Pub Date : 2025-03-01DOI: 10.1016/j.esci.2024.100329
Huan Bi , Jiaqi Liu , Liang Wang , Tuo Liu , Zheng Zhang , Qing Shen , Shuzi Hayase
This review provides a comprehensive overview of the utilization of self-assembled monolayers (SAMs) in perovskite solar cells (PSCs), with a specific focus on their potential as hole transport layers (HTLs). Perovskite materials have garnered significant attention in photovoltaic technology owing to their unique optoelectronic properties. SAMs present a promising solution as efficient and stable HTLs by forming well-ordered thin films on transparent conductive oxide surfaces. This review commences with an introduction to the structure and properties of perovskite materials, followed by a discussion on the operational principles and compositions of functional layers in PSCs. It subsequently delves into the structure, preparation methodologies, and applications of SAMs in PSCs, highlighting their role in enhancing cell efficiency as HTLs. We also discuss their application as electron transport layers. The paper concludes by exploring the potential integration of SAMs into commercial PSC production processes and suggesting future research avenues.
{"title":"Selective contact self-assembled molecules for high-performance perovskite solar cells","authors":"Huan Bi , Jiaqi Liu , Liang Wang , Tuo Liu , Zheng Zhang , Qing Shen , Shuzi Hayase","doi":"10.1016/j.esci.2024.100329","DOIUrl":"10.1016/j.esci.2024.100329","url":null,"abstract":"<div><div>This review provides a comprehensive overview of the utilization of self-assembled monolayers (SAMs) in perovskite solar cells (PSCs), with a specific focus on their potential as hole transport layers (HTLs). Perovskite materials have garnered significant attention in photovoltaic technology owing to their unique optoelectronic properties. SAMs present a promising solution as efficient and stable HTLs by forming well-ordered thin films on transparent conductive oxide surfaces. This review commences with an introduction to the structure and properties of perovskite materials, followed by a discussion on the operational principles and compositions of functional layers in PSCs. It subsequently delves into the structure, preparation methodologies, and applications of SAMs in PSCs, highlighting their role in enhancing cell efficiency as HTLs. We also discuss their application as electron transport layers. The paper concludes by exploring the potential integration of SAMs into commercial PSC production processes and suggesting future research avenues.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 2","pages":"Article 100329"},"PeriodicalIF":42.9,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512422","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.esci.2024.100311
Hua Zhang , Nianpeng Li , Sanshuang Gao , Anran Chen , Qihang Qian , Qingquan Kong , Bao Yu Xia , Guangzhi Hu
Developing non-noble metal hydrogen evolution reaction (HER) electrocatalysts with high activity and durability at ampere-level current densities is vital for emerging anion exchange membrane (AEM) water electrolysis, but it remains challenging. Here we present an atom-stepped nickel–cobalt bimetallic sulfide (AS-Ni3S2/Co3S4) heterostructure that exhibits superior HER performance, with ultra-low overpotentials of 28 and 195 mV at current densities of 10 and 2000 mA cm−2, respectively. Experimental analyses and theoretical calculations revealed that the work-function-induced interfacial built-in electric field drives electron transfer from Ni3S2 to Co3S4 via Ni–S–Co interfacial bridging, which effectively accelerates water activation and optimizes hydrogen adsorption and desorption. An AEM electrolyzer using an AS-Ni3S2/Co3S4 heterostructure as the cathode required cell voltages of only 1.71 and 1.79 V to reach 1.0 and 2.0 A cm−2, respectively, and operated stably for 1200 h without activity degradation.
开发在安培电流密度下具有高活性和耐久性的非贵金属析氢反应（HER）电催化剂对于新兴的阴离子交换膜（AEM）电解至关重要，但仍具有挑战性。在这里，我们提出了一种原子梯级镍钴双金属硫化物（AS-Ni3S2/Co3S4）异质结构，具有优异的HER性能，在电流密度为10和2000 mA cm−2时，其过电位分别为28和195 mV。实验分析和理论计算表明，功函数诱导的界面内置电场驱动电子通过Ni-S-Co界面桥接从Ni3S2转移到Co3S4，有效地加速了水的活化，优化了氢的吸附和解吸。采用as - ni3s2 /Co3S4异质结构作为阴极的AEM电解槽，电池电压仅为1.71 V和1.79 V，分别达到1.0和2.0 A cm−2，并稳定运行1200 h而不降低活性。
{"title":"Quenching-induced atom-stepped bimetallic sulfide heterointerface catalysts for industrial hydrogen generation","authors":"Hua Zhang , Nianpeng Li , Sanshuang Gao , Anran Chen , Qihang Qian , Qingquan Kong , Bao Yu Xia , Guangzhi Hu","doi":"10.1016/j.esci.2024.100311","DOIUrl":"10.1016/j.esci.2024.100311","url":null,"abstract":"<div><div>Developing non-noble metal hydrogen evolution reaction (HER) electrocatalysts with high activity and durability at ampere-level current densities is vital for emerging anion exchange membrane (AEM) water electrolysis, but it remains challenging. Here we present an atom-stepped nickel–cobalt bimetallic sulfide (AS-Ni<sub>3</sub>S<sub>2</sub>/Co<sub>3</sub>S<sub>4</sub>) heterostructure that exhibits superior HER performance, with ultra-low overpotentials of 28 and 195 mV at current densities of 10 and 2000 mA cm<sup>−2</sup>, respectively. Experimental analyses and theoretical calculations revealed that the work-function-induced interfacial built-in electric field drives electron transfer from Ni<sub>3</sub>S<sub>2</sub> to Co<sub>3</sub>S<sub>4</sub> via Ni–S–Co interfacial bridging, which effectively accelerates water activation and optimizes hydrogen adsorption and desorption. An AEM electrolyzer using an AS-Ni<sub>3</sub>S<sub>2</sub>/Co<sub>3</sub>S<sub>4</sub> heterostructure as the cathode required cell voltages of only 1.71 and 1.79 V to reach 1.0 and 2.0 A cm<sup>−2</sup>, respectively, and operated stably for 1200 h without activity degradation.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 2","pages":"Article 100311"},"PeriodicalIF":42.9,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.esci.2025.100398
Linbo Jiang, Lintao Jiang, Xu Luo, Ruidong Li, Qingqu Zhou, Weihao Zeng, Jun Yu, Lei Chen, Shichun Mu
In recent years, substantial effort has been dedicated to improving the intrinsic catalytic activity of catalysts through structural modification, component regulation, and chemical state optimization. However, complexity in the design and construction of catalysts, and the possibility of encountering performance ceilings, may constrain their widespread use. Currently, the introduction of in situ external fields, such as force, electric, magnetic, acoustic, light, and thermal fields, is an attractive approach to enhance the catalytic efficiency of catalysts. Such in situ physical fields feature continuity, reversibility, and controllability, and can exert external force or energy on catalysts, thereby affecting their microscopic structures and electron arrangements, accelerating their mass transfer and reaction kinetics. Mutual coupling and conversion among different external fields are also worth exploring. Various in situ external field effects work in multifaceted ways to promote catalysis in energy-environment systems by optimizing mass/energy transfer processes, modifying structures, and accelerating catalytic reaction kinetics, thereby significantly improving the catalytic properties of materials. This review summarizes and analyzes the latest developments in external field-assisted methods for boosting catalyst performance. The external field effect, related catalysis mechanism, and external field-enhanced catalysis are highlighted, and we discuss future challenges, countermeasures, and opportunities for external field-assisted catalysis and beyond.
{"title":"External field-assisted catalysis","authors":"Linbo Jiang, Lintao Jiang, Xu Luo, Ruidong Li, Qingqu Zhou, Weihao Zeng, Jun Yu, Lei Chen, Shichun Mu","doi":"10.1016/j.esci.2025.100398","DOIUrl":"10.1016/j.esci.2025.100398","url":null,"abstract":"<div><div>In recent years, substantial effort has been dedicated to improving the intrinsic catalytic activity of catalysts through structural modification, component regulation, and chemical state optimization. However, complexity in the design and construction of catalysts, and the possibility of encountering performance ceilings, may constrain their widespread use. Currently, the introduction of <em>in situ</em> external fields, such as force, electric, magnetic, acoustic, light, and thermal fields, is an attractive approach to enhance the catalytic efficiency of catalysts. Such <em>in situ</em> physical fields feature continuity, reversibility, and controllability, and can exert external force or energy on catalysts, thereby affecting their microscopic structures and electron arrangements, accelerating their mass transfer and reaction kinetics. Mutual coupling and conversion among different external fields are also worth exploring. Various <em>in situ</em> external field effects work in multifaceted ways to promote catalysis in energy-environment systems by optimizing mass/energy transfer processes, modifying structures, and accelerating catalytic reaction kinetics, thereby significantly improving the catalytic properties of materials. This review summarizes and analyzes the latest developments in external field-assisted methods for boosting catalyst performance. The external field effect, related catalysis mechanism, and external field-enhanced catalysis are highlighted, and we discuss future challenges, countermeasures, and opportunities for external field-assisted catalysis and beyond.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 6","pages":"Article 100398"},"PeriodicalIF":36.6,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340505","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 : 2025-03-01DOI: 10.1016/j.esci.2024.100313
Longfei Wen , Jiyu Zhang , Jian Zhang , Lingfei Zhao , Xin Wang , Sen Wang , Siyu Ma , Wenbin Li , Jun Luo , Junmin Ge , Weihua Chen
Alluaudite-type iron-based sulfates are prospective positive-electrode active materials for sodium-ion batteries given their low-cost and high operation voltage, yet suffer from poor intrinsic ionic conductivity and (electro) chemical instability at high temperatures. Herein, a cation-modified Na2.466Fe1.724Mg0.043(SO4)3 with micron-sized spherical structure was reported. The substitutive MgO6 octahedron featured stronger covalent bonding interactions and enriched the ion transfer pathways within the crystals, facilitating the ionic kinetics in bulk. Using in situ mass spectrometry and quartz crystal microbalance techniques, Mg cations were demonstrated to lower the electron density around O atoms and surficial nucleophilicity of materials, which effectively suppressed their side reactions with H2O in air and active ester molecule in electrolyte. This interaction enables an inorganic-rich and uniform interphase to stabilize the cathode/electrolyte interface at high voltage (4.5 V vs. Na+/Na). The as-prepared cathode exhibits a high discharge capacity of 102.2 mAh g−1 (voltage platform at 3.74 V), remarkable reaction reversibility (average Coulomb efficiency of 99.3 % over 300 cycles) at high loading (9.0−9.6 mg cm−2) and temperature (60 °C), as well as long-lasting cyclability (70.8 %, 5000 cycles). Its application was verified in assembled sodium-ion full cells with a hard carbon negative electrode, showing a long cycling lifetime over 190 cycles.
冲积型铁基硫酸盐具有低成本和高工作电压的优点，是钠离子电池极具前景的正极活性材料，但其固有离子电导率差，且在高温下存在（电）化学不稳定性。本文报道了一种具有微米级球形结构的阳离子改性Na2.466Fe1.724Mg0.043(SO4)3。取代的MgO6八面体具有更强的共价键相互作用，丰富了晶体内的离子转移途径，有利于整体离子动力学。利用原位质谱法和石英晶体微天平技术，证明了Mg阳离子可以降低材料O原子周围的电子密度和表面亲核性，从而有效抑制材料与空气中的H2O和电解质中的活性酯分子的副反应。这种相互作用使富无机和均匀的界面相能够在高压下稳定阴极/电解质界面（4.5 V vs. Na+/Na）。制备的阴极在高负载（9.0 ~ 9.6 mg cm−2）和温度（60°C）下具有102.2 mAh g−1的高放电容量（电压平台为3.74 V），显著的反应可逆性（平均库仑效率为99.3%，超过300次循环），以及持久的可循环性（70.8%，5000次循环）。在硬碳负极组装钠离子电池中验证了其应用，显示出超过190次的长循环寿命。
{"title":"Cation-inspired polyhedral distortion boosting moisture/electrolyte stability of iron sulfate cathode for durable high-temperature sodium-ion storage","authors":"Longfei Wen , Jiyu Zhang , Jian Zhang , Lingfei Zhao , Xin Wang , Sen Wang , Siyu Ma , Wenbin Li , Jun Luo , Junmin Ge , Weihua Chen","doi":"10.1016/j.esci.2024.100313","DOIUrl":"10.1016/j.esci.2024.100313","url":null,"abstract":"<div><div>Alluaudite-type iron-based sulfates are prospective positive-electrode active materials for sodium-ion batteries given their low-cost and high operation voltage, yet suffer from poor intrinsic ionic conductivity and (electro) chemical instability at high temperatures. Herein, a cation-modified Na<sub>2.466</sub>Fe<sub>1.724</sub>Mg<sub>0.043</sub>(SO<sub>4</sub>)<sub>3</sub> with micron-sized spherical structure was reported. The substitutive MgO<sub>6</sub> octahedron featured stronger covalent bonding interactions and enriched the ion transfer pathways within the crystals, facilitating the ionic kinetics in bulk. Using <em>in situ</em> mass spectrometry and quartz crystal microbalance techniques, Mg cations were demonstrated to lower the electron density around O atoms and surficial nucleophilicity of materials, which effectively suppressed their side reactions with H<sub>2</sub>O in air and active ester molecule in electrolyte. This interaction enables an inorganic-rich and uniform interphase to stabilize the cathode/electrolyte interface at high voltage (4.5 V vs. Na<sup>+</sup>/Na). The as-prepared cathode exhibits a high discharge capacity of 102.2 mAh g<sup>−1</sup> (voltage platform at 3.74 V), remarkable reaction reversibility (average Coulomb efficiency of 99.3 % over 300 cycles) at high loading (9.0−9.6 mg cm<sup>−2</sup>) and temperature (60 °C), as well as long-lasting cyclability (70.8 %, 5000 cycles). Its application was verified in assembled sodium-ion full cells with a hard carbon negative electrode, showing a long cycling lifetime over 190 cycles.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 2","pages":"Article 100313"},"PeriodicalIF":42.9,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512455","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.esci.2024.100328
Shaojie Zhang , Yanhua Wan , Yu Cao , Yiming Zhang , Haochen Gong , Xu Liang , Baoshan Zhang , Xiaoyi Wang , Siyu Fang , Jiahong Wang , Wei Li , Jie Sun
Black phosphorus (BP) anode with high capacity (2596 mAh g−1) and suitable lithiation potential (0.7 V vs. Li+/Li) is an ideal candidate for high-energy-density and high-safety lithium-ion batteries, however, the practical implementation is greatly limited by its slow reaction kinetics and huge volume expansion. Here, inspired by nature, liquid metal (LM) is explored as a self-heal agent, which can well stabilize the BP anode through buffering the volumetric expansion and re-activating “dead P and LixP”. Moreover, LM also acts as a good catalyst, which can adjust Li ion concentration and reduce the activation energy of delithiation reaction, thus prolonging the cycling life. Therefore, the LM modified BP/graphite (G) composite delivers an excellent high-rate performance of 1123 mAh g−1 at 4 C with 80.0 % capacity retention after 200 cycles, a superior wide-temperature performance of 1547.5 mAh g−1 and 569.0 mAh g−1 at 50 °C and −20 °C, respectively.
黑磷（BP）阳极具有高容量（2596 mAh g−1）和适宜的锂化电位（0.7 V vs. Li+/Li），是高能量密度和高安全性锂离子电池的理想阳极，但其反应动力学缓慢和体积膨胀大，极大地限制了其实际应用。在这里，受大自然的启发，探索液态金属（LM）作为一种自愈剂，通过缓冲体积膨胀和重新激活“死P和LixP”，可以很好地稳定BP阳极。同时，LM也是一种很好的催化剂，可以调节Li离子浓度，降低降解反应的活化能，从而延长循环寿命。因此，LM改性的BP/石墨(G)复合材料在4℃下具有1123 mAh G - 1的优异性能，200次循环后容量保持率为80.0%，在50℃和- 20℃下分别具有1547.5 mAh G - 1和569.0 mAh G - 1的优异宽温性能。
{"title":"Delithiation-accelerating and self-healing strategies realizes high-capacity and high-rate black phosphorus anode in wide temperature range","authors":"Shaojie Zhang , Yanhua Wan , Yu Cao , Yiming Zhang , Haochen Gong , Xu Liang , Baoshan Zhang , Xiaoyi Wang , Siyu Fang , Jiahong Wang , Wei Li , Jie Sun","doi":"10.1016/j.esci.2024.100328","DOIUrl":"10.1016/j.esci.2024.100328","url":null,"abstract":"<div><div>Black phosphorus (BP) anode with high capacity (2596 mAh g<sup>−1</sup>) and suitable lithiation potential (0.7 V vs. Li<sup>+</sup>/Li) is an ideal candidate for high-energy-density and high-safety lithium-ion batteries, however, the practical implementation is greatly limited by its slow reaction kinetics and huge volume expansion. Here, inspired by nature, liquid metal (LM) is explored as a self-heal agent, which can well stabilize the BP anode through buffering the volumetric expansion and re-activating “dead P and Li<sub>x</sub>P”. Moreover, LM also acts as a good catalyst, which can adjust Li ion concentration and reduce the activation energy of delithiation reaction, thus prolonging the cycling life. Therefore, the LM modified BP/graphite (G) composite delivers an excellent high-rate performance of 1123 mAh g<sup>−1</sup> at 4 C with 80.0 % capacity retention after 200 cycles, a superior wide-temperature performance of 1547.5 mAh g<sup>−1</sup> and 569.0 mAh g<sup>−1</sup> at 50 °C and −20 °C, respectively.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 2","pages":"Article 100328"},"PeriodicalIF":42.9,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.esci.2024.100312
Juan Xu , Xinwei Huang , Jing Peng , Shunxing Li , Jian-Feng Li
The integration of surface plasmons with catalysis has opened a new frontier in the field of chemical energy conversion, offering unprecedented opportunities for enhancing reaction activity and selectivity. This review delves into the optical properties of plasmonic materials, the intricate mechanisms of plasmon-assisted chemical reactions (PACRs), and the fabrication of plasmonic catalysts, highlighting the significance of the structure–performance relationship. The mechanisms of PACRs are summarized to understand their synergistic contributions to reactions. The review further examines modern experimental strategies for characterizing surface plasmon resonance properties, including scanning probe microscope, in situ spectroscopy, and ultrafast laser pump-probe techniques, which provide real-time, dynamic insights into molecular interactions and structural changes with high spatial and temporal resolution. We conclude by outlining the challenges and future prospects for PACRs, emphasizing the need for innovative strategies to fully exploit the potential of PACRs for sustainable energy conversion and environmental remediation.
{"title":"Insights into plasmon-assisted chemical reactions: From fabrication to characterization","authors":"Juan Xu , Xinwei Huang , Jing Peng , Shunxing Li , Jian-Feng Li","doi":"10.1016/j.esci.2024.100312","DOIUrl":"10.1016/j.esci.2024.100312","url":null,"abstract":"<div><div>The integration of surface plasmons with catalysis has opened a new frontier in the field of chemical energy conversion, offering unprecedented opportunities for enhancing reaction activity and selectivity. This review delves into the optical properties of plasmonic materials, the intricate mechanisms of plasmon-assisted chemical reactions (PACRs), and the fabrication of plasmonic catalysts, highlighting the significance of the structure–performance relationship. The mechanisms of PACRs are summarized to understand their synergistic contributions to reactions. The review further examines modern experimental strategies for characterizing surface plasmon resonance properties, including scanning probe microscope, <em>in situ</em> spectroscopy, and ultrafast laser pump-probe techniques, which provide real-time, dynamic insights into molecular interactions and structural changes with high spatial and temporal resolution. We conclude by outlining the challenges and future prospects for PACRs, emphasizing the need for innovative strategies to fully exploit the potential of PACRs for sustainable energy conversion and environmental remediation.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 2","pages":"Article 100312"},"PeriodicalIF":42.9,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-27DOI: 10.1016/j.esci.2025.100397
Mingming Wang , Jiale Ma , Yahan Meng , Peiyan Tong , Ruihao Luo , Dongyang Shen , Xinhua Zheng , Na Chen , Mingying Zhang , Li Song , Ziqi Zhang , Dongjun Li , Chengming Wang , Hao Cheng , Yingying Lu , Zhenyu Li , Wei Chen
Aqueous Zn batteries (AZBs) suffer from poor Zn anode reversibility. To address this issue, excess Zn foil is often utilized to prolong the cycle life, but it reduces the actual battery energy density. In this work, we use methylurea molecules to in situ form a solid electrolyte interphase (SEI) layer on the Zn anode, achieving reversible Zn plating/stripping with a maximal Coulombic efficiency (CE) of 99.99% and extending the anode's lifespan to 4500 cycles. Leveraging this highly reversible chemistry, we fabricate and test various anode-free Zn batteries. An anode-free Zn–AC cell exhibits stable cycling for exceeding 5000 cycles, an anode-free Zn–I2 battery with high specific capacities achieves a stable cycle life of 1000 cycles, and an anode-free Zn–Br2 battery with a high areal capacity of 4 mAh cm−2 demonstrates a stable cycle life of 450 cycles. Characterization of the SEI using TEM and DFT calculations reveal the formation mechanisms of the ZnCO3- and ZnS-rich amorphous SEI layer. These results indicate that the design of desirable SEI compositions could pave the way for developing low-cost, high-performance anode-free AZBs.
水锌电池（azb）存在锌阳极可逆性差的问题。为了解决这个问题，过量的锌箔经常被用来延长循环寿命，但它降低了电池的实际能量密度。在这项工作中，我们使用甲基脲分子在锌阳极上原位形成固体电解质间相（SEI）层，实现了可逆的锌电镀/剥离，最大库仑效率（CE）达到99.99%，并将阳极的寿命延长到4500次。利用这种高度可逆的化学反应，我们制造和测试了各种无阳极锌电池。无阳极Zn-AC电池具有超过5000次循环的稳定循环，具有高比容量的无阳极Zn-I2电池具有1000次循环的稳定循环寿命，具有4 mAh cm - 2的高面积容量的无阳极Zn-Br2电池具有450次循环的稳定循环寿命。利用TEM和DFT计算对SEI进行表征，揭示了富ZnCO3-和富zns -非晶SEI层的形成机制。这些结果表明，设计理想的SEI组合物可以为开发低成本、高性能的无阳极azb铺平道路。
{"title":"In situ formation of solid electrolyte interphase facilitates anode-free aqueous zinc battery","authors":"Mingming Wang , Jiale Ma , Yahan Meng , Peiyan Tong , Ruihao Luo , Dongyang Shen , Xinhua Zheng , Na Chen , Mingying Zhang , Li Song , Ziqi Zhang , Dongjun Li , Chengming Wang , Hao Cheng , Yingying Lu , Zhenyu Li , Wei Chen","doi":"10.1016/j.esci.2025.100397","DOIUrl":"10.1016/j.esci.2025.100397","url":null,"abstract":"<div><div>Aqueous Zn batteries (AZBs) suffer from poor Zn anode reversibility. To address this issue, excess Zn foil is often utilized to prolong the cycle life, but it reduces the actual battery energy density. In this work, we use methylurea molecules to <em>in situ</em> form a solid electrolyte interphase (SEI) layer on the Zn anode, achieving reversible Zn plating/stripping with a maximal Coulombic efficiency (CE) of 99.99% and extending the anode's lifespan to 4500 cycles. Leveraging this highly reversible chemistry, we fabricate and test various anode-free Zn batteries. An anode-free Zn–AC cell exhibits stable cycling for exceeding 5000 cycles, an anode-free Zn–I<sub>2</sub> battery with high specific capacities achieves a stable cycle life of 1000 cycles, and an anode-free Zn–Br<sub>2</sub> battery with a high areal capacity of 4 mAh cm<sup>−2</sup> demonstrates a stable cycle life of 450 cycles. Characterization of the SEI using TEM and DFT calculations reveal the formation mechanisms of the ZnCO<sub>3</sub>- and ZnS-rich amorphous SEI layer. These results indicate that the design of desirable SEI compositions could pave the way for developing low-cost, high-performance anode-free AZBs.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 5","pages":"Article 100397"},"PeriodicalIF":36.6,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144890864","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 : 2025-02-26DOI: 10.1016/j.esci.2025.100396
Yizhe Chen , Zeyu Jin , Jialin Sun , Shengli Chen , Jiujun Zhang , Shiming Zhang
Nanostructured platinum (Pt)-skin alloys are promising electrocatalysts for oxygen reduction reaction (ORR) due to their tunable strain and ligand effects which essentially regulate the surface electronic structures. In addition to the chemical nature of alloying elements, the layer numbers of Pt-skin crucially determine the strain and ligand effects. So far, the effects of Pt-skin layer numbers have been generally investigated through vapor deposition on bulk metals and alloys with extended surfaces, while the precise Pt-skin control of nanostructured alloy electrocatalysts in wet chemical synthesis remains fairly challenging. Herein, we develop a Pt-skin engineering strategy to construct a family of dendrite-like porous PtCu@PtnL nanospheres (NSs) with precisely controlled Pt-skin layers by adjusting the reducibility of Cu ions. Density functional theory calculations and X-ray photoelectron spectroscopy-based valence band spectra results indicate a concave parabolic trend of d-band center with varying the Pt-skin layer from 0 to 5, jointly resulting from the skin layer-dependent electron transfer numbers and compression strain. The two-layer Pt-skin alloy, PtCu@Pt2L NS, is identified to have the lowest d-band center and therefore locates at the summit of ORR activity volcano. Accordingly, this carbon supported PtCu@Pt2L NSs catalyst achieves excellent ORR electrocatalysis in H2–O2 proton exchange membrane fuel cells.
{"title":"Precise Pt-skin manipulation of strain and ligand effects for oxygen reduction","authors":"Yizhe Chen , Zeyu Jin , Jialin Sun , Shengli Chen , Jiujun Zhang , Shiming Zhang","doi":"10.1016/j.esci.2025.100396","DOIUrl":"10.1016/j.esci.2025.100396","url":null,"abstract":"<div><div>Nanostructured platinum (Pt)-skin alloys are promising electrocatalysts for oxygen reduction reaction (ORR) due to their tunable strain and ligand effects which essentially regulate the surface electronic structures. In addition to the chemical nature of alloying elements, the layer numbers of Pt-skin crucially determine the strain and ligand effects. So far, the effects of Pt-skin layer numbers have been generally investigated through vapor deposition on bulk metals and alloys with extended surfaces, while the precise Pt-skin control of nanostructured alloy electrocatalysts in wet chemical synthesis remains fairly challenging. Herein, we develop a Pt-skin engineering strategy to construct a family of dendrite-like porous PtCu@Pt<sub>nL</sub> nanospheres (NSs) with precisely controlled Pt-skin layers by adjusting the reducibility of Cu ions. Density functional theory calculations and X-ray photoelectron spectroscopy-based valence band spectra results indicate a concave parabolic trend of <em>d</em>-band center with varying the Pt-skin layer from 0 to 5, jointly resulting from the skin layer-dependent electron transfer numbers and compression strain. The two-layer Pt-skin alloy, PtCu@Pt<sub>2L</sub> NS, is identified to have the lowest <em>d</em>-band center and therefore locates at the summit of ORR activity volcano. Accordingly, this carbon supported PtCu@Pt<sub>2L</sub> NSs catalyst achieves excellent ORR electrocatalysis in H<sub>2</sub>–O<sub>2</sub> proton exchange membrane fuel cells.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 5","pages":"Article 100396"},"PeriodicalIF":36.6,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144887427","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 : 2025-02-15DOI: 10.1016/j.esci.2025.100380
Heyu Zhou , Jinjin Ban , Yonglong Shen , Yilong Ning , Shanshan Zhang , Fanfan Liu , Guoqin Cao , GuoSheng Shao , S. Ravi P. Silva , Junhua Hu
Layered double hydroxides (LDHs) have emerged as highly promising oxygen evolution reaction (OER) catalysts because of their naturally forming two-dimensional (2D) layer structure and intrinsic oxygen vacancies. Numerous efforts to develop synthesis methods as well as modify the structure and composition of LDHs have helped to improve their electrocatalytic performance. Recent strategies to optimize LDHs have gone beyond regulating oxygen vacancies via metal modifications, with innovative ideas of atomic loading and anion-based lattice modification being proposed. In this review, a fundamental understanding of the structural design and its close relationship with the OER mechanism in alkaline media are discussed. Based on the inherent defects and structural characterization of LDHs at an atomic scale, novel progress in promoting OER development activity is summarized, including heteroatomic doping, intercalation, composite construction and single-atom loading. Furthermore, the concept of heteroatoms as electronic defects is emphasized, with the regulation mechanism behind these elucidated by summarizing recent advances in LDHs as highly active OER catalysts. Finally, key challenges to further optimize performance in LDHs catalyst by overcoming the bottleneck of the scaling relationship, expansion of active components and preparation of functionalization, shed light on future research and development directions.
{"title":"Strategies to maximize the oxygen evolution reaction in layered double hydroxides by electronic defect engineering","authors":"Heyu Zhou , Jinjin Ban , Yonglong Shen , Yilong Ning , Shanshan Zhang , Fanfan Liu , Guoqin Cao , GuoSheng Shao , S. Ravi P. Silva , Junhua Hu","doi":"10.1016/j.esci.2025.100380","DOIUrl":"10.1016/j.esci.2025.100380","url":null,"abstract":"<div><div>Layered double hydroxides (LDHs) have emerged as highly promising oxygen evolution reaction (OER) catalysts because of their naturally forming two-dimensional (2D) layer structure and intrinsic oxygen vacancies. Numerous efforts to develop synthesis methods as well as modify the structure and composition of LDHs have helped to improve their electrocatalytic performance. Recent strategies to optimize LDHs have gone beyond regulating oxygen vacancies <em>via</em> metal modifications, with innovative ideas of atomic loading and anion-based lattice modification being proposed. In this review, a fundamental understanding of the structural design and its close relationship with the OER mechanism in alkaline media are discussed. Based on the inherent defects and structural characterization of LDHs at an atomic scale, novel progress in promoting OER development activity is summarized, including heteroatomic doping, intercalation, composite construction and single-atom loading. Furthermore, the concept of heteroatoms as electronic defects is emphasized, with the regulation mechanism behind these elucidated by summarizing recent advances in LDHs as highly active OER catalysts. Finally, key challenges to further optimize performance in LDHs catalyst by overcoming the bottleneck of the scaling relationship, expansion of active components and preparation of functionalization, shed light on future research and development directions.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 5","pages":"Article 100380"},"PeriodicalIF":36.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144887358","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 : 2025-02-13DOI: 10.1016/j.esci.2025.100379
Lei Li , Siqi Liu , Jie Luo , Xunan Hou , Junhua Kong , Qichong Zhang , Wenyong Lai , Chaobin He
Affordable, easily recycled organics with electroactive centers have drawn attention in the pursuit of high-performance aqueous zinc organic batteries (AZOBs). However, intrinsic barriers such as high solubility, undesirable potential, and inferior conductivity hinder their further development. To this end, we have designed an advanced cathode material for AZOBs, comprising an n-type polymer with a three-dimensional (3D) building block (HAT-TP) formed by polymerizing 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexazepenanthrene (HAT-CN) and 3D 2,3,6,7,14,15-hexaaminotriptycene (THA-NH2). The introduction of a 3D architecture not only bolsters the insolubility but also exposes redox-active sites for cation coordination, while the material's extended conjugated system promotes electronic delocalization to increase the redox potential and conductivity. As a result, a HAT-TP battery exhibits a notable initial discharge voltage of 1.32 V at 0.1 A g−1, followed by a midpoint voltage of 1.17 V. Remarkably, an ultrastable capacity retention ratio of up to 93.4% is achieved, even after 40,000 cycles at 5 A g−1. Theoretical simulations reveal that the elevated discharge potential results from the strong electronic delocalization of HAT-TP, which improves the affinity with cations. Ex situ characterizations and theoretical calculations verify that the reversible Zn2+/H+ co-storage mechanism involves only electroactive C=N sites and the best possible coordination paths between them.
{"title":"Three-dimensional architecture design enables hexaazatriphenylene-based polymers as high-voltage, long-lifespan cathodes for aqueous zinc–organic batteries","authors":"Lei Li , Siqi Liu , Jie Luo , Xunan Hou , Junhua Kong , Qichong Zhang , Wenyong Lai , Chaobin He","doi":"10.1016/j.esci.2025.100379","DOIUrl":"10.1016/j.esci.2025.100379","url":null,"abstract":"<div><div>Affordable, easily recycled organics with electroactive centers have drawn attention in the pursuit of high-performance aqueous zinc organic batteries (AZOBs). However, intrinsic barriers such as high solubility, undesirable potential, and inferior conductivity hinder their further development. To this end, we have designed an advanced cathode material for AZOBs, comprising an n-type polymer with a three-dimensional (3D) building block (HAT-TP) formed by polymerizing 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexazepenanthrene (HAT-CN) and 3D 2,3,6,7,14,15-hexaaminotriptycene (THA-NH<sub>2</sub>). The introduction of a 3D architecture not only bolsters the insolubility but also exposes redox-active sites for cation coordination, while the material's extended conjugated system promotes electronic delocalization to increase the redox potential and conductivity. As a result, a HAT-TP battery exhibits a notable initial discharge voltage of 1.32 V at 0.1 A g<sup>−1</sup>, followed by a midpoint voltage of 1.17 V. Remarkably, an ultrastable capacity retention ratio of up to 93.4% is achieved, even after 40,000 cycles at 5 A g<sup>−1</sup>. Theoretical simulations reveal that the elevated discharge potential results from the strong electronic delocalization of HAT-TP, which improves the affinity with cations. <em>Ex situ</em> characterizations and theoretical calculations verify that the reversible Zn<sup>2+</sup>/H<sup>+</sup> co-storage mechanism involves only electroactive C=N sites and the best possible coordination paths between them.</div></div>","PeriodicalId":100489,"journal":{"name":"eScience","volume":"5 4","pages":"Article 100379"},"PeriodicalIF":42.9,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144308024","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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