Electrochimica Acta最新文献_第9页

Machine learning predictions of onset and oxidation potentials for methanol and ethanol electrooxidation: Comprehensive analysis and experimental validation 甲醇和乙醇电氧化起始电位和氧化电位的机器学习预测：综合分析与实验验证

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-31 DOI: 10.1016/j.electacta.2024.145285

Theodora Wrobel von Zuben , Airton Gonçalves Salles Jr. , Juliano Alves Bonacin , Sylvio Barbon Junior

The onset and oxidation potentials of electrochemical reactions are pivotal in assessing catalytic energy efficiency, spanning applications across various domains, including sustainable energy generation. However, predicting these potentials presents a complex and uncharted challenge. In this study, we present a pioneering approach to developing predictive models for the onset and oxidation potentials within electrochemical reactions linked to the oxidation of methanol and ethanol. We have devised a comprehensive pipeline from Data Collection, Information Extraction, and Preprocessing and assessed the performance of different regression models: Linear, Random Forest, and XGBoost. For the oxidation potential prediction, an RMSE of 0.169 and an R

^{2}

value of 0.814 were achieved. Similarly, for the onset potential prediction, the model yielded an RMSE of 0.185 and an R

^{2}

value of 0.839. The models were further evaluated using feature importance and SHAP values, enhancing our understanding of their predictive mechanisms and providing more comprehension of the features. Additionally, we conducted experimental validations by comparing the predicted outcomes to actual results obtained from methanol and ethanol oxidation experiments carried out in a chemical laboratory. This validation process included the utilization of platinum, gold, nickel foam, steel and RuO

_{2}

/FTO electrodes. Encouragingly, the experimental validation yielded promising findings, exhibiting an RMSE of 0.0967 for the onset potential and an RMSE of 0.0234 for the oxidation potential.

电化学反应的起始电位和氧化电位是评估催化能效的关键，其应用横跨各个领域，包括可持续能源发电。然而，预测这些电位是一项复杂而未知的挑战。在本研究中，我们提出了一种开创性的方法，为甲醇和乙醇氧化相关电化学反应的起始电位和氧化电位开发预测模型。我们设计了一个从数据收集、信息提取到预处理的综合管道，并评估了不同回归模型的性能：线性模型、随机森林模型和 XGBoost 模型。在氧化潜能预测方面，RMSE 为 0.169，R2 值为 0.814。同样，在起始电位预测方面，模型的 RMSE 为 0.185，R2 值为 0.839。我们使用特征重要性和 SHAP 值对模型进行了进一步评估，从而加深了我们对其预测机制的理解，并提供了对特征的更多理解。此外，我们还进行了实验验证，将预测结果与在化学实验室进行的甲醇和乙醇氧化实验的实际结果进行了比较。验证过程包括使用铂、金、泡沫镍、钢和 RuO2/FTO 电极。令人鼓舞的是，实验验证结果令人鼓舞，起始电位的均方根误差为 0.0967，氧化电位的均方根误差为 0.0234。

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引用次数: 0

Microstructure and corrosion properties of AlCrFe2Ni2Bx (x = 0, 0.04, 0.1, 0.2) high entropy alloy AlCrFe2Ni2Bx (x=0, 0.04, 0.1, 0.2) 高熵合金的微观结构和腐蚀特性

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-31 DOI: 10.1016/j.electacta.2024.145303

Yinan Wang , Rui Fan , Zhenjie Zang , Xin Zhang , Bo Cui

This study examined how varying B element concentrations (x = 0, 0.04, 0.1, and 0.2 at.%) affect the microstructure, corrosion resistance, and characteristics of passive films in AlCrFe₂Ni₂B_x high-entropy alloys. The findings indicated that as-cast AlCrFe₂Ni₂B_x alloys transitioned from distinct grain structures to dendritic structures. Increased B content significantly enhanced inter-dendritic regions, resulting in notable grain refinement during this transition. In a 3.5 wt.% NaCl solution, B content increase from 0 at.% to 0.1 at.% improved corrosion resistance, while a 0.2 at.% concentration slightly reduced resistance. These effects stemmed from microstructural changes and variations in passive film composition.

本研究探讨了不同的 B 元素浓度（x=0、0.04、0.1 和 0.2 at.%）如何影响 AlCrFe2Ni2Bx 高熵合金的微观结构、耐腐蚀性和被动膜的特性。研究结果表明，铸态铝铬铁镍2Bx合金从明显的晶粒结构过渡到树枝状结构。B 含量的增加显著增强了树枝状结构间区域，从而在这一转变过程中实现了明显的晶粒细化。在重量百分比为 3.5 的氯化钠溶液中，硼含量从 0%增加到 0.1%可提高耐腐蚀性，而 0.2%的硼含量则会略微降低耐腐蚀性。这些影响源于微观结构的变化和被动膜成分的变化。

引用次数: 0

Optimization of electrochromic Mo doping WO3 films: A study on dual-phase stacked structures for energy-efficient smart windows 电致变色钼掺杂 WO₃ 薄膜的优化：用于高能效智能窗户的双相叠层结构研究

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-30 DOI: 10.1016/j.electacta.2024.145295

Jinshuo Bai , Yinan Zhang , Zixin Pan , Xiangru Yin , Guixiang Yang , Dequan Zhang , Hua Zhou , Xiaoping Liang

Amorphous tungsten trioxide (a-WO₃) films were prepared on ITO conductive glass via electrodeposition and subsequently crystallized to obtain crystalline WO₃ (c-WO₃) films by heating a-WO₃. A dual-phase stacked WO₃ film was fabricated by covering Mo-a-WO₃ film onto c-WO₃/ITO substrate using electrodeposition and thermal-assisted electrodeposition methods, respectively. Optimization of electrochromic performance was achieved by varying Mo doping levels (0∼5 atom%). Results demonstrate that appropriate Mo doping (3 atom%) enhances the electrochromic properties of a-WO₃ films. Mo doping introduced structural distortions that reduced energy barriers and enhanced ion mobility, leading to improved electrochemical and electrochromic properties. The intermediate c-WO₃ layer improves adhesion between a-WO₃ top film and ITO glass substrate, while the porous structure of a-WO₃ layer increases the number of active sites for electrochromic reactions. Mo3-a-WO₃/c-WO₃ dual-phase stacked film with doping 3 atom% Mo shows an optical modulation range of 83.4 % at 633 nm, a coloration efficiency of 74.3 cm²/C, rapid response time (bleaching/coloration: 3.4 s/6.1 s), and 86.6 % retention of its maximum current density after 2000 cycles, respectively. The high oxidation ion diffusion coefficient (3.53 × 10⁻¹⁰ cm²/s) and reduction diffusion coefficient (1.55 × 10⁻¹⁰ cm²/s) were also observed. This dual-phase stacked film shows significant improvements in electrochromic performance due to the synergistic effects between the dual phases and Mo-doping. Electrochromic device (ECD) assembled with Mo3-a-WO₃/c-WO₃ dual-phase films as the working electrode, ITO glass as the counter electrode, and 1 mol/L LiClO4/PC solution as the electrolyte exhibited an optical modulation range of 74.2 % and response time (bleaching/ coloring) of 6.8 s/3.7 s. These findings confirm that ECD with Mo-a-WO₃/c-WO₃ dual-phase films offer excellent electrochromic performance.

通过电沉积法在 ITO 导电玻璃上制备了无定形三氧化钨（a-WO3）薄膜，随后通过加热 a-WO3 结晶得到了晶体 WO3（c-WO3）薄膜。采用电沉积法和热辅助电沉积法，分别将 Mo-a-WO3 薄膜覆盖在 c-WO3/ITO 基底上，制备出了双相叠层 WO3 薄膜。通过改变钼的掺杂水平（0∼5atom%）实现了电致变色性能的优化。结果表明，适当的钼掺杂（3atom%）可增强 a-WO3 薄膜的电致变色性能。钼掺杂引入了结构畸变，从而降低了能障并提高了离子迁移率，从而改善了电化学和电致变色特性。中间的 c-WO3 层提高了 a-WO3 表层薄膜与 ITO 玻璃基底之间的附着力，而 a-WO3 层的多孔结构则增加了电致变色反应的活性位点数量。掺杂了 3 原子%钼的 Mo3-a-WO3/c-WO3 双相叠层薄膜在 633 纳米波长下的光学调制范围为 83.4%，着色效率为 74.3 cm²/C，响应时间快（漂白/着色：3.4 秒/6.1 秒），循环 2,000 次后最大电流密度的保持率为 86.6%。氧化离子扩散系数（3.53 × 10-¹⁰ cm²/s）和还原离子扩散系数（1.55 × 10-¹⁰ cm²/s）也很高。由于双相和掺杂钼之间的协同效应，这种双相叠层薄膜的电致变色性能有了显著提高。以 Mo3-a-WO3/c-WO3 双相薄膜为工作电极、ITO 玻璃为对电极、1 mol/L LiClO4/PC 溶液为电解液组装的电致变色器件（ECD）的光学调制范围为 74.2%，响应时间（漂白/着色）为 6.8 秒/3.7 秒。

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引用次数: 0

Aqueous solution-based synthesis approach for carbon-disordered rocksalt composite cathode development and its limitations 基于水溶液的碳异构岩盐复合阴极开发合成方法及其局限性

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-30 DOI: 10.1016/j.electacta.2024.145302

Venkata Sai Avvaru , Mateusz Zuba , Beth L. Armstrong , Shilong Wang , Dong-Min Kim , Isik Su Buyuker , Carrie Siu , Brett A Helms , Ozgenur Kahvecioglu , Haegyeom Kim

Disordered rocksalt cathodes exhibit high specific capacities and high energy density; however, their low electronic conductivity poses a great challenge. Herein, we explored an aqueous-solution-based synthesis route that involves controlling the surface charges of Li_1.2Mn_0.6Ti_0.2O_1.8F_0.2 (LMTOF) to be anchored by a few-layer reduced graphene oxide (rGO) for the first time. The uniform rGO wrapping on the surface of the LMTOF particles is achieved by electrostatic attraction between the negatively charged rGO and positively charged LMTOF particles. Although the initial specific capacity of rGO-LMTOF composite increased by 58 % compared to the pristine LMTOF, the composite experienced a severe capacity fade over cycling. The synthesis process in an aqueous medium resulted in Li⁺/H⁺ exchange and TM dissolution as evidenced from inductively coupled plasmon analysis and X-ray diffraction analysis. Therefore, this work suggests the search for alternative media or conditions for the synthesis of carbon-disordered rock salt cathode composite.

无序的岩盐阴极具有高比容量和高能量密度，但其低电子传导性是一个巨大的挑战。在此，我们首次探索了一种基于水溶液的合成路线，该路线涉及控制 Li1.2Mn0.6Ti0.2O1.8F0.2 （LMTOF）的表面电荷，使其被几层还原氧化石墨烯（rGO）锚定。带负电荷的 rGO 和带正电荷的 LMTOF 颗粒之间的静电吸引实现了 LMTOF 颗粒表面均匀的 rGO 包裹。虽然与原始 LMTOF 相比，rGO-LMTOF 复合材料的初始比容量增加了 58%，但该复合材料在循环过程中出现了严重的容量衰减。从电感耦合等离子体分析和 X 射线衍射分析中可以看出，在水介质中的合成过程导致了 Li+/H+ 交换和 TM 溶解。因此，这项工作表明需要寻找合成碳-有序岩盐阴极复合材料的替代介质或条件。

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引用次数: 0

Methanol, ethylene glycol, and glycerol photoelectrochemical oxidation reactions on BiVO4: Zr,Mo/Pt thin films: A comparative study BiVO4:Zr,Mo/Pt 薄膜上的甲醇、乙二醇和甘油光电化学氧化反应：比较研究

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-30 DOI: 10.1016/j.electacta.2024.145300

Cristian Hessel , Lauren Moreti , Victor Yoiti Yukuhiro , Pablo S. Fernández , Elton Sitta

The green H₂ production plays a key role in the energy transition, however it still needs improvements to be applied in a large scale. The water oxidation reaction, as an anodic process to provide both protons and electrons for H₂ production, possesses kinetic limitations. Therefore, the use of an alternative process like the oxidation of biomass-derivative species is extremely desired to replace water oxidation during H₂ production. In this work, we provide a comparative study of different small organic molecules (methanol, ethylene glycol (EG), and glycerol) as alternatives to water oxidation at pristine BiVO₄, Mo-Zr dopped BiVO₄, and Pt co-catalyst BiVO₄ photoanodes in neutral media. While the band energy diagram and surface morphology are similar for the distinct materials, the presence of Zr-Mo increases the charge carriers density. The presence of Pt acts as co-catalyst for the organic molecules. Regardless of the material employed, the activity order for each organic molecule reaction was: j_water < j_methanol < j_EG < j_glycerol affeered by both linear potential sweep and chronoamperometry at 1.23 V vs RHE. The presence of both Zr-Mo and Pt increases the photoactivity for the alcohol's oxidation, however the presence of Pt is more advantageous for glycerol oxidation than for other species, maintaining 80 % of activity after 24 h electrolysis. The reactivity of alcohols can be tentatively explained by the greater stability of radicals formed from larger molecules.

绿色 H2 生产在能源转型中发挥着关键作用，但仍需改进才能大规模应用。水氧化反应作为一个为 H2 生产提供质子和电子的阳极过程，具有动力学上的局限性。因此，在 H2 生产过程中，使用生物质衍生物氧化等替代工艺来取代水氧化反应是非常有必要的。在这项工作中，我们比较研究了不同的小有机分子（甲醇、乙二醇 (EG) 和甘油）在中性介质中原始 BiVO4、掺杂 Mo-Zr 的 BiVO4 和铂辅助催化剂 BiVO4 光阳极上作为水氧化的替代物的情况。虽然不同材料的能带图和表面形态相似，但 Zr-Mo 的存在增加了电荷载流子密度。铂的存在对有机分子起到了辅助催化剂的作用。无论采用哪种材料，在 1.23 V 与 RHE 的线性电位扫频和计时器中，每种有机分子反应的活性顺序为：jwater < jmethanol < jEG < jglycerol。Zr-Mo 和铂的存在提高了醇氧化的光活性，但铂的存在对甘油氧化比对其他物质更有利，在电解 24 小时后仍能保持 80% 的活性。醇的反应活性可通过不同大小的自由基的形成得到初步解释。

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引用次数: 0

High-performance composite solid-state electrolyte combining NASICON-type Li1.5Al0.5Ti1.5(PO4)3 with ionic liquid and polymeric binders 将 NASICON 型 Li1.5Al0.5Ti1.5(PO4)3 与离子液体和聚合物粘合剂相结合的高性能复合固态电解质

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-30 DOI: 10.1016/j.electacta.2024.145299

Hugo Salazar , Bruna F. Gonçalves , Ainara Valverde , Renato Gonçalves , Carlos M. Costa , Leide P. Cavalcanti , José M. Porro , Viktor Petrenko , Senentxu Lanceros-Mendez , Qi Zhang

The use of composite solid-state electrolytes (CSEs) in Li-ion batteries presents a promising future for a new generation of solid-state battery technology. These composites address current limitations like poor room temperature ionic conductivity, low mechanical strength, and unstable interfaces. In this study, a NASICON-type Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) ceramic was prepared using a cold sintering process (CSP), incorporating LATP, poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE), and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]). This three-component CSE demonstrated reduced sintering temperature, energy, time, and operational costs compared to traditional methods. The LATP-based pellet achieved high density and a prismatic structure without impurities. The addition of a polymeric binder and an ionic liquid improved the nanostructuration, dispersion, mechanical properties, and relative density of the CSEs. Small-angle neutron scattering revealed nanostructuration changes, decreasing air pore size. Notably, room temperature ionic conductivities between 10^–4 – 10^–3 S cm^-1 were achieved, with a maximum conductivity of 7.02 × 10^–3 S cm^-1 and lithium-transference number of 0.35 for the sample with 99 wt.% LATP and 1 wt.% polymeric binder. Additionally, a room temperature discharge capacity of 141 mAh.g^-1 at C/10 rate was attained after 50 cycles, validating this three-component structure as a promising platform for high-performance CSEs in solid-state batteries.

在锂离子电池中使用复合固态电解质（CSE）为新一代固态电池技术带来了广阔的前景。这些复合材料可以解决目前存在的局限性，如室温离子导电性差、机械强度低和界面不稳定等。本研究采用冷烧结工艺（CSP）制备了 NASICON 型 Li1.5Al0.5Ti1.5(PO4)3 (LATP)陶瓷，将 LATP、聚偏氟乙烯-三氟乙烯-氯氟乙烯（PVDF-TrFE-CFE）和 1-乙基-3-甲基咪唑鎓双(三氟甲基磺酰基)亚胺（[EMIM][TFSI]）结合在一起。与传统方法相比，这种三组份 CSE 降低了烧结温度、能耗、时间和操作成本。基于 LATP 的颗粒实现了高密度和无杂质的棱柱结构。聚合物粘合剂和离子液体的加入改善了 CSE 的纳米结构、分散性、机械性能和相对密度。小角中子散射显示了纳米结构的变化，气孔尺寸减小。值得注意的是，室温离子电导率介于 10-4 - 10-3 S cm-1 之间，其中含有 99 wt.% LATP 和 1 wt.% 聚合物粘合剂的样品的最大电导率为 7.02 × 10-3 S cm-1，锂转移率为 0.35。此外，经过 50 次循环后，在 C/10 速率下的室温放电容量达到了 141 mAh.g-1，验证了这种三组份结构是固态电池中高性能 CSE 的理想平台。

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引用次数: 0

Biocatalyst for carbon veil anode in microbial fuel cells: The effect of precursor and catalyst loading on overall performance 用于微生物燃料电池碳纱阳极的生物催化剂：前驱体和催化剂负载对整体性能的影响

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-30 DOI: 10.1016/j.electacta.2024.145296

Karnapa Ajit, Juliana John, Haribabu Krishnan

Biocatalysts in anodes have been crucial in improving microbial fuel cell (MFC) performance. Biocatalysts derived from biomass such as coconut wood sawdust (SD-B) and pepper processing residue (PS-B), were used to improve the electrocatalytic properties of Carbon Veil (CV) electrodes. The amorphous graphitic carbon biocatalyst with a mesoporous structure was found to have a surface area of 889.31 m²/g for SD-B and 763.56 m²/g for PS-B. Surface functional groups such as -OH which imparts hydrophilicity and -C=O and COOH which promotes bacterial compatibility have been revealed to be present in both catalysts. Catalyst loading played a major role and at an optimal loading of 2 mg/cm², the electrodes exhibited maximum electrocatalytic activity in the case of both biocatalysts. The voltammetric capacitances of SD-B and PS-B modified electrodes were 191.6 mF/cm² and 106.6 mF/cm² demonstrating their pseudocapacitive behaviour too. The performance of MFC with SD-B revealed a maximum power density of 10.1 W/m³ (Open Circuit Voltage (OCV) of 850 mV), followed by PS-B at 6.89 W/m³ (OCV of 825 mV) whereas the plain CV was at 0.168 W/m³ (OCV of 760 mV). Anode polarization studies indicated reduced slopes for biocatalyst-modified anodes, signifying improved electrode kinetics, particularly notable in the SD-B modified MFC where the cathode became the limiting electrode. Coulombic efficiencies of the biocatalyst-modified MFCs increased to 54.50%, (SD-B 2 mg/cm²) and 37.78% (PS-B 2 mg/cm²) respectively from 12.74% as noticed in the case of unmodified MFC. This study emphasizes the potential of biocatalysts as a simple and low-cost means of enhancing the anode properties – porosity, conductivity, hydrophilicity, and biocompatibility.

阳极中的生物催化剂对于提高微生物燃料电池（MFC）的性能至关重要。从椰子木锯末（SD-B）和胡椒加工残渣（PS-B）等生物质中提取的生物催化剂被用来改善碳膜（CV）电极的电催化性能。研究发现，具有介孔结构的无定形石墨碳生物催化剂的比表面积为：SD-B 889.31 m2/g，PS-B 763.56 m2/g。研究发现，这两种催化剂中都含有表面官能团，如具有亲水性的 -OH 和促进细菌相容性的 -C=O 和 COOH。催化剂的负载量起着重要作用，当最佳负载量为 2 mg/cm2 时，两种生物催化剂的电极都表现出最大的电催化活性。SD-B 和 PS-B 修饰电极的伏安电容分别为 191.6 mF/cm2 和 106.6 mF/cm2，这也证明了它们的假电容行为。使用 SD-B 的 MFC 性能显示，最大功率密度为 10.1 W/m3（开路电压 (OCV) 为 850 mV），其次是 PS-B，为 6.89 W/m3（开路电压为 825 mV），而普通 CV 为 0.168 W/m3（开路电压为 760 mV）。阳极极化研究表明，生物催化剂改性阳极的斜率降低，表明电极动力学得到改善，尤其是在 SD-B 改良型 MFC 中，阴极成为限制电极。生物催化剂改性 MFC 的库仑效率从未修改 MFC 的 12.74% 分别提高到 54.50%（SD-B 2 mg/cm2）和 37.78%（PS-B 2 mg/cm2）。这项研究强调了生物催化剂作为一种简单、低成本的方法来增强阳极特性--多孔性、导电性、亲水性和生物相容性--的潜力。

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引用次数: 0

Innovative integrated carbon paper supported Bi/rGO/MnO2 cathode with dual redox reactions for aqueous zinc-ion batteries 用于锌-离子水电池的具有双重氧化还原反应的创新型集成碳纸支撑 Bi/rGO/MnO2 阴极

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-30 DOI: 10.1016/j.electacta.2024.145297

Yingying Cai , Lei Sun , Ziwei Chen , Yi Zhang , Hideaki Morikawa , Chunhong Zhu

Developing cathode materials with dual redox reactions is an effective strategy to improve the electrochemical performance of aqueous zinc-ion batteries (AZIBs), and rational selection of the two electroactive components is the key to achieving this target. Herein, an integrated carbon paper supported Bi/rGO/MnO₂ cathode is prepared via a two-step in situ growth process, in which metallic bismuth (Bi) and manganese dioxide (MnO₂) are served as two types of electroactive components to realize dual redox reactions. The introduction of reduced graphene oxide (rGO) mitigates the interfacial mismatch of Bi and MnO₂, meanwhile further increasing the electrochemical activity by reducing the size of Bi and preventing its self-aggregation. Featuring nanostructured Bi and MnO₂, the integrated cathode enables dual redox reactions with enhanced reaction kinetics. This structural and compositional refinement of the Zn//Bi/rGO/MnO₂ battery leads to superior electrochemical performance, evidenced by a significant specific capacity (388.3 mAh g⁻¹ at 0.1 A g⁻¹), high energy density (464.6 Wh kg⁻¹) and great rate performance. This work underscores the potential of using MnO₂ and Bi as dual electroactive components for AZIBs cathode, providing a pathway towards high performance energy storage systems.

开发具有双重氧化还原反应的阴极材料是提高锌离子水电池（AZIB）电化学性能的有效策略，而合理选择两种电活性成分是实现这一目标的关键。本文通过两步原位生长工艺制备了一种集成碳纸支撑的Bi/rGO/MnO2阴极，其中金属铋（Bi）和二氧化锰（MnO2）作为两种电活性组分实现了双重氧化还原反应。还原氧化石墨烯（rGO）的引入减轻了铋和二氧化锰的界面失配，同时通过减小铋的尺寸和防止其自聚集进一步提高了电化学活性。这种集成阴极具有纳米结构的 Bi 和 MnO2，可实现双重氧化还原反应，并增强反应动力学。Zn//Bi/rGO/MnO2 电池在结构和成分上的改进带来了卓越的电化学性能，具体表现为显著的比容量（0.1 A g-1 时为 388.3 mAh g-1）、高能量密度（464.6 Wh kg-1）和良好的速率性能。这项工作强调了将 MnO2 和 Bi 作为 AZIBs 阴极的双重电活性成分的潜力，为实现高性能储能系统提供了一条途径。

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引用次数: 0

Enhanced stability of highly porous nanostructured gold anodes via polyaniline coating for abiotic glucose fuel cell 通过聚苯胺涂层提高非生物葡萄糖燃料电池高多孔纳米结构金阳极的稳定性

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-29 DOI: 10.1016/j.electacta.2024.145281

Asghar Niyazi , Benjamin Metcalfe , Hannah S. Leese , Mirella Di Lorenzo

In recent years, advances in micro- and nano-electronics have enabled implantable and wearable ultra-low power bioelectronics to become a viable therapeutic option for the effective management of non-communicable diseases. Glucose fuel cells (GFCs) have significant potential as power sources for these devices, facilitating miniaturisation and, consequently, widening the application opportunities. For GFC technology to be deployable, the stability of the electrodes in physiological conditions is a major requirement. Accordingly, in this study, the use of a conductive polymeric coating was investigated to enhance the stability of nanostructured highly porous gold (hPG) films deposited onto gold electrodes on a printed circuit board to be used as the anode of an abiotic glucose fuel cell. Polyaniline (PANI) was electro-polymerised onto hPG, with the optimal polymerisation conditions identified as: 0.1 M monomer (aniline), 0.3 M dopant (HClO₄), and a three-minute deposition time. Subsequently, the optimised PANI/hPG/Au nanocomposite electrode was tested in a GFC. Although halving the electrochemical activity, in terms of power output, the PANI coating significantly stabilises the hPG electrode, with an overall activity loss, after 7 days of operation, of only 6 %, compared to a 97 % activity loss observed in the absence of PANI. The stabilisation effect of PANI is also maintained in the presence of Cl⁻¹ ions (concentration 10 mM), present in physiological fluids and known to negatively impact on the electroactivity of hPG towards glucose. Overall, this study demonstrates an effective route for electrode stabilisation in abiotic GFCs, paving the way for their practical application in bioelectronics.

近年来，微电子学和纳米电子学的进步使植入式和可穿戴式超低功耗生物电子学成为有效治疗非传染性疾病的可行疗法。葡萄糖燃料电池（GFC）作为这些设备的动力源具有巨大的潜力，有利于实现微型化，从而扩大应用机会。要部署葡萄糖燃料电池技术，电极在生理条件下的稳定性是一个主要要求。因此，本研究调查了导电聚合物涂层的使用情况，以提高沉积在印刷电路板金电极上的纳米结构高多孔金（hPG）薄膜的稳定性，从而用作非生物葡萄糖燃料电池的阳极。聚苯胺（PANI）被电聚合到 hPG 上，最佳聚合条件为最佳聚合条件为：0.1 M 单体（苯胺）、0.3 M 掺杂剂（HClO4）和三分钟沉积时间。随后，经过优化的 PANI/hPG/Au 纳米复合电极在 GFC 中进行了测试。虽然就输出功率而言，PANI 涂层使电化学活性减半，但它极大地稳定了 hPG 电极，在运行 7 天后，整体活性损失仅为 6%，而在没有 PANI 的情况下，活性损失高达 97%。PANI 的稳定效果在 Cl-1 离子（浓度为 10 mM）存在时也能保持，Cl-1 离子存在于生理液体中，已知会对 hPG 对葡萄糖的电活性产生负面影响。总之，这项研究证明了非生物 GFC 中电极稳定的有效途径，为其在生物电子学中的实际应用铺平了道路。

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引用次数: 0

Unveiling the mechanism of lithium dendrite infiltration into solid state electrolyte through the coupling of electrochemical and in-situ optical characterization 通过电化学和原位光学特性分析揭示锂枝晶渗入固态电解质的机理

IF 5.5 3区材料科学 Q1 ELECTROCHEMISTRY

Electrochimica Acta

Pub Date : 2024-10-29 DOI: 10.1016/j.electacta.2024.145294

Weichang Guo , Anli Wang , Xinlin He , Yang Lei , Yunpeng Li , Zhiyi Zhou , Chunli Li , Xiaoxiu Lv , Haiqiang Wang , Fei Shen , Kaiming Wang , Xiaogang Han

Garnet type solid-state electrolyte Li₇La₃Zr₂O₁₂ (LLZO) is a promising choice for solid-state Lithium (Li) batteries due to its high ion conductivity and high stability to Li metal. However, LLZO based Li batteries also suffer from the problem of Li dendrite infiltration, in which the growth mode of Li dendrite is indefinite. To explore the scientific problem, electrochemical characterizations combined with in-situ optical observation are employed to reveal the origin of Li dendrite, the relationship between Li dendrite evolution and electrochemical properties. It shows that poor interface contact leads a high polarization voltage at Li dissolution step, and the upcoming Li deposition step is likely to form Li dendrite and cause short circuit. The electric field distribution simulation of the Li/LLZO interface also demonstrates that the deterioration of interface contact can lead to uneven electric field distribution, which may trigger Li dendrite growth during the Li deposition process. In-situ optical observation using a transparent LLZO electrolyte is carried out and confirms the above results directly. Meanwhile, the connection between the behavior of Li dendrite and the voltage profile is established that high polarization voltage before the deposition process is an indicator of Li dendrite formation, which is expected to provide guidance for the predicting work of short circuit in advance. These findings can promote a thorough understanding for the failure mechanism of solid-state cells caused by Li dendrite.

石榴石型固态电解质 Li7La3Zr2O12（LLZO）具有高离子传导性和对锂金属的高稳定性，是固态锂（Li）电池的理想选择。然而，基于 LLZO 的锂电池也存在锂枝晶浸润问题，即锂枝晶的生长模式不确定。为了探索这一科学问题，我们采用了电化学表征与原位光学观测相结合的方法，以揭示锂枝晶的起源、锂枝晶演化与电化学性能之间的关系。结果表明，界面接触不良导致锂溶解步骤极化电压过高，而即将到来的锂沉积步骤很可能形成锂枝晶并导致短路。锂/LLZO 界面的电场分布模拟也表明，界面接触不良会导致电场分布不均，从而可能在锂沉积过程中引发锂枝晶的生长。利用透明 LLZO 电解质进行的原位光学观测直接证实了上述结果。同时，建立了锂枝晶行为与电压曲线之间的联系，即沉积过程前的高极化电压是锂枝晶形成的指标，有望为提前预测短路工作提供指导。这些发现有助于深入理解锂枝晶导致固态电池失效的机理。

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