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Understanding synergistic catalysis on Pt–Cu diatomic sites via operando X-ray absorption spectroscopy in sulfur redox reactions 通过 X 射线吸收光谱了解硫氧化还原反应中 Pt-Cu 二原子位点的协同催化作用
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-10-01 DOI: 10.1016/j.esci.2023.100222
Sulfur redox reactions render lithium–sulfur (Li–S) batteries with an energy density of > 500 ​Wh ​kg−1 but suffer a low practical capacity and fast capacity fade due to sluggish sulfur redox reaction (SRR) kinetics, which lies in the complex reaction process that involves a series of reaction intermediates and proceeds via a cascade reaction. Here, we present a Pt–Cu dual-atom catalyst (Pt/Cu-NG) as an electrocatalyst for sulfur redox reactions. Pt/Cu-NG enabled the rapid conversion of soluble polysulfide intermediates into insoluble Li2S2/Li2S, and consequently, it prevented the accumulation and shuttling of lithium polysulfides, thus outperforming the corresponding single-atom catalysts (SACs) with individual Pt or Cu sites. Operando X-ray absorption spectroscopy and density functional theory calculations revealed that a synergistic effect between the paired Pt and Cu atoms modifies the electronic structure of the Pt site through d-orbital interactions, resulting in an optimal moderate interaction of the metal atom with the different sulfide species. This optimal interaction enhanced charge transfer kinetics and promoted sulfur redox reactions. Our work thus provides important insights on the atomic scale into the synergistic effects operative in dual-atom catalysts and will thus pave the way to electrocatalysts with enhanced efficiency for high-performance Li–S batteries.
硫氧化还原反应可使锂硫(Li-S)电池的能量密度达到 > 500 Wh kg-1,但由于硫氧化还原反应动力学缓慢,实际容量低且容量衰减快,这主要是因为反应过程复杂,涉及一系列反应中间体,并通过级联反应进行。在此,我们提出了一种铂铜双原子催化剂(Pt/Cu-NG)作为硫氧化还原反应的电催化剂。Pt/Cu-NG 能够将可溶性多硫化物中间产物快速转化为不溶性 Li2S2/Li2S,从而防止了多硫化锂的积累和穿梭,因此性能优于具有单独 Pt 或 Cu 位点的相应单原子催化剂 (SAC)。操作X射线吸收光谱和密度泛函理论计算显示,成对的铂原子和铜原子之间的协同效应通过d-轨道相互作用改变了铂位点的电子结构,从而使金属原子与不同的硫化物产生了最佳的适度相互作用。这种最佳相互作用增强了电荷转移动力学,促进了硫氧化还原反应。因此,我们的工作提供了在原子尺度上了解双原子催化剂协同效应的重要视角,从而为高性能锂-S 电池的高效电催化剂铺平了道路。
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引用次数: 0
Towards high performance polyimide cathode materials for lithium–organic batteries by regulating active-site density, accessibility, and reactivity 通过调节活性位密度、可及性和反应性,为锂有机电池开发高性能聚酰亚胺正极材料
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-08-01 DOI: 10.1016/j.esci.2023.100224

Organic carbonyl electrode materials offer promising prospects for future energy storage systems due to their high theoretical capacity, resource sustainability, and structural diversity. Although much progress has been made in the research of high-performance carbonyl electrode materials, systematic and in-depth studies on the underlying factors affecting their electrochemical properties are rather limited. Herein, five polyimides containing different types of diamine linkers are designed and synthesized as cathode materials for Li-ion batteries. First, the incorporation of carbonyl groups increases the active-site density in both conjugated and non-conjugated systems. Second, increased molecular rigidity can improve the accessibility of the active sites. Third, the introduction of the conjugated structure between two carbonyl groups can increase the reactivity of the active sites. Consequently, the incorporation of carbonyl structures and conjugated structures increases the capacity of polyimides. PTN, PAN, PMN, PSN, and PBN exhibit 212, 198, 199, 151, and 115 ​mAh ​g−1 ​at 50 ​mA ​g−1, respectively. In addition, the introduction of a carbonyl structure and a conjugated structure is also beneficial for improving cycling stability and rate performance. This work can deepen the understanding of the structure–function relationship for the rational design of polyimide electrode materials and can be extended to the molecular design of other organic cathode materials.

有机羰基电极材料因其理论容量高、资源可持续性和结构多样性,为未来的储能系统提供了广阔的前景。虽然高性能羰基电极材料的研究取得了很大进展,但对影响其电化学性能的基本因素的系统深入研究却相当有限。本文设计并合成了五种含有不同类型二胺连接体的聚酰亚胺作为锂离子电池的阴极材料。首先,在共轭和非共轭体系中,羰基的加入都会增加活性位密度。其次,增加分子刚性可提高活性位点的可及性。第三,在两个羰基之间引入共轭结构可以提高活性位点的反应活性。因此,羰基结构和共轭结构的加入提高了聚酰亚胺的容量。在 50 mA g-1 的条件下,PTN、PAN、PMN、PSN 和 PBN 的电容量分别为 212、198、199、151 和 115 mAh g-1。此外,引入羰基结构和共轭结构也有利于提高循环稳定性和速率性能。这项工作可以加深对结构-功能关系的理解,从而合理设计聚酰亚胺电极材料,并可扩展到其他有机阴极材料的分子设计。
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引用次数: 0
Sustainable nanostructured electrolyte additives for stable metal anodes 用于稳定金属阳极的可持续纳米结构电解质添加剂
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-08-01 DOI: 10.1016/j.esci.2024.100248

Metal anodes (e.g., Li and Zn) are promising candidates for high-energy and high-power rechargeable batteries. However, the commercialization of metal anodes is hampered by irregular dendrite growth, which severely deteriorates the safety and cyclability of metal anodes. Optimizing the electrolyte by nanostructured additives to regulate the metal deposition shows great potential since the electrochemically nonreactive feature endows the regulation function with good sustainability. In this manuscript, the fundamental dendrite formation models and key parameters for stabilizing metal anode are first discussed. The progress and functional mechanism of nanostructured additives for regulating the metal deposition are summarized in terms of regulatory model, i.e., deposition-, adsorption- and dispersion-type. Finally, we also provide a detailed concluding outlook, pointing out the future trend of selecting new nanostructured additive candidates and elucidating synergistic effects and underlying mechanisms with the key attention being given to the assessments of practicality.

金属阳极(如锂和锌)是高能量和高功率充电电池的理想候选材料。然而,金属阳极的商业化受到不规则枝晶生长的阻碍,这严重降低了金属阳极的安全性和循环性。通过纳米结构添加剂优化电解质以调节金属沉积显示出巨大的潜力,因为电化学非反应特性使调节功能具有良好的可持续性。本手稿首先讨论了树枝晶形成的基本模型和稳定金属阳极的关键参数。从沉积型、吸附型和分散型等调控模式的角度,总结了纳米结构添加剂调控金属沉积的进展和功能机理。最后,我们还进行了详细的总结性展望,指出了选择新的纳米结构添加剂候选物、阐明协同效应和内在机制的未来趋势,并重点关注了实用性评估。
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引用次数: 0
Correlating phase transition with heat generation through calorimetric data 通过量热数据将相变与发热相关联
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-08-01 DOI: 10.1016/j.esci.2023.100226

Despite the widespread utilization of Lithium-ion batteries (LIBs), concerns regarding safety during operation persist owing to accidents and potential risks of fires and explosions. To comprehend the thermal dynamics that underlie severe LIB incidents, calorimetry tests have been prevalently employed for over three decades to examine the exothermic/endothermic behavior, reaction kinetics, and thermal interactions among LIB materials. There exists a substantial volume of calorimetry test results on various LIB electrodes, electrolytes, and other components. However, this data showcases low consistency, yielding an unreliable database that obstructs a thorough understanding of LIB thermal behavior. In this research, a comparative analysis of differential scanning calorimetry (DSC) results from materials utilized in the most commercialized LIB systems is conducted. The analysis unveils notable discrepancies in DSC data amassed by different researchers, identifies five predominant causes of data inconsistency, proposes a standardized DSC operational procedure, and generates a set of self-consistent data. Subsequently, an intrinsic safety spectrum is delineated and compared with X-ray diffraction (XRD) outcomes to elucidate the correlation between the crystal lattice structure and the thermal behavior of the material. This work aids in the formation of a comparative DSC database, utilizing the vast but inconsistent literature data. Moreover, it clarifies the linkage between the material structure and thermal behavior, facilitating data-driven thermal analysis of LIBs.

尽管锂离子电池(LIB)得到了广泛应用,但由于事故以及潜在的火灾和爆炸风险,人们对其运行过程中的安全性一直存在担忧。为了理解导致严重锂离子电池事故的热动力学,三十多年来,人们普遍采用量热测试来研究锂离子电池材料的放热/散热行为、反应动力学和热相互作用。针对各种锂电池电极、电解质和其他组件的量热测试结果数量可观。然而,这些数据的一致性很低,形成了一个不可靠的数据库,阻碍了对锂电池热行为的全面了解。在这项研究中,我们对大多数商业化锂离子电池系统中使用的材料的差示扫描量热法(DSC)结果进行了比较分析。分析揭示了不同研究人员所积累的 DSC 数据中存在的显著差异,确定了造成数据不一致的五个主要原因,提出了标准化 DSC 操作程序,并生成了一组自洽数据。随后,划定了内在安全光谱,并将其与 X 射线衍射 (XRD) 结果进行比较,以阐明晶格结构与材料热行为之间的相关性。这项工作有助于利用大量不一致的文献数据建立一个 DSC 比较数据库。此外,它还阐明了材料结构与热行为之间的联系,有助于对锂电池进行数据驱动的热分析。
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引用次数: 0
Mesoscale interplay among composition heterogeneity, lattice deformation, and redox stratification in single-crystalline layered oxide cathode 单晶层状氧化物阴极中成分异质性、晶格变形和氧化还原分层之间的中尺度相互作用
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-08-01 DOI: 10.1016/j.esci.2024.100251

Single-crystalline layered oxide materials for lithium-ion batteries are featured by their excellent capacity retention over their polycrystalline counterparts, making them sought-after cathode candidates. Their capacity degradation, however, becomes more severe under high-voltage cycling, hindering many high-energy applications. It has long been speculated that the interplay among composition heterogeneity, lattice deformation, and redox stratification could be a driving force for the performance decay. The underlying mechanism, however, is not well-understood. In this study, we use X-ray microscopy to systematically examine single-crystalline NMC particles at the mesoscale. This technique allows us to capture detailed signals of diffraction, spectroscopy, and fluorescence, offering spatially resolved multimodal insights. Focusing on early high-voltage charging cycles, we uncover heterogeneities in valence states and lattice structures that are inherent rather than caused by electrochemical abuse. These heterogeneities are closely associated with compositional variations within individual particles. Our findings provide useful insights for refining material synthesis and processing for enhanced battery longevity and efficiency.

用于锂离子电池的单晶层状氧化物材料与多晶材料相比,具有出色的容量保持能力,因此成为备受追捧的正极候选材料。然而,在高压循环条件下,它们的容量衰减会变得更加严重,从而阻碍了许多高能量应用。长期以来,人们一直推测成分异质性、晶格变形和氧化还原分层之间的相互作用可能是性能衰减的驱动力。然而,人们对其内在机制还不甚了解。在本研究中,我们使用 X 射线显微镜在中尺度上对单晶 NMC 粒子进行了系统检测。通过这种技术,我们可以捕捉到衍射、光谱和荧光的详细信号,从而提供空间分辨的多模态洞察力。以早期高压充电循环为重点,我们发现了价态和晶格结构的异质性,这些异质性是固有的,而不是电化学滥用造成的。这些异质性与单个颗粒内部的成分变化密切相关。我们的研究结果为改进材料合成和加工以提高电池寿命和效率提供了有益的启示。
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引用次数: 0
Fabrication pressures and stack pressures in solid-state battery 固态电池的制造压力和叠片压力
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-08-01 DOI: 10.1016/j.esci.2024.100247

Solid-state batteries (SSBs) have received widespread attention with their high safety and high energy density characteristics. However, solid-solid contacts in the internal electrode material and the electrode material/solid electrolyte (SE) interfaces, as well as the severe electrochemo-mechanical effects caused by the internal stress due to the volume change of the active material, these problems hinder ion/electron transport within the SSBs, which significantly deteriorates the electrochemical performance. Applying fabrication pressures and stack pressures are effective measures to improve solid-solid contact and solve electrochemo-mechanical problems. Herein, the influences of different pressures on cathode material, anode material, SEs, and electrode/SEs interface are briefly summarized from the perspective of interface ion diffusion, transmission of electrons and ions in internal particles, current density and ion diffusion kinetics, and the volume changes of Li+ stripping/plating based on two physical contact models, and point out the direction for the future research direction of SSBs and advancing industrialization by building the relationship between pressures and SSBs electrochemistry.

固态电池(SSB)以其高安全性和高能量密度的特点受到广泛关注。然而,内部电极材料和电极材料/固体电解质(SE)界面的固-固接触,以及活性材料体积变化引起的内应力所造成的严重电化学-机械效应,这些问题阻碍了固态电池内部的离子/电子传输,从而大大降低了电化学性能。施加制造压力和堆叠压力是改善固-固接触和解决电化学-机械问题的有效措施。本文基于两个物理接触模型,从界面离子扩散、内部粒子的电子和离子传输、电流密度和离子扩散动力学、Li+剥离/电镀的体积变化等角度,简要总结了不同压力对阴极材料、阳极材料、SEs、电极/SEs界面的影响,并通过构建压力与SSBs电化学之间的关系,为SSBs未来的研究方向和推进产业化指明了方向。
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引用次数: 0
Highly efficient chemical production via electrified, transient high-temperature synthesis 通过电气化瞬态高温合成实现高效化学生产
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-08-01 DOI: 10.1016/j.esci.2024.100253

In response to the current energy and environmental challenges, reducing or replacing reliance on fossil fuels and striving for carbon neutrality seems to be the only viable choice. Recently, a cutting-edge, eco-friendly method of chemical synthesis via transient Joule heating (JH) demonstrated significant promise across various domains, including methane reforming, ammonia synthesis, volatile organic compounds removal, plastic recycling, the synthesis of functional carbon materials from repurposed solid waste, etc. In this review, the advantages, and latest developments in thermochemical synthesis by flash and transient JH are comprehensively outlined. Unlike the ongoing heating process of conventional furnaces that consume fossil fuels, dynamic and transient JH can get significantly higher reaction rates, energy efficiency, flexibility, and versatility. Subsequently, the transient reaction mechanism, data science optimization, and scale-up production models are discussed, and prospects for the integration of the electrified chemical industry with renewable energy for carbon neutrality and long-term energy storage are also envisioned.

为应对当前的能源和环境挑战,减少或取代对化石燃料的依赖并努力实现碳中和似乎是唯一可行的选择。最近,一种通过瞬态焦耳加热(JH)进行化学合成的前沿环保方法在多个领域展现出巨大前景,包括甲烷重整、氨合成、挥发性有机化合物去除、塑料回收、从再利用固体废弃物中合成功能性碳材料等。在这篇综述中,我们将全面概述闪蒸和瞬时 JH 热化学合成的优势和最新发展。与消耗化石燃料的传统炉子的持续加热过程不同,动态和瞬态 JH 可以显著提高反应速率、能效、灵活性和通用性。随后,还讨论了瞬态反应机理、数据科学优化和放大生产模型,并展望了电气化化学工业与可再生能源的整合,以实现碳中和和长期能源储存的前景。
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引用次数: 0
Metal–organic frameworks and their derivatives for optimizing lithium metal anodes 优化锂金属阳极的金属有机框架及其衍生物
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-08-01 DOI: 10.1016/j.esci.2023.100189

Lithium metal anodes (LMAs) have been considered the ultimate anode materials for next-generation batteries. However, the uncontrollable lithium dendrite growth and huge volume expansion that can occur during charge and discharge seriously hinder the practical application of LMAs. Metal–organic framework (MOF) materials, which possess the merits of huge specific surface area, excellent porosity, and flexible composition/structure tunability, have demonstrated great potential for resolving both of these issues. This article first explores the mechanism of lithium dendrite formation as described by four influential models. Subsequently, based on an in-depth understanding of these models, we propose potential strategies for utilizing MOFs and their derivatives to suppress lithium dendrite growth. We then provide a comprehensive review of research progress with respect to various applications of MOFs and their derivatives to suppress lithium dendrites and inhibit volume expansion. The paper closes with a discussion of perspectives on future modifications of MOFs and their derivatives to achieve stable and dendrite-free lithium metal batteries.

锂金属阳极(LMAs)被认为是下一代电池的终极负极材料。然而,充放电过程中锂枝晶生长不可控和体积膨胀严重阻碍了LMAs的实际应用。金属有机框架(MOF)材料具有巨大的比表面积、优异的孔隙率和灵活的组成/结构可调性等优点,在解决这两个问题方面显示出巨大的潜力。本文首先探讨了锂枝晶形成的四种有影响的模型。随后,基于对这些模型的深入理解,我们提出了利用mof及其衍生物抑制锂枝晶生长的潜在策略。然后,我们全面回顾了mof及其衍生物在抑制锂枝晶和抑制体积膨胀方面的各种应用的研究进展。本文最后讨论了mof及其衍生物未来的改进前景,以实现稳定的无枝晶锂金属电池。
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引用次数: 0
High density iridium synergistic sites boosting CO-tolerate performance for PEMFC anode 高密度铱协同位点可提高 PEMFC 阳极的一氧化碳溶解性能
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-08-01 DOI: 10.1016/j.esci.2024.100230

The usage of cheap crude H2 in proton-exchange membrane fuel cells (PEMFCs) is still unrealistic to date, due to the suffering of the current Pt based nano-catalysts from impurities such as CO in anode. Recently, synergistic active sites between single atom (SA) and nanoparticle (NP) have been found to be promising for overcoming the poisoning problem. However, lengthening the nanoparticle-single atom (SA–NP) interface, i.e., constructing high density synergistic active sites, remains highly challenging. Herein, we present a new strategy based on molecular fusion strategy to create abundant SA–NP interfaces, with high density SA–NP interfaces created on a two dimensional nitrogen doped carbon nanosheets (Ir-SACs&NPs/NC). Owing to the abundance of SA–NP interface sites, the catalyst was empowered with a high tolerance towards up to 1000 ​ppm CO in H2 feed. These findings provide guidelines for the design and construction of active and anti-poisoning catalysts for PEMFC anode.

在质子交换膜燃料电池(PEMFCs)中使用廉价的粗制 H2 至今仍不现实,原因是目前的铂基纳米催化剂受到阳极中 CO 等杂质的影响。最近,人们发现单原子(SA)和纳米粒子(NP)之间的协同活性位点有望克服中毒问题。然而,延长纳米粒子-单原子(SA-NP)界面,即构建高密度的协同活性位点,仍然极具挑战性。在此,我们提出了一种基于分子融合策略的新策略,在二维掺氮碳纳米片(Ir-SACs&NPs/NC)上创建高密度的SA-NP界面,从而创建丰富的SA-NP界面。由于存在大量的 SA-NP 界面位点,催化剂对 H2 进料中高达 1000 ppm 的 CO 具有很高的耐受性。这些发现为设计和制造用于 PEMFC 阳极的活性抗中毒催化剂提供了指导。
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引用次数: 0
Solvated metal complexes for balancing stability and activity of sulfur free radicals 用于平衡硫自由基稳定性和活性的溶解金属复合物
IF 42.9 Q1 ELECTROCHEMISTRY Pub Date : 2024-08-01 DOI: 10.1016/j.esci.2023.100225

Free radicals can improve the reaction rate, but most of them are unstable due to unpaired electrons. Simultaneously maintaining their stability and activity is challenging. Herein, taking sulfur (S) radicals as an example, we propose a strategy in which solvated metal complexes constructed by Al(acetylacetonate)3 and different solvents can stabilize high concentrations of S radicals with good activity through ion–dipole interactions. Based on this strategy, it is first demonstrated that S4· is selectively stabilized by controlling the configurations of the solvated complexes. As a result, the reaction rate of S↔Li2S is increased by 8 times, and the energy efficiency and rate capability of the Li–S batteries are significantly improved, especially the 5-fold increase in cell capacities at a low electrolyte/sulfur ratio. This work provides an important strategy in which solvated metal complexes balance the activity and stability of free radicals to accelerate reactions and their application in various fields.

自由基可以提高反应速度,但由于其电子不配对,大多数自由基都不稳定。同时保持自由基的稳定性和活性具有挑战性。在此,我们以硫(S)自由基为例,提出了一种策略,即由乙酰丙酮铝(Al(acetylacetonate)3)和不同溶剂构建的溶解金属配合物可以通过离子-偶极子相互作用稳定高浓度的 S 自由基,并使其具有良好的活性。基于这种策略,研究人员首次证明,通过控制溶解络合物的构型,可以选择性地稳定 S4--。因此,S↔Li2S 的反应速率提高了 8 倍,锂-S 电池的能量效率和速率能力得到显著提高,尤其是在低电解质/硫比条件下,电池容量提高了 5 倍。这项工作提供了一种重要的策略,即溶解金属复合物可以平衡自由基的活性和稳定性,从而加速反应并将其应用于各个领域。
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引用次数: 0
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