Trong Huy Pham,Hung D. T. Lai,Thao-Nguyen Ho,Tai Nguyen,Eduardo Henrique Dias,Viktoria Golovanova,F. Pelayo García de Arquer,Colin P. O'Brien,Christine M. Gabardo,Jackson Crane,David Sinton,Cao-Thang Dinh
Alkaline carbon dioxide (CO2) electrolysis is particularly attractive due to its low cell voltage, high faradaic efficiency (FE), high energy efficiency (EE), and compatibility with non-noble metal catalysts. Practical deployment, however, remains constrained by carbonate chemistry: salt precipitation on cathodic gas diffusion electrodes (GDEs) and carbonate crossover cause performance decay and increase system-level energy costs through CO2 utilization and separation penalties. Here we introduce a dual-function, hydrophilic porous mass-transport control layer that simultaneously suppresses carbonate formation and serves as the wetted separator in a membrane electrode assembly (MEA). Unlike a conventional ion-exchange membrane, the porous layer moderates alkaline electrolyte access to the cathode and reduces homogeneous CO2–OH− reactions, thereby lowering carbonate generation and suppressing carbonate crossover by 60–75% relative to a membrane-free alkaline flow-cell configuration. Using a polyvinylidene fluoride (PVDF) porous film as the dual-function layer, we first observe substantially lower carbonate crossover compared with operation without the layer. We then employ the same PVDF layer as the separator in a MEA, together with a benchmark Cu-sputtered polytetrafluoroethylene (PTFE) cathode and a Ni foam anode and achieve high C2 product selectivity (80–85%) at current densities of 110–147 mA cm−2 with low cell voltages of 2.3–2.6 V. At 110 mA cm−2, the system delivers over 500 h of cumulative operation with an ethylene (C2H4) FE of 65% and a C2 energy efficiency of 40%, corresponding to a total energy cost of 353 GJ t−1 C2H4. These results demonstrate a transport-regulated strategy that breaks the traditional stability-energy efficiency trade-off in alkaline CO2 electrolysis, providing a general design principle for stable and energy-efficient CO2 conversion using low-cost materials.
碱性二氧化碳（CO2）电解因其低电池电压、高法拉第效率（FE）、高能量效率（EE）以及与非贵金属催化剂的相容性而特别具有吸引力。然而，实际应用仍然受到碳酸盐化学的限制：阴极气体扩散电极（GDEs）上的盐沉淀和碳酸盐交叉会导致性能下降，并通过二氧化碳利用和分离带来的损失增加系统级能源成本。在这里，我们介绍了一种双重功能的亲水多孔质输运控制层，它同时抑制碳酸盐的形成，并作为膜电极组件（MEA）中的湿式分离器。与传统的离子交换膜不同，多孔层减缓了碱性电解质进入阴极，减少了均匀的CO2-OH -反应，从而减少了碳酸盐的产生，并抑制了碳酸盐的交叉，相对于无膜的碱性流动电池结构，减少了60-75%。使用聚偏氟乙烯（PVDF）多孔膜作为双功能层，我们首先观察到与不使用该层的操作相比，碳酸盐交叉明显降低。然后，我们在MEA中使用相同的PVDF层作为分离器，再加上基准的cu溅射聚四氟乙烯（PTFE）阴极和Ni泡沫阳极，在电流密度为110-147 mA cm - 2，电池电压为2.3-2.6 V的情况下，实现了高C2产品选择性（80-85%）。在110 mA cm−2的条件下，该系统累计运行超过500小时，乙烯（C2H4） FE为65%，C2能效为40%，相当于总能源成本为353 GJ t−1 C2H4。这些结果证明了一种运输调节策略，打破了碱性CO2电解中传统的稳定性和能效权衡，为使用低成本材料进行稳定和节能的CO2转化提供了一般设计原则。
{"title":"Suppressing carbonate formation in alkaline CO electrolysis","authors":"Trong Huy Pham,Hung D. T. Lai,Thao-Nguyen Ho,Tai Nguyen,Eduardo Henrique Dias,Viktoria Golovanova,F. Pelayo García de Arquer,Colin P. O'Brien,Christine M. Gabardo,Jackson Crane,David Sinton,Cao-Thang Dinh","doi":"10.1039/d6ee02989b","DOIUrl":"https://doi.org/10.1039/d6ee02989b","url":null,"abstract":"Alkaline carbon dioxide (CO2) electrolysis is particularly attractive due to its low cell voltage, high faradaic efficiency (FE), high energy efficiency (EE), and compatibility with non-noble metal catalysts. Practical deployment, however, remains constrained by carbonate chemistry: salt precipitation on cathodic gas diffusion electrodes (GDEs) and carbonate crossover cause performance decay and increase system-level energy costs through CO2 utilization and separation penalties. Here we introduce a dual-function, hydrophilic porous mass-transport control layer that simultaneously suppresses carbonate formation and serves as the wetted separator in a membrane electrode assembly (MEA). Unlike a conventional ion-exchange membrane, the porous layer moderates alkaline electrolyte access to the cathode and reduces homogeneous CO2–OH− reactions, thereby lowering carbonate generation and suppressing carbonate crossover by 60–75% relative to a membrane-free alkaline flow-cell configuration. Using a polyvinylidene fluoride (PVDF) porous film as the dual-function layer, we first observe substantially lower carbonate crossover compared with operation without the layer. We then employ the same PVDF layer as the separator in a MEA, together with a benchmark Cu-sputtered polytetrafluoroethylene (PTFE) cathode and a Ni foam anode and achieve high C2 product selectivity (80–85%) at current densities of 110–147 mA cm−2 with low cell voltages of 2.3–2.6 V. At 110 mA cm−2, the system delivers over 500 h of cumulative operation with an ethylene (C2H4) FE of 65% and a C2 energy efficiency of 40%, corresponding to a total energy cost of 353 GJ t−1 C2H4. These results demonstrate a transport-regulated strategy that breaks the traditional stability-energy efficiency trade-off in alkaline CO2 electrolysis, providing a general design principle for stable and energy-efficient CO2 conversion using low-cost materials.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"9 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172459","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}
Tengfeng Guo,Yiliang He,Xinmin Zhang,Yaping Lu,Shiwu Ma,Quanquan Pang,Yatao Liu
Layered transition metal oxides (LTMOs) are promising cathodes for sodium-ion batteries (SIBs) owing to their high specific capacity and structural tunability, but their practical application is plagued by severe structural degradation, transition metal dissolution, oxygen loss, and unstable cathode–electrolyte interphases (CEIs). Electrolytes play a critical role in mitigating these issues by modulating solvation structures, controlling interfacial chemistry, and stabilizing the LTMO surface. This review systematically analyzes the degradation mechanisms of LTMOs from an electrolyte perspective, including phase transitions, oxygen loss, transition metal dissolution, CEI dynamics, and intrinsic electrolyte properties. We propose design principles for electrolyte engineering, emphasizing the regulation of solvation structures and the construction of robust CEI protecting layers. Furthermore, we summarize recent advances in traditional and emerging electrolyte systems, including high-entropy, weakly solvating, and localized high-concentration electrolytes, along with functional additives. Finally, we propose a forward-looking perspective on the integration of in situ characterization, machine learning, and molecular-level design to accelerate the development of high-performance, stable LTMO-based SIBs.
{"title":"Electrolyte design toward stable layered oxide cathodes of sodium-ion batteries","authors":"Tengfeng Guo,Yiliang He,Xinmin Zhang,Yaping Lu,Shiwu Ma,Quanquan Pang,Yatao Liu","doi":"10.1039/d6ee03563a","DOIUrl":"https://doi.org/10.1039/d6ee03563a","url":null,"abstract":"Layered transition metal oxides (LTMOs) are promising cathodes for sodium-ion batteries (SIBs) owing to their high specific capacity and structural tunability, but their practical application is plagued by severe structural degradation, transition metal dissolution, oxygen loss, and unstable cathode–electrolyte interphases (CEIs). Electrolytes play a critical role in mitigating these issues by modulating solvation structures, controlling interfacial chemistry, and stabilizing the LTMO surface. This review systematically analyzes the degradation mechanisms of LTMOs from an electrolyte perspective, including phase transitions, oxygen loss, transition metal dissolution, CEI dynamics, and intrinsic electrolyte properties. We propose design principles for electrolyte engineering, emphasizing the regulation of solvation structures and the construction of robust CEI protecting layers. Furthermore, we summarize recent advances in traditional and emerging electrolyte systems, including high-entropy, weakly solvating, and localized high-concentration electrolytes, along with functional additives. Finally, we propose a forward-looking perspective on the integration of in situ characterization, machine learning, and molecular-level design to accelerate the development of high-performance, stable LTMO-based SIBs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"90 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172460","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}
A [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz) self-assembled monolayer (SAM) has emerged as a viable solution to the buried interface issues in inverted perovskite solar cells (PSCs). However, intrinsic limitations such as aggregation tendency, weak phosphate anchoring on NiOx, poor wettability and energy-level misalignment with perovskites induce substantial interfacial losses, which collectively impede further improvements in power conversion efficiency (PCE) and long-term stability. Herein, we propose a supramolecular hybridization strategy through co-assembly of carbazole dicarboxylic acid (CDA) with Me-4PACz to optimize the heterojunction interface. The π–π stacking within the hybrid system alleviates Me-4PACz aggregation, thereby reducing voids and disorder at the contact interface. The co-assembled SAMs modulate the NiOx surface charge state, suppress pinhole formation at the perovskite/substrate interface, and facilitate the growth of residual stress-free perovskite crystals with enhanced crystallinity. This bridged bilateral passivation enables the engineering of interfacial dipoles, promoting hole extraction and minimizing recombination losses. Leveraging the interface dipole-tunable contact, the champion PSCs deliver a PCE of 26.94% and a remarkable fill factor (FF) of 86.02%, with the encapsulated device retaining 92.6% of the initial PCE after 1500 h of maximum power point tracking (MPPT). This molecular-level interface engineering strategy provides significant insights for advancing the diversified applications of PSCs.
{"title":"Multifunctional π–π conjugated molecular bridges for perovskite solar cells","authors":"Jiaxi Niu,Qiankai Zhang,Zhonghao Zhou,Wenhan Yang,Lei Fu,Yuxin Tan,Yingjie Zhu,Sen Jiang,Fenqi Du,Yuexin Lin,Wenye Jiang,Kai Wu,Nan Zhang,Shiqi Sui,Dechun Zou,Jun Zhou,Chao Liang","doi":"10.1039/d6ee05749g","DOIUrl":"https://doi.org/10.1039/d6ee05749g","url":null,"abstract":"A [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz) self-assembled monolayer (SAM) has emerged as a viable solution to the buried interface issues in inverted perovskite solar cells (PSCs). However, intrinsic limitations such as aggregation tendency, weak phosphate anchoring on NiOx, poor wettability and energy-level misalignment with perovskites induce substantial interfacial losses, which collectively impede further improvements in power conversion efficiency (PCE) and long-term stability. Herein, we propose a supramolecular hybridization strategy through co-assembly of carbazole dicarboxylic acid (CDA) with Me-4PACz to optimize the heterojunction interface. The π–π stacking within the hybrid system alleviates Me-4PACz aggregation, thereby reducing voids and disorder at the contact interface. The co-assembled SAMs modulate the NiOx surface charge state, suppress pinhole formation at the perovskite/substrate interface, and facilitate the growth of residual stress-free perovskite crystals with enhanced crystallinity. This bridged bilateral passivation enables the engineering of interfacial dipoles, promoting hole extraction and minimizing recombination losses. Leveraging the interface dipole-tunable contact, the champion PSCs deliver a PCE of 26.94% and a remarkable fill factor (FF) of 86.02%, with the encapsulated device retaining 92.6% of the initial PCE after 1500 h of maximum power point tracking (MPPT). This molecular-level interface engineering strategy provides significant insights for advancing the diversified applications of PSCs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"11 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172438","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}
Proton exchange membrane water electrolysis (PEMWE) represents a cornerstone towards low-carbon energy transition. However, its deployment at large scale remains limited by two major challenges: (i) the scarcity of Ir-based anodes required to catalyze the sluggish oxygen evolution reaction (OER), and (ii) the limited understanding of the nature, performance, and durability of OER active sites. In this study, the structural and chemical dynamics governing the activity and stability of an attractive Ir-based aerogel catalyst are investigated in PEMWE notably by means of operando X-ray total scattering combined with atomic pair distribution function analysis, together with operando near-ambient-pressure X-ray photoelectron spectroscopy. These advanced characterization techniques reveal that the instability of the Ir-based aerogel during accelerated stress tests in PEMWE stems from a structural resistance to surface passivation under dynamic operation. Building on this insight, a flash calcination strategy is developed to structurally stabilize the aerogel porous architecture. This procedure significantly improved both catalytic activity and stability, providing a pathway toward efficient and durable Ir-based catalysts for PEMWE. Beyond the Ir-based aerogel system investigated here, both the operando methodology and the flash calcination stabilization strategy are readily extensible to a broad range of electrocatalytic materials in which the interplay between surface chemistry, structural dynamics, and catalytic performance governs long-term durability.
{"title":"From active site dynamics to durable Ir-based aerogel: operando insights and flash calcination strategy for the oxygen evolution reaction in proton exchange membrane water electrolyser","authors":"Meryem Ennaji,Morgane Stodel,Amir Gasmi,Tomáš Hrbek,Michal Ronovsky,Estelle Guyennot,Rémi Bacabe,Rodrigo Schneider,Marc Dupont,Frédéric Lecoeur,Sara Cavaliere,Pierre-Yves Blanchard,Frederic Maillard,Frederic Jaouen,Jakub Drnec,Raphaël Chattot","doi":"10.1039/d6ee04327e","DOIUrl":"https://doi.org/10.1039/d6ee04327e","url":null,"abstract":"Proton exchange membrane water electrolysis (PEMWE) represents a cornerstone towards low-carbon energy transition. However, its deployment at large scale remains limited by two major challenges: (i) the scarcity of Ir-based anodes required to catalyze the sluggish oxygen evolution reaction (OER), and (ii) the limited understanding of the nature, performance, and durability of OER active sites. In this study, the structural and chemical dynamics governing the activity and stability of an attractive Ir-based aerogel catalyst are investigated in PEMWE notably by means of operando X-ray total scattering combined with atomic pair distribution function analysis, together with operando near-ambient-pressure X-ray photoelectron spectroscopy. These advanced characterization techniques reveal that the instability of the Ir-based aerogel during accelerated stress tests in PEMWE stems from a structural resistance to surface passivation under dynamic operation. Building on this insight, a flash calcination strategy is developed to structurally stabilize the aerogel porous architecture. This procedure significantly improved both catalytic activity and stability, providing a pathway toward efficient and durable Ir-based catalysts for PEMWE. Beyond the Ir-based aerogel system investigated here, both the operando methodology and the flash calcination stabilization strategy are readily extensible to a broad range of electrocatalytic materials in which the interplay between surface chemistry, structural dynamics, and catalytic performance governs long-term durability.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"167 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172440","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}
Nannan Li,Leila Zouridi,Vassilios Binas,Aayan Banerjee,Wisse Merlijn Hersbach,Penghui Hou,Shaoqi Zhan,Henk H. van de Bovenkamp,John Irvine,Vasileios Kyriakou
Protonic ceramic electrolysis cells (PCECs) can unlock direct electrification of catalytic processes towards intensification and operation at intermediate temperatures (400-650 oC). A primary challenge however is the development of the steam splitting electrocatalyst (positrode) that will enable the hydrogen production. Here we have developed highly efficient and self-configured positrodes, consisting of a triple-conducting (H+, O2-, e-) Pr0.95Ca0.05Ni0.5Co0.5O3-δ perovskite matrix and exsolved praseodymium oxide nanoparticles. We show for the first time that the nanoparticle nucleation is triggered by the cross electrode-electrolyte interface ion diffusion by simply sintering in ambient air. To boost nanoparticles’ population, we also employ strategies such as acid treatment to control surface defects. This approach doubles the electrochemical performance compared to the pristine cell, accompanied with >95% faradaic efficiency and exceptional durability for >500 h. Our work exemplifies how the previously unexplored interfacial ion interactions can be engineered to enable highly efficient renewable hydrogen production at industrially relevant temperatures.
{"title":"Cross-Interface Diffusion-Driven Exsolution of Praseodymium Oxide Nanoparticles for Enabling Electrolysis at Industrially Relevant Temperatures in Protonic Ceramic Cells","authors":"Nannan Li,Leila Zouridi,Vassilios Binas,Aayan Banerjee,Wisse Merlijn Hersbach,Penghui Hou,Shaoqi Zhan,Henk H. van de Bovenkamp,John Irvine,Vasileios Kyriakou","doi":"10.1039/d6ee03199d","DOIUrl":"https://doi.org/10.1039/d6ee03199d","url":null,"abstract":"Protonic ceramic electrolysis cells (PCECs) can unlock direct electrification of catalytic processes towards intensification and operation at intermediate temperatures (400-650 oC). A primary challenge however is the development of the steam splitting electrocatalyst (positrode) that will enable the hydrogen production. Here we have developed highly efficient and self-configured positrodes, consisting of a triple-conducting (H+, O2-, e-) Pr0.95Ca0.05Ni0.5Co0.5O3-δ perovskite matrix and exsolved praseodymium oxide nanoparticles. We show for the first time that the nanoparticle nucleation is triggered by the cross electrode-electrolyte interface ion diffusion by simply sintering in ambient air. To boost nanoparticles’ population, we also employ strategies such as acid treatment to control surface defects. This approach doubles the electrochemical performance compared to the pristine cell, accompanied with >95% faradaic efficiency and exceptional durability for >500 h. Our work exemplifies how the previously unexplored interfacial ion interactions can be engineered to enable highly efficient renewable hydrogen production at industrially relevant temperatures.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"4 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172437","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}
Organic materials inherently exhibit significant electron-phonon coupling due to the strong dependence of electronic structures on molecular nuclear configurations, often resulting in substantial non-radiative voltage losses (ΔVnr) of organic photovoltaics compared to their optical gaps. A primary challenge is quantifying the energy losses attributed to electron-phonon interactions, limiting rational design rules of molecules to reduce these losses. In this study, we demonstrate that molecular isomerization reshapes excited-state dynamics at the molecular level to reduce energy losses. By integrating first-principles modeling, ultrafast spectroscopy, and device analysis, we reveal that isomerization induces degeneracy between the second excited state (S2) and first excited state (S1), creating a hot exciton manifold that circumvents Kasha's rule and facilitates efficient anti-Kasha emission. This provides a novel molecular design strategy to minimize voltage losses by redirecting excited-state energy flow through high-lying excited states, rather than relying solely on suppression of vibronic coupling in the S₁ state. A multi-excited-state Marcus theory analysis indicates that isomerization materials function within an ultralow electron-phonon coupling regime with a theoretical prediction for the lower limit of ΔVnr is 0.136 eV-significantly lower than experimental reported values (ΔVnr ~0.20 eV). Quantitative evaluation of isomerized donor-acceptor systems consistently demonstrates a reduced ΔVnr (0.184 eV vs. 0.265 eV) and a corresponding improved open-circuit voltage (VOC) of 0.92 V compared to 0.81 V. Ultimately, we highlight two key molecular design guidelines: conformational locking to reduce Franck-Condon displacements, and isomerization to induce excitedstate degeneracy to eliminate non-radiative pathways.
由于电子结构对分子核构型的强烈依赖，有机材料固有地表现出显著的电子-声子耦合，这通常导致有机光伏电池的非辐射电压损失（ΔVnr）与其光学间隙相比。一个主要的挑战是量化归因于电子-声子相互作用的能量损失，限制分子的合理设计规则以减少这些损失。在这项研究中，我们证明了分子异构化在分子水平上重塑激发态动力学以减少能量损失。通过综合第一性原理建模、超快光谱和器件分析，我们发现异构化诱导第二激发态（S2）和第一激发态（S1）之间的简并，形成热激子流形，从而绕过Kasha规则，促进有效的反Kasha发射。这提供了一种新的分子设计策略，通过高激发态重定向激发态能量流，而不是仅仅依靠抑制S₁状态的振动耦合，从而最大限度地减少电压损失。多激发态Marcus理论分析表明，异构化材料在超低电子-声子耦合区内运行，理论预测ΔVnr下限为0.136 eV，显著低于实验报告值（ΔVnr ~0.20 eV）。对异构化供体-受体体系的定量评价一致表明ΔVnr降低了（0.184 eV vs. 0.265 eV），开路电压（VOC）相应提高了0.92 V，而0.81 V。最后，我们强调了两个关键的分子设计准则：构象锁定以减少弗兰克-康登位移，异构化诱导激发态简并以消除非辐射途径。
{"title":"Breaking the Electron-Phonon Coupling Bottleneck via Conformational Restriction for Ultra-Low Voltage Loss","authors":"Yulong Hai,Yongmin Luo,Yi Chan,Yao Li,Kezou Fan,Ruijie Ma,Lunbi Wu,Tao Jia,Gang Li,Kam Sing WONG,Jiaying Wu","doi":"10.1039/d6ee05330k","DOIUrl":"https://doi.org/10.1039/d6ee05330k","url":null,"abstract":"Organic materials inherently exhibit significant electron-phonon coupling due to the strong dependence of electronic structures on molecular nuclear configurations, often resulting in substantial non-radiative voltage losses (ΔVnr) of organic photovoltaics compared to their optical gaps. A primary challenge is quantifying the energy losses attributed to electron-phonon interactions, limiting rational design rules of molecules to reduce these losses. In this study, we demonstrate that molecular isomerization reshapes excited-state dynamics at the molecular level to reduce energy losses. By integrating first-principles modeling, ultrafast spectroscopy, and device analysis, we reveal that isomerization induces degeneracy between the second excited state (S2) and first excited state (S1), creating a hot exciton manifold that circumvents Kasha's rule and facilitates efficient anti-Kasha emission. This provides a novel molecular design strategy to minimize voltage losses by redirecting excited-state energy flow through high-lying excited states, rather than relying solely on suppression of vibronic coupling in the S₁ state. A multi-excited-state Marcus theory analysis indicates that isomerization materials function within an ultralow electron-phonon coupling regime with a theoretical prediction for the lower limit of ΔVnr is 0.136 eV-significantly lower than experimental reported values (ΔVnr ~0.20 eV). Quantitative evaluation of isomerized donor-acceptor systems consistently demonstrates a reduced ΔVnr (0.184 eV vs. 0.265 eV) and a corresponding improved open-circuit voltage (VOC) of 0.92 V compared to 0.81 V. Ultimately, we highlight two key molecular design guidelines: conformational locking to reduce Franck-Condon displacements, and isomerization to induce excitedstate degeneracy to eliminate non-radiative pathways.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"53 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152707","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}
Aqueous Zn-I2 batteries are promising for energy storage, yet suffer from sluggish iodine conversion kinetics and polyiodide shuttling effect, severely limiting the rate capability and cycling durability. Conventional M-N4 single-atom catalysts (SACs) face a binding trade-off, where Fe/Co/Mn adsorb iodine species too strongly, while Zn-N4 (3d10) binds too weakly and cannot adsorb I2 spontaneously. To overcome this, we introduce highly polar Br atoms into ZIF-8-derived Zn-N-C SACs to modulate the local polarity of Zn-N4 sites. Br atoms covalently bond to the carbon framework adjacent to Zn centers, forming a well defined local dipole that moderately enhances iodine intermediate adsorption, renders I2 uptake spontaneous, and lowers the I2/I- conversion barrier, as confirmed by theoretical calculation. Consequently, the optimized Br-Zn SA/NC@I2 cathode delivers high specific capacity of 240.16 mAh g-1, retains 92.8% capacity after 50,000 cycles at 10 A g-1, and enables pouch cells with 12.3 mg cm-2 I2 loading to maintain 99.2% capacity over 120 cycles. This work demonstrates that local polarity tuning offers a viable route to optimize Zn single atom adsorption behavior for high performance Zn-I2 batteries.
锌- i2水溶液电池是一种很有前途的储能电池，但其碘转化动力学缓慢，多碘离子穿梭效应严重限制了电池的倍率能力和循环耐久性。传统的M-N4单原子催化剂（SACs）面临着一种结合权衡，其中Fe/Co/Mn对碘的吸附作用太强，而Zn-N4 （3d10）的吸附作用太弱，不能自发吸附I2。为了克服这个问题，我们在zif -8衍生的Zn-N-C SACs中引入了高极性的Br原子来调节Zn-N4位点的局部极性。理论计算证实，Br原子与Zn中心附近的碳骨架共价结合，形成一个明确的局部偶极子，适度增强碘中间吸附，使I2自发吸收，并降低I2/I-转化势垒。因此，优化后的Br-Zn SA/NC@I2阴极具有240.16 mAh g-1的高比容量，在10 A g-1下进行50,000次循环后保持92.8%的容量，并且使负载为12.3 mg cm-2的袋状电池在120次循环后保持99.2%的容量。本研究表明，局部极性调整为优化高性能Zn- i2电池的Zn单原子吸附行为提供了一条可行的途径。
{"title":"Br-tailored local polarity of Zn single-atom catalyst for shuttle-free Zn-I2 batteries with fast iodine redox kinetics","authors":"Hetong Pan,Dan He,Chang Liu,Xiaodong Shi,Ziyi Wang,Zhaoyu Wang,Yichen Li,Tianyu Yuan,Lihui Dong,Yanxin Li,Bingxian Chu,Qichen Wang","doi":"10.1039/d6ee06020j","DOIUrl":"https://doi.org/10.1039/d6ee06020j","url":null,"abstract":"Aqueous Zn-I2 batteries are promising for energy storage, yet suffer from sluggish iodine conversion kinetics and polyiodide shuttling effect, severely limiting the rate capability and cycling durability. Conventional M-N4 single-atom catalysts (SACs) face a binding trade-off, where Fe/Co/Mn adsorb iodine species too strongly, while Zn-N4 (3d10) binds too weakly and cannot adsorb I2 spontaneously. To overcome this, we introduce highly polar Br atoms into ZIF-8-derived Zn-N-C SACs to modulate the local polarity of Zn-N4 sites. Br atoms covalently bond to the carbon framework adjacent to Zn centers, forming a well defined local dipole that moderately enhances iodine intermediate adsorption, renders I2 uptake spontaneous, and lowers the I2/I- conversion barrier, as confirmed by theoretical calculation. Consequently, the optimized Br-Zn SA/NC@I2 cathode delivers high specific capacity of 240.16 mAh g-1, retains 92.8% capacity after 50,000 cycles at 10 A g-1, and enables pouch cells with 12.3 mg cm-2 I2 loading to maintain 99.2% capacity over 120 cycles. This work demonstrates that local polarity tuning offers a viable route to optimize Zn single atom adsorption behavior for high performance Zn-I2 batteries.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"33 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152704","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}
Nonuniform deposition, interfacial instability, and dendrite growth at metal anodes drive capacity fade and increase the risk of short circuits, limiting their practical deployment in high-energy-density batteries. In the metal-anode literature, Sand’s time has often been used to denote times associated with concentration depletion, voltage inflections, morphological instability, and even short-circuit failure during metal deposition, thereby conflating distinct physical events into a single timescale. Here, we clarify the physical meaning of Sand’s time in metal-anode deposition and propose that Sand-related timescales be distinguished as classical Sand’s time, apparent Sand-type time, morphology-onset time, and short-circuit/electrical-failure time. Classical Sand’s time is a transport-depletion benchmark defined by a transport model and an interfacial depletion condition, rather than a “dendrite clock” directly defined by voltage inflections, morphological changes, or short-circuit signals. We further outline how a calibrated pre-depletion concentration-polarization signal can be used to estimate an operational Sand-type time. Together, this framework helps distinguish whether an observed improvement reflects a delay in transport depletion, morphology onset, or electrical failure.
{"title":"Rethinking Sand's Time as a Transport-Depletion Benchmark for Metal-Anode Batteries","authors":"Yao Wu,Bofang Shi,Mingbo Ma,Honghui Yang","doi":"10.1039/d6ee05007g","DOIUrl":"https://doi.org/10.1039/d6ee05007g","url":null,"abstract":"Nonuniform deposition, interfacial instability, and dendrite growth at metal anodes drive capacity fade and increase the risk of short circuits, limiting their practical deployment in high-energy-density batteries. In the metal-anode literature, Sand’s time has often been used to denote times associated with concentration depletion, voltage inflections, morphological instability, and even short-circuit failure during metal deposition, thereby conflating distinct physical events into a single timescale. Here, we clarify the physical meaning of Sand’s time in metal-anode deposition and propose that Sand-related timescales be distinguished as classical Sand’s time, apparent Sand-type time, morphology-onset time, and short-circuit/electrical-failure time. Classical Sand’s time is a transport-depletion benchmark defined by a transport model and an interfacial depletion condition, rather than a “dendrite clock” directly defined by voltage inflections, morphological changes, or short-circuit signals. We further outline how a calibrated pre-depletion concentration-polarization signal can be used to estimate an operational Sand-type time. Together, this framework helps distinguish whether an observed improvement reflects a delay in transport depletion, morphology onset, or electrical failure.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"85 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152703","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 ‘A nonflammable electrolyte for ultrahigh-voltage (4.8 V-class) Li||NCM811 cells with a wide temperature range of 100 °C’ by Peitao Xiao et al., Energy Environ. Sci., 2022, 15, 2435–2444, https://doi.org/10.1039/d1ee02959b.
{"title":"Correction: A nonflammable electrolyte for ultrahigh-voltage (4.8 V-class) Li‖NCM811 cells with a wide temperature range of 100 °C","authors":"Peitao Xiao,Yun Zhao,Zhihong Piao,Baohua Li,Guangmin Zhou,Hui-Ming Cheng","doi":"10.1039/d6ee90093c","DOIUrl":"https://doi.org/10.1039/d6ee90093c","url":null,"abstract":"Correction for ‘A nonflammable electrolyte for ultrahigh-voltage (4.8 V-class) Li||NCM811 cells with a wide temperature range of 100 °C’ by Peitao Xiao et al., Energy Environ. Sci., 2022, 15, 2435–2444, https://doi.org/10.1039/d1ee02959b.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"11 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152705","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}
Dafu Zhao,Shijian Huang,Jieheng Lv,Xiaowei Lv,Panpan Sun,Xiaohua Sun,Lingmin Wu,Dongyuan Zhao,Yong Liu
The coupling between interfacial stress and electronic interactions at heterogeneous interfaces remains a largely unexplored dimension in catalysis, yet it holds the key to establishing universal principles for high-efficiency energy conversion. Here we introduce an interfacial stress–electronic coupling framework that links interfacial coordination constraints with electronic modulation in catalytic systems. Using a low-temperature molten-salt pyrolysis strategy, we construct hollow porous carbon nanocages hosting asymmetric dual single-atom centers (FeN4 and ZnN3S1) closely integrated with Zn0.73Fe0.27S nanoparticles, yielding a hierarchical porous catalyst, denoted as FeZnS-NSC. The nanoparticles act simultaneously as interfacial stress inducers and electronic coupling mediators, accompanied by measurable Fe–N (1.84 → 1.77 Å) and Zn–N (2.01 → 1.84 Å) bond compression and downshifting the d-band center. Multiscale simulations and operando spectroscopy reveal that this dual coupling optimizes *OH desorption and lowers the ORR rate-determining barrier from 1.31 to 0.55 eV. Consequently, FeZnS-NSC surpasses Pt/C (E1/2 = 0.92 vs. 0.87 V) and delivers record-breaking Zn–air battery performance, achieving a peak power density of 525 mW cm−2 in the quasi-solid-state. In liquid-state devices, it delivers an unprecedented open-circuit voltage of 1.62 V and an ultralong cycling stability exceeding 1300 h, representing the highest values reported to date for non-precious-metal electrocatalysts. These findings establish an “interface stress–electronic coupling” paradigm for non-precious metal catalysis and underscore porous nanocage confinement as a universal strategy for high-performance electrochemical energy devices.
非均相界面上的界面应力和电子相互作用之间的耦合在催化领域仍然是一个很大程度上未被探索的维度，但它是建立高效能量转换通用原理的关键。在这里，我们介绍了一个界面应力-电子耦合框架，将催化系统中的界面配位约束与电子调制联系起来。采用低温熔盐热解策略，我们构建了含有不对称双单原子中心（FeN4和ZnN3S1）的中空多孔碳纳米笼，并与Zn0.73Fe0.27S纳米颗粒紧密结合，得到了层次化多孔催化剂FeZnS-NSC。纳米粒子同时作为界面应力诱导剂和电子耦合介质，Fe-N（1.84→1.77 Å）和Zn-N（2.01→1.84 Å）键压缩和d带中心降移。多尺度模拟和操作光谱表明，这种双耦合优化了*OH脱附，并将ORR速率决定势垒从1.31 eV降低到0.55 eV。因此，FeZnS-NSC超过了Pt/C (E1/2 = 0.92 vs. 0.87 V)，并提供了破纪录的锌空气电池性能，在准固态下实现了525 mW cm - 2的峰值功率密度。在液态设备中，它提供了前所未有的1.62 V开路电压和超过1300小时的超长循环稳定性，代表了迄今为止报道的非贵金属电催化剂的最高值。这些发现为非贵金属催化建立了“界面应力-电子耦合”范式，并强调了多孔纳米笼约束作为高性能电化学能源装置的通用策略。
{"title":"Interfacial stress–electronic coupling in confined dual single-atom catalysts for record-performance zinc–air batteries","authors":"Dafu Zhao,Shijian Huang,Jieheng Lv,Xiaowei Lv,Panpan Sun,Xiaohua Sun,Lingmin Wu,Dongyuan Zhao,Yong Liu","doi":"10.1039/d6ee05203g","DOIUrl":"https://doi.org/10.1039/d6ee05203g","url":null,"abstract":"The coupling between interfacial stress and electronic interactions at heterogeneous interfaces remains a largely unexplored dimension in catalysis, yet it holds the key to establishing universal principles for high-efficiency energy conversion. Here we introduce an interfacial stress–electronic coupling framework that links interfacial coordination constraints with electronic modulation in catalytic systems. Using a low-temperature molten-salt pyrolysis strategy, we construct hollow porous carbon nanocages hosting asymmetric dual single-atom centers (FeN4 and ZnN3S1) closely integrated with Zn0.73Fe0.27S nanoparticles, yielding a hierarchical porous catalyst, denoted as FeZnS-NSC. The nanoparticles act simultaneously as interfacial stress inducers and electronic coupling mediators, accompanied by measurable Fe–N (1.84 → 1.77 Å) and Zn–N (2.01 → 1.84 Å) bond compression and downshifting the d-band center. Multiscale simulations and operando spectroscopy reveal that this dual coupling optimizes *OH desorption and lowers the ORR rate-determining barrier from 1.31 to 0.55 eV. Consequently, FeZnS-NSC surpasses Pt/C (E1/2 = 0.92 vs. 0.87 V) and delivers record-breaking Zn–air battery performance, achieving a peak power density of 525 mW cm−2 in the quasi-solid-state. In liquid-state devices, it delivers an unprecedented open-circuit voltage of 1.62 V and an ultralong cycling stability exceeding 1300 h, representing the highest values reported to date for non-precious-metal electrocatalysts. These findings establish an “interface stress–electronic coupling” paradigm for non-precious metal catalysis and underscore porous nanocage confinement as a universal strategy for high-performance electrochemical energy devices.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"72 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152706","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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