Journal of Energy Chemistry最新文献_第9页

Fabrication of carbon-supported Al2O3 nanoparticles via spontaneous cross-linking to enhance selective hydrogenation of furfural 通过自发交联制备碳支撑 Al2O3 纳米粒子，以提高糠醛的选择性氢化能力

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-17 DOI: 10.1016/j.jechem.2024.08.059

Weiwei Yu, Xinbao Zhang, Hongyu Chen, Yanan Wang, Shaoguo Li, Fucun Chen, Zhenni Liu, Xiujie Li, Xiangxue Zhu

Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of CC over CO. Herein, a novel Al₂O₃/C-u hybrid catalyst, composed of N-modified dendritic carbon networks supporting Al₂O₃ nanoparticles, was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate, Al³⁺ and urea_. The obtained carbon-supported Al₂O₃ hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state. The introduction of urea enhances the surface N content, the ratio of pyrrolic N, and specific surface area of catalyst, leading to improved adsorption capacity of CO and the accessibility of active sites. In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor, Al₂O₃/C-u catalyst achieved a 90% conversion of furfural with 98.0% selectivity to furfuryl alcohol, outperforming that of commercial γ-Al₂O₃. Moreover, Al₂O₃/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al₂O₃ nanoparticles. This work provides an innovative and facile strategy for fabrication of carbon-supported Al₂O₃ hybrid catalysts with rich Al^V species, serving as a high selective hydrogenation catalyst through MPV reaction route.

由于热力学上 CC 比 CO 优先加氢，因此将糠醛选择性加氢为糠醇是加氢领域的一大挑战。本文通过对海藻酸盐、Al3+ 和尿素自发交联的冻干凝胶进行碳化，成功制备了一种新型 Al2O3/C-u 混合催化剂，该催化剂由支撑 Al2O3 纳米颗粒的 N 改性树枝状碳网络组成。所获得的碳支撑 Al2O3 混合催化剂中，五面体配位状态的 Al 种类比例较高（31%）。尿素的引入提高了催化剂的表面 N 含量、吡咯烷 N 比例和比表面积，从而提高了 CO 的吸附能力和活性位点的可及性。在以异丙醇为供氢体的糠醛加氢反应中，Al2O3/C-u 催化剂的糠醛转化率达到 90%，对糠醇的选择性达到 98.0%，优于商用 γ-Al2O3 催化剂。此外，Al2O3/C-u 在循环测试中表现出优异的催化稳定性，这归功于丰富的弱路易斯酸位点和碳网络对 Al2O3 纳米颗粒的锚定作用的协同效应。这项工作为制备富含 AlV 物种的碳支撑 Al2O3 混合催化剂提供了一种创新而简便的策略，可通过 MPV 反应路线用作高选择性加氢催化剂。

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引用次数: 0

Optimizing battery deployment: Aging trajectory prediction enabling homogenous performance grouping 优化电池部署：老化轨迹预测实现同质性能分组

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-16 DOI: 10.1016/j.jechem.2024.09.012

Shuquan Wang , Feng Gao , Zhan Ma , Hao Tian , Yusen Zhang

As battery deployments in electric vehicles and energy storage systems grow, ensuring homogeneous performance across units is crucial. We propose a multi-derivative imaging fusion (MDIF) model, employing advanced imaging and machine learning to predict battery aging trajectories from minimal initial data, thus facilitating effective performance grouping before deployment. Utilizing a derivative strategy and Gramian Angular Difference Field for dimensional enhancement, the MDIF model uncovers subtle predictive features from discharge curve data after only ten cycles. The architecture includes a parallel convolutional neural network with lateral connections to enhance feature integration and extraction. Tested on a self-developed dataset, the model achieves an average root-mean-square error of 0.047 Ah and an average mean absolute percentage error of 1.60%, demonstrating high precision and reliability. Its robustness is further validated through transfer learning on two publicly available datasets, adapting with minimal retraining. This approach significantly reduces the testing cycles required, lowering both time and costs associated with battery testing. By enabling precise battery behavior predictions with limited data, the MDIF model optimizes battery utilization and deployment strategies, enhancing system efficiency and sustainability.

随着电动汽车和储能系统中电池部署的增加，确保各单元的性能均匀至关重要。我们提出了一种多衍生成像融合（MDIF）模型，利用先进的成像和机器学习技术，从最少的初始数据中预测电池老化轨迹，从而在部署前进行有效的性能分组。MDIF 模型利用导数策略和格拉米安角差场进行维度增强，仅在十个周期后就能从放电曲线数据中发现微妙的预测特征。该架构包括一个具有横向连接的并行卷积神经网络，以加强特征整合和提取。该模型在自主开发的数据集上进行了测试，其平均均方根误差为 0.047 Ah，平均绝对百分比误差为 1.60%，显示了较高的精度和可靠性。通过在两个公开数据集上进行迁移学习，该模型的稳健性得到了进一步验证，只需最小限度的再训练即可适应。这种方法大大减少了所需的测试周期，降低了与电池测试相关的时间和成本。通过利用有限的数据实现精确的电池行为预测，MDIF 模型优化了电池利用和部署策略，提高了系统效率和可持续性。

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引用次数: 0

A mild, configurable, flexible CoNi-LDH(v)/Zn battery based on H-vacancy-induced reversible Zn2+ intercalation 基于氢空位诱导的可逆 Zn2+ 插层的温和、可配置、灵活的 CoNi-LDH(v)/Zn 电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-16 DOI: 10.1016/j.jechem.2024.09.013

Xinyue Cheng , Dingsheng Wu , Hao Gao , Qingqing Wang , Pengfei Lv , Sam S. Yoon , Qufu Wei

Flexible Zn-based batteries have attracted increasing research interest as essential components of wearable energy storage devices. However, the advancement of flexible aqueous Zn-based batteries based on Co-Ni layered double hydroxide (CoNi-LDH) as the cathode material is hampered by their poor cycling stability and the corrosiveness of alkaline electrolytes. Herein, CoNi-LDH nanosheets enriched with H vacancies (CoNi-LDH_(v)) were constructed on a flexible carbon cloth (CC) substrate via electrochemical deposition and activation. The Zn-based battery comprising CoNi-LDH_(v)@CC as the cathode exhibited highly reversible conversion reactions and stable operation in 3 M ZnSO₄ electrolyte (pH = 4). The battery delivered an excellent specific capacity (225 mA h g⁻¹, 0.26 mA h cm⁻²), acceptable cycling stability (53.9%, 900 cycles), and high discharging voltage. The abundant H vacancies served as active sites for the reversible intercalation of Zn²⁺ and the extravasation of NO₃⁻ generated channels and space for Zn²⁺ transport and storage, together enabling an excellent Zn²⁺ storage capacity. Furthermore, a sandwich-structured solid-state CoNi-LDH_(v)@CC//Zn@CC battery was fabricated and was found to exhibit a noteworthy electrochemical performance and mechanical durability. As a proof of concept, the unencapsulated battery powered a digital watch under various deformation conditions and operated stably for 80 h. Additionally, the flexible battery displayed outstanding customizability, maintaining an open-circuit voltage of 1.42 V even after being cut twice. The proposed engineering strategy contributes to the realization of textiles with truly wearable energy-storage devices.

作为可穿戴储能设备的重要组成部分，柔性锌基电池吸引了越来越多的研究兴趣。然而，以钴镍层状双氢氧化物（CoNi-LDH）为正极材料的柔性锌基水溶液电池循环稳定性差，且易受碱性电解质的腐蚀，这阻碍了其发展。本文通过电化学沉积和活化，在柔性碳布（CC）基底上构建了富含 H 空位（CoNi-LDH(v)）的 CoNi-LDH 纳米片。以 CoNi-LDH(v)@CC 为阴极的锌基电池在 3 M ZnSO4 电解液（pH = 4）中表现出高度可逆的转换反应和稳定的运行。该电池具有出色的比容量（225 mA h g-1，0.26 mA h cm-2）、可接受的循环稳定性（53.9%，900 次循环）和较高的放电电压。丰富的 H 空位是 Zn2+ 可逆插层的活性位点，而 NO3- 的外渗则为 Zn2+ 的传输和储存提供了通道和空间，从而实现了出色的 Zn2+ 储存能力。此外，还制备了一种夹层结构的 CoNi-LDH(v)@CC//Zn@CC 固态电池，并发现该电池具有显著的电化学性能和机械耐久性。作为概念验证，未封装电池在各种变形条件下为数字手表供电，并稳定工作了 80 小时。此外，柔性电池显示出出色的可定制性，即使被切割两次后仍能保持 1.42 V 的开路电压。所提出的工程策略有助于实现具有真正可穿戴储能装置的纺织品。

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引用次数: 0

Few-shot learning for screening 2D Ga2CoS4−x supported single-atom catalysts for hydrogen production 筛选二维 Ga2CoS4-x 支持的单原子制氢催化剂的少量学习方法

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-16 DOI: 10.1016/j.jechem.2024.09.009

Nabil Khossossi, Poulumi Dey

Hydrogen generation and related energy applications heavily rely on the hydrogen evolution reaction (HER), which faces challenges of slow kinetics and high overpotential. Efficient electrocatalysts, particularly single-atom catalysts (SACs) on two-dimensional (2D) materials, are essential. This study presents a few-shot machine learning (ML) assisted high-throughput screening of 2D septuple-atomic-layer Ga₂CoS₄₋_x supported SACs to predict HER catalytic activity. Initially, density functional theory (DFT) calculations showed that 2D Ga₂CoS₄ is inactive for HER. However, defective Ga₂CoS₄₋_x (x = 0–0.25) monolayers exhibit excellent HER activity due to surface sulfur vacancies (SVs), with predicted overpotentials (0–60 mV) comparable to or lower than commercial Pt/C, which typically exhibits an overpotential of around 50 mV in the acidic electrolyte, when the concentration of surface SV is lower than 8.3%. SVs generate spin-polarized states near the Fermi level, making them effective HER sites. We demonstrate ML-accelerated HER overpotential predictions for all transition metal SACs on 2D Ga₂CoS₄₋_x. Using DFT data from 18 SACs, an ML model with high prediction accuracy and reduced computation time was developed. An intrinsic descriptor linking SAC atomic properties to HER overpotential was identified. This study thus provides a framework for screening SACs on 2D materials, enhancing catalyst design.

制氢及相关能源应用在很大程度上依赖于氢进化反应（HER），而氢进化反应面临着动力学速度慢和过电位高的挑战。高效的电催化剂，尤其是二维（2D）材料上的单原子催化剂（SAC）至关重要。本研究通过机器学习（ML）辅助高通量筛选二维七原子层 Ga2CoS4-x 支持的单原子催化剂，预测 HER 催化活性。最初，密度泛函理论（DFT）计算表明，二维 Ga2CoS4 对 HER 没有活性。然而，有缺陷的 Ga2CoS4-x（x = 0-0.25）单层由于表面硫空位（SV）而表现出卓越的 HER 活性，其预测过电位（0-60 mV）与商用 Pt/C 相当或更低，当表面 SV 的浓度低于 8.3% 时，商用 Pt/C 在酸性电解质中通常表现出约 50 mV 的过电位。SV 在费米级附近产生自旋极化态，使其成为有效的 HER 位点。我们展示了二维 Ga2CoS4-x 上所有过渡金属 SAC 的 ML 加速 HER 过电势预测。利用 18 种 SAC 的 DFT 数据，我们开发出了一种预测精度高、计算时间短的 ML 模型。确定了将 SAC 原子特性与 HER 过电势联系起来的内在描述因子。因此，这项研究为筛选二维材料上的 SAC 提供了一个框架，从而提高了催化剂的设计水平。

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引用次数: 0

Structural designs and mechanism insights into electrocatalytic oxidation of 5-hydroxymethylfurfural 5-hydroxymethylfurfural 电催化氧化的结构设计和机理启示

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-16 DOI: 10.1016/j.jechem.2024.08.066

Jing Lei , Huijie Zhang , Jian Yang , Jia Ran , Jiqiang Ning , Haiyan Wang , Yong Hu

Biomass conversion offers an efficient approach to alleviate the energy and environmental issues. Electrochemical oxidation of 5-hydroxymethylfurfural (HMF) has attracted tremendous attention in the latest few years for the mild synthesis conditions and high conversion efficiency to obtain 2,5-furan dicarboxylic acid (FDCA), but there still remain problems such as limited yield, short cycle life, and ambiguous reaction mechanism. Despite many reviews highlighting a variety of electrocatalysts for electrochemical oxidation of HMF, a detailed discussion of the structural modulation of catalyst and the underlying catalytic mechanism is still lacking. We herein provide a comprehensive summary of the recent development of electrochemical oxidation of HMF to FDCA, particularly focusing on the mechanism studies as well as the advanced strategies developed to regulate the structure and optimize the performance of the electrocatalysts, including heterointerface construction, defect engineering, single-atom engineering, and in situ reconstruction. Experimental characterization techniques and theoretical calculation methods for mechanism and active site studies are elaborated, and challenges and future directions of electrochemical oxidation of HMF are also prospected. This review will provide guidance for designing advanced catalysts and deepening the understanding of the reaction mechanism beneath electrochemical oxidation of HMF to FDCA.

生物质转化是缓解能源和环境问题的有效方法。最近几年，5-羟甲基糠醛（HMF）的电化学氧化因其温和的合成条件和高转化效率以获得 2,5-呋喃二羧酸（FDCA）而备受关注，但仍存在产率有限、循环寿命短和反应机理不明确等问题。尽管许多综述重点介绍了多种用于 HMF 电化学氧化的电催化剂，但仍缺乏对催化剂结构调控和催化机理的详细讨论。我们在本文中全面总结了 HMF 电化学氧化为 FDCA 的最新进展，尤其侧重于机理研究以及为调节结构和优化电催化剂性能而开发的先进策略，包括异质界面构建、缺陷工程、单原子工程和原位重构。此外，还阐述了用于机理和活性位点研究的实验表征技术和理论计算方法，并展望了 HMF 电化学氧化所面临的挑战和未来的发展方向。本综述将为设计先进的催化剂和加深对 HMF 电化学氧化为 FDCA 反应机理的理解提供指导。

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引用次数: 0

Green synthesis of glycolic acid through the electrocatalytic reduction of oxalic acid over black TiO2: An experimental and theoretical study 在黑色 TiO2 上通过电催化还原草酸绿色合成乙醇酸：实验和理论研究

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-16 DOI: 10.1016/j.jechem.2024.09.011

Hugo Olvera-Vargas , Oscar Andrés Jaramillo-Quintero , Luis Darío Alarcón León , Orlando Castro-Ocampo , Christian A. Celaya , Marina E. Rincón , Jesús Muñiz

Herein, we present the electrocatalytic four-electron hydrogenation of oxalic acid into glycolic acid using black TiO₂ as an electrocatalyst. Oxalic acid is an abundant compound found in several sources of organic waste. The results showed a high selectivity of black TiO₂ toward glycolic acid, with the formation of glyoxylic acid being the rate-limiting step (glyoxylic acid is the two-electron intermediate). The highest Faradaic efficiency (FE) of 69.6% ± 8.3% was achieved at 10.2 mA cm⁻² in 4 h of electrolysis using an H-type cell operated at room temperature, with 50.2% ± 3.8% of oxalic acid conversion (degradation kinetic constant k = 0.0042 ± 0.0001 min⁻¹), 58.8% ± 7.0% of reaction yield and 1.2 ± 0.18 g L⁻¹ of glycolic acid production. A theoretical model of black TiO₂ coming from anatase TiO₂ was implemented by introducing Ti³⁺ defects, which gave black TiO₂ the theoretical capability to easily transform oxalic acid into glycolic acid as experimentally observed. The reaction mechanism was supported and described in detail by density functional theory calculations, which revealed that surface Ti³⁺ states were the main catalytic sites. This is the first time that a detailed step-by-step mechanism at the atomic level has been proposed for this electrocatalytic reaction, which represents a valuable contribution to the understanding of this process of high energy/environmental interest. This is also the first time that black TiO₂ has been used as an electrocatalyst for this sustainable process.

在此，我们介绍了以黑色 TiO2 为电催化剂将草酸氢化成乙醇酸的电催化四电子氢化过程。草酸是一种存在于多种有机废物中的丰富化合物。研究结果表明，黑色二氧化钛对乙醇酸具有高选择性，乙醛酸的形成是限速步骤（乙醛酸是双电子中间体）。使用室温下运行的 H 型电池，在 10.2 mA cm-2 的条件下电解 4 小时，法拉第效率（FE）最高，为 69.6% ± 8.3%，草酸转化率为 50.2% ± 3.8%（降解动力学常数 k = 0.0042 ± 0.0001 min-1），反应产率为 58.8% ± 7.0%，乙醇酸产量为 1.2 ± 0.18 g L-1。通过引入 Ti3+ 缺陷，实现了由锐钛矿型二氧化钛衍生出黑色二氧化钛的理论模型，从而使黑色二氧化钛理论上能够像实验观察到的那样轻松地将草酸转化为乙醇酸。密度泛函理论计算支持并详细描述了反应机理，发现表面 Ti3+ 状态是主要催化位点。这是首次在原子水平上为这一电催化反应提出详细的分步机理，对理解这一具有高能量/环境意义的过程做出了宝贵贡献。这也是黑色二氧化钛首次被用作这一可持续过程的电催化剂。

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引用次数: 0

Dielectric-ion-conductive ZnNb2O6 layer enabling rapid desolvation and diffusion for dendrite-free Zn metal batteries 介电离子导电 ZnNb2O6 层可实现无枝晶锌金属电池的快速脱溶和扩散

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-16 DOI: 10.1016/j.jechem.2024.09.010

Haifeng Yang , Jian Wang , Panpan Zhang , Xiaomin Cheng , Qinghua Guan , Jing Dong , Bixian Chen , Lujie Jia , Jing Zhang , Yongzheng Zhang , Yunjian Liu , Hongzhen Lin

Rechargeable aqueous zinc-metal batteries (AZMBs) are promising candidates for large-scale energy storage systems due to their low cost and high safety. However, their performance and sustainability are significantly hindered by the sluggish desolvation kinetics at the electrode/electrolyte interface and the corresponding hydrogen evolution reaction where active water molecules tightly participate in the Zn(H₂O)₆²⁺ solvation shell. Herein, learnt from self-generated solid electrolyte interphase (SEI) in anodes, the dielectric but ion-conductive zinc niobate nanoparticles artificial layer is constructed on metallic Zn surface (ZNB@Zn), acting as a rapid desolvation promotor. The zincophilic and dielectric-conductive properties of ZNB layer accelerate interfacial desolvation/diffusion and suppress surface corrosion or dendrite formation, achieving uniform Zn plating/stripping behavior, as confirmed by electronic/optical microscopies and interface spectroscopical measurements together with theoretical calculations. Consequently, the as-prepared ZNB@Zn electrode exhibits excellent cycling stability of over 2000 h and robust reversibility (99.54%) even under high current density and depth of discharge conditions. Meanwhile, the assembled ZNB@Zn-based full cell displays high capacity-retention rate of 80.21% after 3000 cycles at 5 A g⁻¹ and outstanding rate performance up to 10 A g⁻¹. The large-areal pouch cell is stabilized for hundreds of cycles, highlighting the bright prospects of the dielectric but ion-conductive layer in further application of AZMBs.

可充电水溶液锌金属电池（AZMB）具有成本低、安全性高等优点，是大规模储能系统的理想候选材料。然而，电极/电解质界面上迟缓的解溶胶动力学以及相应的氢进化反应（活性水分子紧密地参与到 Zn(H2O)62+ 溶胶壳中）极大地阻碍了它们的性能和可持续性。在此，我们从阳极中自生成的固体电解质相（SEI）中汲取灵感，在金属锌表面构建了介电但具有离子导电性的纳米铌酸锌人工层（ZNB@Zn），作为一种快速脱溶促进剂。电子/光学显微镜和界面光谱测量以及理论计算均证实，纳米铌酸锌层的亲锌和导电特性可加速界面脱溶/扩散，抑制表面腐蚀或枝晶的形成，实现均匀的镀锌/剥离行为。因此，制备的 ZNB@Zn 电极即使在高电流密度和深度放电条件下，也能表现出超过 2000 小时的优异循环稳定性和稳健的可逆性（99.54%）。同时，组装后的 ZNB@Zn 全电池在 5 A g-1 条件下循环 3000 次后显示出 80.21% 的高容量保持率和高达 10 A g-1 的出色速率性能。大实心小袋电池在数百次循环后仍能保持稳定，凸显了介电但离子导电层在 AZMB 进一步应用中的广阔前景。

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引用次数: 0

Staged dendrite suppression for high safe and stable lithium-sulfur batteries 分阶段抑制枝晶，实现安全稳定的锂硫电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-14 DOI: 10.1016/j.jechem.2024.09.006

Jun Jiang , Zhenjie Lu , Yanwen Ding , Shujun Liu , Zhijie Qi , Tian Tang , Yunfan Zhang , Zhiyuan Ma , Jingwen Sun , Liang Xue , Wenyao Zhang , Pan Xiong , Xin Wang , Junwu Zhu , Yongsheng Fu

The unavoidable dendrite growth and shuttle effect have long been stranglehold challenges limiting the safety and practicality of lithium-sulfur batteries. Herein, we propose a dual-action strategy to address the lithium dendrite issue in stages by constructing a multifunctional surface-negatively-charged nanodiamond layer with high ductility and robust puncture resistance on polypropylene (PP) separator. The uniformly loaded compact negative layer can not only significantly enhance electron transmission efficiency and promote uniform lithium deposition, but also reduce the formation of dendrite during early deposition stage. Most importantly, under the strong puncture stress encountered during the deterioration of lithium dendrite growth under limiting current, the high ductility and robust puncture resistance (145.88 MPa) of as-obtained nanodiamond layer can effectively prevent short circuits caused by unavoidable lithium dendrite. The Li||Li symmetrical cells assembled with nanodiamond layer modified PP demonstrated a stable cycle of over 1000 h at 2 mA cm⁻² with a polarization voltage of only 29.3 mV. Additionally, the negative charged layer serves as a physical barrier blocking lithium polysulfide ions, effectively mitigating capacity attenuation. The improved cells achieved a capacity decay of only 0.042% per cycle after 700 cycles at 3 C, demonstrating effective suppression of dendrite growth and capacity attenuation, showing promising prospect.

长期以来，不可避免的枝晶生长和穿梭效应一直是制约锂硫电池安全性和实用性的难题。在此，我们提出了一种双效策略，通过在聚丙烯（PP）隔膜上构建具有高延展性和强抗穿刺性的多功能表面负电荷纳米金刚石层，分阶段解决锂枝晶问题。均匀负载的致密负电层不仅能显著提高电子传输效率，促进锂的均匀沉积，还能减少沉积初期枝晶的形成。最重要的是，在限流条件下，锂枝晶生长恶化过程中会遇到强大的穿刺应力，而纳米金刚石层具有高延展性和强大的抗穿刺能力（145.88 兆帕），可有效防止不可避免的锂枝晶造成的短路。用纳米金刚石层改性聚丙烯组装的锂||锂对称电池在 2 mA cm-2 的条件下可稳定循环 1000 小时以上，极化电压仅为 29.3 mV。此外，带负电的层还起到了阻挡多硫化锂离子的物理屏障作用，有效缓解了容量衰减。改进后的电池在 3 C 下循环 700 次后，每次循环的容量衰减仅为 0.042%，这表明树枝状突起的生长和容量衰减得到了有效抑制，前景十分广阔。

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引用次数: 0

Electrocatalytic cleavage of a lignin β-O-4 model compound and coupling with nitrogen-containing aromatics using Prussian blue analogue-derived nickel–cobalt spinel 使用普鲁士蓝类似物衍生的镍钴尖晶石电催化裂解木质素 β-O-4 模型化合物并与含氮芳烃耦合

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-14 DOI: 10.1016/j.jechem.2024.08.065

Yi Qi , Xueying Chen , Bowen Liu , Xuliang Lin , Xueqing Qiu , Yanlin Qin

Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential. We demonstrate the targeted synthesis and cation modulation of NiCo₂O₄ spinel nanoboxes, synthesized via cation exchange and calcination oxidation. These catalysts exhibit excellent efficacy in the electrocatalytic conversion of lignin model compounds, specifically 2-phenoxy-1-phenylethanol, into nitrogen-containing aromatics, achieving high conversion rates and selectivities. These catalysts were synthesized via a cation exchange and calcination oxidation process, using Prussian blue nanocubes as precursors. The porous architecture and polymetallic composition of the NiCo₂O₄ spinel demonstrated superior performance in electrocatalytic oxidative coupling, achieving a 99.2 wt% conversion rate of the 2-phenoxy-1-phenylethanol with selectivities of 37.5 wt% for quinoline derivatives and 31.5 wt% for phenol. Key innovations include the development of a sustainable one-pot synthesis method for quinoline derivatives, the elucidation of a multistage reaction pathway involving CO bond cleavage, hydroxyaldol condensation, and CN bond formation, and a deeper mechanistic understanding derived from DFT simulations. This work establishes a new strategy for lignin valorization, offering a sustainable route to produce high-value nitrogen-containing aromatics from renewable biomass under mild conditions, without the need for additional reagents.

电化学转化木质素以生产高价值的杂环芳香化合物具有巨大的潜力。我们展示了通过阳离子交换和煅烧氧化合成的 NiCo2O4 尖晶石纳米盒的定向合成和阳离子调控。这些催化剂在木质素模型化合物（特别是 2-苯氧基-1-苯乙醇）电催化转化为含氮芳烃的过程中表现出卓越的功效，实现了高转化率和高选择性。这些催化剂是以普鲁士蓝纳米立方体为前驱体，通过阳离子交换和煅烧氧化工艺合成的。NiCo2O4 尖晶石的多孔结构和多金属成分在电催化氧化偶联中表现出卓越的性能，2-苯氧基-1-苯乙醇的转化率达到 99.2 wt%，对喹啉衍生物的选择性为 37.5 wt%，对苯酚的选择性为 31.5 wt%。主要创新点包括：开发了一种可持续的喹啉衍生物一锅合成方法；阐明了涉及 CO 键裂解、羟基甲醛缩合和 CN 键形成的多级反应途径；以及通过 DFT 模拟加深了对机理的理解。这项工作确立了木质素价值化的新策略，为在温和条件下从可再生生物质中生产高价值的含氮芳烃提供了一条可持续的途径，而且不需要额外的试剂。

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引用次数: 0

Regulating crystallization and retarding oxidation in Sn-Pb perovskite via 1D cation engineering for high performance all-perovskite tandem solar cells 通过一维阳离子工程调节锡铅包晶石的结晶和延缓氧化，实现高性能全包晶串联太阳能电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-09-13 DOI: 10.1016/j.jechem.2024.09.007

Ranran Liu , Xin Zheng , Zaiwei Wang , Miaomiao Zeng , Chunxiang Lan , Shaomin Yang , Shangzhi Li , Awen Wang , Min Li , Jing Guo , Xuefei Weng , Yaoguang Rong , Xiong Li

All-perovskite tandem solar cells have the potential to surpass the theoretical efficiency limit of single junction solar cells by reducing thermalization losses. However, the challenges encompass the oxidation of Sn²⁺ to Sn⁴⁺ and uncontrolled crystallization kinetics in Sn-Pb perovskites, leading to nonradiative recombination and compositional heterogeneity to decrease photovoltaic efficiency and operational stability. Herein, we introduced an ionic liquid additive, 1-ethyl-3-methylimidazolium iodide (EMIMI) into Sn-Pb perovskite precursor to form low-dimensional Sn-rich/pure-Sn perovskites at grain boundaries, which mitigates oxidation of Sn²⁺ to Sn⁴⁺ and regulates the film-forming dynamics of Sn/Pb-based perovskite films. The optimized single-junction Sn-Pb perovskite devices incorporating EMIMI achieved a high efficiency of 22.87%. Furthermore, combined with wide-bandgap perovskite sub-cells in tandem device, we demonstrate 2-terminal all-perovskite tandem solar cells with a power conversion efficiency of 28.34%, achieving improved operational stability.

全过氧化物串联太阳能电池通过减少热化损耗，有望超越单结太阳能电池的理论效率极限。然而，所面临的挑战包括 Sn2+ 氧化成 Sn4+ 以及 Sn-Pb 包晶体中不受控制的结晶动力学，从而导致非辐射重组和成分异质性，降低光伏效率和运行稳定性。在此，我们将离子液体添加剂 1-ethyl-3-methylimidazolium iodide (EMIMI) 引入到锡铅包晶前驱体中，在晶界处形成低维富锡/纯锡包晶石，从而减缓 Sn2+ 氧化为 Sn4+，并调节锡铅基包晶薄膜的成膜动力学。含有 EMIMI 的优化单结 Sn-Pb 类包晶石器件的效率高达 22.87%。此外，结合串联器件中的宽带隙包晶子电池，我们展示了功率转换效率为 28.34% 的双端全包晶串联太阳能电池，并提高了运行稳定性。

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引用次数: 0