Electrochimica Acta最新文献_第9页

Electrorefining of zinc from hot-dip galvanizing slag in a choline chloride/ethylene glycol based deep eutectic solvent 在氯化胆碱/乙二醇基深度共晶溶剂中电精炼热镀锌渣中的锌

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-04 DOI: 10.1016/j.electacta.2025.147959

Haotian Tang , Mengwei Guo , Rongrong Deng , Mingyuan Gao , Qibo Zhang

This study investigates the electrorefining of zinc derived from hot-dip galvanizing (HDG) slag, employing a deep eutectic solvent (DES) composed of choline chloride and ethylene glycol, commonly referred to as Ethaline DES. A thorough electrochemical analysis was carried out to examine the oxidative dissolution behaviors of metallic zinc and associated impurity metals, along with the reduction behavior of Zn(II) ions. These findings demonstrate that, in the Ethaline-ZnCl₂ DES system, zinc undergoes oxidation preferentially compared to impurities, enabling selective extraction of zinc from HDG slag. Furthermore, the reduction potential of Zn(II) is observed to be more positive than that of the impurity metal ions, favoring its preferential deposition at the cathode. Increasing the temperature and incorporating an appropriate quantity of water significantly reduce the viscosity and improve conductivity of the Ethaline DES system, thereby enhancing charge transfer and diffusion of Zn(II) ions while lowering the energy barrier for Zn(II) reduction. Under optimized electrorefining conditions, the resulting cathodic zinc achieves a purity of 99.967 %, with a current efficiency of 95.14 % and an energy consumption of 787 ± 26 kWh/t. This work proposes a sustainable and energy-efficient method for the electrorefining of zinc from HDG slag, presenting a viable pathway for the valorization of this metallurgical byproduct.

本研究采用氯化胆碱和乙二醇（通常称为Ethaline DES）组成的深度共晶溶剂（DES）对热镀锌（HDG）渣中的锌进行了电精炼，并对金属锌和伴生杂质金属的氧化溶解行为以及Zn（II）离子的还原行为进行了深入的电化学分析。这些发现表明，在乙烷- zncl2 DES体系中，锌比杂质更容易被氧化，从而可以从HDG渣中选择性地提取锌。此外，Zn（II）的还原电位高于杂质金属离子的还原电位，有利于其在阴极的优先沉积。提高温度和加入适量的水可以显著降低Ethaline DES体系的粘度，提高其导电性，从而增强Zn（II）离子的电荷转移和扩散，同时降低Zn（II）还原的能垒。在优化的电精炼条件下，阴极锌纯度为99.967%，电流效率为95.14%，能耗为787±26 kWh/t。本研究提出了一种可持续的、节能的从HDG渣中电精炼锌的方法，为该冶金副产品的增值提供了一条可行的途径。

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引用次数: 0

Theoretical investigation on the energy storage properties of T-VS2 electrode materials in supercapacitors 超级电容器中T-VS2电极材料储能性能的理论研究

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-04 DOI: 10.1016/j.electacta.2025.147961

Yuan Yuan , Guangmin Yang , Jianyan Lin , Qiang Xu

The increasingly serious energy problem has promoted the development of new energy storage devices. The energy density of electrochemical double-layer capacitors (EDLCs) is primarily influenced by quantum capacitance (C_Q) and double-layer capacitance (C_D). Therefore, it is necessary to improve C_Q and C_D by adjusting the electronic structure of the electrodes and the combination of electrode electrolytes. Vanadium disulfide (VS₂) is a transition metal disulfide (TMD) that has attracted much attention in the field of energy storage due to its graphene-like two-dimensional layered structure and unique electronic properties. This study compares H-VS₂, T-VS₂, and hydroxylated T-VS₂(OH)₂ electrodes using theoretical and simulation methods. The overall double-layer capacitance of metal T-VS₂ (5.4 μF/cm²) is slightly higher than that of H-VS₂, but it exhibits a marked advantage at 0 V. Hydroxyl functionalization further boosts C_Q of T-VS₂(OH)₂ to 362.12 μF/cm². Hydrogen bonding between -OH groups of T-VS₂(OH)₂ and hydrogen in electrolyte leads an enhanced C_D of 13.24 μF/cm². The total interfacial capacitance is fitted as 12.77 μF/cm². This study reveals that the surface properties of electrodes and electrolyte ions jointly regulate the capacitance value of capacitors through the combined effects of quantum effects and double layer effects. The results provide a theoretical basis for improving the energy density of SCs based on VS₂ electrode designs.

日益严重的能源问题促进了新型储能装置的发展。电化学双层电容器的能量密度主要受量子电容（CQ）和双层电容（CD）的影响。因此，有必要通过调整电极的电子结构和电极电解质的组合来改善CQ和CD。二硫化钒（VS2）是一种过渡金属二硫化物（TMD），由于其具有类似石墨烯的二维层状结构和独特的电子性质，在储能领域受到了广泛的关注。本研究采用理论和模拟方法对H-VS2、T-VS2和羟基化T-VS2(OH)2电极进行了比较。金属T-VS2的整体双层电容（5.4 μF/cm²）略高于H-VS2，但在0 V时表现出明显的优势。羟基功能化进一步提高T-VS2(OH)2的CQ至362.12 μF/cm2。T-VS2(OH)2的-OH基团与电解质中的氢之间的氢键导致CD增强13.24 μF/cm2。总界面电容拟合为12.77 μF/cm2。本研究揭示了电极和电解质离子的表面性质通过量子效应和双层效应的联合作用共同调节电容器的电容值。研究结果为基于VS2电极设计提高SCs的能量密度提供了理论依据。

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引用次数: 0

Residual alkali-driven LiNbO3 coating and bulk-doping structural reinforcement for high-nickel layered oxides 高镍层状氧化物的残碱驱动LiNbO3涂层和块体掺杂结构增强

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-03 DOI: 10.1016/j.electacta.2025.147948

Shiyou Li , Yue Gao , Yulong Zhang , Ningshuang Zhang , Dongni Zhao

LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90) has attracted significant attention due to its high theoretical capacity (>200 mAh g^-1) and lower cobalt content. However, the unavoidable residual alkaline (e.g., Li₂CO₃ and LiOH) on its surfaces often induces interfacial side reactions and accelerates structural degradation. Herein, an in situ Nb⁵⁺-based modification strategy is developed to utilizes these residuals to construct a thin, dense and strongly adherent LiNbO₃ coating via direct reaction with Nb₂O₅. Meanwhile, Nb⁵⁺ is partially doped into the TM layer via the diffusion-infiltration effect. This dual-functional design significantly enhances both interfacial stability and bulk structural integrity. Unlike conventional inert coatings, the as-generated LiNbO₃ layer acts as a fast Li⁺ conductor, mitigating electrolyte corrosion and transition metal (TM) ion dissolution and enhancing Li⁺ transport kinetics. Simultaneously, Nb⁵⁺ doping suppresses cation migration, oxygen vacancy formation and irreversible H₂→H₃ phase transitions, and thus achieves bulk structure reinforcement. Results show that the modified sample exhibited a capacity retention of 82.42 % after 200 cycles at 0.2 C and 25 °C, 28.18 % higher than the pristine sample. Notably, it still exhibits excellent cycling performance under high temperature (55 °C) and moderate rate (1.0 C). This study not only proposes a suitable pathway for residual alkali treatment on high-nickel cathode surfaces but also highlights the critical role of the “interface passivation + structural stabilization” dual-modification.

LiNi0.9Co0.05Mn0.05O2 （NCM90）由于具有较高的理论容量（>200 mAh g-1）和较低的钴含量而备受关注。然而，其表面不可避免的残留碱（如Li2CO3和LiOH）往往引起界面副反应，加速结构降解。本文提出了一种基于Nb5+的原位改性策略，通过与Nb2O5直接反应，利用这些残留物构建薄、致密且附着力强的LiNbO3涂层。同时，Nb5+通过扩散-渗透作用部分掺杂到TM层中。这种双功能设计显著提高了界面稳定性和整体结构完整性。与传统惰性涂层不同，生成的LiNbO3层充当快速Li+导体，减轻电解质腐蚀和过渡金属（TM）离子溶解，增强Li+传输动力学。同时，Nb5+掺杂抑制了阳离子迁移、氧空位形成和不可逆的H2→H3相变，从而实现了体结构的强化。结果表明，改性后的样品在0.2 ℃和25 ℃下循环200次后的容量保留率为82.42%，比原始样品高28.18%。值得注意的是，它在高温（55 °C）和中等速率（1.0 °C）下仍具有优异的循环性能。本研究不仅提出了高镍阴极表面残碱处理的合适途径，而且强调了“界面钝化 + 结构稳定化”双改性的关键作用。

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引用次数: 0

Fouled electrodes: Density gradient-driven convection augments aqueous electrosynthetic yields 污染电极：密度梯度驱动对流增加水电合成收率

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-03 DOI: 10.1016/j.electacta.2025.147958

Wathsala Prasadini Kapuralage, Simone Ciampi

Organic electrosynthesis offers sustainable pathways for chemical manufacturing. Electrode surface properties strongly influence electrosynthetic efficiency; hence, electrode contamination by non-conductive materials generally suppresses reaction rates. However, recent studies indicate that lateral surface heterogeneity – conductive regions interspersed with insulating domains – induces density gradients that, under gravity, augment rates by promoting natural convection in otherwise quiescent systems. Here, we show that convection triggered by partial electrode fouling enhances the rate of model electrosynthetic processes. We have quantitatively assessed the extent to which fouling promotes mass transport and increases net electrolytic rates per unit area for the electro-reduction of levulinic acid (LA) to valeric acid (VA) and for the electro-oxidation of l-ascorbic acid (LAA) to dehydroascorbic acid (DHAA). Specific patterns of microscopic insulating features were deposited on glassy carbon, lead, and indium tin oxide electrodes through photolithography. Despite a reduction in electroactive area, fouled electrodes showed higher yields than pristine ones. Large-scale patterns of relatively hydrophilic novolak resin (nLOF 2035) enhanced LA-to-VA conversion by up to 1.8–fold, while the epoxy-based SU-8 2002 photoresist improved LAA oxidation by 1.22–fold. Moreover, when electrodes were aligned vertically relative to gravity, buoyancy-driven convection, hence electrolytic rates, are further amplified. This work establishes a new framework for reactor and electrode design in which controlled surface blocking is harnessed to augment, rather than hinder mass transport, opening new opportunities for organic electrosynthesis.

有机电合成为化学制造提供了可持续的途径。电极表面性质对电合成效率影响很大；因此，电极被非导电材料污染通常会抑制反应速率。然而，最近的研究表明，侧向表面的非均质性——导电区域与绝缘区域穿插在一起——会引起密度梯度，在重力作用下，通过促进静止系统中的自然对流来增加密度梯度。在这里，我们发现由部分电极污垢引发的对流提高了模型电合成过程的速率。我们定量地评估了污染促进质量运输的程度，并增加了乙酰丙酸（LA）电还原为戊酸（VA）和l -抗坏血酸（LAA）电氧化为脱氢抗坏血酸（DHAA）的单位面积净电解速率。通过光刻技术在玻碳、铅和氧化铟锡电极上沉积了显微绝缘特征的特定图案。尽管电活性面积减少，但污染电极的产率高于未污染电极。大规模的亲水novolak树脂（nLOF 2035）将la到va的转化率提高了1.8倍，而基于环氧树脂的SU-8 2002光抗蚀剂将LAA氧化提高了1.22倍。此外，当电极相对于重力垂直排列时，浮力驱动的对流，因此电解速率进一步放大。这项工作为反应器和电极设计建立了一个新的框架，其中利用受控的表面阻塞来增强而不是阻碍质量传递，为有机电合成开辟了新的机会。

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引用次数: 0

Electrochemical response of hierarchical porous carbon derived silicon oxycarbide materials employing different nucleophilic etching 不同亲核蚀刻方式下层叠多孔碳源碳化硅材料的电化学响应

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-03 DOI: 10.1016/j.electacta.2025.147947

J.M. Mayta , J. Rubio , M.A. Mazo

Nucleophilic attack (i.e. F⁻ or OH⁻) was used to remove selectively the Si-O bonds present in the silicon oxycarbide (SiOC) matrix, increasing both the specific surface area and the amount of carbon (C (%)) in the related carbon derived silicon oxycarbide (SiOC-DC) materials. We compare two different etchings: 1) HF at room temperature (RT) studying the influence of the time from 1 to 120 h and 2) NaOH during 24 h employing mild temperature conditions from RT to 90 °C. In addition, two different SiOC systems were evaluated, containing or not polydimetilsiloxane (PDMS) (within the pristine hybrid material) that facilitates the Si-O etching. The SiOC materials were obtained after pyrolysis at 1100 °C of sol-gel hybrids, a relatively low temperature in order to reduce the cost of the overall process.

The best results were obtained for SiOC where PDMS were added after the HF etching during 24 h, considering the major extraction of silica nano-domains, which renders in a hierarchical porous microstructure with the highest specific surface area (582 m²g⁻¹) and optimized pore size (micro, meso and macro), C values (54 %), and heteroatom functionalization (F, O) highly demanded in carbon electrodes for supercapacitor applications. The device with two electrodes Swagelok® configuration employing aqueous H₂SO₄ 1 M displays high specific capacitance values of 189, 83, 76 Fg⁻¹ at 0.1, 1, 5 Ag⁻¹ and energy density of 16.5 Wh⁻¹kg⁻¹ at the power density of 0.5 kWkg⁻¹ with a Coulombic efficiency >95 % after 10,000 cycles (0.5 Ag⁻¹).

Finally, the materials obtained after NaOH etching at 90 °C also reach very interesting characteristics (C = 39 % and 118 m²g⁻¹) due to the actual necessity of find more sustainable and environmentally friendly processes to produce hierarchical highly porous carbon derived materials very demanded for cutting-edge technological applications.

使用亲核攻击（即F−或OH−）选择性地去除存在于碳化硅（SiOC）基体中的Si-O键，增加了相关碳衍生碳化硅（SiOC- dc）材料的比表面积和碳量（C(%)）。我们比较了两种不同的蚀刻：1)室温下的HF （RT）研究了时间从1到120小时的影响；2)在24小时内的NaOH （RT到90°C的温和温度条件下）。此外，还评估了两种不同的SiOC体系，其中包含或不包含促进Si-O蚀刻的聚二甲硅氧烷（PDMS）（在原始杂化材料中）。为了降低整个过程的成本，SiOC材料是在1100℃的溶胶-凝胶杂化温度下热解得到的。考虑到主要的二氧化硅纳米结构域的提取，在HF蚀刻24小时后加入PDMS的SiOC获得了最好的结果，这使得分层多孔结构具有最高的比表面积（582 m2 - 1）和优化的孔径（微观，中观和宏观），C值（54%）和杂原子功能化（F， O），这是超级电容器应用中碳电极非常需要的。该器件采用双电极Swagelok®配置，采用水溶液H2SO4 1m，在0.1、1.5 Ag−1条件下，比电容值高达189、83、76 Fg−1，功率密度为0.5 kWkg−1时，比电容密度为16.5 Wh−1kg−1，在10,000次循环（0.5 Ag−1）后，库仑效率为95%。最后，在90°C下NaOH蚀刻后获得的材料也达到了非常有趣的特性（C = 39%和118 m2g−1），因为实际需要找到更可持续和环保的工艺来生产分层高多孔碳衍生材料，这是尖端技术应用非常需要的。

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引用次数: 0

Ternary deep eutectic solvent-mediated dual-crosslinked microalgae eutectogel electrolytes for wide-temperature flexible supercapacitors 三元深共晶溶剂介导双交联微藻共晶电解质用于宽温柔性超级电容器

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-03 DOI: 10.1016/j.electacta.2025.147953

Shaojunyan Tan, Xingming Wei, Rui Huang, Liuying Jiang, Yujie Yu, Shijie Zhang, Jianyong Yin

Gel-polymer electrolytes (GPEs) for flexible supercapacitors (FSCs) are limited by poor mechanical properties, narrow temperature tolerance, and solvent volatility. Herein, we present a novel strategy mediated by a ternary deep eutectic solvent (DES: ChCl–EG–Urea), enabling the fabrication of dual-crosslinked microalgae eutectogel electrolytes. The resulting materials exhibit exceptional self-healing capability and robust performance over a wide temperature range. The fabrication process that integrates ternary DES and microalgae creates a hydrogen-bond template, guiding the subsequent in-situ polymerization with acrylic acid and leading to the formation of both covalent and hydrogen-bond crosslinks. This dual-crosslinked architecture delivers remarkable enhancements: tensile strength increased by 747 % (12 to 101.7 kPa), elongation at break by 413 % (150 % to 770 %), glass transition temperature decreased from -19.2 °C to -40.0 °C, and ionic conductivity reached 5.12 mS cm⁻¹. Notably, the eutectogel demonstrated complete self-healing within 1 min with 82 % capacitance retention after multiple cut-heal cycles, and zero mass loss over 24 h without encapsulation. Quantum chemical calculations revealed that the ternary DES components form stronger hydrogen-bond networks (binding energy:−21.24 kcal/mol) with the polymer matrix. The assembled FSCs operated stably from -40 °C to 75 °C, maintaining 95.01 % capacitance after 5000 cycles and exhibiting excellent flexibility at 180° bending. This ternary DES-mediated approach offers a sustainable pathway for developing robust, self-healing electrolytes for next-generation flexible energy storage devices.

用于柔性超级电容器（FSCs）的凝胶聚合物电解质（gpe）受到机械性能差，温度耐受性窄和溶剂挥发性的限制。在此，我们提出了一种新的策略，由三元深共晶溶剂（DES: chcl - eg -尿素）介导，使双交联微藻共聚电解质的制备成为可能。所得到的材料在很宽的温度范围内表现出卓越的自愈能力和坚固的性能。将三元DES和微藻结合在一起的制造过程创造了一个氢键模板，指导随后与丙烯酸的原位聚合，并导致共价和氢键交联的形成。这种双交联结构提供了显著的增强：抗拉强度提高了747%(12至101.7 kPa)，断裂伸长率提高了413%(150%至770%)，玻璃化温度从-19.2°C降低到-40.0°C，离子电导率达到5.12 mS cm⁻¹。值得注意的是，共晶层在1分钟内表现出完全的自愈，在多次切割愈合循环后保持82%的电容，并且在没有封装的情况下24小时内零质量损失。量子化学计算表明，三元DES组分与聚合物基体形成更强的氢键网络（结合能：-21.24 kcal/mol）。组装的FSCs在-40°C至75°C范围内稳定工作，在5000次循环后保持95.01%的电容，并在180°弯曲时表现出优异的灵活性。这种三元des介导的方法为开发下一代柔性储能设备的强大、自修复电解质提供了一条可持续的途径。

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引用次数: 0

Electrochemically active area quantification in all-solid-state batteries through an integrated galvanostatic–impedance framework 全固态电池的电化学活性区量化，采用集成的恒流阻抗框架

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-03 DOI: 10.1016/j.electacta.2025.147949

So-Young Joo, Heon-Cheol Shin

Reliable quantification of the electrochemically active area (EAA), which reflects the interfacial contact between the active material and the solid electrolyte in all-solid-state batteries (ASSBs), is essential for performance analysis and optimization. Here, we refine and extend an integrated galvanostatic–impedance framework to ASSB composite cathodes and propose a systematic procedure to estimate the EAA. First, an area-independent diffusion coefficient is extracted from the Warburg–blocking transition in the impedance spectra using a spherical finite-diffusion model. This coefficient is then fixed as a reference, and the EAA is obtained via a one-step constraint that estimates only the area-sensitive component of the initial galvanostatic response. Applied to Ni-rich cathodes with sulfide electrolytes, the EAA decreases with increasing lithium content, consistent with the reduction of electrochemically accessible sites, and the EAA values agreed quantitatively with theoretical predictions. As a function of stack pressure, the EAA exhibits nonlinear contact behavior: a rapid rise at low pressure, a moderate increase at intermediate pressure, and saturation near a critical region, in quantitative accord with prior studies. The proposed one-step constraining approach offers a practical, nondestructive, and quantitative framework for evaluating interfacial contact in ASSB composite electrodes, particularly the EAA, and is broadly applicable to contact-degradation monitoring, process/composition optimization, and constructing pressure–performance maps.

电化学活性区（EAA）反映了全固态电池（assb）中活性物质与固体电解质之间的界面接触，对其性能分析和优化至关重要。在这里，我们完善和扩展了一个集成的恒流阻抗框架，以ASSB复合阴极，并提出了一个系统的程序来估计EAA。首先，利用球面有限扩散模型从阻抗谱中的Warburg-blocking过渡中提取面积无关的扩散系数；然后将该系数固定为参考，并通过仅估计初始恒流响应的面积敏感分量的一步约束获得EAA。应用于含硫化物电解质的富镍阴极，EAA随锂含量的增加而降低，与电化学可达位点的减少一致，EAA值与理论预测在定量上一致。作为堆压的函数，EAA表现出非线性接触行为，在低压下快速上升，在中压下适度上升，并在临界区域附近饱和，定量与前人研究一致。提出的一步约束方法为评估ASSB复合电极（特别是EAA）的界面接触提供了一个实用、无损和定量的框架，广泛适用于接触退化监测、工艺/成分优化和构建压力性能图。

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引用次数: 0

Nano-coating PEDOT improves the stability of the LiNi0.5Mn1.5O4 by In-Situ Polymerization 通过原位聚合，纳米涂层PEDOT提高了LiNi0.5Mn1.5O4的稳定性

IF 6.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-03 DOI: 10.1016/j.electacta.2025.147951

Lingbing Wu, Hongwei Zhang, Ruida Zhao, Rui Chang, Youlong Xu

LiNi_0.5Mn_1.5O₄ (LNMO) is a promising candidate for high-energy-density batteries, owing to its high operating voltage. However, the interface reactions and the structural instability during the cycling are the main obstacles to realizing its practical application. PEDOT (poly(3,4-ethylenedioxythiophene)) exhibits high electrical conductivity (10-1000 S/cm) and electrochemical stability, making it an ideal choice for addressing the interface problem of LNMO.This study revealed that the LNMO and the EDOT monomer possess opposite zeta potentials. Based on the principle of electrostatic adsorption, through precise control of the monomer content, a nano-PEDOT coating was successfully fabricated on the LNMO surface and named as LNMO@PEDOT-X (X = 0, 1%, 3%, 5%). SEM and TEM morphology analyzed that the coating layer of LNMO@PEDOT-3% was uniformly coated on the spinel surface, with a thickness of approximately 10 nanometers. XRF analysis demonstrated 80% mitigation in Mn deposition on the Li counter electrode after 1000 cycles at 1C. In addition, the material exhibited a two-order-of-magnitude enhancement in electronic conductivity. Notably, the LNMO@PEDOT-3% has a doubled specific capacity over 100 mAh·g⁻¹, demonstrating a promising strategy for addressing interfacial issues.

LiNi0.5Mn1.5O4 （LNMO）具有较高的工作电压，是高能量密度电池的理想材料。然而，循环过程中的界面反应和结构不稳定性是实现其实际应用的主要障碍。PEDOT（聚（3,4-乙烯二氧噻吩））具有高导电性（10-1000 S/cm）和电化学稳定性，是解决LNMO界面问题的理想选择。研究表明，LNMO和EDOT单体具有相反的zeta电位。基于静电吸附原理，通过对单体含量的精确控制，在LNMO表面成功制备了纳米pedot涂层，命名为LNMO@PEDOT-X （X = 0,1%,3%,5%）。SEM和TEM形貌分析表明，LNMO@PEDOT-3%的涂层均匀地涂覆在尖晶石表面，厚度约为10纳米。XRF分析表明，在1C下循环1000次后，锂对电极上的Mn沉积减少了80%。此外，该材料在电子导电性方面表现出两个数量级的增强。值得注意的是，LNMO@PEDOT-3%的比容量在100 mAh·g−1以上增加了一倍，展示了解决界面问题的有希望的策略。

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引用次数: 0

EPR and UV−Vis−NIR spectroscopic features of radical ions of amino substituted thienyl ketones 氨基取代噻吩酮自由基的EPR和紫外-可见-近红外光谱特征

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-02 DOI: 10.1016/j.electacta.2025.147925

Evgenia Dmitrieva , Alexey Popov , Horst Hartmann

A series of amino-substituted mono- and bis-thienyl ketones were characterized by means of cyclic voltammetry, ultraviolet−visible−near infrared (UV−Vis−NIR) absorption spectroscopy, and in situ electron paramagnetic resonance (EPR)/UV−Vis−NIR spectroelectrochemistry. The molecular structures of bis-thienyl ketones contain morpholine (3a–c) or N,N´-disubstituted amino (3d–f) groups. The electrochemical reduction of the ketones leads to the formation of stable radical anions, and their EPR and UV−Vis−NIR spectral features were analyzed in detail. In contrast, the radical cations are not stable and undergo follow-up chemical reactions with formation of redox-active dimers. The EPR data and DFT calculations provide information about the charge/spin localization in the electrochemically generated radical ions.

采用循环伏安法、紫外-可见-近红外（UV - Vis - NIR）吸收光谱和原位电子顺磁共振(EPR)/紫外-可见-近红外（UV - Vis - NIR）光谱电化学对一系列氨基取代的单噻吩酮和双噻吩酮进行了表征。双噻吩基酮的分子结构中含有啉（3a-c）或N，N′-二取代氨基（3d-f）基团。酮类化合物的电化学还原生成了稳定的自由基阴离子，并对其EPR和UV - Vis - NIR光谱特征进行了详细分析。相反，自由基阳离子不稳定，并发生后续化学反应，形成氧化还原活性二聚体。EPR数据和DFT计算提供了电化学生成的自由基离子中电荷/自旋定位的信息。

引用次数: 0

Temperature-pressure-flow rate synergy effect on corrosion behavior of supercritical CO2 pipelines: Optimal conditions and FeCO₃ film mechanism 温度-压力-流量协同效应对超临界CO2管道腐蚀行为的影响：最优条件和FeCO₃膜机理

IF 5.6 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2025-12-02 DOI: 10.1016/j.electacta.2025.147943

Zihong Liu, Jiazhu Bao, Jie Wang, Jiguang Wang, Yu Liu, Yongchen Song, Lunxiang Zhang

Supercritical CO₂ corrosion represents a significant technological bottleneck for pipeline-scale applications, posing serious risks to the safe operation of carbon capture, utilization, and storage (CCUS) systems. However, the influence of the synergistic effects of temperature, pressure, and flow rate on the corrosion mechanism remains poorly understood. Notably, studies investigating the optimal temperature-pressure interval across varying flow rates are scarce, which hinders the development of effective corrosion control strategies. The findings reveal a pronounced "optimal temperature-pressure-flow rate combination" effect in supercritical CO₂ corrosion; this specific combination yields the lowest corrosion rate while deviations from it result in significantly elevated rates. To address potential misjudgments arising from reliance on a single electrochemical parameter, we propose a closed-loop validation method that integrates "electrochemical parameters - corrosion mechanism - morphological features." This study demonstrates for the first time that temperature, pressure, and flow rate regulate the nucleation-growth-sedimentation kinetic processes of FeCO₃. These factors directly impact film layer densification and consequently control the overall corrosion rate. The results not only support safe applications of supercritical CO₂ technology but also provide an essential experimental foundation for developing robust corrosion control strategies within CCUS systems.

超临界CO2腐蚀是管道规模应用的一个重要技术瓶颈，对碳捕集、利用和封存（CCUS）系统的安全运行构成严重风险。然而，温度、压力和流量的协同效应对腐蚀机理的影响仍然知之甚少。值得注意的是，研究不同流量下的最佳温度-压力区间的研究很少，这阻碍了有效腐蚀控制策略的发展。结果表明，超临界CO2腐蚀存在明显的“最佳温度-压力-流量组合”效应；这种特殊的组合产生最低的腐蚀速率，而偏离它会导致腐蚀速率显著升高。为了解决由于依赖单一电化学参数而产生的潜在误判，我们提出了一种集成“电化学参数-腐蚀机理-形态特征”的闭环验证方法。本研究首次证明了温度、压力和流速对FeCO3成核-生长-沉积动力学过程的调控作用。这些因素直接影响膜层致密化，从而控制整体腐蚀速率。研究结果不仅支持超临界CO2技术的安全应用，而且为CCUS系统中开发强大的腐蚀控制策略提供了重要的实验基础。

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