Solid State Ionics最新文献

{"title":"Conduction of lithium ions in polymer-based electrolytes","authors":"Zixuan Wang,&nbsp;Jialong Fu,&nbsp;Xin Guo","doi":"10.1016/j.ssi.2025.116858","DOIUrl":"10.1016/j.ssi.2025.116858","url":null,"abstract":"<div><div>Polymer electrolytes have been extensively studied due to their high safety, low cost, and ease of processing, and they have received significant attention in the development of solid-state lithium batteries with high energy density and enhanced safety. An ideal polymer-based electrolyte must exhibit a combination of properties, with fast ion conduction being particularly critical. This paper reviews the lithium-ion conduction mechanisms in solid, composite, and quasi-solid polymer electrolytes. The effects of inorganic fillers on Li⁺ conduction in composite polymer electrolytes, as well as the effects of liquid plasticizers on Li⁺ conduction in quasi-solid polymer electrolytes, are discussed. In addition, the application prospects of polymer electrolytes in high energy density, high safety solid-state lithium metal batteries are explored. Finally, the challenges and perspectives for the development of high-performance lithium batteries using polymer electrolytes are presented.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"424 ","pages":"Article 116858"},"PeriodicalIF":3.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143785485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electronic and Li-ion diffusion properties in Fe0.875M0.125S2 (M = Ti, V)(001)|Li2S(110) interface by the first-principles study","authors":"Baogang Liu ,&nbsp;Chengdong Wei ,&nbsp;Fenning Zhao ,&nbsp;Jian Xu ,&nbsp;Jihong Li ,&nbsp;Hongtao Xue ,&nbsp;Fuling Tang","doi":"10.1016/j.ssi.2025.116857","DOIUrl":"10.1016/j.ssi.2025.116857","url":null,"abstract":"<div><div>The structure and nature of the interface between the electrode and the discharge product have an important impact on the performance of Lithium‑sulfur (Li<img>S) batteries. We investigated the effects of transition metals Ti and V doped into FeS₂ on the high-rate performance of the interface formed with Li₂S(110). Using the first-principles calculations, we have investigated the interface between FeS₂(001) with doping transition metal Ti and V, and Li₂S(110). The investigation covered aspects such as lattice structure, electrochemical properties, diffusion of Li⁺ at the interface, distribution of charge, and work function. The results indicate that doping with transition metals Ti and V reduces the Li⁺ diffusion barrier. The interfacial density of states introduces metallic properties. Additionally, analysis of work function revealed that Ti doping promotes the establishment of an internal electric field in the interfacial structure which accelerates cycling and migration of Li⁺. This study enhances our understanding of interfacial structure and electrochemical properties between cathode host material and Li₂S.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"424 ","pages":"Article 116857"},"PeriodicalIF":3.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143785484","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}

{"title":"Trade-off between lithium diffusivity and transference in solid ternary polymer ionic liquid electrolytes","authors":"Mark Weijers ,&nbsp;Pranav Karanth ,&nbsp;Gerrit Homann ,&nbsp;Boaz Izelaar ,&nbsp;Aleksandra Kondakova ,&nbsp;Swapna Ganapathy ,&nbsp;Ruud Kortlever ,&nbsp;Corsin Battaglia ,&nbsp;Fokko M. Mulder","doi":"10.1016/j.ssi.2025.116854","DOIUrl":"10.1016/j.ssi.2025.116854","url":null,"abstract":"<div><div>For battery architectures that need a solid ion conductor with good contacting performance and high stability against electrochemical oxidation, polymerized ionic liquids (PIL) pose a valuable class of materials. The low conductivity of the binary PIL/ lithium salt system can be increased using a ternary ionic liquid acting as plasticiser. The conductive mechanism of the ternary system is however not fully understood. This work shows the shift in conduction mechanism for the ternary Li−/[1,3]PYR-/PDADMA-FSI system by increasing the lithium salt concentration and comparing the transfer mechanism to binary ionic liquid (IL) electrolyte analogues using pulsed field gradient (PFG) nuclear magnetic resonance (NMR), NMR relaxometry, Raman spectroscopy and electrochemical techniques. Two conducting regimes were found which show a strong trade-off between conductivity and transference number. In the low lithium salt regime (≤35 wt% LiFSI), cluster diffusion of aggregated lithium is the dominating mechanism leading to low transference numbers (0.04–0.15 at room temperature (RT)). The high salt regime (≥50 wt% LiFSI) shows diffusion through free lithium ion hopping transfer, which has a stronger dependence on temperature and yields higher transference numbers (0.31 at RT). Increasing lithium salt concentration shows an inverse linear correlation with conductivity. The electrochemical characteristics of ternary IL/PIL/lithium salt are shown to be highly tuneable by varying the lithium salt fraction, while it maintains excellent characteristics like processability, stability and mechanical function.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"424 ","pages":"Article 116854"},"PeriodicalIF":3.0,"publicationDate":"2025-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783459","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Zirconia-free fine-grained NASICON-type solid electrolyte prepared from Mg2+, Y3+ co-doping zirconia precursors","authors":"Tianrun Li,&nbsp;Meihua Liu,&nbsp;Xiaolin Zhang,&nbsp;Guoqiang Li,&nbsp;Shixin Xiao","doi":"10.1016/j.ssi.2025.116856","DOIUrl":"10.1016/j.ssi.2025.116856","url":null,"abstract":"<div><div>The increasing demand for all-solid-state batteries with high energy density and enhanced safety has attracted attention to the development of high-performance solid-state electrolytes. NASICON-structured Na₃Zr₂Si₂PO₁₂ is considered as a promising solid-state electrolyte material due to its superior thermal and chemical stability. However, its practical application is constrained by the presence of monoclinic ZrO₂ (m-ZrO₂) impurity phase and low ionic conductivity at room temperature. This study presents the synthesis of fine-grained (0.5–0.7 μm) NASICON-type materials free from m-ZrO₂ impurity phase via a solid-state method, and using Mg²⁺ and Y³⁺ co-doped zirconia precursor as a substitute for conventional zirconia. The elimination of the m-ZrO₂ impurity phase and the implementation of Mg²⁺ and Y³⁺ co-doping strategy simultaneously optimized the bulk and grain boundary structure, reduced resistance, and enlarged the bottleneck size of Na⁺ ion transport channels. AC impedance spectroscopy analysis revealed that the room temperature conductivity of Na_3.32Mg_0.16Zr_1.84Si₂PO₁₂ doped with 8 mol% MgO increased from 0.43 mS cm⁻¹ to 1.10 mS cm⁻¹, and further increased to 2.32 mS cm⁻¹ upon substitution of MgO with 2 mol% Y₂O₃ in Na_3.32Mg_0.12Y_0.08Zr_1.84Si₂PO₁₂. This study presents a feasible approach to enhance the ionic conductivity of NASICON-structured solid-state electrolytes through the regulation of multiple factors.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"424 ","pages":"Article 116856"},"PeriodicalIF":3.0,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776761","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}

{"title":"Practical assessment of cobalt-free Li2MnO3-based layered materials for Li battery applications","authors":"Yosuke Ugata ,&nbsp;Chihaya Motoki ,&nbsp;Tokuhiko Handa ,&nbsp;Naoaki Yabuuchi","doi":"10.1016/j.ssi.2025.116855","DOIUrl":"10.1016/j.ssi.2025.116855","url":null,"abstract":"<div><div>As cost-effective and Co-free positive electrode materials, a solid solution material between Li₂MnO₃ and LiNi_0.5Mn_0.5O₂, Li_1.2Ni_0.2Mn_0.6O₂, delivers a large reversible capacity over 220 mA h g⁻¹ through reversible anionic redox of oxide ions. However, a practical problem of this material is found in the insufficient reversibility as electrode materials associated with partial oxygen loss during charging process. In this study, Li_1.2Al_0.04Ni_0.18Mn_0.58O₂, where Ni and Mn ions in Li_1.2Ni_0.2Mn_0.6O₂ are partially substituted with Al ions, is synthesized <em>via</em> a solid-state reaction. Li_1.2Al_0.04Ni_0.18Mn_0.58O₂ samples with the optimized surface area are further synthesized at different calcination temperatures. Al³⁺-substituted sample with the optimized surface area partially suppresses the capacity fading and voltage decay on continuous electrochemical cycles, ∼ 500 cycles. Moreover, the use of highly concentrated electrolytes with high oxidative stability efficiently improves electrode reversibility of Li_1.2Al_0.04Ni_0.18Mn_0.58O₂. Nevertheless, important practical problems are still found in inevitable voltage decay and inferior charge rate capability, both originating from the character of anionic redox reaction. Further research efforts are necessary to overcome these drawbacks and to adopt Mn-based electrode materials with anionic redox for practical battery applications, especially for electric vehicles.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"424 ","pages":"Article 116855"},"PeriodicalIF":3.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143760330","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fluoride-ion conductivity of scheelite-type LiYb1-xMxF4±x (M = Mg, Ca, Sr, Hf)","authors":"Kota Onuki ,&nbsp;Naoki Matsui ,&nbsp;Kota Suzuki ,&nbsp;Masaaki Hirayama ,&nbsp;Ryoji Kanno","doi":"10.1016/j.ssi.2025.116851","DOIUrl":"10.1016/j.ssi.2025.116851","url":null,"abstract":"<div><div>Fluorite-type fluoride-ion conductors have been widely studied, whereas fluorite-derivative structures remain untapped material spaces as fluoride-ion conductors. In this study, fluoride-ion conductivities in scheelite-type LiYb_1-<em>x</em><em>M</em>_<em>x</em>F_{4±<em>x</em>} (<em>M</em> = Mg, Ca, Sr, and Hf) solid solutions were investigated. Introduction of fluorine-vacancy through aliovalent cation-substitution significantly enhanced ionic conductivity, with 15 % Ca²⁺ substitution for Yb³⁺ exhibiting a maximum conductivity of 1.7 × 10⁻⁵ S cm⁻¹ at 473 K. Structural analysis confirmed the formation of F vacancies, whereas bond valence energy landscape calculations revealed low-barrier conduction pathways. Furthermore, molecular dynamics simulations revealed distinct fluoride migration pathway near the Ca²⁺-doped and undoped regions. These findings offer new insights into the fluoride-ion conduction mechanisms in fluorite-related structures.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"424 ","pages":"Article 116851"},"PeriodicalIF":3.0,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143748040","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}

{"title":"Solvent reconstruction and interfacial fluorination strategy for high-performance polyether lithium metal batteries","authors":"Haofeng Peng,&nbsp;Zixuan Fang,&nbsp;Ming Zhang,&nbsp;Mengqiang Wu","doi":"10.1016/j.ssi.2025.116849","DOIUrl":"10.1016/j.ssi.2025.116849","url":null,"abstract":"<div><div>Lithium metal batteries based on in situ semi-solid-state polyether electrolytes have emerged as a focal point of contemporary research due to their straightforward fabrication process, high energy density, and reliable safety. The DOL monomers exhibit characteristics of low viscosity and polymerization initiated by lithium salts at room temperature, presenting a significant commercial potential for the preparation of PDOL semi-solid-state electrolytes via in situ ring-opening polymerization for high-performance lithium metal batteries. However, the intrinsic performance deficiencies and poor antioxidant properties of polyether electrolytes have severely impeded their practical application. The utilization of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) as a diluent and fluoroethylene carbonate (FEC) as an additive for solvent reconstruction and interfacial fluorination of the semi-solid-state polyether electrolytes has effectively mitigated these issues. Density functional theory and molecular dynamics simulations demonstrate that the TTE diluent can optimize the solvent structure and enhance anionic coordination, thereby improving the electrochemical performance of PDOL-based electrolytes, which enables stable cycling of Li/Li symmetric batteries for over 2000 h at 0.1 mA cm ⁻ ². Furthermore, the introduction of the fluorinated additive FEC has achieved exceptional performance in Li/NCM811 high-voltage lithium metal batteries, with an initial discharge specific capacity of 206.3 mAh g⁻¹ at 0.1C and stable charge-discharge cycling at 0.3C.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116849"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695911","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}

{"title":"Economical, ecofriendly and easy to handle polymer-in-salt-electrolyte","authors":"Dipti Yadav,&nbsp;Kanak Aggarwal,&nbsp;Neelam Srivastava","doi":"10.1016/j.ssi.2025.116848","DOIUrl":"10.1016/j.ssi.2025.116848","url":null,"abstract":"<div><div>Polymer-In-Salt-Electrolytes (PISEs) are an emerging branch of polymer electrolytes which are supposed to address the shortcomings (slow ion movement due to polymer coupled motion and small cationic transference number) of Salt-In-Polymer-Electrolytes (SIPEs), but a PISE, which may be commercially used for fabrication of energy device is still a dream because of recrystallization and brittle matrix at higher salt concentration. Our group has developed a simple solution casting protocol for synthesis of an economical, eco-friendly and easy to handle PISEs from crosslinked starches, where there is no need of getting the molten state salt/salt-mixture. The thought process behind this protocol and selection of starch as host polymer is that the salt breaks the starch into smaller molecules resulting in generation new –OH and –H to interact with salt, i.e. increasing salt concentration itself creates a favorable atmosphere for its acceptance. Starch is hydrophilic in nature and presence of large amount of salt adds up to it, and such materials have moisture content varying from ∼5 % to 25 %, depending to salt and starch combination and concentration, which is a favorable property leading the synthesized PISEs to behave as Water-In-Polymer-Salt-Electrolytes (WiPSEs). By exposing the freshly synthesized samples to high humidity these materials were stabilized with respect to ambient humidity changes. These materials lead to ESR &lt;10 Ω (reaching to as low as &lt;1 Ω), wide electrochemical stability window (ESW &gt; 2.5 V) and ion relaxation time is of the order of μSec. The supercapacitor fabricated using synthesized PISEs with commonly available supercapacitor electrodes have behavior at par with other electrolytes reported in the literature. With lab-synthesized activated carbons, a capacity of ∼125 F/g has been obtained with columbic efficiency &gt;98 %. Since the synthesis protocol and chemicals used are economical, the starch-based PISEs are economical and also environment benign, because starch is a renewable polymer and the process uses only one extra chemical (methanol as solvent). The material is flexible and can be molded in the desired shape and size and hence is a potential candidate to reach at the commercial level, if explored in detail.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116848"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143704090","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}

{"title":"Exploring structural, optical, dielectric and electrical attributes of a La based complex perovskite","authors":"Lipsa Priyadarshini ,&nbsp;L. Biswal ,&nbsp;Sujata Rout ,&nbsp;Karubaki Moharana ,&nbsp;Amit Kumar Parida ,&nbsp;R.N.P. Choudhary ,&nbsp;Santosh Kumar Satpathy","doi":"10.1016/j.ssi.2025.116840","DOIUrl":"10.1016/j.ssi.2025.116840","url":null,"abstract":"<div><div>A rare-earth based novel compound with a disordered perovskite structure has been synthesised using the conventional solid-state reaction approach. The structural phase of the compound is analysed using room temperature X-ray diffraction (XRD) data. The refinement of XRD data suggested formation of compound in trigonal phase with R-3c symmetry. Position of peaks in Raman spectra obtained at room temperature further support the proposition of above structure and symmetry of formation. Using scanning electron microscope (SEM) images, the microstructure of the compound and the surface morphology is revealed. EDX analysis presented semi-quantitative information on distribution and weight percentage of elements present, from which the synthesis of the expected compound is substantiated. Examination of optical characteristics via UV–Visible absorption spectroscopy revealed a band gap of 3.2 eV suggesting possible potential applications in optoelectronic and photovoltaic devices. The electric polarisation and relaxation phenomena prevailing in the material as a function of frequency and temperature are extensively studied using data acquired via complex impedance spectroscopy (CIS) technique. A temperature and frequency stable dielectric response in high frequency region recommends use of compound for application at high frequency and temperature. Dominating bulk contribution to overall electrical response and negative temperature coefficient of resistance (NTCR) behaviour is observed. The frequency-dependent ac conductivity data adheres to Jonscher's power law. To estimate the activation energy, which facilitates the identification of the specific charges involved in the ac conduction process, the temperature-dependant ac conductivity data is utilised.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116840"},"PeriodicalIF":3.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143683756","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}

{"title":"Atomistic insights into the carbonation behavior of olivine minerals: Role of metal cation composition","authors":"Saisai Zhang,&nbsp;Xinyu Zhang,&nbsp;Li Zhang,&nbsp;Donglin Li,&nbsp;Xuemao Guan,&nbsp;Jianping Zhu,&nbsp;Songhui Liu","doi":"10.1016/j.ssi.2025.116845","DOIUrl":"10.1016/j.ssi.2025.116845","url":null,"abstract":"<div><div>Olivine minerals possess significant potential for CO₂ sequestration through carbonation reactions, with their reactivity highly influenced by cation composition. This study employs first-principles calculations to systematically investigate the impact of metal cations (Mg²⁺, Ca²⁺, Mn²⁺, Fe²⁺, Co²⁺) on the carbonation behavior of five olivine structures: forsterite (Mg₂SiO₄), calcio-olivine (γ-Ca₂SiO₄), tephroite (α-Mn₂SiO₄), fayalite (α-Fe₂SiO₄), and Co-olivine. Analyses of bond characteristics, total bond order density, and local density of states reveal fundamental differences between alkaline earth and transition metal olivines. We have found that in alkaline earth (AE) olivines, carbonation primarily involves an electrophilic attack of O²⁻ by H⁺ and a nucleophilic attack of metal cations by HCO₃⁻/CO₃²⁻ species. Calcio-olivine exhibits higher reactivity than forsterite due to enhanced Ca²⁺ nucleophilicity. Conversely, transition metal (TM) olivine reactivity is governed by the multivalent cations, contributing significantly to both electrophilic and nucleophilic pathways. Considering both mineral reserves and carbonation reaction mechanisms, calcio-olivine is determined to be the most advantageous among the five olivine minerals in terms of carbonation reactivity. This atomic-scale understanding guides the development of olivine-based materials with improved carbonation performance for efficient CO₂ sequestration and utilization in carbon capture, utilization, and storage technologies.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116845"},"PeriodicalIF":3.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143642962","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}