Solid State Ionics最新文献

Atomistic insights into the carbonation behavior of olivine minerals: Role of metal cation composition

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-19 DOI: 10.1016/j.ssi.2025.116845

Saisai Zhang, Xinyu Zhang, Li Zhang, Donglin Li, Xuemao Guan, Jianping Zhu, Songhui Liu

Olivine minerals possess significant potential for CO₂ sequestration through carbonation reactions, with their reactivity highly influenced by cation composition. This study employs first-principles calculations to systematically investigate the impact of metal cations (Mg²⁺, Ca²⁺, Mn²⁺, Fe²⁺, Co²⁺) on the carbonation behavior of five olivine structures: forsterite (Mg₂SiO₄), calcio-olivine (γ-Ca₂SiO₄), tephroite (α-Mn₂SiO₄), fayalite (α-Fe₂SiO₄), and Co-olivine. Analyses of bond characteristics, total bond order density, and local density of states reveal fundamental differences between alkaline earth and transition metal olivines. We have found that in alkaline earth (AE) olivines, carbonation primarily involves an electrophilic attack of O²⁻ by H⁺ and a nucleophilic attack of metal cations by HCO₃⁻/CO₃²⁻ species. Calcio-olivine exhibits higher reactivity than forsterite due to enhanced Ca²⁺ nucleophilicity. Conversely, transition metal (TM) olivine reactivity is governed by the multivalent cations, contributing significantly to both electrophilic and nucleophilic pathways. Considering both mineral reserves and carbonation reaction mechanisms, calcio-olivine is determined to be the most advantageous among the five olivine minerals in terms of carbonation reactivity. This atomic-scale understanding guides the development of olivine-based materials with improved carbonation performance for efficient CO₂ sequestration and utilization in carbon capture, utilization, and storage technologies.

{"title":"Atomistic insights into the carbonation behavior of olivine minerals: Role of metal cation composition","authors":"Saisai Zhang, Xinyu Zhang, Li Zhang, Donglin Li, Xuemao Guan, Jianping Zhu, Songhui Liu","doi":"10.1016/j.ssi.2025.116845","DOIUrl":"10.1016/j.ssi.2025.116845","url":null,"abstract":"<div><div>Olivine minerals possess significant potential for CO2 sequestration through carbonation reactions, with their reactivity highly influenced by cation composition. This study employs first-principles calculations to systematically investigate the impact of metal cations (Mg2+, Ca2+, Mn2+, Fe2+, Co2+) on the carbonation behavior of five olivine structures: forsterite (Mg2SiO4), calcio-olivine (γ-Ca2SiO4), tephroite (α-Mn2SiO4), fayalite (α-Fe2SiO4), and Co-olivine. Analyses of bond characteristics, total bond order density, and local density of states reveal fundamental differences between alkaline earth and transition metal olivines. We have found that in alkaline earth (AE) olivines, carbonation primarily involves an electrophilic attack of O2− by H+ and a nucleophilic attack of metal cations by HCO3−/CO32− species. Calcio-olivine exhibits higher reactivity than forsterite due to enhanced Ca2+ nucleophilicity. Conversely, transition metal (TM) olivine reactivity is governed by the multivalent cations, contributing significantly to both electrophilic and nucleophilic pathways. Considering both mineral reserves and carbonation reaction mechanisms, calcio-olivine is determined to be the most advantageous among the five olivine minerals in terms of carbonation reactivity. This atomic-scale understanding guides the development of olivine-based materials with improved carbonation performance for efficient CO2 sequestration and utilization in carbon capture, utilization, and storage technologies.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116845"},"PeriodicalIF":3.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143642962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Distinct influence of Cd in the electrocatalyst of Ni-Co-Cd/CNFs nanoparticles as a catalyst in direct alcohol fuel cells (DAFCs)

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-19 DOI: 10.1016/j.ssi.2025.116846

Al-Anood M. Al-Dies , Somia Awad

Different percentages of less expensive metal alloy-decorated nanofiber catalysts have been successfully manufactured using the electrospinning method to replace platinum in direct alcohol fuel cells (DAFC). The synthesis and characterization of catalysts, namely Ni-Co-Cd/CNFs, with a metal fixed ratio of 20 % wt. for DAFC applications are the main goals of this work. Two different catalyst concentrations were prepared with fixed nickel concentrations (Ni₁₂Co₆Cd₂ & Ni₁₂Co₄Cd₄). This research represents the first preparation of ternary Ni-Co-Cd/CNF for DAFC applications. Various methods, including electrochemical tests, transmission electron microscopy, scanning electron microscopy, and x-ray diffraction, are used to characterize the catalysts. Scanning electron microscopy (SEM) revealed that the fabricated sample exhibited a good nanofiber form and a distinct nanoparticle look. The samples' capacity for alcohol electrocatalysis was assessed using cyclic voltammetry, impedance spectroscopy, chronoamperometry, scan rate, and response time. The oxidation peak current density and electrode stability both rise when the concentration of Cd in Ni-Co-Cd/CNF increases. The oxidation peak current density of Ni₁₂Co₄Cd₄ at the optimum ethanol concentration (1 M ethanol in 1 M KOH) is found to be 29.7 mA/cm². While the maximum current density is found to equal 38.86 mA/cm². In addition, the CV results yield the oxidation peak current density to be 3.5 mA/cm² at the optimum methanol concentration (1 M methanol in 1 M KOH). Ni₁₂Co₄Cd₄ exhibits promoted electrochemical properties to ethanol electrooxidation rather than methanol oxidation. Furthermore, these findings are enhanced by the highly calculated diffusion coefficient of Ni₁₂Co₄Cd₄ towards ethanol in comparison with methanol (2.30 × 10⁻⁶ cm²/s for ethanol and 3.07 × 10⁻⁷ cm²/s for methanol). This work has demonstrated how to use a unique technique to develop an efficient alcohol electrooxidation catalyst based on nickel, cobalt, and cadmium nanoparticles.

{"title":"Distinct influence of Cd in the electrocatalyst of Ni-Co-Cd/CNFs nanoparticles as a catalyst in direct alcohol fuel cells (DAFCs)","authors":"Al-Anood M. Al-Dies , Somia Awad","doi":"10.1016/j.ssi.2025.116846","DOIUrl":"10.1016/j.ssi.2025.116846","url":null,"abstract":"<div><div>Different percentages of less expensive metal alloy-decorated nanofiber catalysts have been successfully manufactured using the electrospinning method to replace platinum in direct alcohol fuel cells (DAFC). The synthesis and characterization of catalysts, namely Ni-Co-Cd/CNFs, with a metal fixed ratio of 20 % wt. for DAFC applications are the main goals of this work. Two different catalyst concentrations were prepared with fixed nickel concentrations (Ni12Co6Cd2 & Ni12Co4Cd4). This research represents the first preparation of ternary Ni-Co-Cd/CNF for DAFC applications. Various methods, including electrochemical tests, transmission electron microscopy, scanning electron microscopy, and x-ray diffraction, are used to characterize the catalysts. Scanning electron microscopy (SEM) revealed that the fabricated sample exhibited a good nanofiber form and a distinct nanoparticle look. The samples' capacity for alcohol electrocatalysis was assessed using cyclic voltammetry, impedance spectroscopy, chronoamperometry, scan rate, and response time. The oxidation peak current density and electrode stability both rise when the concentration of Cd in Ni-Co-Cd/CNF increases. The oxidation peak current density of Ni12Co4Cd4 at the optimum ethanol concentration (1 M ethanol in 1 M KOH) is found to be 29.7 mA/cm2. While the maximum current density is found to equal 38.86 mA/cm2. In addition, the CV results yield the oxidation peak current density to be 3.5 mA/cm2 at the optimum methanol concentration (1 M methanol in 1 M KOH). Ni12Co4Cd4 exhibits promoted electrochemical properties to ethanol electrooxidation rather than methanol oxidation. Furthermore, these findings are enhanced by the highly calculated diffusion coefficient of Ni12Co4Cd4 towards ethanol in comparison with methanol (2.30 × 10−6 cm2/s for ethanol and 3.07 × 10−7 cm2/s for methanol). This work has demonstrated how to use a unique technique to develop an efficient alcohol electrooxidation catalyst based on nickel, cobalt, and cadmium nanoparticles.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116846"},"PeriodicalIF":3.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143642963","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

Structural transformations and proton conductivity of Me4NHSO4 and nanocomposites Me4NHSO4 - SiO2

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-17 DOI: 10.1016/j.ssi.2025.116810

V.G. Ponomareva, I.N. Bagryantseva, E.S. Shutova, T.N. Drebushchak, N.F. Uvarov

The study is devoted to the quaternary ammonium compounds - Me₄NHSO₄. The detailed analysis of the proton conductivity and structural transformations of Me₄NHSO₄ in a wide temperature range was carried out firstly. A phase transition of Me₄NHSO₄ at 120°С associated with the appearance of intermediate phase with some orientational disorder of sulfate tetrahedra was observed. The slow rate phase transition at 210 °C to a high-temperature phase was firstly observed. Presumably the high-temperature phase corresponds to a tetragonal syngony. The temperature dependence of the proton conductivity fully corresponds to the structural phase transitions with the significant change of the activation energy at 120 °C from 1.8 eV to 0.7 eV up to 250 °C. The proton conductivity of Me₄NHSO₄ of the high temperature phase is an order of magnitude higher than that of the related Et₄NHSO₄ compound and reaches 4*10⁻⁴ S/cm at 250 °C. The electrotransport and structural characteristics of Me₄NHSO₄ and dispersed silicon dioxide containing composites were also investigated. The investigated (1-x)Me₄NHSO₄–xSiO₂ composites (x = 0.5 and 0.7) are characterized by the different degree of salt amorhpization and the conductivity increase.

{"title":"Structural transformations and proton conductivity of Me4NHSO4 and nanocomposites Me4NHSO4 - SiO2","authors":"V.G. Ponomareva, I.N. Bagryantseva, E.S. Shutova, T.N. Drebushchak, N.F. Uvarov","doi":"10.1016/j.ssi.2025.116810","DOIUrl":"10.1016/j.ssi.2025.116810","url":null,"abstract":"<div><div>The study is devoted to the quaternary ammonium compounds - Me4NHSO4. The detailed analysis of the proton conductivity and structural transformations of Me4NHSO4 in a wide temperature range was carried out firstly. A phase transition of Me4NHSO4 at 120°С associated with the appearance of intermediate phase with some orientational disorder of sulfate tetrahedra was observed. The slow rate phase transition at 210 °C to a high-temperature phase was firstly observed. Presumably the high-temperature phase corresponds to a tetragonal syngony. The temperature dependence of the proton conductivity fully corresponds to the structural phase transitions with the significant change of the activation energy at 120 °C from 1.8 eV to 0.7 eV up to 250 °C. The proton conductivity of Me4NHSO4 of the high temperature phase is an order of magnitude higher than that of the related Et4NHSO4 compound and reaches 4*10−4 S/cm at 250 °C. The electrotransport and structural characteristics of Me4NHSO4 and dispersed silicon dioxide containing composites were also investigated. The investigated (1-x)Me4NHSO4–xSiO2 composites (x = 0.5 and 0.7) are characterized by the different degree of salt amorhpization and the conductivity increase.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116810"},"PeriodicalIF":3.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631949","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 and electrochemical performance enhancement of Li2MnSiO4 cathode material for lithium-ion batteries via Mn-site Cr doping

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-17 DOI: 10.1016/j.ssi.2025.116847

Yuqi Yao , Xin Yan , Shao-hua Luo , Jing Guo

Li₂MnSiO₄ stands out as a promising cathode material for lithium-ion batteries (LIBs) because of its remarkable theoretical capacity, excellent thermal stability, low cost, and environmental benefits. However, its practical application is hindered by poor electronic conductivity and lithium-ion diffusion rates. To overcome these challenges, Li₂Mn_1-xCr_xSiO₄ cathode materials were prepared through solid-state doping and a two-step calcination method. By doping Cr into the Mn site of Li₂MnSiO₄, the electrochemical performance can be significantly improved. TG-DTA tests were conducted to determine the optimal calcination temperature to ensure stable synthesis of the material. The research found that an optimal Cr doping level of 0.06 resulted in superior electrochemical performance, achieving a discharge capacity of 174.9 mAh g⁻¹ at 0.1C. This improvement is due to the reduction in grain size, which increases the specific surface area and enhances Li⁺ diffusion. Additionally, the larger ionic radius of Cr creates more vacancies in the lattice, facilitating electron and ion migration. The CrO bond, being stronger than the MnO bond, further contributes to improved structural stability. Thus, Cr doping effectively addresses conductivity and diffusion limitations, leading to superior electrochemical performance and advancing high-performance LIBs.

{"title":"Synthesis and electrochemical performance enhancement of Li2MnSiO4 cathode material for lithium-ion batteries via Mn-site Cr doping","authors":"Yuqi Yao , Xin Yan , Shao-hua Luo , Jing Guo","doi":"10.1016/j.ssi.2025.116847","DOIUrl":"10.1016/j.ssi.2025.116847","url":null,"abstract":"<div><div>Li2MnSiO4 stands out as a promising cathode material for lithium-ion batteries (LIBs) because of its remarkable theoretical capacity, excellent thermal stability, low cost, and environmental benefits. However, its practical application is hindered by poor electronic conductivity and lithium-ion diffusion rates. To overcome these challenges, Li2Mn1-xCrxSiO4 cathode materials were prepared through solid-state doping and a two-step calcination method. By doping Cr into the Mn site of Li2MnSiO4, the electrochemical performance can be significantly improved. TG-DTA tests were conducted to determine the optimal calcination temperature to ensure stable synthesis of the material. The research found that an optimal Cr doping level of 0.06 resulted in superior electrochemical performance, achieving a discharge capacity of 174.9 mAh g−1 at 0.1C. This improvement is due to the reduction in grain size, which increases the specific surface area and enhances Li+ diffusion. Additionally, the larger ionic radius of Cr creates more vacancies in the lattice, facilitating electron and ion migration. The Cr<img>O bond, being stronger than the Mn<img>O bond, further contributes to improved structural stability. Thus, Cr doping effectively addresses conductivity and diffusion limitations, leading to superior electrochemical performance and advancing high-performance LIBs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116847"},"PeriodicalIF":3.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631948","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

Interface design for enhancing the performance of solid oxide cell contact layers between interconnects and solid oxide cells

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-17 DOI: 10.1016/j.ssi.2025.116841

Takayuki Nakao , Shuichi Inoue

In a planar solid oxide cell (SOC) stack, the assembly consists of metal materials and ceramic cells in which various ceramics (such as electrolytes and electrodes) are laminated in multiple layers. Notably, the interface between the air-side electrode and the coated interconnector plays a critical role in determining the performance of the SOC stack, during the manufacturing process. Unlike other SOC cell components, which are typically sintered at high temperature (e.g., over 1000 °C), the contact material at this interface is constructed during the SOC stacking process, generally at a lower temperature range of 750 °C–850 °C. Consequently, the contact material connecting the air electrode and the coated interconnector must exhibit high adhesion and low electrical resistance at 800 °C. In this study, a low-resistance, highly adhesive interface between the air electrode and the interconnector in the SOC stack is developed through diffusion bonding and metal addition at lower temperatures. CoMn spinel oxides are employed as both the contact material and the coating layer, and a concentration gradient is achieved in the contact material and coating layer, with high adhesion and low resistance facilitated by the interdiffusion of Co and Mn. The heat generated during the oxidation of the added metallic Co promotes sintering, further enhancing adhesion. The diffusion bonding interface and the metal-added diffusion bonding interface were subjected to continuous durability tests over 10,000 h, and no deterioration was observed.

{"title":"Interface design for enhancing the performance of solid oxide cell contact layers between interconnects and solid oxide cells","authors":"Takayuki Nakao , Shuichi Inoue","doi":"10.1016/j.ssi.2025.116841","DOIUrl":"10.1016/j.ssi.2025.116841","url":null,"abstract":"<div><div>In a planar solid oxide cell (SOC) stack, the assembly consists of metal materials and ceramic cells in which various ceramics (such as electrolytes and electrodes) are laminated in multiple layers. Notably, the interface between the air-side electrode and the coated interconnector plays a critical role in determining the performance of the SOC stack, during the manufacturing process. Unlike other SOC cell components, which are typically sintered at high temperature (e.g., over 1000 °C), the contact material at this interface is constructed during the SOC stacking process, generally at a lower temperature range of 750 °C–850 °C. Consequently, the contact material connecting the air electrode and the coated interconnector must exhibit high adhesion and low electrical resistance at 800 °C. In this study, a low-resistance, highly adhesive interface between the air electrode and the interconnector in the SOC stack is developed through diffusion bonding and metal addition at lower temperatures. Co<img>Mn spinel oxides are employed as both the contact material and the coating layer, and a concentration gradient is achieved in the contact material and coating layer, with high adhesion and low resistance facilitated by the interdiffusion of Co and Mn. The heat generated during the oxidation of the added metallic Co promotes sintering, further enhancing adhesion. The diffusion bonding interface and the metal-added diffusion bonding interface were subjected to continuous durability tests over 10,000 h, and no deterioration was observed.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116841"},"PeriodicalIF":3.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631947","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

Enhancing ionic conductivity in Li₇P₃S₁₁ solid electrolytes via doping strategies: Implications for solid-state lithium-sulfur batteries

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-15 DOI: 10.1016/j.ssi.2025.116844

Amirhossein Mirtaleb, Ruigang Wang

Solid-state electrolytes in the Li₂S-P₂S₅ system have emerged as promising candidates for next-generation all-solid-state batteries (ASSBs) due to their high ionic conductivity and superior electrochemical stability. Among these, the Li₇P₃S₁₁ phase exhibits exceptional ionic conductivity (∼10⁻³ S cm⁻¹ at room temperature), making it a focal point for materials research. This review provides a comprehensive analysis of dopant-driven modifications in Li₇P₃S₁₁, emphasizing their impact on structural evolution, ionic transport, electrochemical performance, and long-term stability. Both cationic (e.g., transition and alkali metals) and anionic (e.g., oxygen) doping strategies are examined, offering insights into their roles in optimizing ionic conductivity and interfacial compatibility. Sulfide dopants enhance lithium-ion mobility and interfacial stability with lithium metal and sulfur cathodes, while oxide dopants improve air stability and suppress dendrite formation. Nitride dopants, though beneficial for interfacial compatibility, may introduce additional resistance at electrode-electrolyte interfaces. Despite these advancements, challenges such as dopant-induced phase instability, synthesis complexity, and environmental sensitivity persist, necessitating a strategic approach to doping. By categorizing dopants based on their chemical interactions with the Li₇P₃S₁₁ matrix, this review outlines a framework for rational dopant selection and design. The insights presented herein provide a foundation for advancing doped solid electrolytes, accelerating the development of high-performance lithium‑sulfur batteries for next-generation energy storage applications.

锂₂S-P₂S₅体系的固态电解质具有高离子电导率和优异的电化学稳定性，因此已成为下一代全固态电池（ASSB）的理想候选材料。其中，Li₇P₃S₁₁相表现出卓越的离子导电性（室温下为 ∼10-3 S cm-1），使其成为材料研究的焦点。本综述全面分析了 Li₇P₃S₁₁ 中掺杂剂驱动的改性，强调了它们对结构演化、离子传输、电化学性能和长期稳定性的影响。本文研究了阳离子（如过渡金属和碱金属）和阴离子（如氧）掺杂策略，深入探讨了它们在优化离子传导性和界面相容性方面的作用。硫化物掺杂物提高了锂离子迁移率以及与锂金属和硫阴极的界面稳定性，而氧化物掺杂物则改善了空气稳定性并抑制了枝晶的形成。氮化物掺杂剂虽然有利于界面兼容性，但可能会在电极-电解质界面产生额外的电阻。尽管取得了这些进步，但掺杂剂引起的相不稳定性、合成复杂性和环境敏感性等挑战依然存在，因此必须采取战略性的掺杂方法。本综述根据掺杂剂与 Li₇P₃S₁₁ 基质的化学作用对掺杂剂进行分类，从而勾勒出合理选择和设计掺杂剂的框架。本文提出的见解为推动掺杂固体电解质的发展奠定了基础，从而加速了下一代储能应用中高性能锂硫电池的开发。

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引用次数: 0

SiO2 doped halogen-rich argyrodites for high-performance all-solid-state lithium–sulfur batteries

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-14 DOI: 10.1016/j.ssi.2025.116813

Jie-Fu Zhuo , Zhi-Feng Yao

The argyrodite-type sulfide electrolytes (Li₆PS₅X, X = Cl, Br, I) have demonstrated numerous benefits for high-performance and secure all-solid-state lithium‑sulfur batteries (ASSLSBs). These advantages include their rapid lithium (Li) ion conduction and exceptional compatibility with the anode. Nevertheless, despite these benefits, the key obstacles for their implementation are the need for higher room-temperature ionic conductivity, improved air/moisture compatibility, and enhanced electrochemical stability. In this study, we propose a halogen-rich argyrodite (Li_5.3PS_4.3Cl_1.7-xBr_x) to obtain ultrafast ionic conductivity at ambient temperature. To enhance the ionic transport channel, the anion disorder on the site is optimized and the Li vacancies in the structure are increased by substituting anions with halogens (Cl/Br). The Li_5.3PS_4.3Cl_0.85Br_0.85 is synthesized effectively by a high-energy ball milling process, resulting in a remarkable ionic conductivity of 9.07 mS⋅cm⁻¹ at room temperature. In addition, a SiO₂ dopant is utilized to strengthen the lattice structure of the solid-state electrolyte (Li_5.3+ySi_yP_1-yS_4.3-2yO_2yCl_0.85Br_0.85) in order to improve its resistance to air/moisture and enhance its electrochemical stability within specific voltage ranges. The Li_5.4Si_0.1P_0.9S_4.1O_0.2Cl_0.85Br_0.85 with optimized composition demonstrates an ionic conductivity of 8.2 mS⋅cm⁻¹ at room temperature and exceptional stability in air. The ASSLSBs containing Li_5.4Si_0.1P_0.9S_4.1O_0.2Cl_0.85Br_0.85 exhibit impressive specific capacities of 1191 mAh⋅g⁻¹ (0.1C after the initial cycle) and 989 mAh⋅g⁻¹ (0.1C after 100 cycles) at room temperature. Additionally, they demonstrate significant cyclability (83.04 % after 100 cycles) and excellent Coulombic efficiency (>99.5 %). This study presents a novel strategy to promote the application of sulfide electrolytes in fabricating ASSLSBs.

{"title":"SiO2 doped halogen-rich argyrodites for high-performance all-solid-state lithium–sulfur batteries","authors":"Jie-Fu Zhuo , Zhi-Feng Yao","doi":"10.1016/j.ssi.2025.116813","DOIUrl":"10.1016/j.ssi.2025.116813","url":null,"abstract":"<div><div>The argyrodite-type sulfide electrolytes (Li6PS5X, X = Cl, Br, I) have demonstrated numerous benefits for high-performance and secure all-solid-state lithium‑sulfur batteries (ASSLSBs). These advantages include their rapid lithium (Li) ion conduction and exceptional compatibility with the anode. Nevertheless, despite these benefits, the key obstacles for their implementation are the need for higher room-temperature ionic conductivity, improved air/moisture compatibility, and enhanced electrochemical stability. In this study, we propose a halogen-rich argyrodite (Li5.3PS4.3Cl1.7-xBrx) to obtain ultrafast ionic conductivity at ambient temperature. To enhance the ionic transport channel, the anion disorder on the site is optimized and the Li vacancies in the structure are increased by substituting anions with halogens (Cl/Br). The Li5.3PS4.3Cl0.85Br0.85 is synthesized effectively by a high-energy ball milling process, resulting in a remarkable ionic conductivity of 9.07 mS⋅cm−1 at room temperature. In addition, a SiO2 dopant is utilized to strengthen the lattice structure of the solid-state electrolyte (Li5.3+ySiyP1-yS4.3-2yO2yCl0.85Br0.85) in order to improve its resistance to air/moisture and enhance its electrochemical stability within specific voltage ranges. The Li5.4Si0.1P0.9S4.1O0.2Cl0.85Br0.85 with optimized composition demonstrates an ionic conductivity of 8.2 mS⋅cm−1 at room temperature and exceptional stability in air. The ASSLSBs containing Li5.4Si0.1P0.9S4.1O0.2Cl0.85Br0.85 exhibit impressive specific capacities of 1191 mAh⋅g−1 (0.1C after the initial cycle) and 989 mAh⋅g−1 (0.1C after 100 cycles) at room temperature. Additionally, they demonstrate significant cyclability (83.04 % after 100 cycles) and excellent Coulombic efficiency (>99.5 %). This study presents a novel strategy to promote the application of sulfide electrolytes in fabricating ASSLSBs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"423 ","pages":"Article 116813"},"PeriodicalIF":3.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620999","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

Rational molecular design of partly fluorinated fuel cell membranes with high proton conductivity under low-humidity conditions

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-13 DOI: 10.1016/j.ssi.2025.116837

Haiyue Gong, Hannes Nederstedt, Seung-Young Choi, Patric Jannasch

Research on proton exchange membranes (PEMs) is closely tied to the development of PEM fuel cells, and the need to overcome the shortcomings of perfluorosulfonic acid PEMs. One of the key challenges is to devise efficient molecular designs towards PEMs with sufficient durability and proton conductivity under reduced humidity. Here, we report on a series of partly fluorinated PEMs based on high-molecular weight poly(arylene tetrafluorophenylsulfonic acid)s, synthesized in polyhydroxyalkylations of perfluoroacetophenone and balanced mixtures of bipenyl and p-terphenyl. Sulfonic acid groups were then introduced on the pendant pentafluorophenyl groups of the resulting polymers through an efficient thiolation-oxidation procedure. The fluorine content of these aromatic polymers was approximately 1/6 of the Nafion® benchmark. Foldable flexible PEMs were produced by tape-casting and showed thermal stability up to 260 °C, as well as excellent radical resistance. The proton conductivity increased with the acid content, and the PEM based on merely biphenyl reached 250 mS cm⁻¹ at 120 °C under fully humidified conditions, exceeding Nafion® NR212 by a factor 1.6. Under 30 % relative humidity at 80 °C, the same PEM achieved an outstanding 50 mS cm⁻¹, surpassing Nafion® by a factor 2.3. With a considerably higher acidity and lower ion exchange capacity than typical sulfonated hydrocarbon polyphenylene PEMs such as Pemion®, and significantly lower fluorine content and higher conductivity than Nafion®, the characteristics of the present PEMs may offer distinct advantages for fuel cells operating under reduced humidity.

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引用次数: 0

Construction organic composite gel polymer electrolyte for stable solid-state lithium metal batteries

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-11 DOI: 10.1016/j.ssi.2025.116821

Xianli Song , Lipeng Yang , Yi Liu , Gongying Wang

Gel polymer electrolytes (GPEs) synergizing the advantages of both solid and liquid electrolytes are promising electrolyte candidates for lithium metal batteries (LMBs). However, due to the presence of the liquid medium, mechanical performance and thermal stability are compromised. To address this issue, we designed and prepared an organic composite GPEs by immersing a PVDF-HFP fiber membrane in a polyIL-in-salt ionic solution. This process imparts exceptional high-temperature stability (decomposition temperature of 340 °C) and enhanced mechanical performance (Young's modulus of about 6.7 MPa) to the GPEs. The incorporation of polyIL-in-salt ionic solutions is found to enhance the ionic conductivity of GPEs to 0.69 mS cm⁻¹ at 25 °C, facilitating a homogeneous distribution and accelerating ionic migration. The Li||Li battery utilizing this electrolyte effectively alleviates the concentration polarization and achieves the stable cycle performance over 1200 h at 0.25 mA cm⁻² at 50 °C. Additionally, the lithium metal battery, which incorporates the organic composite gel polymer electrolytes, has exhibited an extraordinary specific capacity of 167.3 mAh g⁻¹, accompanied by a retention rate of 99.1 % at 50 °C, even after 100 cycles. This study asserts that the innovative organic composite GPEs exhibit considerable potential for practical applications in lithium metal batteries (LMBs).

凝胶聚合物电解质（GPE）协同了固态和液态电解质的优点，是锂金属电池（LMB）的理想电解质。然而，由于液态介质的存在，其机械性能和热稳定性会受到影响。为了解决这个问题，我们设计并制备了一种有机复合 GPEs，方法是将 PVDF-HFP 纤维膜浸入盐离子溶液中的 polyIL 中。这一工艺赋予了 GPE 超强的高温稳定性（分解温度为 340 °C）和更高的机械性能（杨氏模量约为 6.7 兆帕）。在盐离子溶液中加入 polyIL 可将 GPE 的离子电导率提高到 25 °C 时的 0.69 mS cm-1，从而促进均匀分布并加速离子迁移。使用这种电解质的锂电池可有效缓解浓度极化，并在 50 °C 条件下以 0.25 mA cm-2 实现 1200 小时以上的稳定循环性能。此外，结合了有机复合凝胶聚合物电解质的金属锂电池显示出了 167.3 mAh g-1 的超凡比容量，即使在 50 °C 下循环 100 次后，保持率仍高达 99.1%。这项研究表明，创新的有机复合凝胶聚合物电解质在锂金属电池（LMB）的实际应用中具有相当大的潜力。

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引用次数: 0

Investigation of the effects of magnetic field on the stability and transport properties of lithium ions

IF 3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-03-10 DOI: 10.1016/j.ssi.2025.116819

Guanqiang Ruan , Yupeng Tian , Jing Hua , Zixi Liu , Kuo Yang , Xing Hu

Lithium-ion battery is considered to be the most ideal energy storage material due to its high theoretical specific capacity and low reduction potential. However, the lithium dendrites generated during the charge and discharge cycling hinder its further application. Using density functional theory (DFT) and molecular dynamics methods, the lithium ions transport mechanism on the cathode of LiFePO₄ battery is studied. The influence of magnetic field on the stability and transport properties of lithium-ion battery surface is analyzed. The magnetic field could play a crucial role in enhancing the stability and transport of lithium ions at the interface by promoting a more orderly charge distribution and reinforcing the interfacial bonding. The results show that the magnetic field could effectively enhance the transport of lithium ions. When the magnetic induction intensity is 0.6 T, the surface stability of the electrode material could be effectively promoted, and the electrochemical performance of the battery is the best. In addition, after the introduction of magnetic field, the ion transport properties of the battery are improved. This leads to a reduction in the lithium-ion concentration at the anode, which in turn weakens the driving force and effectively inhibits the formation of lithium dendrites. This study could provide a deeper insight into the effects of magnetic field on lithium-ion battery compared to previous research, filling a gap in the existing knowledge base.

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引用次数: 0