energy density, the development of all-solid-state lithium batteries relies critically on the advancement of high-performance composite solid electrolytes (CSEs). In this study, LATP inorganic fillers were incorporated into a PEO/PLA/LiTFSI matrix for the first time to fabricate a novel organic–inorganic composite solid electrolyte (CSE) membrane. Using this membrane, an all-solid-state graphite anode battery with an LFP│CSE│C (graphite) configuration was assembled. The CSE film containing 15 wt% LATP demonstrated superior overall performance, exhibiting a room-temperature ionic conductivity of 1.6 × 10<sup>−4</sup> S/cm. This represents an enhancement of approximately five orders of magnitude compared to the pure PEO/PLA/LiTFSI solid polymer electrolyte. At 60 °C, the ionic conductivity reached 9.6 × 10<sup>−2</sup> S/cm, reflecting a 600 % improvement over its room-temperature value. The electrolyte exhibited an electrochemical stability window of 4.8 V and an ion transference number of 0.7. After 100 cycles, the battery demonstrated excellent cycling durability at 0.2C and 60 °C, retaining 96.5 % of its initial capacity—a 10 % improvement in capacity retention—with a Coulombic efficiency of 99.56 %. The PEO/PLA/LiTFSI/LATP composite solid electrolyte (CSE) represents a promising flexible electrolyte system for all-solid-state lithium batteries, offering a viable strategy for advancing the development of current all-solid-state lithium batteries with graphite anodes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117055"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360231","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: 2025-10-17DOI: 10.1016/j.ssi.2025.117050
Yongsheng Chen , Siman Yang , Jianbin Zheng , Mingwei Hu , Mingdeng Wei , Peixun Xiong
As an excellent cathode material, lithium iron phosphate (LiFePO4) has been widely used in commercial lithium-ion batteries (LIBs). However, the impact of synthetic conditions on LiFePO4 cathode derived from amorphous iron phosphate (FePO4) remains underexplored. In the present study, the effects of Li/P molar ratio on the crystallinity and electrochemical properties of LiFePO4 were investigated in detail using FePO4 as a precursor. When the Li/P molar ratio in LiFePO4 was approximately 1, the material exhibited an excellent long-term cycling stability with a high capacity retention of 97 % after 500 cycles. In addition, multiple characterizations demonstrate that the higher molar ratio of the Li/P resulted in the higher concentration of defects in LiFePO4 crystals, which not only reduced the reversible capacity but also compromised the structural stability, leading to a poor cyclic stability and quick capacity degradation. Therefore, such a work could provide a scientific insight for rational design and synthesis of high-performance LiFePO4 cathodes from amorphous FePO4 precursor.
{"title":"Synthesis of LiFePO4 cathode materials from amorphous FePO4 precursor: Effects of Li/P molar ratio on crystal defect formation and electrochemical performance","authors":"Yongsheng Chen , Siman Yang , Jianbin Zheng , Mingwei Hu , Mingdeng Wei , Peixun Xiong","doi":"10.1016/j.ssi.2025.117050","DOIUrl":"10.1016/j.ssi.2025.117050","url":null,"abstract":"<div><div>As an excellent cathode material, lithium iron phosphate (LiFePO<sub>4</sub>) has been widely used in commercial lithium-ion batteries (LIBs). However, the impact of synthetic conditions on LiFePO<sub>4</sub> cathode derived from amorphous iron phosphate (FePO<sub>4</sub>) remains underexplored. In the present study, the effects of Li/P molar ratio on the crystallinity and electrochemical properties of LiFePO<sub>4</sub> were investigated in detail using FePO<sub>4</sub> as a precursor. When the Li/P molar ratio in LiFePO<sub>4</sub> was approximately 1, the material exhibited an excellent long-term cycling stability with a high capacity retention of 97 % after 500 cycles. In addition, multiple characterizations demonstrate that the higher molar ratio of the Li/P resulted in the higher concentration of defects in LiFePO<sub>4</sub> crystals, which not only reduced the reversible capacity but also compromised the structural stability, leading to a poor cyclic stability and quick capacity degradation. Therefore, such a work could provide a scientific insight for rational design and synthesis of high-performance LiFePO<sub>4</sub> cathodes from amorphous FePO<sub>4</sub> precursor.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"432 ","pages":"Article 117050"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145323001","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: 2025-11-18DOI: 10.1016/j.ssi.2025.117071
Hengheng Xia , Chongyang Yang , Zhongxun An , Yue-Ling Bai , Jiaqiang Xu
Hybrid sodium ion battery capacitor (SIBC) is a type of internal hybrid electrochemical energy storage device featuring a dual-energy storage mechanism, capable of delivering high energy and power densities. In this work, we have developed high-energy SIBCs using bi-material cathodes composed of NaNi1/3Fe1/3Mn1/3O2 (NFM) and activated carbon (AC), paired with presodiation-free hard carbon anodes. NFM offers high capacity but suffers from poor conductivity and rate capability, whereas AC enhances kinetics but limits energy density. Through optimization of the AC/NFM mass ratio in commercial-scale pouch-type full cells, we demonstrate that a hybrid cathode with 9.1 wt% AC (R1/10) achieves optimal electrochemical performance. This design effectively balances battery-type (NFM) and capacitor-type (AC) materials, resulting in a significant reduction in electrode resistance from 19.4 mΩ to 10.8 mΩ, along with decreased interfacial film resistance and charge transfer resistance, thereby enhancing capacitive contribution. The R1/10 SIBC delivers a high energy density of 161.3 Wh kg−1 at 74.8 W kg−1 and maintains 62.3 Wh kg−1 at 11.8 kW kg−1, outperforming pure NFM cells. It also exhibits enhanced low-temperature performance with 38.0 % capacity retention at −20 °C (5C), superior cycling stability with 72.2 % capacity retention after 10,000 cycles at 10C, and minimal self-discharge at 60 °C (0.5 mV h−1). The synergy between AC and NFM mitigates polarization, accelerates reaction kinetics, and broadens the practical applicability of high-power energy storage systems.
混合钠离子电池电容器（SIBC）是一种具有双能量存储机制的内部混合电化学储能装置，能够提供高能量密度和功率密度。在这项工作中，我们开发了高能SIBCs，使用由NaNi1/3Fe1/3Mn1/3O2 （NFM）和活性炭（AC）组成的双材料阴极，搭配无预沉淀的硬碳阳极。NFM提供高容量，但电导率和速率能力差，而交流电提高了动力学，但限制了能量密度。通过优化商业规模的袋式全电池中AC/NFM的质量比，我们证明了9.1 wt% AC （R1/10）的混合阴极获得了最佳的电化学性能。这种设计有效地平衡了电池型（NFM）和电容器型（AC）材料，使电极电阻从19.4 mΩ显著降低到10.8 mΩ，同时降低了界面膜电阻和电荷转移电阻，从而提高了电容的贡献。R1/10 SIBC在74.8 W kg - 1时提供161.3 Wh kg - 1的高能量密度，在11.8 kW kg - 1时保持62.3 Wh kg - 1，优于纯NFM电池。它还表现出增强的低温性能，在- 20°C （5C）下容量保持率为38.0%，在10°C下循环10000次后容量保持率为72.2%，在60°C （0.5 mV h - 1）下自放电最小。AC和NFM之间的协同作用减轻了极化，加速了反应动力学，拓宽了大功率储能系统的实际适用性。
{"title":"Bi-material cathodes based on O3-type NaNi1/3Fe1/3Mn1/3O2 and activated carbon for high-energy hybrid sodium ion battery capacitors","authors":"Hengheng Xia , Chongyang Yang , Zhongxun An , Yue-Ling Bai , Jiaqiang Xu","doi":"10.1016/j.ssi.2025.117071","DOIUrl":"10.1016/j.ssi.2025.117071","url":null,"abstract":"<div><div>Hybrid sodium ion battery capacitor (SIBC) is a type of internal hybrid electrochemical energy storage device featuring a dual-energy storage mechanism, capable of delivering high energy and power densities. In this work, we have developed high-energy SIBCs using bi-material cathodes composed of NaNi<sub>1/3</sub>Fe<sub>1/3</sub>Mn<sub>1/3</sub>O<sub>2</sub> (NFM) and activated carbon (AC), paired with presodiation-free hard carbon anodes. NFM offers high capacity but suffers from poor conductivity and rate capability, whereas AC enhances kinetics but limits energy density. Through optimization of the AC/NFM mass ratio in commercial-scale pouch-type full cells, we demonstrate that a hybrid cathode with 9.1 wt% AC (R<sub>1/10</sub>) achieves optimal electrochemical performance. This design effectively balances battery-type (NFM) and capacitor-type (AC) materials, resulting in a significant reduction in electrode resistance from 19.4 mΩ to 10.8 mΩ, along with decreased interfacial film resistance and charge transfer resistance, thereby enhancing capacitive contribution. The R<sub>1/10</sub> SIBC delivers a high energy density of 161.3 Wh kg<sup>−1</sup> at 74.8 W kg<sup>−1</sup> and maintains 62.3 Wh kg<sup>−1</sup> at 11.8 kW kg<sup>−1</sup>, outperforming pure NFM cells. It also exhibits enhanced low-temperature performance with 38.0 % capacity retention at −20 °C (5C), superior cycling stability with 72.2 % capacity retention after 10,000 cycles at 10C, and minimal self-discharge at 60 °C (0.5 mV h<sup>−1</sup>). The synergy between AC and NFM mitigates polarization, accelerates reaction kinetics, and broadens the practical applicability of high-power energy storage systems.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"433 ","pages":"Article 117071"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145578272","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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