Pub Date : 2025-04-24DOI: 10.1016/j.esci.2025.100425
Jiping Sun , Bichao Wu , Guangchao Li , Zhixing Wang , Xinhai Li , Huajun Guo , Guochun Yan , Hui Duan , Wenchao Zhang , Min Liu , Jiexi Wang
The electrocatalytic C–N coupling reaction involving carbon dioxide (CO2) and nitrogenous small molecules has recently emerged as a subject of considerable interest within the field of urea synthesis. This approach has the potential to facilitate the clean, sustainable production of urea, thereby contributing to the attainment of carbon neutrality and the advancement of artificial nitrogen cycling. Nevertheless, electrocatalytic urea synthesis still faces significant challenges due to the difficulty of balancing the co-activation of carbon and nitrogen sources and the subsequent catalytic C–N coupling of in situ-generated species, as well as competing reactions. To overcome these challenges, there is a growing emphasis on the research of gas diffusion electrodes (GDEs) and the design of electrode materials. This article provides a comprehensive review of the C–N coupling mechanisms, the classification of catalysts, the electrocatalyst design and optimization strategies, and the fundamental functions and importance of GDEs in electrocatalytic C–N coupling reactions. It also provides insights and perspectives on the major challenges and future research directions for GDEs and electrocatalysts in electrocatalytic urea synthesis.
{"title":"Catalyst and gas diffusion electrode design toward C–N coupling for urea electrosynthesis","authors":"Jiping Sun , Bichao Wu , Guangchao Li , Zhixing Wang , Xinhai Li , Huajun Guo , Guochun Yan , Hui Duan , Wenchao Zhang , Min Liu , Jiexi Wang","doi":"10.1016/j.esci.2025.100425","DOIUrl":"10.1016/j.esci.2025.100425","url":null,"abstract":"<div><div>The electrocatalytic C–N coupling reaction involving carbon dioxide (CO<sub>2</sub>) and nitrogenous small molecules has recently emerged as a subject of considerable interest within the field of urea synthesis. This approach has the potential to facilitate the clean, sustainable production of urea, thereby contributing to the attainment of carbon neutrality and the advancement of artificial nitrogen cycling. Nevertheless, electrocatalytic urea synthesis still faces significant challenges due to the difficulty of balancing the co-activation of carbon and nitrogen sources and the subsequent catalytic C–N coupling of <em>in situ</em>-generated species, as well as competing reactions. To overcome these challenges, there is a growing emphasis on the research of gas diffusion electrodes (GDEs) and the design of electrode materials. This article provides a comprehensive review of the C–N coupling mechanisms, the classification of catalysts, the electrocatalyst design and optimization strategies, and the fundamental functions and importance of GDEs in electrocatalytic C–N coupling reactions. It also provides insights and perspectives on the major challenges and future research directions for GDEs and electrocatalysts in electrocatalytic urea synthesis.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"6 1","pages":"Article 100425"},"PeriodicalIF":36.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145842681","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aqueous zinc-ion batteries (AZIBs) represent a forefront technology for grid-scale energy storage, distinguished by inherent safety, economic viability, and ecological compatibility. Nevertheless, prevailing AZIBs research remains tethered to conventional methods, thereby hindering both mechanism elucidation and real-world interdisciplinary application. In this review, we commence by critically examining recent advancements in methodological innovations pertaining to the optimization of cathode, anode, and electrolyte in AZIBs. Subsequently, we elucidate pioneering applications of AZIBs in emerging domains, with particular emphasis on their enormous potential in biomedical technologies. To conclude, we unveil contemporary challenges, propose evidence-based strategies, and delineate future directions to establish robust theoretical cornerstones and practical roadmaps for the commercial scalability of AZIBs. By integrating foundational science with cross-disciplinary research achievements, this review aims to substantially advance fundamental comprehension of AZIBs while accelerating their multidisciplinary progress across diverse technological frontiers.
{"title":"Novel approaches to aqueous zinc-ion batteries: Challenges, strategies, and prospects","authors":"Wei Lv, Junlin Liu, Zilei Shen, Xudong Li, Chao Xu","doi":"10.1016/j.esci.2025.100410","DOIUrl":"10.1016/j.esci.2025.100410","url":null,"abstract":"<div><div>Aqueous zinc-ion batteries (AZIBs) represent a forefront technology for grid-scale energy storage, distinguished by inherent safety, economic viability, and ecological compatibility. Nevertheless, prevailing AZIBs research remains tethered to conventional methods, thereby hindering both mechanism elucidation and real-world interdisciplinary application. In this review, we commence by critically examining recent advancements in methodological innovations pertaining to the optimization of cathode, anode, and electrolyte in AZIBs. Subsequently, we elucidate pioneering applications of AZIBs in emerging domains, with particular emphasis on their enormous potential in biomedical technologies. To conclude, we unveil contemporary challenges, propose evidence-based strategies, and delineate future directions to establish robust theoretical cornerstones and practical roadmaps for the commercial scalability of AZIBs. By integrating foundational science with cross-disciplinary research achievements, this review aims to substantially advance fundamental comprehension of AZIBs while accelerating their multidisciplinary progress across diverse technological frontiers.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100410"},"PeriodicalIF":36.6,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340507","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-18DOI: 10.1016/j.esci.2025.100409
Shasha Wang , Leqian Wei , Fujun Wang , Lu Wang , Jifu Mao
Implantable electronic medical devices (IEMDs) are revolutionary advancements in healthcare, enabling continuous health monitoring and disease treatments. To support their further development, IESDs that include supercapacitors (SCs) and batteries are now garnering intensive worldwide research efforts. In this review, we discuss and analyze the research advancements and challenges associated with batteries and SCs in the realm of IESDs. First, we summarize the main components of IESDs, including electrodes, electrolytes, and encapsulation materials. Subsequently, we elucidate the main application scenarios of multifunctional energy storage devices, specifically biosafe, stretchable/self-healing, biodegradable, miniaturized, injectable, and edible IESDs. We then summarize research progress to date on the integration of IESDs with energy harvesters and wireless charging. State-of-the-art studies of IESDs categorized by human organ systems are covered in depth, including cardiovascular, nervous, gastrointestinal, musculoskeletal, vision, and systemic recording and stimulation. We close by briefly outlining the challenges and future prospects for IESDs.
{"title":"Advanced implantable energy storage for powering medical devices","authors":"Shasha Wang , Leqian Wei , Fujun Wang , Lu Wang , Jifu Mao","doi":"10.1016/j.esci.2025.100409","DOIUrl":"10.1016/j.esci.2025.100409","url":null,"abstract":"<div><div>Implantable electronic medical devices (IEMDs) are revolutionary advancements in healthcare, enabling continuous health monitoring and disease treatments. To support their further development, IESDs that include supercapacitors (SCs) and batteries are now garnering intensive worldwide research efforts. In this review, we discuss and analyze the research advancements and challenges associated with batteries and SCs in the realm of IESDs. First, we summarize the main components of IESDs, including electrodes, electrolytes, and encapsulation materials. Subsequently, we elucidate the main application scenarios of multifunctional energy storage devices, specifically biosafe, stretchable/self-healing, biodegradable, miniaturized, injectable, and edible IESDs. We then summarize research progress to date on the integration of IESDs with energy harvesters and wireless charging. State-of-the-art studies of IESDs categorized by human organ systems are covered in depth, including cardiovascular, nervous, gastrointestinal, musculoskeletal, vision, and systemic recording and stimulation. We close by briefly outlining the challenges and future prospects for IESDs.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 5","pages":"Article 100409"},"PeriodicalIF":36.6,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144887426","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-11DOI: 10.1016/j.esci.2025.100408
Huieun Ahn , Raja Arumugam Senthil , Sieon Jung , Anuj Kumar , Mohd Ubaidullah , Myong Yong Choi
Herein, we report the synthesis of selectively face-centered cubic structured ruthenium nanospheres covered in graphitic carbon (denoted as Ru@C) using an effective and innovative pulsed laser ablation in liquid strategy. The Ru@C‒200 catalyst exhibited a low overpotential of 48 mV for hydrogen evolution reaction (HER) and an ultralow oxidation potential of −8 mV (vs. reversible hydrogen electrode) for hydrazine oxidation reaction (HzOR) at 10 mA cm−2, maintaining long-term durability for over 100 h, demonstrating its dual-functional activity. This performance was attributed to the robust synergistic coupling between the Ru core and C shell, as confirmed by in situ electrochemical studies and density functional theory investigations. As a result, overall hydrazine splitting (OHzS) in the Ru@C‒200||Ru@C‒200 system requires only low cell voltages of 0.11 and 0.70 V at 10 and 100 mA cm−2, respectively. Moreover, a rechargeable zinc–hydrazine (Zn–Hz) battery, fabricated using the Ru@C‒200 catalyst as the cathode and Zn foil as the anode, exhibited a high energy efficiency of 90% and efficient H2 production, validating its remarkable ability for practical applications. Notably, coupling Zn–Hz battery with OHzS system encourages self-powered H2 production. This study provides potential guidance for engineering robust electrocatalysts for large-scale H2 production while purifying hydrazine-containing industrial sewage.
在此，我们报告了使用有效和创新的液体脉冲激光烧蚀策略合成石墨碳覆盖的选择性面心立方结构钌纳米球（表示为Ru@C）。Ru@C -200催化剂在10 mA cm−2下，析氢反应（HER）的过电位为48 mV，肼氧化反应（HzOR）的氧化电位为- 8 mV（相对于可逆氢电极），保持了超过100 h的长期使用寿命，显示了其双功能活性。现场电化学研究和密度泛函理论研究证实，这种性能归因于Ru芯和C壳之间强大的协同耦合。因此，在Ru@C -200 ||Ru@C -200体系中，总肼分裂（OHzS）只需要在10和100 mA cm - 2下分别为0.11 V和0.70 V的低电池电压。此外，以Ru@C -200催化剂为阴极，锌箔为阳极制备的可充电锌-肼（Zn - hz）电池，具有高达90%的高能效和高效的产氢能力，验证了其卓越的实际应用能力。值得注意的是，将Zn-Hz电池与OHzS系统耦合可以促进自供电制氢。该研究为大规模制氢同时净化含肼工业污水的工程稳健电催化剂提供了潜在的指导。
{"title":"Pulsed laser-tuned ruthenium@carbon interface for self-powered hydrogen production via zinc–hydrazine battery coupled hybrid electrolysis","authors":"Huieun Ahn , Raja Arumugam Senthil , Sieon Jung , Anuj Kumar , Mohd Ubaidullah , Myong Yong Choi","doi":"10.1016/j.esci.2025.100408","DOIUrl":"10.1016/j.esci.2025.100408","url":null,"abstract":"<div><div>Herein, we report the synthesis of selectively face-centered cubic structured ruthenium nanospheres covered in graphitic carbon (denoted as Ru@C) using an effective and innovative pulsed laser ablation in liquid strategy. The Ru@C‒200 catalyst exhibited a low overpotential of 48 mV for hydrogen evolution reaction (HER) and an ultralow oxidation potential of −8 mV (vs. reversible hydrogen electrode) for hydrazine oxidation reaction (HzOR) at 10 mA cm<sup>−2</sup>, maintaining long-term durability for over 100 h, demonstrating its dual-functional activity. This performance was attributed to the robust synergistic coupling between the Ru core and C shell, as confirmed by <em>in situ</em> electrochemical studies and density functional theory investigations. As a result, overall hydrazine splitting (OHzS) in the Ru@C‒200||Ru@C‒200 system requires only low cell voltages of 0.11 and 0.70 V at 10 and 100 mA cm<sup>−2</sup>, respectively. Moreover, a rechargeable zinc–hydrazine (Zn–Hz) battery, fabricated using the Ru@C‒200 catalyst as the cathode and Zn foil as the anode, exhibited a high energy efficiency of 90% and efficient H<sub>2</sub> production, validating its remarkable ability for practical applications. Notably, coupling Zn–Hz battery with OHzS system encourages self-powered H<sub>2</sub> production. This study provides potential guidance for engineering robust electrocatalysts for large-scale H<sub>2</sub> production while purifying hydrazine-containing industrial sewage.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 5","pages":"Article 100408"},"PeriodicalIF":36.6,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144890862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Macroscopic films assembled from graphene sheets could be ideal for lightweight and flexible electromagnetic interference shielding applications if the excellent mechanical strength and electrical conductivity of individual graphene can be replicated on the macroscale. However, in practice, a large performance gap remains between individual graphene and graphene-based macroscopic films. In this work, we report macroscopic graphene-based films with high mechanical strength and electrical conductivity (1.70 ± 0.05 GPa and 1170 ± 60 S cm−1) obtained by introducing a covalent conjugating aromatic amide group to bridge graphene edges. The bridging was achieved by reacting a doctor-bladed GO film with 1,2,4,5-benzenetetraamine hydrochloride followed by chemical reduction. Impact load tests demonstrated efficient stress transfer in these films, with stress spread uniformly well beyond the impact area. This is in sharp contrast to previously reported films, which showed the immediate initiation of cracks followed by crack extension in random directions. Our conducting films achieved a shielding effectiveness of 114.1 dB for a 120 μm thick film, and the specific shielding effectiveness was calculated to be 67.9 dB cm3 g−1, which significantly exceeds those of currently known shielding materials as well as graphene films synthesized under similar conditions without thermal annealing. Owing to the graphene films’ mechanical robustness, the shielding performance was maintained even after repeated folding.
如果单个石墨烯优异的机械强度和导电性可以在宏观尺度上复制，那么由石墨烯片组装而成的宏观薄膜将是轻质和柔性电磁干扰屏蔽应用的理想选择。然而，在实际应用中，单个石墨烯和石墨烯基宏观薄膜之间仍然存在很大的性能差距。在这项工作中，我们报道了通过引入共价共轭芳酰胺基团来桥接石墨烯边缘而获得的具有高机械强度和电导率（1.70±0.05 GPa和1170±60 S cm−1）的宏观石墨烯基薄膜。桥接是通过将氧化石墨烯薄膜与1,2,4,5-苯四胺盐酸盐反应，然后进行化学还原来实现的。冲击载荷试验表明，在这些薄膜中有效的应力传递，应力均匀地扩散到冲击区域之外。这与先前报道的薄膜形成鲜明对比，后者显示裂纹立即开始，随后裂纹向随机方向扩展。在120 μm厚的薄膜上，我们的导电膜的屏蔽效率达到114.1 dB，比屏蔽效率为67.9 dB cm3 g−1，大大超过了目前已知的屏蔽材料以及在类似条件下未经热处理合成的石墨烯薄膜。由于石墨烯薄膜的机械坚固性，即使经过多次折叠也能保持屏蔽性能。
{"title":"Bridging graphene for films with superior mechanical and electrical performance for electromagnetic interference shielding","authors":"Jiawen Zhang , Tianqi Xu , Ling Ding , Jinpeng Ji , Jianxin Geng , Huynh Thien Ngo , Ke Zhou , Xiankai Chen , Fengxia Geng","doi":"10.1016/j.esci.2025.100407","DOIUrl":"10.1016/j.esci.2025.100407","url":null,"abstract":"<div><div>Macroscopic films assembled from graphene sheets could be ideal for lightweight and flexible electromagnetic interference shielding applications if the excellent mechanical strength and electrical conductivity of individual graphene can be replicated on the macroscale. However, in practice, a large performance gap remains between individual graphene and graphene-based macroscopic films. In this work, we report macroscopic graphene-based films with high mechanical strength and electrical conductivity (1.70 ± 0.05 GPa and 1170 ± 60 S cm<sup>−1</sup>) obtained by introducing a covalent conjugating aromatic amide group to bridge graphene edges. The bridging was achieved by reacting a doctor-bladed GO film with 1,2,4,5-benzenetetraamine hydrochloride followed by chemical reduction. Impact load tests demonstrated efficient stress transfer in these films, with stress spread uniformly well beyond the impact area. This is in sharp contrast to previously reported films, which showed the immediate initiation of cracks followed by crack extension in random directions. Our conducting films achieved a shielding effectiveness of 114.1 dB for a 120 μm thick film, and the specific shielding effectiveness was calculated to be 67.9 dB cm<sup>3</sup> g<sup>−1</sup>, which significantly exceeds those of currently known shielding materials as well as graphene films synthesized under similar conditions without thermal annealing. Owing to the graphene films’ mechanical robustness, the shielding performance was maintained even after repeated folding.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 5","pages":"Article 100407"},"PeriodicalIF":36.6,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144890863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1016/j.esci.2025.100405
Yongjian Li , Tong Sun , Chenxing Yang , Yuefeng Su , Cai Liu , Xinyu Zhu , Yihong Wang , Siyuan Ma , Xinyu Wang , Yizhi Zhai , Wenlong Kang , Lai Chen , Meng Wang , Liang Zhang , Bin Wang , Qing Huang , Yibiao Guan , Feng Wu , Ning Li
Although lithium-rich manganese-based (LRM) cathode materials have high capacity (> 250 mAh g−1) due to their multi-electron redox mechanisms and offer cost advantages due to their high Mn content, challenges remain before they can achieve commercialization as replacements for lithium cobalt oxides which have high volumetric energy density. Here, we construct a hierarchically structured LRM cathode, featuring primary micro-bricks and abundant exposure of lithium-ion active transport facets ({010} planes). Benefiting from these densely packed bricks and rapid lithium-ion active planes, the hierarchical material achieves an optimal compaction density of 3.4 g cm−3 and an ultrahigh volumetric energy density of 3431.0 Wh L−1, which is the highest performance level to date. Advanced characterizations, including hard X-ray absorption spectra and wide-angle X-ray scattering spectra, combined with density functional theory calculations, demonstrate that the hierarchical material shows a highly reversible charge compensation process and low-strain structural evolution. In addition, when the material has appropriate Li/Ni intermixing, it is not prone to shearing or sliding along the two-dimensional lithium-ion diffusion planes, which promotes robust architectural stability under high-pressure calendering and long-term cycling. This work should promote the development of advanced cathode materials for rechargeable batteries with high volumetric energy density.
尽管富锂锰基（LRM）正极材料由于其多电子氧化还原机制而具有高容量（> 250 mAh g - 1），并且由于其高锰含量而具有成本优势，但在它们作为具有高体积能量密度的锂钴氧化物的替代品实现商业化之前仍然存在挑战。在这里，我们构建了一个分层结构的LRM阴极，具有初级微砖和大量暴露的锂离子主动输运面（{010}平面）。得益于这些密集堆积的砖块和快速锂离子活性层，分层材料实现了3.4 g cm−3的最佳压实密度和3431.0 Wh L−1的超高体积能量密度，这是迄今为止的最高性能水平。通过硬x射线吸收光谱和广角x射线散射光谱的高级表征，结合密度泛函理论计算，表明分层材料表现出高度可逆的电荷补偿过程和低应变的结构演化。此外，当材料具有适当的Li/Ni混合时，它不容易沿着二维锂离子扩散面剪切或滑动，从而在高压压延和长期循环下促进了强大的结构稳定性。这项工作将促进高体积能量密度可充电电池正极材料的发展。
{"title":"Li-rich oxide micro-bricks with exposed {010} planes to construct ultrahigh-compaction hierarchical cathodes for Li-ion batteries","authors":"Yongjian Li , Tong Sun , Chenxing Yang , Yuefeng Su , Cai Liu , Xinyu Zhu , Yihong Wang , Siyuan Ma , Xinyu Wang , Yizhi Zhai , Wenlong Kang , Lai Chen , Meng Wang , Liang Zhang , Bin Wang , Qing Huang , Yibiao Guan , Feng Wu , Ning Li","doi":"10.1016/j.esci.2025.100405","DOIUrl":"10.1016/j.esci.2025.100405","url":null,"abstract":"<div><div>Although lithium-rich manganese-based (LRM) cathode materials have high capacity (> 250 mAh g<sup>−1</sup>) due to their multi-electron redox mechanisms and offer cost advantages due to their high Mn content, challenges remain before they can achieve commercialization as replacements for lithium cobalt oxides which have high volumetric energy density. Here, we construct a hierarchically structured LRM cathode, featuring primary micro-bricks and abundant exposure of lithium-ion active transport facets ({010} planes). Benefiting from these densely packed bricks and rapid lithium-ion active planes, the hierarchical material achieves an optimal compaction density of 3.4 g cm<sup>−3</sup> and an ultrahigh volumetric energy density of 3431.0 Wh L<sup>−1</sup>, which is the highest performance level to date. Advanced characterizations, including hard X-ray absorption spectra and wide-angle X-ray scattering spectra, combined with density functional theory calculations, demonstrate that the hierarchical material shows a highly reversible charge compensation process and low-strain structural evolution. In addition, when the material has appropriate Li/Ni intermixing, it is not prone to shearing or sliding along the two-dimensional lithium-ion diffusion planes, which promotes robust architectural stability under high-pressure calendering and long-term cycling. This work should promote the development of advanced cathode materials for rechargeable batteries with high volumetric energy density.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 5","pages":"Article 100405"},"PeriodicalIF":36.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144890910","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1016/j.esci.2025.100406
Haoxiang Sun , Youxuan Ni , Xinyao Wu , Dongjie Shi , Zhenhua Yan , Kai Zhang , Fangyi Cheng , Weiwei Xie , Wei Zhang , Jun Chen
Migration of transition metal (TM) ions out of the TM layer is detrimental and unavoidable in lithium-rich layered oxides, which drives in-plane cation migration, O2 release and energy loss. Since out-of-plane migration generally occurs through tetrahedral interstices (TLi) in the Li layer, doping TLi sites has been believed as a promising way to block migration pathways at the dopant site. However, with only trace dopants (<1 at.%) sparsely distributed in bulk, the ability of isolated dopants to suppress cation disorder in undoped regions remains unknown—largely due to no suitable model materials. Here, combining atomic-scale imaging, X-ray diffraction measurements and first-principles calculations, we demonstrate that W6+ ions (0.75 at.%) can occupy TLi sites in Li1·2Mn0·6Ni0·2O2. TLi-site doping maximizes dopant efficiency, as each single W6+ ion exerts a long-range Coulomb repulsion on TM/Li+ ions in the TM layer, suppressing both in-plane and out-of-plane cation migration over a broad range (∼2 nm diameter), in contrast to local stabilization via other doping techniques. Remarkably, cation ordering is preserved for over 250 cycles, far exceeding the limited structural stability (∼50 cycles) typically achieved with conventional modification strategies. Consequently, O2 release and formation of low-voltage Mn3+/Mn4+ redox couple are inhibited, resulting in negligible voltage decay.
{"title":"Single-dopant long-range stabilization in long-cycled Li-rich layered cathodes via trace tetrahedral-site doping","authors":"Haoxiang Sun , Youxuan Ni , Xinyao Wu , Dongjie Shi , Zhenhua Yan , Kai Zhang , Fangyi Cheng , Weiwei Xie , Wei Zhang , Jun Chen","doi":"10.1016/j.esci.2025.100406","DOIUrl":"10.1016/j.esci.2025.100406","url":null,"abstract":"<div><div>Migration of transition metal (TM) ions out of the TM layer is detrimental and unavoidable in lithium-rich layered oxides, which drives in-plane cation migration, O<sub>2</sub> release and energy loss. Since out-of-plane migration generally occurs through tetrahedral interstices (T<sub>Li</sub>) in the Li layer, doping T<sub>Li</sub> sites has been believed as a promising way to block migration pathways at the dopant site. However, with only trace dopants (<1 at.%) sparsely distributed in bulk, the ability of isolated dopants to suppress cation disorder in undoped regions remains unknown—largely due to no suitable model materials. Here, combining atomic-scale imaging, X-ray diffraction measurements and first-principles calculations, we demonstrate that W<sup>6+</sup> ions (0.75 at.%) can occupy T<sub>Li</sub> sites in Li<sub>1</sub><sub>·</sub><sub>2</sub>Mn<sub>0·6</sub>Ni<sub>0·2</sub>O<sub>2</sub>. T<sub>Li</sub>-site doping maximizes dopant efficiency, as each single W<sup>6+</sup> ion exerts a long-range Coulomb repulsion on TM/Li<sup>+</sup> ions in the TM layer, suppressing both in-plane and out-of-plane cation migration over a broad range (∼2 nm diameter), in contrast to local stabilization via other doping techniques. Remarkably, cation ordering is preserved for over 250 cycles, far exceeding the limited structural stability (∼50 cycles) typically achieved with conventional modification strategies. Consequently, O<sub>2</sub> release and formation of low-voltage Mn<sup>3+</sup>/Mn<sup>4+</sup> redox couple are inhibited, resulting in negligible voltage decay.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100406"},"PeriodicalIF":36.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145366120","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two-dimensional (2D) reticular framework films featuring highly accessible surface areas, tunable active sites, and well-defined channels are promising candidates for flexible in-plane micro-supercapacitor (MSC) electrodes. However, the interlayer Van der Waals forces in 2D heterojunctions can limit mass/charge transport. Herein, we design a non-Van der Waals force bonded heterojunction of covalent organic frameworks (COFs) and metal–organic frameworks (MOFs) linked by metal-ion coordination. A COF@MOF monolithic nanofilm is constructed by growing MOF (M3(HHTP)2) in situ on the COF (COFTD) surface, using nickel (Ni) as the optimal metal to connect the two layers and form a sandwich electrode. We further explore various transition metals in M3(HHTP)2, from manganese (Mn) to zinc (Zn), to adjust the electronic structure and charge redistribution. The optimal MSC-Ni-COFTD@Co3(HHTP)2 device exhibits an impressive specific capacitance (1645.3 F cm−3 at 10 mV s−1), a high energy density (146.3 mWh cm−3), as well as superior cycling and bending stability. This work offers an innovative perspective on overcoming the mass transfer and electron migration limitations of 2D reticular frameworks for miniaturization and wearable energy storage electronics.
二维（2D）网状框架薄膜具有高度可接近的表面积、可调的活性位点和明确的通道，是柔性面内微超级电容器（MSC）电极的有希望的候选者。然而，二维异质结中的层间范德华力会限制质量/电荷输运。本文设计了共价有机骨架（COFs）和金属-有机骨架（MOFs）通过金属离子配位连接的非范德华力键异质结。通过在COF （COFTD）表面原位生长MOF (M3(HHTP)2)，以镍（Ni）作为连接两层的最佳金属，形成夹层电极，构建了COF@MOF单片纳米膜。我们进一步探索了M3(HHTP)2中的各种过渡金属，从锰（Mn）到锌（Zn），以调节电子结构和电荷再分配。最佳的MSC-Ni-COFTD@Co3(HHTP)2器件具有令人印象深刻的比电容（10mv s - 1时1645.3 F cm - 3），高能量密度（146.3 mWh cm - 3），以及优越的循环和弯曲稳定性。这项工作为克服小型化和可穿戴储能电子设备的二维网状框架的传质和电子迁移限制提供了一个创新的视角。
{"title":"Metal ion-bonded two-dimensional framework non-Van der Waals sandwich heterojunctions for fast mass transfer in flexible in-plane micro-supercapacitors","authors":"Xiaoyang Xu , Zhenni Zhang , Zihao Zhang , Xiaomi Tang , Hong Chen , Tian Li , Jia Zhang , Qingliang Feng , Shanlin Qiao","doi":"10.1016/j.esci.2025.100404","DOIUrl":"10.1016/j.esci.2025.100404","url":null,"abstract":"<div><div>Two-dimensional (2D) reticular framework films featuring highly accessible surface areas, tunable active sites, and well-defined channels are promising candidates for flexible in-plane micro-supercapacitor (MSC) electrodes. However, the interlayer Van der Waals forces in 2D heterojunctions can limit mass/charge transport. Herein, we design a non-Van der Waals force bonded heterojunction of covalent organic frameworks (COFs) and metal–organic frameworks (MOFs) linked by metal-ion coordination. A COF@MOF monolithic nanofilm is constructed by growing MOF (M<sub>3</sub>(HHTP)<sub>2</sub>) <em>in situ</em> on the COF (COF<sub>TD</sub>) surface, using nickel (Ni) as the optimal metal to connect the two layers and form a sandwich electrode. We further explore various transition metals in M<sub>3</sub>(HHTP)<sub>2</sub>, from manganese (Mn) to zinc (Zn), to adjust the electronic structure and charge redistribution. The optimal MSC-Ni-COF<sub>TD</sub>@Co<sub>3</sub>(HHTP)<sub>2</sub> device exhibits an impressive specific capacitance (1645.3 F cm<sup>−3</sup> at 10 mV s<sup>−1</sup>), a high energy density (146.3 mWh cm<sup>−3</sup>), as well as superior cycling and bending stability. This work offers an innovative perspective on overcoming the mass transfer and electron migration limitations of 2D reticular frameworks for miniaturization and wearable energy storage electronics.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100404"},"PeriodicalIF":36.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145366121","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-25DOI: 10.1016/j.esci.2025.100403
Zhiang Hu , Han Wu , Xue Yong , Geoffrey I.N. Waterhouse , Zhiyong Tang , Junbiao Chang , Jiangwei Chang , Siyu Lu
The oxygen evolution reaction (OER), owing to its low kinetics, is a major obstacle to electrochemical water-splitting, which is essential for converting sustainable energy into clean and stable hydrogen energy carriers. The growing need for high-performance electrocatalysts to meet industrial demands, along with a deepening exploration of the OER catalytic process, has led to advancements in OER catalyst design—from conventional single-site mechanisms (SSMs) to more sophisticated dual-site mechanisms (DSMs). However, DSMs, with their complex reaction pathways, still face multiple challenges in progressing towards industrial application, making a deeper understanding of these mechanisms essential. This review first examines the latest DSMs associated with the OER and compares them with conventional SSMs. On this basis, we highlight the structure–activity relationships and design principles of catalysts that align with DSMs by integrating experimental evidence with theoretical analysis. In addition, quasi in situ and in situ spectral detection techniques for DSM analysis are introduced, and the challenges and prospects for these new detection techniques are discussed.
{"title":"Advances in dual-site mechanisms for designing high-performance oxygen evolution electrocatalysts","authors":"Zhiang Hu , Han Wu , Xue Yong , Geoffrey I.N. Waterhouse , Zhiyong Tang , Junbiao Chang , Jiangwei Chang , Siyu Lu","doi":"10.1016/j.esci.2025.100403","DOIUrl":"10.1016/j.esci.2025.100403","url":null,"abstract":"<div><div>The oxygen evolution reaction (OER), owing to its low kinetics, is a major obstacle to electrochemical water-splitting, which is essential for converting sustainable energy into clean and stable hydrogen energy carriers. The growing need for high-performance electrocatalysts to meet industrial demands, along with a deepening exploration of the OER catalytic process, has led to advancements in OER catalyst design—from conventional single-site mechanisms (SSMs) to more sophisticated dual-site mechanisms (DSMs). However, DSMs, with their complex reaction pathways, still face multiple challenges in progressing towards industrial application, making a deeper understanding of these mechanisms essential. This review first examines the latest DSMs associated with the OER and compares them with conventional SSMs. On this basis, we highlight the structure–activity relationships and design principles of catalysts that align with DSMs by integrating experimental evidence with theoretical analysis. In addition, quasi in situ and in situ spectral detection techniques for DSM analysis are introduced, and the challenges and prospects for these new detection techniques are discussed.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100403"},"PeriodicalIF":36.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340506","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-18DOI: 10.1016/j.esci.2025.100401
Kun Zhang , You Pan , Xingyu Guo , Jifeng Wang , Chuanfa Li , Jiaxin Li , Meng Liao , Yi Jiang , Wenjun Li , Kailin Zhang , Qian Ye , Longmei Ma , Xiaocheng Gong , Kai Li , Ying Wang , Yue Gao , Xin-Gao Gong , Huisheng Peng , Bingjie Wang
Organic electrode materials with the versatility of molecular engineering emerge as promising alternatives to construct high-performance batteries. However, a weak binding force between active layers leads to poor structural stability accompanied by a multi-electron redox, thus hindering the construction of practical devices based on organic materials. Herein, we report a structural engineering approach to improve the structural stability of organic molecules by pre-intercalating potassium ions (K+) as pillars into the adjacent rhodizonate (C6O62−) layers. This enhanced binding, with increased coordination sites of K-O, effectively prevents the exfoliation of C6O62− layers and provides stable diffusion channels for lithium ions (Li+). The resulting batteries exhibit accelerated reaction kinetics and enhanced Li+ diffusion, leading to a high energy density of 722 Wh kg−1 (based on active materials) and reversible capacity of 315 mAh g−1 at 1.0 C, with a capacity retention of 225 mAh g−1 after 500 cycles. In addition, by virtue of the flexible nature, a Li-K2C6O6 battery has been made into flexible fibers for next-generation wearable systems, offering a new avenue for realizing practical devices based on organic single molecules. This work presents a general and efficient strategy to unlock theoretically high-performance organic electrode materials for advanced Li-organic batteries.
有机电极材料具有分子工程的多功能性，是构建高性能电池的有希望的替代品。然而，由于活性层之间的结合力较弱，导致结构稳定性差，并伴有多电子氧化还原，从而阻碍了基于有机材料的实用器件的构建。在此，我们报告了一种结构工程方法，通过将钾离子（K+）作为支柱预插到相邻的rhodizonate （C6O62−）层中来提高有机分子的结构稳定性。随着K-O配位位点的增加，这种增强的结合有效地防止了C6O62−层的脱落，并为锂离子（Li+）提供了稳定的扩散通道。所得电池表现出加速的反应动力学和增强的Li+扩散，导致722 Wh kg−1的高能量密度（基于活性材料）和315 mAh g−1的可逆容量，在1.0℃下循环500次后容量保持为225 mAh g−1。此外，凭借其柔性特性，Li-K2C6O6电池已被制成用于下一代可穿戴系统的柔性纤维，为实现基于有机单分子的实用设备提供了新的途径。这项工作提出了一种通用而有效的策略来解锁理论上高性能的有机锂有机电池电极材料。
{"title":"Connecting adjacent active layers with structural pillars for high-performance Li-organic batteries","authors":"Kun Zhang , You Pan , Xingyu Guo , Jifeng Wang , Chuanfa Li , Jiaxin Li , Meng Liao , Yi Jiang , Wenjun Li , Kailin Zhang , Qian Ye , Longmei Ma , Xiaocheng Gong , Kai Li , Ying Wang , Yue Gao , Xin-Gao Gong , Huisheng Peng , Bingjie Wang","doi":"10.1016/j.esci.2025.100401","DOIUrl":"10.1016/j.esci.2025.100401","url":null,"abstract":"<div><div>Organic electrode materials with the versatility of molecular engineering emerge as promising alternatives to construct high-performance batteries. However, a weak binding force between active layers leads to poor structural stability accompanied by a multi-electron redox, thus hindering the construction of practical devices based on organic materials. Herein, we report a structural engineering approach to improve the structural stability of organic molecules by pre-intercalating potassium ions (K<sup>+</sup>) as pillars into the adjacent rhodizonate (C<sub>6</sub>O<sub>6</sub><sup>2−</sup>) layers. This enhanced binding, with increased coordination sites of K-O, effectively prevents the exfoliation of C<sub>6</sub>O<sub>6</sub><sup>2−</sup> layers and provides stable diffusion channels for lithium ions (Li<sup>+</sup>). The resulting batteries exhibit accelerated reaction kinetics and enhanced Li<sup>+</sup> diffusion, leading to a high energy density of 722 Wh kg<sup>−1</sup> (based on active materials) and reversible capacity of 315 mAh g<sup>−1</sup> at 1.0 C, with a capacity retention of 225 mAh g<sup>−1</sup> after 500 cycles. In addition, by virtue of the flexible nature, a Li-K<sub>2</sub>C<sub>6</sub>O<sub>6</sub> battery has been made into flexible fibers for next-generation wearable systems, offering a new avenue for realizing practical devices based on organic single molecules. This work presents a general and efficient strategy to unlock theoretically high-performance organic electrode materials for advanced Li-organic batteries.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100401"},"PeriodicalIF":36.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145366081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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