Chemistry of Materials最新文献_第7页

Lithiophilic Covalent Organic Framework-Bridged Interface Enables Fast Ion Transport in Ultrathin Gel Polymer Electrolyte Membranes 亲锂共价有机框架-桥接界面实现超薄凝胶聚合物电解质膜中的快速离子传输

IF 7.1 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-17 DOI: 10.1021/acs.chemmater.6c01447

Hongmin Guo, Lu Yan, Chenxi Li, Yuan Zhong, Weizong Wang, Shuang Long, Hui Liu, Yaqiong Su, Liangwei Fu, Bingqing Xu, Gen Zhang

{"title":"Lithiophilic Covalent Organic Framework-Bridged Interface Enables Fast Ion Transport in Ultrathin Gel Polymer Electrolyte Membranes","authors":"Hongmin Guo, Lu Yan, Chenxi Li, Yuan Zhong, Weizong Wang, Shuang Long, Hui Liu, Yaqiong Su, Liangwei Fu, Bingqing Xu, Gen Zhang","doi":"10.1021/acs.chemmater.6c01447","DOIUrl":"10.1021/acs.chemmater.6c01447","url":null,"abstract":"Gelpolymer electrolytes (GPEs) require a homogeneouspolymericstructure, processability, and excellent chemical stability for high-performancelithium metal battery configurations. However, heterogeneous electrolytepolymerization, which constrains ion transport, limits the practicaldeployment of GPEs. Herein, a universal interface engineering strategyis proposed to construct an oligomer-functionalized covalent organicframework bridging layer on PVDF nanofibers, which bridges the GPEand forms an integrated architecture. Its distinctive nanoconfinementeffect efficiently immobilizes guest molecules and homogenizes theLi+ flux, thereby connecting the two phases to form a homogeneous,continuous ion-conductive network. The modified electrolyte with aminimal thickness of 17 μm exhibits significantly enhanced ionicconductivity, reaching 2.96 × 10–4 S cm–1 at 30 °C. Additionally, Li|Li symmetric cellswith the modified electrolyte can achieve highly stable cycling over1000 h at 0.2 mA cm–2, and the LFP|Li cells demonstrateexceptional electrochemical performance, achieving 98.35% capacityretention after 200 cycles at 1 C rate. As a broadly applicable approach,this strategy not only provides enhanced structural integrity butalso forms continuous Li+ transport channels, offeringconsiderable potential for practical application in high-performanceenergy storage systems.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10001–10012"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973931","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Regioisomeric Fluorination in Donor–Acceptor Conjugated Polymers for Organic Thermoelectrics 有机热电用给受体共轭聚合物的区域异构体氟化

IF 7.1 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-24 DOI: 10.1021/acs.chemmater.6c01323

Guan-Lin Chen, Jhih-Min Lin, Leeyih Wang, Cheng-Liang Liu

{"title":"Regioisomeric Fluorination in Donor–Acceptor Conjugated Polymers for Organic Thermoelectrics","authors":"Guan-Lin Chen, Jhih-Min Lin, Leeyih Wang, Cheng-Liang Liu","doi":"10.1021/acs.chemmater.6c01323","DOIUrl":"10.1021/acs.chemmater.6c01323","url":null,"abstract":"Fluorinated donor–acceptor(D–A) conjugated polymersare promising organic thermoelectric (OTE) materials; however, theeffects of fluorination pattern on their charge transport and dopingbehavior remain unclear. Herein, we present a regioisomeric designstrategy wherein fluorine atoms were selectively introduced into eitherthe donor or acceptor unit of benzothiadiazole-quaterthiophene polymersto generate F-D and F-A, respectively. This regioselective fluorinationinduced distinct molecular conformations and electronic distributions,thereby influencing charge transport and charge transfer with moleculardopants. Consequently, the donor-fluorinated polymer F-D exhibitedenhanced backbone planarity, higher carrier mobility, and a more favorablebalance between carrier concentration and the Seebeck coefficient.Specifically, doped F-D achieved a higher maximum power factor of43.5 μW m–1 K–2 than F-A(23.0 μW m–1 K–2) and deliveredsuperior thermoelectric performance, with figures of merit of 0.056for F-D and 0.026 for F-A. Notably, F-D also exhibited greater airstability, retaining 82% of its initial power factor after 7 daysunder ambient conditions, compared with 39% for F-A. Collectively,these results highlight the critical role of fluorinated regioisomerismin determining the thermoelectric performance and air stability ofD–A conjugated polymers, thereby providing valuable guidancefor the molecular design of advanced OTE materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9939–9948"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049213","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Semiautomated Synthesis and Interactive Visualization of Zeolitic Imidazolate Framework-Based Biocomposites 咪唑酸分子筛骨架生物复合材料的半自动合成与交互可视化

IF 7.1 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-29 DOI: 10.1021/acs.chemmater.6c01702

Xue Chen, Aleksandar Kondinski, Jing Yang, Helmar Wiltsche, Bernd Nidetzky, Francesco Carraro, Paolo Falcaro

{"title":"Semiautomated Synthesis and Interactive Visualization of Zeolitic Imidazolate Framework-Based Biocomposites","authors":"Xue Chen, Aleksandar Kondinski, Jing Yang, Helmar Wiltsche, Bernd Nidetzky, Francesco Carraro, Paolo Falcaro","doi":"10.1021/acs.chemmater.6c01702","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01702","url":null,"abstract":"Zeolitic imidazolateframework (ZIF) biocomposites are widely studiedfor their potential in biocatalysis and biomedicine. However, theirpreparation is highly sensitive to precursor composition, concentration,washing conditions, and operator-dependent handling procedures. Here,we combine a semiautomated syringe-pump system, high-throughput samplepreparation, and digital data visualization to map synthesis–structure–propertyrelationships in ZIF biocomposites. A programmable four-syringe pumpplatform was used to systematically prepare 360 distinct samples intriplicate, yielding 1080 samples. The investigated synthetic parameterswere relative amounts of metal, ligand, protein, the total precursorconcentration, and the washing protocol. Structural, chemical, andfunctional characterization yielded a data set of ∼2250 entriescomprising crystalline-to-amorphous ratios, IR-based protein-to-frameworkratios, encapsulation efficiency, and loading capacity. We note thatexploring such a large data set manually can be challenging and thatcurrent static visualizations can hide meaningful trends. With theaim of enabling a customized and interactive exploration of the data,we designed the ZIF Biocomposite Explorer App (ZIF-BEA), which supportsuser-defined navigation in the space of the variables, providing directaccess to experimental data and material properties. We anticipatethat integrating large experimental data sets with interactive digitalplatforms may expedite the design of MOF-based biocomposites, whileproviding a transferable tool for the exploration of other classesof functional materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10135–10148"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

In-situ Electrochemical Spectroscopic Ellipsometry Characterization of Polymer and MXene Films 聚合物和MXene薄膜的原位电化学光谱椭偏表征

IF 7.1 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-10-01 DOI: 10.1021/acs.chemmater.6c00768

Hui Fang, Manushree Tanwar, Hannah S. Nedzbala, Anupma Thakur, Sophia LaPorta, Howe Chen, Colton J. Sheehan, Babak Anasori, James M. Mayer, Zahra Fakhraai

{"title":"In-situ Electrochemical Spectroscopic Ellipsometry Characterization of Polymer and MXene Films","authors":"Hui Fang, Manushree Tanwar, Hannah S. Nedzbala, Anupma Thakur, Sophia LaPorta, Howe Chen, Colton J. Sheehan, Babak Anasori, James M. Mayer, Zahra Fakhraai","doi":"10.1021/acs.chemmater.6c00768","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c00768","url":null,"abstract":"In-situ electrochemical spectroscopicellipsometry(EC-SE) can enable real-time monitoring of optical properties andthickness changes of surfaces and thin films. This method can providea broad range of information on the evolution of the microenvironmentof an electrode during electrochemical reactions. However, to avoidmodeling artifacts, accurate data analysis is critical. Here, we outlinekey steps in data analysis that can help prevent overfitting and misinterpretationof results. For example, determining the refractive index of the electrolyteat the air/electrolyte interface, along with measurements of the electrode’sdielectric data in dry conditions, can yield more accurate resultsthan simultaneous fitting of all parameters for the electrolyte andelectrode. We also present detailed modeling strategies tailored tofitting in-situ cyclic voltammetry (CV) data on varioustypes of thin films, by providing two distinct examples: the thicknesschange of catalyst polymer films due to swelling by the electrolyte,and the simultaneous change in thickness and optical properties ofTi3C2Tx MXene filmsdue to both reversible (electrochromic effect) and irreversible (degradation)processes. These details can help guide the informed selection ofmodels in similar conditions by providing practical guidelines. Thestep-by-step approach to modeling can be more broadly adopted to enhancethe accuracy and reproducibility of EC-SE experiments for interfacialstudies relevant to energy conversion and storage, as well as otherelectrochemical reactions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9736–9753"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Sub-Surface Patterning of Polymers with Inorganics by Area-Selective Vapor Phase Infiltration 无机物聚合物的区域选择性气相渗透亚表面图案化

IF 7.1 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-10-01 DOI: 10.1021/acs.chemmater.6c01454

Silvia Mirallas García, Gabriele Botta, Ivan Pavlov, Christopher Tollan, Evgeny Modin, Beatriz Martín-García, Mato Knez

{"title":"Sub-Surface Patterning of Polymers with Inorganics by Area-Selective Vapor Phase Infiltration","authors":"Silvia Mirallas García, Gabriele Botta, Ivan Pavlov, Christopher Tollan, Evgeny Modin, Beatriz Martín-García, Mato Knez","doi":"10.1021/acs.chemmater.6c01454","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01454","url":null,"abstract":"The inherent flexibility and processability of polymersmake themindispensable for next-generation flexible electronics, yet theirintrinsic electrical properties remain critical bottlenecks. A powerfulworkaround lies in hybrid materials that challenge this bottleneckby merging organic and inorganic components to unlock unprecedentedfunctionalities through synergies. Beyond composition, area-selectivefunctionalization is equally critical to the practical constructionof electronic devices. Here, we demonstrate infiltration of ZnO intoa lithographically patterned poly(ethylene terephthalate) (PET) matrix,locally transferring the pattern to the polymer subsurface. Followingour approach of area-selective vapor-phase infiltration (AS-VPI),both the region and the depth of infiltration become controllable,even to the micrometer scale. With linear patterns, we demonstrateanisotropic electrical conductivity, showing a difference in resistanceof more than 7 orders of magnitude between directions parallel andperpendicular to the infiltrated pattern. The benefit of using VPIto embed ZnO within the polymeric matrix rather than simply coatingthe surface is demonstrated by the preservation of electrical resistanceafter bending and deliberate scratching of the sample, as conductivepathways in the subsurface maintain current flow. AS-VPI is thereforedemonstrated as an effective strategy for producing electrically functionalizedpolymers suitable for the design of flexible and wearable electronicdevices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10013–10023"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173469","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Direct Cytosolic Protein Delivery via Near-Infrared-Driven Membrane-Intercalating Conjugated Oligoelectrolytes 通过近红外驱动的膜插层共轭寡电解质直接传递细胞质蛋白

IF 7.1 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-28 DOI: 10.1021/acs.chemmater.6c01810

Xue Zhai, Fangxin Xu, Peng Su, Zhentao Xie, Tianqi Liu, Tianyu Zhou, Miaomiao Xu, Biqing Bao, Lianhui Wang

{"title":"Direct Cytosolic Protein Delivery via Near-Infrared-Driven Membrane-Intercalating Conjugated Oligoelectrolytes","authors":"Xue Zhai, Fangxin Xu, Peng Su, Zhentao Xie, Tianqi Liu, Tianyu Zhou, Miaomiao Xu, Biqing Bao, Lianhui Wang","doi":"10.1021/acs.chemmater.6c01810","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01810","url":null,"abstract":"The intracellular delivery of functional proteins remainsa majorchallenge due to the impermeability of the plasma membrane and inefficientendosomal escape. Here, we report a membrane-intercalating conjugatedoligoelectrolyte (MI-COE, BBTN) that enables near-infrared (NIR)-triggereddirect cytosolic protein delivery through molecular photoporation.Distinct from conventional carriers that require complex formulationsand rely on endocytic uptake, BBTN spontaneously inserts into thelipid bilayer, enabling localized NIR-responsive membrane modulation.Upon mild NIR irradiation, BBTN induces transient and reversible membranepermeabilization, facilitating the direct transport of proteins intothe cytosol while maintaining high cell viability. This loading-freeplatform exhibits broad compatibility with diverse proteins, includingfluorescent proteins (GFP and R-PE), enzymes (β-galactosidaseand horseradish peroxidase), and therapeutic proteins (caspase 3 andRNase A), while preserving their biological functions after delivery.Furthermore, BBTN enables NIR-II fluorescence imaging-guided proteindelivery in vivo and enhances the therapeutic efficacy of RNase Aagainst solid tumors. These results establish membrane-intercalatingconjugated oligoelectrolytes as a versatile materials platform forintracellular macromolecular delivery and biomedical applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10162–10173"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173791","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High-Throughput Discovery of Superionic Conductors Featuring Symmetrically Equivalent Interstitial Sites 具有对称等效间隙位的超离子导体的高通量发现

IF 7.1 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-09-23 DOI: 10.1021/acs.chemmater.6c01341

Xizhe Zhang, Yizhou Zhu

{"title":"High-Throughput Discovery of Superionic Conductors Featuring Symmetrically Equivalent Interstitial Sites","authors":"Xizhe Zhang, Yizhou Zhu","doi":"10.1021/acs.chemmater.6c01341","DOIUrl":"10.1021/acs.chemmater.6c01341","url":null,"abstract":"Superionic conductors exhibit exceptionally high ionicconductivity,making them crucial in next-generation solid-state batteries and solidoxide fuel cells. However, their scarcity remains an obstacle to practicalapplications, and current discovery strategies are largely guidedby chemistry-specific design principles. Here, we observed that thelow-temperature phases of a few well-known superionic conductors containinterstitial sites that possess nearly identical local chemical environmentsto those of lattice sites, which become activated at elevated temperaturesand facilitate ion transport. Based on this insight, we proposed asymmetry-based strategy to identify materials containing symmetry-equivalentinterstitial sites that satisfy similarity in local chemical environments.By integrating high-throughput screening with molecular dynamics simulationsbased on a universal machine-learning force field, we identified five,four, and three new oxygen-based, lithium-based, and sodium-basedsuperionic conductors with ionic diffusion properties comparable toleading materials, respectively. Diffusion pathway analysis confirmsthat these interstitial sites contribute to forming interconnectedconduction channels at elevated temperatures. Our work introducesa general design principle and a computationally efficient approachfor accelerating the discovery of superionic conductors.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9949–9960"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Accelerating Identification of Relevant Polarons in Batteries 加速电池中相关极化子的识别

IF 7.1 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-10-01 DOI: 10.1021/acs.chemmater.6c00709

Tavinder Singh, Yu-Te Chan, Shoeb Athar, Christoph Scheurer, Matthias Kick, Harald Oberhofer

{"title":"Accelerating Identification of Relevant Polarons in Batteries","authors":"Tavinder Singh, Yu-Te Chan, Shoeb Athar, Christoph Scheurer, Matthias Kick, Harald Oberhofer","doi":"10.1021/acs.chemmater.6c00709","DOIUrl":"10.1021/acs.chemmater.6c00709","url":null,"abstract":"Many of the materialsunder consideration as battery electrodesare known to exhibit polarons─charge carriers localized throughpolarizing their environments, which are unfortunately quite costlyto tackle by theory. Next to costly ab initio methods and geometryoptimizations, the main problem is the sheer number of possible configurationspolarons can adopt in a material. This problem is exacerbated by symmetry-breakingdefects such as oxygen vacancies ubiquitous in oxide materials. Fortunately,a majority of polaron configurations tend to be too high in energyto ever be adopted at normal operating temperatures. In this work,we therefore present a data-driven approach based on gradient-boosteddecision trees as a descriptor for relative polaron energies. We demonstratethe efficacy of this approach to weed out those configurations thatare energetically unlikely in three simulation cells of defected spinelLithium4Titanium5Oxygen12 (LTO).The first two cells differ by their 16d-site occupational disorderand the position of the oxygen vacancy, which in both cases leadsto the formation of two polarons in the cells. In contrast, the thirdsimulation cell contains an extra lithium ion, which leads to threepolarons. Our approach allows us to reduce the number of necessaryfirst-principles calculations by roughly two-thirds. It can easilybe adapted to other materials and simulation cells, greatly speedingup their theoretical treatment.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"9782–9790"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090880","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Lithium Makes the Difference─Evolution of Lithium Vacancy Disorder during Temperature-Induced Phase Transitions of the Li-Ion Conductor Li4SnS4 锂离子导体Li4SnS4温度诱导相变过程中锂空位无序的演化

IF 7.1 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 Epub Date: 2026-10-01 DOI: 10.1021/acs.chemmater.6c02187

Lucas G. Balzat, Sebastian Bette, Jakob Blahusch, Christian Schneider, Emmanuelle Suard, Anjali Menakath, Kristina Gjorgjevikj, Simon Krause, Bettina V. Lotsch

{"title":"Lithium Makes the Difference─Evolution of Lithium Vacancy Disorder during Temperature-Induced Phase Transitions of the Li-Ion Conductor Li4SnS4","authors":"Lucas G. Balzat, Sebastian Bette, Jakob Blahusch, Christian Schneider, Emmanuelle Suard, Anjali Menakath, Kristina Gjorgjevikj, Simon Krause, Bettina V. Lotsch","doi":"10.1021/acs.chemmater.6c02187","DOIUrl":"10.1021/acs.chemmater.6c02187","url":null,"abstract":"Sulfide-based lithium-ionsolid electrolytes are promisingcandidatesfor solid-state batteries due to their high ionic conductivities,although they typically exhibit high moisture sensitivity. Li4SnS4 has recently attracted scientific interestbecause it exhibits higher moisture resistance than most other sulfideelectrolytes. Two orthorhombic Li4SnS4 polymorphs(α and β) are known, yet their temperature-dependent phasebehavior remains unexplored. Differential scanning calorimetry andtemperature-dependent powder X-ray diffraction revealed that α-Li4SnS4 transitions to β-Li4SnS4 at 96 °C. Furthermore, we identified a second, previouslyunknown reversible phase transition from β-Li4SnS4 to a new γ-polymorph at 196 °C. Other phase transitionsfrom −150°C to 1000°C were not identified. All polymorphscrystallize in space group Pnma (no. 62) and featureidentical zig-zag-like arrangements of SnS44– tetrahedra. The main structural differences lie in the orderingof the lithium substructure. By combining temperature-dependent powderX-ray and neutron diffraction with high-temperature 7Liand 119Sn NMR as well as Raman spectroscopy, we show thatLi4SnS4 transitions from the lithium-vacancy-disorderedα-phase to the ordered β-phase and finally to the disorderedγ-Li4SnS4. Using electrochemical impedancespectroscopy, we measured ionic conductivities from 10–6 S cm–1 to 10–1 S cm–1 between 25 °C to 220 °C. Conductivity changes are gradual,consistent with the subtle structural variations among all polymorphs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 19","pages":"10330–10340"},"PeriodicalIF":7.1,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090914","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Magnetic andElectrochemical Properties of the AltermagneticLayered Antiperovskite Na2Mn2OS2 变磁膜化反钙钛矿Na2Mn2OS2的磁性和电化学性质

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2026-10-13 DOI: 10.1021/acs.chemmater.6c01897

James I. Murrell,Aurélie Champagne,Kohei Daijo,Antonella Iadecola,Baptiste Vignolle,Sophie Tencé,Fabio Denis Romero,Emmanuel Petit,Jacob Olchowka,Hiroshi Kageyama,Cédric Tassel

{"title":"Magnetic and\u0000Electrochemical Properties of the Altermagnetic\u0000Layered Antiperovskite Na2Mn2OS2","authors":"James I. Murrell,Aurélie Champagne,Kohei Daijo,Antonella Iadecola,Baptiste Vignolle,Sophie Tencé,Fabio Denis Romero,Emmanuel Petit,Jacob Olchowka,Hiroshi Kageyama,Cédric Tassel","doi":"10.1021/acs.chemmater.6c01897","DOIUrl":"https://doi.org/10.1021/acs.chemmater.6c01897","url":null,"abstract":"Abstract Incorporating multiple anions into perovskite-type frameworks provides a handle to design innovative lattices and trigger exotic properties. Inverse Lieb lattices have been receiving substantial interest as hosts for d-wave altermagnetism. One mixed-anion system in which these lattices have been experimentally realized is layered oxychalcogenides. By employing a high-pressure, high-temperature synthesis method, we introduce Na2Mn2OS2 as an additional member of this family of compounds. Na2Mn2OS2 adopts an antiperovskite-derived structure, consisting of layers of face-sharing MnO2S4 octahedra. Magnetization and neutron diffraction data reveal that the phase undergoes magnetic ordering below 144 K. The low-temperature magnetic structure has zero net magnetization and is invariant under a combination of rotation and time reversal, thereby fulfilling the symmetry criteria to be considered as an altermagnet candidate. Electronic band structure calculations demonstrate that the phase contains spin-polarized bands, providing further evidence that Na2Mn2OS2 can be described as an altermagnet. An electrochemical investigation of this compound was performed, aiming both to tailor the physicochemical properties of the material through desodiation and to yield a possible Na-ion cathode material. While there are indications of Na-deintercalation, the charge compensation mechanism appears to involve irreversible sulfur oxidation rather than manganese oxidation, thus preventing the application of Na2Mn2OS2 as a positive electrode for Na-ion batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"160 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0