Solid State Ionics最新文献

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Low-dimensional Li+ ion dynamics in the lithiated Buckminster fullerene Li4C60 锂化巴克明斯特富勒烯 Li4C60 中的低维 Li+ 离子动力学
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-24 DOI: 10.1016/j.ssi.2025.116805
Bernhard Gadermaier , H. Martin R. Wilkening
{"title":"Low-dimensional Li+ ion dynamics in the lithiated Buckminster fullerene Li4C60","authors":"Bernhard Gadermaier ,&nbsp;H. Martin R. Wilkening","doi":"10.1016/j.ssi.2025.116805","DOIUrl":"10.1016/j.ssi.2025.116805","url":null,"abstract":"<div><div>Lithiated Buckminster fullerene (Li<sub>4</sub>C<sub>60</sub>) has recently been identified as a fast Li<sup>+</sup> ion conductor. Here, we present a comprehensive NMR-based analysis of <sup>7</sup>Li dynamics in Li<sub>4</sub>C<sub>60</sub>. Our findings indicate that long-range lithium hopping is to be characterized by an activation energy of 0.26 eV. At 378 K, the Li<sup>+</sup> jump rate turned out to be in the order of 10<sup>9</sup> s<sup>−1</sup>, which translates into Einstein-Smoluchowski diffusion coefficients <em>D</em> ranging from ca. 2 to 5 × 10<sup>−7</sup> cm<sup>2</sup> s<sup>−1</sup>, depending on the jump distance chosen (3.6–5 Å) to convert the jump rate into <em>D</em>. The corresponding Arrhenius pre-factor reaches 3 × 10<sup>12</sup> s<sup>−1</sup> and lies in the range of typical phonon frequencies. Comparing our relaxation rates with those presented in the literature earlier suggests low-dimensional Li<sup>+</sup> diffusion in Li<sub>4</sub>C<sub>60</sub>. For short-range or localized Li<sup>+</sup> jump processes, presumably governed by motional correlation effects, we find much lower activation energies ranging from 0.08 eV to 0.17 eV.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116805"},"PeriodicalIF":3.0,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143474564","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}
引用次数: 0
The unique properties of the monomolecular surface layer of reduced ceria 还原氧化铈单分子表面层的独特性质
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-15 DOI: 10.1016/j.ssi.2025.116807
Ilan Riess
{"title":"The unique properties of the monomolecular surface layer of reduced ceria","authors":"Ilan Riess","doi":"10.1016/j.ssi.2025.116807","DOIUrl":"10.1016/j.ssi.2025.116807","url":null,"abstract":"<div><div>Experimental results of the defect concentrations in highly reduced, monomolecular surface layer of ceria-based oxides, are discussed. The data is XPS vs. oxygen pressure relations of reduced Pr<sub>0.1</sub>Ce<sub>0.9</sub>O<sub>2.-x</sub> (PCO), CeO<sub>2-x</sub> and Sm<sub>0.2</sub>Ce<sub>0.8</sub>O<sub>1.9-x</sub> (SDC). In PCO the analysis predicts that the surface layer is negatively charged and the concentration of Pr<sup>3+</sup> ions is higher than in the bulk. A double layer exists between the surface layer and the bulk. In CeO<sub>2</sub> and SDC the concentration of Ce<sup>3+</sup> ions and oxygen vacancies in the surface is higher than in the bulk. The surface is neutral. The analysis predicts that the surface layer is metallic, i.e. the electrons on Ce<sup>3+</sup> are delocalized and not localized small polarons. The bulk is a semiconductor. The Ce<sup>3+</sup> ions are randomly distributed on the Ce sublattice and not in the boundary of oxygen vacancies. The latter are doubly ionized vacancies <span><math><msup><msub><mtext>V</mtext><mtext>O</mtext></msub><mrow><mo>•</mo><mo>•</mo></mrow></msup></math></span>despite the presence of a high concentration of quasi free electrons. It is also predicted that the surface of ceria or SDC has a phase diagram of temperature vs. oxygen vacancy concentration, at <em>T</em> &gt; 450 °C, like that of ceria bulk or SDC bulk, respectively. Further, the phase diagram of SDC bulk (and surface) is like that of ceria bulk shifted to a higher oxygen vacancy concentration and doping has no other effect at elevated temperature. Both in ceria and SDC the difference between the surface and the corresponding bulk is only in the oxygen pressure at which a level of reduction is reached, with the surface more easily being reduced than the bulk.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116807"},"PeriodicalIF":3.0,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143420359","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}
引用次数: 0
Mechanistic insights into oxygen reduction reaction on metal/perovskite catalysts: Interfacial interactions and reaction pathways 金属/钙钛矿催化剂上氧还原反应的机理:界面相互作用和反应途径
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-15 DOI: 10.1016/j.ssi.2025.116808
Wenhao Li , Vadym Drozd , Md Shariful Islam Sozal , Meng Li , Zhe Cheng
{"title":"Mechanistic insights into oxygen reduction reaction on metal/perovskite catalysts: Interfacial interactions and reaction pathways","authors":"Wenhao Li ,&nbsp;Vadym Drozd ,&nbsp;Md Shariful Islam Sozal ,&nbsp;Meng Li ,&nbsp;Zhe Cheng","doi":"10.1016/j.ssi.2025.116808","DOIUrl":"10.1016/j.ssi.2025.116808","url":null,"abstract":"<div><div>The oxygen reduction reaction (ORR) is a critical process in energy conversion systems, influencing the efficiency and performance of various devices such as fuel cells, batteries, and electrolyzers. Perovskite-supported metal materials (metal/perovskite) offer several advantages as ORR electrocatalysts, including strong metal-support interactions, oxygen vacancy formation in the perovskite lattice, and synergistic triple-phase boundary (TPB) activity at the interface. Despite their significance, the mechanistic understanding of ORR on metal/perovskite catalysts remains incomplete, particularly at metal/perovskite interfaces. This study investigates ORR on BaZrO<sub>3</sub> (BZO) perovskite-supported metal clusters (Pt or Ag) using density functional theory (DFT) to unravel critical insights into charge redistribution at the metal/BZO interface. Energy profiles for elemental steps along two different ORR pathways—oxygen adsorption on the metal cluster surface and direct oxygen adsorption at the TPB—were calculated to explore the effects of different active sites. The results provide a deeper understanding of ORR on metal/perovskite catalysts, emphasizing the role of interfacial interactions and pathway-dependent reaction mechanisms. This work paves the way for guiding the design of high-performance electrocatalysts for ORR in terms of composition, interface design, and local environment modification for a broad range of energy applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116808"},"PeriodicalIF":3.0,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143420426","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}
引用次数: 0
Highly ordered Li(Ni0.6Ti0.2Co0.2)O2 (NTC622) cathode material made by all-dry synthesis 采用全干法合成高有序Li(Ni0.6Ti0.2Co0.2)O2 (NTC622)正极材料
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-11 DOI: 10.1016/j.ssi.2025.116806
Macgregor F. Macintosh , P. Popli , Andrew George , M.N. Obrovac
{"title":"Highly ordered Li(Ni0.6Ti0.2Co0.2)O2 (NTC622) cathode material made by all-dry synthesis","authors":"Macgregor F. Macintosh ,&nbsp;P. Popli ,&nbsp;Andrew George ,&nbsp;M.N. Obrovac","doi":"10.1016/j.ssi.2025.116806","DOIUrl":"10.1016/j.ssi.2025.116806","url":null,"abstract":"<div><div>Phase pure and highly ordered Li(Ni<sub>0.6</sub>Ti<sub>0.2</sub>Co<sub>0.2</sub>)O<sub>2</sub> (NTC622) with the O3 structure was synthesized using an all-dry method from metal oxide precursors. To our knowledge, this is the first report of highly ordered NTC622. A major impediment for NTC622 synthesis was found to be the slow diffusion of Ti during sintering. This was overcome by utilizing high-energy ball milling to maximized homogeneous transition metal distribution. In addition, a pure oxygen atmosphere during the sintering step was found to minimize LiTiO<sub>2</sub> formation. The synthesized NTC622 exhibited a reversible capacity of 120 mAh/g, low voltage polarization, and a discharge capacity retention of 93.7 % after 100 cycles. Additionally, the NTC622 demonstrated comparable high-rate performance to NMC622. This demonstrates that layered oxides with high Ti-content are attractive cathode materials. Additionally, this study shows that all-dry methods are an effective means for composition exploration in layered oxide materials.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116806"},"PeriodicalIF":3.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388255","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}
引用次数: 0
Structural analysis of the LiCoO2 cathodes/garnet-type Li6.5La3Zr1.5Ta0.5O12 solid electrolyte interface LiCoO2阴极/石榴石型Li6.5La3Zr1.5Ta0.5O12固体电解质界面结构分析
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-10 DOI: 10.1016/j.ssi.2025.116804
K. Niitsu , F. Ichihara , S. Miyoshi , M. Ode , K. Mitsuishi , T. Masuda , K. Takada
{"title":"Structural analysis of the LiCoO2 cathodes/garnet-type Li6.5La3Zr1.5Ta0.5O12 solid electrolyte interface","authors":"K. Niitsu ,&nbsp;F. Ichihara ,&nbsp;S. Miyoshi ,&nbsp;M. Ode ,&nbsp;K. Mitsuishi ,&nbsp;T. Masuda ,&nbsp;K. Takada","doi":"10.1016/j.ssi.2025.116804","DOIUrl":"10.1016/j.ssi.2025.116804","url":null,"abstract":"<div><div>The sinterability of oxide cathode LiCoO<sub>2</sub> and garnet-type solid electrolyte Li<sub>7-<em>x</em></sub>La<sub>3</sub>Zr<sub>2-<em>x</em></sub>Ta<sub><em>x</em></sub>O<sub>12</sub> (<em>x</em> = 0.5) at 980 and 1080 °C has been studied using an integrated suite of scanning transmission electron microscopy and spectroscopic techniques, with a particular focus on the LiCoO<sub>2</sub>/Li<sub>7-<em>x</em></sub>La<sub>3</sub>Zr<sub>2-<em>x</em></sub>Ta<sub><em>x</em></sub>O<sub>12</sub> interfaces. Whereas the densification hardly progresses and the interdiffusion is limited to the vicinity of the interface at 980 °C, dramatic densification can be achieved at 1080 °C at the expense of severe interfacial modification. The structural, chemical, and electronic characteristics of the interphases are systematically investigated. Two kinds of interphases are formed: one has a disordered LiCoO<sub>2</sub> structure, thickly forming in contact with LiCoO<sub>2</sub>, and the other has a structural and chemical character similar to Li<sub>7-<em>x</em></sub>La<sub>3</sub>Zr<sub>2-<em>x</em></sub>Ta<sub><em>x</em></sub>O<sub>12</sub>, thinly forming in contact with Li<sub>7-<em>x</em></sub>La<sub>3</sub>Zr<sub>2-<em>x</em></sub>Ta<sub><em>x</em></sub>O<sub>12</sub>. The former is assumed to play a vital role in the densification of the pellet. Analysis using energy-dispersive spectroscopy and electron energy loss spectroscopy reveals that the disordered LiCoO<sub>2</sub> interphase is somewhat depleted of Li and contaminated with La, Zr, and Ta. These properties are considered less favorable for achieving undisturbed ionic conductivity.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116804"},"PeriodicalIF":3.0,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377493","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}
引用次数: 0
Stable structure and pair distribution function analysis of 0.4Li2MnO3–0.6Li(Mn1/3Ni1/3Co1/3)O2 as cathode materials lithium ion secondary batteries during charge-discharge process using first-principle calculation and quantum beam 用第一性原理计算和量子束分析正极材料锂离子二次电池充放电过程中的稳定结构和对分布函数
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-08 DOI: 10.1016/j.ssi.2025.116793
Chiaki Ishibashi , Ryohei Kosasa , Yuiko Koitabashi , Naoto Kitamura , Yasushi Idemoto
{"title":"Stable structure and pair distribution function analysis of 0.4Li2MnO3–0.6Li(Mn1/3Ni1/3Co1/3)O2 as cathode materials lithium ion secondary batteries during charge-discharge process using first-principle calculation and quantum beam","authors":"Chiaki Ishibashi ,&nbsp;Ryohei Kosasa ,&nbsp;Yuiko Koitabashi ,&nbsp;Naoto Kitamura ,&nbsp;Yasushi Idemoto","doi":"10.1016/j.ssi.2025.116793","DOIUrl":"10.1016/j.ssi.2025.116793","url":null,"abstract":"<div><div>In this study, first-principles calculations were conducted to identify a local structure model that replicates both the pristine state and the state of the electrode after five charge and discharge cycles at 25 and 60 °C. The material studied was 0.4Li<sub>2</sub>MnO<sub>3</sub>–0.6Li(Mn<sub>1/3</sub>Ni<sub>1/3</sub>Co<sub>1/3</sub>)O<sub>2</sub>, which is used as a Li-ion battery positive electrode. The stable structures obtained were compared with the pair distribution function <em>G</em>(r) derived from synchrotron X-ray total scattering measurements. Our calculated <em>G</em>(r) models are in good agreement with the observed <em>G</em>(r) values from these measurements. In the model that reproduces the stable structure during the fifth cycle charging at 25 and 60 °C, Li atoms in the transition metal (TM) layer, surrounded by Mn and not adjacent to Co, move toward the Li layer due to weak Li<img>O bonding, partially creating vacancies. The coordination number of Mn near these vacancies in the TM layer changed during charging. During discharging, the model in which Li ions were locally coordinated away from the vacancies in the TM layer was stable. In the 25 °C-charging model, compared to the pristine model, less changes were observed in Mn<img>O bonds within the Mn<img>O<sub>6</sub> octahedra, which are most abundant in the TM layer. Furthermore, less distortion in the Mn-O₆ octahedra was observed, resulting in minimal changes to the host structure during charging and discharging. Therefore, compared to 60 °C, the cycle characteristics were evidently improved when charging and discharging at 25 °C.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116793"},"PeriodicalIF":3.0,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143350263","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}
引用次数: 0
Hydrochloric acid-free synthesis of LiNbOCl4 superionic conductor for all-solid-state Li batteries 全固态锂电池超导导体LiNbOCl4的无盐酸合成
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-05 DOI: 10.1016/j.ssi.2025.116791
Seongjin Jeon , Kern-Ho Park , Woosuk Cho , Goojin Jeong , Jisang Yu , Yong Joon Park , KyungSu Kim
{"title":"Hydrochloric acid-free synthesis of LiNbOCl4 superionic conductor for all-solid-state Li batteries","authors":"Seongjin Jeon ,&nbsp;Kern-Ho Park ,&nbsp;Woosuk Cho ,&nbsp;Goojin Jeong ,&nbsp;Jisang Yu ,&nbsp;Yong Joon Park ,&nbsp;KyungSu Kim","doi":"10.1016/j.ssi.2025.116791","DOIUrl":"10.1016/j.ssi.2025.116791","url":null,"abstract":"<div><div>Bulk-type all-solid-state Li batteries (ASLBs) employing inorganic solid electrolytes are considered a next-generation energy storage system due to their potentials to overcome the limitations of current lithium-ion batteries (LIBs) such as a safety concern and narrow operating temperature. Inorganic solid electrolytes (SEs) with high ionic conductivity, good chemical- and electrochemical stability are crucial for high-performance ASLBs. Among them, halide SEs have gained attention for their high-voltage stability, high ionic conductivity, and potentially lower cost compared to sulfide counterparts. Notably, the recently reported LiNbOCl<sub>4</sub> exhibiting high ionic conductivity (≥ 10 mS cm<sup>−1</sup>) can be a promising candidate. However, in the literature, LiNbOCl<sub>4</sub> was prepared by the reaction of LiOH and NbCl<sub>5</sub>, producing caustic HCl as a by-product. This is problematic for large-scale production and may hinder potential improvement through compositional modification. In this work, we demonstrate an alternative hydrochloric acid-free synthesis route using NbOCl<sub>3</sub> that can yield LiNbOCl<sub>4</sub> with the same crystal structure and high ionic conductivity of 8.4 mS cm<sup>−1</sup> at 25 °C. To confirm its feasibility for the bulk-type ASLB application, its electrochemical properties and dry room stability were also investigated.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116791"},"PeriodicalIF":3.0,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143131190","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}
引用次数: 0
Synthesis of a Li3−xInCl6−x solid electrolyte and its application in all-solid-state batteries Li3−xInCl6−x固态电解质的合成及其在全固态电池中的应用
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-03 DOI: 10.1016/j.ssi.2025.116792
Nguyen Anh Khoa , Nguyen Thi Minh Nguyet , Tran Viet Toan , Ly Minh Dang , Nguyen Xuan Manh , Tran Anh Tu , Nguyen Huu Huy Phuc
{"title":"Synthesis of a Li3−xInCl6−x solid electrolyte and its application in all-solid-state batteries","authors":"Nguyen Anh Khoa ,&nbsp;Nguyen Thi Minh Nguyet ,&nbsp;Tran Viet Toan ,&nbsp;Ly Minh Dang ,&nbsp;Nguyen Xuan Manh ,&nbsp;Tran Anh Tu ,&nbsp;Nguyen Huu Huy Phuc","doi":"10.1016/j.ssi.2025.116792","DOIUrl":"10.1016/j.ssi.2025.116792","url":null,"abstract":"<div><div>The ionic conductivity and electrochemical stability of Li<sub>3</sub>InCl<sub>6</sub> solid electrolytes (SEs) can be enhanced through covalent substitutions of In and Cl. Although the ionic conductivity of Li3InCl6 has been extensively studied, the dynamics of Li ions in these systems have been rarely reported. In this study, Li<sub>3−x</sub>InCl<sub>6−x</sub> (0 ≤ x ≤ 0.1) SEs were synthesized via planetary ball-milling, followed by heat treatment at 260 °C for 4 h in a dry Ar atmosphere. The structures of the resulting samples were characterized using X-ray diffraction and scanning electron microscopy–energy-dispersive spectroscopy. Crystal structures were confirmed via Rietveld refinement using Fullprof software, and the mean crystallite size was estimated using the Halder–Wagner–Langford plot. Lattice strain was determined using the Williamson–Hall equation. The sample with x = 0.05 exhibited the highest ionic conductivity (4.57 × 10<sup>−3</sup> Scm<sup>−1</sup>) at 30 °C. Results show that ion carrier formation is the main barrier to Li ion movement in the Li<sub>3−x</sub>InCl<sub>6−x</sub> (0 ≤ x ≤ 0.1). Furthermore, an all-solid-state cell with Li<sub>2.95</sub>InCl<sub>5.95</sub> SE remained stable after 50 cycles, demonstrating the compatibility of the SE with bare LiNi<sub>0.5</sub>Mn<sub>0.3</sub>Co<sub>0.2</sub>O<sub>2</sub>.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116792"},"PeriodicalIF":3.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143131189","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}
引用次数: 0
Mimicking Na+ ion transport in superionic Na3PS4 solid electrolytes through amorphization 通过非晶化模拟超离子Na3PS4固体电解质中Na+离子的输运
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-03 DOI: 10.1016/j.ssi.2025.116802
A. Dive , S. Banerjee
{"title":"Mimicking Na+ ion transport in superionic Na3PS4 solid electrolytes through amorphization","authors":"A. Dive ,&nbsp;S. Banerjee","doi":"10.1016/j.ssi.2025.116802","DOIUrl":"10.1016/j.ssi.2025.116802","url":null,"abstract":"<div><div>Identifying solid electrolytes with superior Na<sup>+</sup> ion conductivity at room temperature is critical for designing safe and high energy density solid-state batteries with enhanced rate capabilities. Sodium thiophosphate (Na<sub>3</sub>PS<sub>4</sub>) based solid electrolytes have shown excellent promise with relatively high ionic conductivity. In particular, the orthorhombic γ – Na<sub>3</sub>PS<sub>4</sub> phase exhibits superionic behavior (ionic conductivity ∼10–50 mS/cm) compared to that of the cubic (ionic conductivity ∼0.1 mS/cm) and tetragonal (ionic conductivity ∼0.001–0.01 mS/cm) Na<sub>3</sub>PS<sub>4</sub> phases at room temperature. However, the reported γ – Na<sub>3</sub>PS<sub>4</sub> phase is stable only at high temperatures and, therefore, does not contribute towards improving ionic conductivity at room temperature. In this study, we report ab initio molecular dynamics calculations to gain fundamental insights into the superionic behavior of the γ – Na<sub>3</sub>PS<sub>4</sub> phase. These insights were applied to simulate and develop correlations between structure and ionic conductivity in amorphous Na<sub>3</sub>PS<sub>4</sub> glassy electrolytes. Our results indicate that the concentration of local structural units in the glasses impact the ionic conductivity. We found out that glasses with a relatively higher concentration of isolated PS<sub>4</sub> and PS<sub>3</sub> units exhibit greater Na<sup>+</sup> ion diffusivity at temperatures below 500 K. Tuning the concentration of these structural units can be achieved through appropriate heat treatment of the amorphous Na<sub>3</sub>PS<sub>4</sub> to achieve high ionic conductivity for novel glass-ceramic type Na<sub>3</sub>PS<sub>4</sub> solid electrolytes at room temperature. Overall, our results qualitatively suggest guidelines for achieving superior ionic conductivity in Na<sub>3</sub>PS<sub>4</sub> glass-ceramic electrolytes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"421 ","pages":"Article 116802"},"PeriodicalIF":3.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143131182","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}
引用次数: 0
Interfacial ionic conductivity and cyclic performance of lithium metal battery using in-situ polymerized poly(vinylene carbonate)-Li6.4Ga0.2La3Zr1.4O12 solid electrolytes 原位聚合聚乙烯醇-Li6.4Ga0.2La3Zr1.4O12固体电解质的界面离子电导率及循环性能研究
IF 3 4区 材料科学
Solid State Ionics Pub Date : 2025-02-01 DOI: 10.1016/j.ssi.2024.116771
Wenfeng Shi , Shiyu Cao , Gang Zhang , Chong Mao , Xiaobing Dai , Guanchao Yin , Fei Chen
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