Pub Date : 2025-07-29DOI: 10.1016/j.ssi.2025.116974
Robert A. Jackson , Peter Fielitz , Günter Borchardt
The calculated migration energies of the constituent elements of LaAlO3 are comparable to the corresponding calculated migration energies of LaGaO3 available in the literature. The resulting calculated ranking of the migration energies, , is valid for various nominally undoped oxide perovskites (ABO3). From this ranking it must be concluded that for a specific temperature the ranking of the self-diffusivities of the constituent elements in nominally undoped oxide perovskites reads . The low cation mobilities in undoped oxide perovskites hamper the experimental determination of the diffusivities of the cations considerably. That is predominantly true for the B site elements which probably migrate via an antisite mechanism in the A sublattice. This conjecture is rationalized by an appropriate mechanistic model which is principally valid for any ternary oxide system with very different defect concentrations and cation mobilities in the two cation sublattices.
{"title":"Migration energies of the constituent ions in LaAlO3","authors":"Robert A. Jackson , Peter Fielitz , Günter Borchardt","doi":"10.1016/j.ssi.2025.116974","DOIUrl":"10.1016/j.ssi.2025.116974","url":null,"abstract":"<div><div>The calculated migration energies of the constituent elements of LaAlO<sub>3</sub> are comparable to the corresponding calculated migration energies of LaGaO<sub>3</sub> available in the literature. The resulting calculated ranking of the migration energies, <span><math><mi>Δ</mi><msubsup><mi>E</mi><mi>m</mi><mtext>Oxygen</mtext></msubsup><mo><</mo><mi>Δ</mi><msubsup><mi>E</mi><mi>m</mi><mtext>A site cation</mtext></msubsup><mo><</mo><mi>Δ</mi><msubsup><mi>E</mi><mi>m</mi><mtext>B site cation</mtext></msubsup></math></span>, is valid for various nominally undoped oxide perovskites (ABO<sub>3</sub>). From this ranking it must be concluded that for a specific temperature the ranking of the self-diffusivities of the constituent elements in nominally undoped oxide perovskites reads <span><math><msub><mi>D</mi><mtext>Oxygen</mtext></msub><mo>≫</mo><msub><mi>D</mi><mtext>A site cation</mtext></msub><mo>≫</mo><msub><mi>D</mi><mtext>B site cation</mtext></msub></math></span>. The low cation mobilities in undoped oxide perovskites hamper the experimental determination of the diffusivities of the cations considerably. That is predominantly true for the B site elements which probably migrate via an antisite mechanism in the A sublattice. This conjecture is rationalized by an appropriate mechanistic model which is principally valid for any ternary oxide system with very different defect concentrations and cation mobilities in the two cation sublattices.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116974"},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720879","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}
Pub Date : 2025-07-29DOI: 10.1016/j.ssi.2025.116986
Bin Li , Wenlin Gong , Mingyao Yang , Si Lin , Yan Liu , Jiayi Su , Jie Zhang , Guocong Liu
The practical application of fast-charging lithium-ion batteries is hindered by interfacial instability at graphite anodes, primarily due to uncontrolled electrolyte decomposition and the formation of resistive solid electrolyte interphase (SEI) layers. Herein, we report ethyl difluoroacetate (EDFA) as a fluorinated additive for conventional LiPF₆/EC-EMC electrolytes to address these challenges. Electrochemical measurements demonstrate that EDFA undergoes preferential reduction to form a stable, fluorine-rich SEI, which enhances interfacial stability and facilitates Li+ transport. As a result, graphite/Li half-cells with EDFA exhibit significantly improved performance, with capacity retention increasing from 81.8 % to 93.4 % after 100 cycles and 3C-rate capacity rising from 49.1 to 99.5 mAh·g−1. SEM, TEM, and XPS analyses confirm the formation of a uniform, compact and fluorine-rich SEI that mitigates parasitic reactions and reduces impedance. This work provides a viable strategy to enhance fast-charging performance in commercial battery systems through additive engineering.
{"title":"Ethyl difluoroacetate additive engineering for fast-charging and durable graphite anodes in lithium-ion batteries","authors":"Bin Li , Wenlin Gong , Mingyao Yang , Si Lin , Yan Liu , Jiayi Su , Jie Zhang , Guocong Liu","doi":"10.1016/j.ssi.2025.116986","DOIUrl":"10.1016/j.ssi.2025.116986","url":null,"abstract":"<div><div>The practical application of fast-charging lithium-ion batteries is hindered by interfacial instability at graphite anodes, primarily due to uncontrolled electrolyte decomposition and the formation of resistive solid electrolyte interphase (SEI) layers. Herein, we report ethyl difluoroacetate (EDFA) as a fluorinated additive for conventional LiPF₆/EC-EMC electrolytes to address these challenges. Electrochemical measurements demonstrate that EDFA undergoes preferential reduction to form a stable, fluorine-rich SEI, which enhances interfacial stability and facilitates Li<sup>+</sup> transport. As a result, graphite/Li half-cells with EDFA exhibit significantly improved performance, with capacity retention increasing from 81.8 % to 93.4 % after 100 cycles and 3C-rate capacity rising from 49.1 to 99.5 mAh·g<sup>−1</sup>. SEM, TEM, and XPS analyses confirm the formation of a uniform, compact and fluorine-rich SEI that mitigates parasitic reactions and reduces impedance. This work provides a viable strategy to enhance fast-charging performance in commercial battery systems through additive engineering.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116986"},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720846","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}
Pub Date : 2025-07-26DOI: 10.1016/j.ssi.2025.116973
Tatsuya Kawada
<div><div>Oxygen exchange kinetics was investigated to model the current-potential relationship of mixed conducting oxide electrodes used in SOFC and SOEC. Focusing on La<sub>0.6</sub>Sr<sub>0.4</sub>CoO<sub>3</sub> as a model material, experimental evidence so far obtained in our group were summarized and reanalyzed. The reaction order analysis suggested a complex reaction mechanism, for which we came to think of two series kinetics, surface process and subsurface process. The former refers to an exchange process between gas-phase oxygen molecules and some sort of surface oxygen species. The latter refers to the exchange of surface oxygen with bulk oxide ions, and the reaction barrier is not necessarily oxygen transport, but may be electron transport/transfer for oxygen in/ex-corporation This hypothesis appeared to resolve some of our remaining questions regarding the experimental results, such as scattered <em>p</em><sub>O<sub>2</sub></sub> dependence in high partial pressure range, the higher isotope exchange rates than electrochemical impedance, and the reaction rate enhancement in the presence of the LaSrCoO<sub>4</sub> phase. While a single piece of such experimental evidence is insufficient to prove the hypothesis, considering all the results together provides strong support. We then tried to separate the contributions of surface and subsurface processes by measuring the surface oxygen potential using a porous oxygen sensor. It revealed that the surface process is written as <span><math><msub><mi>J</mi><mi>s</mi></msub><mo>=</mo><msub><mi>J</mi><mrow><mi>s</mi><mo>,</mo><mn>0</mn></mrow></msub><mo>∙</mo><mi>δ</mi><mo>∙</mo><mfenced><mrow><msubsup><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>s</mi></mrow><mn>2</mn></msubsup><mo>−</mo><msub><mi>p</mi><mrow><msub><mi>O</mi><mn>2</mn></msub><mo>,</mo><mi>g</mi></mrow></msub></mrow></mfenced></math></span> and the subsurface process as <span><math><msub><mi>J</mi><mi>ss</mi></msub><mo>=</mo><msub><mi>J</mi><mrow><mi>ss</mi><mo>,</mo><mn>0</mn></mrow></msub><mo>∙</mo><mfenced><mrow><msub><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>e</mi></mrow></msub><msubsup><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>s</mi></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msubsup><mo>−</mo><msubsup><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>e</mi></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msubsup><msub><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>s</mi></mrow></msub></mrow></mfenced><mo>=</mo><msub><mi>J</mi><mrow><mi>ss</mi><mo>,</mo><mn>0</mn></mrow></msub><mfenced><mrow><mi>exp</mi><mfenced><mfrac><mrow><mi>β</mi><mo>∆</mo><msub><mi>μ</mi><msub><mi>O</mi><mn>2</mn></msub></msub></mrow><mi>RT</mi></mfrac></mfenced><mo>−</mo><mi>exp</mi><mfenced><mrow><mo>−</mo><mfrac><mrow><mfenced><mrow><mn>1</mn><mo>−</mo><mi>β</mi></mrow></mfenced><mo>∆</mo><msub><mi>μ</mi><msub><mi>O</mi><mn>2</mn></msub></msub></mrow><mi>RT</mi></mfrac></mrow></mfenced></mrow></mfenced></math></span>, which are in good agreement with the experimental data even for f
{"title":"High temperature oxygen exchange reaction on dense and porous La0.6Sr0.4CoO3-δ electrodes: An overview of the experimental evidence for modeling","authors":"Tatsuya Kawada","doi":"10.1016/j.ssi.2025.116973","DOIUrl":"10.1016/j.ssi.2025.116973","url":null,"abstract":"<div><div>Oxygen exchange kinetics was investigated to model the current-potential relationship of mixed conducting oxide electrodes used in SOFC and SOEC. Focusing on La<sub>0.6</sub>Sr<sub>0.4</sub>CoO<sub>3</sub> as a model material, experimental evidence so far obtained in our group were summarized and reanalyzed. The reaction order analysis suggested a complex reaction mechanism, for which we came to think of two series kinetics, surface process and subsurface process. The former refers to an exchange process between gas-phase oxygen molecules and some sort of surface oxygen species. The latter refers to the exchange of surface oxygen with bulk oxide ions, and the reaction barrier is not necessarily oxygen transport, but may be electron transport/transfer for oxygen in/ex-corporation This hypothesis appeared to resolve some of our remaining questions regarding the experimental results, such as scattered <em>p</em><sub>O<sub>2</sub></sub> dependence in high partial pressure range, the higher isotope exchange rates than electrochemical impedance, and the reaction rate enhancement in the presence of the LaSrCoO<sub>4</sub> phase. While a single piece of such experimental evidence is insufficient to prove the hypothesis, considering all the results together provides strong support. We then tried to separate the contributions of surface and subsurface processes by measuring the surface oxygen potential using a porous oxygen sensor. It revealed that the surface process is written as <span><math><msub><mi>J</mi><mi>s</mi></msub><mo>=</mo><msub><mi>J</mi><mrow><mi>s</mi><mo>,</mo><mn>0</mn></mrow></msub><mo>∙</mo><mi>δ</mi><mo>∙</mo><mfenced><mrow><msubsup><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>s</mi></mrow><mn>2</mn></msubsup><mo>−</mo><msub><mi>p</mi><mrow><msub><mi>O</mi><mn>2</mn></msub><mo>,</mo><mi>g</mi></mrow></msub></mrow></mfenced></math></span> and the subsurface process as <span><math><msub><mi>J</mi><mi>ss</mi></msub><mo>=</mo><msub><mi>J</mi><mrow><mi>ss</mi><mo>,</mo><mn>0</mn></mrow></msub><mo>∙</mo><mfenced><mrow><msub><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>e</mi></mrow></msub><msubsup><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>s</mi></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msubsup><mo>−</mo><msubsup><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>e</mi></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msubsup><msub><mi>a</mi><mrow><mi>O</mi><mo>,</mo><mi>s</mi></mrow></msub></mrow></mfenced><mo>=</mo><msub><mi>J</mi><mrow><mi>ss</mi><mo>,</mo><mn>0</mn></mrow></msub><mfenced><mrow><mi>exp</mi><mfenced><mfrac><mrow><mi>β</mi><mo>∆</mo><msub><mi>μ</mi><msub><mi>O</mi><mn>2</mn></msub></msub></mrow><mi>RT</mi></mfrac></mfenced><mo>−</mo><mi>exp</mi><mfenced><mrow><mo>−</mo><mfrac><mrow><mfenced><mrow><mn>1</mn><mo>−</mo><mi>β</mi></mrow></mfenced><mo>∆</mo><msub><mi>μ</mi><msub><mi>O</mi><mn>2</mn></msub></msub></mrow><mi>RT</mi></mfrac></mrow></mfenced></mrow></mfenced></math></span>, which are in good agreement with the experimental data even for f","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116973"},"PeriodicalIF":3.0,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144704384","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}
Pub Date : 2025-07-25DOI: 10.1016/j.ssi.2025.116972
Paul Nizet , Francesco Chiabrera , Alex Morata , Albert Tarancón
Electrochemical Impedance Spectroscopy (EIS) is the conventional technique for studying the electrical response of individual materials or complete energy devices such as batteries, fuel cells, and supercapacitors. However, EIS has several limitations, including its spatial resolution, the description of ion insertion phenomena (especially when multiple ion species are involved), and the presence of porous electrodes. In this paper, Generalized Ionic Impedance Spectroscopy (GIIS) is proposed to address these issues by complementing traditional EIS to analyze ionic concentration changes under an AC voltage stimulus. A broad range of characterization techniques can be employed to analyze such ionic concentration variations, as these significantly modify the functional properties of the material, such as optical, magnetic, and electrical behavior. Some of these techniques also offer high spatial resolution, enabling lateral and depth profiling analysis. This study provides a theoretical framework for the development of GIIS in the field of energy, analyzing battery-like and fuel cell-like devices while resolving the major limitations of EIS mentioned above. The proven versatility of GIIS opens new pathways for the detailed characterization of energy materials and devices, advancing the understanding of low-frequency fundamental electrochemical processes and broadening the scope of their applications. While many of the discussed cases are experimentally validated, others are presented as perspectives of GIIS applications.
{"title":"When ions are in charge: Generalized ionic impedance spectroscopy for characterizing energy materials and devices","authors":"Paul Nizet , Francesco Chiabrera , Alex Morata , Albert Tarancón","doi":"10.1016/j.ssi.2025.116972","DOIUrl":"10.1016/j.ssi.2025.116972","url":null,"abstract":"<div><div>Electrochemical Impedance Spectroscopy (EIS) is the conventional technique for studying the electrical response of individual materials or complete energy devices such as batteries, fuel cells, and supercapacitors. However, EIS has several limitations, including its spatial resolution, the description of ion insertion phenomena (especially when multiple ion species are involved), and the presence of porous electrodes. In this paper, Generalized Ionic Impedance Spectroscopy (GIIS) is proposed to address these issues by complementing traditional EIS to analyze ionic concentration changes under an AC voltage stimulus. A broad range of characterization techniques can be employed to analyze such ionic concentration variations, as these significantly modify the functional properties of the material, such as optical, magnetic, and electrical behavior. Some of these techniques also offer high spatial resolution, enabling lateral and depth profiling analysis. This study provides a theoretical framework for the development of GIIS in the field of energy, analyzing battery-like and fuel cell-like devices while resolving the major limitations of EIS mentioned above. The proven versatility of GIIS opens new pathways for the detailed characterization of energy materials and devices, advancing the understanding of low-frequency fundamental electrochemical processes and broadening the scope of their applications. While many of the discussed cases are experimentally validated, others are presented as perspectives of GIIS applications.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116972"},"PeriodicalIF":3.0,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144702473","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}
Pub Date : 2025-07-25DOI: 10.1016/j.ssi.2025.116976
Akanksha Yadav , Yeting Wen , Xi Yang , Dunji Yu , Yan Chen , Kevin Huang
Solid oxide ion electrolytes (SOEs) play a crucial role in determining the operating temperature, cost, and lifetime of solid oxide electrochemical devices. The most competitive SOEs are typically found in cubic-structured fluorides (e.g., ZrO2-based and CeO2-based) and perovskites (e.g., LaGaO3-based and Ba(Zr,Ce)O3-based). However, the discovery of new high-conductivity SOE systems has been very limited in the history of solid state ionics. Here, we explore a new cubic-structured perovskite, Ba1-xNaxZr1-xGaxO3-x (BNZG), as a potential oxide-ion conductor. Compared to La0.8Sr0.2Ga0.8Mg0.2O2.8 (LSGM), a state-of-the-art perovskite electrolyte, BNZG exhibits a comparable bulk ionic conductivity (∼0.01 S/cm at 600°C) while reducing Ga content by 40 %. Additionally, compared to BaZr0.8Y0.2O2.9 (BZY), another widely studied perovskite electrolyte, BNZG shows excellent sinterability at lower temperatures. Ab Initio molecular dynamics (AIMD) simulations suggest that BNZG is an oxide-ion conductor, particularly at higher temperatures, which is also confirmed by high oxide-ion transport number (>0.99) and conductivity independent of oxygen and water vapor partial pressures. Furthermore, BNZG is stable in CO2/air and compatible with active perovskite cathodes such as La1-xSrxCoO3-δ without the use of barrier layer. We also show that the high grain-boundary resistance originated from Ga segregation could be one critical issue for BNZG application in intermediate temperature solid oxide cells.
{"title":"High Oxide-ion Conductivity in Cubic Perovskite Na- and Ga-doped BaZrO3","authors":"Akanksha Yadav , Yeting Wen , Xi Yang , Dunji Yu , Yan Chen , Kevin Huang","doi":"10.1016/j.ssi.2025.116976","DOIUrl":"10.1016/j.ssi.2025.116976","url":null,"abstract":"<div><div>Solid oxide ion electrolytes (SOEs) play a crucial role in determining the operating temperature, cost, and lifetime of solid oxide electrochemical devices. The most competitive SOEs are typically found in cubic-structured fluorides (e.g., ZrO<sub>2</sub>-based and CeO<sub>2</sub>-based) and perovskites (e.g., LaGaO<sub>3</sub>-based and Ba(<em>Zr</em>,<em>Ce</em>)O<sub>3</sub>-based). However, the discovery of new high-conductivity SOE systems has been very limited in the history of solid state ionics. Here, we explore a new cubic-structured perovskite, Ba<sub>1-x</sub>Na<sub>x</sub>Zr<sub>1-x</sub>Ga<sub>x</sub>O<sub>3-x</sub> (BNZG), as a potential oxide-ion conductor. Compared to La<sub>0.8</sub>Sr<sub>0.2</sub>Ga<sub>0.8</sub>Mg<sub>0.2</sub>O<sub>2.8</sub> (LSGM), a state-of-the-art perovskite electrolyte, BNZG exhibits a comparable bulk ionic conductivity (∼0.01 S/cm at 600°C) while reducing Ga content by 40 %. Additionally, compared to BaZr<sub>0.8</sub>Y<sub>0.2</sub>O<sub>2.9</sub> (BZY), another widely studied perovskite electrolyte, BNZG shows excellent sinterability at lower temperatures. Ab Initio molecular dynamics (AIMD) simulations suggest that BNZG is an oxide-ion conductor, particularly at higher temperatures, which is also confirmed by high oxide-ion transport number (>0.99) and conductivity independent of oxygen and water vapor partial pressures. Furthermore, BNZG is stable in CO<sub>2</sub>/air and compatible with active perovskite cathodes such as La<sub>1-x</sub>Sr<sub>x</sub>CoO<sub>3-δ</sub> without the use of barrier layer. We also show that the high grain-boundary resistance originated from Ga segregation could be one critical issue for BNZG application in intermediate temperature solid oxide cells.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116976"},"PeriodicalIF":3.0,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144702474","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}
Pub Date : 2025-07-24DOI: 10.1016/j.ssi.2025.116966
Chuanxiang Zhang , Hao Zhang , Qingyang Hu , Yuhan Zhang , Zhixin Liu , Xingxu Gao , Tao Wang
The uncontrollable growth of lithium dendrites has a huge impact on the practical application of lithium metal batteries. The separator is an integral element of the battery and fulfils two functions: firstly, it ensures the normal operation of the battery, and secondly, it is effective in inhibiting the growth of lithium dendrites. The present paper proposes the establishment of a two-dimensional phase field model, with the objective of investigating the effects of the ceramic composite diaphragm phase and the PE separator diaphragm phase on lithium dendrite growth. This investigation is conducted under conditions of stress and temperature fields. It has been shown that the elastic modulus of ceramic particles is greater than that of lithium metal. Therefore, the ceramic separator can effectively prevent the growth of lithium dendrites under stress-coupled conditions. In addition, at higher temperatures, it is beneficial to the transport of lithium ions and increases the deposition of lithium dendrites in the tip and non-tip regions, thereby reducing the length of lithium dendrites at high temperatures. This study reveals the important influence of the ceramic separator on inhibiting the growth of lithium dendrites under the conditions of stress field and temperature field.
{"title":"Phase field simulation of effect of ceramic composite separator on the growth of lithium dendrites","authors":"Chuanxiang Zhang , Hao Zhang , Qingyang Hu , Yuhan Zhang , Zhixin Liu , Xingxu Gao , Tao Wang","doi":"10.1016/j.ssi.2025.116966","DOIUrl":"10.1016/j.ssi.2025.116966","url":null,"abstract":"<div><div>The uncontrollable growth of lithium dendrites has a huge impact on the practical application of lithium metal batteries. The separator is an integral element of the battery and fulfils two functions: firstly, it ensures the normal operation of the battery, and secondly, it is effective in inhibiting the growth of lithium dendrites. The present paper proposes the establishment of a two-dimensional phase field model, with the objective of investigating the effects of the ceramic composite diaphragm phase and the PE separator diaphragm phase on lithium dendrite growth. This investigation is conducted under conditions of stress and temperature fields. It has been shown that the elastic modulus of ceramic particles is greater than that of lithium metal. Therefore, the ceramic separator can effectively prevent the growth of lithium dendrites under stress-coupled conditions. In addition, at higher temperatures, it is beneficial to the transport of lithium ions and increases the deposition of lithium dendrites in the tip and non-tip regions, thereby reducing the length of lithium dendrites at high temperatures. This study reveals the important influence of the ceramic separator on inhibiting the growth of lithium dendrites under the conditions of stress field and temperature field.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116966"},"PeriodicalIF":3.0,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144695115","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}
Pub Date : 2025-07-23DOI: 10.1016/j.ssi.2025.116971
Moran Lifshitz , Anna Greenbaum , Inbar Anconina , Thomas Leirikh , Mounesha Garaga Nagendrachar , Ivan Popov , Harmandeep Singh , Gaukhar Toleutay , Yuri Feldman , Alexei P. Sokolov , Steve Greenbaum , Diana Golodnitsky
Composite solid electrolytes, in which superionic ceramics materials are combined with ion-conducting polymers, could revolutionize electrochemical-energy-storage devices enabling higher energy density, providing greater stability during operation and enhanced safety. However, the interfacial resistance between the ceramic and polymer phases strongly suppresses the ionic conductivity and presents the main obstacle for the practical uses.
In the current article, an attempt has been made to improve composite conductivity by significantly increasing ceramic concentration in combination with the polymerized ionic liquid (PolyIL). The film was prepared by the electrophoretic deposition method. We believe this is the first demonstration of a PolyIL as a multifunctional additive in EPD, enabling both field-driven deposition and an integrated electrolyte architecture that ensures mechanical cohesion and continuous ion transport pathways. We deposited thirty-micron-thick composite film, which contains more than 90 wt% of LAGP. It has porous structure, in which single ceramic particles and their aggregates are coated by PolyIL. Broad Band Dielectric Spectroscopy method is used for the understanding of ion transport in composite polymer-in-ceramic electrolyte. We observed no improvement in conductivity and assign this to the dominating effect of interfacial energy barriers limiting Li transport in composites.
{"title":"Electrophoretically deposited polymer-in-ceramic electrolyte comprising polymerized ionic liquid","authors":"Moran Lifshitz , Anna Greenbaum , Inbar Anconina , Thomas Leirikh , Mounesha Garaga Nagendrachar , Ivan Popov , Harmandeep Singh , Gaukhar Toleutay , Yuri Feldman , Alexei P. Sokolov , Steve Greenbaum , Diana Golodnitsky","doi":"10.1016/j.ssi.2025.116971","DOIUrl":"10.1016/j.ssi.2025.116971","url":null,"abstract":"<div><div>Composite solid electrolytes, in which superionic ceramics materials are combined with ion-conducting polymers, could revolutionize electrochemical-energy-storage devices enabling higher energy density, providing greater stability during operation and enhanced safety. However, the interfacial resistance between the ceramic and polymer phases strongly suppresses the ionic conductivity and presents the main obstacle for the practical uses.</div><div>In the current article, an attempt has been made to improve composite conductivity by significantly increasing ceramic concentration in combination with the polymerized ionic liquid (PolyIL). The film was prepared by the electrophoretic deposition method. We believe this is the first demonstration of a PolyIL as a multifunctional additive in EPD, enabling both field-driven deposition and an integrated electrolyte architecture that ensures mechanical cohesion and continuous ion transport pathways. We deposited thirty-micron-thick composite film, which contains more than 90 wt% of LAGP. It has porous structure, in which single ceramic particles and their aggregates are coated by PolyIL. Broad Band Dielectric Spectroscopy method is used for the understanding of ion transport in composite polymer-in-ceramic electrolyte. We observed no improvement in conductivity and assign this to the dominating effect of interfacial energy barriers limiting Li transport in composites.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116971"},"PeriodicalIF":3.0,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144685903","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}
Pub Date : 2025-07-22DOI: 10.1016/j.ssi.2025.116965
Fusheng Song , Hongbing Wei , Zongyang Shen , Zhumei Wang , Yueming Li
The sulfurization pathways of pure and Na-doped CeO2 with CS₂ were investigated to elucidate the mechanism by which Na+ doping lowers γ-Ce2S3 synthesis temperature. For undoped CeO2, the synthesis of γ-Ce2S3 typically encompasses three primary steps: (1) deoxidation, where oxygen in CeO2 is substituted by sulfur to form CeS2; (2) reduction of CeS2 to α-Ce2S3; (3) a phase transition sequence from α-Ce2S3 to β-Ce2S3, and subsequently to γ-Ce2S3. This process requires a high synthesis temperature of up to 1300 °C. Remarkably, Na+ introduction fundamentally altered this pathway, bypassing α and β intermediates to directly yield pure γ-Ce2S3 at 900 °C. This is attributed to Na+-promoted formation of NaCeS2 and Ce2O2S intermediates that facilitate direct γ-phase crystallization. The resultant γ-[Na]-Ce2S3 solid solution exhibits modified band structure and enhanced thermal stability compared to undoped γ-Ce2S3.
{"title":"Exploring the reaction process and properties of γ-Ce2S3 derived from pure and Na-doped CeO2 sulfurization with CS2","authors":"Fusheng Song , Hongbing Wei , Zongyang Shen , Zhumei Wang , Yueming Li","doi":"10.1016/j.ssi.2025.116965","DOIUrl":"10.1016/j.ssi.2025.116965","url":null,"abstract":"<div><div>The sulfurization pathways of pure and Na-doped CeO<sub>2</sub> with CS₂ were investigated to elucidate the mechanism by which Na<sup>+</sup> doping lowers <em>γ</em>-Ce<sub>2</sub>S<sub>3</sub> synthesis temperature. For undoped CeO<sub>2</sub>, the synthesis of <em>γ</em>-Ce<sub>2</sub>S<sub>3</sub> typically encompasses three primary steps: (1) deoxidation, where oxygen in CeO<sub>2</sub> is substituted by sulfur to form CeS<sub>2</sub>; (2) reduction of CeS<sub>2</sub> to <em>α</em>-Ce<sub>2</sub>S<sub>3</sub>; (3) a phase transition sequence from <em>α</em>-Ce<sub>2</sub>S<sub>3</sub> to <em>β</em>-Ce<sub>2</sub>S<sub>3</sub>, and subsequently to <em>γ</em>-Ce<sub>2</sub>S<sub>3</sub>. This process requires a high synthesis temperature of up to 1300 °C. Remarkably, Na<sup>+</sup> introduction fundamentally altered this pathway, bypassing <em>α</em> and <em>β</em> intermediates to directly yield pure <em>γ</em>-Ce<sub>2</sub>S<sub>3</sub> at 900 °C. This is attributed to Na<sup>+</sup>-promoted formation of NaCeS<sub>2</sub> and Ce<sub>2</sub>O<sub>2</sub>S intermediates that facilitate direct <em>γ</em>-phase crystallization. The resultant <em>γ</em>-[Na]-Ce<sub>2</sub>S<sub>3</sub> solid solution exhibits modified band structure and enhanced thermal stability compared to undoped <em>γ</em>-Ce<sub>2</sub>S<sub>3</sub>.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116965"},"PeriodicalIF":3.0,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144679942","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}
Olivine-type lithium iron phosphate is widely used as a cathode material for lithium-ion batteries because of its moderate operating voltage, excellent stability, and high safety. However, the high rate capability of LiFePO4 is limited by its low electrical conductivity. Additionally, its interface and internal structure would degrade under high-rate conditions. To address these issues, Li3BO3 was prepared via sol-gel method as the surface decoration to enhance the rate performance of LiFePO4. The Li3BO3 decorated LiFePO4 (B-LiFePO4) maintains the structural integrity during cycling under large current densities, furthermore, it induces the formation of favorable cathode-electrolyte interface (CEI) with less Li2CO3 and more Li2O contents, and reduces the activation energy of Li+ diffusion in the CEI layer and charge transfer, thus the high capacity and long cycle performances of LiFePO4 are achieved when cycled at high current densities. At ambient environment and 30C, B-LiFePO4 delivers a high reversible capacity of 63.1 mAh g−1, and a capacity retention of 90 % can be realized over 600 cycles at 1C. In contrast, the original LiFePO4 delivers only 27.8 mAh g−1 at 30C and a capacity retention of 67.2 % after 600 cycles at 1C. Besides, B-LiFePO4 demonstrates good low temperature performance, it exhibits high capacities of 122.1 and 80.7 mAh g−1 at 1C, 0 °C and − 20 °C, respectively. This study provides a simple method to enhance the reaction kinetics of LiFePO4 cathode, which would benefit the development of LiFePO4 based lithium ion batteries with high rate performance.
橄榄石型磷酸铁锂因其工作电压适中、稳定性好、安全性高而被广泛用作锂离子电池的正极材料。然而，LiFePO4的高倍率性能受到其低导电性的限制。此外，它的界面和内部结构在高速率条件下会退化。为了解决这些问题，采用溶胶-凝胶法制备Li3BO3作为LiFePO4的表面装饰，以提高LiFePO4的速率性能。经过Li3BO3修饰的LiFePO4 （B-LiFePO4）在大电流密度循环过程中保持了结构的完整性，形成了Li2CO3含量少、Li2O含量高的阴极-电解质界面（CEI），降低了CEI层中Li+扩散和电荷转移的活化能，从而实现了LiFePO4在大电流密度循环时的高容量和长周期性能。在室温和30C下，B-LiFePO4可提供63.1 mAh g−1的高可逆容量，并且在1C下可实现超过600次循环的90%的容量保持。相比之下，原始的LiFePO4在30C下仅提供27.8 mAh g - 1，在1C下循环600次后容量保持率为67.2%。此外，B-LiFePO4具有良好的低温性能，在1C、0°C和- 20°C时，其容量分别为122.1和80.7 mAh g - 1。本研究为提高LiFePO4正极的反应动力学提供了一种简单的方法，这将有利于LiFePO4基锂离子电池的高倍率性能的发展。
{"title":"Li3BO3 decoration endows fast reaction kinetics of LiFePO4 cathode for lithium ion batteries","authors":"Kaihua Li, Jiajin Li, Haoyu Qi, Jinze Song, Diaohan Wang, Lijun Fu, Yuping Wu","doi":"10.1016/j.ssi.2025.116944","DOIUrl":"10.1016/j.ssi.2025.116944","url":null,"abstract":"<div><div>Olivine-type lithium iron phosphate is widely used as a cathode material for lithium-ion batteries because of its moderate operating voltage, excellent stability, and high safety. However, the high rate capability of LiFePO<sub>4</sub> is limited by its low electrical conductivity. Additionally, its interface and internal structure would degrade under high-rate conditions. To address these issues, Li<sub>3</sub>BO<sub>3</sub> was prepared via sol-gel method as the surface decoration to enhance the rate performance of LiFePO<sub>4</sub>. The Li<sub>3</sub>BO<sub>3</sub> decorated LiFePO<sub>4</sub> (B-LiFePO<sub>4</sub>) maintains the structural integrity during cycling under large current densities, furthermore, it induces the formation of favorable cathode-electrolyte interface (CEI) with less Li<sub>2</sub>CO<sub>3</sub> and more Li<sub>2</sub>O contents, and reduces the activation energy of Li<sup>+</sup> diffusion in the CEI layer and charge transfer, thus the high capacity and long cycle performances of LiFePO<sub>4</sub> are achieved when cycled at high current densities. At ambient environment and 30C, B-LiFePO<sub>4</sub> delivers a high reversible capacity of 63.1 mAh g<sup>−1</sup>, and a capacity retention of 90 % can be realized over 600 cycles at 1C. In contrast, the original LiFePO<sub>4</sub> delivers only 27.8 mAh g<sup>−1</sup> at 30C and a capacity retention of 67.2 % after 600 cycles at 1C. Besides, B-LiFePO<sub>4</sub> demonstrates good low temperature performance, it exhibits high capacities of 122.1 and 80.7 mAh g<sup>−1</sup> at 1C, 0 °C and − 20 °C, respectively. This study provides a simple method to enhance the reaction kinetics of LiFePO<sub>4</sub> cathode, which would benefit the development of LiFePO<sub>4</sub> based lithium ion batteries with high rate performance.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116944"},"PeriodicalIF":3.0,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144671017","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}
Pub Date : 2025-07-18DOI: 10.1016/j.ssi.2025.116956
N.N.A. Hafidz , N.M. Ghazali , N.F. Mazuki , M. Diantoro , Y. Nagao , A.S. Samsudin
This study explores the effect of graphene oxide (GO) incorporation on the structural and electrochemical properties of alginate–poly(vinyl alcohol) (PVA) polymer electrolytes doped with ammonium nitrate (NH₄NO₃) for supercapacitor applications. FTIR analysis revealed specific molecular interactions between graphene oxide (GO) and the polymer host, while XRD results confirmed the enhanced amorphous nature of the composite. At 2 wt.% GO loading, the system exhibited peak ionic conductivity of 1.07 × 10−3 S cm−1 at room temperature, with a high ionic transference number (tₙ ≈ 0.98) and an extended electrochemical stability window of 2.85 V. Symmetric supercapacitors fabricated with these electrolytes achieved a specific capacitance of 240.78 F g−1, an energy density of 131 Wh kg−1, and long-term cycling stability up to 10,000 cycles. These results demonstrate that GO-induced structural modulation significantly enhances proton transport and electrochemical performance, offering a promising biopolymer-based platform for next-generation energy storage devices.
本研究探讨了氧化石墨烯（GO）掺入对掺杂硝酸铵（NH₄NO₃）的海藻酸盐-聚乙烯醇（PVA）聚合物电解质的结构和电化学性能的影响。FTIR分析揭示了氧化石墨烯（GO）与聚合物主体之间的特定分子相互作用，而XRD结果证实了复合材料的非晶态性质增强。当氧化石墨烯（GO）负载为2 wt.%时，该体系在室温下的离子电导率峰值为1.07 × 10−3 S cm−1，具有较高的离子转移数（t≈0.98）和2.85 V的扩展电化学稳定窗口。用这些电解质制成的对称超级电容器的比电容为240.78 F g−1，能量密度为131 Wh kg−1，长期循环稳定性高达10,000次循环。这些结果表明，氧化石墨烯诱导的结构调制显著提高了质子传输和电化学性能，为下一代储能设备提供了一个有前途的基于生物聚合物的平台。
{"title":"Graphene oxide-enhanced alginate-PVA biopolymer electrolytes with improved proton conductivity and electrochemical stability for supercapacitor applications","authors":"N.N.A. Hafidz , N.M. Ghazali , N.F. Mazuki , M. Diantoro , Y. Nagao , A.S. Samsudin","doi":"10.1016/j.ssi.2025.116956","DOIUrl":"10.1016/j.ssi.2025.116956","url":null,"abstract":"<div><div>This study explores the effect of graphene oxide (GO) incorporation on the structural and electrochemical properties of alginate–poly(vinyl alcohol) (PVA) polymer electrolytes doped with ammonium nitrate (NH₄NO₃) for supercapacitor applications. FTIR analysis revealed specific molecular interactions between graphene oxide (GO) and the polymer host, while XRD results confirmed the enhanced amorphous nature of the composite. At 2 wt.% GO loading, the system exhibited peak ionic conductivity of 1.07 × 10<sup>−3</sup> S cm<sup>−1</sup> at room temperature, with a high ionic transference number (tₙ ≈ 0.98) and an extended electrochemical stability window of 2.85 V. Symmetric supercapacitors fabricated with these electrolytes achieved a specific capacitance of 240.78 F g<sup>−1</sup>, an energy density of 131 Wh kg<sup>−1</sup>, and long-term cycling stability up to 10,000 cycles. These results demonstrate that GO-induced structural modulation significantly enhances proton transport and electrochemical performance, offering a promising biopolymer-based platform for next-generation energy storage devices.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"429 ","pages":"Article 116956"},"PeriodicalIF":3.0,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144656006","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}
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