Siddhartha Nanda, Andrei Dolocan, Ayrton Yanyachi, Saurabh S. Satpute, Doosoo Kim, Kami Hull, Donal P Finegan, Ofodike Ezekoye, Hadi Khani
Potassium(K)-ion batteries are an attractive alternative to lithium-ion due to their resource abundance, graphite-anode compatibility, manufacturability, and reduced reliance on critical metals. Yet their thermal safety remains poorly defined. Here, we investigate a widely accepted “safer” anode–electrolyte pair, a graphite anode with a low-flammable electrolyte, 2.5 M potassium bis(fluorosulfonyl)imide (KFSI) in triethyl phosphate (TEP), to clarify decomposition pathways and interfacial reactivity. This work shows that stand-alone TEP primarily volatilizes, whereas in the presence of KFSI it thermally decomposes via FSI-derived intermediates, producing exothermic reactions totaling ~264 J g‒1 above 200 °C and generating organophosphate/fluorophosphate species (e.g., diethyl fluorophosphate) with SO2, HNO3, and SOF2. This is roughly twice the heat released by a conventional LiPF6 carbonate electrolyte, underscoring that low flammability does not equate to safety. With potassiated graphite (KC8), potassium leaching at ~63–80 °C triggers an early interfacial exotherm that builds an inorganic-rich secondary SEI and temporarily suppresses further anode attack up to ~200 °C. Beyond this temperature, electrolyte and anode–electrolyte reactions contribute a total of ~262 J g‒1, which is lower than that of the Li-ion analogue (~431 J g‒1) but occurs at an earlier onset (~65 vs ~100 °C). Interfacial analysis shows that heating transforms the initially stratified SEI into a K-rich, chemically homogenized interphase. Our findings demonstrate that low flammability alone does not ensure thermal safety; rather, interfacial reactivity governs risk. Engineering the SEI composition, controlling salt–solvent coordination, and selecting suitable binders are essential for suppressing sub-100 °C reactivity while maintaining electrochemical performance.
{"title":"Thermal Decomposition Pathways and Interfacial Reactivity in Potassium-Ion Batteries: Focus on Electrolyte and Anode","authors":"Siddhartha Nanda, Andrei Dolocan, Ayrton Yanyachi, Saurabh S. Satpute, Doosoo Kim, Kami Hull, Donal P Finegan, Ofodike Ezekoye, Hadi Khani","doi":"10.1039/d5ee06908d","DOIUrl":"https://doi.org/10.1039/d5ee06908d","url":null,"abstract":"Potassium(K)-ion batteries are an attractive alternative to lithium-ion due to their resource abundance, graphite-anode compatibility, manufacturability, and reduced reliance on critical metals. Yet their thermal safety remains poorly defined. Here, we investigate a widely accepted “safer” anode–electrolyte pair, a graphite anode with a low-flammable electrolyte, 2.5 M potassium bis(fluorosulfonyl)imide (KFSI) in triethyl phosphate (TEP), to clarify decomposition pathways and interfacial reactivity. This work shows that stand-alone TEP primarily volatilizes, whereas in the presence of KFSI it thermally decomposes via FSI-derived intermediates, producing exothermic reactions totaling ~264 J g‒1 above 200 °C and generating organophosphate/fluorophosphate species (e.g., diethyl fluorophosphate) with SO2, HNO3, and SOF2. This is roughly twice the heat released by a conventional LiPF6 carbonate electrolyte, underscoring that low flammability does not equate to safety. With potassiated graphite (KC8), potassium leaching at ~63–80 °C triggers an early interfacial exotherm that builds an inorganic-rich secondary SEI and temporarily suppresses further anode attack up to ~200 °C. Beyond this temperature, electrolyte and anode–electrolyte reactions contribute a total of ~262 J g‒1, which is lower than that of the Li-ion analogue (~431 J g‒1) but occurs at an earlier onset (~65 vs ~100 °C). Interfacial analysis shows that heating transforms the initially stratified SEI into a K-rich, chemically homogenized interphase. Our findings demonstrate that low flammability alone does not ensure thermal safety; rather, interfacial reactivity governs risk. Engineering the SEI composition, controlling salt–solvent coordination, and selecting suitable binders are essential for suppressing sub-100 °C reactivity while maintaining electrochemical performance.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"193 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022033","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}
Lei Zhao, Jie Zhang, Yikun Hua, Xinyue Song, Chao Wu, Ruiqian Chen, Yang Feng, Haoran Deng, Jiacheng Su, Lei Gu, Hui Wei, Weiyuan Chen, Chunming Yang, Lin Song
Constructing two-dimensional/three-dimensional (2D/3D) perovskite heterojunctions has emerged as an effective interfacial engineering strategy to passivate surface defects, optimize energy-level alignment, and suppress ion migration. However, conventional 2D layers are typically formed by surface stacking of bulky organic cations, which often result in weak interfacial coupling and hindered carrier transport, thereby limiting device performance. In this work, a single-molecule dual-functional surface-passivation strategy is proposed, in which 5-methyltryptamne hydrochloride (Me-TACl) treatment constructs a stable 2D perovskite passivation layer on top of 3D perovskite films and establishes a chemical bridge between them. This "chemically bridged heterojunction passivation" enhances interfacial coupling, suppresses surface defects, and optimizes energy level alignment. As a result, the Me-TACl treated devices exhibit remarkable enhancement in photovoltaic performance. The champion device achieves a power conversion efficiency (PCE) of 26.35%, with a stabilized power output (SPO) of 26.20% over 300 s, outperforming the control device (24.67%). Moreover, the flexible device retains 92% of its initial efficiency (24.12%) after bending at a curvature radius of 5 mm for 5000 cycles, demonstrating outstanding mechanical durability. This post-treatment strategy simultaneously enhances efficiency, stability, and flexibility, offering insights for scalable high-efficiency perovskite photovoltaics and a viable interfacial design for next-generation devices.
{"title":"Chemical Bridging in 2D/3D Heterojunction via Dual-Anchoring Functionalized Molecules for Efficient, Stable and Flexible Perovskite Solar Cells","authors":"Lei Zhao, Jie Zhang, Yikun Hua, Xinyue Song, Chao Wu, Ruiqian Chen, Yang Feng, Haoran Deng, Jiacheng Su, Lei Gu, Hui Wei, Weiyuan Chen, Chunming Yang, Lin Song","doi":"10.1039/d5ee03302k","DOIUrl":"https://doi.org/10.1039/d5ee03302k","url":null,"abstract":"Constructing two-dimensional/three-dimensional (2D/3D) perovskite heterojunctions has emerged as an effective interfacial engineering strategy to passivate surface defects, optimize energy-level alignment, and suppress ion migration. However, conventional 2D layers are typically formed by surface stacking of bulky organic cations, which often result in weak interfacial coupling and hindered carrier transport, thereby limiting device performance. In this work, a single-molecule dual-functional surface-passivation strategy is proposed, in which 5-methyltryptamne hydrochloride (Me-TACl) treatment constructs a stable 2D perovskite passivation layer on top of 3D perovskite films and establishes a chemical bridge between them. This \"chemically bridged heterojunction passivation\" enhances interfacial coupling, suppresses surface defects, and optimizes energy level alignment. As a result, the Me-TACl treated devices exhibit remarkable enhancement in photovoltaic performance. The champion device achieves a power conversion efficiency (PCE) of 26.35%, with a stabilized power output (SPO) of 26.20% over 300 s, outperforming the control device (24.67%). Moreover, the flexible device retains 92% of its initial efficiency (24.12%) after bending at a curvature radius of 5 mm for 5000 cycles, demonstrating outstanding mechanical durability. This post-treatment strategy simultaneously enhances efficiency, stability, and flexibility, offering insights for scalable high-efficiency perovskite photovoltaics and a viable interfacial design for next-generation devices.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"258 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022035","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}
Jiaxue Zhai, Huān Bì, Shiji Zhang, Lin Xie, Bin Wu, Peng Wang, Shifeng Ge, Shafidah Shafian, Jiayan Chen, Wenhua Zhang, Yong Zhang, Nam-Gyu Park, Yong Hua
Precise control of perovskite crystallization remains challenging because hydrogen bonds (H-bonds), which govern precursor interactions and nucleation pathways, are often treated as static rather than dynamic entities. Here, we propose a novel dynamic H-bond network strategy to regulate perovskite crystallization via the steric modulation of the H-bond donor in a deep eutectic solvent (DES). Replacing urea with N-methylurea (NMU) reconfigures the H-bond network of NMU-DES, which increases the number of moderately coordinating sites and promotes self-association with long H-bond lifetimes, thereby prolonging the halide···H interactions between NMU-DES and PbI2，yielding a stable precursor reservoir. Urea-based DES generates flexible and transient interactions that retard perovskite nucleation, whereas NMU-DES induces stronger, spatially localized interactions that self-assemble into an interfacial H-bond network, thereby regulating perovskite nucleation and crystal growth and yielding films with reduced defect densities. As a result, NMU-DES–based devices achieve a power conversion efficiency of 26.33% and outstanding operational stability, retaining >94% of their initial efficiency after 1,570 h of continuous illumination. This dynamic-network strategy transcends static passivation, offering rational control of weak forces as a generalizable pathway toward highly efficient and stable perovskite and other solution-processed optoelectronic materials.
{"title":"Dynamic Reconfiguration of Hydrogen-Bonded Networks to Modulate Perovskite Crystallization","authors":"Jiaxue Zhai, Huān Bì, Shiji Zhang, Lin Xie, Bin Wu, Peng Wang, Shifeng Ge, Shafidah Shafian, Jiayan Chen, Wenhua Zhang, Yong Zhang, Nam-Gyu Park, Yong Hua","doi":"10.1039/d5ee07159c","DOIUrl":"https://doi.org/10.1039/d5ee07159c","url":null,"abstract":"Precise control of perovskite crystallization remains challenging because hydrogen bonds (H-bonds), which govern precursor interactions and nucleation pathways, are often treated as static rather than dynamic entities. Here, we propose a novel dynamic H-bond network strategy to regulate perovskite crystallization via the steric modulation of the H-bond donor in a deep eutectic solvent (DES). Replacing urea with N-methylurea (NMU) reconfigures the H-bond network of NMU-DES, which increases the number of moderately coordinating sites and promotes self-association with long H-bond lifetimes, thereby prolonging the halide···H interactions between NMU-DES and PbI2，yielding a stable precursor reservoir. Urea-based DES generates flexible and transient interactions that retard perovskite nucleation, whereas NMU-DES induces stronger, spatially localized interactions that self-assemble into an interfacial H-bond network, thereby regulating perovskite nucleation and crystal growth and yielding films with reduced defect densities. As a result, NMU-DES–based devices achieve a power conversion efficiency of 26.33% and outstanding operational stability, retaining >94% of their initial efficiency after 1,570 h of continuous illumination. This dynamic-network strategy transcends static passivation, offering rational control of weak forces as a generalizable pathway toward highly efficient and stable perovskite and other solution-processed optoelectronic materials.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"14 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022032","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}
Flexible perovskite solar cells (f-PSCs) hold great promise for complementing traditional silicon solar cells in portable power applications, but their commercialization depends on the ability to scale-up solution-based deposition. So far, inhomogeneous perovskite deposition on self-assembled molecules (SAMs) poses a substantial challenge in fabricating uniform, pinhole-free films over large areas. Here, we developed an amphiphilic cross-linkable monomer (TBA) that simultaneously promotes perovskite growth on flexible substrates and ensures homogeneous deposition during scaling-up. The incorporation of TBA increase the wettability and adhesion of the perovskite ink to the underlying hydrophobic SAMs layer, enabling high-quality, uniform perovskite films on both rigid and flexible substrates, demonstrating its potential for scalable fabrication. As a result, the modified PSCs achieved remarkable power conversion efficiencies (PCEs) of 27.12% (certified 26.41%, rigid) and 24.95% (flexible), with excellent mechanical and operational stability. The TBA-modified f-PSCs retained over 90% of their initial PCE after 10,000 bending cycles and 1,000 hours of continuous operation. Additionally, large-area perovskite solar modules (PSMs) demonstrated notable PCEs of 23.10% (rigid) and 20.38% (flexible), showcasing the scalability of this approach. This strategy paves a new way for the industrial-scale development of high-performance f-PSCs.
{"title":"Exploring a Scalable Route for Efficient Flexible Perovskite Solar Cells via Amphiphilic Cross-linkable Monomer","authors":"Chenfan Xing, Weifu Zhang, Hengyu Zhou, Jiahan Xie, Shuaizhen Huang, Simeng Gao, Leixi He, Zhongqiang Wang, Lin Xie, Mengjin Yang, Wei Song, Ziyi Ge","doi":"10.1039/d5ee07050c","DOIUrl":"https://doi.org/10.1039/d5ee07050c","url":null,"abstract":"Flexible perovskite solar cells (f-PSCs) hold great promise for complementing traditional silicon solar cells in portable power applications, but their commercialization depends on the ability to scale-up solution-based deposition. So far, inhomogeneous perovskite deposition on self-assembled molecules (SAMs) poses a substantial challenge in fabricating uniform, pinhole-free films over large areas. Here, we developed an amphiphilic cross-linkable monomer (TBA) that simultaneously promotes perovskite growth on flexible substrates and ensures homogeneous deposition during scaling-up. The incorporation of TBA increase the wettability and adhesion of the perovskite ink to the underlying hydrophobic SAMs layer, enabling high-quality, uniform perovskite films on both rigid and flexible substrates, demonstrating its potential for scalable fabrication. As a result, the modified PSCs achieved remarkable power conversion efficiencies (PCEs) of 27.12% (certified 26.41%, rigid) and 24.95% (flexible), with excellent mechanical and operational stability. The TBA-modified f-PSCs retained over 90% of their initial PCE after 10,000 bending cycles and 1,000 hours of continuous operation. Additionally, large-area perovskite solar modules (PSMs) demonstrated notable PCEs of 23.10% (rigid) and 20.38% (flexible), showcasing the scalability of this approach. This strategy paves a new way for the industrial-scale development of high-performance f-PSCs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"38 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995790","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}
Triethyl phosphate (TEP) electrolytes hold significant promise for high-safety lithium metal batteries (LMBs) due to their eco-friendliness and intrinsic nonflammability. However, parasitic reactions with lithium metal, coupled with sluggish reaction kinetics, hinder their practical deployment in LMBs. Hence, we propose a sustainable TEP-based localized high-concentration electrolyte (LHCE) by molecularly regulating the coordination ability and reduction chemistry of anisole diluents, thereby simultaneously overcoming the thermodynamic and kinetic limitations associated with high-concentration electrolytes and conventional LHCEs. The optimized p-methylanisole (pMA) diluent modulates Li–TEP coordination and facilitates anions to enter primary solvation sheath through Hδ+–Oδ− hydrogen-bonding interactions, while the weak ion–dipole interaction between Li+ and pMA promotes pMA participation in interfacial reactions and preserves the cation-hopping transport mechanism. This strategy yields robust LiF/Li2O-rich interphases and accelerates reaction kinetics, enabling lithium metal to achieve a high average coulombic efficiency of 98.7% over 650 cycles and an ultralong-lifespan exceeding 1600 h. When deployed in LMBs paired with 2.5 mAh cm−2 sulfurized polyacrylonitrile cathodes, the batteries demonstrate an extended lifespan over 600 cycles with an average capacity decay of only 0.03% per cycle. Furthermore, the molecular-level design of diluents is broadly applicable to other alkali–metal batteries, offering a new pathway toward the development of high-energy LMBs.
磷酸三乙酯（TEP）电解质由于其环保性和固有的不可燃性，在高安全性锂金属电池（lmb）中具有重要的应用前景。然而，与锂金属的寄生反应，加上缓慢的反应动力学，阻碍了它们在lmb中的实际部署。因此，我们提出了一种可持续的基于tep的局部高浓度电解质（LHCE），通过分子调节苯甲醚稀释剂的配位能力和还原化学，从而同时克服了高浓度电解质和传统LHCE相关的热力学和动力学限制。优化后的pMA稀释剂通过Hδ+ -Oδ−氢键相互作用调节Li - tep配位，促进阴离子进入原生溶剂化鞘层，而Li+与pMA之间的弱离子偶极子相互作用促进pMA参与界面反应，并保持阳离子跳跃传递机制。该策略产生了强大的富LiF/ li20界面，并加速了反应动力学，使锂金属在650次循环中实现了98.7%的高平均库仑效率和超过1600小时的超长寿命。当将lmb与2.5 mAh cm - 2硫化聚丙烯腈阴极配对时，电池的寿命延长了600次循环，平均每循环容量衰减仅为0.03%。此外，稀释剂的分子水平设计广泛适用于其他碱金属电池，为高能lmb的开发提供了新的途径。
{"title":"Electron push–pull engineering enables sustainable, anti-corrosive, and nonflammable phosphate electrolytes for long-lifespan lithium–sulfur batteries","authors":"Quanyan Man, Yongbiao Mu, Lin Yang, Maokun Li, Huicun Gu, Xiaoqian Xu, Zijian Qiu, Chao Yang, Meisheng Han, Guangmin Zhou, Lin Zeng","doi":"10.1039/d5ee05956a","DOIUrl":"https://doi.org/10.1039/d5ee05956a","url":null,"abstract":"Triethyl phosphate (TEP) electrolytes hold significant promise for high-safety lithium metal batteries (LMBs) due to their eco-friendliness and intrinsic nonflammability. However, parasitic reactions with lithium metal, coupled with sluggish reaction kinetics, hinder their practical deployment in LMBs. Hence, we propose a sustainable TEP-based localized high-concentration electrolyte (LHCE) by molecularly regulating the coordination ability and reduction chemistry of anisole diluents, thereby simultaneously overcoming the thermodynamic and kinetic limitations associated with high-concentration electrolytes and conventional LHCEs. The optimized <em>p</em>-methylanisole (<em>p</em>MA) diluent modulates Li–TEP coordination and facilitates anions to enter primary solvation sheath through H<small><sup><em>δ</em>+</sup></small>–O<small><sup><em>δ</em>−</sup></small> hydrogen-bonding interactions, while the weak ion–dipole interaction between Li<small><sup>+</sup></small> and <em>p</em>MA promotes <em>p</em>MA participation in interfacial reactions and preserves the cation-hopping transport mechanism. This strategy yields robust LiF/Li<small><sub>2</sub></small>O-rich interphases and accelerates reaction kinetics, enabling lithium metal to achieve a high average coulombic efficiency of 98.7% over 650 cycles and an ultralong-lifespan exceeding 1600 h. When deployed in LMBs paired with 2.5 mAh cm<small><sup>−2</sup></small> sulfurized polyacrylonitrile cathodes, the batteries demonstrate an extended lifespan over 600 cycles with an average capacity decay of only 0.03% per cycle. Furthermore, the molecular-level design of diluents is broadly applicable to other alkali–metal batteries, offering a new pathway toward the development of high-energy LMBs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"390 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972271","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}
Daxian Zuo, Jiaming Tian, Yu Sun, Xin Yu, Bo Peng, Tao Yu, Chengrong Xu, Xiang-Qun Xu, Yigang Wang, Yiwen Liu, Tianze Shi, Yinhui Feng, Jie Yang, Haoshen Zhou, Shaohua Guo
The application of medium-/high-entropy materials has revolutionized the design of solid-state electrolytes (SSEs) by stabilizing single-phase solutions from otherwise incompatible elements. However, navigating the vast compositional space of entropy-stabilized materials remains a significant challenge. To overcome this, we introduce a machine learning (ML)-accelerated approach to identify multi-cation NASICON oxide SSEs. By training a Gaussian Naive Bayes model on four key descriptors (ionic radius, electronegativity, valence state, and configurational entropy), we found four promising compositions incorporating Zr, Ti, Hf, Lu, Ga, and Sc. These compositions exhibit notable entropy-driven stabilization, demonstrated by the complete suppression of Na3PO4/ZrO2 impurity formation. Among them, the medium-entropy phase Na3.5Zr1.0Ti0.5Lu0.5Si2PO12 achieved remarkable performance, delivering an ionic conductivity of 1.3 mS cm-1 at room temperature, a critical current density of 1.9 mA cm-2, and over 10,000 hours of stable Na plating/stripping. When integrated into all-solid-state sodium batteries with a high-voltage Na3V2(PO4)2F3 cathode and a sodium anode, it further demonstrated exceptional battery performance indicators, including high-rate capability (110 mAh g-1 at 5 C) and long-term cycling stability (80% capacity retention after 700 cycles at 2 C). This work establishes entropy engineering, coupled with ML guidance, as a powerful paradigm for the rational design of next-generation SSEs.
中/高熵材料的应用通过稳定来自其他不相容元素的单相溶液，彻底改变了固态电解质的设计。然而，导航熵稳定材料的巨大组成空间仍然是一个重大挑战。为了克服这个问题，我们引入了一种机器学习（ML）加速方法来识别多阳离子的NASICON氧化物sse。通过对四个关键描述符（离子半径、电负性、价态和构型熵）的高斯朴素贝叶斯模型进行训练，我们发现了四种有前途的成分，包括Zr、Ti、Hf、Lu、Ga和Sc。这些成分表现出明显的熵驱动稳定性，完全抑制了Na3PO4/ZrO2杂质的形成。其中，中熵相Na3.5Zr1.0Ti0.5Lu0.5Si2PO12表现优异，室温下离子电导率为1.3 mS cm-1，临界电流密度为1.9 mA cm-2，稳定镀/剥离时间超过10,000小时。当集成到具有高压Na3V2(PO4)2F3阴极和钠阳极的全固态钠电池中时，它进一步展示了卓越的电池性能指标，包括高倍率容量（110 mAh g-1在5℃）和长期循环稳定性（在2℃下循环700次后容量保持80%）。这项工作建立了熵工程，加上ML指导，作为下一代sse合理设计的强大范例。
{"title":"Machine learning-accelerated discovery of multi-cation entropy-stabilized NASICON solid electrolytes with 10,000 hours of stable Na plating/stripping for all-solid-state sodium batteries","authors":"Daxian Zuo, Jiaming Tian, Yu Sun, Xin Yu, Bo Peng, Tao Yu, Chengrong Xu, Xiang-Qun Xu, Yigang Wang, Yiwen Liu, Tianze Shi, Yinhui Feng, Jie Yang, Haoshen Zhou, Shaohua Guo","doi":"10.1039/d5ee06594a","DOIUrl":"https://doi.org/10.1039/d5ee06594a","url":null,"abstract":"The application of medium-/high-entropy materials has revolutionized the design of solid-state electrolytes (SSEs) by stabilizing single-phase solutions from otherwise incompatible elements. However, navigating the vast compositional space of entropy-stabilized materials remains a significant challenge. To overcome this, we introduce a machine learning (ML)-accelerated approach to identify multi-cation NASICON oxide SSEs. By training a Gaussian Naive Bayes model on four key descriptors (ionic radius, electronegativity, valence state, and configurational entropy), we found four promising compositions incorporating Zr, Ti, Hf, Lu, Ga, and Sc. These compositions exhibit notable entropy-driven stabilization, demonstrated by the complete suppression of Na3PO4/ZrO2 impurity formation. Among them, the medium-entropy phase Na3.5Zr1.0Ti0.5Lu0.5Si2PO12 achieved remarkable performance, delivering an ionic conductivity of 1.3 mS cm-1 at room temperature, a critical current density of 1.9 mA cm-2, and over 10,000 hours of stable Na plating/stripping. When integrated into all-solid-state sodium batteries with a high-voltage Na3V2(PO4)2F3 cathode and a sodium anode, it further demonstrated exceptional battery performance indicators, including high-rate capability (110 mAh g-1 at 5 C) and long-term cycling stability (80% capacity retention after 700 cycles at 2 C). This work establishes entropy engineering, coupled with ML guidance, as a powerful paradigm for the rational design of next-generation SSEs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"38 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972272","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}
Hongbing Li, Wei Feng, Jianan Wei, Qingchen He, Haojiang Shen, Yi He, Shi Chen, Hao Yang, Christoph J Brabec, Yaohua Mai, Fei Guo
Monolithic all-perovskite tandem solar cells based on mixed cation lead-tin (Pb-Sn) have advanced rapidly in recent years. However, the presence of a considerable amount of volatile methylammonium (MA) adversely constrains stability of the solar devices. Here, we first quantitatively evaluated the thermal stability of Pb-Sn perovskite films containing different types of A-site cations. In comparison to the all-MA and MA-FA binary counterparts, all-formamidinium (FA) Pb-Sn films exhibit the highest decomposition activation energy of 149.13 kJ mol-1. On this basis, high-quality all-FA Pb-Sn perovskite films are prepared by blade coating with addition of a small amount of hydrazinium dichloride (HDC) to the perovskite precursor. The selectively strong coordination of HDC with Sn2+ ions not only suppresses the oxidation of Sn2+ but, more importantly, balances the nucleation of the Sn- and Pb-based species, resulting in perovskite films with markedly improved homogeneity of Pb-Sn alloyed phase. The prepared single-junction all-FA Pb-Sn PSCs and MA-free tandem devices yield champion efficiencies of 21.81% and 27.40%, respectively. Moreover, the unencapsulated all-FA Pb-Sn devices maintain >80% of their initial efficiencies following 190 h of thermal stress at 85 °C.
{"title":"Synchronizing Crystallization Enables Thermally Stable All-FA Pb-Sn Perovskites for Printable MA-Free All-Perovskite Tandem Solar Cells","authors":"Hongbing Li, Wei Feng, Jianan Wei, Qingchen He, Haojiang Shen, Yi He, Shi Chen, Hao Yang, Christoph J Brabec, Yaohua Mai, Fei Guo","doi":"10.1039/d5ee04529k","DOIUrl":"https://doi.org/10.1039/d5ee04529k","url":null,"abstract":"Monolithic all-perovskite tandem solar cells based on mixed cation lead-tin (Pb-Sn) have advanced rapidly in recent years. However, the presence of a considerable amount of volatile methylammonium (MA) adversely constrains stability of the solar devices. Here, we first quantitatively evaluated the thermal stability of Pb-Sn perovskite films containing different types of A-site cations. In comparison to the all-MA and MA-FA binary counterparts, all-formamidinium (FA) Pb-Sn films exhibit the highest decomposition activation energy of 149.13 kJ mol-1. On this basis, high-quality all-FA Pb-Sn perovskite films are prepared by blade coating with addition of a small amount of hydrazinium dichloride (HDC) to the perovskite precursor. The selectively strong coordination of HDC with Sn2+ ions not only suppresses the oxidation of Sn2+ but, more importantly, balances the nucleation of the Sn- and Pb-based species, resulting in perovskite films with markedly improved homogeneity of Pb-Sn alloyed phase. The prepared single-junction all-FA Pb-Sn PSCs and MA-free tandem devices yield champion efficiencies of 21.81% and 27.40%, respectively. Moreover, the unencapsulated all-FA Pb-Sn devices maintain >80% of their initial efficiencies following 190 h of thermal stress at 85 °C.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"12 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993184","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 applications of Zn-I2 batteries are plagued by severe side reactions, including the polyiodide shuttle on the cathode and parasitic by-products on the zinc anode. Herein, we introduce an amino acid derivative, D-penicillamine (DPL), as a molecular-level mediator to simultaneously resolve these challenges. Its functional groups effectively anchor iodine species and catalyze polyiodide conversion, thus suppressing the shuttle effect for highly reversible iodine redox. Concurrently, its preferential adsorption and favorable electronic structure enable the protection on the zinc anode, which inhibits dendrite growth and gas evolution reaction. Consequently, the DPL-containing electrolyte enables exceptional long-term stability: a symmetric Zn||Zn cell operates stably for over 1500 h at 5 mA cm-2 and 1 mAh cm-2, while a full Zn-I2 cell endures an unprecedented 12000 cycles at 10 A g-1 with 87.6% capacity retention. Especially at high I2 loading of 14.7 mg cm-2, the corresponding pouch cell exhibits impressive reversible capacity of 160 mA h g-1 and considerable retention ratio of 95.2% after 100 cycles at low current density of 0.5 A g-1. This paper demonstrates that employing molecular mediators is a powerful strategy to design and develop high-performance Zn-I2 batteries.
锌- i2电池的应用受到严重副反应的困扰，包括阴极上的多碘化物穿梭和锌阳极上的寄生副产物。在这里，我们引入了一种氨基酸衍生物，d -青霉胺（DPL），作为分子水平的介质来同时解决这些挑战。其官能团能有效地锚定碘种并催化多碘化物转化，从而抑制高可逆碘氧化还原的穿梭效应。同时，其优越的吸附和良好的电子结构对锌阳极起到保护作用，抑制枝晶生长和析气反应。因此，含有dpl的电解液具有卓越的长期稳定性：对称Zn||锌电池在5 mA cm-2和1 mAh cm-2下稳定工作超过1500小时，而完整的Zn- i2电池在10 a g-1下可承受前所未有的12000次循环，容量保持率为87.6%。特别是在高I2负载14.7 mg cm-2时，相应的袋状电池表现出令人印象深刻的160 mA h g-1的可逆容量和可观的保留率，在低电流密度0.5 A g-1下循环100次后达到95.2%。本文论证了采用分子介质是设计和开发高性能锌- i2电池的有力策略。
{"title":"Amino acid-based functional additive enables fast polyiodide conversion kinetics for durable Zn-I2 batteries","authors":"Xinran Fu, Yicai Pan, Zhixiang Chen, Fulong Li, Yongqiang Yang, Min Chen, Haoran Tu, Tianyu Qiu, Zhenyue Xing, Peng Rao, Zhenye Kang, Wenjun Zhang, Xiaodong Shi, Lutong Shan, Xinlong Tian","doi":"10.1039/d5ee06668a","DOIUrl":"https://doi.org/10.1039/d5ee06668a","url":null,"abstract":"The applications of Zn-I2 batteries are plagued by severe side reactions, including the polyiodide shuttle on the cathode and parasitic by-products on the zinc anode. Herein, we introduce an amino acid derivative, D-penicillamine (DPL), as a molecular-level mediator to simultaneously resolve these challenges. Its functional groups effectively anchor iodine species and catalyze polyiodide conversion, thus suppressing the shuttle effect for highly reversible iodine redox. Concurrently, its preferential adsorption and favorable electronic structure enable the protection on the zinc anode, which inhibits dendrite growth and gas evolution reaction. Consequently, the DPL-containing electrolyte enables exceptional long-term stability: a symmetric Zn||Zn cell operates stably for over 1500 h at 5 mA cm-2 and 1 mAh cm-2, while a full Zn-I2 cell endures an unprecedented 12000 cycles at 10 A g-1 with 87.6% capacity retention. Especially at high I2 loading of 14.7 mg cm-2, the corresponding pouch cell exhibits impressive reversible capacity of 160 mA h g-1 and considerable retention ratio of 95.2% after 100 cycles at low current density of 0.5 A g-1. This paper demonstrates that employing molecular mediators is a powerful strategy to design and develop high-performance Zn-I2 batteries.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"56 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968883","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}
Mengxiao Li, Yu Li, Huijie Wang, Mingjun Hu, Jun Yang
Aqueous alkaline nickel-based batteries are regarded as ideal candidates for large-scale energy storage due to their high safety and inherent low cost, but they are plagued by the toxicity, side reactions and high cost of conventional metal anode materials, such as Cd, Zn, metal hydride alloys. Herein, we report an azo-linked conjugated organic polymer (PBPA) synthesised via in situ electrochemical reduction and coupling of nitro groups on 2,8,14-trinitrohexaazatrinaphthalene (HATN-3NO2) in a high-concentration alkaline electrolyte with low free water activity. This resulting polymer, featuring a high density of active C=N and N=N groups and enhanced electron delocalization, emerges as a promising anode owing to its low cost, excellent cyclability, and low redox potential. When assembled into a PBPA//Ni(OH)2 full cell, it demonstrates remarkable performance, including a high anode-specific capacity of 324.9 mAh g-1, exceptional durability over 30,000 cycles at 10 A g-1, and outstanding low-temperature capabilities (117% capacity retention after 560 cycles at -60 °C), which outperform commercial nickel-hydrogen batteries and most reported aqueous alkaline systems. This potential is further highlighted by the fabrication of a high-mass loading (14.4 mg cm-2) self-supporting electrode, which delivers a high operating voltage of 1.25 V with minimal capacity decay, underscoring the significant promise of this system for practical energy storage applications.
水碱性镍基电池因其高安全性和低成本而被认为是大规模储能的理想候选者，但其存在传统金属负极材料（如Cd、Zn、金属氢化物合金）的毒性、副反应和高成本等问题。在此，我们报道了一种偶氮连接的有机聚合物（PBPA），通过原位电化学还原和在2,8,14-三硝基六氮杂萘（HATN-3NO2）上的硝基偶联，在高浓度碱性低游离水活性电解质中合成。这种聚合物具有高密度的活性C=N和N=N基团和增强的电子离域，由于其低成本、优异的可循环性和低氧化还原电位而成为一种有前途的阳极。当组装成PBPA//Ni(OH)2电池时，它表现出卓越的性能，包括高达324.9 mAh g-1的阳极比容量，在10 a g-1下超过30,000次循环的优异耐久性，以及出色的低温性能（在-60°C下560次循环后容量保持117%），优于商用镍氢电池和大多数报道的水性碱性系统。高质量负载（14.4 mg cm-2）自支撑电极的制造进一步突出了这一潜力，该电极提供1.25 V的高工作电压，容量衰减最小，强调了该系统在实际储能应用中的重要前景。
{"title":"An in-situ engineered azo-linked conjugated polymer anode enabling ultra-stable, high-energy aqueous alkaline batteries at -60 ℃","authors":"Mengxiao Li, Yu Li, Huijie Wang, Mingjun Hu, Jun Yang","doi":"10.1039/d5ee06874f","DOIUrl":"https://doi.org/10.1039/d5ee06874f","url":null,"abstract":"Aqueous alkaline nickel-based batteries are regarded as ideal candidates for large-scale energy storage due to their high safety and inherent low cost, but they are plagued by the toxicity, side reactions and high cost of conventional metal anode materials, such as Cd, Zn, metal hydride alloys. Herein, we report an azo-linked conjugated organic polymer (PBPA) synthesised via in situ electrochemical reduction and coupling of nitro groups on 2,8,14-trinitrohexaazatrinaphthalene (HATN-3NO2) in a high-concentration alkaline electrolyte with low free water activity. This resulting polymer, featuring a high density of active C=N and N=N groups and enhanced electron delocalization, emerges as a promising anode owing to its low cost, excellent cyclability, and low redox potential. When assembled into a PBPA//Ni(OH)2 full cell, it demonstrates remarkable performance, including a high anode-specific capacity of 324.9 mAh g-1, exceptional durability over 30,000 cycles at 10 A g-1, and outstanding low-temperature capabilities (117% capacity retention after 560 cycles at -60 °C), which outperform commercial nickel-hydrogen batteries and most reported aqueous alkaline systems. This potential is further highlighted by the fabrication of a high-mass loading (14.4 mg cm-2) self-supporting electrode, which delivers a high operating voltage of 1.25 V with minimal capacity decay, underscoring the significant promise of this system for practical energy storage applications.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"57 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993356","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}
Wide-bandgap (WBG) perovskite solar cells (PSCs) serve as essential top cells in perovskite/organic tandem solar cells (POTSCs), where their optoelectronic properties profoundly impact overall device performance. However, WBG PSCs with high bromine content suffer from substantial energy losses due to inferior film crystalline and severe phase segregation, which hinder the advancement of efficient POTSCs. Herein, propanedioic acid (PPDA) is designed and adopted as a crystallization regulator to modulate the nucleation and crystal growth kinetics of 1.85 eV WBG perovskites. This strategy enhances film crystallinity and effectively suppresses phase segregation. Additionally, PPDA strengthens field-effect coupling at the perovskite surface through hydrogen bonding with the upper propane-1,3-diammonium iodide (PDAI2) interlayer, thereby significantly reducing the interfacial non-radiative voltage loss. Consequently, the 1.85 eV WBG PSC achieves a record power conversion efficiency (PCE) of 19.35% with an exceptional open-circuit voltage (VOC) of 1.38 V, along with great operational stability. When integrated with organic sub-cells in a two-terminal tandem configuration, the POTSC delivers an impressive PCE of 26.25% and a notable VOC of 2.22 V. This work elucidates a synergistic mechanism for simultaneous crystallization regulation and interface enhancement in perovskite photovoltaics, providing valuable insights for developing high-performance WBG and tandem devices.
宽带隙（WBG）钙钛矿太阳能电池（PSCs）是钙钛矿/有机串联太阳能电池（POTSCs）中必不可少的顶层电池，其光电性能深刻影响着器件的整体性能。然而，高溴含量的WBG PSCs由于薄膜结晶性差和相偏析严重，导致能量损失较大，阻碍了高效poscs的发展。本文设计并采用丙二酸（PPDA）作为结晶调节剂，调节1.85 eV WBG钙钛矿的成核和晶体生长动力学。这种策略提高了薄膜的结晶度，有效地抑制了相偏析。此外，PPDA通过与上部丙烷-1,3-碘化二铵（PDAI2）中间层的氢键，加强了钙钛矿表面的场效应耦合，从而显著降低了界面非辐射电压损失。因此，1.85 eV WBG PSC在1.38 V的开路电压（VOC）下实现了19.35%的创纪录功率转换效率（PCE），同时具有很高的工作稳定性。当与有机子电池以双端串联配置集成时，POTSC提供了令人印象深刻的26.25%的PCE和显著的2.22 V VOC。这项工作阐明了钙钛矿光伏电池中同时结晶调节和界面增强的协同机制，为开发高性能WBG和串联器件提供了有价值的见解。
{"title":"Hydrogen-bond-driven synergistic regulation of crystallization and interfacial coupling in 1.85 eV wide-bandgap perovskites for high-performance organic tandem solar cells","authors":"Qi Wang, Yingying Wang, Wei Hui, Lin Song, Xiaopeng Xu, Yihui Wu, Qiang Peng","doi":"10.1039/d5ee06814b","DOIUrl":"https://doi.org/10.1039/d5ee06814b","url":null,"abstract":"Wide-bandgap (WBG) perovskite solar cells (PSCs) serve as essential top cells in perovskite/organic tandem solar cells (POTSCs), where their optoelectronic properties profoundly impact overall device performance. However, WBG PSCs with high bromine content suffer from substantial energy losses due to inferior film crystalline and severe phase segregation, which hinder the advancement of efficient POTSCs. Herein, propanedioic acid (PPDA) is designed and adopted as a crystallization regulator to modulate the nucleation and crystal growth kinetics of 1.85 eV WBG perovskites. This strategy enhances film crystallinity and effectively suppresses phase segregation. Additionally, PPDA strengthens field-effect coupling at the perovskite surface through hydrogen bonding with the upper propane-1,3-diammonium iodide (PDAI2) interlayer, thereby significantly reducing the interfacial non-radiative voltage loss. Consequently, the 1.85 eV WBG PSC achieves a record power conversion efficiency (PCE) of 19.35% with an exceptional open-circuit voltage (VOC) of 1.38 V, along with great operational stability. When integrated with organic sub-cells in a two-terminal tandem configuration, the POTSC delivers an impressive PCE of 26.25% and a notable VOC of 2.22 V. This work elucidates a synergistic mechanism for simultaneous crystallization regulation and interface enhancement in perovskite photovoltaics, providing valuable insights for developing high-performance WBG and tandem devices.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"39 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962206","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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