Solid State Ionics最新文献_第7页

Thin-film X-ray diffractometry for evaluating effect of BaCO3 coating on the electrolyte of protonic ceramic fuel cells 用薄膜x射线衍射法评价BaCO3涂层对质子陶瓷燃料电池电解质的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-27 DOI: 10.1016/j.ssi.2025.117030

Katsuhiro Nomura, Hiroyuki Shimada, Yuki Yamaguchi, Masaya Fujioka, Hirofumi Sumi, Yasunobu Mizutani

The manufacturing of protonic ceramic fuel cells (PCFCs) involves high-temperature sintering at ∼1500 °C to form a dense electrolyte film. This process results in Ba evaporation, which complicates the control of the electrolyte surface composition. To address this problem, we herein examined the effect of modifying the electrolyte (Ba_0.97Zr_0.8Yb_0.2O_3−δ, BZYb20d) surface in anode-supported PCFCs by BaCO₃ slurry coating followed by firing at 1300 °C. X-ray diffractometry (θ–2θ measurements) indicated a decrease in the amount of Yb₂O₃ precipitated on the surface of the thus treated BZYb20d, and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy revealed a decrease in the segregation of Yb₂O₃ at the treated electrolyte surface. Thin-film X-ray diffractometry (ω–2θ measurement) revealed a change in the lattice constant of the BZYb20d electrolyte (thickness = 10 μm) in a BZYb20d/NiO-BZYb20d half-cell as a function of the X-ray penetration depth from the surface to the bulk (i.e., near the BZYb20d/NiO-BZYb20d interface) at 25–900 °C in air, dry N₂, and wet N₂. At 900 °C, the lattice constant of BZYb20d after the BaCO₃ treatment hardly changed upon going from the surface to the bulk, which suggested that the Ba content at the BZYb20d electrolyte surface was almost the same as that in the bulk. The thermal expansion coefficients and chemical expansion rates of the BZYb20d film electrolyte bulk were lower (∼0.66 and ∼ 0.33 times, respectively) than those of BaZr_0.8Y_0.2O_2.9 and BaZr_0.8Yb_0.2O_3−δ bulk. The BaCO₃ treatment increased the maximum power density of the corresponding PCFC from ∼0.5 to ∼0.6 W cm⁻². The cathode fabricated using the modified BZYb20d electrolyte showed a lower polarization resistance (0.07 Ω cm²) than that based on the unmodified electrolyte (0.22 Ω cm²). The Ba deficiency of the BZYb20d electrolyte surface that developed during high-temperature sintering was alleviated by the BaCO₃ coating, and the interfacial resistance between the air electrode and electrolyte therefore decreased.

质子陶瓷燃料电池（pcfc）的制造需要在~ 1500°C的高温烧结以形成致密的电解质膜。这一过程导致Ba蒸发，使电解液表面成分的控制变得复杂。为了解决这一问题，我们研究了BaCO3浆液涂层在1300℃烧制后对阳极负载型pcfc的电解质（Ba0.97Zr0.8Yb0.2O3−δ, BZYb20d）表面进行改性的效果。x射线衍射（θ-2θ测量）表明，处理后的BZYb20d表面的Yb2O3析出量减少，扫描电镜和能量色散x射线能谱分析表明，处理后的电解质表面的Yb2O3偏析减少。薄膜x射线衍射（ω-2θ测量）揭示了在25-900℃空气、干N2和湿N2条件下，BZYb20d/NiO-BZYb20d半电池中BZYb20d电解质（厚度= 10 μm）的晶格常数随x射线从表面到本体（即BZYb20d/NiO-BZYb20d界面附近）的穿透深度的变化。在900℃时，经过BaCO3处理的BZYb20d从表面到体块的晶格常数几乎没有变化，说明BZYb20d电解质表面的Ba含量与体块中的Ba含量基本相同。BZYb20d薄膜电解质体的热膨胀系数和化学膨胀率分别为BaZr0.8Y0.2O2.9和BaZr0.8Yb0.2O3−δ体的约0.66倍和约0.33倍。BaCO3处理使相应PCFC的最大功率密度从~ 0.5增加到~ 0.6 W cm−2。用改性BZYb20d电解液制备的阴极极化电阻（0.07 Ω cm2）比未改性电解液制备的阴极极化电阻（0.22 Ω cm2）低。BZYb20d电解质表面在高温烧结过程中产生的Ba缺乏症通过BaCO3涂层得到缓解，从而降低了空气电极与电解质之间的界面阻力。

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引用次数: 0

Ca2+ conduction in melilite structure type compound Ca2Ga2SiO7 钙离子在镁铝石结构型化合物Ca2Ga2SiO7中的传导

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-25 DOI: 10.1016/j.ssi.2025.117028

Koichiro Fukuda, Aya Miyasawa, Daisuke Urushihara, Toru Asaka

The potential for Ca²⁺ conduction along the 〈001〉 and 〈110〉 directions in the melilite structure type compound Ca₂Ga₂SiO₇ (space group P

\bar{4}

2₁m) has been elucidated through the utilization of the bond valence energy landscape method. The randomly grain-oriented polycrystal exhibited an increase in bulk conductivity for Ca²⁺ (σ_bulk) from 6.24 × 10⁻¹⁰ S cm⁻¹ at 573 K to 2.09 × 10⁻⁵ S cm⁻¹ at 1073 K, with an activation energy of 1.146(10) eV. The transference number at 1073 K was 0.982. The σ_bulk-value of Ca₂Ga₂SiO₇ at each temperature from 673 to 1073 K was intermediate between those of the grossite structure type compounds CaGa₄O₇ and CaAl₄O₇, while the σ_bulk-value of the NASICON-type compound (Ca_0.05Hf_0.9)_4/3.9Nb(PO₄)₃ at each temperature from 573 to 873 K was superior to those of these three compounds. The total conductivity for Ca²⁺ of Ca₂Ga₂SiO₇ was more than 12.4 times larger than that of the NASICON-type compound CaZr₄(PO₄)₆ at each temperature from 923 to 1073 K.

利用键价能景观法，研究了钙离子在立方石结构型化合物Ca2Ga2SiO7（空间群P4¯21m）中沿< 001 >和< 110 >方向的传导电位。随机晶粒取向的多晶Ca2+的体电导率（σbulk）从573 K时的6.24 × 10−10 S cm−1增加到1073 K时的2.09 × 10−5 S cm−1，活化能为1.146(10)eV。1073 K时迁移数为0.982。Ca2Ga2SiO7在673 ~ 1073 K温度下的σ体积值介于复合结构型化合物CaGa4O7和CaAl4O7之间，而nasicon型化合物（Ca0.05Hf0.9）4/3.9Nb(PO4)3在573 ~ 873 K温度下的σ体积值优于上述3种化合物。在923 ~ 1073 K的温度范围内，Ca2Ga2SiO7的Ca2+总电导率是nasicon型化合物CaZr4(PO4)6的12.4倍以上。

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引用次数: 0

Structure and electrochemical properties of MgAl co-doped spinel LiMn2O4 cathode material MgAl共掺尖晶石LiMn2O4正极材料的结构与电化学性能

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-25 DOI: 10.1016/j.ssi.2025.117031

Yongsheng Yang PhD, Long Shi, Junming Guo

MgAl co-doping and single-crystal truncated octahedral morphology strategy was employed to suppress and mitigate the Jahn-Teller distortion and Mn dissolution in spinel-type LiMn₂O₄ materials. LiMg_0.10Al_yMn_1.90-yO₄ (y = 0.03, 0.05, 0.08, 0.10, and 0.12) cathode materials were synthesized via solid-phase combustion method and the effects of varying Al contents on the crystal structures, single-crystal truncated octahedral morphology, valence states of doped elements, rate and long-cycle electrochemical performance, and Li⁺ ion migration kinetics of spinel-type LiMn₂O₄ materials were investigated. The results indicate that MgAl co-doping promotes the crystalline development of spinel-type LiMn₂O₄ material and the preferential growth of {111}, {100}, and {110} crystal planes, forming complete single-crystal truncated octahedral morphology. Among samples with different Mg and Al doping levels, the MgAl co-doped sample LiMg_0.10Al_0.05Mn_1.85O₄ exhibits superior capacity and cycle stability. At a low rate of 1C, the initial discharge specific capacity is 114.7 mAh·g⁻¹, with an 93.6 % capacity retention after 200 cycles; at high rates of 10, 15, and 20C, the initial discharge specific capacities are 94.4, 92.4, and 84.5 mAh·g⁻¹ respectively, with capacity retention rates of 84.1 %, 76.9.2 %, and 81.7 % after 1000 cycles; at high temperatures of 55 °C and rates of 1C, 5C and 10C, the initial discharge specific capacities are 113.7, 111.1 and 100.5 mAh·g⁻¹ respectively, with retention rates of 68.6 %, 46.1 % and 37.8 % after 200, and 500 cycles. The LiMg_0.10Al_0.05Mn₁₈₅O₄ sample has the lowest charge transfer resistance (168.6 Ω) and apparent activation energy (32.39 kJ·mol⁻¹), and the highest Li⁺ diffusion coefficient (1.20 × 10⁻¹¹ cm²·s⁻¹). This indicates that during charging and discharging, Li⁺ ions in this sample encounter lower resistance and energy barriers, resulting in faster migration rates, which can enhance the material's rate capacity and cycling stability.

采用MgAl共掺杂和单晶截断八面体形貌策略抑制和减轻尖晶石型LiMn2O4材料中的Jahn-Teller畸变和Mn溶解。采用固相燃烧法合成了LiMg0.10AlyMn1.90-yO4 （y = 0.03, 0.05, 0.08, 0.10, 0.12）正极材料，研究了Al含量对尖晶石型LiMn2O4材料的晶体结构、单晶截断八面体形态、掺杂元素价态、速率和长周期电化学性能以及Li+离子迁移动力学的影响。结果表明：MgAl共掺杂促进了尖晶石型LiMn2O4材料的结晶发育，{111}、{100}和{110}晶面优先生长，形成完整的单晶截断八面体形貌；在不同Mg和Al掺杂水平的样品中，MgAl共掺杂样品LiMg0.10Al0.05Mn1.85O4表现出优异的容量和循环稳定性。在低倍率1C下，初始放电比容量为114.7 mAh·g−1,200次循环后容量保持率为93.6%；在10、15和20℃高倍率下，初始放电比容量分别为94.4、92.4和84.5 mAh·g−1,1000次循环后容量保持率分别为84.1%、76.9.2%和81.7%；在55°C高温和1C、5C和10C倍率下，电池的初始放电比容量分别为113.7、111.1和100.5 mAh·g−1，循环200次和500次后的保留率分别为68.6%、46.1%和37.8%。LiMg0.10Al0.05Mn185O4样品的电荷转移电阻最低（168.6 Ω），表观活化能最低（32.39 kJ·mol−1），Li+扩散系数最高（1.20 × 10−11 cm2·s−1）。这说明在充放电过程中，该样品中的Li+离子遇到更低的电阻和能量势垒，迁移速度更快，可以增强材料的倍率容量和循环稳定性。

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引用次数: 0

Study on the structure and electrochemical properties of double-doped regulated P2/O3 cophasic sodium-ion batteries 双掺杂调控P2/O3共相钠离子电池的结构与电化学性能研究

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-23 DOI: 10.1016/j.ssi.2025.117029

Zhenhong Tian , Li-ang Zhu , Jingxiu Tian , Hongshun Miao , Yinghui Jiang , Rongkang Tan , Xiangxin Li , Yan Liu

A trace Ti/Mg co-doped Na_0.8Ni_0.35Mn_0.48Ti_0.12Mg_0.05O₂ (TiMg-NNM) cathode was synthesized, where Ti ions are located in the transition metal layers and Mg ions are incorporated into the sodium layers. The co-doping expands the Na-layer spacing within the layered structure, thereby lowering the diffusion barrier for Na-ions. Structural stability is significantly enhanced due to the robust TiO bond and the pillar-like effect of Mg ions, which also helps to minimize surface side reactions with the electrolyte. The merits endow a high reversible capacity of TiMg-NNM cathode with 130.5 mAh/g at 1C, the 85.8 % capacity retention rate at 100 cycles at 1C, much greater than 35.6 % of NNM. The synergistic effect of P2 and O3 phases was strengthened by the doping of Mg and Ti, so that the obtained NNMMT had high electrochemical stability. The research offers a practical approach and fresh perspectives for designing high-performance layered oxide cathode materials with improved structural and interfacial stability for SIBs.

合成了微量Ti/Mg共掺杂的Na0.8Ni0.35Mn0.48Ti0.12Mg0.05O2 （TiMg-NNM）阴极，其中Ti离子位于过渡金属层，Mg离子掺入钠层。共掺杂扩大了层状结构内的na层间距，从而降低了na离子的扩散势垒。由于强大的TiO键和Mg离子的柱状效应，结构稳定性显著增强，这也有助于减少与电解质的表面副反应。这些优点赋予了TiMg-NNM阴极在1C下具有130.5 mAh/g的高可逆容量，在1C下100次循环的容量保持率为85.8%，远高于NNM的35.6%。通过Mg和Ti的掺杂，增强了P2和O3相的协同作用，使所制得的NNMMT具有较高的电化学稳定性。该研究为设计具有更好结构和界面稳定性的高性能sib层状氧化物正极材料提供了实用的方法和新的视角。

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引用次数: 0

Exploring the structural and conductivity behaviours of mechanochemically and hydrothermally synthesized Ce3+-doped BaSnF4 solid electrolytes for all-solid-state fluoride-ion batteries 机械化学和水热合成Ce3+掺杂BaSnF4全固态氟离子电池固体电解质的结构和导电性研究

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-23 DOI: 10.1016/j.ssi.2025.117032

K. Ramakrushna Achary , Sumit Khatua , Kshatri Durga Lalitha Bai , Guruprasad Sahoo , L.N. Patro

Recent studies on batteries have drawn significant attention to all-solid-state fluoride-ion batteries (FIBs) as potential alternatives to the conventional Li-ion batteries because of their higher theoretical energy densities. On the solid electrolyte side, efforts are being made to develop a suitable material with improved ionic conductivity (∼ 10⁻³ S/cm) and enhanced electrochemical stability. SnF₂-based solid electrolyte, BaSnF₄ crystallizes in the PbSnF₄ structure and is frequently considered as a potential solid electrolyte for FIBs operating at room temperature (RT). In this study, the conductivity results of BaSnF₄ are influenced by doping with rare-earth ions (Ce³⁺) at different concentrations and by the synthesis methodology. The structural and transport behaviours of Ce³⁺-doped BaSnF₄ solid electrolytes, prepared by mechanical milling and hydrothermal methods, are compared. The formation of the doped materials, which exhibit a tetragonal phase, is confirmed by X-ray diffraction. The presence of Ce³⁺ in the doped materials prepared by both methods is confirmed by their photoluminescence characteristics. Among the materials investigated in this study, 2 mol% Ce³⁺-doped BaSnF₄, prepared by mechanical milling (Ba_0.98Ce_0.02SnF_4.02-MM) exhibits the highest ionic conductivity and electrochemical stability. The conductivity (RT) exhibited by Ba_0.98Ce_0.02SnF_4.02-MM is higher compared to earlier reports on different rare-earth ion-doped BaSnF₄, which were primarily prepared by solution-based methods. Ion transport number measurement using dc polarization technique revealed that the conductivity exhibited by Ba_0.98Ce_0.02SnF_4.02-MM is mainly due to ionic conduction. The observation of a higher ionic conductivity value in Ba_0.98Ce_0.02SnF_4.02-MM highlights its great potential for use as a solid electrolyte in the fabrication of FIBs.

全固态氟离子电池（FIBs）具有较高的理论能量密度，是传统锂离子电池的潜在替代品，近年来的电池研究引起了人们的极大关注。在固体电解质方面，人们正在努力开发一种合适的材料，该材料具有改善的离子电导率（~ 10−3 S/cm）和增强的电化学稳定性。基于snf2的固体电解质，BaSnF4以PbSnF4结构结晶，经常被认为是在室温（RT）下工作的fib的潜在固体电解质。在本研究中，掺杂不同浓度的稀土离子（Ce3+）和合成方法对BaSnF4的电导率结果产生了影响。比较了机械研磨法和水热法制备的Ce3+掺杂BaSnF4固体电解质的结构和输运行为。x射线衍射证实了掺杂材料的形成，其表现为四方相。两种方法制备的掺杂材料的光致发光特性证实了Ce3+的存在。在所研究的材料中，机械铣削法制备的2 mol% Ce3+掺杂BaSnF4 （Ba0.98Ce0.02SnF4.02-MM）具有最高的离子电导率和电化学稳定性。与先前报道的不同稀土离子掺杂BaSnF4相比，Ba0.98Ce0.02SnF4.02-MM的电导率（RT）更高，主要是通过溶液法制备的。利用直流极化技术测量离子输运数，发现Ba0.98Ce0.02SnF4.02-MM的电导率主要是离子传导。在Ba0.98Ce0.02SnF4.02-MM中观察到较高的离子电导率值，突出了其作为固体电解质在FIBs制造中的巨大潜力。

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引用次数: 0

Optoionics – Controlling ions with light 光电学-用光控制离子

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-17 DOI: 10.1016/j.ssi.2025.117018

A. Gouder , B.V. Lotsch

Optoionics has recently emerged at the intersection of optoelectronics and solid state ionics, triggered by fundamental work on light-induced ionic conductivity enhancement in methylammonium lead iodide (MAPI). This perspective traces the evolution of optoionics from early 20th century studies on photoionics to contemporary research, elucidating the semantic nuances and historical development of light–ion interactions. We follow the first observations such as copper photoionization and subsequent conceptual extensions such as molecular photoionics and photo-ionic cells, leading on to the current definition and understanding of optoionics. We then proceed to apply this understanding on light–ion interactions in carbon nitrides, distinguishing between intrinsic and extrinsic optoionic effects depending on whether one or more distinct phases are involved. This nuanced understanding is essential for the design of optoionic devices that exploit light–ion interactions to couple light harvesting and electrochemical energy storage. Finally, we provide an outlook on emerging optoionic devices at the intersection of energy conversion and storage and discuss smart circuit elements that integrate optoionic principles for advanced technological applications.

近年来，由于在甲基碘化铅（MAPI）中进行了光诱导离子电导率增强的基础工作，光电子学在光电子学和固体离子学的交叉领域兴起。这一视角追溯了光电子学从20世纪早期的光电子学研究到当代研究的演变，阐明了光离子相互作用的语义细微差别和历史发展。我们遵循最初的观察，如铜光电离和随后的概念扩展，如分子光离子和光离子细胞，导致当前的定义和理解的光离子。然后，我们继续将这一理解应用于氮化碳中的光离子相互作用，根据是否涉及一个或多个不同的相来区分内在和外在的光离子效应。这种细微的理解对于利用光离子相互作用耦合光收集和电化学能量存储的光离子器件的设计至关重要。最后，我们展望了新兴的光离子器件在能量转换和存储的交叉点，并讨论了集成光离子原理的智能电路元件的先进技术应用。

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引用次数: 0

Apparent non-monotonic electrical conductivity relaxation of 1 % Gd-doped ceria 1% gd掺杂二氧化铈的非单调电导率弛豫

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-17 DOI: 10.1016/j.ssi.2025.117016

Yizhou Shen, Reidar Haugsrud

Steady-state and transient electrical conductivities of 1 % Gd-substituted ceria have been characterized from 550 to 800 °C under oxidizing conditions. The temperature and oxygen pressure dependencies of the steady-state conductivity resemble those of pristine ceria, with predominant n-type conductivity and some contribution of p-type conductivity under the most oxidizing conditions. Depending on temperature and oxygen partial pressure, the relaxation of the conductivity follows one-fold monotonic, two-fold monotonic, or non-monotonic behavior, despite the predominance of two charge carriers in the bulk material. Possible explanations for this peculiar phenomenon are discussed based on surface-exchange-limited oxygen exchange.

在550 ~ 800℃的氧化条件下，对1% gd取代的氧化铈的稳态和瞬态电导率进行了表征。稳态电导率的温度和氧压依赖性与原始氧化铈相似，在大多数氧化条件下以n型电导率为主，p型电导率有一定贡献。根据温度和氧分压的不同，电导率的弛豫遵循单次单调、双次单调或非单调行为，尽管在块状材料中两种载流子占主导地位。基于表面交换限制氧交换，讨论了对这一特殊现象的可能解释。

引用次数: 0

Hydration and conduction behavior of Sc and Zr-substituted Ba7Nb4MoO20 Sc和zr取代Ba7Nb4MoO20的水化和导电行为

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-16 DOI: 10.1016/j.ssi.2025.117027

Sara Adeeba Ismail , Lulu Jiang , Hui Guo , Wenhao Li , Donglin Han

Ba₇Nb₄MoO₂₀ has acceptably high ionic conductivity at 600–800 °C and is attractive for potential application in high temperature solid state electrochemical devices. Up to now, most of the research focuses on isovalent and donor-doping to improve the electrical properties of Ba₇Nb₄MoO₂₀. In this work, an acceptor-doping strategy was taken by doping Sc and Zr to partially substitute Nb. More vacant oxygen sites thereby form for charge compensation, leading to the increasing proton concentration following the compositional sequence of hydrated Ba₇Nb₄MoO₂₀ < Ba₇Nb_3.97Zr_0.03MoO_19.985 < Ba₇Nb_3.97Sc_0.03MoO_19.97. Notably, both the H₂O/D₂O isotope effect and EMF measurements indicate that the proton conduction – if there is any – is negligibly small, and the Sc and Zr-doped Ba₇Nb₄MoO₂₀ is essentially an oxide ion conductor in the temperature range studied in this work.

Ba7Nb4MoO20在600-800°C具有可接受的高离子电导率，在高温固态电化学器件中具有潜在的应用前景。目前，为了改善Ba7Nb4MoO20的电学性能，大部分的研究都集中在同价掺杂和给体掺杂上。在这项工作中，采用了一种受体掺杂策略，通过掺杂Sc和Zr来部分取代Nb。从而形成更多的空氧位进行电荷补偿，导致质子浓度按照水合Ba7Nb4MoO20 <； Ba7Nb3.97Zr0.03MoO19.985 < Ba7Nb3.97Sc0.03MoO19.97的组成顺序递增。值得注意的是，H2O/D2O同位素效应和EMF测量都表明，质子传导-如果有的话-是可以忽略不计的小，并且Sc和zr掺杂的Ba7Nb4MoO20在本工作研究的温度范围内基本上是氧化物离子导体。

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引用次数: 0

Influence of Germanium oxide nanoparticles on the electrical conductivity of Li-ion conducting NaCMC/PVA nanocomposite films 氧化锗纳米颗粒对锂离子导电NaCMC/PVA纳米复合膜电导率的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-09 DOI: 10.1016/j.ssi.2025.117015

Seshan T.N , Vipin Cyriac , Demappa T , Ismayil

This study examines the influence of GeO₂ nanoparticles (NPs) on the ionic conductivity and structural properties of NaCMC/PVA/LiBr-based solid polymer electrolytes synthesized via solution casting technique. XRD analysis revealed enhanced amorphous character with increasing GeO₂ content. FTIR spectra confirmed interactions between GeO₂ NPs and the polymer-salt matrix. SEM and EDX analyses were used to investigate morphology and elemental composition. UV–Vis spectroscopy showed a redshift in absorption edge and a bandgap reduction from 5.70 to 5.50 eV with GeO₂ addition. Impedance spectroscopy (100 Hz - 5 MHz) indicated improved ionic conductivity, following Jonscher's universal power law, with a maximum value of (1.13 ± 0.02) × 10⁻⁵ S cm⁻¹ at 5 wt% GeO₂. LSV confirmed electrochemical stability up to 2.7 V. Dielectric studies revealed an increase in permittivity due to interfacial polarization. Transference number measurement evaluates the relative contributions of ionic and electronic charge carriers in solid polymer electrolytes using polarization technique. These results highlight the potential of GeO₂-dispersed NaCMC/PVA/LiBr films for energy storage applications.

本研究考察了纳米GeO2对溶液铸造法制备的NaCMC/PVA/ lib基固体聚合物电解质的离子电导率和结构性能的影响。XRD分析表明，随着GeO2含量的增加，非晶态特性增强。FTIR光谱证实了GeO2 NPs与聚合物盐基质之间的相互作用。SEM和EDX分析研究了其形貌和元素组成。紫外可见光谱显示，添加GeO2后，吸收边红移，带隙从5.70 eV减小到5.50 eV。阻抗谱（100 Hz - 5 MHz）表明离子电导率提高，符合Jonscher的通用幂定律，在5 wt%的GeO2下，最大值为（1.13±0.02）× 10−5 S cm−1。LSV确认电化学稳定性高达2.7 V。介电研究表明，由于界面极化，介电常数增加。转移数测量是利用极化技术评价固体聚合物电解质中离子载流子和电子载流子的相对贡献。这些结果突出了geo2分散NaCMC/PVA/LiBr薄膜在储能应用中的潜力。

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引用次数: 0

The extraction of hopping frequencies of mobile fluorine ions in the superionic conductor Ba0.5La0.5F2.5 from electrical modulus spectroscopy data 利用电模谱数据提取超离子导体Ba0.5La0.5F2.5中可移动氟离子的跳频

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-07 DOI: 10.1016/j.ssi.2025.117017

N.I. Sorokin

The spectra of the complex electrical modulus M*(ν) = M ^/+iM ^// for a single crystal of the superionic conductor Ba_0.5La_0.5F_2.5 with a fluorite-type structure (sp. gr.

Fm \bar{3} m

) were studied in the frequency range of 10⁻¹–10⁷ Hz at temperatures of 210–407 K. The diagrams of the complex modulus M ^/(ν), M ^//(ν) take the Cole-Cole form and are characterized by the presence of a distribution of relaxation times of mobile ion carriers. On the frequency dependences of the imaginary part of the complex modulus M ^//(ν), the relaxation peaks are observed, caused by hopping rates of mobile interstitial fluorine ions (charge carriers). Based on the temperature change in the position of relaxation maxima, calculations were made of the activation enthalpy ΔH_h and the average frequency ν_h of carrier jumps. The calculated values of ΔH_h and ν_h are in satisfactory agreement with the results obtained by the Almond-West method for this crystal. Within the framework of the crystallophysical model, the carrier mobility μ_mob and mobile ion concentration n_mob were calculated. Research using the method of modular spectroscopy is of undoubted interest for the further search and creation of fluorine-conducting solid electrolytes.

在210 ~ 407 K的频率范围内，研究了具有荧光型结构的超离子导体Ba0.5La0.5F2.5 （sp. gr. Fm3¯M）单晶的复电模量M*(ν) = M /+iM //的光谱。复模量M /(ν)和M //(ν)的图采用Cole-Cole形式，其特征是存在一个移动离子载流子的弛豫时间分布。在复模量M //(ν)虚部的频率依赖上，观察到由移动间隙氟离子（载流子）的跳变率引起的弛豫峰。根据弛豫最大值位置的温度变化，计算了活化焓ΔHh和载流子跳变的平均频率νh。该晶体的ΔHh和νh的计算值与Almond-West法的计算结果吻合得很好。在晶体物理模型的框架内，计算了载流子迁移率μmob和迁移离子浓度nmob。使用模光谱方法的研究无疑对进一步寻找和创造氟导电固体电解质具有重要意义。

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引用次数: 0