Many challenges in lithium‐sulfur (Li–S) batteries are associated with the radical change in lithium polysulfide (LPS) solubility during cycling, but chemical approaches to address such inconsistency are still lacking. Here, the use of a strong Lewis acidic fluorinated organoboron, tri(2,2,2‐trifluoroethyl) borate (TFEB), is reported as a multi‐functional mediator to simultaneously overcome multiple technical barriers in practical Li–S batteries. TFEB acts as an anion acceptor and forms strong molecular complexes with Lewis basic LPS. The TFEB‐LPS complexes have consistent solubility across the full polysulfide spectrum and deliver several times improved better redox kinetics, unlocking a true redox catalytic mechanism that covers the majority of redox events in thick sulfur cathodes. As a result, Li–S batteries evaluated under practical conditions exhibit significantly improved discharge capacity, rate capability, and cycling stability with the addition of the TFEB additive. More importantly, TFEB also contributes to the stabilization of lithium anode in the presence of polysulfides by generating strong interfacial film. These attributes significantly improve the cycling stability of practical Li–S pouch cells, which are assembled with a unit energy density of 219 Wh kg−1. The results provide new molecular insights on the design of unlocking solvation networks of practical Li–S systems.
{"title":"A Fluorinated Lewis Acidic Organoboron Tunes Polysulfide Complex Structure for High‐Performance Lithium–Sulfur Batteries","authors":"Siyuan Gao, Bomin Li, Qijia Zhu, Jingtian Yang, Jiayi Xu, Bowen An, Cong Liu, Qin Wu, Qian Liu, Zhengcheng Zhang, Yingwen Cheng","doi":"10.1002/aenm.202403439","DOIUrl":"https://doi.org/10.1002/aenm.202403439","url":null,"abstract":"Many challenges in lithium‐sulfur (Li–S) batteries are associated with the radical change in lithium polysulfide (LPS) solubility during cycling, but chemical approaches to address such inconsistency are still lacking. Here, the use of a strong Lewis acidic fluorinated organoboron, tri(2,2,2‐trifluoroethyl) borate (TFEB), is reported as a multi‐functional mediator to simultaneously overcome multiple technical barriers in practical Li–S batteries. TFEB acts as an anion acceptor and forms strong molecular complexes with Lewis basic LPS. The TFEB‐LPS complexes have consistent solubility across the full polysulfide spectrum and deliver several times improved better redox kinetics, unlocking a true redox catalytic mechanism that covers the majority of redox events in thick sulfur cathodes. As a result, Li–S batteries evaluated under practical conditions exhibit significantly improved discharge capacity, rate capability, and cycling stability with the addition of the TFEB additive. More importantly, TFEB also contributes to the stabilization of lithium anode in the presence of polysulfides by generating strong interfacial film. These attributes significantly improve the cycling stability of practical Li–S pouch cells, which are assembled with a unit energy density of 219 Wh kg<jats:sup>−1</jats:sup>. The results provide new molecular insights on the design of unlocking solvation networks of practical Li–S systems.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142236244","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Selenium (Se) shows promise as a cathode candidate for all-solid-state lithium (Li) batteries due to its impressive theoretical volumetric energy density, much higher electronic conductivity, and improved safety in comparison to those for sulfur (S). An active cathode additive, lithium iodide (LiI) is demonstrated, to address the major challenge for all-solid-state Li–Se batteries, namely the sluggish redox kinetics resulting from the huge solid-state conversion barrier. The LiI additive enhances Li+ transport and provides catalytic sites for Se cathode, thus endowing the batteries with accelerated reaction kinetics and extra capacity. DFT calculation and experimental analysis clearly reveal that LiI additive efficiently accelerates the conversion between polyselenide intermediates and Li2Se. With the above advantages, the battery with LiI using Li6PS5Br electrolyte gives an outstanding capacity of 862 mAh gSe−1 beyond the theoretical specific capacity of Se and a superlong life over 1800 cycles at 1C under room temperature. This work offers a simple strategy to facilitate the kinetics of all-solid-state Se cathodes and paves the way for the practicality of high-capacity and long-life all-solid-state Li–Se batteries.
与硫（S）相比，硒（Se）具有令人印象深刻的理论体积能量密度、更高的电子导电性和更好的安全性，因此有望成为全固态锂（Li）电池的阴极候选材料。我们展示了一种活性正极添加剂--碘化锂（LiI），以解决全固态锂-硒电池面临的主要挑战，即巨大的固态转换障碍导致的缓慢氧化还原动力学。LiI 添加剂增强了 Li+ 的传输，并为硒阴极提供了催化位点，从而加快了电池的反应动力学并提高了电池容量。DFT 计算和实验分析清楚地表明，LiI 添加剂能有效加速多硒化物中间体与 Li2Se 之间的转化。由于上述优点，使用 Li6PS5Br 电解质的 LiI 电池可产生 862 mAh gSe-1 的出色容量，超过了 Se 的理论比容量，并且在室温下 1C 循环 1800 次以上，具有超长寿命。这项工作为促进全固态 Se 阴极的动力学提供了一种简单的策略，并为高容量、长寿命全固态锂-Se 电池的实用化铺平了道路。
{"title":"High-Capacity, Long-Life All-Solid-State Lithium–Selenium Batteries Enabled by Lithium Iodide Active Additive","authors":"Huilin Ge, Dulin Huang, Chuannan Geng, Xichen Cui, Qiang Li, Xu Zhang, Chunpeng Yang, Zhen Zhou, Quan-Hong Yang","doi":"10.1002/aenm.202403449","DOIUrl":"https://doi.org/10.1002/aenm.202403449","url":null,"abstract":"Selenium (Se) shows promise as a cathode candidate for all-solid-state lithium (Li) batteries due to its impressive theoretical volumetric energy density, much higher electronic conductivity, and improved safety in comparison to those for sulfur (S). An active cathode additive, lithium iodide (LiI) is demonstrated, to address the major challenge for all-solid-state Li–Se batteries, namely the sluggish redox kinetics resulting from the huge solid-state conversion barrier. The LiI additive enhances Li<sup>+</sup> transport and provides catalytic sites for Se cathode, thus endowing the batteries with accelerated reaction kinetics and extra capacity. DFT calculation and experimental analysis clearly reveal that LiI additive efficiently accelerates the conversion between polyselenide intermediates and Li<sub>2</sub>Se. With the above advantages, the battery with LiI using Li<sub>6</sub>PS<sub>5</sub>Br electrolyte gives an outstanding capacity of 862 mAh g<sub>Se</sub><sup>−1</sup> beyond the theoretical specific capacity of Se and a superlong life over 1800 cycles at 1C under room temperature. This work offers a simple strategy to facilitate the kinetics of all-solid-state Se cathodes and paves the way for the practicality of high-capacity and long-life all-solid-state Li–Se batteries.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Solid‐state batteries (SSBs) have attracted much attention for high‐energy‐density and high‐safety energy storage devices. Solid polymer electrolytes (SPEs) have emerged as a critical component in the advancement of SSBs, owing to the compelling advantages of strong molecular structure‐designability, low cost, easy manufacturing, and no liquid leakage. However, linear SPEs usually have low room‐temperature ionic conductivity due to crystallization, and melting at high temperature. Thus, crosslinked SPEs have been proposed in that the chemical bonding between internal molecule chains can maintain solid state to expand operational temperature, disrupt regularity of segment, and diminish crystalline degree, leading to an enhancement of room‐temperature ionic conductivity. Furthermore, the integration of functional groups within crosslinked SPE network can significantly augment the electrochemical performance of SPEs. Herein, according to the network structure, crosslinked SPEs are categorized into four types: simple network, AB crosslinked polymers (ABCP), semi‐interpenetrating network (semi‐IPN), and interpenetrating network (IPN), then the structure features and advantages and disadvantages of commonly used polymers for these types of crosslinked SPEs are reviewed. In addition, crosslinked SPEs with self‐healing, flame‐retardant, degradable, and recyclability are introduced. Finally, challenges and prospects of crosslinked SPEs are summarized, hoping to provide guidance for the molecular design of SPEs in the future.
{"title":"Advanced Crosslinked Solid Polymer Electrolytes: Molecular Architecture, Strategies, and Future Perspectives","authors":"Xiaoyue Zeng, Xuewei Liu, Huirong Zhu, Jiaxing Zhu, Jinle Lan, Yunhua Yu, Young‐Seak Lee, Xiaoping Yang","doi":"10.1002/aenm.202402671","DOIUrl":"https://doi.org/10.1002/aenm.202402671","url":null,"abstract":"Solid‐state batteries (SSBs) have attracted much attention for high‐energy‐density and high‐safety energy storage devices. Solid polymer electrolytes (SPEs) have emerged as a critical component in the advancement of SSBs, owing to the compelling advantages of strong molecular structure‐designability, low cost, easy manufacturing, and no liquid leakage. However, linear SPEs usually have low room‐temperature ionic conductivity due to crystallization, and melting at high temperature. Thus, crosslinked SPEs have been proposed in that the chemical bonding between internal molecule chains can maintain solid state to expand operational temperature, disrupt regularity of segment, and diminish crystalline degree, leading to an enhancement of room‐temperature ionic conductivity. Furthermore, the integration of functional groups within crosslinked SPE network can significantly augment the electrochemical performance of SPEs. Herein, according to the network structure, crosslinked SPEs are categorized into four types: simple network, AB crosslinked polymers (ABCP), semi‐interpenetrating network (semi‐IPN), and interpenetrating network (IPN), then the structure features and advantages and disadvantages of commonly used polymers for these types of crosslinked SPEs are reviewed. In addition, crosslinked SPEs with self‐healing, flame‐retardant, degradable, and recyclability are introduced. Finally, challenges and prospects of crosslinked SPEs are summarized, hoping to provide guidance for the molecular design of SPEs in the future.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142236354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jinhao Li, Zixian Li, Qiuhong Sun, Yujun Wang, Yang Li, Yung-Kang Peng, Ye Li, Ce Zhang, Bin Liu, Yufei Zhao
Photocatalysis and electrocatalysis have emerged as promising technologies for addressing the energy crisis and environmental issues. However, the widespread application of these technologies is hampered by the challenge of scaling up the production of photo/electrocatalysts that are not only highly active and stable but also cost-effective and environmentally benign. This review delves into the latest advancements in the large-scale synthesis of photo/electrocatalysts. The factors to be considered in the large-scale production of catalysts are discussed first. The synthesis methods for batch preparation of photo/electrocatalysts are then comprehensively introduced, with a thorough discussion of their respective advantages and limitations. Moreover, the data analysis via machine learning techniques, which not only accelerates the identification and refinement of potential new catalysts but also offers insights for enhancing the high-throughput synthesis of catalysts, is introduced in detail. Then the representative examples are presented to illustrate the applications of large-scale catalysts in the field of industrial-level photo/electrocatalysis. Finally, the challenges and prospects in the development of large-scale production of photo/electrocatalysts are discussed. By bridging the gap between laboratory research and industrial application, this review aims to provide a reference for the future of large-scale preparation of photo/electrocatalysts in sustainable energy conversion and beyond.
{"title":"Recent Advances in the Large-Scale Production of Photo/Electrocatalysts for Energy Conversion and beyond","authors":"Jinhao Li, Zixian Li, Qiuhong Sun, Yujun Wang, Yang Li, Yung-Kang Peng, Ye Li, Ce Zhang, Bin Liu, Yufei Zhao","doi":"10.1002/aenm.202402441","DOIUrl":"https://doi.org/10.1002/aenm.202402441","url":null,"abstract":"Photocatalysis and electrocatalysis have emerged as promising technologies for addressing the energy crisis and environmental issues. However, the widespread application of these technologies is hampered by the challenge of scaling up the production of photo/electrocatalysts that are not only highly active and stable but also cost-effective and environmentally benign. This review delves into the latest advancements in the large-scale synthesis of photo/electrocatalysts. The factors to be considered in the large-scale production of catalysts are discussed first. The synthesis methods for batch preparation of photo/electrocatalysts are then comprehensively introduced, with a thorough discussion of their respective advantages and limitations. Moreover, the data analysis via machine learning techniques, which not only accelerates the identification and refinement of potential new catalysts but also offers insights for enhancing the high-throughput synthesis of catalysts, is introduced in detail. Then the representative examples are presented to illustrate the applications of large-scale catalysts in the field of industrial-level photo/electrocatalysis. Finally, the challenges and prospects in the development of large-scale production of photo/electrocatalysts are discussed. By bridging the gap between laboratory research and industrial application, this review aims to provide a reference for the future of large-scale preparation of photo/electrocatalysts in sustainable energy conversion and beyond.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235450","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rongxin Chen, Li Cheng, Xize Dai, Xinyu He, Trang Thuy Nguyen, Ze Xiang Shen
As a type of 2D materials, layered double hydroxides (LDHs) have emerged as potential candidates for electrochemical energy storage materials. To address their challenges of limited active sites and sluggish charge transfer kinetics, etc., this work presents an ingenious synchronous topochemical pathway (STP) method that enables the in situ anchoring of numerous nanosized Co9S8 on the rigid layers of LDHs. These n‐type anti‐barrier layers, generated by the ohmic contact between a quasi‐metal (Co9S8) and n‐type semiconductor (LDHs), alter the energy band structure and electron states near the Fermi level, optimizing the intrinsic conductivity and deprotonation reaction barriers of LDH materials. The prepared NiCoAl‐LDHs@Co9S8 (LCS) electrode exhibits remarkable electrochemical capacity (473.2 mAh g−¹ at 1 A g−¹) and operational stability (91.2% capacity retention after 20,000 cycles). Furthermore, an aqueous battery device constructed with LCS cathode and Fe‐Ni sulfide (FNS) anode demonstrates an impressive energy density of 118.5 Wh kg−¹ at a power density of 800 W kg−¹. This generalized structural design strategy achieves multiple enhancements in active sites, charge transfer efficiency, and structural stability of LDH materials, providing insights into the potential relationships between energy band and electrochemical performance in energy storage materials.
作为二维材料的一种，层状双氢氧化物（LDHs）已成为电化学储能材料的潜在候选材料。为解决其活性位点有限、电荷转移动力学缓慢等难题，本研究提出了一种巧妙的同步拓扑化学途径（STP）方法，可在 LDHs 的刚性层上原位锚定大量纳米级 Co9S8。这些由准金属（Co9S8）和 n 型半导体（LDHs）之间的欧姆接触产生的 n 型反势垒层改变了费米级附近的能带结构和电子状态，优化了 LDH 材料的内在电导率和去质子化反应势垒。所制备的镍钴铝-LDHs@Co9S8（LCS）电极具有显著的电化学容量（1 A g-¹ 时为 473.2 mAh g-¹）和操作稳定性（20,000 次循环后容量保持率为 91.2%）。此外，使用 LCS 阴极和硫化铁-镍（FNS）阳极构建的水电池装置在功率密度为 800 W kg-¹ 时，能量密度达到了惊人的 118.5 Wh kg-¹。这种通用结构设计策略实现了 LDH 材料在活性位点、电荷转移效率和结构稳定性方面的多重提升，为了解储能材料的能带和电化学性能之间的潜在关系提供了启示。
{"title":"Rational Construction of Heterostructures with n‐Type Anti‐Barrier Layer for Enhanced Electrochemical Energy Storage","authors":"Rongxin Chen, Li Cheng, Xize Dai, Xinyu He, Trang Thuy Nguyen, Ze Xiang Shen","doi":"10.1002/aenm.202402930","DOIUrl":"https://doi.org/10.1002/aenm.202402930","url":null,"abstract":"As a type of 2D materials, layered double hydroxides (LDHs) have emerged as potential candidates for electrochemical energy storage materials. To address their challenges of limited active sites and sluggish charge transfer kinetics, etc., this work presents an ingenious synchronous topochemical pathway (STP) method that enables the in situ anchoring of numerous nanosized Co<jats:sub>9</jats:sub>S<jats:sub>8</jats:sub> on the rigid layers of LDHs. These n‐type anti‐barrier layers, generated by the ohmic contact between a quasi‐metal (Co<jats:sub>9</jats:sub>S<jats:sub>8</jats:sub>) and n‐type semiconductor (LDHs), alter the energy band structure and electron states near the Fermi level, optimizing the intrinsic conductivity and deprotonation reaction barriers of LDH materials. The prepared NiCoAl‐LDHs@Co<jats:sub>9</jats:sub>S<jats:sub>8</jats:sub> (LCS) electrode exhibits remarkable electrochemical capacity (473.2 mAh g<jats:sup>−</jats:sup>¹ at 1 A g<jats:sup>−</jats:sup>¹) and operational stability (91.2% capacity retention after 20,000 cycles). Furthermore, an aqueous battery device constructed with LCS cathode and Fe‐Ni sulfide (FNS) anode demonstrates an impressive energy density of 118.5 Wh kg<jats:sup>−</jats:sup>¹ at a power density of 800 W kg<jats:sup>−</jats:sup>¹. This generalized structural design strategy achieves multiple enhancements in active sites, charge transfer efficiency, and structural stability of LDH materials, providing insights into the potential relationships between energy band and electrochemical performance in energy storage materials.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142236245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Stretchable organic photovoltaics (OPVs) are pivotal for advancing conformable electronics, yet achieving both efficient and intrinsically stretchable OPVs remains a significant challenge. The main issue is maintaining electronic and mechanical properties under deformation. Here, a ternary blend system, PTzBI-oF:PYIT:EVA is presented, incorporating ethylene-vinyl acetate (EVA) to establish a conjugated and elastomeric dual-network morphology. The elastomer network dissipates applied stress, preserving the crystalline packing of the conjugated network and enabling improved mechanical stability of charge carrier generation and transport. Specifically, with 15% EVA content, the ternary blend achieved a power conversion efficiency (PCE) of 15.28% in rigid devices and exhibited a crack onset strain of 17.23%. Notably, the stretchable OPVs retained over 80% of their initial PCE under 30% strain. These findings underscore the potential of conjugated and elastomeric dual-network morphology in developing high-performance stretchable electronics for various applications.
{"title":"Achieving Efficient Intrinsically Stretchable Organic Photovoltaics with a Conjugated and Elastomeric Dual-Network Morphology","authors":"Wenyu Yang, Xuanang Luo, Mingke Li, Chuqi Shi, Zaiyu Wang, Zhiyuan Yang, Jiaming Wu, Xiaowei Zhang, Wenbo Huang, Dongge Ma, Cheng Wang, Wenkai Zhong, Lei Ying","doi":"10.1002/aenm.202403259","DOIUrl":"https://doi.org/10.1002/aenm.202403259","url":null,"abstract":"Stretchable organic photovoltaics (OPVs) are pivotal for advancing conformable electronics, yet achieving both efficient and intrinsically stretchable OPVs remains a significant challenge. The main issue is maintaining electronic and mechanical properties under deformation. Here, a ternary blend system, PTzBI-oF:PYIT:EVA is presented, incorporating ethylene-vinyl acetate (EVA) to establish a conjugated and elastomeric dual-network morphology. The elastomer network dissipates applied stress, preserving the crystalline packing of the conjugated network and enabling improved mechanical stability of charge carrier generation and transport. Specifically, with 15% EVA content, the ternary blend achieved a power conversion efficiency (PCE) of 15.28% in rigid devices and exhibited a crack onset strain of 17.23%. Notably, the stretchable OPVs retained over 80% of their initial PCE under 30% strain. These findings underscore the potential of conjugated and elastomeric dual-network morphology in developing high-performance stretchable electronics for various applications.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jianpei Feng, Chun Hong Mak, Guohua Jia, Bin Han, Hsin-Hui Shen, Shella Permatasari Santoso, Ji-Jung Kai, Mingjian Yuan, Haisheng Song, Juan Carlos Colmenares, Hsien-Yi Hsu
To combat the energy crisis and environmental pollution, developing renewable energy technology such as hydrogen (H2) production is necessary. The sulfur–iodine thermochemical cycle has high commercial potential in conducting hydrogen iodide (HI) splitting for H2 generation, but it requires high-temperature conditions. In comparison, photocatalytic HI splitting of halide perovskites is non-polluted and low-cost for H2 production at room temperature. Herein, an in situ constructed multidimensional bismuth (Bi)-based 3D/2D EDABiI5/MA3Bi2I9 perovskite heterojunction is developed first by synergistically integrating dimensionality control with heterostructure engineering. Accordingly, the optimal EDABiI5/MA3Bi2I9 without any co-catalysts exhibits the H2 evolution rate of 213.63 µmol h−1g−1 under irradiation. Equally importantly, interfacial dynamics of solid/solid and solid/liquid interfaces play a crucial role in photocatalytic performance. Therefore, using temperature-dependent transient photoluminescence and electrochemical voltammetric techniques, it is confirmed that the exciton transportation of EDABiI5/MA3Bi2I9 is accelerated by stronger electronic coupling arising from an enhanced overlap of electronic wavefunctions. Moreover, the effective diffusion coefficient and electron transfer rate of EDABiI5/MA3Bi2I9 demonstrate efficient heterogeneous electron transfer, resulting in improved photocatalytic hydrogen production. Consequently, the in situ formation of perovskite heterostructures studied by a combination of photophysical and electrochemical techniques provides new insights into green hydrogen evolution and interfacial interaction dynamics for commercial applications of solar-to-fuel technology.
{"title":"Unlocking Interfacial Interactions of In Situ Grown Multidimensional Bismuth-Based Perovskite Heterostructures for Photocatalytic Hydrogen Evolution","authors":"Jianpei Feng, Chun Hong Mak, Guohua Jia, Bin Han, Hsin-Hui Shen, Shella Permatasari Santoso, Ji-Jung Kai, Mingjian Yuan, Haisheng Song, Juan Carlos Colmenares, Hsien-Yi Hsu","doi":"10.1002/aenm.202402785","DOIUrl":"https://doi.org/10.1002/aenm.202402785","url":null,"abstract":"To combat the energy crisis and environmental pollution, developing renewable energy technology such as hydrogen (H<sub>2</sub>) production is necessary. The sulfur–iodine thermochemical cycle has high commercial potential in conducting hydrogen iodide (HI) splitting for H<sub>2</sub> generation, but it requires high-temperature conditions. In comparison, photocatalytic HI splitting of halide perovskites is non-polluted and low-cost for H<sub>2</sub> production at room temperature. Herein, an in situ constructed multidimensional bismuth (Bi)-based 3D/2D EDABiI<sub>5</sub>/MA<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> perovskite heterojunction is developed first by synergistically integrating dimensionality control with heterostructure engineering. Accordingly, the optimal EDABiI<sub>5</sub>/MA<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> without any co-catalysts exhibits the H<sub>2</sub> evolution rate of 213.63 µmol h<sup>−1</sup>g<sup>−1</sup> under irradiation. Equally importantly, interfacial dynamics of solid/solid and solid/liquid interfaces play a crucial role in photocatalytic performance. Therefore, using temperature-dependent transient photoluminescence and electrochemical voltammetric techniques, it is confirmed that the exciton transportation of EDABiI<sub>5</sub>/MA<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> is accelerated by stronger electronic coupling arising from an enhanced overlap of electronic wavefunctions. Moreover, the effective diffusion coefficient and electron transfer rate of EDABiI<sub>5</sub>/MA<sub>3</sub>Bi<sub>2</sub>I<sub>9</sub> demonstrate efficient heterogeneous electron transfer, resulting in improved photocatalytic hydrogen production. Consequently, the in situ formation of perovskite heterostructures studied by a combination of photophysical and electrochemical techniques provides new insights into green hydrogen evolution and interfacial interaction dynamics for commercial applications of solar-to-fuel technology.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142234301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jin Cao, Yan Jin, Haiyang Wu, Yilei Yue, Dongdong Zhang, Ding Luo, Lulu Zhang, Jiaqian Qin, Xuelin Yang
The cost-effectiveness and environmental benefits of aqueous zinc-ion batteries (ZIBs) have attracted considerable attention. However, practical applications are hindered by side processes including dendritic growth and hydrogen evolution corrosion. Herein, gallium ions (Ga3+) have been chosen as a multifunctional electrolyte additive to improve the reversibility of zinc-ion batteries (ZIBs). Remarkably, Ga3+ ions adhere to the anode surface, establishing a dynamic electrostatic shielding layer that modulates Zn2+ deposition and prevents side reactions. Typically, Ga3+ ions preferentially adsorb onto the (002) and (110) planes of Zn, facilitating preferential deposition on the (100) plane, resulting in a dendrites-free zinc anode. Consequently, the Zn||Zn symmetrical cell with Ga3+-modified electrolyte demonstrates a prolonged lifespan of 4000 h, while the Zn||Ti asymmetric cell exhibits an impressive coulombic efficiency of 99.12% for zinc stripping and plating at 2 mA cm−2. Additionally, the Zn||VO2 cell maintains high capacity retention after 1500 cycles at 5 A g−1. This work presents Ga3+ ions as an electrolyte additive, facilitating the development of a durable dynamic electrostatic shielding effect and preferential (100) plane electroplating, ensuring zinc deposition free from dendrite formation. Such discoveries form a basis for future investigations into novel materials to propel advancements in metal battery technology.
{"title":"Enhancing Zinc Anode Stability with Gallium Ion-Induced Electrostatic Shielding and Oriented Plating","authors":"Jin Cao, Yan Jin, Haiyang Wu, Yilei Yue, Dongdong Zhang, Ding Luo, Lulu Zhang, Jiaqian Qin, Xuelin Yang","doi":"10.1002/aenm.202403175","DOIUrl":"https://doi.org/10.1002/aenm.202403175","url":null,"abstract":"The cost-effectiveness and environmental benefits of aqueous zinc-ion batteries (ZIBs) have attracted considerable attention. However, practical applications are hindered by side processes including dendritic growth and hydrogen evolution corrosion. Herein, gallium ions (Ga<sup>3+</sup>) have been chosen as a multifunctional electrolyte additive to improve the reversibility of zinc-ion batteries (ZIBs). Remarkably, Ga<sup>3+</sup> ions adhere to the anode surface, establishing a dynamic electrostatic shielding layer that modulates Zn<sup>2+</sup> deposition and prevents side reactions. Typically, Ga<sup>3+</sup> ions preferentially adsorb onto the (002) and (110) planes of Zn, facilitating preferential deposition on the (100) plane, resulting in a dendrites-free zinc anode. Consequently, the Zn||Zn symmetrical cell with Ga<sup>3+</sup>-modified electrolyte demonstrates a prolonged lifespan of 4000 h, while the Zn||Ti asymmetric cell exhibits an impressive coulombic efficiency of 99.12% for zinc stripping and plating at 2 mA cm<sup>−2</sup>. Additionally, the Zn||VO<sub>2</sub> cell maintains high capacity retention after 1500 cycles at 5 A g<sup>−1</sup>. This work presents Ga<sup>3+</sup> ions as an electrolyte additive, facilitating the development of a durable dynamic electrostatic shielding effect and preferential (100) plane electroplating, ensuring zinc deposition free from dendrite formation. Such discoveries form a basis for future investigations into novel materials to propel advancements in metal battery technology.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142234304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Elizabeth Cepero-Rodríguez, Ana Sousa-Castillo, Lucas V. Besteiro, Begoña Puértolas, Margarita Vázquez-González, M.A Correa-Duarte
Photocatalytic CO2 reduction is gaining more interest as a sustainable route to produce methanol, a key starting material in the synthesis of many chemicals and a potential energy carrier. Here, metal-organic frameworks (MOFs) are used as platforms to integrate plasmonic Au nanospheres and Cu active centers in joint bifunctional hybrid photocatalysts. The methodology followed in obtaining stable Au@UiO-67-bpy-Cu MOFs is based on synthesizing Au@UiO-67-bypiridine (bpy) MOFs through a core-shell procedure, and then modifying them with Cu ions after their coordination with the bpy ligands. This gains the final structure regular coverage of active metal centers that can be excited by the interaction with the plasmonic nanospheres. In the absence of Au, the system demonstrates selectivity toward the formation of methanol under hole scavenger-free conditions owing to the excitation of the bpy-Cu complex with visible light. The obtained yield duplicates upon Au nanospheres incorporation as a result of the injection of hot electrons, excited by surface-mediated intraband processes, to the bpy-Cu states, thus increasing their CO2 reduction efficiency. Additionally, the catalytic activity remains stable during four consecutive cycles.
{"title":"Bifunctional Au@UiO-67-bpy-Cu Plasmonic Nanostructures for the Solar-Driven CO2 Reduction to Methanol","authors":"Elizabeth Cepero-Rodríguez, Ana Sousa-Castillo, Lucas V. Besteiro, Begoña Puértolas, Margarita Vázquez-González, M.A Correa-Duarte","doi":"10.1002/aenm.202401887","DOIUrl":"https://doi.org/10.1002/aenm.202401887","url":null,"abstract":"Photocatalytic CO<sub>2</sub> reduction is gaining more interest as a sustainable route to produce methanol, a key starting material in the synthesis of many chemicals and a potential energy carrier. Here, metal-organic frameworks (MOFs) are used as platforms to integrate plasmonic Au nanospheres and Cu active centers in joint bifunctional hybrid photocatalysts. The methodology followed in obtaining stable Au@UiO-67-bpy-Cu MOFs is based on synthesizing Au@UiO-67-bypiridine (bpy) MOFs through a core-shell procedure, and then modifying them with Cu ions after their coordination with the bpy ligands. This gains the final structure regular coverage of active metal centers that can be excited by the interaction with the plasmonic nanospheres. In the absence of Au, the system demonstrates selectivity toward the formation of methanol under hole scavenger-free conditions owing to the excitation of the bpy-Cu complex with visible light. The obtained yield duplicates upon Au nanospheres incorporation as a result of the injection of hot electrons, excited by surface-mediated intraband processes, to the bpy-Cu states, thus increasing their CO<sub>2</sub> reduction efficiency. Additionally, the catalytic activity remains stable during four consecutive cycles.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142234302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Seokjae Hong, Kwang Ho Shin, Seulgi Kim, Seok Hyun Song, Kyoung Sun Kim, Dongju Lee, Seung-Ho Yu, Sung-Kyun Jung, Hyungsub Kim
Cubic-garnet solid electrolyte has garnered significant attention in all-solid-state batteries (ASSBs) due to its ionic conductivity and chemical robustness against Li metal. However, the short-circuit formation at low current density poses a significant obstacle with the main cause remaining ambiguous. Here, the lithium-penetration mode originating from phase transformation is unveiled at the sintered pellet surface via mechanically induced lithiation. Mechanical stress applied during polishing under excess lithium content induces lithiation into the cubic-garnet structure, leading to partial structural evolution into the tetragonal phase. This surface alteration induces current constriction, hindered by sluggish interfacial Li-ion transport from the tetragonal phase, which exhibits low ionic conductivity, causing short circuits. By reducing mechanical stress, mitigating surface strain, and restoring the cubic phase, stable operation is ensured without short-circuit formation in both Li symmetric and hybrid-full cells. This insights illuminate the origin of lithium penetration related to phase transition at the surface of cubic-garnet and pave the way for enhancements in ASSB development.
{"title":"Mechanical-Stress-Induced Lithiation and Structural Evolution Driven by Excess Lithium Predisposing Short Circuits at the Surface of Garnet Solid Electrolytes","authors":"Seokjae Hong, Kwang Ho Shin, Seulgi Kim, Seok Hyun Song, Kyoung Sun Kim, Dongju Lee, Seung-Ho Yu, Sung-Kyun Jung, Hyungsub Kim","doi":"10.1002/aenm.202402666","DOIUrl":"https://doi.org/10.1002/aenm.202402666","url":null,"abstract":"Cubic-garnet solid electrolyte has garnered significant attention in all-solid-state batteries (ASSBs) due to its ionic conductivity and chemical robustness against Li metal. However, the short-circuit formation at low current density poses a significant obstacle with the main cause remaining ambiguous. Here, the lithium-penetration mode originating from phase transformation is unveiled at the sintered pellet surface via mechanically induced lithiation. Mechanical stress applied during polishing under excess lithium content induces lithiation into the cubic-garnet structure, leading to partial structural evolution into the tetragonal phase. This surface alteration induces current constriction, hindered by sluggish interfacial Li-ion transport from the tetragonal phase, which exhibits low ionic conductivity, causing short circuits. By reducing mechanical stress, mitigating surface strain, and restoring the cubic phase, stable operation is ensured without short-circuit formation in both Li symmetric and hybrid-full cells. This insights illuminate the origin of lithium penetration related to phase transition at the surface of cubic-garnet and pave the way for enhancements in ASSB development.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235481","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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