Li Liu, Hongju Zhu, Jin-Yun Wang, Di Wang, Dongdong Cai, Jianbin Wang, Qisheng Tu, Yunlong Ma, Qingdong Zheng
Dimerized M-series small-molecule acceptors feature highly planar conjugated backbones, enabling ordered stacking and enhanced morphological stability. However, rotatable bonds introduced during dimerization often induce conformational disorder, undermining efficient charge generation and transport. Here, we report two rationally designed M-series dimers, DM-TF and DMF-T, which both incorporate strategic intramolecular fluorine···hydrogen interactions to enhance conformational rigidity. DM-TF, which features fluorinated thiophene π-bridges interacting with hydrogen atoms on the central end groups, exhibits superior conformational rigidity, reduced energetic disorder, improved crystallinity, and enhanced charge transport properties compared to DMF-T. Consequently, DM-TF-based organic solar cells (OSCs) deliver a power conversion efficiency of 18.40%, surpassing the DMF-T-based devices (17.77%). Additionally, they demonstrate exceptional thermal stability, exhibiting negligible performance loss after being heated at 80 °C for 2000 hours. Furthermore, incorporating DM-TF as a third component into PM6:M36 blends boosts the efficiency of the resulting devices to 19.16%, which is the highest reported value among all non-Y-series acceptors. These results underscore the effectiveness of engineering intramolecular non-covalent interactions in the molecular design of acceptor materials and highlight the great potential of dimerized M-series acceptors for high-efficiency and stable OSCs.
{"title":"Conformational Locking through Intramolecular F···H Interactions in Dimerized M-Series Acceptors Boosts Efficiency and Stability of Organic Solar Cells","authors":"Li Liu, Hongju Zhu, Jin-Yun Wang, Di Wang, Dongdong Cai, Jianbin Wang, Qisheng Tu, Yunlong Ma, Qingdong Zheng","doi":"10.1039/d5ee06043e","DOIUrl":"https://doi.org/10.1039/d5ee06043e","url":null,"abstract":"Dimerized M-series small-molecule acceptors feature highly planar conjugated backbones, enabling ordered stacking and enhanced morphological stability. However, rotatable bonds introduced during dimerization often induce conformational disorder, undermining efficient charge generation and transport. Here, we report two rationally designed M-series dimers, DM-TF and DMF-T, which both incorporate strategic intramolecular fluorine···hydrogen interactions to enhance conformational rigidity. DM-TF, which features fluorinated thiophene π-bridges interacting with hydrogen atoms on the central end groups, exhibits superior conformational rigidity, reduced energetic disorder, improved crystallinity, and enhanced charge transport properties compared to DMF-T. Consequently, DM-TF-based organic solar cells (OSCs) deliver a power conversion efficiency of 18.40%, surpassing the DMF-T-based devices (17.77%). Additionally, they demonstrate exceptional thermal stability, exhibiting negligible performance loss after being heated at 80 °C for 2000 hours. Furthermore, incorporating DM-TF as a third component into PM6:M36 blends boosts the efficiency of the resulting devices to 19.16%, which is the highest reported value among all non-Y-series acceptors. These results underscore the effectiveness of engineering intramolecular non-covalent interactions in the molecular design of acceptor materials and highlight the great potential of dimerized M-series acceptors for high-efficiency and stable OSCs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"43 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718067","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}
Efficient metal-free catalysts are crucial for advancing aluminum-air batteries (AABs), yet their development has been hindered by poor electronic structure optimization and sluggish mass transport. In this work, we developed a hierarchically porous N/S co-doped carbon nanoreactor via an etching-doping pyrolysis strategy, achieving an ultrahigh surface area of 2630 m 2 /g and a wellorganized pore network. The resulting catalyst demonstrated outstanding oxygen reduction reaction (ORR) activity, with half-wave potentials of 0.952 V (vs. RHE; RHE stands for reversible hydrogen electrode) in alkaline and 0.754 V (vs. RHE) in acidic media. When assembled into AABs, it delivered a peak power density of 265 mW/cm 2 and an energy density of 3929 Wh/kg, along with excellent cycling stability. Finite element simulations showed that the hierarchical porosity promoted oxygen diffusion and enhanced reaction kinetics. Furthermore, in-situ characterizations and theoretical calculations revealed that S-C-N configurations dynamically transformed into O pre -S-C-N groups under working conditions, which modulated the electronic structure of adjacent
{"title":"Self-Optimizing Metal-Free Porous Reactors with Dynamic Active Sites Unlock Record Oxygen Reduction Activity","authors":"Lei Zhang, Qiaoling Xu, Mengshan Chen, Yongcai Zhang, Yingtang Zhou, Guangzhi Hu, Hermenegildo Garcia","doi":"10.1039/d5ee03645c","DOIUrl":"https://doi.org/10.1039/d5ee03645c","url":null,"abstract":"Efficient metal-free catalysts are crucial for advancing aluminum-air batteries (AABs), yet their development has been hindered by poor electronic structure optimization and sluggish mass transport. In this work, we developed a hierarchically porous N/S co-doped carbon nanoreactor via an etching-doping pyrolysis strategy, achieving an ultrahigh surface area of 2630 m 2 /g and a wellorganized pore network. The resulting catalyst demonstrated outstanding oxygen reduction reaction (ORR) activity, with half-wave potentials of 0.952 V (vs. RHE; RHE stands for reversible hydrogen electrode) in alkaline and 0.754 V (vs. RHE) in acidic media. When assembled into AABs, it delivered a peak power density of 265 mW/cm 2 and an energy density of 3929 Wh/kg, along with excellent cycling stability. Finite element simulations showed that the hierarchical porosity promoted oxygen diffusion and enhanced reaction kinetics. Furthermore, in-situ characterizations and theoretical calculations revealed that S-C-N configurations dynamically transformed into O pre -S-C-N groups under working conditions, which modulated the electronic structure of adjacent","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"7 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711353","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}
In aqueous zinc (Zn) metal secondary batteries, some interfacial side reactions, such as hydrogen evolution reaction (HER), anode corrosion and dendrite growth, often lead to short circuit and cycling performance deterioration. Here we sift four kinds of amino acid monomers (i.e., Lysine, Glutamate, Cysteine and Phenylalanine) with different polarity side chain groups to tailor pentapeptides, successfully constructing a thermodynamically stable colloid dispersion electrolyte system with Tyndall effect for Zn metal secondary batteries. The proposed electrolyte system composed of the tailored lysine pentapeptide (LP) effectively suppresses Zn dendrite growth through regulating the (002) crystalline plane orientation. Furthermore, the LP has strong attraction towards H2O molecules, thereby achieving desolvation of Zn2+ ions and reducing anode corrosion as well as HER. In this LP-based colloid dispersion electrolyte, the Zn//Zn symmetric cell demonstrated an unprecedented ultralong cycling time beyond 10000 hours (416 days) at 2 mA cm-2. The developed Zn-ion pouch cells with a high cathode mass loading of ~ 28.7 mg cm-2 displayed a capacity retention of ~83.7% after 1000 cycles at 0.5 A g-1, which is superior to most recently reported zinc-ion pouch cells. The proposed thermodynamically stable colloid dispersion electrolyte is a new aqueous electrolyte system for economical, safe and long-lifespan Zn metal secondary batteries.
在含水锌（Zn）金属二次电池中，析氢反应（HER）、阳极腐蚀和枝晶生长等界面副反应往往会导致电池短路和循环性能下降。本文通过筛选具有不同极性侧链基团的4种氨基酸单体（赖氨酸、谷氨酸、半胱氨酸和苯丙氨酸）来定制五肽，成功构建了具有Tyndall效应的锌金属二次电池热稳定胶体分散电解质体系。由定制赖氨酸五肽（LP）组成的电解质体系通过调节（002）晶面取向，有效抑制Zn枝晶生长。此外，LP对H2O分子有很强的吸引力，从而实现Zn2+离子的脱溶，减少阳极腐蚀和HER。在这种基于lp的胶体分散电解质中，锌/锌对称电池在2 mA cm-2下的超长循环时间超过了10000小时（416天）。在0.5 a g-1条件下，经过1000次循环后，锌离子袋电池的容量保持率为83.7%，其阴极质量负载高达~ 28.7 mg cm-2，优于最近报道的锌离子袋电池。本文提出的热稳定胶体分散电解质是一种经济、安全、长寿命锌金属二次电池的新型水电解质体系。
{"title":"Thermodynamically stable colloid dispersion electrolytes with Tyndall effect for practical zinc-ion pouch cells","authors":"Yu Liu, Jiaxin Meng, Mohan Yue, Changmei Jiao, Zhiyuan Zhao, Yuzhen Sun, Yingna Chang, Huayu Wu, Xiaoli Yan, Kefan Song, Jindi Wang, Weizhai Bao, Guozhen Zhang, Rong Xing, Jingfa Li, Feng Yu, Faxing Wang, Yuping Wu","doi":"10.1039/d5ee05434f","DOIUrl":"https://doi.org/10.1039/d5ee05434f","url":null,"abstract":"In aqueous zinc (Zn) metal secondary batteries, some interfacial side reactions, such as hydrogen evolution reaction (HER), anode corrosion and dendrite growth, often lead to short circuit and cycling performance deterioration. Here we sift four kinds of amino acid monomers (i.e., Lysine, Glutamate, Cysteine and Phenylalanine) with different polarity side chain groups to tailor pentapeptides, successfully constructing a thermodynamically stable colloid dispersion electrolyte system with Tyndall effect for Zn metal secondary batteries. The proposed electrolyte system composed of the tailored lysine pentapeptide (LP) effectively suppresses Zn dendrite growth through regulating the (002) crystalline plane orientation. Furthermore, the LP has strong attraction towards H2O molecules, thereby achieving desolvation of Zn2+ ions and reducing anode corrosion as well as HER. In this LP-based colloid dispersion electrolyte, the Zn//Zn symmetric cell demonstrated an unprecedented ultralong cycling time beyond 10000 hours (416 days) at 2 mA cm-2. The developed Zn-ion pouch cells with a high cathode mass loading of ~ 28.7 mg cm-2 displayed a capacity retention of ~83.7% after 1000 cycles at 0.5 A g-1, which is superior to most recently reported zinc-ion pouch cells. The proposed thermodynamically stable colloid dispersion electrolyte is a new aqueous electrolyte system for economical, safe and long-lifespan Zn metal secondary batteries.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"150 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718095","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 synergistic regulation of steam utilization and proton transport at the oxygen electrode is crucial for proton ceramic electrolysis cells (PCECs). Ruddlesden–Popper (RP) perovskites leverage interlayer water intercalation features to achieve rapid proton uptake even under low-steam conditions. Herein, an RP-type oxygen electrode capable of reversible phase transitions and hydrated oxyhydroxide formation under high-temperature steam was constructed, successfully transcending the hydration limits of single perovskites. By integrating the structural analysis employing microcrystal electron diffraction (MicroED) and density functional theory (DFT) calculations, it is revealed that the interlayer proton-trapping sites significantly boost the steam adsorption/hydration and lower the energy barrier for proton migration across layers. The Sr3(Co0.8Fe0.1Nb0.1)2O7−δ (SCFN-RP) electrode demonstrates excellent catalytic activity, reaching 1.01 A cm−2@1.3 V at 550 °C. This work emphasizes the crucial role of reversible hydrated oxyhydroxides in RP perovskites and offers a novel conception for the design of high-performance oxygen electrodes for PCECs.
蒸汽利用和质子在氧电极上传输的协同调节对质子陶瓷电解电池（PCECs）至关重要。Ruddlesden-Popper （RP）钙钛矿利用层间水嵌入特性，即使在低蒸汽条件下也能快速吸收质子。本文构建了一种rp型氧电极，能够在高温蒸汽下实现可逆相变和水合氢氧化物的生成，成功地超越了单一钙钛矿的水化极限。通过结合微晶电子衍射（MicroED）和密度泛函理论（DFT）计算的结构分析，揭示了层间质子捕获位点显著提高了蒸汽吸附/水合作用，降低了质子跨层迁移的能垒。Sr3(Co0.8Fe0.1Nb0.1)2O7−δ (SCFN-RP)电极表现出优异的催化活性，在550℃时达到1.01 A cm−2@1.3 V。本研究强调了可逆水合氢氧化物在RP钙钛矿中的重要作用，并为pcec高性能氧电极的设计提供了新的思路。
{"title":"The interlayer proton capture and transport mechanism in oxygen electrodes boosts proton ceramic electrolysis","authors":"Meijuan Fei, Zhaohui Cai, Peng Chen, Dongliang Liu, Cheng Huang, Jianqiu Zhu, Linjuan Zhang, Wei Wang, Chuan Zhou, Wei Zhou, Zongping Shao","doi":"10.1039/d5ee05802c","DOIUrl":"https://doi.org/10.1039/d5ee05802c","url":null,"abstract":"The synergistic regulation of steam utilization and proton transport at the oxygen electrode is crucial for proton ceramic electrolysis cells (PCECs). Ruddlesden–Popper (RP) perovskites leverage interlayer water intercalation features to achieve rapid proton uptake even under low-steam conditions. Herein, an RP-type oxygen electrode capable of reversible phase transitions and hydrated oxyhydroxide formation under high-temperature steam was constructed, successfully transcending the hydration limits of single perovskites. By integrating the structural analysis employing microcrystal electron diffraction (MicroED) and density functional theory (DFT) calculations, it is revealed that the interlayer proton-trapping sites significantly boost the steam adsorption/hydration and lower the energy barrier for proton migration across layers. The Sr<small><sub>3</sub></small>(Co<small><sub>0.8</sub></small>Fe<small><sub>0.1</sub></small>Nb<small><sub>0.1</sub></small>)<small><sub>2</sub></small>O<small><sub>7−<em>δ</em></sub></small> (SCFN-RP) electrode demonstrates excellent catalytic activity, reaching 1.01 A cm<small><sup>−2</sup></small>@1.3 V at 550 °C. This work emphasizes the crucial role of reversible hydrated oxyhydroxides in RP perovskites and offers a novel conception for the design of high-performance oxygen electrodes for PCECs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"29 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711352","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}
Deng Hu, Hang Luo, Guanghu He, Xi Chen, Yuting Wan, Fan Wang, Xiaona Li, Huan Wang, Haoran Xie, Dou Zhang
Film capacitors are indispensable in electrical engineering; however, balancing the insulation and thermal stability of polymer dielectrics remains a key challenge for high-temperature energy storage. Aromatic polyimide (PI) exhibits a high glass transition temperature (Tg, >300 °C), facilitating the formation of charge transfer complexes (CTCs). Semi-aromatic PIs mitigate this order, but insufficient thermal stability leads to poor performance above 200 °C. To resolve this contradiction, we incorporated a sp3-centered monomer, tris(4-aminophenyl)methane (TAPM), into a semi-aromatic PI (MPD-PI), constructing a spatially disordered architecture that suppresses short-range π–π stacking and CTCs, enhancing dielectric insulation and thermal stability. The resulting copolymer specifically achieves a discharged energy density of 7.13 J cm−3 at 200 °C with 90% efficiency and 5.18 J cm−3 at 250 °C, representing 341% and 280% improvements compared to those of MPD-PI, respectively. The improved thermal stability also imparts excellent cycling stability (3 × 105 cycles at 200 °C and 300 MV m−1) and a state-of-the-art breakdown strength of 596.2 MV m−1 at 250 °C. The conformational-engineering strategy of this work provides a versatile route for high-temperature polymer dielectrics.
薄膜电容器在电气工程中是不可缺少的；然而，平衡聚合物电介质的绝缘性和热稳定性仍然是高温储能的关键挑战。芳香族聚酰亚胺（PI）具有较高的玻璃化转变温度（Tg, >300℃），有利于电荷转移配合物（ctc）的形成。半芳香族pi减轻了这一顺序，但热稳定性不足导致200°C以上性能不佳。为了解决这一矛盾，我们将sp3为中心的单体三（4-氨基苯基）甲烷（TAPM）加入到半芳香PI （MPD-PI）中，构建了一种空间无序结构，抑制了短程π -π堆叠和ctc，提高了介电绝缘性和热稳定性。该共聚物在200°C时的放电能量密度为7.13 J cm−3，效率为90%；在250°C时的放电能量密度为5.18 J cm−3，与MPD-PI相比，分别提高了341%和280%。改进的热稳定性也赋予了优异的循环稳定性（在200°C和300 MV m - 1下循环3 × 105次）和250°C下596.2 MV m - 1的最先进击穿强度。这项工作的构象工程策略为高温聚合物电介质提供了一条通用的途径。
{"title":"Disruption of short-range π–π stacking via a disordered spatial architecture for energy storage at 250 °C","authors":"Deng Hu, Hang Luo, Guanghu He, Xi Chen, Yuting Wan, Fan Wang, Xiaona Li, Huan Wang, Haoran Xie, Dou Zhang","doi":"10.1039/d5ee05932a","DOIUrl":"https://doi.org/10.1039/d5ee05932a","url":null,"abstract":"Film capacitors are indispensable in electrical engineering; however, balancing the insulation and thermal stability of polymer dielectrics remains a key challenge for high-temperature energy storage. Aromatic polyimide (PI) exhibits a high glass transition temperature (<em>T</em><small><sub>g</sub></small>, >300 °C), facilitating the formation of charge transfer complexes (CTCs). Semi-aromatic PIs mitigate this order, but insufficient thermal stability leads to poor performance above 200 °C. To resolve this contradiction, we incorporated a sp<small><sup>3</sup></small>-centered monomer, tris(4-aminophenyl)methane (TAPM), into a semi-aromatic PI (MPD-PI), constructing a spatially disordered architecture that suppresses short-range π–π stacking and CTCs, enhancing dielectric insulation and thermal stability. The resulting copolymer specifically achieves a discharged energy density of 7.13 J cm<small><sup>−3</sup></small> at 200 °C with 90% efficiency and 5.18 J cm<small><sup>−3</sup></small> at 250 °C, representing 341% and 280% improvements compared to those of MPD-PI, respectively. The improved thermal stability also imparts excellent cycling stability (3 × 10<small><sup>5</sup></small> cycles at 200 °C and 300 MV m<small><sup>−1</sup></small>) and a state-of-the-art breakdown strength of 596.2 MV m<small><sup>−1</sup></small> at 250 °C. The conformational-engineering strategy of this work provides a versatile route for high-temperature polymer dielectrics.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"166 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704751","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}
Ziqi Liu, Yiming Zhang, Shanshan Pan, Yong Chen, Keer Yang, Shanxi Wu, Musong Liu, Lei Hu, Shuaicheng Jiang, Xiaopeng Wang, Guoxiu Wang, Meng Yao
The rapid growth of electric vehicles (EVs) is driving an urgent demand for lithium-ion batteries (LIBs) with higher specific energy, longer life, and uncompromised safety. Ni-rich layered oxides (LiNixCoyMn(1−x−y)O2, x ≥ 0.8) have emerged as leading cathode materials for next-generation LIBs, owing to their high capacity and energy density. Further increasing Ni content is essential for improved performance and cost reduction. However, it also introduces new obstacles, necessitating thoughtful design of cathode composition, morphology, and microstructure, as well as the development of electrolyte formulations. In this review, we discuss the multiple failure mechanisms of Ni-rich cathodes in terms of two major aspects: structural degradation and gas release. We elucidate the key factors contributing to chemical, crystallographic, and microstructural degradation in Ni-rich cathodes, and summarize the various origins of gas evolution associated with these materials. Another key theme of this review is the modification of Ni-rich cathodes to address the practical hurdles that limit their use in long-range and high-safety EVs. Accordingly, we present a comprehensive overview of the latest Ni-rich cathode modification strategies for next-generation EV platforms.
{"title":"Addressing the fundamental issues in Ni-rich cathodes: degradation mechanisms and mitigation strategies","authors":"Ziqi Liu, Yiming Zhang, Shanshan Pan, Yong Chen, Keer Yang, Shanxi Wu, Musong Liu, Lei Hu, Shuaicheng Jiang, Xiaopeng Wang, Guoxiu Wang, Meng Yao","doi":"10.1039/d5ee04213e","DOIUrl":"https://doi.org/10.1039/d5ee04213e","url":null,"abstract":"The rapid growth of electric vehicles (EVs) is driving an urgent demand for lithium-ion batteries (LIBs) with higher specific energy, longer life, and uncompromised safety. Ni-rich layered oxides (LiNi<small><sub><em>x</em></sub></small>C<small><sub>o<em>y</em></sub></small>Mn<small><sub>(1−<em>x</em>−<em>y</em>)</sub></small>O<small><sub>2</sub></small>, <em>x</em> ≥ 0.8) have emerged as leading cathode materials for next-generation LIBs, owing to their high capacity and energy density. Further increasing Ni content is essential for improved performance and cost reduction. However, it also introduces new obstacles, necessitating thoughtful design of cathode composition, morphology, and microstructure, as well as the development of electrolyte formulations. In this review, we discuss the multiple failure mechanisms of Ni-rich cathodes in terms of two major aspects: structural degradation and gas release. We elucidate the key factors contributing to chemical, crystallographic, and microstructural degradation in Ni-rich cathodes, and summarize the various origins of gas evolution associated with these materials. Another key theme of this review is the modification of Ni-rich cathodes to address the practical hurdles that limit their use in long-range and high-safety EVs. Accordingly, we present a comprehensive overview of the latest Ni-rich cathode modification strategies for next-generation EV platforms.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"1 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704846","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}
Correction for ‘Ion exchange-induced LixMgyBOz coating synergized with reinforced bulk doping enables fast-charging long-cycling high-voltage LiCoO2’ by Ting Wang et al., Energy Environ. Sci., 2025, 18, 10444–10459, https://doi.org/10.1039/d5ee04240b.
Aqueous zinc-ion batteries are promising for grid-scale energy storage due to inherent safety and low cost. However, their practical application under high current densities is severely limited by the hydrogen evolution reaction (HER) at the zinc anode. Traditional interfacial modifications struggle to overcome the fundamental trade-off between suppressing proton transport and maintaining Zn 2+ conduction, often leading to rapid failure under high current densities. Herein, we propose a "Dual-Pathway Proton Transport Blockade" strategy via a molecularly engineered membrane. Composed of PVA blended with a minimal amount of zwitterion-grafted PPy, the membrane physically suppresses water-induced swelling and chemically disrupts hydrogen-bond networks, blocking the proton hopping pathway (Grotthuss mechanism). Concurrently, it restricts free water penetration, cutting off the hydrated proton path (Vehicle mechanism). Sulfonate groups serve as Zn 2+ -philic sites to enrich ions and facilitate desolvation, while quaternary ammonium groups repel protons. The membrane exhibits exceptional selectivity, reducing proton conductivity by over 100-fold versus Nafion while retaining a high Zn 2+ conductivity. Consequently, Zn||Zn cells achieve >2000 h cycling at 10 mA cm -2 /10 mAh cm -2 , and Zn||I₂ full cells reach 22,000 cycles. Notably, under practical conditions with high cathode loading (49.3 mg cm -2 ) or in pouch-cell configurations, capacity retention exceeds 96% after hundreds of cycles.
水锌离子电池由于其固有的安全性和低成本，在电网规模的储能方面有很大的发展前景。然而，它们在高电流密度下的实际应用受到锌阳极析氢反应（HER）的严重限制。传统的界面修饰难以克服抑制质子输运和维持Zn 2+传导之间的基本权衡，往往导致在高电流密度下快速失效。在此，我们提出了一种通过分子工程膜的“双途径质子运输阻断”策略。该膜由PVA与少量两性离子接枝的PPy混合而成，物理上抑制了水诱导的膨胀，化学上破坏了氢键网络，阻断了质子跳跃途径（Grotthuss机制）。同时，它限制了自由水的渗透，切断了水合质子的路径（Vehicle机制）。磺酸基作为亲Zn 2+的位置，富集离子，促进脱溶，而季铵基排斥质子。该膜表现出优异的选择性，与Nafion相比，质子电导率降低了100倍以上，同时保持了较高的zn2 +电导率。因此，Zn||锌电池在10 mA cm -2 /10 mAh cm -2下可以达到2000小时的循环，而Zn||I 2充满电池可以达到22000次循环。值得注意的是，在高阴极负载（49.3 mg cm -2）或袋式电池配置的实际条件下，数百次循环后的容量保持率超过96%。
{"title":"Dual-Pathway Proton Transport Blockade Enabling High Areal Loading Aqueous Zinc Metal Batteries","authors":"Xiaofeng Cui, Limin Liu, Xinyang Li, Na Gao, Jie Feng, Dandan Yin, Lanya Zhao, Hetong Qi, Xiangyang Li, Hongyang Zhao, Chunhui Xiao, Shujiang Ding, Wei Yu","doi":"10.1039/d5ee06001j","DOIUrl":"https://doi.org/10.1039/d5ee06001j","url":null,"abstract":"Aqueous zinc-ion batteries are promising for grid-scale energy storage due to inherent safety and low cost. However, their practical application under high current densities is severely limited by the hydrogen evolution reaction (HER) at the zinc anode. Traditional interfacial modifications struggle to overcome the fundamental trade-off between suppressing proton transport and maintaining Zn 2+ conduction, often leading to rapid failure under high current densities. Herein, we propose a \"Dual-Pathway Proton Transport Blockade\" strategy via a molecularly engineered membrane. Composed of PVA blended with a minimal amount of zwitterion-grafted PPy, the membrane physically suppresses water-induced swelling and chemically disrupts hydrogen-bond networks, blocking the proton hopping pathway (Grotthuss mechanism). Concurrently, it restricts free water penetration, cutting off the hydrated proton path (Vehicle mechanism). Sulfonate groups serve as Zn 2+ -philic sites to enrich ions and facilitate desolvation, while quaternary ammonium groups repel protons. The membrane exhibits exceptional selectivity, reducing proton conductivity by over 100-fold versus Nafion while retaining a high Zn 2+ conductivity. Consequently, Zn||Zn cells achieve >2000 h cycling at 10 mA cm -2 /10 mAh cm -2 , and Zn||I₂ full cells reach 22,000 cycles. Notably, under practical conditions with high cathode loading (49.3 mg cm -2 ) or in pouch-cell configurations, capacity retention exceeds 96% after hundreds of cycles.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"29 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696952","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}
Thomas Webb, VANIN Francesco, Danpeng Gao, Lei Zhu, William Tremlett, Amanz Azaden, Alice Rodgers, Polina Jacoutot, Andrew J P White, Saiful Islam, Nicholas J Long, Zonglong Zhu, Saif Ahmed Haque
The generation of free carriers through extrinsic doping is essential in transforming the electronic properties of organic semiconductors (OSCs). Doped OSCs play a crucial role in the successful operation of a wide range of electrical and optoelectronic devices, but challenges associated with dopant design, such as processability, stability and efficacy, remain. Herein, we introduce a class of versatile p-type dopants based on metallocenium salts with the general formula ([M(C10H10-n)(X)n]+[Y]-) that meets these requirements. Critical to this approach is the ability to independently tune the cation via the redox-active metal cation (M) and the functionality (X) on the cyclopentadiene ring, allowing control over the oxidation strength. Simultaneously, the ability to tune the counter-anion (Y) allows control over the doping efficacy and stability of the resultant doped OSC+ salt. In this study, we systematically investigate the effect of cation and anion structure on the doping of OSCs and elucidate structure-property relationships for dopant design. We unravel the doping mechanism and demonstrate that such dopants can be used to enhance the hole extraction yield by 45% at perovskite / OSC heterojunctions. Perovskite / OSC photoactive layers using metallocenium dopants show significantly increased tolerance to moisture induced degradation as compared to films using conventional LiTFSI based dopants. Finally, we showcase the use of our optimised ferrocenium dopant in n-i-p configuration perovskite solar cells, demonstrating LiTFSI-free and additive-free devices with impressive solar-light to electrical power conversion efficiencies reaching 25.30 %.
{"title":"Metallocenium Salts as Tunable Dopants for Enhanced Efficiency of Perovskite Solar Cells","authors":"Thomas Webb, VANIN Francesco, Danpeng Gao, Lei Zhu, William Tremlett, Amanz Azaden, Alice Rodgers, Polina Jacoutot, Andrew J P White, Saiful Islam, Nicholas J Long, Zonglong Zhu, Saif Ahmed Haque","doi":"10.1039/d5ee05482f","DOIUrl":"https://doi.org/10.1039/d5ee05482f","url":null,"abstract":"The generation of free carriers through extrinsic doping is essential in transforming the electronic properties of organic semiconductors (OSCs). Doped OSCs play a crucial role in the successful operation of a wide range of electrical and optoelectronic devices, but challenges associated with dopant design, such as processability, stability and efficacy, remain. Herein, we introduce a class of versatile p-type dopants based on metallocenium salts with the general formula ([M(C10H10-n)(X)n]+[Y]-) that meets these requirements. Critical to this approach is the ability to independently tune the cation via the redox-active metal cation (M) and the functionality (X) on the cyclopentadiene ring, allowing control over the oxidation strength. Simultaneously, the ability to tune the counter-anion (Y) allows control over the doping efficacy and stability of the resultant doped OSC+ salt. In this study, we systematically investigate the effect of cation and anion structure on the doping of OSCs and elucidate structure-property relationships for dopant design. We unravel the doping mechanism and demonstrate that such dopants can be used to enhance the hole extraction yield by 45% at perovskite / OSC heterojunctions. Perovskite / OSC photoactive layers using metallocenium dopants show significantly increased tolerance to moisture induced degradation as compared to films using conventional LiTFSI based dopants. Finally, we showcase the use of our optimised ferrocenium dopant in n-i-p configuration perovskite solar cells, demonstrating LiTFSI-free and additive-free devices with impressive solar-light to electrical power conversion efficiencies reaching 25.30 %.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"1 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674644","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}
Dual-deposition aqueous Zn||I2 batteries, via reversible Zn plating/stripping and four-electron (4e-) iodine redox, represent promising high-energy systems. However, their practical application is hindered by low areal capacity and limited cycle life, stemming from severe shuttling, hydrolysis, the insulating nature of iodine species, and Zn corrosion. Here, we introduce a coordination-escorted organo-interhalogen conversion strategy employing choline cation (Ch+) and 2-acetbromamide (BrAce) as coregulators to address these challenges. Ch+ coordinates strongly with key intermediates (I3-, I2, and organo-interhalogen complexes), effectively suppressing the shuttle effect and stabilizing organo-interhalogen complexes. This coordination induces a smooth semiliquid iodine deposition/dissolution process during the 4e- conversion, significantly improving electrical contact and redox kinetics. Simultaneously, the interface shielding effect of Ch+ effectively protects the deposited Zn anode. Markedly outperforming existing systems, this battery achieves a well-balanced capacity between the I-/I0 and I0/I+ steps, a threefold increase in iodine utilization (∼70%), and a tenfold longer cycle life (exceeding 12,000 cycles) at 20 mA cm-2 under a practical areal capacity of 2.5 mA h cm-2. A dual-deposition configuration also delivers 800 cycles with nearly 100% retention. This approach concurrently addresses critical issues in 4e- iodine redox and Zn anode chemistry, offering a universal paradigm to explore other dual-deposition high-energy systems.
通过可逆镀锌/剥离和四电子（4e-）碘氧化还原的双沉积水锌||I2电池是一种很有前途的高能系统。然而，由于严重的穿梭、水解、碘的绝缘性质和锌的腐蚀，它们的面积容量低，循环寿命有限，阻碍了它们的实际应用。在这里，我们介绍了一种配合的有机卤素间转化策略，采用胆碱阳离子（Ch+）和2-乙溴酰胺（BrAce）作为共调节剂来解决这些挑战。Ch+与关键中间体（I3-、I2和有机卤素间配合物）强配位，有效抑制穿梭效应，稳定有机卤素间配合物。在4e-转化过程中，这种配位诱导了一个平滑的半液态碘沉积/溶解过程，显著改善了电接触和氧化还原动力学。同时，Ch+的界面屏蔽作用有效地保护了沉积的Zn阳极。该电池明显优于现有系统，在I-/I0和I0/I+步骤之间实现了良好的平衡容量，碘利用率增加了三倍（约70%），在实际面积容量为2.5 mA h cm-2的情况下，在20 mA cm-2下的循环寿命延长了十倍（超过12,000次循环）。双沉积配置还可提供800次循环，保留率接近100%。该方法同时解决了4e-碘氧化还原和Zn阳极化学中的关键问题，为探索其他双沉积高能系统提供了一个通用范例。
{"title":"Coordination-Escorted Organo-Interhalogen Conversion Enables Durable Dual-Deposition Zn||I2 Batteries with High Areal Capacities","authors":"Zhiheng Shi, Guigui Liu, Haolong Huang, Ziyuan He, Chuanping Lei, Fubin Zheng, Minghui Ye, Yufei Zhang, Zhipeng Wen, Wencheng Du, Xiaoqing Liu, Yue Wei, Qi Yang, Yongchao Tang, Cheng Chao Li","doi":"10.1039/d5ee06160a","DOIUrl":"https://doi.org/10.1039/d5ee06160a","url":null,"abstract":"Dual-deposition aqueous Zn||I2 batteries, via reversible Zn plating/stripping and four-electron (4e-) iodine redox, represent promising high-energy systems. However, their practical application is hindered by low areal capacity and limited cycle life, stemming from severe shuttling, hydrolysis, the insulating nature of iodine species, and Zn corrosion. Here, we introduce a coordination-escorted organo-interhalogen conversion strategy employing choline cation (Ch+) and 2-acetbromamide (BrAce) as coregulators to address these challenges. Ch+ coordinates strongly with key intermediates (I3-, I2, and organo-interhalogen complexes), effectively suppressing the shuttle effect and stabilizing organo-interhalogen complexes. This coordination induces a smooth semiliquid iodine deposition/dissolution process during the 4e- conversion, significantly improving electrical contact and redox kinetics. Simultaneously, the interface shielding effect of Ch+ effectively protects the deposited Zn anode. Markedly outperforming existing systems, this battery achieves a well-balanced capacity between the I-/I0 and I0/I+ steps, a threefold increase in iodine utilization (∼70%), and a tenfold longer cycle life (exceeding 12,000 cycles) at 20 mA cm-2 under a practical areal capacity of 2.5 mA h cm-2. A dual-deposition configuration also delivers 800 cycles with nearly 100% retention. This approach concurrently addresses critical issues in 4e- iodine redox and Zn anode chemistry, offering a universal paradigm to explore other dual-deposition high-energy systems.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"3 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145690091","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：