Journal of Energy Chemistry最新文献

Tailoring Na-ion flux homogenization strategy towards long-cycling and fast-charging sodium metal batteries 针对长循环快充钠金属电池的钠离子通量均匀化策略

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-24 DOI: 10.1016/j.jechem.2024.10.057

Lin Zhou , Shengwei Dong , Zhuomin Qiang , Chaoqun Zhang , Anran Shi , Yanbin Ning , Ziwei Liu , Cong Chen , Yan Zhang , Dalong Li , Shuaifeng Lou

Sodium metal batteries (SMBs) are promising candidates for next-generation energy storage devices owing to their excellent safety performance and natural abundance of sodium. However, the insurmountable obstacles of dendrite formation and quick capacity decay are caused by an unstable and inhomogeneous solid electrolyte interphase that resulted from the immediate interactions between the Na metal anode and organic liquid electrolyte. Herein, a customised glass fibre separator coupled with chitosan (CS@GF) was developed to modulate the sodium ion (Na⁺) flux. The CS@GF separator facilitates the Na⁺ homogeneous deposition on the anode side through redistribution at the chitosan polyactive sites and by inhibiting the decomposition of the electrolyte to robust solid electrolyte interphase (SEI) formation. Multiphysics simulations show that chitosan incorporated into SMBs through the separator can make the local electric field around the anode uniform, thus facilitating the transfer of cations. Na|Na symmetric cells utilising a CS@GF separator exhibited an outstanding cycle stability of over 600 h (0.5 mA cm⁻²). Meanwhile, the Na|Na₃V₅(PO₄)₃ full cell exhibited excellent fast-charging performance (93.47% capacity retention after 1500 cycles at 5C). This study presents a promising strategy for inhibiting dendrite growth and realizes stable Na metal batteries, which significantly boosts the development of high-performance SMBs.

钠金属电池（SMBs）因其优异的安全性能和天然丰富的钠含量而成为下一代储能设备的有希望的候选者。然而，由于Na金属阳极和有机液体电解质之间的直接相互作用造成了不稳定和不均匀的固体电解质界面，导致了枝晶形成和快速容量衰减的不可逾越的障碍。在此，开发了一种定制的玻璃纤维分离器，偶联壳聚糖（CS@GF）来调节钠离子（Na+）通量。CS@GF分离器通过壳聚糖多活性位点的重新分配和抑制电解质分解成坚固的固体电解质界面相（SEI）的形成，促进Na+在阳极侧的均匀沉积。多物理场模拟结果表明，壳聚糖通过分离器掺入到smb中，使阳极周围的局部电场均匀，有利于阳离子的转移。使用CS@GF分离器的Na|Na对称电池表现出超过600小时（0.5 mA cm−2）的出色循环稳定性。同时，na| Na3V5(PO4)3全电池表现出优异的快速充电性能，在5C下循环1500次后，电池容量保持率达到93.47%。本研究提出了一种抑制枝晶生长和实现稳定的Na金属电池的有希望的策略，这将大大促进高性能smb的发展。

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引用次数: 0

The electrochemical performance deterioration mechanism of LiNi0.83Mn0.05Co0.12O2 in aqueous slurry and a mitigation strategy lini0.83 mn0.05 co0.120 o2在水浆中电化学性能劣化机理及缓解策略

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-22 DOI: 10.1016/j.jechem.2024.11.015

Qingyu Dong , Jizhen Qi , Jian Wang , Lianghao Jia , Xuechun Wang , Liyi Zhao , Yuwei Qian , Haiyang Zhang , Hui Shao , Yanbin Shen , Liwei Chen

Integrating high-nickel layered oxide cathodes with aqueous slurry electrode preparation routes holds the potential to simultaneously meet the demands for high energy density and low-cost production of lithium-ion batteries. However, the influence of dual exposure to air and liquid water as well as the heating treatment during aqueous slurry electrode processing on the high-nickel layered oxide electrode is yet to be understood. In this study, we systematically investigate the structural evolution and electrochemical behaviors when LiNi_0.83Mn_0.05Co_0.12O₂ (NMC83) is subjected to aqueous slurry processing. It was observed that the crystal structure near the surface of NMC83 is partially reconstructed to contain a mixture of rock-salt and layered phases when exposed to water, leading to the deteriorated rate capability of the NMC83 electrodes. This partial surface reconstruction layer completely converts into a pure rock-salt phase upon cycling, accompanied by the release of O₂, Ni leaching, catalyzed decomposition of the electrolyte, and the formation of a thick cathode electrolyte interphase layer. The byproducts of the electrolyte and dissolved Ni could shuttle to the Li metal side, causing a crosstalk effect that results in a thick and unstable solid electrolyte interphase layer on the Li surface. These in combination severely undermined the cycling stability of the NMC83 electrodes obtained from the aqueous slurry. A mitigation strategy using molecular self-assembly technique was demonstrated to enhance the surface stability of water-treated NMC83. Our findings offer new insights for tailoring ambient environment stability and aqueous slurry processability for ultra-high nickel layered oxide and other water-sensitive cathode materials.

将高镍层状氧化物阴极与水浆电极制备路线相结合，有可能同时满足锂离子电池高能量密度和低成本生产的需求。然而，空气和液态水的双重暴露以及水浆电极加工过程中的加热处理对高镍层状氧化物电极的影响尚不清楚。在本研究中，我们系统地研究了lini0.83 mn0.05 co0.120 o2 （NMC83）在水浆处理过程中的结构演变和电化学行为。结果表明，NMC83表面附近的晶体结构部分重构为岩盐相和层状相的混合物，导致NMC83电极的速率性能劣化。这部分表面重构层经过循环后完全转化为纯岩盐相，并伴有O2的释放、Ni的浸出、电解质的催化分解，形成较厚的阴极电解质间相层。电解质的副产物和溶解的Ni可以穿梭到Li金属侧，引起串扰效应，导致Li表面上厚而不稳定的固体电解质界面层。这些因素的结合严重破坏了从水泥浆中获得的NMC83电极的循环稳定性。采用分子自组装技术的缓释策略可增强水处理后的NMC83的表面稳定性。我们的发现为定制超高镍层状氧化物和其他水敏阴极材料的环境稳定性和水浆可加工性提供了新的见解。

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引用次数: 0

In situ preparation of zincophilic covalent–organic frameworks with low surface work function and high rigidity to stabilize zinc metal anodes 原位制备具有低表面功函数和高刚性的亲锌共价有机框架以稳定锌金属阳极

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-22 DOI: 10.1016/j.jechem.2024.11.019

Yunyu Zhao, Kaiyong Feng, Yingjian Yu

Zinc-ion batteries (ZIBs) are inexpensive and safe, but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications. In this study, 1,3,5-triformylphloroglycerol (Tp) and various diamine monomers (p-phenylenediamine (Pa), benzidine (BD), and 4,4′’-diamino-p-terphenyl (DATP)) were used to synthesize a series of two-dimensional covalent-organic frameworks (COFs). The resulting COFs were named TpPa, TpBD, and TpDATP, respectively, and they showed uniform zincophilic sites, different pore sizes, and high Young’s moduli on the Zn anode. Among them, TpPa and TpBD showed lower surface work functions and higher ion transfer numbers, which were conducive to uniform galvanizing/stripping zinc and inhibited dendrite growth. Theoretical calculations showed that TpPa and TpBD had wider negative potential region and greater adsorption capacity for Zn²⁺ than TpDATP, providing more electron donor sites to coordinate with Zn²⁺. Symmetric cells protected by TpPa and TpBD stably cycled for more than 2300 h, whereas TpDATP@Zn and the bare zinc symmetric cells failed after around 150 and 200 h. The full cells containing TpPa and TpBD modification layers also showed excellent cycling capacity at 1 A/g. This study provides comprehensive insights into the construction of highly reversible Zn anodes via COF modification layers for advanced rechargeable ZIBs.

锌离子电池（zbs）价格低廉且安全，但锌阳极的副反应和锌枝晶的生长阻碍了其实际应用。本研究以1,3,5-三甲酰间苯三甘油酯（Tp）和多种二胺单体（对苯二胺（Pa）、联苯胺（BD）和4,4”-二氨基-对三苯基（DATP））为原料合成了一系列二维共价有机框架（COFs）。得到的COFs分别被命名为TpPa、TpBD和TpDATP，它们在Zn阳极上表现出均匀的亲锌位点、不同的孔径和高的杨氏模量。其中，TpPa和TpBD具有较低的表面功函数和较高的离子转移数，有利于锌的均匀镀锌/剥离，抑制枝晶生长。理论计算表明，与TpDATP相比，TpPa和TpBD对Zn2+具有更宽的负电位区和更大的吸附容量，提供了更多的电子给体位点与Zn2+配合。经TpPa和TpBD保护的对称电池可稳定循环2300 h以上，而TpDATP@Zn和裸锌对称电池在约150 h和200 h后失效。含有TpPa和TpBD修饰层的完整电池在1 A/g时也表现出良好的循环能力。该研究为通过COF修饰层构建高可逆锌阳极提供了全面的见解。

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引用次数: 0

Opportunities and challenges in transformer neural networks for battery state estimation: Charge, health, lifetime, and safety 用于电池状态估计的变压器神经网络的机遇和挑战：充电、健康、寿命和安全

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-22 DOI: 10.1016/j.jechem.2024.11.011

Jingyuan Zhao , Xuebing Han , Yuyan Wu , Zhenghong Wang , Andrew F. Burke

Battery technology plays a crucial role across various sectors, powering devices from smartphones to electric vehicles and supporting grid-scale energy storage. To ensure their safety and efficiency, batteries must be evaluated under diverse operating conditions. Traditional modeling techniques, which often rely on first principles and atomic-level calculations, struggle with practical applications due to incomplete or noisy data. Furthermore, the complexity of battery dynamics, shaped by physical, chemical, and electrochemical interactions, presents substantial challenges for precise and efficient modeling. The Transformer model, originally designed for natural language processing, has proven effective in time-series analysis and forecasting. It adeptly handles the extensive, complex datasets produced during battery cycles, efficiently filtering out noise and identifying critical features without extensive preprocessing. This capability positions Transformers as potent tools for tackling the intricacies of battery data. This review explores the application of customized Transformers in battery state estimation, emphasizing crucial aspects such as charging, health assessment, lifetime prediction, and safety monitoring. It highlights the distinct advantages of Transformer-based models and addresses ongoing challenges and future opportunities in the field. By combining data-driven AI techniques with empirical insights from battery analysis, these pre-trained models can deliver precise diagnostics and comprehensive monitoring, enhancing performance metrics like health monitoring, anomaly detection, and early-warning systems. This integrated approach promises significant improvements in battery technology management and application.

电池技术在各个领域发挥着至关重要的作用，为从智能手机到电动汽车的各种设备供电，并支持电网规模的储能。为了确保电池的安全性和效率，必须在不同的工作条件下对电池进行评估。传统的建模技术通常依赖于第一性原理和原子水平的计算，由于数据不完整或有噪声而难以实际应用。此外，由物理、化学和电化学相互作用形成的电池动力学的复杂性为精确和有效的建模提出了实质性的挑战。Transformer模型最初是为自然语言处理而设计的，已被证明在时间序列分析和预测方面是有效的。它熟练地处理电池循环过程中产生的大量复杂数据集，有效地滤除噪声并识别关键特征，而无需大量预处理。这种能力使变压器成为处理复杂电池数据的有力工具。本文探讨了定制变压器在电池状态评估中的应用，重点介绍了充电、健康评估、寿命预测和安全监测等关键方面。它突出了基于变压器的模型的独特优势，并解决了该领域正在面临的挑战和未来的机遇。通过将数据驱动的人工智能技术与电池分析的经验见解相结合，这些预训练模型可以提供精确的诊断和全面的监测，从而提高健康监测、异常检测和预警系统等性能指标。这种综合方法有望在电池技术管理和应用方面取得重大进展。

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引用次数: 0

Single-atomic iron synergistic atom-cluster induce remote enhancement toward oxygen reduction reaction 单原子铁协同原子团簇诱导氧还原反应的远程增强

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-20 DOI: 10.1016/j.jechem.2024.11.012

Yayin Li , Haomin Jiang , Liu Lin , Zemin Sun , Genban Sun

The oxygen reduction reaction (ORR) could be effectively regulated by adjusting electron configurations and optimizing chemical bonds. Herein, we have achieved the modulation of electron distribution in Fe single atomic (Fe_SA) sites through Fe atomic clusters (Fe_AC) via a confined pyrolysis approach, thereby enhancing their intrinsic ORR activity. X-ray absorption spectroscopy has confirmed that the presence of iron atomic clusters could influence the electron distribution at Fe-N₄ sites. The Fe_SA/Fe_AC-NC catalyst exhibits a half-wave potential of 0.88 V, surpassing the individual Fe_SA-NC structure. Through electronic structure analysis, it could be seen that iron atom clusters can affect Fe-N₄ sites through long-range effects, and then effectively lower reaction barriers and enhance the reaction kinetics at Fe-N₄ sites. The synthetic approach might pave the way for constructing highly active catalysts with tunable atomic structures, representing an effective and universal technique for electron modulation in M-N-C systems. This work provides enlightenment for the exploration of more efficient single-atom electrocatalysts and the optimization of the performance of atomic electrocatalysts. Furthermore, a zinc-air battery assembled using it on their cathode deliver a high peak power density (205.7 mW cm⁻²) and a high-specific capacity of 807.5 mA h g⁻¹. This study offers a fresh approach to effectively enhance the synergistic interaction of between Fe single atom and Fe atomic clusters for improving ORR activity and energy storage.

通过调整电子构型和优化化学键可以有效地调控氧还原反应。在此，我们通过限制性热解方法通过铁原子团簇（FeAC）实现了铁单原子（FeSA）位点的电子分布调制，从而增强了它们的本征ORR活性。x射线吸收光谱证实了铁原子团簇的存在会影响Fe-N4位点的电子分布。FeSA/FeAC-NC催化剂的半波电位为0.88 V，超过了单个FeSA- nc结构。通过电子结构分析可知，铁原子团簇可以通过远程效应影响Fe-N4位点，从而有效降低Fe-N4位点的反应势垒，提高反应动力学。该合成方法可能为构建具有可调原子结构的高活性催化剂铺平道路，代表了M-N-C系统中电子调制的有效和通用技术。这项工作为探索更高效的单原子电催化剂和优化原子电催化剂的性能提供了启示。此外，在阴极上使用它组装的锌空气电池提供了高峰值功率密度（205.7 mW cm - 2）和807.5 mA h g - 1的高比容量。该研究为有效增强Fe单原子与Fe原子团簇之间的协同相互作用以提高ORR活性和能量储存提供了新的途径。

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引用次数: 0

Insights into the doping functions on redox chemistry of layered Ni-rich cathodes 层状富镍阴极的掺杂作用及其氧化还原化学研究

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.jechem.2024.11.005

Zhenxing Wang, Yong Chen

In pursuit of low cost and long life for lithium-ion batteries in electric vehicles, the most promising strategy is to replace the commercial LiCoO₂ with a high-energy-density Ni-rich cathode. However, the irreversible redox couples induce rapid capacity decay, poor long-term cycling life, vast gas evolution, and unstable structure transformations of the Ni-rich cathode, limiting its practical applications. Element doping has been considered as the most promising strategy for addressing these issues. However, the relationships between element doping functions and redox chemistry still remain confused. To clarify this connection, this review places the dynamic evolution of redox couples (Li⁺, Ni²⁺/Ni³⁺/Ni⁴⁺-e⁻, O²⁻/Oⁿ⁻/O₂-e⁻) as the tree trunk. The material structure, degradation mechanisms, and addressing element doping strategies are considered as the tree branches. This comprehensive summary aims to provide an overview of the current understanding and progress of Ni-rich cathode materials. In the last section, promising strategies based on element doping functions are provided to encourage the practical application of Ni-rich cathodes. These strategies also offer a new approach for the development of other intercalated electrode materials in Na and K-based battery systems.

为了追求电动汽车锂离子电池的低成本和长寿命，最有希望的策略是用高能量密度富镍阴极取代商用LiCoO2。然而，不可逆氧化还原对导致富镍阴极容量衰减快、长期循环寿命差、气体析出量大、结构转变不稳定，限制了其实际应用。元素掺杂被认为是解决这些问题最有希望的策略。然而，元素掺杂功能与氧化还原化学之间的关系尚不清楚。为了阐明这种联系，本文将氧化还原对（Li+, Ni2+/Ni3+/Ni4+-e−,O2−/On−/O2-e−）的动态演变作为树干。材料结构、降解机制和寻址元素掺杂策略被视为树枝。本文综述了目前对富镍阴极材料的认识和研究进展。在最后一节中，提出了基于元素掺杂函数的有前途的策略，以促进富镍阴极的实际应用。这些策略也为钠基电池系统中其他插层电极材料的开发提供了新的途径。

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引用次数: 0

Understanding characteristic electrochemical impedance spectral data of redox flow batteries with multiphysics modeling 利用多物理场建模理解氧化还原液流电池的特征电化学阻抗谱数据

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.jechem.2024.11.007

Ayoob Alhammadi, Abdulmonem Fetyan, Rahmat Agung Susantyoko, Ibrahim Mustafa, Musbaudeen O. Bamgbopa

Electrochemical impedance spectroscopy (EIS) is a robust characterization method to probe prevalent (electro)chemical processes in an electrochemical system. Despite its extensive utilization in fuel cell research, the application of EIS in redox flow battery systems particularly for simplified two-electrode full-cell configurations is more limited. Herein we attempt to strengthen the understanding of characteristic EIS data of vanadium redox flow batteries by a combination of equivalent circuit modeling with a validated Multiphysics model analyzed under hydrodynamic conditions in frequency domain. Following a highlight of system linearity and stability concerns for EIS in redox flow batteries, we specifically use our combinatory approach to investigate the effects of different cell component properties on observed galvanostatic EIS spectra and accompanying fitted equivalent circuit element parameters. For the investigated two-electrode full-cell flow battery configuration with the same electrode material on both sides, the EIS spectral data is observed to be dominated by different mass or charge transport processes at different ends of the spectrum. Sensitivity analyses of both obtained EIS spectral data and fitted circuit elements parameters show that electrode morphological properties, membrane porosity, and electrolyte inflow conditions predominantly define the EIS spectral data. Insights from the type of analyses performed herein can facilitate flow battery cell/stack diagnostics and targeted performance improvement efforts.

电化学阻抗光谱（EIS）是一种强大的表征方法，可用于探测电化学系统中普遍存在的（电）化学过程。尽管 EIS 在燃料电池研究中得到了广泛应用，但在氧化还原液流电池系统中的应用，尤其是简化的双电极全电池配置中的应用，则较为有限。在此，我们尝试将等效电路建模与经过验证的多物理场模型相结合，在频域流体力学条件下进行分析，以加强对钒氧化还原液流电池特征 EIS 数据的理解。在强调了氧化还原液流电池中 EIS 的系统线性和稳定性问题之后，我们特别使用我们的组合方法来研究不同电池组件特性对观察到的电静态 EIS 光谱和伴随的拟合等效电路元件参数的影响。对于所研究的两侧电极材料相同的双电极全电芯液流电池配置，观察到 EIS 光谱数据在光谱的不同端点由不同的质量或电荷传输过程主导。对获得的 EIS 光谱数据和拟合电路元件参数进行的灵敏度分析表明，电极形态特性、隔膜孔隙率和电解液流入条件主要决定了 EIS 光谱数据。从本文所做的分析类型中获得的启示可促进液流电池电池/电池组的诊断和有针对性的性能改进工作。

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引用次数: 0

“Tennis racket” hydrogel electrolytes to synchronously regulate cathode and anode of zinc-iodine batteries “网球拍”水凝胶电解质同步调节锌碘电池正极和阳极

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.jechem.2024.11.004

Tian-Yi Yang , Ting-Ting Su , Hai-Long Wang , Kun Li , Wen-Feng Ren , Run-Cang Sun

Aqueous zinc-iodine (Zn-I₂) batteries show great potential as energy storage candidates due to their high-safety and low-cost, but confronts hydrogen evolution reaction (HER) and dendrite growth at anode side and polyiodide shuttling at cathode side. Herein, “tennis racket” (TR) hydrogel electrolytes were prepared by the co-polymerization and co-blending of polyacrylamide (PAM), sodium lignosulfonate (SL), and sodium alginate (SA) to synchronously regulate cathode and anode of Zn-I₂ batteries. “Gridline structure” of TR can induce the uniform transportation of Zn²⁺ ions through the coordination effect to hinder HER and dendrite growth at anode side, as well as hit I₃⁻ ions as “tennis” via the strong repulsion force to avoid shuttle effect at cathode side. The synergistic effect of TR electrolyte endows Zn-Zn symmetric battery with high cycling stability over 4500 h and Zn-I₂ cell with the stably cycling life of 15000 cycles at 5 A g⁻¹, outperforming the reported works. The practicability of TR electrolyte is verified by flexible Zn-I₂ pouch battery. This work opens a route to synchronously regulate cathode and anode to enhance the electrochemical performance of Zn-I₂ batteries.

水相锌碘（Zn-I2）电池以其高安全性和低成本的优点显示出巨大的储能潜力，但在阳极侧存在析氢反应（HER）和枝晶生长问题，在阴极侧存在多碘化物穿梭问题。采用聚丙烯酰胺（PAM）、木质素磺酸钠（SL）和海藻酸钠（SA）共聚共混制备了“网球拍”（TR）水凝胶电解质，用于同步调节Zn-I2电池的正极和阳极。TR的“网格线结构”可以通过配位效应诱导Zn2+离子均匀输运，阻碍阳极侧HER和枝晶的生长，并通过强大的斥力将I3−离子打成“网球”，避免阴极侧的穿梭效应。TR电解液的协同作用使Zn-Zn对称电池具有超过4500 h的高循环稳定性，Zn-I2电池在5 A g−1下具有15000次的稳定循环寿命，优于报道的工作。用柔性锌- i2袋电池验证了TR电解液的实用性。本工作开辟了同步调节阴极和阳极以提高锌- i2电池电化学性能的途径。

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引用次数: 0

Influence of p-π conjugation in π-π stacking molecules on passivating defects for efficient and stable perovskite solar cells π-π堆积分子中的 p-π 共轭对高效稳定的过氧化物太阳能电池钝化缺陷的影响

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.jechem.2024.11.009

Changqing Liu , Benlin He , Fanliang Bao , Qihang Cheng , Zhe Yang , Meng Wei , Zhiwei Ma , Haiyan Chen , Jialong Duan , Qunwei Tang

A comprehensive understanding of the relevance between molecular structure and passivation ability to screen efficient modifiers is essential for enhancing the performance of perovskite solar cells (PSCs). Here, three similar π-π stacking molecules namely benzophenone (BPN), diphenyl sulfone (DPS), and diphenyl sulfoxide (DPSO) are used as back-interface modifiers in carbon-based CsPbBr₃ PSCs. After investigation, the results demonstrate the positive effect of the p-π conjugation characteristic in π-π stacking molecules on maximizing their passivation ability. The p-π conjugation of DPSO enables a higher coordinative activity of oxygen atom in its SO group than that in OSO group of DPS and CO group of BPN, which gives a superior passivation effect of DPSO on defects of perovskite films. The modification of DPSO also significantly improves the p-type behavior of perovskite films and the back-interfacial energetics matching, inducing an increase of hole extraction and a decrease of energy loss. Finally, the unencapsulated carbon-based CsPbBr₃ PSCs with DPSO achieve a maximum power conversion efficiency of 10.60% and outstanding long-term stability in high-temperature, high-humidity (85 °C, 85% relative humidity) air environment. This work provides insights into the influence of the structure of π-π stacking molecules on their ability to improve the perovskite films quality and therefore the PSCs performance.

全面了解分子结构与钝化能力之间的相关性以筛选高效改性剂，对于提高过氧化物太阳能电池（PSC）的性能至关重要。本文将三种类似的π-π堆积分子（即二苯甲酮（BPN）、二苯砜（DPS）和二苯基亚砜（DPSO））用作碳基 CsPbBr3 PSCs 的背界面改性剂。研究结果表明，π-π堆叠分子中的π-π共轭特性对最大限度地提高其钝化能力具有积极作用。与 DPS 的 OSO 基团和 BPN 的 CO 基团相比，DPSO 的 p-π 共轭使其 SO 基团中的氧原子具有更高的配位活性，从而使 DPSO 对包晶石薄膜的缺陷具有更好的钝化效果。DPSO 的改性还显著改善了包晶薄膜的 p 型行为和背界面能量匹配，从而提高了空穴萃取率，降低了能量损失。最后，含有 DPSO 的未封装碳基 CsPbBr3 PSCs 在高温、高湿（85 °C，85% 相对湿度）空气环境中实现了 10.60% 的最大功率转换效率和出色的长期稳定性。这项研究深入探讨了π-π堆叠分子结构对改善包晶薄膜质量以及 PSCs 性能的影响。

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引用次数: 0

Insights into reaction mechanisms: Water’s role in enhancing in-situ hydrogen production from methane conversion in sandstone 对反应机制的洞察：水在提高砂岩中甲烷转化的原位产氢中的作用

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.jechem.2024.10.055

Keju Yan , Krishna Prasad Shrestha , Mohamed Amine Ifticene , Qingwang Yuan

In-situ conversion of subsurface hydrocarbons via electromagnetic (EM) heating has emerged as a promising technology for producing carbon-zero and affordable hydrogen (H₂) directly from natural gas reservoirs. However, the reaction pathways and role of water as an additional hydrogen donor in EM-assisted methane-to-hydrogen (CH₄-to-H₂) conversion are poorly understood. Herein, we employ a combination of lab-scale EM-heating experiments and reaction modeling analyses to unravel reaction pathways and elucidate water’s role in enhancing hydrogen production. The labelled hydrogen isotope of deuterium oxide (D₂O) is used to trace the sources of hydrogen. The results show that water significantly boosts hydrogen yield via coke gasification at around 400 °C and steam methane reforming (SMR) reaction at over 600 °C in the presence of sandstone. Water-gas shift reaction exhibits a minor impact on this enhancement. Reaction mechanism analyses reveal that the involvement of water can initiate auto-catalytic loop reactions with methane, which not only generates extra hydrogen but also produces OH radicals that enhance the reactants’ reactivity. This work provides crucial insights into the reaction mechanisms involved in water-carbon-methane interactions and underscores water’s potential as a hydrogen donor for in-situ hydrogen production from natural gas reservoirs. It also addresses the challenges related to carbon deposition and in-situ catalyst regeneration during EM heating, thus derisking this technology and laying a foundation for future pilots.

通过电磁（EM）加热对地下碳氢化合物进行原位转化，已经成为一项有前途的技术，可以直接从天然气储层中生产零碳和价格合理的氢（H2）。然而，在em辅助甲烷-氢（CH4-to-H2）转化过程中，水作为额外的氢供体的反应途径和作用尚不清楚。本文采用实验室规模的电磁加热实验和反应模型分析相结合的方法来揭示反应途径，并阐明水在促进氢生产中的作用。氧化氘（D2O）的标记氢同位素用于追踪氢的来源。结果表明，在砂岩存在下，在400℃左右的焦炭气化和600℃以上的蒸汽甲烷重整（SMR）反应中，水显著提高了氢的产率。水气转换反应对这种增强的影响较小。反应机理分析表明，水的参与可以引发与甲烷的自催化环反应，不仅产生多余的氢，还会产生OH自由基，提高反应物的反应活性。这项工作为水-碳-甲烷相互作用的反应机制提供了重要的见解，并强调了水作为天然气储层原位制氢的氢供体的潜力。它还解决了与EM加热过程中碳沉积和原位催化剂再生相关的挑战，从而降低了该技术的风险，为未来的试点奠定了基础。

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