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论文
Cone Shaped Surface Array Structure on an Alkaline Polymer Electrolyte Membrane Improves Fuel Cell Performance
Jingwen Zhang , Hualong Ma , Jun Ma , Meixue Hu , Qihao Li , Sheng Chen , Tianshu Ning , Chuangxin Ge , Xi Liu , Li Xiao , Lin Zhuang , Yixiao Zhang , Liwei Chen
2023, 39(2): 2111037-0  doi: 10.3866/PKU.WHXB202111037
[Abstract](192) [FullText HTML] [PDF 2530KB](8)
Abstract:
燃料电池作为一种清洁高效的能量转换装置,被认为是构建未来社会可再生能源结构的关键一环。不同于质子交换膜燃料电池(PEMFC),碱性聚合物电解质燃料电池(APEFC)的出现使非贵金属催化剂的使用成为可能,因而受到了日益广泛的关注和研究。APEFC的关键结构是膜电极,主要由聚合物电解质膜和阴阳极(含催化层、气体扩散层)组成,膜电极是电化学反应发生的场所,其优劣直接决定着电池性能的好坏。因此,基于现有的碱性聚合物电解质及催化剂体系,如何构筑更加优化的膜电极结构,使APEFC发挥出更高的电池性能是亟待开展的研究。本文首先通过模板法在碱性聚合物电解质膜的表面构建出有序的锥形阵列,再将具有阵列结构的一侧作为阴极来构筑膜电极,同时,作为对比,制备了由无阵列结构的聚合物电解质膜构筑而成的膜电极,最后对基于两种不同膜电极的APEFC的电化学性能进行了对比研究。实验结果表明,锥形阵列结构可以将APEFC的峰值功率密度由1.04 W·cm−2显著提高到1.48 W·cm−2,这主要归因于在APEFC的阴极侧具有锥形阵列结构的聚合物电解质膜的亲水性的提升和催化剂电化学活性面积的增加。本工作为碱性聚合物电解质燃料电池的膜电极结构设计与优化提供了新思路。
Interface Strengthening of Composite Current Collectors for High-Safety Lithium-Ion Batteries
Ru Wang , Zhikang Liu , Chao Yan , Long Qie , Yunhui Huang
2023, 39(2): 2203043-0  doi: 10.3866/PKU.WHXB202203043
[Abstract](172) [FullText HTML] [PDF 4788KB](9)
Abstract:
面向高能量密度电池的高比容量三元正极材料的应用,使锂离子电池更容易发生热失控,这不仅降低了其安全性, 也限制了锂离子电池的进一步发展。如何在提高能量密度的同时保证电池的安全性是亟待解决的问题。以绝缘高分子薄膜为支撑基材,两侧沉积金属层得到了具有夹芯结构的铝复合集流体能有效保证电池在针刺条件下的安全性,且更轻的复合集流体的使用能进一步提高电池能量密度。但高分子基材与铝金属层之间界面结合力较差,这会导致复合集流体在高温电解液浸泡中发生脱层现象,从而影响其在电池中的使用。本研究采用聚对苯二甲酸乙二醇酯(PET)作为支撑基材,通过在铝金属镀层与高分子基材之间引入氧化物中间层,有效地增强了金属与高分子基材之间的界面结合力,提升复合集流体的电解液兼容性。此外,复合集流体良好的机械性能使其能很好地兼容现有的电池制备技术,利用其制备的软包电池表现出与使用传统铝箔为集流体的电池相当的电化学性能。进一步的针刺测试表明,复合集流体能有效阻止锂电池在针刺过程中的热失控,显著改善了电池的安全性能。
Operando Electrochemical UV-Vis Absorption Spectroscopy with Microsecond Time Resolution
Ruifang Wei , Dongfeng Li , Heng Yin , Xiuli Wang , Can Li
2023, 39(2): 2207035-0  doi: 10.3866/PKU.WHXB202207035
[Abstract](160) [FullText HTML] [PDF 715KB](9)
Abstract:
工况光谱表征技术是深入理解电催化反应机理的有效手段,但是目前所使用的大多数工况表征技术都是基于(准)稳态的光谱技术,对发生在毫微秒时间尺度的瞬态变化过程很难直接进行观测。本研究通过在时间分辨紫外可见吸收光谱系统中引入电压脉冲,并在时间上同步电脉冲信号与光谱信号,实现了时间分辨率高达3 μs的工况电化学紫外可见吸收光谱测量系统。利用此光谱系统和方法研究了水合铁等电催化剂的水氧化动力学机理,直接揭示了电催化剂表面水氧化中间物种在毫微秒时间尺度的形成、转化和反应动力学。微秒时间分辨的工况电化学紫外可见吸收光谱,可以促进电催化反应动力学机理的研究和认识,指导新型高效电催化剂的设计合成。
Article
Two-Step Sequential Blade-Coating Large-Area FA-Based Perovskite Thin Film via a Controlled PbI2 Microstructure
Yongtao Wen , Jing Li , Xiaofeng Gao , Congcong Tian , Hao Zhu , Guomu Yu , Xiaoli Zhang , Hyesung Park , Fuzhi Huang
2023, 39(2): 2203048-0  doi: 10.3866/PKU.WHXB202203048
[Abstract](139) [FullText HTML] [PDF 2192KB](4)
Abstract:
Solar cells, which are excellent alternatives to traditional fossil fuels, can efficiently convert sunlight into electricity. The intensive development of high-performance photovoltaic materials plays an important role in environmental protection and the utilization of renewable energy. Organic–inorganic hybrid perovskite materials, with a formula of ABX3 (A = methylammonium (MA) or formamidinium (FA); B = Pb or Sn; X = Cl, I, or Br), have exhibited remarkable commercial prospects in high-performance photovoltaic devices owing to their long carrier diffusion length, excellent light absorption properties, high charge carrier mobility, and weak exciton binding energy. Recently, perovskite solar cells, fabricated using halide perovskite materials as light-absorbing layers, have achieved remarkable results; their certified power conversion efficiency has continuously improved and reached 25.7%. However, high-performance devices are usually fabricated using spin-coating methods with active areas below 0.1 cm2. Hence, long-term research goals include achieving a large-scale uniform preparation of high-quality photoactive layers. The current one-step preparation of perovskite films involves the nucleation-crystalline growth process of perovskite. Auxiliary processes, such as using an anti-solvent, are often required to increase the nucleation rate and density of the film, which is not suitable for industrial large-area preparation. Additionally, the large-area preparation of perovskite films by spin-coating will result in different film thicknesses in the center and edge regions of the film due to an uneven centrifugal force. This will cause intense carrier recombination in the thicker area of the film and weak light absorption in the thinner area, which will reduce the performance of the device. To address these problems, the development of a large-area fabrication method for high-performance perovskite light-absorbing layers is essential. In this study, a two-step sequential blade-coating strategy was developed to prepare the FA-based perovskite layer. In general, PbI2 easily forms a dense film; therefore, formamidinium iodide (FAI) cannot deeply penetrate to completely react with PbI2. The PbI2 residue is therefore detrimental to charge transportation. To fabricate the desired porous PbI2 film, tetrahydrothiophene 1-oxide (THTO) was introduced into the PbI2 precursor solution. By forming PbI2·THTO complexes, PbI2 crystallization is controlled, resulting in the formation of vertically packed PbI2 flaky crystals. These crystals provide nanochannels for easy FAI penetration. The 5 cm × 5 cm modules fabricated through this strategy achieved a high efficiency of 18.65% with excellent stability. This indicates that the two-step sequential blade-coating strategy has considerable potential for scaling up the production of perovskite solar cells.
Oxygen Vacancy-Rich Amorphous Copper Oxide Enables Highly Selective Electroreduction of Carbon Dioxide to Ethylene
Tianran Wei , Shusheng Zhang , Qian Liu , Yuan Qiu , Jun Luo , Xijun Liu
2023, 39(2): 2207026-0  doi: 10.3866/PKU.WHXB202207026
[Abstract](172) [FullText HTML] [PDF 2765KB](1)
Abstract:
The ever-increasing carbon dioxide (CO2) emissions caused by excessive fossil fuel consumption induce environmental issues such as global warming. To overcome this, the electrocatalytic CO2 reduction (ECR) under ambient conditions offers an appealing approach for converting CO2 to value-added chemicals and realizing a closed carbon loop. Among the ECR products, ethylene (C2H4), an important building block for plastics and other chemicals, has attracted considerable attention owing to its compatibility with existing infrastructure and the promising substitution of industrial steam cracking. In recent years, numerous efforts have been devoted to developing highly active and selective catalysts for converting CO2 to C2H4, with most studies having focused on Cu-based materials. Despite the significant advancements made to date, the development of the ECR-to-C2H4 process is still hindered by the lack of suitable catalysts that can effectively activate CO2 and strengthen the surface binding of *CO and *COH species. In this study, an amorphous copper oxide (CuOx) nanofilm that is rich in oxygen vacancies was prepared via a facile vacuum evaporation method for the efficient electrocatalytic conversion of CO2 to C2H4. It was expected that the nano-scale electrode thickness would greatly accelerate charge- and mass-transfer during CO2 electrolysis. Moreover, the introduction of oxygen vacancies favored the adsorption of CO2 and intermediates. As a result, in a typical H-cell, the synthesized defective catalyst delivered a maximum Faradaic efficiency of 85 ± 3% at −1.3 V versus the reversible hydrogen electrode and maintained a stable C2H4 selectivity over 48 h in a 0.1 M potassium bicarbonate solution. Interestingly, the performance observed with the synthesized electrocatalyst in this study is comparable with that of state-of-the-art Cu-based ECR catalysts. Additional structural and chemical characterizations confirmed the robust nature of the as-prepared catalyst. Moreover, when the catalyst was utilized in a membrane electrode assembly cell, it achieved a maximum C2H4 partial current density of approximately 115.4 mA∙cm−2 at a cell voltage of −1.95 V and Faradaic efficiency of 78 ± 2% at a cell voltage of −1.75 V. Furthermore, theoretical and experimental analyses revealed that oxygen defects not only favored CO2 adsorption but also enabled strong affinities for *CO and *COH intermediates, which synergistically contributed to a high selectivity for C2H4 formation. We believe that our present work will motivate the exploration of amorphous Cu-based materials for achieving efficient CO2-to-C2H4 electrolysis and be a guide towards fundamentally understanding the mechanism of catalytic CO2 reduction.
Communication
Cobalt-Vanadium Layered Double Hydroxides Nanosheets as High-Performance Electrocatalysts for Urea Oxidation Reaction
Yaoyu Liu , Yuchen Wang , Biying Liu , Mahmoud Amer , Kai Yan
2023, 39(2): 2205028-0  doi: 10.3866/PKU.WHXB202205028
[Abstract](166) [FullText HTML] [PDF 2482KB](3)
Abstract:
Hydrogen is considered as a desirable clean energy source for supporting human life in the future. Electrochemical water splitting is a promising method for generating carbon-free hydrogen. However, the relatively high overpotential of anodic oxygen evolution reaction (OER) is the main obstacle hindering the widespread popularity of water electrocatalysis technology. Recently, urea oxidation reaction (UOR) has gained significant attention as a potential alternative to OER for hydrogen production since the equilibrium potential of UOR is 0.86 V lower than that of OER. Transition metal-based layered double hydroxides (TM-LDHs) have been explored as promising UOR electrocatalysts, with the advantages of diversified metal species, stable two-dimensional layered structure and exchangeability of interlayer anions. To date, most studies have focused on TM-LDHs of late transition metals (e.g., Ni, Co, and Fe). In this work, by combining early and late transition metals, CoV-LDHs nanosheets were fabricated via a simple one-step coprecipitation method as high-performance UOR electrocatalysts. Additionally, cobalt hydroxide (Co(OH)2), with a similar lamellar structure, was synthesized via the same method. When compared with Co(OH)2, CoV-LDHs nanosheets exhibited better UOR performance owing to the following advantages: 1) The nanosheet structure of the as-fabricated CoV-LDHs electrocatalyst exposed a high number of active sites for the electrocatalytic conversion of urea. 2) The introduction of V enhanced the wettability of the CoV-LDHs electrocatalyst; thus, increasing its intrinsic electrocatalytic kinetics. 3) The d-electron compensation effect between Co (3d74s2) and V (3d34s2) was conducive to promoting the adsorption of urea. Therefore, the CoV-LDHs electrocatalyst exhibited a low electrochemical potential (1.52 V vs. the reversible hydrogen electrode, RHE) to achieve a current density of 10 mA∙cm−2 in 1 mol∙L−1 of potassium hydroxide containing 0.33 mol∙L−1 urea, which was 70 mV less than that of Co(OH)2. The Tafel slope value of the CoV-LDHs electrocatalyst (99.9 mV∙dec−1) was lower than that of Co(OH)2 (115.9 mV∙dec−1), indicating faster UOR kinetics over the CoV-LDHs electrocatalyst. Furthermore, the CoV-LDHs electrocatalyst displayed high stability, with a negligible potential increase after a 10-h chronopotentiometry test by maintaining the current density of 10 mA∙cm−2. In conclusion, the present work not only shows that the d-electron compensation effect between early and late transition metals could adjust the local electronic structure of TM-LDHs to improve the UOR efficiency, but also provides a feasible route to design dedicated nanostructured TM-LDHs as high-performance UOR electrocatalysts.
综述
Electrolyte Regulation Strategies for Improving the Electrochemical Performance of Aqueous Zinc-Ion Battery Cathodes
Yae Qi , Yongyao Xia
2023, 39(2): 2205045-0  doi: 10.3866/PKU.WHXB202205045
[Abstract](167) [FullText HTML] [PDF 6695KB](6)
Abstract:
水系锌离子电池(ZIBs)因安全性高、成本低、环境友好,以及负极锌高的理论容量(820 mAh∙g−1)和低的氧化还原电位(−0.76 V vs. SHE)等优点而受到研究者们的广泛关注,有望应用于大规模储能领域,但循环寿命仍是限制其规模化应用的瓶颈之一。通过电解液优化调控策略,可有效抑制正极材料的溶解、结构坍塌和界面副反应等问题,从而提高水系ZIBs的电化学性能。本文综述了电解液调控策略提升水系ZIBs正极材料电化学性能的研究进展,讨论了该策略所解决的具体问题和局限性,并对电解液体系的发展方向进行了展望。
Cathode Materials for Rechargeable Magnesium-Ion Batteries: A Review
Mochun Zhang , Shuo Feng , Yunling Wu , Yanguang Li
2023, 39(2): 2205050-0  doi: 10.3866/PKU.WHXB202205050
[Abstract](148) [FullText HTML] [PDF 3047KB](5)
Abstract:
镁离子电池(MIBs)因镁资源储量丰富、体积能量密度大、金属镁空气中相对稳定等优势,被认为是具有大规模储能应用潜力的电池体系。然而,镁离子较高的电荷密度和较强的溶剂化作用导致其在正极材料中的可逆脱嵌和固-液界面上的离子扩散相当缓慢,严重影响了MIBs的电化学性能。近年来,人们针对MIBs正极材料开展了大量工作,取得了一定进展,但是还存在不少问题。本文先从MIBs体系的特点出发,阐述其优势和目前所面临的主要挑战,然后从无机正极材料和有机正极材料两方面展开,梳理并总结了各类正极材料的局限性及其解决策略,对优化方法和材料性能间的相关性进行归纳和讨论,为今后进一步发展具有优异电化学性能的MIBs正极材料提供可能的参考。
Recent Advances and Future Prospects on Industrial Catalysts for Green Hydrogen Production in Alkaline Media
Siran Xu , Qi Wu , Bang-An Lu , Tang Tang , Jia-Nan Zhang , Jin-Song Hu
2023, 39(2): 2209001-0  doi: 10.3866/PKU.WHXB202209001
[Abstract](147) [FullText HTML] [PDF 6471KB](3)
Abstract:
电解水制氢技术的发展对于加快实现全球碳中和目标具有重要意义。然而,碱性介质中缓慢的析氢/析氧反应动力学过程目前是阻碍该技术发展的瓶颈问题。基于此,本文首先综述了碱性环境下析氢反应与析氧反应不同的动力学理论机制,总结了针对改善动力学反应过程的理论设计策略。随后,介绍了目前电解水催化剂的设计理念及方向。对新兴的“绿氢”技术而言,探索在高电流密度下高性能电催化剂对这项技术在工业化应用推广中起着核心作用。同时,大规模合成策略是辅助合成工业电极的关键技术。进一步,我们在推进“绿氢”工业化应用的基础上总结了目前常用三种电解槽,介绍了目前电解槽设计的局限性及对应解决方案。总之,深入研究适用于碱性环境中的工业电催化剂、商业膜或电解槽的设计,提高对工业设计原则的理解,对于获得效率更高、安全性更高、实用性更强的工业电解槽具有重要意义。
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