Chemical Science最新文献_第7页

Simulating enzyme catalysis with electrostatically embedded machine learning potentials 用静电嵌入的机器学习电位模拟酶催化

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-10 DOI: 10.1039/d6sc01156j

Valentin Gradisteanu, Elliot W. Chan, Lester Hedges, Meritxell Malagarriga, Rolf David, Miguel de la Puente, Damien Laage, Iñaki Tuñón, Marc W. van der Kamp, Kirill Zinovjev

To simulate enzyme reactions, multiscale quantum mechanics/molecular mechanics (QM/MM) approaches are well established and popular. However, accurately and efficiently estimating enzyme activity is a challenge, because in general, precise methods are too computationally expensive. Here, we demonstrate that enzyme catalysis can be captured by coupling efficient, reactive machine-learned potentials (MLPs) trained on gas phase data to the wider enzyme environment using electrostatic machine learning embedding (EMLE). The EMLE scheme is first applied to the natural Diels–Alderase AbyU, showing that it correctly differentiates the catalytic action on different enzyme–substrate conformations. Then, we show that training a reaction-specific EMLE model allows us to accurately capture the enzyme catalytic effects of the conversion of chorismate to prephenate, a reaction with a highly polarizable and charged transition state. In both cases, in contrast to mechanical embedding approaches, the EMLE scheme allows accurate and efficient predictions of enzyme catalysis, agreeing with high-level QM/MM reference calculations. This approach facilitates the use of gas phase-trained MLPs in MLP/molecular mechanics (ML/MM) simulations and should thus be highly beneficial for computational activity screening of enzyme biocatalysts.

为了模拟酶的反应，多尺度量子力学/分子力学（QM/MM）方法已经建立并流行起来。然而，准确和有效地估计酶活性是一个挑战，因为一般来说，精确的方法计算成本太高。在这里，我们证明了酶催化可以通过使用静电机器学习嵌入（EMLE）将在气相数据上训练的高效、反应性机器学习电位（mlp）耦合到更广泛的酶环境中来捕获。EMLE方案首次应用于天然Diels-Alderase AbyU，表明它正确区分了不同酶-底物构象的催化作用。然后，我们证明，训练一个反应特异性的EMLE模型使我们能够准确地捕捉到氯酸盐转化为预苯酸盐的酶催化效应，这是一个具有高度极化和带电过渡态的反应。在这两种情况下，与机械嵌入方法相比，EMLE方案可以准确有效地预测酶催化，符合高水平的QM/MM参考计算。这种方法有利于在MLP/分子力学（ML/MM）模拟中使用气相训练的MLP，因此对酶生物催化剂的计算活性筛选非常有益。

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引用次数: 0

Combined Electrodeposition and Electropolymerization Method to Produce Surface-Bound Polystyrenyl NHC Thin Films 电沉积与电聚合相结合制备表面结合聚苯乙烯NHC薄膜

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-10 DOI: 10.1039/d6sc00603e

Paul J. Ragogna, Jessica L Bosso, Garima Garg, Jordan N Bentley, Monika R Snowdon, Justin T. Lomax, Wai-Tung Shiu, Matthew J Turnbull, James J Noel, Cathleen Crudden, Joe Gilroy

Polymeric N-heterocyclic carbene (NHC) films offer a promising strategy for generating durable protective coatings on metals. Polystyrenyl NHC films were constructed on gold in a one step process that combined electrodeposition and electropolymerization of styrenyl benzimidazolium halide precursors at -1.3 V vs Ag/AgCl for 5 min. Ellipsometry confirmed the nanometer scale films on Au were formed with thicknesses of 1.16 – 2.92 ± 0.15 nm, while non-polymerizable controls were ≤ 0.8 nm. Cyclic voltammetry showed strong surface passivation for all polystyrenyl NHC films relative to the monomeric analogues. Area selective deposition on the NHC precursors was evaluated on patterned Au/SiO2 with excellent selectivity factors up to 0.90. These results establish polystyrenyl NHC films as robust nanometer-thick inhibitor coatings that couple strong NHC–metal bonding with the hydrophobic insulating character of polystyrene.

聚合n -杂环碳（NHC）薄膜是一种很有前途的金属表面持久保护涂层。在-1.3 V vs Ag/AgCl条件下，采用电沉积和电聚合相结合的一步法制备了苯并咪唑卤化物前驱体聚苯乙烯NHC膜。椭偏仪证实，在Au上形成的纳米级薄膜厚度为1.16 ~ 2.92±0.15 nm，而不可聚合对照的薄膜厚度≤0.8 nm。循环伏安法表明，相对于单体类似物，所有聚苯乙烯NHC膜都具有较强的表面钝化作用。NHC前驱体在Au/SiO2上的区域选择性沉积具有优异的选择性因子，可达0.90。这些结果表明，聚苯乙烯NHC薄膜是一种坚固的纳米厚抑制剂涂层，它将聚苯乙烯的疏水绝缘特性与强NHC -金属键结合在一起。

引用次数: 0

Metal-Centered X-ray Absorption and Emission Spectroscopy of Iron Corroles: Implications for Ligand Non-Innocence † 铁的金属中心x射线吸收和发射光谱：配体非无罪的意义

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-10 DOI: 10.1039/d6sc00669h

Meiyuan Guo, Abraham Alemayehu, Augustin Braun, Sang-Jun Lee, Dimosthenis Sokaras, Edward I. Solomon, Abhik Ghosh, Thomas Kroll

Determining the electronic structure of transition metal complexes with non-innocent ligands is challenging, both experimentally and theoretically. In this study, we investigate the electronic structure of iron corrole nitrosyl (Fe[TPC](NO), TPC=meso-triphenylcorrole) using a combination of Fe L-edge and K pre-edge X-ray absorption spectroscopy (XAS), Kβ X-ray emission spectroscopy (XES), and multiconfigurational calculations. A key debate revolves around the distribution of radical character on the ligand and the spin/oxidation state of the iron center. The experimental spectra reveal that the Fe center adopts a low-spin configuration, characterized as either Fe II or Fe III with strong π backbonding and little spin polarization. Calculations identified Fe[TPC](NO) primarily as {FeNO} 6 with a corrole 3 -, where {FeNO} 6 unit exhibits ferric character. However, no localized hole was found in the iron t 2g orbital due to strong covalent mixing with NO π* orbitals. The occupation of the Fe 3dz 2 orbital, and thus the radical character on the corrole ligand, is highly sensitive to the axial ligand environment. This was supported by wavefunction analysis over varying Fe-NO distances and comparison with iron corrole chloride (Fe[TPC]Cl), which displayed significant radical character on the corrole ligand due to the weak axial ligand. These findings provide critical insights into ligand innocence and covalency in metal corrole systems, offering a foundation for understanding other highly covalent transition metal systems.

确定过渡金属配合物与非无害配体的电子结构是具有挑战性的，实验和理论。在本研究中，我们利用Fe l边和K前边x射线吸收光谱（XAS）、Kβ x射线发射光谱（XES）和多构型计算相结合的方法研究了铁螯合物亚硝基（Fe[TPC](NO)， TPC=中三苯基螯合物）的电子结构。一个关键的争论围绕着配体上自由基特征的分布和铁中心的自旋/氧化态。实验光谱表明，Fe中心呈低自旋构型，具有较强的π背键和较小的自旋极化。计算结果表明，Fe[TPC]（NO）主要为{FeNO} 6，其中{FeNO} 6具有铁元素特征。然而，由于与no π*轨道的强共价混合，在铁t 2g轨道上没有发现局域空穴。Fe 3dz2轨道的占据，以及相应配体上的自由基特征，对轴向配体环境高度敏感。不同Fe- no距离的波函数分析和与氯化铁（Fe[TPC]Cl）的比较支持了这一点，由于弱轴向配体，氯化铁在氯化铁配体上表现出明显的自由基特征。这些发现提供了对金属辅助体系中配体无性和共价的重要见解，为理解其他高共价过渡金属体系提供了基础。

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引用次数: 0

Why and When Does Lattice Oxygen Participate in Oxygen Evolution? 晶格氧为什么以及何时参与氧演化？

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-10 DOI: 10.1039/d6sc00812g

Arun Karmakar, Asha K Satheesan, Subrata Kundu

Why does lattice oxygen contribute to the oxygen evolution reaction (OER) in some oxides and hydroxides, while remaining completely inactive in others that seem to have similar electronic properties? This Perspective argues that lattice oxygen redox does not occur merely due to high metal valence or strong metal-oxygen covalency. It only takes place when two linked conditions are met: (i) the oxidation of transition metals reaches an electronic saturation point that adds oxidative charge to oxygen ligands, and (ii) the lattice can structurally adapt to oxygen removal and vacancy healing during turnover. We demonstrate that various surface-engineering strategies-such as doping, creating heterostructures, modifying interlayers, and anchoring single atoms-work together by lowering charge-transfer energy, improving TM-O covalency, and making additional metal oxidation less stable. However, only materials with enough lattice flexibility can turn this electronic state into functional lattice oxygen redox. By separating the electronic basis of oxygen hole formation from the structural need for vacancy accommodation, this perspective offers a chemistry-based framework that clarifies both the development and the scarcity of the lattice oxygen mechanism in OER catalysts.

为什么晶格氧在一些氧化物和氢氧化物中有助于析氧反应（OER），而在其他似乎具有类似电子性质的物质中却完全不活跃？这一观点认为，晶格氧氧化还原不仅仅是由于高金属价或强金属氧共价而发生的。它只有在满足两个相关条件时才会发生：(i)过渡金属的氧化达到电子饱和点，从而为氧配体增加氧化电荷；（ii）晶格在结构上能够适应氧的去除和空位的修复。我们证明了各种表面工程策略，如掺杂、创造异质结构、修饰中间层和锚定单原子，通过降低电荷转移能、提高TM-O共价和降低额外金属氧化的稳定性来协同工作。然而，只有具有足够晶格柔韧性的材料才能将这种电子态转化为功能晶格氧氧化还原。通过将氧空穴形成的电子基础与空位容纳的结构需求分离开来，这一观点提供了一个基于化学的框架，澄清了OER催化剂中晶格氧机制的发展和稀缺性。

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引用次数: 0

Photoluminescence of ligand-protected gold nanoclusters: progress in experimental and theoretical studies 配体保护金纳米团簇的光致发光：实验与理论研究进展

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-10 DOI: 10.1039/d6sc00001k

Kang Li, Pu Wang, Yong Pei

Ligand-protected gold nanoclusters, with their small sizes and atomically precise structures, exhibit unique photophysical properties that position them as promising candidates for applications in bioimaging, sensing, and optoelectronics. However, except for a few ligand-protected gold nanoclusters, their photoluminescence quantum yield (PLQY) is still relatively low, and the underlying emission mechanisms are not yet fully elucidated. This review highlights recent experimental and theoretical advances aimed at enhancing and elucidating the photoluminescence (PL) mechanisms of ligand-protected gold nanoclusters. Experimentally, strategies such as heterometallic doping, ligand engineering, and structural rigidification have been employed to promote radiative transitions and suppress nonradiative decay, resulting in substantial improvements in PLQY. Theoretically, methods including density functional theory (DFT), time-dependent density functional theory (TDDFT), and nonadiabatic molecular dynamics (NA-MD) have provided important insights into the PL origin, emission pathways, and excited-state dynamics of ligand-protected gold nanoclusters. These advances will deepen our understanding of structure–property relationships in ligand-protected gold nanoclusters and pave the way for the rational design of highly emissive gold nanoclusters.

配体保护的金纳米团簇具有小尺寸和原子精确的结构，具有独特的光物理特性，这使它们成为生物成像、传感和光电子学应用的有希望的候选者。然而，除了少数配体保护的金纳米团簇外，它们的光致发光量子产率（PLQY）仍然相对较低，其潜在的发射机制尚未完全阐明。本文综述了近年来旨在加强和阐明配体保护金纳米团簇光致发光机制的实验和理论进展。实验上，异质金属掺杂、配体工程和结构刚性等策略被用于促进辐射跃迁和抑制非辐射衰变，从而大大改善了PLQY。从理论上讲，包括密度泛函理论（DFT）、时间依赖密度泛函理论（TDDFT）和非绝热分子动力学（NA-MD）在内的方法为研究配体保护金纳米团簇的PL起源、发射途径和激发态动力学提供了重要的见解。这些进展将加深我们对配体保护金纳米团簇结构-性能关系的理解，并为合理设计高发射金纳米团簇铺平道路。

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引用次数: 0

Spin-regulated d-p hybridization enables high energy density and wide temperature operation of Na₃V₂(PO₄)₂O₂F-type cathodes for sodium-ion batteries. 自旋调节d-p杂化使钠离子电池用Na3V2(PO4) 2o2f型阴极具有高能量密度和宽温度工作特性。

IF 7.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-10 DOI: 10.1039/d6sc00912c

Qiang Fu, Qin He, Fangxiang Song, Xianquan Ao, Hanxiao Liu, Yang Cao, Rong Li, Keliang Wang, Jing Li, Cuiqin Li, Yao Xiao

As a member of the sodium superionic conductor (NASICON) family, Na₃V₂(PO₄)₂O₂F (NVPOF) has attracted tremendous research interest owing to its high operating voltage and excellent structural stability. It is well established that NVPOF cathodes are electron-ion mixed conductors. However, improving electron or ionic conductivity via a single approach fails to effectively enhance the rapid sodium storage capability, which impedes their practical application in sodium-ion batteries. Herein, the electronic and ionic conductivities were enhanced through a transition-metal/fluorine dual-doping method. The introduction of transition metals with different spin states adjusted the spacing between the V 3d _xz -O 2p _x bond and the Fermi level, thereby improving the material's intrinsic conductivity. Meanwhile, the introduction of F atoms effectively optimized the diffusion kinetics of Na⁺. In particular, Na₃(VO)_1.9Fe_0.1(PO₄)₂F_1.1 (NVPOF-Fe) is obtained by dual-doping with high-spin Fe³⁺/F^-. It has considerable specific capacity and power density at 100C (80 mA h g^-1, 245 Wh kg^-1) and retains 90.6% capacity after 2500 cycles at 20C. The assembled NVPOF-Fe‖hard-carbon full cell exhibits excellent capacity and cycling stability at -20 °C, 25 °C, and 45 °C, respectively. This work provides a new paradigm for the development of advanced sodium-ion battery cathodes.

Na3V2(PO4)2O2F （NVPOF）作为钠超离子导体（NASICON）家族的一员，由于其高工作电压和优异的结构稳定性而引起了广泛的研究兴趣。NVPOF阴极是一种电子-离子混合导体。然而，通过单一途径提高电子或离子电导率并不能有效提高钠的快速存储能力，这阻碍了它们在钠离子电池中的实际应用。在此，通过过渡金属/氟双掺杂方法增强了电子和离子电导率。引入具有不同自旋态的过渡金属调整了v3d xz -O 2p x键与费米能级之间的间距，从而提高了材料的本征电导率。同时，F原子的引入有效地优化了Na+的扩散动力学。通过高自旋Fe3+/F-双掺杂，得到了Na3(VO)1.9Fe0.1(PO4)2F1.1 （NVPOF-Fe）。它在100C （80 mA h g- 1,245 Wh kg-1）下具有相当大的比容量和功率密度，在20C下循环2500次后仍保持90.6%的容量。组装的NVPOF-Fe‖硬碳全电池分别在-20°C， 25°C和45°C下表现出优异的容量和循环稳定性。这项工作为开发先进的钠离子电池阴极提供了新的范例。

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引用次数: 0

Photoinduced intramolecular S-α-C(sp³)-H functionalization enabled by an electron donor-acceptor complex-Mediated radical relay. 由电子供体-受体络合物介导的自由基接力实现的光诱导分子内S-α-C(sp3)-H功能化。

IF 7.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-10 DOI: 10.1039/d6sc01281g

Tiantian Xu, Ran Hong, Tong Lu, Denghua Zhu, Jiong Yu, Min Wang, Pinhua Li

We describe a consecutive reaction of 2-alkynylthioanisoles and 4-cyanopyridine enabled by EDA complex photoactivation, which facilitates the sequential S-α-C(sp³)-H bond activation, cyclization and radical coupling under mild conditions. A variety of 3-(4-pyridylbenzyl)benzothiophenes and benzoselenophenes were synthesized via a single-step process. Mechanistic investigations indicate that EDA complexes between thioethers and 4-cyanopyridines are crucial to this process.

我们描述了一个由EDA光激活引发的2-炔基硫甲醚与4-氰吡啶的连续反应，在温和的条件下促进了S-α-C(sp3)-H键的顺序活化、环化和自由基偶联。采用一步法合成了多种3-（4-吡啶基苄基）苯并噻吩和苯并硒吩。机理研究表明，硫醚和4-氰吡啶之间的EDA配合物对这一过程至关重要。

引用次数: 0

Formation of Cyclopentanes and Cyclopropanes through Alkylation of Benzylic Anions using Ethers, Thioethers and Alcohols as substrates under Grubbs-Stoltz (Et3SiH/KOtBu) conditions. 在grubb - stoltz （Et3SiH/KOtBu）条件下，以醚、硫醚和醇为底物，苯基阴离子烷基化生成环戊烷和环丙烷。

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-10 DOI: 10.1039/d5sc10055k

Alexander J. Stewart, Daniela Dimitrova, Scott T. M. Logan, Cassie Pratley, Jonathan D. Bell, Katy McGonigal, Anna Lauer, Sabine Fenner, Simon M. Nicolle, Stuart G. Leach, John Murphy

Reaction of diarylmethanes with the Grubbs-Stoltz reagent (KOtBu + Et₃SiH) using THF as solvent led to diarylcyclopentanes through an unprecedented double-alkylation reaction, with four of the carbons of the cyclopentane coming from THF. In like manner, reaction of diarylmethanes with the same reagent in 1,4-dioxane as solvent led to double-alkylation to form diarylcyclopropanes, with two of the cyclopropane carbons coming from 1,4-dioxane. Monoalkylated substrates that were likely intermediates on the dialkylation pathway were subjected to the same conditions, leading to cyclisations to form cyclopentanes and cyclopropanes. The cyclisation chemistry also extended to formation of monoarylcyclopropanes from reaction of the corresponding benzylpotassium reagents with ethers, alcohols, sulfides, sulfoxides and sulfones.

二芳基甲烷以四氢呋喃为溶剂与grubb - stoltz试剂（KOtBu + Et3SiH）反应，通过前所未有的双烷基化反应生成二芳基环戊烷，其中环戊烷的四个碳来自四氢呋喃。同样，二芳基甲烷以同样的试剂在1,4-二恶烷作溶剂下反应，双烷基化生成二芳基环丙烷，其中两个环丙烷碳来自1,4-二恶烷。可能是二烷基化途径中间体的单烷基化底物受到相同的条件，导致环化形成环戊烷和环丙烷。环化化学还扩展到由相应的苯钾试剂与醚、醇、硫化物、亚砜和砜反应生成单芳基环丙烷。

引用次数: 0

Chiral manganese halide isomers: decoding spatial stacking effect on second-Harmonic generation circular dichroism 手性卤化锰异构体：解码二次谐波代圆二色性的空间堆叠效应

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-10 DOI: 10.1039/d5sc09866a

Jing Li, Jianwu Wei, Qiulian Luo, Wei Pang, Hongming Liu, Peican Chen, Liya Zhou, Jin Zhong Zhang, Binbin Luo, qi pang

Chiral hybrid metal halides (CHMHs) represent promising candidates for chiral optoelectronics and nonlinear optics (NLO). However, the effect of spatial stacking on second-harmonic generation circular dichroism (SHG-CD) in CHMHs has not been well understood. Herein, we constructed two pairs of chiral manganese(II) halide isomers (R)-α-Mn, (S)-α-Mn, (R)-β-Mn and (S)-β-Mn, which crystallize in chiral space groups C2221 and P21, respectively. They exhibit near-unity photoluminescence quantum yields and efficient circularly polarized luminescence with asymmetry factors (glum) of ~1.0×10-3. Additionally, these isomers show significant NLO responses with SHG intensity of 2.03 and 1.30 times that of KH2PO4 and polarization ratios of up to 0.87 and 0.57 for (R)-α-Mn and (R)-β-Mn, respectively. More importantly, (R)-α-Mn demonstrates an intense SHG-CD response with a SHG-CD factor (gSHG-CD) value of –0.56, about 1.86 times larger than that of (R)-β-Mn (–0.30). Compared to (R)- and (S)-β-Mn, the stacking mode of (R)- and (S)-α-Mn generates a more dense asymmetric hydrogen-bonding network, which greatly distorts [MnBr4]2- tetrahedra and enhances the dipole moment, thereby significantly improving the SHG-CD value. This work elucidates the pivotal role of spatial stacking in chiral NLO materials.

手性杂化金属卤化物（CHMHs）是手性光电子学和非线性光学（NLO）领域有前景的研究对象。然而，空间叠加对chmh中二次谐波产生的圆二色性（SHG-CD）的影响尚不清楚。本文构建了两对手性卤化锰（II）异构体(R)-α-Mn, (S)-α-Mn, (R)-β-Mn和(S)-β-Mn，它们分别在C2221和P21的手性空间群中结晶。它们表现出接近统一的光致发光量子产率和有效的圆偏振发光，不对称因子（胶）为~1.0×10-3。这些异构体的SHG强度分别是KH2PO4的2.03倍和1.30倍，(R)-α-Mn和(R)-β-Mn的极化比分别高达0.87和0.57。更重要的是，(R)-α-Mn表现出强烈的SHG-CD响应，其SHG-CD因子（gSHG-CD）值为-0.56，约为(R)-β-Mn的1.86倍（-0.30）。与(R)-和(S)-β- mn相比，(R)-和(S)-α- mn的堆叠模式产生了更致密的不对称氢键网络，使[MnBr4]2-四面体发生了极大的扭曲，偶极矩增强，从而显著提高了SHG-CD值。这项工作阐明了空间堆叠在手性NLO材料中的关键作用。

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引用次数: 0

High-Temperature Chemical Oxidation Pathways in Lithium-ion Batteries: Mechanistic insights into Ethylene Carbonate Decomposition 锂离子电池中的高温化学氧化途径：对碳酸乙烯分解的机理见解

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2026-03-09 DOI: 10.1039/d6sc00426a

Leon Schmidt, Kie Hankins, Jorge Valenzuela, Rene Windiks, Adrian Lindner, Ruth Witzel, Yuchen Qiu, Edwin Knobbe, Ulrike Krewer

A thermal event remains a safety challenge for lithium-ion batteries due to the selfreinforcing nature of the exothermic reactions occurring at elevated temperatures. Higher states of charge have been shown to exacerbate the onset and severity of a thermal event. For cells containing Ni-rich layered oxide-based electrodes, this has been attributed to the increased instability of the material leading to lattice oxygen release. The degradation reactions on the electrode/electrolyte interface triggered by this oxygen remain insufficiently understood. In this study, we investigate high-temperature degradation pathways of ethylene carbonate (EC)-based electrolytes in contact with Ni-rich positive electrode active materials up to 130 °C. By combining in-situ high-temperature online electrochemical mass spectrometry with post-mortem analyses, we identify and validate key degradation intermediates and products. Two distinct EC oxidation pathways are revealed: one activated at high voltages, and the other one initiated by traces of water impurities. Complementary density functional theory calculations show the reactions are thermodynamically favorable and quantify the heat release associated with each pathway. Both pathways produce significant heat and lead to gassing of CO₂ and H₂ . These findings suggest significant contribution of EC to thermal gas evolution and exothermicity under abuse conditions, thereby establishing a mechanistic link between electrolyte chemistry and thermal events. This integrated experimental-computational approach provides critical insights to guide improved electrolyte formulations and predictive thermal models.

热事件仍然是锂离子电池的安全挑战，因为在高温下发生的放热反应具有自我强化的性质。较高的电荷状态已被证明会加剧热事件的发生和严重程度。对于含有富镍层状氧化物基电极的电池，这归因于材料不稳定性的增加，导致晶格氧释放。这种氧在电极/电解质界面上引发的降解反应尚不清楚。在这项研究中，我们研究了碳酸乙烯基（EC）电解质与富镍正极活性材料接触时高达130°C的高温降解途径。通过将原位高温在线电化学质谱法与死后分析相结合，我们确定并验证了关键的降解中间体和产物。揭示了两种不同的EC氧化途径：一种是在高压下激活的，另一种是由微量的水杂质引起的。互补密度泛函理论计算表明，这些反应在热力学上是有利的，并量化了与每个途径相关的热释放。这两种途径都会产生大量的热量，并导致二氧化碳和氢气的产生。这些发现表明，在滥用条件下，EC对热气体演化和放热有重要贡献，从而建立了电解质化学和热事件之间的机制联系。这种集成的实验计算方法为指导改进的电解质配方和预测热模型提供了关键的见解。

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引用次数: 0