Solid State Ionics最新文献_第6页

Conductivity of 2-adamantanone with lithium bis(trifluoromethanesulfonyl)imide: Impact of residual solvent and temperature 2-金刚烷酮与二（三氟甲烷磺酰）亚胺锂的电导率：残余溶剂和温度的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-13 DOI: 10.1016/j.ssi.2025.117043

Joshua Budde, Ingo Bardenhagen, Julian Schwenzel

This study investigates the ionic conductivity of a mixture comprising 2-adamantanone and lithium bis(trifluoromethanesulfonyl)imide, with focus on the impact of temperature and residual tetrahydrofuran. Previous investigations have shown that the plastic crystal 2-adamantanone, when paired with lithium bis(trifluoromethanesulfonyl)imide, exhibits an ionic conductivity of 1.2 × 10⁻⁴ S cm⁻¹ and a considerable oxidation potential of 5.1 V. Nonetheless, the influence of any residual processing solvent on the ionic conductivity is not yet fully understood. The Design of Experiments methodology was utilized to analyze a broad spectrum of potential compositions of 2-adamantanone, lithium bis(trifluoromethanesulfonyl)imide, and tetrahydrofuran. We measured the ionic conductivity of the samples using electrochemical impedance spectroscopy and conducted structural studies via differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction and solid-state NMR. Our findings indicate that the leftover amount of THF enhances ionic conductivity more strongly than the molarity. Moreover, compared to crystallization from the solvent, ionic conductivity increases by over an order of magnitude following recrystallization from the melt. We suggest that the residual solvent is integrated into the crystal structure of the 2-adamantanone, thereby increasing the free volume and facilitating lithium-ion transport. At elevated temperatures, the optimized formulation transforms from a solid to a wax-like consistency, functioning as a solid electrolyte with a high ionic conductivity of 2.6 × 10⁻⁴ S cm⁻¹ at room temperature, making it a promising candidate for electrolyte applications.

本研究考察了2-金刚烷酮和锂二（三氟甲烷磺酰）亚胺混合物的离子电导率，重点研究了温度和残余四氢呋喃的影响。先前的研究表明，塑料晶体2-金刚烷酮与双（三氟甲烷磺酰）亚胺锂配对时，离子电导率为1.2 × 10−4 S cm−1，氧化电位为5.1 V。然而，任何残留的加工溶剂对离子电导率的影响尚不完全清楚。利用实验设计方法分析了2-金刚烷酮、锂二（三氟甲烷磺酰基）亚胺和四氢呋喃的广谱潜在成分。我们使用电化学阻抗谱测量了样品的离子电导率，并通过差示扫描量热法、傅里叶变换红外光谱、x射线衍射和固态核磁共振进行了结构研究。我们的研究结果表明，剩余的THF量比摩尔浓度更能增强离子电导率。此外，与溶剂结晶相比，熔体再结晶后离子电导率增加了一个数量级以上。我们认为残留的溶剂被整合到2-金刚烷酮的晶体结构中，从而增加了自由体积，促进了锂离子的传输。在高温下，优化的配方从固体转变为蜡状稠度，在室温下具有2.6 × 10−4 S cm−1的高离子电导率的固体电解质，使其成为电解质应用的有希望的候选者。

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引用次数: 0

Poly(ionic liquid)/expanded pore NH2-UiO-66 composite solid-state electrolyte for high-performance solid-state lithium-ion batteries 高性能固态锂离子电池用聚（离子液体）/膨胀孔NH2-UiO-66复合固态电解质

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-13 DOI: 10.1016/j.ssi.2025.117040

Yang Zhang , Donghao Zhang , Jian Zhang, Xin Li, Xiaoling Hu, Ping Guan, Xin Wang

The development of high-performance solid electrolytes is essential for advancing ion batteries. This research introduces a novel approach for the simultaneous construction of poly(ionic liquid) and ionic conductors, creating a synergistic system that integrates a new polycationic ionic liquid matrix with ionic liquid-modified ionic conductors (Li-IL@PA-UiO-66-NH₂). This method markedly improves the interfacial compatibility between the polymer substrate and the functional filler. The filler enhances the composite electrolyte, achieving a higher transference number and ionic conductivity documented in recent studies, alongside improved voltage stability. We engineer and manufacture poly(1-vinyl-3-dodecylimidazole) bis(trifluoromethanesulfonimide) ([P(VIM-R)]TFSI) ionic liquids, which are subsequently utilized as the primary polymer, resulting in the formation of a poly(ionic liquid) solid-state electrolyte (P-GPE). Subsequently, we integrate it with the Li-IL@PA-UiO-66-NH₂ ionic conductor to formulate a poly(ionic liquid) composite solid-state electrolyte (P-CPE). The findings indicate that the ionic conductivity of P-CPE at 30 °C is 2.35 × 10⁻⁴ S cm⁻¹, with a transference number of 0.77. This value is 1.85 and 1.33 times higher than that of P-GPE, and the material can function safely up to 5 V. This study emphasizes the role of solid-state electrolytes in advancing the development of next-generation solid-state batteries.

高性能固体电解质的开发对离子电池的发展至关重要。本研究介绍了一种同时构建聚离子液体和离子导体的新方法，创建了一种将新型聚阳离子离子液体基质与离子液体修饰的离子导体相结合的协同体系（Li-IL@PA-UiO-66-NH2）。该方法显著改善了聚合物基板与功能填料之间的界面相容性。在最近的研究中，填料增强了复合电解质，实现了更高的转移数和离子电导率，同时改善了电压稳定性。我们设计和制造聚（1-乙烯基-3-十二烷基咪唑）双（三氟甲烷磺酰亚胺）（[P(VIM-R)]TFSI）离子液体，随后将其用作初级聚合物，从而形成聚（离子液体）固态电解质（P- gpe）。随后，我们将其与Li-IL@PA-UiO-66-NH2离子导体集成，形成聚（离子液体）复合固态电解质（P-CPE）。结果表明，P-CPE在30℃时的离子电导率为2.35 × 10−4 S cm−1，迁移数为0.77。该值分别是P-GPE的1.85倍和1.33倍，该材料在5v电压下可以安全工作。这项研究强调了固态电解质在推动下一代固态电池发展中的作用。

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引用次数: 0

Enhancement of oxide ion and proton conductivity in Sr3-xCaxV2O8 palmierites through tuning of the crystal structure 通过调整晶体结构增强Sr3-xCaxV2O8棕榈石中氧化离子和质子的电导率

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-11 DOI: 10.1016/j.ssi.2025.117041

Sophie G. Martin , Oscar J.B. Ballantyne , Clemens Ritter , Ying Zhou , Frazer N. Forrester , James A. Dawson , Abbie C. Mclaughlin

Sizeable oxide ion and proton conductivity have recently been reported in A₃V₂O₈ (A = Ba, Sr) palmierites. The solid solution Sr_3-xCa_xV₂O₈ (x = 0.0–0.2) has been synthesised and investigated by electrochemical characterisation and atomistic modelling, revealing key insights into the design principles for enhancing oxide and proton conduction in palmierites. Neutron diffraction data shows that at 20 °C there is a reduction in crystal symmetry from

R \bar{3} m

to

C 2 / c

for x ≥ 0.05. Upon heating to 600 °C,

R \bar{3} m

symmetry is restored for all phases. An increase in both the oxide ion and proton conductivity are observed with Ca²⁺ doping. The oxide ion conductivity scales with the magnitude of displacement of the V⁵⁺ cation and VO2 bond length.

最近报道了A3V2O8 （A = Ba, Sr）棕榈岩中较大的氧化物离子和质子电导率。合成了固溶体Sr3-xCaxV2O8 (x = 0.0-0.2)，并通过电化学表征和原子建模对其进行了研究，揭示了增强棕榈石中氧化物和质子传导的设计原理。中子衍射数据表明，在20℃时，当x≥0.05时，晶体对称性从R3¯m降低到C2/ C。当加热到600°C时，所有相的R3¯m对称性恢复。钙离子掺杂后，氧化离子和质子电导率均有所提高。氧化离子的电导率与V5+阳离子的位移大小和VO2键的长度成正比。

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引用次数: 0

Investigation on electrochemical behavior and degradation mechanism of a reversible solid oxide cell operating at high current densities 高电流密度下可逆固体氧化物电池的电化学行为及降解机理研究

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-10 DOI: 10.1016/j.ssi.2025.117044

Haoshen Wang , Qing Shao , Yue Lu , Dun Jin , Fupeng Cheng , Chengzhi Guan , Zhi Li , Guoping Xiao , Juncai Sun , Jian-Qiang Wang

Reversible solid oxide cell have significant potential for storing energy from intermittent renewable sources. However, the current densities must be increased to improve the energy conversion efficiency and reduce system costs. In this study, a fuel electrode-supported cell with an effective area of 16 cm² was operated for 288 h, switching between solid oxide fuel cell and solid oxide electrolysis cell modes at the current densities of ±1.88 A cm⁻². The electrochemical impedance spectroscopy collected at the open-circuit voltage were analyzed using the distribution of relaxation times and equivalent circuit modeling methods to evaluate the contribution of each electrode process to degradation. The results demonstrated that charge transfer reactions in the fuel and oxygen electrodes were the primary cause of cell performance degradation. According to the post-test analysis, the primary degradation mechanisms are the migration of nickel from the active layer to support layer and the coarsening of nickel in the fuel electrode. Other degradation mechanisms included the segregation of strontium and valence fluctuations of cobalt, which acted synergistically to the oxygen electrode. At elevated current densities, the concurrent migration of nickel in the same direction reduced to a reduction in the triple-phase boundary, which could not be adequately compensated for. This phenomenon significantly impaired the cell performance.

可逆固体氧化物电池在存储间歇性可再生能源方面具有重要的潜力。然而，为了提高能量转换效率和降低系统成本，必须增加电流密度。在本研究中，有效面积为16 cm2的燃料电极支撑电池在±1.88 a cm−2的电流密度下工作288 h，在固体氧化物燃料电池和固体氧化物电解电池模式之间切换。利用弛豫时间分布和等效电路建模方法对开路电压下采集的电化学阻抗谱进行分析，评价各电极过程对降解的贡献。结果表明，燃料电极和氧电极中的电荷转移反应是导致电池性能下降的主要原因。后测分析表明，镍的主要降解机制是镍从活性层向支撑层的迁移和燃料电极中镍的粗化。其他降解机制包括锶的分离和钴的价态波动，它们对氧电极起协同作用。在较高的电流密度下，镍在同一方向上的同时迁移减少为三相边界的减少，这无法得到充分补偿。这种现象严重损害了电池的性能。

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引用次数: 0

Highly conductive solid electrolytes in the PbF2-CaF2-KF system: mechanochemical synthesis, electrical properties, microstructure and stability PbF2-CaF2-KF体系中高导电性固体电解质：机械化学合成、电学性能、微观结构及稳定性

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-10 DOI: 10.1016/j.ssi.2025.117037

Qianlong Ji, Natalia A. Melnikova, Oleg V. Glumov, Igor V. Murin

Fluorite-structure solid solutions with ultrahigh fluoride ion mobility are widely recognized as promising solid electrolytes for applications in solid-state electrochemical devices like fluoride ion batteries (FIBs). Herein, solid solutions in the PbF₂-CaF₂-KF system were prepared by mechanochemical synthesis. The structure and morphology of the synthesized solid solutions are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The fluoride ion conductivity of the samples is investigated by the electrochemical impedance spectroscopy (EIS). The results show that the fluorite-structure solid electrolyte β-Pb_0.75Ca_0.2K_0.05F_1.95 with high ionic conductivity (1.46 × 10⁻³ S/cm at 20 °C) can be obtained combined with brief low-temperature heat treatment.

具有超高氟离子迁移率的萤石结构固溶体被广泛认为是一种有前途的固体电解质，可用于氟离子电池等固态电化学器件。本文采用机械化学合成法制备了pb_2 - caf_2 - kf体系的固溶体。采用x射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）和高分辨率透射电子显微镜（HRTEM）研究了合成的固溶体的结构和形貌。用电化学阻抗谱（EIS）研究了样品的氟离子电导率。结果表明：结合低温短暂热处理，可获得离子电导率高达1.46 × 10−3 S/cm（20℃时）的荧光晶体结构固体电解质β-Pb0.75Ca0.2K0.05F1.95；

引用次数: 0

Separating grain vs. grain boundary conductivity in Li2OHCl antiperovskite solid electrolytes during and after synthesis Li2OHCl反钙钛矿固体电解质合成过程中与合成后晶粒分离与晶界电导率的关系

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-07 DOI: 10.1016/j.ssi.2025.117038

Kai-Wei Lan , Mebatsion S. Gebre , Beniamin Zahiri , Paul V. Braun , Daniel P. Shoemaker , Nicola H. Perry

Oxychloride antiperovskite Li conductors represent compelling candidates for battery solid electrolytes (SEs), owing to their stability vs. Li and ductility. However, the influence of synthesis route and resulting microstructure on transport behavior remains incompletely studied. We prepared Li₂OHCl in 3 ways: a) cold-pressing of solid-state-synthesized orthorhombic and cubic Li₂OHCl powders, b) sintering of these powders into pellets, and c) reactive sintering of high-energy ball-milled LiCl and LiOH reagents. We studied the impedance spectra for route a) at 25 °C, for route b) from ∼25–270 °C, and for route c) during the reactive sintering process to form the cubic phase, coupled to in-situ XRD. Cold-pressed powders typically exhibited a single impedance arc, while ex-situ sintered pellets exhibited an offset resistance with lower activation energy (∼0.44–0.48 eV) >60 °C and an arc with higher activation energy (∼0.6–1.2 eV). With increasing temperature, the offset feature increasingly dominated the impedance spectra, and its associated conductivity (1.9 × 10⁻³ Scm⁻¹) was in good agreement with the total conductivity magnitude (1.3 × 10⁻³ Scm⁻¹) and activation energy (0.42 eV) measured during reactive sintering of reagents once the cubic phase was obtained (>160 °C). Spectra were simulated using the brick layer model corresponding to the microstructure observed by SEM and varied specific conductivities and permittivities. Based on the above results, we attribute the offset feature to grains and the arc to blocking grain boundaries. A signature of possible proton transport in adsorbed H₂O layers was observed in non-Arrhenius behavior below ∼60 °C, rendering separation of grain and grain boundary Li transport challenging at room temperature.

氯氧反钙钛矿锂导体由于其相对于锂的稳定性和延展性而成为电池固体电解质（SEs）的令人信服的候选者。然而，合成路线和合成后的微观结构对输运行为的影响尚未得到充分的研究。我们采用三种方法制备Li2OHCl: a)冷压固态合成的正交和立方Li2OHCl粉末，b)将这些粉末烧结成球团，c)高能球磨LiCl和LiOH试剂的反应烧结。我们研究了路线a)在25°C时的阻抗谱，路线b)在~ 25 - 270°C时的阻抗谱，以及路线C)在反应烧结过程中形成立方相的阻抗谱，并与原位XRD相结合。冷压粉末通常表现为单阻抗电弧，而非原位烧结颗粒表现为具有较低活化能（~ 0.44-0.48 eV） >；60°C的偏移电阻和具有较高活化能（~ 0.6-1.2 eV）的电弧。随着温度的升高，偏置特征在阻抗谱中占主导地位，其相关的电导率（1.9 × 10−3 Scm−1）与获得立方相（>160°C）时反应烧结时测量的总电导率（1.3 × 10−3 Scm−1）和活化能（0.42 eV）吻合良好。采用与SEM观察到的微观结构相对应的砖层模型模拟了光谱，并改变了比电导率和介电常数。基于上述结果，我们将偏移特征归因于晶粒，将圆弧归因于阻挡晶界。在~ 60℃以下，在非arrhenius行为中观察到吸附H2O层中可能的质子输运特征，这使得在室温下晶粒和晶界Li输运的分离变得困难。

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引用次数: 0

Self-rectifying hysteresis with dynamic conductance modulation in amorphous-nanocrystalline lanthanum nickelate based memristive devices 非晶纳米镍酸镧基忆阻器件中动态电导调制的自整流磁滞

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-06 DOI: 10.1016/j.ssi.2025.117039

Aleksandra Koroleva , Dmitry Kuzmichev , Laetitia Rapenne , Hervé Roussel , Carmen Jiménez , Christoph Schlueter , Céline Ternon , Elena-Ioana Vatajelu , Mónica Burriel

In this work, an investigation of the structural properties of the lanthanum nickelate (LNO) films grown by metal-organic chemical vapor deposition (MOCVD) at 450 °C as well as the memristive properties of the TiN/LNO/Pt devices based on the back-end-of-the-line-compatible LNO films is carried out. We show that the films deposited at 450 °C consist of incipient nanocrystals of the La₂NiO_4+δ phase randomly distributed within the amorphous matrix. This peculiar nanostructure gives rise to the self-rectifying double-pinched hysteresis effect in TiN/LNO/Pt devices. In addition, the device demonstrates area dependence of the resistance in the high and low resistance states, which together with the absence of a forming process indicates nonfilamentary resistive switching, based on space charge accumulation under applied bias. The memory window can be increased through the application of a higher voltage amplitude or subsequent sweeps at constant voltage, which indicates the ability of the device for dynamic conductance modulation. Overall, self-selective and forming-free nonfilamentary TiN/LNO/Pt devices can be integrated in neuromorphic arrays without the additional selector, which allows for increased integration density.

在这项工作中，研究了在450°C下由金属有机化学气相沉积（MOCVD）生长的镍酸镧（LNO）薄膜的结构性能以及基于后端相容LNO薄膜的TiN/LNO/Pt器件的记忆性。结果表明，在450°C下沉积的薄膜由La2NiO4+δ相的纳米晶组成，这些纳米晶随机分布在非晶基体中。这种特殊的纳米结构在TiN/LNO/Pt器件中产生了自整流双箝位迟滞效应。此外，该器件在高电阻和低电阻状态下显示出电阻的面积依赖性，加上没有形成过程，表明基于施加偏压下的空间电荷积累的非丝状电阻开关。存储器窗口可以通过施加更高的电压幅值或随后的恒电压扫描来增加，这表明该器件具有动态电导调制的能力。总的来说，自选择和无形成的非丝状TiN/LNO/Pt器件可以集成在神经形态阵列中，而无需额外的选择器，这可以增加集成密度。

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引用次数: 0

Effects of TiO2 on the performance of Li4Ti5O12 prepared by solid-state method TiO2对固态法制备Li4Ti5O12性能的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-10-06 DOI: 10.1016/j.ssi.2025.117036

Yin Zou, Litao Li , Yuxuan Zhang, Guiling Yang

Li₄Ti₅O₁₂-TiO₂ materials have been prepared in many literatures with either hydrothermal or sol-gel methods for higher performance. However, residual TiO₂ was considered as an impurity that could degrade the performance of Li₄Ti₅O₁₂ prepared by solid-state reaction method. Therefore, in order to determine the true effect of residual TiO₂ on Li₄Ti₅O₁₂ in solid-state method preparation, Li₄Ti₅O₁₂-TiO₂ composites with different TiO₂ content and TiO₂ crystal structures are synthesized in air and argon atmospheres. XRD results indicate that Li₂CO₃ promotes the transition of anatase TiO₂ to rutile TiO₂, and the phase transition rate of TiO₂ in argon atmosphere is higher than that in air atmosphere. SEM results show the presence of small particles in the L85-Ar sample, which are identified as TiO₂ by lattice fringes, elemental distribution, and electron diffraction in selected regions. In electrochemical tests, the initial discharge capacity and the low-rate capacity of the materials continuously decrease as the TiO₂ content increases. However, due to the abundant phase interfaces in the composite, the high-rate performance does not decline and the cycle performance improves. After 500 cycles at a rate of 10C, L85-Ar has a capacity retention of 85.4 %, which is a 22.7 % improvement over L105-Ar. Based on the EIS and CV results, the composite exhibits lower electrochemical impedance and higher peak current.

为了获得更高的性能，许多文献采用水热法或溶胶-凝胶法制备了Li4Ti5O12-TiO2材料。然而，残留的TiO2被认为是一种杂质，会降低固相反应法制备的Li4Ti5O12的性能。因此，为了确定固相法制备中残余TiO2对Li4Ti5O12的真实影响，在空气和氩气气氛下合成了不同TiO2含量和不同TiO2晶体结构的Li4Ti5O12-TiO2复合材料。XRD结果表明，Li2CO3促进了锐钛矿型TiO2向金红石型TiO2的转变，且TiO2在氩气气氛中的相变速率高于在空气气氛中的相变速率。SEM结果表明，L85-Ar样品中存在小颗粒，通过点阵条纹、元素分布和选定区域的电子衍射鉴定为TiO2。在电化学测试中，随着TiO2含量的增加，材料的初始放电容量和低倍率容量不断降低。然而，由于复合材料中丰富的相界面，高速率性能没有下降，循环性能得到提高。在10C下循环500次后，L85-Ar的容量保持率为85.4%，比L105-Ar提高22.7%。EIS和CV结果表明，复合材料具有较低的电化学阻抗和较高的峰值电流。

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引用次数: 0

Optimization of Ba0.5Sr0.5Co0.8Fe0.2O3-δ-BaCe0.7Zr0.1Y0.1Yb0.1O3-δ composite electrodes: Influence of component ratio and current collector Ba0.5Sr0.5Co0.8Fe0.2O3-δ- bace0.7 zr0.1 y0.1 yb0.1 o3 -δ复合电极的优化：组分比和集流器的影响

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-30 DOI: 10.1016/j.ssi.2025.117035

Kristina Fedorova , Egor Gordeev , Olga Seliverstova , Ekaterina Antonova

Composite Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ-BaCe_0.7Zr_0.1Y_0.1Yb_0.1O_3-δ electrodes were studied as promising cathodes for application in electrochemical devices based on a proton-conducting electrolyte. Electrochemical activity of electrodes with different ratio of components was investigated by impedance spectroscopy in the oxygen-containing atmospheres, humidified with H₂O and D₂O. The optimal ratio of components in the electrode was found to be 80/20 wt% Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ/BaCe_0.7Zr_0.1Y_0.1Yb_0.1O_3-δ. The polarization resistance of the electrode of such a composition is 0.8 Ohm*cm² at 650 °C in a H₂O-humidified air atmosphere. The use of a current collector made it possible to reduce the polarization resistance to 0.5 Ohm*cm² under the same conditions. For all investigated compositions and conditions, the H/D isotope effect in the electrode response was detected. The influence of the ratio of the electrode components and the current collector on the mechanism of the electrode reaction is discussed.

研究了复合电极Ba0.5Sr0.5Co0.8Fe0.2O3-δ- bace0.7 zr0.1 y0.1 yb0.1 o3 -δ在质子导电电解质电化学器件中的应用前景。采用阻抗谱法研究了不同组分比例的电极在含氧气氛中，用H2O和D2O加湿后的电化学活性。电极中各组分的最佳配比为80/20 wt% Ba0.5Sr0.5Co0.8Fe0.2O3-δ/BaCe0.7Zr0.1Y0.1Yb0.1O3-δ。这种组合物的电极在650℃的水湿空气环境中极化电阻为0.8欧姆*cm2。在相同条件下，使用集流器可以将极化电阻降低到0.5欧姆*平方厘米。对于所有研究的成分和条件，H/D同位素效应在电极响应中被检测到。讨论了电极组分与集流器配比对电极反应机理的影响。

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引用次数: 0

Synthesis and electrochemical performances of lithium-rich manganese-based oxides materials for next-generation batteries 下一代电池用富锂锰基氧化物材料的合成与电化学性能研究

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-09-27 DOI: 10.1016/j.ssi.2025.117034

Fuliang Guo , Jieyun Zheng , Guogan Xu , Zhenyu Zhang , Ronggang Wang , Xingyu Chen , Liang Yin

Lithium-rich manganese-based oxides materials (LROs) have been extensively studied for next-generation lithium-ion batteries owing to their high capacity and low cost. However, challenges remain in addressing which pose significant barriers to achieving scalable manufacturing throughput, especially industrial-scale fabrication methodology. Herein, we explore the synthetic conditions including sintering temperature, lithium transition metal molar ratios (Li/TM) and sintering duration time to optimize electrochemical performances by using the Ni_0.1625Co_0.1625Mn_0.6750CO₃ carbonate precursor. Results demonstrate that electrochemical performances are significantly affected by sintering temperatures and Li/TM ratios. LROs powders annealed at 350 °C for 2 h, 600 °C for 15 h and 900 °C for 2 h step by step under a Li/TM ratio of 1.35 achieved exceptional electrochemical performance: first discharge capacity of 287.12 mAh·g⁻¹ at 25 mA·g⁻¹ with a coulombic efficiency of 82.13 %, and retains 91.28 % of its capacity after 200 cycles at 250 mA·g⁻¹. Moreover, this study elucidates the influence of sintering temperature, Li/TM ratios, and sintering duration time on the critical properties of LROs, including particle size, morphology, and phase composition, thereby offering a solid reference for scalable production.

富锂锰基氧化物材料（LROs）由于其高容量和低成本的特点，在下一代锂离子电池中得到了广泛的研究。然而，挑战仍然存在，这些挑战对实现可扩展的制造吞吐量构成了重大障碍，特别是工业规模的制造方法。本文以Ni0.1625Co0.1625Mn0.6750CO3碳酸盐为前驱体，研究了烧结温度、锂过渡金属摩尔比（Li/TM）和烧结时间等合成条件，以优化电化学性能。结果表明，烧结温度和Li/TM比对材料的电化学性能有显著影响。在Li/TM为1.35的条件下，分别在350℃、600℃和900℃条件下退火2 h的LROs粉末获得了优异的电化学性能：在25 mA·g−1条件下首次放电容量为287.12 mAh·g−1，库仑效率为82.13%，在250 mA·g−1条件下200次循环后仍保持91.28%的容量。此外，本研究阐明了烧结温度、Li/TM比和烧结时间对LROs的粒度、形貌和相组成等关键性能的影响，从而为规模化生产提供了坚实的参考。

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引用次数: 0