The practical application of Na3V2(PO4)3, a polyanionic cathode for sodium-ion batteries, is constrained by its poor electronic conductivity, limited specific capacity, and slow kinetics. In this study, an integrated polyanion-layered oxide cathode embedded within a porous carbon framework is designed. This cathode features an intergrown biphasic heterostructure, consisting of a Na-rich polyanionic compound, Na3.5V1.5Fe0.5(PO4)3 (NVFP), and a layered oxide, V2O3, (NVFP-VO) which is optimized to enhance Na-ion storage performance. Fe doping reduces the bandgap of Na3V2(PO4)3 and activates its V4+/V5+ redox couple, enhancing both electronic conductivity and specific capacity. The porous carbon framework further improves the electronic conductivity of the integrated cathode and accommodates volume fluctuations during cycling. The heterostructure lowers ion transport barriers and accelerates reaction kinetics. Additionally, the low-strain V2O3 phase functions as a stabilizer, effectively buffering volume fluctuations and stress gradients in NVFP. The spontaneous activation of V2O3 further increases the capacity of the integrated cathode. Consequently, the cathode achieves a high reversible capacity of over 130 mAh g−1 at 0.1 C and exhibits unprecedented cyclability, maintaining over 100,000 cycles with 72.6% capacity retention at 100 C in half-cells. This represents the longest cycle life reported among polyanion-based cathodes. In addition, our prepared Ah-level pouch cells exhibit a high energy density of 153.4 W h kg-1 and a long cycle life exceeding 500 cycles. This study demonstrates that synergistic effects in multiphase integrated cathodes promote the development of advanced cathode materials for high-energy-density, fast-charging, and long-life sodium-ion batteries.
Na3V2(PO4)3是一种用于钠离子电池的聚阴离子阴极，其电子导电性差，比容量有限，动力学慢，限制了其实际应用。在本研究中，设计了一种嵌入多孔碳框架内的集成聚阴离子层状氧化物阴极。该阴极具有互生的双相异质结构，由富含na的聚阴离子化合物Na3.5V1.5Fe0.5(PO4)3 （NVFP）和层状氧化物V2O3 （NVFP- vo）组成，该氧化物经过优化以提高na离子的存储性能。Fe掺杂减小了Na3V2(PO4)3的带隙，激活了其V4+/V5+氧化还原对，提高了电导率和比容量。多孔碳框架进一步提高了集成阴极的电子导电性，并适应循环过程中的体积波动。异质结构降低了离子传递障碍，加速了反应动力学。此外，低应变V2O3相作为稳定剂，有效缓冲NVFP中的体积波动和应力梯度。V2O3的自发活化进一步提高了集成阴极的容量。因此，阴极在0.1 C下获得了超过130 mAh g−1的高可逆容量，并表现出前所未有的可循环性，在100 C的半电池中保持超过100,000次循环，容量保持率为72.6%。这代表了在聚阴离子基阴极中报道的最长的循环寿命。此外，我们制备的ah级袋状电池具有153.4 W h kg-1的高能量密度和超过500次循环的长循环寿命。该研究表明，多相集成阴极的协同效应促进了高能量密度、快速充电和长寿命钠离子电池的先进阴极材料的发展。
{"title":"Integrated Polyanion-Layered Oxide Cathodes Enabling 100,000 Cycle Life for Sodium-Ion Batteries","authors":"Zhiyu Zou, Yongbiao Mu, Meisheng Han, Youqi Chu, Jie Liu, Kunxiong Zheng, Qing Zhang, Manrong Song, JIAN Qinping, Yilin Wang, Hengyuan Hu, Fenghua Yu, Wenjia Li, Lei Wei, Lin Zeng, Tianshou Zhao","doi":"10.1039/d4ee05110f","DOIUrl":"https://doi.org/10.1039/d4ee05110f","url":null,"abstract":"The practical application of Na<small><sub>3</sub></small>V<small><sub>2</sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small>, a polyanionic cathode for sodium-ion batteries, is constrained by its poor electronic conductivity, limited specific capacity, and slow kinetics. In this study, an integrated polyanion-layered oxide cathode embedded within a porous carbon framework is designed. This cathode features an intergrown biphasic heterostructure, consisting of a Na-rich polyanionic compound, Na<small><sub>3.5</sub></small>V<small><sub>1.5</sub></small>Fe<small><sub>0.5</sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> (NVFP), and a layered oxide, V<small><sub>2</sub></small>O<small><sub>3</sub></small>, (NVFP-VO) which is optimized to enhance Na-ion storage performance. Fe doping reduces the bandgap of Na<small><sub>3</sub></small>V<small><sub>2</sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> and activates its V<small><sup>4+</sup></small>/V<small><sup>5+</sup></small> redox couple, enhancing both electronic conductivity and specific capacity. The porous carbon framework further improves the electronic conductivity of the integrated cathode and accommodates volume fluctuations during cycling. The heterostructure lowers ion transport barriers and accelerates reaction kinetics. Additionally, the low-strain V<small><sub>2</sub></small>O<small><sub>3</sub></small> phase functions as a stabilizer, effectively buffering volume fluctuations and stress gradients in NVFP. The spontaneous activation of V<small><sub>2</sub></small>O<small><sub>3</sub></small> further increases the capacity of the integrated cathode. Consequently, the cathode achieves a high reversible capacity of over 130 mAh g<small><sup>−1</sup></small> at 0.1 C and exhibits unprecedented cyclability, maintaining over 100,000 cycles with 72.6% capacity retention at 100 C in half-cells. This represents the longest cycle life reported among polyanion-based cathodes. In addition, our prepared Ah-level pouch cells exhibit a high energy density of 153.4 W h kg<small><sup>-1</sup></small> and a long cycle life exceeding 500 cycles. This study demonstrates that synergistic effects in multiphase integrated cathodes promote the development of advanced cathode materials for high-energy-density, fast-charging, and long-life sodium-ion batteries.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"28 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020798","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}
Halide segregation under light exposure is a critical factor contributing to performance degradation of wide-bandgap perovskite solar cells (WBG PSCs). While this degradation has been traditionally linked to deficits in open-circuit voltage, our study identifies an initial sharp loss in short-circuit current density (JSC) as a significant inducement in the efficiency decline, particularly within the first ~240 seconds of light irradiation. By systematically varying the thickness of perovskite films, we observed two distinct migration modes of halide ions. Our results indicate that the rapid formation of I-rich terminal domains (~760 nm; ~1.63 eV) plays a pivotal role in the JSC loss, rather than the gradually red-shifted phases typically seen in perovskite films. We found that in thicker films (~420 nm), significant compressive strain in the crystal-stacked structure accelerates the formation of these I-rich domains. In contrast, thinner films (~190 nm) exhibit a structure of vertically oriented crystals, despite having higher defect concentration and more pronounced photoinduced halide segregation, which enhances carrier extraction and stabilizes JSC output. These findings highlight the importance of crystallization regulation in perovskite films as a strategy to mitigate JSC loss and improve the photostability of WBG PSCs. Our research provides new insights into the mechanisms behind halide segregation and its impact on device performance, offering practical solutions for enhancing the long-term performance of WBG PSCs.
{"title":"Unveiling the impact of photoinduced halide segregation on performance degradation in wide-bandgap perovskite solar cells","authors":"Yuxiao Guo, Cong Zhang, Linqin Wang, Xingtian Yin, Bihui Sun, Changting Wei, Xin Luo, Shiyu Yang, Licheng Sun, Bo Xu","doi":"10.1039/d4ee05604c","DOIUrl":"https://doi.org/10.1039/d4ee05604c","url":null,"abstract":"Halide segregation under light exposure is a critical factor contributing to performance degradation of wide-bandgap perovskite solar cells (WBG PSCs). While this degradation has been traditionally linked to deficits in open-circuit voltage, our study identifies an initial sharp loss in short-circuit current density (JSC) as a significant inducement in the efficiency decline, particularly within the first ~240 seconds of light irradiation. By systematically varying the thickness of perovskite films, we observed two distinct migration modes of halide ions. Our results indicate that the rapid formation of I-rich terminal domains (~760 nm; ~1.63 eV) plays a pivotal role in the JSC loss, rather than the gradually red-shifted phases typically seen in perovskite films. We found that in thicker films (~420 nm), significant compressive strain in the crystal-stacked structure accelerates the formation of these I-rich domains. In contrast, thinner films (~190 nm) exhibit a structure of vertically oriented crystals, despite having higher defect concentration and more pronounced photoinduced halide segregation, which enhances carrier extraction and stabilizes JSC output. These findings highlight the importance of crystallization regulation in perovskite films as a strategy to mitigate JSC loss and improve the photostability of WBG PSCs. Our research provides new insights into the mechanisms behind halide segregation and its impact on device performance, offering practical solutions for enhancing the long-term performance of WBG PSCs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"6 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992360","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}
While the effects of Sr segregation on the performance and stability of perovskite electrodes in solid oxide electrolysis cells (SOECs) have been widely studied, most attention has been focused on surface Sr segregates, with the impact of the resulting Sr deficiencies within the bulk phase of the electrodes largely ignored. Here, we report our findings from an investigation into the impact of Sr deficiency in SrCo0.7Fe0.3O3-δ (SCF) lattice and surface Sr segregates on the electrochemical behavior of well-controlled anode materials. Results demonstrate that Sr deficiencies in the perovskite lattice significantly enhance bulk oxygen ion transport, while surface Sr segregates surpress oxygen vacancy formation at interfaces, resulting in a reduced rate of oxygen exchange and lower surface electrical conductivity. Our study provides critical insights into the roles of bulk Sr deficiencies and surface Sr segregates, particularly their effects on oxygen vacancy formation, electrical conductivity, oxygen ion transport, and the overall rate of high-temperature oxygen evolution reactions.
{"title":"A Comprehensive Investigation of Sr Segregation Effects on the High-temperature Oxygen Evolution Reaction Rate","authors":"Weicheng Feng, Geng Zou, Tianfu Liu, Rongtan Li, Jingcheng Yu, Yige Guo, Qingxue Liu, Xiaomin Zhang, Junhu Wang, Na Ta, Mingrun Li, Peng Zhang, Xing-Zhong Cao, Runsheng Yu, Yuefeng Song, Meilin Liu, Guoxiong Wang, Xinhe Bao","doi":"10.1039/d4ee05056h","DOIUrl":"https://doi.org/10.1039/d4ee05056h","url":null,"abstract":"While the effects of Sr segregation on the performance and stability of perovskite electrodes in solid oxide electrolysis cells (SOECs) have been widely studied, most attention has been focused on surface Sr segregates, with the impact of the resulting Sr deficiencies within the bulk phase of the electrodes largely ignored. Here, we report our findings from an investigation into the impact of Sr deficiency in SrCo0.7Fe0.3O3-δ (SCF) lattice and surface Sr segregates on the electrochemical behavior of well-controlled anode materials. Results demonstrate that Sr deficiencies in the perovskite lattice significantly enhance bulk oxygen ion transport, while surface Sr segregates surpress oxygen vacancy formation at interfaces, resulting in a reduced rate of oxygen exchange and lower surface electrical conductivity. Our study provides critical insights into the roles of bulk Sr deficiencies and surface Sr segregates, particularly their effects on oxygen vacancy formation, electrical conductivity, oxygen ion transport, and the overall rate of high-temperature oxygen evolution reactions.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"32 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992368","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}
Hyun Woo Lim, Tae Kyung Lee, Subin Park, Dwi Sakti Aldianto Pratama, Bingyi Yan, Sung Jong Yoo, Chan Woo Lee, Jin Young Kim
Anion-exchange-membrane water electrolysis (AEMWE) is an emerging technology for hydrogen production. While nanoparticles are used as catalysts to enhance catalytic activity, they face durability challenges due to high surface energy and reactivity. Here we present a core–shell nanocluster catalyst featuring a Ru metal core encapsulated in a porous/reduced titania monolayer, incorporating Mo atoms. This core–shell structure not only protects the unstable metal core but also lowers the energy barriers for water dissociation. The synergistic interface formed by the titania heterostructure and Mo doping modulates the electron density distribution of ruthenium active sites, fine-tuning the d-band electronic structure and optimizing the intermediate binding strengths. As a result, exceptionally low overpotentials of just 2 mV at 10 mA cm−2 and 120 mV at 500 mA cm−2 could be achieved. In a practical AEMWE system, the core–shell catalyst shows an outstanding current density of 3.35 A cm−2 under a cell voltage of 2.0 V at 60 °C, preserving its activity over 530 h of long-term electrolysis at 0.5 A cm−2.
阴离子交换膜电解是一种新兴的制氢技术。虽然纳米颗粒被用作催化剂来提高催化活性，但由于其高表面能和反应活性，它们面临着耐久性的挑战。在这里，我们提出了一种核壳纳米团簇催化剂，其特征是Ru金属芯被封装在多孔/还原二氧化钛单层中，并结合Mo原子。这种核壳结构不仅保护了不稳定的金属核，而且降低了水解离的能垒。二氧化钛异质结构与Mo掺杂形成的协同界面调节了钌活性位点的电子密度分布，微调了d波段电子结构，优化了中间结合强度。因此，可以实现极低的过电位，在10 mA cm - 2时仅为2 mV，在500 mA cm - 2时为120 mV。在实际的AEMWE系统中，当电池电压为2.0 V，温度为60°C时，核壳催化剂的电流密度为3.35 a cm−2，在0.5 a cm−2的电解条件下，其活性保持在530 h以上。
{"title":"A ruthenium-titania core–shell nanocluster catalyst for efficient and durable alkaline hydrogen evolution","authors":"Hyun Woo Lim, Tae Kyung Lee, Subin Park, Dwi Sakti Aldianto Pratama, Bingyi Yan, Sung Jong Yoo, Chan Woo Lee, Jin Young Kim","doi":"10.1039/d4ee04867a","DOIUrl":"https://doi.org/10.1039/d4ee04867a","url":null,"abstract":"Anion-exchange-membrane water electrolysis (AEMWE) is an emerging technology for hydrogen production. While nanoparticles are used as catalysts to enhance catalytic activity, they face durability challenges due to high surface energy and reactivity. Here we present a core–shell nanocluster catalyst featuring a Ru metal core encapsulated in a porous/reduced titania monolayer, incorporating Mo atoms. This core–shell structure not only protects the unstable metal core but also lowers the energy barriers for water dissociation. The synergistic interface formed by the titania heterostructure and Mo doping modulates the electron density distribution of ruthenium active sites, fine-tuning the d-band electronic structure and optimizing the intermediate binding strengths. As a result, exceptionally low overpotentials of just 2 mV at 10 mA cm<small><sup>−2</sup></small> and 120 mV at 500 mA cm<small><sup>−2</sup></small> could be achieved. In a practical AEMWE system, the core–shell catalyst shows an outstanding current density of 3.35 A cm<small><sup>−2</sup></small> under a cell voltage of 2.0 V at 60 °C, preserving its activity over 530 h of long-term electrolysis at 0.5 A cm<small><sup>−2</sup></small>.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"10 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992359","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}
Lebin Cai, Haoyun Bai, Jilong Li, Feng Xie, Kang Jiang, Ying-Rui Lu, Hui Pan, Yongwen Tan
Electrocatalytic urea oxidation reaction (UOR) has emerged as a promising alternative to oxygen evolution reaction (OER) for wastewater recycling and energy recovery. However, traditional UOR pathway on NiOOH surface faces is hindered by the rate-limiting desorption of *COO and the competition between UOR and OER. In this study, we propose a chemical-electrochemical coupled pathway for direct UOR, achieved through the construction of single-atom W-doped nanoporous P-Ni(OH)2 catalyst (np/W-P-Ni(OH)2). Specifically, np/W-P-Ni(OH)2 catalyst exhibits exceptional UOR performance with an ultralow potential of 1.28 V vs. RHE to reach 10 mA cm-2 and a high UOR selectivity exceeding 90% across the entire potential range. A collection of in-situ spectroscopies and theoretical calculations reveal that single-atom W dopant not only accelerates the formation of Ni(OH)O active intermediates by modulating the O charge in the lattice hydroxyl, but also lowers the energy barrier of the proton-coupled electron transfer step and the cleavage of C−N bond, thus realizing the highly-efficient UOR.
电催化尿素氧化反应（UOR）已成为除氧反应（OER）之外的一种很有前途的废水循环利用和能源回收方法。然而，由于*COO的限速解吸和UOR与OER的竞争，NiOOH表面上传统的UOR途径受到阻碍。在这项研究中，我们提出了一种化学-电化学耦合途径，通过构建单原子w掺杂纳米多孔P-Ni(OH)2催化剂（np/W-P-Ni(OH)2）来实现直接UOR。具体而言，np/W-P-Ni(OH)2催化剂表现出优异的UOR性能，其超低电位为1.28 V，相对于RHE达到10 mA cm-2，并且在整个电位范围内具有超过90%的高UOR选择性。原位光谱和理论计算结果表明，单原子W掺杂剂不仅通过调节晶格羟基中的O电荷加速Ni(OH)O活性中间体的形成，而且还降低了质子耦合电子转移步骤的能垒和C−N键的裂解，从而实现了高效的UOR。
{"title":"Single-atom Tungsten Doping Induced Chemical-electrochemical Coupled Pathway on Ni(OH)2 Enables Efficient Urea Electrooxidation","authors":"Lebin Cai, Haoyun Bai, Jilong Li, Feng Xie, Kang Jiang, Ying-Rui Lu, Hui Pan, Yongwen Tan","doi":"10.1039/d4ee05340k","DOIUrl":"https://doi.org/10.1039/d4ee05340k","url":null,"abstract":"Electrocatalytic urea oxidation reaction (UOR) has emerged as a promising alternative to oxygen evolution reaction (OER) for wastewater recycling and energy recovery. However, traditional UOR pathway on NiOOH surface faces is hindered by the rate-limiting desorption of *COO and the competition between UOR and OER. In this study, we propose a chemical-electrochemical coupled pathway for direct UOR, achieved through the construction of single-atom W-doped nanoporous P-Ni(OH)<small><sub>2</sub></small> catalyst (np/W-P-Ni(OH)<small><sub>2</sub></small>). Specifically, np/W-P-Ni(OH)<small><sub>2</sub></small> catalyst exhibits exceptional UOR performance with an ultralow potential of 1.28 V vs. RHE to reach 10 mA cm<small><sup>-2</sup></small> and a high UOR selectivity exceeding 90% across the entire potential range. A collection of in-situ spectroscopies and theoretical calculations reveal that single-atom W dopant not only accelerates the formation of Ni(OH)O active intermediates by modulating the O charge in the lattice hydroxyl, but also lowers the energy barrier of the proton-coupled electron transfer step and the cleavage of C−N bond, thus realizing the highly-efficient UOR.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"38 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992361","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}
Adil Mansoor, Bushra Jabar, Syed Shoaib Ahmad Shah, Muhammad Sufyan Javed, Tayyaba Najam, Muhammad Ishaq, Shuo Chen, Fu Li, Xiao-Lei Shi, Yuexing Chen, Guang-xing Liang, Zhi-Gang Chen, Zhuang-hao Zheng
Thermoelectric (TE) enables the direct conversion of heat into electricity, but the performance of state-of-the-art layered materials has been limited due to restricted approaches to decoupling carrier and phonon transport. Here, a unique and never-looked feature of intralayer van der Waals bonds/interactions is explored for the atomistic/structural evolution and the transport properties of layered TE materials. The atomistic dynamics governing inversion in van der Waals layers/bonds is established as an innovative material engineering paradigm. We selected layered state-of-the-art Bi0.4Sb1.6Te3 material as a representative prototype to reveal the intralayer transformative role in realizing high TE performance. The induced atomic diffusion at van der Waals layers and prevailed crystal-amorphicity duality optimize electronic and chemical environment with elevated carrier concentration and maintained Seebeck coefficient, which lead to an improved power factor of ≈ 49 µWcm−1K−2. Besides, the atomistic surface reconstruction/defects cause to reduce thermal conductivity to ≈0.97 Wm−1K−1 and in turn leading to an ultra-high figure of merit (ZTmax) of ≈1.54 at ~373 K. Thus, the present work provides a generic and practical avenue to open up a strategy by unique doping-dependent atomistic engineering, which is expected to be implemented in other layered structures to tailor the TE properties.
{"title":"Introducing atomistic dynamics at van der Waals surfaces for enhancing thermoelectric performance in layered Bi0.4Sb1.6Te3","authors":"Adil Mansoor, Bushra Jabar, Syed Shoaib Ahmad Shah, Muhammad Sufyan Javed, Tayyaba Najam, Muhammad Ishaq, Shuo Chen, Fu Li, Xiao-Lei Shi, Yuexing Chen, Guang-xing Liang, Zhi-Gang Chen, Zhuang-hao Zheng","doi":"10.1039/d4ee04930f","DOIUrl":"https://doi.org/10.1039/d4ee04930f","url":null,"abstract":"Thermoelectric (TE) enables the direct conversion of heat into electricity, but the performance of state-of-the-art layered materials has been limited due to restricted approaches to decoupling carrier and phonon transport. Here, a unique and never-looked feature of intralayer van der Waals bonds/interactions is explored for the atomistic/structural evolution and the transport properties of layered TE materials. The atomistic dynamics governing inversion in van der Waals layers/bonds is established as an innovative material engineering paradigm. We selected layered state-of-the-art Bi<small><sub>0.4</sub></small>Sb1.6<small><sub></sub></small>Te3<small><sub></sub></small> material as a representative prototype to reveal the intralayer transformative role in realizing high TE performance. The induced atomic diffusion at van der Waals layers and prevailed crystal-amorphicity duality optimize electronic and chemical environment with elevated carrier concentration and maintained Seebeck coefficient, which lead to an improved power factor of ≈ 49 µWcm−1<small><sup></sup></small>K−2<small><sup></sup></small>. Besides, the atomistic surface reconstruction/defects cause to reduce thermal conductivity to ≈0.97 Wm−1<small><sup></sup></small>K−1<small><sup></sup></small> and in turn leading to an ultra-high figure of merit (ZTmax) of ≈1.54 at ~373 K. Thus, the present work provides a generic and practical avenue to open up a strategy by unique doping-dependent atomistic engineering, which is expected to be implemented in other layered structures to tailor the TE properties.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"2 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992568","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}
Guanghu He, Hang Luo, Yuan Liu, Yuting Wan, Bo Peng, Deng Hu, Fan Wang, Xiaona Li, Jiajun Peng, Huan Wang, Dou Zhang
Polymer-based dielectric capacitors for extreme environments require materials with exceptional electrical insulation. Polyimide (PI) is a promising candidate for high-temperature energy storage, yet it suffers from charge transfer complexes (CTCs) formation under high temperatures and electric fields, compromising its insulation performance. Addressing this critical limitation, our study presents an innovative molecular engineering strategy that simultaneously regulates the short-range ordered structure and crosslinking density within a semi-aromatic polyimide (SAPI) framework. By optimizing imidization temperatures and integrating ethyl side chains into the polymer architecture, we achieved molecular-level control that not only reduces energy losses but also significantly elevates energy storage capabilities under extreme conditions. Notably, the modified SAPI (E-SAPI) demonstrated discharge energy densities (Ud) of 8.61 J cm-³ at 150°C and 6.50 J cm-³ at 200°C, with efficiency (η) exceeding 90%, positioning it among the top-performing materials in the field. Even at 250°C, near its glass transition temperature, E-SAPI maintained a high Ud of 3.94 J cm-³, showcasing exceptional insulation and resistance to catastrophic failure. This approach reveals a new paradigm for designing high-performance dielectric materials, potentially transforming the future of energy storage in harsh environments.
{"title":"Enhanced High-Temperature Energy Storage in Semi-Aromatic Polyimides via Dual Regulation of Short-range Ordered and Crosslinked Architectures","authors":"Guanghu He, Hang Luo, Yuan Liu, Yuting Wan, Bo Peng, Deng Hu, Fan Wang, Xiaona Li, Jiajun Peng, Huan Wang, Dou Zhang","doi":"10.1039/d4ee04519j","DOIUrl":"https://doi.org/10.1039/d4ee04519j","url":null,"abstract":"Polymer-based dielectric capacitors for extreme environments require materials with exceptional electrical insulation. Polyimide (PI) is a promising candidate for high-temperature energy storage, yet it suffers from charge transfer complexes (CTCs) formation under high temperatures and electric fields, compromising its insulation performance. Addressing this critical limitation, our study presents an innovative molecular engineering strategy that simultaneously regulates the short-range ordered structure and crosslinking density within a semi-aromatic polyimide (SAPI) framework. By optimizing imidization temperatures and integrating ethyl side chains into the polymer architecture, we achieved molecular-level control that not only reduces energy losses but also significantly elevates energy storage capabilities under extreme conditions. Notably, the modified SAPI (E-SAPI) demonstrated discharge energy densities (Ud) of 8.61 J cm<small><sup>-</sup></small>³ at 150°C and 6.50 J cm<small><sup>-</sup></small>³ at 200°C, with efficiency (η) exceeding 90%, positioning it among the top-performing materials in the field. Even at 250°C, near its glass transition temperature, E-SAPI maintained a high Ud of 3.94 J cm<small><sup>-</sup></small>³, showcasing exceptional insulation and resistance to catastrophic failure. This approach reveals a new paradigm for designing high-performance dielectric materials, potentially transforming the future of energy storage in harsh environments.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"22 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992570","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}
Wanjie Gao, Yinxu Lu, Xu Tan, Tao Wang, Yueheng Yu, Yuhan Lu, Xinghao Zhang, Jie Wang, Yang Liu, Xi Liu, Bingyan Song, Shafi Ullah, Jiarui He and Yuping Wu
Sodium-metal batteries are considered as attractive energy storage systems because of the high theoretical capacity, low redox potential, and abundant resources of metallic sodium (Na). However, the uncontrolled growth of Na dendrites significantly hinders their practical feasibility, leading to poor coulombic efficiency, limited cycling lifespan, and severe safety issues. To tackle this issue, many strategies focusing on sodiophilic design have been developed to ensure uniform and dendrite-free Na deposition. Unfortunately, it is noteworthy that the latest progress in sodiophilic design lacks a comprehensive and systematic evaluation. This review begins by thoroughly elucidating the formation mechanisms of Na dendrites and the underlying causes of battery failure. Subsequently, the recent scientific advancements for extending the cycling lifespan of Na metal batteries are comprehensively summarized based on a sodiophilic design strategy. Finally, we propose conclusive insights into enhancing the sodiophilic properties of Na metal anodes, which may guide battery design and deepen the understanding of sodiophilicity for the development of Na metal batteries.
{"title":"Sodiophilic design for sodium-metal batteries: progress and prospects","authors":"Wanjie Gao, Yinxu Lu, Xu Tan, Tao Wang, Yueheng Yu, Yuhan Lu, Xinghao Zhang, Jie Wang, Yang Liu, Xi Liu, Bingyan Song, Shafi Ullah, Jiarui He and Yuping Wu","doi":"10.1039/D4EE05871B","DOIUrl":"10.1039/D4EE05871B","url":null,"abstract":"<p >Sodium-metal batteries are considered as attractive energy storage systems because of the high theoretical capacity, low redox potential, and abundant resources of metallic sodium (Na). However, the uncontrolled growth of Na dendrites significantly hinders their practical feasibility, leading to poor coulombic efficiency, limited cycling lifespan, and severe safety issues. To tackle this issue, many strategies focusing on sodiophilic design have been developed to ensure uniform and dendrite-free Na deposition. Unfortunately, it is noteworthy that the latest progress in sodiophilic design lacks a comprehensive and systematic evaluation. This review begins by thoroughly elucidating the formation mechanisms of Na dendrites and the underlying causes of battery failure. Subsequently, the recent scientific advancements for extending the cycling lifespan of Na metal batteries are comprehensively summarized based on a sodiophilic design strategy. Finally, we propose conclusive insights into enhancing the sodiophilic properties of Na metal anodes, which may guide battery design and deepen the understanding of sodiophilicity for the development of Na metal batteries.</p>","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":" 4","pages":" 1630-1657"},"PeriodicalIF":32.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992363","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}
The desired salt-free neutral H2O2 electrosynthesis via a 2-electron oxygen reduction reaction (2e−-ORR) remains challenging due to the absence of efficient electrocatalysts and its well-matched practical process. Herein we report an important progress and understanding of neutral H2O2 electrosynthesis of 2e−-ORR at a scalable rate through combining crystalline nitrogen-doped carbon-anchored Fe3O4 nanoparticles (NPs, Fe3O4@TNC), derived from the pyrolysis of the mixture of g-C3N4 and Fe@Tpy, with the salt-free real-time and continuous H2O2 production process. Based on rotating ring-disk electrodes Fe3O4@TNC achieved nearly 100% selectivity from 0 to 0.75 V vs RHE and the limiting diffusion current density up to 5.2 mA cm−2 at 0 V vs RHE, respectively. It is first revealed that the exposed (220) facet of Fe3O4 NPs obtains a thermodynamically optimal binding of *OOH and rapid *OOH-mediated kinetic pathway. Integration of Fe3O4@TNC into scalable cells that exhibited superior performance and techno-economic potential of neutral H2O2 electrosynthesis, where the industrial-relevant current densities are achieved at the remarkable real-time continuous production while maintaining relatively large Faradaic efficiency. This work with in-depth mechanistic insights into neutral H2O2 electrosynthesis and provides an advanced and economical process for integrating efficient electrocatalysts and scalable electrolyzer for industrial-relevant neutral H2O2 production.
由于缺乏高效的电催化剂和与之匹配的实际工艺，通过2电子氧还原反应（2e−-ORR）实现无盐中性H2O2电合成仍然具有挑战性。本文报道了一项重要进展和对中性H2O2电合成2e−-ORR的理解，通过将g-C3N4和Fe@Tpy混合物热解得到的晶体氮掺杂碳锚定Fe3O4纳米颗粒（NPs, Fe3O4@TNC）与无盐实时连续H2O2生产过程相结合，以可扩展的速率合成中性H2O2。基于旋转环盘电极Fe3O4@TNC在0 ~ 0.75 V vs RHE范围内的选择性接近100%，在0 V vs RHE下的极限扩散电流密度可达5.2 mA cm−2。首次揭示了Fe3O4 NPs暴露的（220）面获得了*OOH的热力学最佳结合和*OOH介导的快速动力学途径。将Fe3O4@TNC集成到可扩展的电池中，这些电池表现出中性H2O2电合成的优异性能和技术经济潜力，在保持相对较高的法拉第效率的同时，实现了与工业相关的实时连续生产电流密度。这项工作深入了解了中性H2O2电合成的机理，并为工业相关的中性H2O2生产提供了一种先进而经济的方法，用于集成高效的电催化剂和可扩展的电解槽。
{"title":"Crystalline nitrogen-doped carbon anchored well-dispersed Fe3O4 nanoparticles for real-time scalable neutral H2O2 electrosynthesis","authors":"Hao Yin, Jili Yuan, Jun Wang, Shiwei Hu, Pingshan Wang, Haibo Xie","doi":"10.1039/d4ee05796a","DOIUrl":"https://doi.org/10.1039/d4ee05796a","url":null,"abstract":"The desired salt-free neutral H2O2 electrosynthesis via a 2-electron oxygen reduction reaction (2e−-ORR) remains challenging due to the absence of efficient electrocatalysts and its well-matched practical process. Herein we report an important progress and understanding of neutral H2O2 electrosynthesis of 2e−-ORR at a scalable rate through combining crystalline nitrogen-doped carbon-anchored Fe3O4 nanoparticles (NPs, Fe3O4@TNC), derived from the pyrolysis of the mixture of g-C3N4 and Fe@Tpy, with the salt-free real-time and continuous H2O2 production process. Based on rotating ring-disk electrodes Fe3O4@TNC achieved nearly 100% selectivity from 0 to 0.75 V vs RHE and the limiting diffusion current density up to 5.2 mA cm−2 at 0 V vs RHE, respectively. It is first revealed that the exposed (220) facet of Fe3O4 NPs obtains a thermodynamically optimal binding of *OOH and rapid *OOH-mediated kinetic pathway. Integration of Fe3O4@TNC into scalable cells that exhibited superior performance and techno-economic potential of neutral H2O2 electrosynthesis, where the industrial-relevant current densities are achieved at the remarkable real-time continuous production while maintaining relatively large Faradaic efficiency. This work with in-depth mechanistic insights into neutral H2O2 electrosynthesis and provides an advanced and economical process for integrating efficient electrocatalysts and scalable electrolyzer for industrial-relevant neutral H2O2 production.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"74 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992362","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}
Current research focuses on regulating Zn plating behavior to address dendrite issue. Although significant improvements in the lifespans of symmetric batteries have been achieved, full batteries do not demonstrate a corresponding increase in overall lifespan. The underlying reasons for this discrepancy remain unexplored. Herein, we identify that this performance mismatch is attributed to the neglect of the initial stripping behavior of the zinc anode in practical full batteries. This initial stripping, characterized by inherent inhomogeneities, causes anomalous and localized detachment of the interface layer. The incompleteness of the interface layer will result in the failure of its protection function. Then a non-destructive stripping strategy involving instantaneous repair of the damaged region is proposed to maintain the structural and functional integrity of interface layer. During prolonged cycling, the copper-zinc species within interface layer undergo irreversible phase reconstruction and spatial redistribution, which facilitate the de-solvation of hydrated Zn2+ and determine the plating of large-sized Zn(002). Utilizing this non-destructive anode, the full battery demonstrates a lifespan increase comparable to that of symmetric battery, achieving an ultralong lifespan (1240 hours, 800 cycles) at a low current density (0.246 A g−1) with an ultrahigh cumulative capacity (847 mAh cm−2), and an Ah-level pouch cell exhibiting 150 stable cycles is also validated.
目前的研究重点是通过调控锌的镀行为来解决枝晶问题。虽然对称电池的寿命已经有了显著的提高，但满电池的整体寿命并没有相应的提高。造成这种差异的根本原因尚不清楚。在本文中，我们发现这种性能不匹配是由于在实际的全电池中忽略了锌阳极的初始剥离行为。这种初始剥离以其固有的不均匀性为特征，导致界面层的异常和局部剥离。接口层的不完备将导致其保护功能失效。然后，提出了一种非破坏性剥离策略，即对损伤区域进行瞬时修复，以保持界面层的结构和功能完整性。在长时间循环过程中，界面层内的铜锌组分发生不可逆的相重构和空间再分布，促进了水合Zn2+的脱溶剂化，决定了大尺寸Zn的电镀（002）。利用这种非破坏性阳极，完整电池的寿命延长与对称电池相当，在低电流密度（0.246 a g−1）下实现超长寿命（1240小时，800次循环），具有超高的累积容量（847 mAh cm−2），并且还验证了具有150次稳定循环的ah级袋状电池。
{"title":"Non-destructive Stripping Electrochemistry Enables Long-Life Zinc Metal Batteries","authors":"Chaojiang Niu, Ruiting Guo, Xiong Liu, Kun Ni, Fan-Jie Xia, Huazhang Zhang, Yu Liu, Xinzhe Dai, Litong Shi, Xuanpeng Wang, Chunhua Han, Liqiang Mai","doi":"10.1039/d4ee05044d","DOIUrl":"https://doi.org/10.1039/d4ee05044d","url":null,"abstract":"Current research focuses on regulating Zn plating behavior to address dendrite issue. Although significant improvements in the lifespans of symmetric batteries have been achieved, full batteries do not demonstrate a corresponding increase in overall lifespan. The underlying reasons for this discrepancy remain unexplored. Herein, we identify that this performance mismatch is attributed to the neglect of the initial stripping behavior of the zinc anode in practical full batteries. This initial stripping, characterized by inherent inhomogeneities, causes anomalous and localized detachment of the interface layer. The incompleteness of the interface layer will result in the failure of its protection function. Then a non-destructive stripping strategy involving instantaneous repair of the damaged region is proposed to maintain the structural and functional integrity of interface layer. During prolonged cycling, the copper-zinc species within interface layer undergo irreversible phase reconstruction and spatial redistribution, which facilitate the de-solvation of hydrated Zn2+ and determine the plating of large-sized Zn(002). Utilizing this non-destructive anode, the full battery demonstrates a lifespan increase comparable to that of symmetric battery, achieving an ultralong lifespan (1240 hours, 800 cycles) at a low current density (0.246 A g−1) with an ultrahigh cumulative capacity (847 mAh cm−2), and an Ah-level pouch cell exhibiting 150 stable cycles is also validated.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"20 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992364","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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