Journal of Energy Chemistry最新文献_第6页

In situ evolved phase and heterostructure boosting nitrate to ammonia synthesis for enhanced energy supply in Zn-NO3− battery 原位演化相和异质结构促进硝酸-氨合成，增强 Zn-NO3 电池的能量供应

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-29 DOI: 10.1016/j.jechem.2024.10.023

Chunming Yang , Feng Yue , Tingting Wei , Xiang Li , Wangchuan Zhu , Chuantao Wang , Yanzhong Zhen , Feng Fu , Yucang Liang

Revealing the dynamic reconfiguration of catalysts and the evolution of active species during catalysis, elucidating and regulating the reconfiguration mechanism are paramount to the development of high-performance electrochemical nitrate reduction (NO₃RR) to ammonia. In-situ characterizations can precisely track reaction process and unveil the origin of activity enhancement. Here, in-situ reconstruction of pre-catalyst Co₃O₄ fabricates a stable heterojunction Co(OH)₂/Co₃O₄ to boost NO₃RR to ammonia. In-situ generated heterojunction accelerates the transformation of *NO₃ to *NO₂, while Co(OH)₂ promotes the dissociation of water to active *H species for the hydrogenation of *N species, and thereby improving the deoxygenation and hydrogenation ability of NO₃RR to NH₃ and achieving a high Faradaic efficiency (FE) about 96.2% and a high NH₃ production rate of 218.5 μmol h⁻¹ mg_cat⁻¹ at −0.3 V. Density functional theory (DFT) calculations verified that in-situ formed active species Co(OH)₂ on Co₃O₄ markedly decreased the energy barrier of *NO₃ → *NO₂ and accelerated the hydrogenation step of *NH → *NH₂ → *NH₃. Co(OH)₂/Co₃O₄ heterostructure-based Zn-NO₃⁻ cell achieves excellent energy supply (1.22 V), a high ammonia yield rate (48.9 µmol h⁻¹ cm⁻²), and a high FE (91%). The establishment of the structure–activity relationship during NO₃RR provides guidance for designing advanced electrode materials, and the in-situ evolution of species on the electrode surface unveils the intrinsic nature of improved catalytic performance.

揭示催化剂的动态重构和催化过程中活性物种的演变，阐明和调节重构机制，对于开发高性能电化学硝酸盐还原（NO3RR）制氨技术至关重要。原位表征可以精确跟踪反应过程并揭示活性增强的起源。在这里，原位重构前催化剂 Co3O4 制造出了稳定的异质结 Co(OH)2/Co3O4，从而促进了 NO3RR 到氨的反应。原位生成的异质结加速了*NO3向*NO2的转化，而Co(OH)2则促进水解离成活性*H物种，用于*N物种的氢化，从而提高了NO3RR向NH3的脱氧和氢化能力，实现了约96.密度泛函理论（DFT）计算证实，在 Co3O4 上原位形成的活性物种 Co(OH)2 显著降低了 *NO3 → *NO2 的能垒，加速了 *NH → *NH2 → *NH3 的氢化步骤。基于 Co(OH)2/Co3O4 异质结构的 Zn-NO3- 电池实现了出色的能量供应（1.22 V）、高氨产率（48.9 µmol h-1 cm-2）和高 FE（91%）。建立 NO3RR 过程中的结构-活性关系为设计先进的电极材料提供了指导，而电极表面物种的原位演化揭示了催化性能改善的内在本质。

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引用次数: 0

Physics-informed battery degradation prediction: Forecasting charging curves using one-cycle data 物理信息电池退化预测：利用单周期数据预测充电曲线

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-28 DOI: 10.1016/j.jechem.2024.10.018

Aihua Tang , Yuchen Xu , Jinpeng Tian , Xing Shu , Quanqing Yu

Accurately predicting battery degradation is crucial for battery system management. However, due to the complexities of aging mechanisms and limitations of historical data, comprehensively indicating battery degradation solely through maximum capacity loss assessment is challenging. While machine learning offers promising solutions, it often overlooks domain knowledge, resulting in reduced accuracy, increased computational burden and decreased interpretability. Here, this study proposes a method to predict the voltage-capacity (V-Q) curve during battery degradation with limited historical data. This process is achieved through two physically interpretable components: a lightweight interpretable physical model and a physics-informed neural network. These components incorporate domain knowledge into machine learning to improve V-Q curve prediction performance and enhance interpretability. Extensive validation was conducted on 52 batteries of different types under different testing conditions. The proposed method can accurately predict future V-Q curves for hundreds of cycles using only one-present-cycle V-Q curve, with root mean square error and mean absolute error basically less than 0.035 Ah and R² basically less than 98.5%. This means that incremental capacity curves can be extracted from the predicted results for a more comprehensive and accurate battery degradation analysis. Furthermore, the method can flexibly adjust prediction length and density to cater to the practical needs of long-cycle prediction and data generation. This study provides a viable method for rapid degradation prediction and is expected to be generalized to in-vehicle implementations.

准确预测电池老化对电池系统管理至关重要。然而，由于老化机制的复杂性和历史数据的局限性，仅通过最大容量损失评估来全面显示电池老化具有挑战性。虽然机器学习提供了有前途的解决方案，但它往往忽略了领域知识，导致准确性降低、计算负担加重和可解释性下降。在此，本研究提出了一种方法，利用有限的历史数据预测电池退化过程中的电压-容量（V-Q）曲线。这一过程是通过两个物理可解释组件实现的：一个轻量级可解释物理模型和一个物理信息神经网络。这些组件将领域知识融入机器学习，以提高 V-Q 曲线预测性能并增强可解释性。在不同测试条件下，对 52 块不同类型的电池进行了广泛的验证。所提出的方法仅使用一次现循环 V-Q 曲线就能准确预测未来数百次循环的 V-Q 曲线，均方根误差和平均绝对误差基本小于 0.035 Ah，R2 基本小于 98.5%。这意味着可以从预测结果中提取增量容量曲线，进行更全面、更准确的电池退化分析。此外，该方法还能灵活调整预测长度和密度，以满足长周期预测和数据生成的实际需要。这项研究为快速退化预测提供了一种可行的方法，并有望推广到车载应用中。

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引用次数: 0

Building Li–S batteries with enhanced temperature adaptability via a redox-active COF-based barrier-trapping electrocatalyst 通过基于氧化还原活性 COF 的势垒捕获电催化剂，构建具有更强温度适应性的锂-S 电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-24 DOI: 10.1016/j.jechem.2024.10.019

Jie Xu , Acheng Zhu , Zhangyu Zheng , Yiming Qi , Yuwen Cheng , Yongjie Cao , Bo Peng , Lianbo Ma , Yonggang Wang

Covalent organic frameworks (COFs) are promising materials for mitigating polysulfide shuttling in lithium-sulfur (Li–S) batteries, but enhancing their ability to convert polysulfides across a wide temperature range remains a challenge. Herein, we introduce a redox-active COF (RaCOF) that functions as both a physical barrier and a kinetic enhancer to improve the temperature adaptability of Li–S batteries. The RaCOF constructed from redox-active anthraquinone units accelerates polysulfide conversion kinetics through reversible C=O/C-OLi transformations within a voltage range of 1.7 to 2.8 V (vs. Li⁺/Li), optimizing sulfur redox reactions in ether-based electrolytes. Unlike conventional COFs, RaCOF provides bidentate trapping of polysulfides, increasing binding energy and facilitating more effective polysulfide management. In-situ XRD and ToF-SIMS analyses confirm that RaCOF enhances polysulfide adsorption and promotes the transformation of lithium sulfide (Li₂S), leading to better sulfur cathode reutilization. Consequently, RaCOF-modified Li–S batteries demonstrate low self-discharge (4.0% decay over a 7-day rest), excellent wide-temperature performance (stable from −10 to + 60 °C), and high-rate cycling stability (94% capacity retention over 500 cycles at 5.0 C). This work offers valuable insights for designing COF structures aimed at achieving temperature-adaptive performance in rechargeable batteries.

共价有机框架（COF）是减轻锂硫（Li-S）电池中多聚硫化物穿梭现象的理想材料，但提高其在宽温度范围内转化多聚硫化物的能力仍是一项挑战。在此，我们介绍一种氧化还原活性 COF（RaCOF），它既是物理屏障，又是动力学增强剂，可提高锂-硫电池的温度适应性。由具有氧化还原活性的蒽醌单元构建而成的 RaCOF 可在 1.7 至 2.8 V（相对于 Li+/Li）的电压范围内通过 C=O/C-OLi 的可逆转化加速多硫化物的转化动力学，从而优化醚基电解质中的硫氧化还原反应。与传统的 COF 不同，RaCOF 提供了对多硫化物的双齿捕集，增加了结合能，有利于更有效地管理多硫化物。原位 XRD 和 ToF-SIMS 分析证实，RaCOF 可增强对多硫化物的吸附，促进硫化锂（Li2S）的转化，从而提高硫阴极的再利用率。因此，RaCOF 改性锂-S 电池表现出较低的自放电率（静置 7 天衰减 4.0%）、优异的宽温性能（在 -10 至 + 60 °C 范围内稳定）和高倍率循环稳定性（在 5.0 C 下循环 500 次，容量保持率 94%）。这项研究为设计 COF 结构以实现充电电池的温度适应性能提供了宝贵的见解。

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引用次数: 0

Introducing strong metal–oxygen bonds to suppress the Jahn-Teller effect and enhance the structural stability of Ni/Co-free Mn-based layered oxide cathodes for potassium-ion batteries 引入强金属氧键以抑制贾恩-泰勒效应并增强用于钾离子电池的无镍/无钴锰基层状氧化物阴极的结构稳定性

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-24 DOI: 10.1016/j.jechem.2024.10.017

Yicheng Lin , Shaohua Luo , Pengyu Li , Jun Cong , Wei Zhao , Lixiong Qian , Qi Sun , Shengxue Yan

Mn-based layered oxides (KMO) have emerged as one of the promising low-cost cathodes for potassium-ion batteries (PIBs). However, due to the multiple-phase transitions and the distortion in the MnO₆ structure induced by the Jahn-Teller (JT) effect associated with Mn-ion, the cathode exhibits poor structural stability. Herein, we propose a strategy to enhance structural stability by introducing robust metal–oxygen (M–O) bonds, which can realize the pinning effect to constrain the distortion in the transition metal (TM) layer. Concurrently, all the elements employed have exceptionally high crustal abundance. As a proof of concept, the designed K_0.5Mn_0.9Mg_0.025Ti_0.025Al_0.05O₂ cathode exhibited a discharge capacity of approximately 100 mA h g⁻¹ at 20 mA g⁻¹ with 79% capacity retention over 50 cycles, and 73% capacity retention over 200 cycles at 200 mA g⁻¹, showcased much better battery performance than the designed cathode with less robust M–O bonds. The properties of the formed M–O bonds were investigated using theoretical calculations. The enhanced dynamics, mitigated JT effect, and improved structural stability were elucidated through the in-situ X-ray diffractometer (XRD), in-situ electrochemical impedance spectroscopy (EIS) (and distribution of relaxation times (DRT) method), and ex-situ X-ray absorption fine structure (XAFS) tests. This study holds substantial reference value for the future design of cost-effective Mn-based layered cathodes for PIBs.

锰基层氧化物（KMO）已成为钾离子电池（PIB）中一种前景广阔的低成本阴极。然而，由于多相转变以及与锰离子相关的贾恩-泰勒（JT）效应引起的 MnO6 结构畸变，该阴极的结构稳定性较差。在此，我们提出了一种增强结构稳定性的策略，即引入稳健的金属氧（M-O）键，从而实现针销效应，限制过渡金属（TM）层的畸变。同时，所采用的所有元素都具有极高的地壳丰度。作为概念验证，所设计的 K0.5Mn0.9Mg0.025Ti0.025Al0.05O2 阴极在 20 mA g-1 下的放电容量约为 100 mA h g-1，在 50 次循环中的容量保持率为 79%，在 200 mA g-1 下的 200 次循环中的容量保持率为 73%。我们通过理论计算研究了所形成的 M-O 键的特性。通过原位 X 射线衍射仪 (XRD)、原位电化学阻抗光谱 (EIS)（和弛豫时间分布 (DRT) 方法）和原位 X 射线吸收精细结构 (XAFS) 测试，阐明了 M-O 键的动态增强、JT 效应减弱和结构稳定性提高。这项研究对今后设计具有成本效益的锰基层状阴极用于 PIB 具有重要的参考价值。

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引用次数: 0

Improving structure stability of single-crystalline Ni-rich cathode at high voltage by element gradient doping and interfacial modification 通过元素梯度掺杂和界面改性提高单晶富镍阴极在高压下的结构稳定性

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-23 DOI: 10.1016/j.jechem.2024.10.015

Ruijuan Wang , Yixu Zhang , Zhi Li , Lei Wu , Jiarui Chen , Xiaolin Liu , Hui Hu , Hao Ding , Shuang Cao , Qiliang Wei , Xianyou Wang

Single-crystalline Ni-rich cathodes can provide high energy density and capacity retention rates for lithium-ion batteries (LIBs). However, single-crystalline Ni-rich cathodes experience severe transition metal dissolution, irreversible phase transitions, and reduced structural stability during prolonged cycling at high voltage, which will significantly hinder their practical application. Herein, a Li₄TeO₅ surface coating along with bulk Te-gradient doping strategy is proposed and developed to solve these issues for single-crystalline Ni-rich LiNi_0.90Co_0.05Mn_0.05O₂ cathode (LTeO-1.0). It has been found that the bulk Te⁶⁺ gradient doping can lead to the formation of robust Te–O bonds that effectively inhibit H2-H3 phase transformations and reinforce the lattice framework, and the in-situ Li₄TeO₅ coating layer can act as a protective layer that suppresses the parasitic reactions and grain fragmentation. Besides, the modified material exhibits a higher Young’s modulus, which will be conducive to maintaining significant structural and electrochemical stability under high-voltage conditions. Especially, the LTeO-1.0 electrode shows the improved Li⁺ diffusion kinetics and thermodynamic stability as well as high capacity retention of 95.83% and 82.12% after 200 cycles at the cut-off voltage of 4.3 and 4.5 V. Therefore, the efficacious dual-modification strategy will definitely contribute to enhancing the structural and electrochemical stability of single-crystalline Ni-rich cathodes and developing their application in LIBs.

单晶富镍阴极可为锂离子电池（LIB）提供高能量密度和容量保持率。然而，单晶富镍阴极在长时间的高电压循环过程中会出现严重的过渡金属溶解、不可逆相变和结构稳定性降低，这将极大地阻碍其实际应用。本文提出并开发了一种 Li4TeO5 表面涂层和块状 Te 梯度掺杂策略，以解决单晶富 Ni-LiNi0.90Co0.05Mn0.05O2 阴极（LTeO-1.0）的这些问题。研究发现，块体 Te6+ 梯度掺杂可形成稳固的 Te-O 键，有效抑制 H2-H3 相变并加固晶格框架，原位 Li4TeO5 涂层可作为保护层抑制寄生反应和晶粒破碎。此外，改性后的材料具有更高的杨氏模量，有利于在高压条件下保持显著的结构和电化学稳定性。特别是，LTeO-1.0 电极在 4.3 V 和 4.5 V 截断电压下循环 200 次后，Li+ 扩散动力学和热力学稳定性得到改善，容量保持率分别达到 95.83% 和 82.12%。因此，高效的双重改性策略必将有助于提高单晶富镍阴极的结构和电化学稳定性，并开发其在 LIB 中的应用。

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引用次数: 0

Functionalized fillers as “ions relay stations” enabling Li+ ordered transport in quasi-solid electrolytes for high-stability lithium metal batteries 作为 "离子中继站 "的功能化填料可实现准固体电解质中 Li+ 的有序传输，用于制造高稳定性锂金属电池

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-23 DOI: 10.1016/j.jechem.2024.09.069

Kang Du, Chen Sun, Yimin Xuan

Quasi-solid-state lithium-metal batteries (QSLMBs) are promising candidates for next-generation battery systems due to their high energy density and enhanced safety. However, their practical application has been hindered by low ionic conductivity and the growth of lithium dendrites. To achieve ordered transport of Li⁺ ions in quasi-solid electrolytes (QSEs), improve ionic conductivity, and homogenize Li⁺ fluxes on the surface of the lithium metal anode (LMA), we propose a novel method. This method involves constructing “ion relay stations” in QSEs by introducing cyano-functionalized boron nitride nanosheets into pentaerythritol tetraacrylate (PETEA)-based polymer electrolytes. The functionalized boron nitride nanosheets promote the dissociation of lithium salts through ion-dipole interactions, optimizing the solvated structure to facilitate the orderly transport of Li⁺ ions, resulting in an ionic conductivity of 2.5 × 10⁻³ S cm⁻¹ at 30 °C. Notably, this strategy regulates the Li⁺ distribution on the surface of the LMA, effectively inhibiting the growth of lithium dendrites. Li||Li symmetrical cells using this type of electrolyte maintain stability for over 2000 h at 2 mA cm⁻² and 2 mAh cm⁻². Additionally, with a high LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) loading of 8.5 mg cm⁻², the cells exhibit excellent cycling performance, retaining a high capacity after 400 cycles. This innovative QSE design strategy represents a significant advancement towards the development of high-performance QSLMBs.

准固态锂金属电池（QSLMB）具有能量密度高、安全性强等优点，是下一代电池系统的理想候选材料。然而，低离子电导率和锂枝晶的生长阻碍了它们的实际应用。为了实现 Li+ 离子在准固体电解质（QSE）中的有序传输，提高离子电导率，并均匀锂金属阳极（LMA）表面的 Li+ 通量，我们提出了一种新方法。这种方法是在季戊四醇四丙烯酸酯（PETEA）基聚合物电解质中引入氰基功能化氮化硼纳米片，从而在 QSE 中构建 "离子中继站"。功能化氮化硼纳米片通过离子-偶极子相互作用促进锂盐解离，优化溶解结构以促进 Li+ 离子的有序传输，从而在 30 °C 时产生 2.5 × 10-3 S cm-1 的离子电导率。值得注意的是，这种策略调节了锂聚合物表面的 Li+ 分布，有效抑制了锂枝晶的生长。使用这种电解质的锂||锂对称电池在 2 mA cm-2 和 2 mAh cm-2 的条件下可保持稳定超过 2000 小时。此外，在锂镍0.8Co0.1Mn0.1O2（NCM811）负载为 8.5 mg cm-2 的情况下，电池表现出卓越的循环性能，在循环 400 次后仍能保持高容量。这种创新的 QSE 设计策略标志着在开发高性能 QSLMB 方面取得了重大进展。

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引用次数: 0

Unraveling the exceptional kinetics of Zn||organic batteries in hydrated deep eutectic solution 揭示锌||有机电池在水合深共晶溶液中的特殊动力学特性

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-23 DOI: 10.1016/j.jechem.2024.10.016

Duo Chen , Yuanhang Wang , Tengyu Yao , Hang Yang , Laifa Shen

Intuitively, the solvation structure featuring stronger interacted sheath in deep eutectic solution (DES) electrolyte would result in sluggish interfacial charge transfer and intense polarization, which obstructs its practical application in emerging Zn based batteries. Unexpectedly, here we discover a Zn||organic battery with exceptional kinetics properties enabled by a hydrated DES electrolyte, which can render higher discharge capacity, smaller voltage polarization, and faster kinetics of charge transfer in comparison with conventional aqueous 3 M ZnCl₂ electrolyte, though its viscosity is two orders of magnitude higher than the latter. The improved kinetics of charge transfer and ion diffusion is demonstrated to originate from the local electron structure regulation of cathode in hydrated DES electrolyte. Furthermore, the DES electrolyte has also been shown to restrict parasitic reaction associated with active water by preferential urea-molecular adsorption on Zn surface and stronger water trapping in solvation structure, giving rise to long-term stable dendrite-free Zn plating/stripping. This work provides a new rationale for understanding electrochemical behaviors of organic cathodes in DES electrolyte, which is conducive to the development of high-performance Zn||organic batteries.

直观地说，深共晶溶液（DES）电解质中具有较强相互作用鞘的溶解结构会导致界面电荷转移迟缓和极化严重，从而阻碍其在新兴锌基电池中的实际应用。与传统的 3 M ZnCl2 水溶液电解液相比，水合 DES 电解液具有更高的放电容量、更小的电压极化和更快的电荷转移动力学，尽管其粘度比后者高出两个数量级。电荷转移和离子扩散动力学的改善源于水合 DES 电解质中阴极局部电子结构的调节。此外，DES 电解质还通过在 Zn 表面优先吸附尿素分子和加强溶解结构中的水捕获作用，限制了与活性水相关的寄生反应，从而实现了长期稳定的无树枝状 Zn 镀层/剥离。这项工作为理解有机阴极在 DES 电解液中的电化学行为提供了新的理论依据，有利于开发高性能 Zn||有机电池。

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引用次数: 0

Realizing interfacial coupled electron/ion transport through reducing the interfacial oxygen density of carbon skeletons for high-performance lithium metal anodes 通过降低高性能锂金属阳极碳骨架的界面氧密度实现界面耦合电子/离子传输

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-22 DOI: 10.1016/j.jechem.2024.09.063

Yao-Lu Ye , Yan Zhou , Huan Ye , Fei-Fei Cao

Lithium plating/stripping occurs at the anode/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase (SEI). The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition. Herein, we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film. This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils. The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film, which stabilized Li⁺ transfer through the Li/electrolyte interface. Moreover, the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction. The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface, which facilitates uniform Li deposition and improves Li anode performance. The Li/C anode shows a high initial Coulombic efficiency of 98% and a long-term lifespan of over 150 cycles at a practical low N/P (negative-to-positive) ratio of 1.44 in full cells.

锂镀层/剥离发生在阳极/电解质界面上，涉及来自集流器的电子流和来自固体-电解质间相（SEI）的锂离子迁移。界面电子/离子的双重连续快速传输是均匀锂沉积所必需的。在此，我们提出了一种通过合理调节界面电子密度和锂离子在 SEI 薄膜中的传输来提高锂金属负极性能的策略。这项关键技术包括通过调节纤维素前体纤维的排列来降低生物质衍生碳宿主的界面氧密度。较高的比表面积和较低的界面氧密度降低了局部电流密度，确保了形成薄而均匀的 SEI 膜，从而稳定了 Li+ 通过锂/电解质界面的转移。此外，改进的石墨化和相互连接的导电网络增强了碳的表面电负性，实现了不间断的电子传导。其结果是在阳极/电解质反应界面上实现了连续、快速的耦合界面电子/离子传输，从而促进了锂的均匀沉积，提高了锂阳极的性能。锂/碳阳极的初始库仑效率高达 98%，在全电池中的实际低 N/P（负极与正极）比为 1.44 时，其长期寿命超过 150 个循环。

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引用次数: 0

P-tuned FeN2 binuclear sites for boosted CO2 electro-reduction 用于促进二氧化碳电还原的 P 调节型 FeN2 双核位点

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-22 DOI: 10.1016/j.jechem.2024.10.011

Cao Guo , Sanshuang Gao , Jun Li , Menglin Zhou , Abdukader Abdukayum , Qingquan Kong , Yingtang Zhou , Guangzhi Hu

The recycling of CO₂ through electrochemical processes offers a promising solution for alleviating the greenhouse effect; however, the activation of CO₂ and desorption of *CO in electrocatalytic CO₂ reduction (ECR) frequently encounter high energy barriers and competitive hydrogen evolution reactions (HERs), which are urgent problems that need to be addressed. In this study, a catalyst (P₁₀₀–Fe–N/C) with homogeneous P–tuned FeN₂ binuclear sites (N₂PFe-FePN₂) was successfully synthesised, demonstrating satisfactory performance in the ECR to CO. P₁₀₀–Fe–N/C attains a peak FE_CO of 98.01% and a normalized TOF of 664.7 h⁻¹ at −0.7 V_RHE, surpassing the performance of the Fe binuclear catalyst without P and single-atoms catalysts. In the MEA cell, a FE_CO exceeding 90% can still be achieved. Density functional theory analysis indicates that the asymmetric coordination configuration induced by the incorporation of P facilitates a reduction in the system’s energy. The modulation of P results in the d-band centre of the catalyst being positioned closer to the Fermi level, which facilitates the interaction of the catalyst with CO₂, allowing more electrons to be injected into the CO₂ molecule at the Fe binuclear sites and inhibiting the HER. The P–tuned FeN₂ binuclear sites effectively lower the *CO desorption barrier.

通过电化学过程回收利用二氧化碳为缓解温室效应提供了一种前景广阔的解决方案；然而，在电催化二氧化碳还原（ECR）过程中，二氧化碳的活化和*CO的解吸经常会遇到高能量障碍和竞争性氢进化反应（HERs），这些都是亟待解决的问题。本研究成功合成了一种具有均相 P 调谐 FeN2 双核位点（N2PFe-FePN2）的催化剂（P100-Fe-N/C），在电催化 CO 还原中表现出令人满意的性能。P100-Fe-N/C 的峰值 FECO 为 98.01%，在 -0.7 VRHE 条件下的归一化 TOF 为 664.7 h-1，超过了不含 P 的 Fe 双核催化剂和单原子催化剂的性能。在 MEA 单元中，FECO 仍可超过 90%。密度泛函理论分析表明，P 的加入引起的不对称配位构型有助于降低系统能量。P 的调制使催化剂的 d 波段中心更接近费米级，从而促进了催化剂与 CO2 的相互作用，使更多的电子在 Fe 双核位点注入 CO2 分子，抑制了 HER。P调谐的 FeN2 双核位点有效降低了*CO 解吸障碍。

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引用次数: 0

Sulfur atom occupying surface oxygen vacancy to boost the charge transfer and stability for aqueous Bi2O3 electrode 硫原子占据表面氧空位，促进水性 Bi2O3 电极的电荷转移和稳定性

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-10-22 DOI: 10.1016/j.jechem.2024.10.012

Guangmin Yang , Jianyan Lin , Guanwu Li , Tian Li , Dong Wang , Weitao Zheng

Oxygen vacancies (O_v) within metal oxide electrodes can enhance mass/charge transfer dynamics in energy storage systems. However, construction of surface O_v often leads to instability in electrode structure and irreversible electrochemical reactions, posing a significant challenge. To overcome these challenges, atomic heterostructures are employed to address the structural instability and enhance the mass/charge transfer dynamics associated with phase conversion mechanism in aqueous electrodes. Herein, we introduce an atomic S–Bi₂O₃ heterostructure (sulfur (S) anchoring on the surface O_v of Bi₂O₃). The integration of S within Bi₂O₃ lattice matrix triggers a charge imbalance at the heterointerfaces, ultimately resulting in the creation of a built-in electric field (BEF). Thus, the BEF attracts OH⁻ ions to be adsorbed onto Bi within the regions of high electron cloud overlap in S–Bi₂O₃, facilitating highly efficient charge transfer. Furthermore, the anchored S plays a pivotal role in preserving structural integrity, thus effectively stabilizing the phase conversion reaction of Bi₂O₃. As a result, the S–Bi₂O₃ electrode achieves 72.3 mA h g⁻¹ at 10 A g⁻¹ as well as high-capacity retention of 81.9% after 1600 cycles. Our innovative S–Bi₂O₃ design presents a groundbreaking approach for fabricating electrodes that exhibit efficient and stable mass and charge transfer capabilities. Furthermore, it enhances our understanding of the underlying reaction mechanism within energy storage electrodes.

金属氧化物电极中的氧空位（Ov）可增强储能系统中的质量/电荷转移动力学。然而，表面氧空位的形成往往会导致电极结构的不稳定性和不可逆的电化学反应，从而带来巨大的挑战。为了克服这些挑战，我们采用原子异质结构来解决结构不稳定问题，并增强水电极中与相转化机制相关的质量/电荷转移动力学。在此，我们介绍一种原子 S-Bi2O3 异质结构（硫（S）锚定在 Bi2O3 的表面 Ov 上）。S 在 Bi2O3 晶格基质中的整合引发了异质界面的电荷不平衡，最终导致内置电场（BEF）的产生。因此，内置电场吸引 OH 离子在 S-Bi2O3 的高电子云重叠区域内吸附到 Bi 上，从而促进了高效的电荷转移。此外，锚定的 S 在保持结构完整性方面起着关键作用，从而有效地稳定了 Bi2O3 的相转化反应。因此，S-Bi2O3 电极在 10 A g-1 的条件下可达到 72.3 mA h g-1，并在 1600 个循环后实现 81.9% 的高容量保持率。我们创新的 S-Bi2O3 设计为制造具有高效稳定的质量和电荷转移能力的电极提供了一种开创性的方法。此外，它还加深了我们对储能电极内部基本反应机制的理解。

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