Solid State Ionics最新文献

英文中文

The unique properties of the monomolecular surface layer of reduced ceria

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-02-15 DOI: 10.1016/j.ssi.2025.116807

Ilan Riess

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_0.1Ce_0.9O_2.-x (PCO), CeO_2-x and Sm_0.2Ce_0.8O_1.9-x (SDC). In PCO the analysis predicts that the surface layer is negatively charged and the concentration of Pr³⁺ ions is higher than in the bulk. A double layer exists between the surface layer and the bulk. In CeO₂ and SDC the concentration of Ce³⁺ 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 Ce³⁺ are delocalized and not localized small polarons. The bulk is a semiconductor. The Ce³⁺ ions are randomly distributed on the Ce sublattice and not in the boundary of oxygen vacancies. The latter are doubly ionized vacancies

{V_{O}}^{• •}

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 T > 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.

{"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 Pr0.1Ce0.9O2.-x (PCO), CeO2-x and Sm0.2Ce0.8O1.9-x (SDC). In PCO the analysis predicts that the surface layer is negatively charged and the concentration of Pr3+ ions is higher than in the bulk. A double layer exists between the surface layer and the bulk. In CeO2 and SDC the concentration of Ce3+ 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 Ce3+ are delocalized and not localized small polarons. The bulk is a semiconductor. The Ce3+ ions are randomly distributed on the Ce sublattice and not in the boundary of oxygen vacancies. The latter are doubly ionized vacancies <math><msup><msub><mtext>V</mtext><mtext>O</mtext></msub><mrow><mo>•</mo><mo>•</mo></mrow></msup></math>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 T > 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

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

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

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 BaZrO₃ (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.

{"title":"Mechanistic insights into oxygen reduction reaction on metal/perovskite catalysts: Interfacial interactions and reaction pathways","authors":"Wenhao Li , Vadym Drozd , Md Shariful Islam Sozal , Meng Li , 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 BaZrO3 (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

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

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

Phase pure and highly ordered Li(Ni_0.6Ti_0.2Co_0.2)O₂ (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 LiTiO₂ 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.

引用次数: 0

Structural analysis of the LiCoO2 cathodes/garnet-type Li6.5La3Zr1.5Ta0.5O12 solid electrolyte interface

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

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

The sinterability of oxide cathode LiCoO₂ and garnet-type solid electrolyte Li_7-xLa₃Zr_2-xTa_xO₁₂ (x = 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 LiCoO₂/Li_7-xLa₃Zr_2-xTa_xO₁₂ 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 LiCoO₂ structure, thickly forming in contact with LiCoO₂, and the other has a structural and chemical character similar to Li_7-xLa₃Zr_2-xTa_xO₁₂, thinly forming in contact with Li_7-xLa₃Zr_2-xTa_xO₁₂. 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 LiCoO₂ interphase is somewhat depleted of Li and contaminated with La, Zr, and Ta. These properties are considered less favorable for achieving undisturbed ionic conductivity.

{"title":"Structural analysis of the LiCoO2 cathodes/garnet-type Li6.5La3Zr1.5Ta0.5O12 solid electrolyte interface","authors":"K. Niitsu , F. Ichihara , S. Miyoshi , M. Ode , K. Mitsuishi , T. Masuda , 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 LiCoO2 and garnet-type solid electrolyte Li7-xLa3Zr2-xTaxO12 (x = 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 LiCoO2/Li7-xLa3Zr2-xTaxO12 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 LiCoO2 structure, thickly forming in contact with LiCoO2, and the other has a structural and chemical character similar to Li7-xLa3Zr2-xTaxO12, thinly forming in contact with Li7-xLa3Zr2-xTaxO12. 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 LiCoO2 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

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

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

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 0.4Li₂MnO₃–0.6Li(Mn_1/3Ni_1/3Co_1/3)O₂, which is used as a Li-ion battery positive electrode. The stable structures obtained were compared with the pair distribution function G(r) derived from synchrotron X-ray total scattering measurements. Our calculated G(r) models are in good agreement with the observed G(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 LiO 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 MnO bonds within the MnO₆ 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.

{"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 , Ryohei Kosasa , Yuiko Koitabashi , Naoto Kitamura , 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 0.4Li2MnO3–0.6Li(Mn1/3Ni1/3Co1/3)O2, which is used as a Li-ion battery positive electrode. The stable structures obtained were compared with the pair distribution function G(r) derived from synchrotron X-ray total scattering measurements. Our calculated G(r) models are in good agreement with the observed G(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>O6 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

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

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

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 LiNbOCl₄ exhibiting high ionic conductivity (≥ 10 mS cm⁻¹) can be a promising candidate. However, in the literature, LiNbOCl₄ was prepared by the reaction of LiOH and NbCl₅, 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 NbOCl₃ that can yield LiNbOCl₄ with the same crystal structure and high ionic conductivity of 8.4 mS cm⁻¹ at 25 °C. To confirm its feasibility for the bulk-type ASLB application, its electrochemical properties and dry room stability were also investigated.

{"title":"Hydrochloric acid-free synthesis of LiNbOCl4 superionic conductor for all-solid-state Li batteries","authors":"Seongjin Jeon , Kern-Ho Park , Woosuk Cho , Goojin Jeong , Jisang Yu , Yong Joon Park , 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 LiNbOCl4 exhibiting high ionic conductivity (≥ 10 mS cm−1) can be a promising candidate. However, in the literature, LiNbOCl4 was prepared by the reaction of LiOH and NbCl5, 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 NbOCl3 that can yield LiNbOCl4 with the same crystal structure and high ionic conductivity of 8.4 mS cm−1 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

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

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

The ionic conductivity and electrochemical stability of Li₃InCl₆ 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_3−xInCl_6−x (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 × 10⁻³ Scm⁻¹) at 30 °C. Results show that ion carrier formation is the main barrier to Li ion movement in the Li_3−xInCl_6−x (0 ≤ x ≤ 0.1). Furthermore, an all-solid-state cell with Li_2.95InCl_5.95 SE remained stable after 50 cycles, demonstrating the compatibility of the SE with bare LiNi_0.5Mn_0.3Co_0.2O₂.

{"title":"Synthesis of a Li3−xInCl6−x solid electrolyte and its application in all-solid-state batteries","authors":"Nguyen Anh Khoa , Nguyen Thi Minh Nguyet , Tran Viet Toan , Ly Minh Dang , Nguyen Xuan Manh , Tran Anh Tu , 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 Li3InCl6 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, Li3−xInCl6−x (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 × 10−3 Scm−1) at 30 °C. Results show that ion carrier formation is the main barrier to Li ion movement in the Li3−xInCl6−x (0 ≤ x ≤ 0.1). Furthermore, an all-solid-state cell with Li2.95InCl5.95 SE remained stable after 50 cycles, demonstrating the compatibility of the SE with bare LiNi0.5Mn0.3Co0.2O2.</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

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-02-03 DOI: 10.1016/j.ssi.2025.116802

A. Dive , S. Banerjee

Identifying solid electrolytes with superior Na⁺ ion conductivity at room temperature is critical for designing safe and high energy density solid-state batteries with enhanced rate capabilities. Sodium thiophosphate (Na₃PS₄) based solid electrolytes have shown excellent promise with relatively high ionic conductivity. In particular, the orthorhombic γ – Na₃PS₄ 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) Na₃PS₄ phases at room temperature. However, the reported γ – Na₃PS₄ 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 – Na₃PS₄ phase. These insights were applied to simulate and develop correlations between structure and ionic conductivity in amorphous Na₃PS₄ 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 PS₄ and PS₃ units exhibit greater Na⁺ ion diffusivity at temperatures below 500 K. Tuning the concentration of these structural units can be achieved through appropriate heat treatment of the amorphous Na₃PS₄ to achieve high ionic conductivity for novel glass-ceramic type Na₃PS₄ solid electrolytes at room temperature. Overall, our results qualitatively suggest guidelines for achieving superior ionic conductivity in Na₃PS₄ glass-ceramic electrolytes.

{"title":"Mimicking Na+ ion transport in superionic Na3PS4 solid electrolytes through amorphization","authors":"A. Dive , 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+ ion conductivity at room temperature is critical for designing safe and high energy density solid-state batteries with enhanced rate capabilities. Sodium thiophosphate (Na3PS4) based solid electrolytes have shown excellent promise with relatively high ionic conductivity. In particular, the orthorhombic γ – Na3PS4 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) Na3PS4 phases at room temperature. However, the reported γ – Na3PS4 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 – Na3PS4 phase. These insights were applied to simulate and develop correlations between structure and ionic conductivity in amorphous Na3PS4 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 PS4 and PS3 units exhibit greater Na+ ion diffusivity at temperatures below 500 K. Tuning the concentration of these structural units can be achieved through appropriate heat treatment of the amorphous Na3PS4 to achieve high ionic conductivity for novel glass-ceramic type Na3PS4 solid electrolytes at room temperature. Overall, our results qualitatively suggest guidelines for achieving superior ionic conductivity in Na3PS4 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

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

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

Solid-state batteries have become an effective way to improve battery safety and achieve high energy density. However, the high interfacial impedance and low ionic conductivity of solid-state electrolytes remain limiting factors in the development of all-solid-state batteries. In this study, a Poly (vinylene carbonate) (PVC)- Li_6.4Ga_0.2La₃Zr₂O₁₂(LLZO) composite electrolyte prepared by in-situ curing technology forms a tight interfacial contact through in-situ curing, reducing the interfacial resistance and enhancing the stability of solid-state batteries. The high LLZO content integrated with the PVC polymer creates a unified structure that facilitates lithium-ion migration and improves stability electrolyte stability.The composite electrolyte achieves an excellent ionic conductivity of 5.1 × 10⁻⁴ S/cm at room temperature, an electrochemical window greater than 4.7 V (vs Li⁺/Li), and a lithium-ion migration number of 0.616. Additionally, the PVC-LLZO composite solid electrolyte demonstrates significantly enhanced stability during lithium deposition and stripping. The solid-state LiFePO₄| PVC-20 wt% LLZO |Li batter shows outstanding cycling stability at 0.2C, with an initial discharge specific capacity of 137 mAh g⁻¹ and a capacity retention of 99.8 % after 160 cycles.

{"title":"Interfacial ionic conductivity and cyclic performance of lithium metal battery using in-situ polymerized poly(vinylene carbonate)-Li6.4Ga0.2La3Zr1.4O12 solid electrolytes","authors":"Wenfeng Shi , Shiyu Cao , Gang Zhang , Chong Mao , Xiaobing Dai , Guanchao Yin , Fei Chen","doi":"10.1016/j.ssi.2024.116771","DOIUrl":"10.1016/j.ssi.2024.116771","url":null,"abstract":"<div><div>Solid-state batteries have become an effective way to improve battery safety and achieve high energy density. However, the high interfacial impedance and low ionic conductivity of solid-state electrolytes remain limiting factors in the development of all-solid-state batteries. In this study, a Poly (vinylene carbonate) (PVC)- Li6.4Ga0.2La3Zr2O12(LLZO) composite electrolyte prepared by in-situ curing technology forms a tight interfacial contact through in-situ curing, reducing the interfacial resistance and enhancing the stability of solid-state batteries. The high LLZO content integrated with the PVC polymer creates a unified structure that facilitates lithium-ion migration and improves stability electrolyte stability.The composite electrolyte achieves an excellent ionic conductivity of 5.1 × 10−4 S/cm at room temperature, an electrochemical window greater than 4.7 V (vs Li+/Li), and a lithium-ion migration number of 0.616. Additionally, the PVC-LLZO composite solid electrolyte demonstrates significantly enhanced stability during lithium deposition and stripping. The solid-state LiFePO4| PVC-20 wt% LLZO |Li batter shows outstanding cycling stability at 0.2C, with an initial discharge specific capacity of 137 mAh g−1 and a capacity retention of 99.8 % after 160 cycles.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"420 ","pages":"Article 116771"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143169444","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

Effects of praseodymium oxide infiltration on the surface segregation behavior and electrocatalytic properties of La0.3Ca0.7Fe0.7Cr0.3O3-δ cathode

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-02-01 DOI: 10.1016/j.ssi.2024.116769

Yong-Qi Lei , Qing Xu , Duan-Ping Huang , Min Chen , Kai Zhao , Dong-Chu Chen , Feng Zhang

Aiming at improving the electrocatalytic properties of La_0.3Ca_0.7Fe_0.7Cr_0.3O_3-δ cathode towards oxygen reduction reaction, precursor solutions nominally containing 3–15 vol% Pr₆O₁₁ were infiltrated into the electrodes and then pyrolyzed. The structure and electrocatalytic activity of the infiltrated electrodes were investigated in relation to infiltrate loading and cathodic polarization history. The infiltrated electrodes presented a bi-phase structure at 800 °C, comprised of La_0.3Ca_0.7Fe_0.7Cr_0.3O_3-δ grains and Pr₇O₁₂ infiltrate deposited on the surface of the perovskite grains. It was shown that the two phases interacted with each other at the elevated temperature, exemplified by a repression of the thermally-induced formation of oxygen vacancies in the La_0.3Ca_0.7Fe_0.7Cr_0.3O_3-δ phase relative to a pure La_0.3Ca_0.7Fe_0.7Cr_0.3O_3-δ and a spillover of electrocatalytic activity beyond the perovskite phase. The electrocatalytic properties of the electrodes were found to be dependent to a great extent on the interaction between the two phases. The optimal infiltrate loading was determined to be 12 vol% in terms of the electrocatalytic activity of the electrodes at 800 °C. The 12 vol% Pr₆O₁₁-infiltrated electrode achieved a polarization resistance of 0.051 cm² at 800 °C, which was lowered by ca. 40 % relative to the pristine electrode. Moreover, the surface calcium segregation behavior of the infiltrated electrode after experiencing cathodic polarization was appreciably alleviated and the stability of the electrode activity against cathodic polarization was substantially improved.

{"title":"Effects of praseodymium oxide infiltration on the surface segregation behavior and electrocatalytic properties of La0.3Ca0.7Fe0.7Cr0.3O3-δ cathode","authors":"Yong-Qi Lei , Qing Xu , Duan-Ping Huang , Min Chen , Kai Zhao , Dong-Chu Chen , Feng Zhang","doi":"10.1016/j.ssi.2024.116769","DOIUrl":"10.1016/j.ssi.2024.116769","url":null,"abstract":"<div><div>Aiming at improving the electrocatalytic properties of La0.3Ca0.7Fe0.7Cr0.3O3-δ cathode towards oxygen reduction reaction, precursor solutions nominally containing 3–15 vol% Pr6O11 were infiltrated into the electrodes and then pyrolyzed. The structure and electrocatalytic activity of the infiltrated electrodes were investigated in relation to infiltrate loading and cathodic polarization history. The infiltrated electrodes presented a bi-phase structure at 800 °C, comprised of La0.3Ca0.7Fe0.7Cr0.3O3-δ grains and Pr7O12 infiltrate deposited on the surface of the perovskite grains. It was shown that the two phases interacted with each other at the elevated temperature, exemplified by a repression of the thermally-induced formation of oxygen vacancies in the La0.3Ca0.7Fe0.7Cr0.3O3-δ phase relative to a pure La0.3Ca0.7Fe0.7Cr0.3O3-δ and a spillover of electrocatalytic activity beyond the perovskite phase. The electrocatalytic properties of the electrodes were found to be dependent to a great extent on the interaction between the two phases. The optimal infiltrate loading was determined to be 12 vol% in terms of the electrocatalytic activity of the electrodes at 800 °C. The 12 vol% Pr6O11-infiltrated electrode achieved a polarization resistance of 0.051 cm2 at 800 °C, which was lowered by ca. 40 % relative to the pristine electrode. Moreover, the surface calcium segregation behavior of the infiltrated electrode after experiencing cathodic polarization was appreciably alleviated and the stability of the electrode activity against cathodic polarization was substantially improved.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"420 ","pages":"Article 116769"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143169462","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

下一页尾页

类型

全部化学•材料生命科学医学物理工程技术环境•农林材料科学地球科学法学管理学化学环境科学与生态学计算机科学教育学经济学农林科学人文科学生物学数学物理与天体物理心理学综合性期刊其他工业工程理学历史学农学文学信息工程

数据库

全部 ACS Publications Elsevier ieeexplore Springer The Royal Society of Chemistry Wiley

期刊

Solid State Ionics

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.

﹀