首页 > 最新文献

Progress in Solid State Chemistry最新文献

英文 中文
Recent synthetic approaches for high-entropy polyelement nanoparticles 高熵多元纳米粒子的合成新方法
IF 10.5 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-12-04 DOI: 10.1016/j.progsolidstchem.2025.100559
Wail Al Zoubi , Park Jaehyung , Mohammad R. Thalji , Chinho Park , Adnan Deep , Nokeun Park
High-entropy polyelement nanoparticles (HEPNs) exhibit unique behaviors distinct from those of the solid phases of individual elements. The disordered nature of multielement compounds introduces structural complexity and unprecedented compositional variations, necessitating a comprehensive understanding of stabilization enthalpy, entropy, and property optimization. HEPNs are particularly desirable when fabrication methods provide precise control comparable to that achieved conventional alloy design. Recent advancements in fabrication techniques have enabled greater control over the inherently disordered structures of HEPNs. This study explores emerging strategies for synthesizing HEPNs with tunable compositions, tailored atomic configurations, and enhanced catalytic activity achieved through the formation of novel active catalytic sites. It discusses fabrication pathways for different types of HEPNs, their stabilization mechanisms, and catalytic performance, providing insights into how of various synthesis approaches influence these properties. Collectively, these strategies enable the rational design and predictable controlled modulation of catalytic activity and atomic order within the disordered lattice, establishing a basis for enhanced applications.
高熵多元素纳米粒子(HEPNs)表现出不同于单个元素固相的独特行为。多元素化合物的无序性引入了结构复杂性和前所未有的组成变化,需要对稳定焓、熵和性能优化有全面的了解。当制造方法提供与传统合金设计相当的精确控制时,HEPNs尤其可取。最近制造技术的进步使得对hepn固有的无序结构有了更好的控制。本研究探索了通过形成新的活性催化位点来合成具有可调成分、定制原子构型和增强催化活性的HEPNs的新策略。它讨论了不同类型HEPNs的制备途径,它们的稳定机制和催化性能,提供了各种合成方法如何影响这些性能的见解。总的来说,这些策略使得在无序晶格内的催化活性和原子顺序的合理设计和可预测的控制调制成为可能,为增强应用奠定了基础。
{"title":"Recent synthetic approaches for high-entropy polyelement nanoparticles","authors":"Wail Al Zoubi ,&nbsp;Park Jaehyung ,&nbsp;Mohammad R. Thalji ,&nbsp;Chinho Park ,&nbsp;Adnan Deep ,&nbsp;Nokeun Park","doi":"10.1016/j.progsolidstchem.2025.100559","DOIUrl":"10.1016/j.progsolidstchem.2025.100559","url":null,"abstract":"<div><div>High-entropy polyelement nanoparticles <strong>(</strong>HEPNs) exhibit unique behaviors distinct from those of the solid phases of individual elements. The disordered nature of multielement compounds introduces structural complexity and unprecedented compositional variations, necessitating a comprehensive understanding of stabilization enthalpy, entropy, and property optimization. HEPNs are particularly desirable when fabrication methods provide precise control comparable to that achieved conventional alloy design. Recent advancements in fabrication techniques have enabled greater control over the inherently disordered structures of HEPNs. This study explores emerging strategies for synthesizing HEPNs with tunable compositions, tailored atomic configurations, and enhanced catalytic activity achieved through the formation of novel active catalytic sites. It discusses fabrication pathways for different types of HEPNs, their stabilization mechanisms, and catalytic performance, providing insights into how of various synthesis approaches influence these properties. Collectively, these strategies enable the rational design and predictable controlled modulation of catalytic activity and atomic order within the disordered lattice, establishing a basis for enhanced applications.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"81 ","pages":"Article 100559"},"PeriodicalIF":10.5,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145735472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Site preference identification and crystal field analysis of high-efficient and thermal-stable NIR-I emission in NaAl11O17:Fe3+: experimental and DFT investigation NaAl11O17:Fe3+中高效热稳定NIR-I发射的位置优选与晶体场分析:实验与DFT研究
IF 10.5 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-12-01 DOI: 10.1016/j.progsolidstchem.2025.100551
Chunli Li , Linyun Zeng , Irina I. Piyanzina , Ziyi Hong , Wenjia Xie , Peican Chen , Liya Zhou , Chunyan Zhou , Jialiang Pan , Wei Liu , Weitao Ren , Xinguo Zhang
Presently Fe3+-doped NIR phosphors exhibit immense potential for multiple applications. However, a more comprehensive understanding of Fe3+ site-occupancy and luminescent mechanism is urgently needed for enhancing material design and synthesis. In this work, a high-efficient NIR-I emitting Fe3+-doped NaAl11O17 phosphor was synthesized and systematically studied. A hybrid density functional theory (DFT) calculation was performed on geometric and electronic structures to study Fe3+ occupation preference and the corresponding optical properties. It is found that Fe3+ prefers to occupy AlO4 sites with lower total energy compared with AlO6 sites. Under 340 nm excitation, NaAl11O17: Fe3+ phosphors exhibited a high-efficient NIR emission of 600∼1000 nm peaking at ∼770 nm, with a high internal quantum efficiency of 78.12 %. Based on both theoretical and experimental results, the 3d energy-level diagram of Fe3+ in NaAl11O17 is constructed and discussed with crystal field strength analysis. The optimal NaAl11O17: Fe3+ phosphor shows good thermal stability while keeping 87 and 45 % of room-temperature intensity at 373 and 473 K. A NIR pc-LED was fabricated and demonstrates applications in nondestructive detection and angiography. This hybrid investigation on Fe3+-doped NaAl11O17 NIR-I phosphor could provide an insight for developing Fe3+-activated NIR luminescent materials with excellent performance and expanding their application prospects.
目前,Fe3+掺杂的近红外荧光粉具有广泛的应用前景。然而,为了提高材料的设计和合成水平,迫切需要更全面地了解Fe3+的占位和发光机理。本文合成了一种高效发射NIR-I的Fe3+掺杂NaAl11O17荧光粉,并对其进行了系统的研究。采用混合密度泛函理论(DFT)对几何结构和电子结构进行了计算,研究了Fe3+的占位偏好和相应的光学性质。结果表明,与AlO6位点相比,Fe3+更倾向于占据总能量较低的AlO4位点。在340 nm激发下,NaAl11O17: Fe3+荧光粉表现出600 ~ 1000 nm的高效近红外发射,在770 nm处达到峰值,具有78.12%的高内量子效率。基于理论和实验结果,构建了NaAl11O17中Fe3+的三维能级图,并用晶体场强分析对其进行了讨论。最优的NaAl11O17: Fe3+荧光粉在373和473 K时的热稳定性分别为室温强度的87%和45%。制作了一种近红外pc-LED,并展示了其在无损检测和血管造影中的应用。本文对Fe3+掺杂NaAl11O17 NIR- i荧光粉的杂化研究,为开发性能优异的Fe3+活化近红外发光材料和拓展其应用前景提供了新的思路。
{"title":"Site preference identification and crystal field analysis of high-efficient and thermal-stable NIR-I emission in NaAl11O17:Fe3+: experimental and DFT investigation","authors":"Chunli Li ,&nbsp;Linyun Zeng ,&nbsp;Irina I. Piyanzina ,&nbsp;Ziyi Hong ,&nbsp;Wenjia Xie ,&nbsp;Peican Chen ,&nbsp;Liya Zhou ,&nbsp;Chunyan Zhou ,&nbsp;Jialiang Pan ,&nbsp;Wei Liu ,&nbsp;Weitao Ren ,&nbsp;Xinguo Zhang","doi":"10.1016/j.progsolidstchem.2025.100551","DOIUrl":"10.1016/j.progsolidstchem.2025.100551","url":null,"abstract":"<div><div>Presently Fe<sup>3+</sup>-doped NIR phosphors exhibit immense potential for multiple applications. However, a more comprehensive understanding of Fe<sup>3+</sup> site-occupancy and luminescent mechanism is urgently needed for enhancing material design and synthesis. In this work, a high-efficient NIR-I emitting Fe<sup>3+</sup>-doped NaAl<sub>11</sub>O<sub>17</sub> phosphor was synthesized and systematically studied. A hybrid density functional theory (DFT) calculation was performed on geometric and electronic structures to study Fe<sup>3+</sup> occupation preference and the corresponding optical properties. It is found that Fe<sup>3+</sup> prefers to occupy AlO<sub>4</sub> sites with lower total energy compared with AlO<sub>6</sub> sites. Under 340 nm excitation, NaAl<sub>11</sub>O<sub>17</sub>: Fe<sup>3+</sup> phosphors exhibited a high-efficient NIR emission of 600∼1000 nm peaking at ∼770 nm, with a high internal quantum efficiency of 78.12 %. Based on both theoretical and experimental results, the 3<em>d</em> energy-level diagram of Fe<sup>3+</sup> in NaAl<sub>11</sub>O<sub>17</sub> is constructed and discussed with crystal field strength analysis. The optimal NaAl<sub>11</sub>O<sub>17</sub>: Fe<sup>3+</sup> phosphor shows good thermal stability while keeping 87 and 45 % of room-temperature intensity at 373 and 473 K. A NIR pc-LED was fabricated and demonstrates applications in nondestructive detection and angiography. This hybrid investigation on Fe<sup>3+</sup>-doped NaAl<sub>11</sub>O<sub>17</sub> NIR-I phosphor could provide an insight for developing Fe<sup>3+</sup>-activated NIR luminescent materials with excellent performance and expanding their application prospects.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100551"},"PeriodicalIF":10.5,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Advances in solid-state lithium–sulfur batteries for next-generation energy storage 下一代储能用固态锂硫电池的研究进展
IF 10.5 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-29 DOI: 10.1016/j.progsolidstchem.2025.100552
Vennila Selvaraj , Baeksang Yoon , Suresh Sagadevan , Byoenghun Oh , Sangwon Noh , Dong Ick Son , Hyung-Kee Seo , Inseok Seo
The increasing demand for high-performance energy storage has intensified the pursuit of alternatives to conventional lithium-ion batteries. Lithium-sulfur (Li–S) batteries has been extensively used due to their high theoretical energy density (2600 Wh kg−1), low cost, and sulfur's environmental benefits. However, traditional Li–S systems face challenges including polysulfide shuttle effects, lithium dendrite formation, and limited cycle life. Incorporating solid-state electrolytes (SSEs) have enhanced the safety and stability by replacing flammable liquids. Recent progress in solid-state Li–S (SSLS) batteries includes development of high-conductivity SSEs (sulfide, halide, polymer-ceramic composites), electrodes provided with the volume changes and minimize interfacial resistance, and improved cathode architectures for optimized ion/electron transport. This review comprehensively analyzes the development in solid-state lithium-sulfur (SSLS) batteries over the past decade. SSLS development is driven by the potential for higher energy density and enhanced safety that have been essential for next-generation energy storage.This review also focuses on solid electrolytes as the key enabler for solid-state lithium-sulfur (SSLS) battery performance, addressing the challenges associated with liquid electrolytes such as flammability, polysulfide shuttle, and lithium dendrite formation. Finally, the review highlights the importance of integrated cell design, where optimized electrode architectures and advanced solid electrolytes work synergistically to maximize performance..
对高性能储能的需求日益增长,促使人们寻求替代传统锂离子电池的方法。锂硫(Li-S)电池因其理论能量密度高(2600 Wh kg−1)、成本低和硫的环境效益而得到广泛应用。然而,传统的Li-S系统面临着多硫化物穿梭效应、锂枝晶形成和有限的循环寿命等挑战。加入固态电解质(sse)取代易燃液体,提高了安全性和稳定性。固态Li-S (SSLS)电池的最新进展包括开发高导电性的ssi(硫化物、卤化物、聚合物-陶瓷复合材料),提供体积变化和最小化界面电阻的电极,以及改进阴极结构以优化离子/电子传输。本文综合分析了近十年来固态锂硫电池的发展情况。SSLS的发展受到更高能量密度和增强安全性的潜力的推动,这对下一代储能至关重要。本文还重点介绍了固体电解质作为固态锂硫(SSLS)电池性能的关键推动因素,解决了与液体电解质相关的挑战,如可燃性、多硫化物穿梭和锂枝晶形成。最后,综述强调了集成电池设计的重要性,其中优化的电极结构和先进的固体电解质协同工作以最大限度地提高性能。
{"title":"Advances in solid-state lithium–sulfur batteries for next-generation energy storage","authors":"Vennila Selvaraj ,&nbsp;Baeksang Yoon ,&nbsp;Suresh Sagadevan ,&nbsp;Byoenghun Oh ,&nbsp;Sangwon Noh ,&nbsp;Dong Ick Son ,&nbsp;Hyung-Kee Seo ,&nbsp;Inseok Seo","doi":"10.1016/j.progsolidstchem.2025.100552","DOIUrl":"10.1016/j.progsolidstchem.2025.100552","url":null,"abstract":"<div><div>The increasing demand for high-performance energy storage has intensified the pursuit of alternatives to conventional lithium-ion batteries. Lithium-sulfur (Li–S) batteries has been extensively used due to their high theoretical energy density (2600 Wh kg<sup>−1</sup>), low cost, and sulfur's environmental benefits. However, traditional Li–S systems face challenges including polysulfide shuttle effects, lithium dendrite formation, and limited cycle life. Incorporating solid-state electrolytes (SSEs) have enhanced the safety and stability by replacing flammable liquids. Recent progress in solid-state Li–S (SSLS) batteries includes development of high-conductivity SSEs (sulfide, halide, polymer-ceramic composites), electrodes provided with the volume changes and minimize interfacial resistance, and improved cathode architectures for optimized ion/electron transport. This review comprehensively analyzes the development in solid-state lithium-sulfur (SSLS) batteries over the past decade. SSLS development is driven by the potential for higher energy density and enhanced safety that have been essential for next-generation energy storage.This review also focuses on solid electrolytes as the key enabler for solid-state lithium-sulfur (SSLS) battery performance, addressing the challenges associated with liquid electrolytes such as flammability, polysulfide shuttle, and lithium dendrite formation. Finally, the review highlights the importance of integrated cell design, where optimized electrode architectures and advanced solid electrolytes work synergistically to maximize performance..</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"81 ","pages":"Article 100552"},"PeriodicalIF":10.5,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Pressure-induced stereochemistry and lone pair (E) localization in BiF3: Ellipsoidal EBi 6s2 / EF 2s2 volumes, perichoresis, and phase transitions 压力诱导的立体化学和孤对(E)定位在bi3:椭球状ebi6s2 / EF 2s2体积,包膜和相变
IF 10.5 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-11-15 DOI: 10.1016/j.progsolidstchem.2025.100550
Samir F. Matar , Alicia Castro , Jean Galy
This original work investigates the high-pressure behavior of BiF3 polymorphs, with emphasis on the stereochemical activity and spatial localization of the 6s2 lone electron pair (E) of Bi3+and the 2 s2 Es of fluoride anions. Using density functional theory (DFT) and electron localization function (ELF) analyses, we characterize the evolution of α-, β-, and γ-BiF3E polymorphs and report two novel high-pressure phases, δ-BiF3E and κ-BiF3E, stabilized at approximately 70 GPa and above 200 GPa, respectively. The β-phase undergoes a clear phase transition near 70 GPa, where structural gliding of fluorine layers induces a symmetry shift from Pnma to Cmcm space group, corresponding to the δ-BiF3E phase. The δ-phase features a base-centered orthorhombic framework with perichoretic localization of the Bi 6s2 lone pair in multiple spatial positions. At pressures exceeding 200 GPa, a previously unobserved polymorph, κ-BiF3E, emerges with a penta-capped triangular antiprismatic coordination environment and a distorted screw-axis symmetry.
In this paper “perichoresis” is introduced as an original conceptual tool to describe the simultaneous localization of lone pairs in multiple spatial domains without invoking electronic delocalization.
The results provide insight into the high-pressure stereochemistry of heavy p-block compounds and offer a predictive model for lone pair behavior under compression.
本文研究了Bi3多晶态的高压行为,重点研究了Bi3+的6s2孤电子对(E)和氟离子的2s2 Es的立体化学活性和空间定位。利用密度泛函理论(DFT)和电子定位函数(ELF)分析了α-、β-和γ-BiF3E多晶型的演化特征,并报道了两个新的高压相δ-BiF3E和κ-BiF3E,它们分别稳定在约70 GPa和200 GPa以上。在70 GPa附近,β-相发生了明显的相变,氟层的结构滑动导致从Pnma到Cmcm空间群的对称位移,对应于δ-BiF3E相。δ相以碱基为中心的正交骨架为特征,Bi 6s2孤对在多个空间位置呈鞘周定位。在超过200gpa的压力下,一种以前未观察到的多晶体κ-BiF3E出现,具有五盖三角形反棱镜配位环境和扭曲的螺旋轴对称。本文提出了一种新颖的概念工具,即“外包电泳”来描述在多个空间域中孤对的同时定位,而无需调用电子离域。该结果为重p-嵌段化合物的高压立体化学提供了新的见解,并为压缩下的孤对行为提供了预测模型。
{"title":"Pressure-induced stereochemistry and lone pair (E) localization in BiF3: Ellipsoidal EBi 6s2 / EF 2s2 volumes, perichoresis, and phase transitions","authors":"Samir F. Matar ,&nbsp;Alicia Castro ,&nbsp;Jean Galy","doi":"10.1016/j.progsolidstchem.2025.100550","DOIUrl":"10.1016/j.progsolidstchem.2025.100550","url":null,"abstract":"<div><div>This original work investigates the high-pressure behavior of BiF<sub>3</sub> polymorphs, with emphasis on the stereochemical activity and spatial localization of the 6s<sup>2</sup> lone electron pair (E) of Bi<sup>3+</sup>and the 2 s<sup>2</sup> Es of fluoride anions. Using density functional theory (DFT) and electron localization function (ELF) analyses, we characterize the evolution of α-, β-, and γ-BiF<sub>3</sub>E polymorphs and report two novel high-pressure phases, δ-BiF<sub>3</sub>E and κ-BiF<sub>3</sub>E, stabilized at approximately 70 GPa and above 200 GPa, respectively. The β-phase undergoes a clear phase transition near 70 GPa, where structural gliding of fluorine layers induces a symmetry shift from <em>Pnma</em> to <em>Cmcm</em> space group, corresponding to the δ-BiF<sub>3</sub>E phase. The δ-phase features a base-centered orthorhombic framework with perichoretic localization of the Bi 6s<sup>2</sup> lone pair in multiple spatial positions. At pressures exceeding 200 GPa, a previously unobserved polymorph, κ-BiF<sub>3</sub>E, emerges with a penta-capped triangular antiprismatic coordination environment and a distorted screw-axis symmetry.</div><div>In this paper “perichoresis” is introduced as an original conceptual tool to describe the simultaneous localization of lone pairs in multiple spatial domains without invoking electronic delocalization.</div><div>The results provide insight into the high-pressure stereochemistry of heavy p-block compounds and offer a predictive model for lone pair behavior under compression.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100550"},"PeriodicalIF":10.5,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145568439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Capping stabilization mechanism of vanadate-stabilized δ-Bi2O3: Experimental and theoretical approaches 钒酸稳定δ-Bi2O3的旋盖稳定机理:实验与理论探讨
IF 10.5 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-10-18 DOI: 10.1016/j.progsolidstchem.2025.100549
Zhe-Hao Lin , Yu-Chun Wu
{"title":"Capping stabilization mechanism of vanadate-stabilized δ-Bi2O3: Experimental and theoretical approaches","authors":"Zhe-Hao Lin ,&nbsp;Yu-Chun Wu","doi":"10.1016/j.progsolidstchem.2025.100549","DOIUrl":"10.1016/j.progsolidstchem.2025.100549","url":null,"abstract":"","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100549"},"PeriodicalIF":10.5,"publicationDate":"2025-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis, structure and properties of substituted cobalt chalcogenides Co7(Se,Te)8 取代钴硫族化合物Co7(Se,Te)8的合成、结构与性质
IF 10.5 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-09-16 DOI: 10.1016/j.progsolidstchem.2025.100548
D.F. Akramov , N.V. Selezneva , E.M. Sherokalova , D.K. Kuznetsov , V.A. Kazantsev , N.V. Baranov
For the first time, polycrystalline samples of Co7(Se1–yTey)8 were synthesized in the entire concentration range (0 ≤ y ≤ 1) and studied by X-ray diffraction, scanning electron microscopy, and by thermal expansion, specific heat capacity and electrical resistivity measurements. Depending on the concentration of tellurium, the solid-phase reaction method (at y < 0.9) and melting method (at y ≥ 0.9) were used to obtain single-phase samples. A change in the crystal structure (P3121 → P-3m1 → P63/mmcP-3m1) due to the disordering of vacancies, significant anisotropy of the thermal atomic displacement, and anisotropic lattice expansion have been observed in this system when selenium is substituted with tellurium. According to specific heat measurements, an increase in tellurium concentration is accompanied by a decrease in the electronic specific heat coefficient, which indicates an increase in the metallicity of the system and is confirmed by electrical resistivity data. In substituted compounds using thermal expansion and temperature-dependent X-ray diffraction, spinodal decomposition of samples was detected upon heating. The second phase in dendritic form was observed using scanning electron microscopy on the surface of slowly cooled tellurium-rich sample.
首次合成了Co7(Se1-yTey)8在整个浓度范围(0≤y≤1)下的多晶样品,并通过x射线衍射、扫描电镜、热膨胀、比热容和电阻率测量对样品进行了研究。根据碲的浓度不同,分别采用固相反应法(y < 0.9)和熔融法(y≥0.9)获得单相样品。当硒被碲取代时,晶体结构发生了变化(P3121→P-3m1→P63/mmc→P-3m1),由于空位的无序性,热原子位移具有显著的各向异性,晶格扩展具有各向异性。根据比热测量,碲浓度的增加伴随着电子比热系数的降低,这表明体系的金属丰度增加,并得到电阻率数据的证实。在取代化合物中,使用热膨胀和温度相关的x射线衍射,在加热时检测到样品的spinodal分解。用扫描电镜观察慢冷富碲试样表面的第二相为枝晶。
{"title":"Synthesis, structure and properties of substituted cobalt chalcogenides Co7(Se,Te)8","authors":"D.F. Akramov ,&nbsp;N.V. Selezneva ,&nbsp;E.M. Sherokalova ,&nbsp;D.K. Kuznetsov ,&nbsp;V.A. Kazantsev ,&nbsp;N.V. Baranov","doi":"10.1016/j.progsolidstchem.2025.100548","DOIUrl":"10.1016/j.progsolidstchem.2025.100548","url":null,"abstract":"<div><div>For the first time, polycrystalline samples of Co<sub>7</sub>(Se<sub>1–<em>y</em></sub>Te<sub><em>y</em></sub>)<sub>8</sub> were synthesized in the entire concentration range (0 ≤ <em>y</em> ≤ 1) and studied by X-ray diffraction, scanning electron microscopy, and by thermal expansion, specific heat capacity and electrical resistivity measurements. Depending on the concentration of tellurium, the solid-phase reaction method (at <em>y</em> &lt; 0.9) and melting method (at <em>y</em> ≥ 0.9) were used to obtain single-phase samples. A change in the crystal structure (<em>P</em>3<sub>1</sub>21 → <em>P</em>-3<em>m</em>1 → <em>P</em>6<sub>3</sub>/<em>mmc</em> → <em>P</em>-3<em>m</em>1) due to the disordering of vacancies, significant anisotropy of the thermal atomic displacement, and anisotropic lattice expansion have been observed in this system when selenium is substituted with tellurium. According to specific heat measurements, an increase in tellurium concentration is accompanied by a decrease in the electronic specific heat coefficient, which indicates an increase in the metallicity of the system and is confirmed by electrical resistivity data. In substituted compounds using thermal expansion and temperature-dependent X-ray diffraction, spinodal decomposition of samples was detected upon heating. The second phase in dendritic form was observed using scanning electron microscopy on the surface of slowly cooled tellurium-rich sample.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100548"},"PeriodicalIF":10.5,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145109780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Temperature-induced structural phase transitions in inorganic compounds: symmetry and information-entropy analysis 无机化合物中温度诱导的结构相变:对称性和信息熵分析
IF 10.5 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-09-10 DOI: 10.1016/j.progsolidstchem.2025.100547
Sergey V. Krivovichev
The tendency of crystal-structure symmetry increasing under increasing temperature (also known as a ‘Landau rule’) is one of the major empirical observations with regard to the temperature-induced phase transitions. The validity of the rule was investigated by means of the statistical analysis of the 502 temperature-driven phase transitions in inorganic compounds with known crystal-structure information for all polymorphs. The analysis was performed from the viewpoint of symmetry considerations (that is, the analysis in terms of the crystal-system hierarchy, where cubic system is the highest and triclinic is the lowest) and information-entropy calculations. It was revealed that the information-based structural complexity parameters (most importantly, the total information content per reduced unit cell) are more sensitive structural symmetry indicators than the symmetry classification in terms of the crystal-system hierarchy. The information-entropy measures decrease under increasing temperature in more than 77 % of phase transitions under consideration, which corresponds to the overall rise of symmetry under heating (the ‘Landau rule’). In contrast, the simple symmetry analysis confirms the ‘Landau rule’ in 60 % of cases only. The information-based parameters are especially efficient for the cases, when crystal system does not change (most numerous are monoclinic-monoclinic and orthorhombic-orthorhombic transitions). The deviations from the rule of increasing symmetry correspond to: phase transition sequences with intermediate (transitional) structures of high complexity, isosymmetric and reentrant phase transitions, and transitions that involve low-temperature metastable polymorphs. There are some exceptions that cannot be assigned to any of the phase-transition types mentioned above, where symmetry is decreasing under heating. The symmetry breaking results in the decrease in vibrational entropy, which may be considered as a major driving force behind the ‘Landau rule’. However, various phenomena such as formation and breaking of bonds, charge and orbital ordering, stereoactive activity of lone electron pairs, etc., may seriously influence polymorphic transformations under temperature changes.
晶体结构对称性随温度升高而增加的趋势(也称为“朗道规则”)是关于温度诱导相变的主要经验观察之一。通过对已知晶体结构信息的无机化合物中502个温度驱动相变的统计分析,验证了该规律的有效性。分析是从对称考虑的角度进行的(即,根据晶体系统层次结构进行分析,其中立方系统最高,三斜系统最低)和信息熵计算。结果表明,基于信息的结构复杂性参数(最重要的是每个简化的单位胞的总信息量)是比对称分类更敏感的结构对称性指标。在考虑的相变中,超过77%的信息熵测量值随着温度的升高而降低,这对应于加热下对称性的整体上升(“朗道规则”)。相比之下,简单的对称分析只在60%的情况下证实了“朗道规则”。在晶体系统不发生变化的情况下(大多数是单斜-单斜和正交-正交转变),基于信息的参数特别有效。与增加对称性规则的偏离对应于:具有高复杂性的中间(过渡)结构的相变序列,等对称和可重入的相变,以及涉及低温亚稳态多晶的相变。有一些例外不能被分配到上述任何相变类型,其中对称性在加热下下降。对称性破缺导致振动熵的减少,这可能被认为是“朗道规则”背后的主要驱动力。然而,各种现象,如键的形成和断裂、电荷和轨道的排序、孤电子对的立体活性等,都可能严重影响温度变化下的多晶转变。
{"title":"Temperature-induced structural phase transitions in inorganic compounds: symmetry and information-entropy analysis","authors":"Sergey V. Krivovichev","doi":"10.1016/j.progsolidstchem.2025.100547","DOIUrl":"10.1016/j.progsolidstchem.2025.100547","url":null,"abstract":"<div><div>The tendency of crystal-structure symmetry increasing under increasing temperature (also known as a ‘Landau rule’) is one of the major empirical observations with regard to the temperature-induced phase transitions. The validity of the rule was investigated by means of the statistical analysis of the 502 temperature-driven phase transitions in inorganic compounds with known crystal-structure information for all polymorphs. The analysis was performed from the viewpoint of symmetry considerations (that is, the analysis in terms of the crystal-system hierarchy, where cubic system is the highest and triclinic is the lowest) and information-entropy calculations. It was revealed that the information-based structural complexity parameters (most importantly, the total information content per reduced unit cell) are more sensitive structural symmetry indicators than the symmetry classification in terms of the crystal-system hierarchy. The information-entropy measures decrease under increasing temperature in more than 77 % of phase transitions under consideration, which corresponds to the overall rise of symmetry under heating (the ‘Landau rule’). In contrast, the simple symmetry analysis confirms the ‘Landau rule’ in 60 % of cases only. The information-based parameters are especially efficient for the cases, when crystal system does not change (most numerous are monoclinic-monoclinic and orthorhombic-orthorhombic transitions). The deviations from the rule of increasing symmetry correspond to: phase transition sequences with intermediate (transitional) structures of high complexity, isosymmetric and reentrant phase transitions, and transitions that involve low-temperature metastable polymorphs. There are some exceptions that cannot be assigned to any of the phase-transition types mentioned above, where symmetry is decreasing under heating. The symmetry breaking results in the decrease in vibrational entropy, which may be considered as a major driving force behind the ‘Landau rule’. However, various phenomena such as formation and breaking of bonds, charge and orbital ordering, stereoactive activity of lone electron pairs, etc., may seriously influence polymorphic transformations under temperature changes.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100547"},"PeriodicalIF":10.5,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Plate-like NiCo2O4 integrated with g-C3N4 nanostructures for hybrid supercapacitors and green energy technologies 集成了g-C3N4纳米结构的片状NiCo2O4用于混合超级电容器和绿色能源技术
IF 10.5 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-09-08 DOI: 10.1016/j.progsolidstchem.2025.100546
Ehtisham Umar , Fozia Shaheen , M. Waqas Iqbal , Mohammed T. Alotaibi , Amel Ayari-Akkari , Ali Akremi , Eman Kashita
The development of nanostructured electrode materials for supercapacitors and green energy applications remains a challenging task, particularly in achieving maximum surface area for optimal electrode-electrolyte interaction. In this study, we synthesize interconnected nanostructured NiCo2O4/g-C3N4 using a cost-effective hydrothermal method. The NiCo2O4/g-C3N4 nanocomposite undergoes comprehensive characterization to analyze its structural, morphological, and electrochemical properties using various techniques. Electrodes fabricated from the NiCo2O4/g-C3N4 material exhibit a high specific capacity (Qs) of 203 C/g. Additionally, the as-fabricated asymmetric supercapacitor (ASC) achieves a remarkable energy density (Ed) of 87.3 Wh/kg and a power density (Pd) of 1038 W/kg at 1.4 A/g, with superior cycling performance, retaining 95.04 % of its capacity after 10,000 cycles. Furthermore, we evaluate the modified NiCo2O4/g-C3N4 electrodes for their electrocatalytic performance in the oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The results indicate that the NiCo2O4/g-C3N4 electrode exhibits the best OER performance (overpotential (η) = 287 mV and Tafel slope = 121 mV/dec at 10 mA/cm2) and demonstrates excellent HER activity (η = 336 mV and Tafel slope = 93 mV/dec at −10 mA/cm2) with exceptional cyclic stability. This research highlights the potential of NiCo2O4/g-C3N4 as a promising material for supercapacitor and green energy technology.
用于超级电容器和绿色能源应用的纳米结构电极材料的开发仍然是一项具有挑战性的任务,特别是在实现最佳电极-电解质相互作用的最大表面积方面。在本研究中,我们采用经济高效的水热法合成了互连的纳米结构NiCo2O4/g-C3N4。采用各种技术对NiCo2O4/g-C3N4纳米复合材料进行了结构、形态和电化学性能的综合表征。NiCo2O4/g- c3n4材料制备的电极具有203 C/g的高比容量(Qs)。此外,所制备的非对称超级电容器(ASC)在1.4 a /g下的能量密度(Ed)为87.3 Wh/kg,功率密度(Pd)为1038 W/kg,具有优异的循环性能,在10,000次循环后仍能保持95.04%的容量。此外,我们还对改性NiCo2O4/g-C3N4电极在析氧反应(OER)和析氢反应(HER)中的电催化性能进行了评价。结果表明,NiCo2O4/g-C3N4电极表现出最佳的OER性能(10 mA/cm2时过电位(η) = 287 mV, Tafel斜率= 121 mV/dec),并表现出优异的HER活性(- 10 mA/cm2时η = 336 mV, Tafel斜率= 93 mV/dec)和优异的循环稳定性。这项研究突出了NiCo2O4/g-C3N4作为超级电容器和绿色能源技术的有前途的材料的潜力。
{"title":"Plate-like NiCo2O4 integrated with g-C3N4 nanostructures for hybrid supercapacitors and green energy technologies","authors":"Ehtisham Umar ,&nbsp;Fozia Shaheen ,&nbsp;M. Waqas Iqbal ,&nbsp;Mohammed T. Alotaibi ,&nbsp;Amel Ayari-Akkari ,&nbsp;Ali Akremi ,&nbsp;Eman Kashita","doi":"10.1016/j.progsolidstchem.2025.100546","DOIUrl":"10.1016/j.progsolidstchem.2025.100546","url":null,"abstract":"<div><div>The development of nanostructured electrode materials for supercapacitors and green energy applications remains a challenging task, particularly in achieving maximum surface area for optimal electrode-electrolyte interaction. In this study, we synthesize interconnected nanostructured NiCo<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub> using a cost-effective hydrothermal method. The NiCo<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub> nanocomposite undergoes comprehensive characterization to analyze its structural, morphological, and electrochemical properties using various techniques. Electrodes fabricated from the NiCo<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub> material exhibit a high specific capacity (Qs) of 203 C/g. Additionally, the as-fabricated asymmetric supercapacitor (ASC) achieves a remarkable energy density (Ed) of 87.3 Wh/kg and a power density (Pd) of 1038 W/kg at 1.4 A/g, with superior cycling performance, retaining 95.04 % of its capacity after 10,000 cycles. Furthermore, we evaluate the modified NiCo<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub> electrodes for their electrocatalytic performance in the oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The results indicate that the NiCo<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub> electrode exhibits the best OER performance (overpotential (<em>η</em>) = 287 mV and Tafel slope = 121 mV/dec at 10 mA/cm<sup>2</sup>) and demonstrates excellent HER activity (<em>η</em> = 336 mV and Tafel slope = 93 mV/dec at −10 mA/cm<sup>2</sup>) with exceptional cyclic stability. This research highlights the potential of NiCo<sub>2</sub>O<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub> as a promising material for supercapacitor and green energy technology.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100546"},"PeriodicalIF":10.5,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Insight into Bi-Sb alloys and their chalcogenide compounds for sodium/potassium ion battery (SIB/PIB) anodes 钠/钾离子电池(SIB/PIB)阳极用Bi-Sb合金及其硫系化合物的研究
IF 10.5 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-09-03 DOI: 10.1016/j.progsolidstchem.2025.100545
Defei Li, Ming-Chun Zhao, Tong Yuan, Ke Cui, Fuqin Zhang
Sodium/potassium ion batteries (SIBs/PIBs), emerging as promising alternatives to lithium-ion batteries (LIBs), show great potential in large-scale electrical energy storage systems owing to their abundant reserves, potential cost advantages, and low standard redox potentials. In recent years, Bi-Sb alloys and their chalcogenide compounds (sulfides, selenides, and tellurides) have garnered significant attention due to their unique bimetallic synergistic effects and tunable energy storage mechanisms. This paper reviews the recent progress in Bi-Sb alloys and their chalcogenide compounds as anode materials for SIBs and PIBs. Highlighting the synergistic effects of Bi-Sb systems, the study emphasizes their high theoretical capacity, reduced volume expansion, and enhanced structural stability compared to monometallic counterparts. Key strategies such as nano-structuring (e.g., nanoporous and 2D layered architectures), composite engineering (e.g., carbon-based matrices), and heterostructure design are discussed to address challenges like electrode pulverization. The electrochemical mechanisms, including multi-step alloying and conversion reactions, are analyzed to elucidate performance enhancements in terms of cycling stability, rate capability, and capacity retention. Specifically, the paper examines the structural properties, modification strategies, and performance optimization mechanisms of these materials, and identifies key pathways for their engineering applications, aiming to provide theoretical support and technological references for designing high-capacity anode materials for SIBs/PIBs. Additionally, critical issues, challenges, and prospects for further development are suggested. This work provides critical insights into material design principles and offers pathways for developing next-generation, cost-effective energy storage technologies.
钠/钾离子电池(SIBs/PIBs)作为锂离子电池(LIBs)的潜在替代品,由于其储量丰富、潜在的成本优势和低标准氧化还原电位,在大规模电能存储系统中显示出巨大的潜力。近年来,铋锑合金及其硫族化合物(硫化物、硒化物和碲化物)因其独特的双金属协同效应和可调的储能机制而受到广泛关注。本文综述了近年来铋锑合金及其硫族化合物作为SIBs和PIBs阳极材料的研究进展。该研究强调了Bi-Sb体系的协同效应,与单金属体系相比,它们具有更高的理论容量、更小的体积膨胀和更高的结构稳定性。讨论了纳米结构(如纳米多孔和二维层状结构)、复合材料工程(如碳基矩阵)和异质结构设计等关键策略,以解决电极粉化等挑战。分析了电化学机制,包括多步合金化和转化反应,以阐明在循环稳定性,速率能力和容量保持方面的性能增强。具体而言,本文研究了这些材料的结构特性、改性策略和性能优化机制,并确定了其工程应用的关键途径,旨在为sib / pib高容量阳极材料的设计提供理论支持和技术参考。此外,还提出了关键问题、挑战和进一步发展的前景。这项工作为材料设计原理提供了重要的见解,并为开发下一代具有成本效益的储能技术提供了途径。
{"title":"Insight into Bi-Sb alloys and their chalcogenide compounds for sodium/potassium ion battery (SIB/PIB) anodes","authors":"Defei Li,&nbsp;Ming-Chun Zhao,&nbsp;Tong Yuan,&nbsp;Ke Cui,&nbsp;Fuqin Zhang","doi":"10.1016/j.progsolidstchem.2025.100545","DOIUrl":"10.1016/j.progsolidstchem.2025.100545","url":null,"abstract":"<div><div>Sodium/potassium ion batteries (SIBs/PIBs), emerging as promising alternatives to lithium-ion batteries (LIBs), show great potential in large-scale electrical energy storage systems owing to their abundant reserves, potential cost advantages, and low standard redox potentials. In recent years, Bi-Sb alloys and their chalcogenide compounds (sulfides, selenides, and tellurides) have garnered significant attention due to their unique bimetallic synergistic effects and tunable energy storage mechanisms. This paper reviews the recent progress in Bi-Sb alloys and their chalcogenide compounds as anode materials for SIBs and PIBs. Highlighting the synergistic effects of Bi-Sb systems, the study emphasizes their high theoretical capacity, reduced volume expansion, and enhanced structural stability compared to monometallic counterparts. Key strategies such as nano-structuring (e.g., nanoporous and 2D layered architectures), composite engineering (e.g., carbon-based matrices), and heterostructure design are discussed to address challenges like electrode pulverization. The electrochemical mechanisms, including multi-step alloying and conversion reactions, are analyzed to elucidate performance enhancements in terms of cycling stability, rate capability, and capacity retention. Specifically, the paper examines the structural properties, modification strategies, and performance optimization mechanisms of these materials, and identifies key pathways for their engineering applications, aiming to provide theoretical support and technological references for designing high-capacity anode materials for SIBs/PIBs. Additionally, critical issues, challenges, and prospects for further development are suggested. This work provides critical insights into material design principles and offers pathways for developing next-generation, cost-effective energy storage technologies.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"80 ","pages":"Article 100545"},"PeriodicalIF":10.5,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145005038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Cation substitution enabled electron rearrangement in high-entropy perovskite oxides for enhanced supercapacitor performance 阳离子取代使高熵钙钛矿氧化物中的电子重排增强了超级电容器的性能
IF 9.1 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-06-24 DOI: 10.1016/j.progsolidstchem.2025.100536
Xiaoying Hu, Bo Wang, Xiaotong Zhou, Junzhi Li
The controllable synthesis of high-entropy perovskite oxides and the modulation of their electronic structures are crucial for enhancing the electrochemical performance of supercapacitors. However, it remains challenging to regulate the electronic configuration of B-site elements via A-site doping. In this study, we have reconstructed the electron configuration of B-site elements in high-entropy perovskites through Sm doping, and obtained high-entropy perovskite oxides La1-xSmx (Mn0·2Fe0·2Co0·2Ni0·2Cr0.2)O3 (LaSmTMO3−x) with abundant valence states. The fabricated LaSmTMO3−0.2 exhibits high specific capacitance of 1367.3 F g−1 at 0.5 A g−1. Besides, the asymmetric supercapacitor (ASC) based on LaSmTMO3−0.2 exhibits an impressive energy density of 41.2 Wh kg−1 at a power density of 400 W kg−1, with a specific capacity retention of 87.1 % after 10000 cycles. The experimental results demonstrate that superior supercapacitor performance can be attributed to electron rearrangement induced by Sm doping, leading to the formation of active metal species with multiple oxidation states. Simultaneously, Sm doping significantly improves structural integrity, electronic conductivity, and ion transfer kinetics. This work emphasizes the importance of A-site regulation of high entropy perovskite oxides for improving electrochemical performance and provides A new direction for the design of perovskite oxides in energy storage and conversion systems.
高熵钙钛矿氧化物的可控合成及其电子结构的调制是提高超级电容器电化学性能的关键。然而,通过掺杂a位来调节b位元素的电子构型仍然具有挑战性。本研究通过Sm掺杂重建了高熵钙钛矿中b位元素的电子构型,得到了价态丰富的高熵钙钛矿氧化物La1-xSmx (Mn0·2Fe0·2Co0·2Ni0·2Cr0.2)O3 (LaSmTMO3−x)。制备的LaSmTMO3−0.2在0.5 A g−1时具有1367.3 F g−1的高比电容。此外,基于LaSmTMO3−0.2的非对称超级电容器(ASC)在功率密度为400 W kg−1时,能量密度为41.2 Wh kg−1,循环10000次后比容量保持率为87.1%。实验结果表明,优异的超级电容器性能可归因于Sm掺杂引起的电子重排,从而形成具有多种氧化态的活性金属。同时,Sm掺杂显著改善了结构完整性、电子导电性和离子转移动力学。本研究强调了高熵钙钛矿氧化物的A位调控对提高电化学性能的重要性,为钙钛矿氧化物在储能和转换系统中的设计提供了新的方向。
{"title":"Cation substitution enabled electron rearrangement in high-entropy perovskite oxides for enhanced supercapacitor performance","authors":"Xiaoying Hu,&nbsp;Bo Wang,&nbsp;Xiaotong Zhou,&nbsp;Junzhi Li","doi":"10.1016/j.progsolidstchem.2025.100536","DOIUrl":"10.1016/j.progsolidstchem.2025.100536","url":null,"abstract":"<div><div>The controllable synthesis of high-entropy perovskite oxides and the modulation of their electronic structures are crucial for enhancing the electrochemical performance of supercapacitors. However, it remains challenging to regulate the electronic configuration of B-site elements via A-site doping. In this study, we have reconstructed the electron configuration of B-site elements in high-entropy perovskites through Sm doping, and obtained high-entropy perovskite oxides La<sub>1-x</sub>Sm<sub>x</sub> (Mn<sub>0·2</sub>Fe<sub>0·2</sub>Co<sub>0·2</sub>Ni<sub>0·2</sub>Cr<sub>0.2</sub>)O<sub>3</sub> (LaSmTMO<sub>3</sub>−x) with abundant valence states. The fabricated LaSmTMO<sub>3</sub>−0.2 exhibits high specific capacitance of 1367.3 F g<sup>−1</sup> at 0.5 A g<sup>−1</sup>. Besides, the asymmetric supercapacitor (ASC) based on LaSmTMO<sub>3</sub>−0.2 exhibits an impressive energy density of 41.2 Wh kg<sup>−1</sup> at a power density of 400 W kg<sup>−1</sup>, with a specific capacity retention of 87.1 % after 10000 cycles. The experimental results demonstrate that superior supercapacitor performance can be attributed to electron rearrangement induced by Sm doping, leading to the formation of active metal species with multiple oxidation states. Simultaneously, Sm doping significantly improves structural integrity, electronic conductivity, and ion transfer kinetics. This work emphasizes the importance of A-site regulation of high entropy perovskite oxides for improving electrochemical performance and provides A new direction for the design of perovskite oxides in energy storage and conversion systems.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"79 ","pages":"Article 100536"},"PeriodicalIF":9.1,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144513655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
期刊
Progress in Solid State Chemistry
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1