Anode-free lithium metal batteries (AFLMBs) offer the highest theoretical energy density among rechargeable systems but suffer from rapid capacity fading caused by uncontrolled lithium loss and unstable solid electrolyte interphase (SEI) formation, particularly in carbonate electrolytes. Although lithium nitrate (LiNO3) is a highly effective additive for stabilizing SEI, its poor solubility in carbonate solvents remains a critical bottleneck. Here, we address this limitation by functionalizing a commercial polypropylene (PP) separator with an electrospun polyvinylidene fluoride (PVDF)/LiNO3 nanofiber coating, enabling localized and sustained release of LiNO3 during cycling. This design delivers three synergistic benefits: (i) piezoelectric beta-phase PVDF nanofibers regulate lithium flux distribution and suppress dendrite growth, (ii) the polar and electronegative nanofiber network enhances Li+ transport, yielding enhanced ionic conductivity (1.22 mS cm−1) and Li+ transference number of 0.50, and (iii) uniform distribution of LiNO3 within the nanofibers acts as a self-replenishing additive reservoir that gradually dissolves to sustain continuous formation of robust Li3N/LiF-rich SEI. As a result, Li symmetric cells exhibit stable cycling for over 500 hours at 3 mA cm−2, while Li||NMC622 full cells retain 83% of their initial capacity after 100 cycles at N/P ratio of 1.8. Most notably, Cu||NMC622 anode-free cells achieve 54% capacity retention after 50 cycles, compared to only 18% for cells with a conventional PP separator. This work demonstrates separator functionalization as a simple, scalable, and broadly applicable strategy to overcome additive solubility limitations and enable long-lasting, dendrite-suppressed anode-free lithium metal batteries.
无阳极锂金属电池（aflmb）在可充电系统中提供最高的理论能量密度，但由于不受控制的锂损失和不稳定的固体电解质间相（SEI）形成，特别是在碳酸盐电解质中，其容量会迅速衰减。虽然硝酸锂（LiNO3）是稳定SEI的高效添加剂，但其在碳酸盐溶剂中的溶解度差仍然是一个关键瓶颈。在这里，我们通过用静电纺聚偏氟乙烯(PVDF)/LiNO3纳米纤维涂层功能化商用聚丙烯（PP）分离器来解决这一限制，使LiNO3在循环过程中局部和持续释放。这种设计具有三个协同效益：(1)压电β相PVDF纳米纤维调节了锂通量分布，抑制了枝晶生长；(2)极性和电负性纳米纤维网络增强了Li+传输，提高了离子电导率（1.22 mS cm - 1）和Li+转移数0.50;(3)纳米纤维内均匀分布的LiNO3充当了一个自我补充的添加剂储层，该储层逐渐溶解，以维持连续形成坚固的Li3N/LiF-rich SEI。结果表明，Li对称电池在3 mA cm−2下稳定循环500小时以上，而Li||NMC622全电池在N/P比为1.8的条件下循环100次后仍能保持83%的初始容量。最值得注意的是，Cu||NMC622无阳极电池在50次循环后的容量保持率为54%，而使用传统PP分离器的电池只有18%。这项工作证明了隔膜功能化是一种简单、可扩展、广泛适用的策略，可以克服添加剂溶解度限制，实现持久、抑制枝晶的无阳极锂金属电池。
{"title":"PVDF Nanofiber Separator with Sustained LiNO3 Additive Release for Dendrite-Suppressed Anode-Free Lithium Metal Batteries","authors":"Aldan Hadziq Haidar, Naufal Hanif Hawari, Dian Anggreini, Febri Baskoro, Ning Ding, Qingyu Yan, Afriyanti Sumboja","doi":"10.1039/d5ta09302c","DOIUrl":"https://doi.org/10.1039/d5ta09302c","url":null,"abstract":"Anode-free lithium metal batteries (AFLMBs) offer the highest theoretical energy density among rechargeable systems but suffer from rapid capacity fading caused by uncontrolled lithium loss and unstable solid electrolyte interphase (SEI) formation, particularly in carbonate electrolytes. Although lithium nitrate (LiNO<small><sub>3</sub></small>) is a highly effective additive for stabilizing SEI, its poor solubility in carbonate solvents remains a critical bottleneck. Here, we address this limitation by functionalizing a commercial polypropylene (PP) separator with an electrospun polyvinylidene fluoride (PVDF)/LiNO<small><sub>3</sub></small> nanofiber coating, enabling localized and sustained release of LiNO<small><sub>3</sub></small> during cycling. This design delivers three synergistic benefits: (i) piezoelectric beta-phase PVDF nanofibers regulate lithium flux distribution and suppress dendrite growth, (ii) the polar and electronegative nanofiber network enhances Li<small><sup>+</sup></small> transport, yielding enhanced ionic conductivity (1.22 mS cm<small><sup>−1</sup></small>) and Li<small><sup>+</sup></small> transference number of 0.50, and (iii) uniform distribution of LiNO<small><sub>3</sub></small> within the nanofibers acts as a self-replenishing additive reservoir that gradually dissolves to sustain continuous formation of robust Li<small><sub>3</sub></small>N/LiF-rich SEI. As a result, Li symmetric cells exhibit stable cycling for over 500 hours at 3 mA cm<small><sup>−2</sup></small>, while Li||NMC622 full cells retain 83% of their initial capacity after 100 cycles at N/P ratio of 1.8. Most notably, Cu||NMC622 anode-free cells achieve 54% capacity retention after 50 cycles, compared to only 18% for cells with a conventional PP separator. This work demonstrates separator functionalization as a simple, scalable, and broadly applicable strategy to overcome additive solubility limitations and enable long-lasting, dendrite-suppressed anode-free lithium metal batteries.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"21 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yaning Liu, Da Yang, Rui Xu, Yijue Wang, Liuyi Hu, Tianqi Yang, Min Fan, Meiqing Feng, Jianping Xu, Zhen Xiao, Ruyi Fang, Jun Zhang, Xinhui Xia, Hui Huang, Xiayin Yao, Wenkui Zhang, Yang Xia
The advancement of all-solid-state lithium metal batteries (ASSLMBs) with high energy density is significantly constrained by the inherent drawbacks of solid polymer electrolytes (SPEs), such as low room-temperature ionic conductivity, inadequate mechanical strength to prevent lithium dendrite growth, and unstable interfaces between electrodes and electrolytes.To overcome these limitations, this study introduces a synergistic modification strategy for poly(ethylene oxide) (PEO)-based SPEs by incorporating calcium fluoride (CaF2), aiming to concurrently improve bulk electrolyte properties and interfacial stability. The introduction of CaF2 effectively inhibited the crystallization of PEO by steric hindrance and Lewis acid, which made the ionic conductivity of the electrolyte reach 8.49 × 10-5 S cm-1 at 40°C (70% higher than that of the original electrolyte) and the lithium-ion migration number increased to 0.34.The composite electrolyte also demonstrates improved mechanical robustness (yield strength of 1.61 MPa) and electrochemical stability window (with decomposition voltage elevated to 5.01 V), enabling a critical current density of 0.8 mA cm-2 . Theoretical and experimental investigations reveal that CaF2 promotes the formation of a hybrid solid electrolyte interphase (SEI) enriched with LiF and Ca-Li alloys, which guides uniform lithium deposition. As a result, Li symmetric cells achieve stable cycling over 1600 hours, and LiFePO4||Li full cells retain 98.1% of their initial capacity after 300 cycles at 0.5 C. This work offers a scalable pathway for designing dendrite-suppressing SPEs through dual optimization of bulk and interfacial characteristics.
高能量密度的全固态锂金属电池（asslmb）的发展受到固体聚合物电解质（spe）固有缺陷的严重制约，如室温离子电导率低、机械强度不足以阻止锂枝晶生长、电极和电解质之间的界面不稳定等。为了克服这些局限性，本研究引入了一种添加氟化钙（CaF2）的聚环氧乙烷（PEO）基spe的协同改性策略，旨在同时改善体电解质性能和界面稳定性。CaF2的引入通过位阻和Lewis酸有效抑制了PEO的结晶，使得电解质在40℃时的离子电导率达到8.49 × 10-5 S cm-1（比原电解质高70%），锂离子迁移数提高到0.34。复合电解质还表现出更好的机械稳稳性（屈服强度为1.61 MPa）和电化学稳定窗口（分解电压提高到5.01 V），使临界电流密度达到0.8 mA cm-2。理论和实验研究表明，CaF2促进了富含LiF和Ca-Li合金的杂化固体电解质界面（SEI）的形成，从而指导了均匀的锂沉积。结果，锂对称电池在1600小时内实现了稳定的循环，而LiFePO4||锂电池在0.5 c下循环300次后仍保持了98.1%的初始容量。这项工作为通过双优化体积和界面特性来设计抑制枝晶的spe提供了可扩展的途径。
{"title":"Synergistic Regulation of Bulk and Interfacial Properties in PEO Electrolyte by CaF2 for Stable Lithium Metal Batteries","authors":"Yaning Liu, Da Yang, Rui Xu, Yijue Wang, Liuyi Hu, Tianqi Yang, Min Fan, Meiqing Feng, Jianping Xu, Zhen Xiao, Ruyi Fang, Jun Zhang, Xinhui Xia, Hui Huang, Xiayin Yao, Wenkui Zhang, Yang Xia","doi":"10.1039/d5ta09885h","DOIUrl":"https://doi.org/10.1039/d5ta09885h","url":null,"abstract":"The advancement of all-solid-state lithium metal batteries (ASSLMBs) with high energy density is significantly constrained by the inherent drawbacks of solid polymer electrolytes (SPEs), such as low room-temperature ionic conductivity, inadequate mechanical strength to prevent lithium dendrite growth, and unstable interfaces between electrodes and electrolytes.To overcome these limitations, this study introduces a synergistic modification strategy for poly(ethylene oxide) (PEO)-based SPEs by incorporating calcium fluoride (CaF<small><sub>2</sub></small>), aiming to concurrently improve bulk electrolyte properties and interfacial stability. The introduction of CaF<small><sub>2</sub></small> effectively inhibited the crystallization of PEO by steric hindrance and Lewis acid, which made the ionic conductivity of the electrolyte reach 8.49 × 10<small><sup>-5</sup></small> S cm<small><sup>-1</sup></small> at 40°C (70% higher than that of the original electrolyte) and the lithium-ion migration number increased to 0.34.The composite electrolyte also demonstrates improved mechanical robustness (yield strength of 1.61 MPa) and electrochemical stability window (with decomposition voltage elevated to 5.01 V), enabling a critical current density of 0.8 mA cm<small><sup>-2</sup></small> . Theoretical and experimental investigations reveal that CaF<small><sub>2</sub></small> promotes the formation of a hybrid solid electrolyte interphase (SEI) enriched with LiF and Ca-Li alloys, which guides uniform lithium deposition. As a result, Li symmetric cells achieve stable cycling over 1600 hours, and LiFePO<small><sub>4</sub></small>||Li full cells retain 98.1% of their initial capacity after 300 cycles at 0.5 C. This work offers a scalable pathway for designing dendrite-suppressing SPEs through dual optimization of bulk and interfacial characteristics.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"48 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiangzhao Wang, Guiping Lin, Zichen Zhang, Kuiyuan Ma, Jun Zhang
Atmospheric icing represents a significant operational hazard for unmanned aerial vehicles (UAVs), accounting for approximately 1/4 of all UAV-related accidents, predominantly due to compromised flight stability caused by ice buildup. Consequently, there is a pressing need to design an icephobic coating specifically tailored for UAV applications. Although anti-/de-icing coating technologies have made significant progress, their icephobic effect often decreases or completely disappears in actual service environments. Here, a novel composite coating (VTEC) is developed by integrating all biobased epoxy resins with oil-stored nano-silica through hybrid cross-linked strategy, demonstrating exceptional hydrophobic performance with 9° sliding angle. The coating’s superior lubricating characteristics confer remarkable anti-adhesion, self-cleaning, and de-icing capabilities (ice adhesion strength: 7.8 kPa), while demonstrating exceptional anti-icing and anti-frosting efficacy under dual stressors of cryogenic temperatures and elevated humidity conditions. Comparative analysis reveals that VTEC achieves a 19.5-fold increase in freezing delay duration and approximately 300% extension in frosting time relative to superhydrophobic coating (SHC), highlighting its superior performance in extreme environmental conditions. Notably, VTEC-coated propellers maintained two ice-shedding events during testing while SHC-coated surfaces failed completely, resulting in 91.6% energy savings. Beyond ice resistance, the multifunctional coating provides UV shielding, corrosion inhibition, antibacterial properties, self-healing capabilities, and recyclability. This technological progress could notably enhance the operational versatility of drones under harsh environmental conditions.
{"title":"Room temperature curing sustainable hybrid cross-linked coating enables efficient dynamic icephobicity of unmanned aerial vehicles","authors":"Xiangzhao Wang, Guiping Lin, Zichen Zhang, Kuiyuan Ma, Jun Zhang","doi":"10.1039/d5ta10286c","DOIUrl":"https://doi.org/10.1039/d5ta10286c","url":null,"abstract":"Atmospheric icing represents a significant operational hazard for unmanned aerial vehicles (UAVs), accounting for approximately 1/4 of all UAV-related accidents, predominantly due to compromised flight stability caused by ice buildup. Consequently, there is a pressing need to design an icephobic coating specifically tailored for UAV applications. Although anti-/de-icing coating technologies have made significant progress, their icephobic effect often decreases or completely disappears in actual service environments. Here, a novel composite coating (VTEC) is developed by integrating all biobased epoxy resins with oil-stored nano-silica through hybrid cross-linked strategy, demonstrating exceptional hydrophobic performance with 9° sliding angle. The coating’s superior lubricating characteristics confer remarkable anti-adhesion, self-cleaning, and de-icing capabilities (ice adhesion strength: 7.8 kPa), while demonstrating exceptional anti-icing and anti-frosting efficacy under dual stressors of cryogenic temperatures and elevated humidity conditions. Comparative analysis reveals that VTEC achieves a 19.5-fold increase in freezing delay duration and approximately 300% extension in frosting time relative to superhydrophobic coating (SHC), highlighting its superior performance in extreme environmental conditions. Notably, VTEC-coated propellers maintained two ice-shedding events during testing while SHC-coated surfaces failed completely, resulting in 91.6% energy savings. Beyond ice resistance, the multifunctional coating provides UV shielding, corrosion inhibition, antibacterial properties, self-healing capabilities, and recyclability. This technological progress could notably enhance the operational versatility of drones under harsh environmental conditions.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"92 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yayue He, Shuangshuang Zhu, Shilun Gao, Xuan Liu, Zhenxi Li, Yurong Liang, Yan Zhai, Pengfei Cao, Huabin Yang
The development of lithium (Li) metal batteries (LMBs) has been significantly impeded by the inherent safety risks of flammable and leaky organic liquid electrolytes. Solid electrolytes offer a promising solution to mitigate these risks and improve overall battery safety. In this study, a novel fluorinated polymer solid-state electrolyte was designed through a targeted material coupling strategy, resulting in functional decoupling within the electrolyte system. A highly electronegative fluorinated polymer backbone was constructed to primarily regulate interfacial reactions, broadening the electrochemical window, and promote Li salt dissociation. Concurrently, a dual-salt system with differentiated coordination capabilities (e.g., LiTFSI and LiBOB) was employed to synergistically ensure Li⁺ conduction in the bulk phase and stabilize the electrolyte/electrode interphase. Consequently, the resulting 3D interconnected fluorinated/ether-based polymer network (D-PFPS) with dual-salt couping exhibits an extended electrochemical window up to 4.9 V. The Li/Li symmetric cells demonstrate exceptional cycling stability exceeding 1,400 h. The LiFePO4/D-PFPS/Li full cell shows a capacity retention of 80 % for over 1,000 cycles at 60 °C and the NCM811/D-PFPS/Li full cell exhibits stable cycling for over 100 cycles, representing excellent cycling performance. This strategy provides a promising pathway towards realizing stable and safe high-energy-density LMBs.
{"title":"Fluorinated Polymer Electrolyte via Dual-Salt Coupling for Solid-State Lithium Metal Batteries","authors":"Yayue He, Shuangshuang Zhu, Shilun Gao, Xuan Liu, Zhenxi Li, Yurong Liang, Yan Zhai, Pengfei Cao, Huabin Yang","doi":"10.1039/d5ta09340f","DOIUrl":"https://doi.org/10.1039/d5ta09340f","url":null,"abstract":"The development of lithium (Li) metal batteries (LMBs) has been significantly impeded by the inherent safety risks of flammable and leaky organic liquid electrolytes. Solid electrolytes offer a promising solution to mitigate these risks and improve overall battery safety. In this study, a novel fluorinated polymer solid-state electrolyte was designed through a targeted material coupling strategy, resulting in functional decoupling within the electrolyte system. A highly electronegative fluorinated polymer backbone was constructed to primarily regulate interfacial reactions, broadening the electrochemical window, and promote Li salt dissociation. Concurrently, a dual-salt system with differentiated coordination capabilities (e.g., LiTFSI and LiBOB) was employed to synergistically ensure Li⁺ conduction in the bulk phase and stabilize the electrolyte/electrode interphase. Consequently, the resulting 3D interconnected fluorinated/ether-based polymer network (D-PFPS) with dual-salt couping exhibits an extended electrochemical window up to 4.9 V. The Li/Li symmetric cells demonstrate exceptional cycling stability exceeding 1,400 h. The LiFePO4/D-PFPS/Li full cell shows a capacity retention of 80 % for over 1,000 cycles at 60 °C and the NCM811/D-PFPS/Li full cell exhibits stable cycling for over 100 cycles, representing excellent cycling performance. This strategy provides a promising pathway towards realizing stable and safe high-energy-density LMBs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"95 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Deepak Kharel, Calvin D. Quilty, Igor I. Bezsonov, Ciara N. Wright, Timothy N. Lambert, Yang-Tse Cheng
Rechargeable alkaline zinc batteries (AZBs) are being actively researched for grid-scale energy storage due to their safety, low toxicity, abundance, low cost, and ease-of-production. However, numerous studies on alkaline Zn–MnO2 batteries have shown that issues such as heterogeneous Zn deposition, passivation, dendrite formation, hydrogen evolution, and formation of chemically irreversible byproducts on the electrode surfaces still limit their rechargeability. Several mitigating strategies have been proposed to improve the rechargeability of alkaline Zn–MnO2 batteries, but the effect of pressure on electrochemical behavior has not been systematically investigated. In this paper, we demonstrate that an externally applied pressure at 20% MnO2 depth-of-discharge (DODMnO2) has a profound effect on impedance, electrochemical cycling behavior, and materials morphology of alkaline Zn–MnO2 batteries. Better electrochemical performance and improved morphology were achieved at 2.12 MPa pressure compared to 0.05 MPa pressure. Moreover, we examined the effect of externally applied pressure from 0 to 5.05 MPa before cycling and found that charge transfer resistance decreases significantly with pressure. Furthermore, we reported stable electrochemical cycling of MnO2‖MnO2 symmetric cells for 500 hours at 20% DOD under 2.12 MPa pressure. Our efforts in understanding the effect of pressure could help design high performance and durable rechargeable alkaline Zn–MnO2 batteries for grid-scale energy storage.
{"title":"Effect of externally applied pressure on rechargeable alkaline zinc batteries at limited depth of discharge","authors":"Deepak Kharel, Calvin D. Quilty, Igor I. Bezsonov, Ciara N. Wright, Timothy N. Lambert, Yang-Tse Cheng","doi":"10.1039/d5ta08160b","DOIUrl":"https://doi.org/10.1039/d5ta08160b","url":null,"abstract":"Rechargeable alkaline zinc batteries (AZBs) are being actively researched for grid-scale energy storage due to their safety, low toxicity, abundance, low cost, and ease-of-production. However, numerous studies on alkaline Zn–MnO<small><sub>2</sub></small> batteries have shown that issues such as heterogeneous Zn deposition, passivation, dendrite formation, hydrogen evolution, and formation of chemically irreversible byproducts on the electrode surfaces still limit their rechargeability. Several mitigating strategies have been proposed to improve the rechargeability of alkaline Zn–MnO<small><sub>2</sub></small> batteries, but the effect of pressure on electrochemical behavior has not been systematically investigated. In this paper, we demonstrate that an externally applied pressure at 20% MnO<small><sub>2</sub></small> depth-of-discharge (DOD<small><sub>MnO<small><sub>2</sub></small></sub></small>) has a profound effect on impedance, electrochemical cycling behavior, and materials morphology of alkaline Zn–MnO<small><sub>2</sub></small> batteries. Better electrochemical performance and improved morphology were achieved at 2.12 MPa pressure compared to 0.05 MPa pressure. Moreover, we examined the effect of externally applied pressure from 0 to 5.05 MPa before cycling and found that charge transfer resistance decreases significantly with pressure. Furthermore, we reported stable electrochemical cycling of MnO<small><sub>2</sub></small>‖MnO<small><sub>2</sub></small> symmetric cells for 500 hours at 20% DOD under 2.12 MPa pressure. Our efforts in understanding the effect of pressure could help design high performance and durable rechargeable alkaline Zn–MnO<small><sub>2</sub></small> batteries for grid-scale energy storage.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"1 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116244","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Youlin Huang, Mengjiao Dai, Zhishan Liang, Bo Ding, Bing Li, Yikang Zeng, Wen-Sheng Zhang, Dongxue Han
The development of high-performance photocatalysts with large specific surface areas, superior efficiency, and robust stability presents a promising solution for antibiotic pollution in aquatic environments. Metal-organic frameworks (MOFs), particularly Cu-MOF (named as Cu-BTC), have emerged as attractive candidates due to their porous crystalline structure and extensive surface area. However, their limited electrical conductivity hinders practical photocatalytic applications. To address this challenge, a novel MOF-based heterojunction by anchoring BiOI nanosheets onto Cu-BTC (Cu-BTC/BiOI) was ingeniously fabricated. This design effectively suppresses photogenerated electron-hole pair recombination under light radiation, while the accumulated charges actively participate in redox reactions to generate superoxide radical (•O 2-), enabling efficient tetracycline (TC) degradation. Notably, the Cu-BTC/BiOI heterostructure exhibits robust environmental stability, preserving superior photocatalytic performance across broad pH ranges, amid various coexisting anions, and in complex Pearl River water samples, demonstrating strong potential for the purification of natural water systems. Notably, the proposed TC degradation pathway is as inferred from LC-MS analysis, with density functional theory (DFT) calculations of the condensed Fukui index providing insight into the reactivity of specific functional groups. This study not only achieves the successful synthesis of a MOF-based heterojunction photocatalyst but also pioneers a new design paradigm for highperformance antibiotic wastewater remediation systems.
{"title":"Engineering a flower-like Cu-BTC/BiOI heterostructure for efficient photodegradation of antibiotics in authentic aquatic environments","authors":"Youlin Huang, Mengjiao Dai, Zhishan Liang, Bo Ding, Bing Li, Yikang Zeng, Wen-Sheng Zhang, Dongxue Han","doi":"10.1039/d5ta10334g","DOIUrl":"https://doi.org/10.1039/d5ta10334g","url":null,"abstract":"The development of high-performance photocatalysts with large specific surface areas, superior efficiency, and robust stability presents a promising solution for antibiotic pollution in aquatic environments. Metal-organic frameworks (MOFs), particularly Cu-MOF (named as Cu-BTC), have emerged as attractive candidates due to their porous crystalline structure and extensive surface area. However, their limited electrical conductivity hinders practical photocatalytic applications. To address this challenge, a novel MOF-based heterojunction by anchoring BiOI nanosheets onto Cu-BTC (Cu-BTC/BiOI) was ingeniously fabricated. This design effectively suppresses photogenerated electron-hole pair recombination under light radiation, while the accumulated charges actively participate in redox reactions to generate superoxide radical (•O 2-), enabling efficient tetracycline (TC) degradation. Notably, the Cu-BTC/BiOI heterostructure exhibits robust environmental stability, preserving superior photocatalytic performance across broad pH ranges, amid various coexisting anions, and in complex Pearl River water samples, demonstrating strong potential for the purification of natural water systems. Notably, the proposed TC degradation pathway is as inferred from LC-MS analysis, with density functional theory (DFT) calculations of the condensed Fukui index providing insight into the reactivity of specific functional groups. This study not only achieves the successful synthesis of a MOF-based heterojunction photocatalyst but also pioneers a new design paradigm for highperformance antibiotic wastewater remediation systems.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"38 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ana Caravaca, Francisco J. Pastor, Andrés Parra-Puerto, Nathalia C. Verissimo, Néstor Guijarro, Teresa Lana-Villareal, Roberto Gómez
The combination of experimental and computational methodologies offers a reliable strategy to not only discover new materials but also rationalize their performance and their intrinsic limitations. Following this concept, fourth-period metal tungstates (RWO4, R = Mn, Fe, Co, Ni, Cu or Zn) have been explored for their application as photoanodes for solar water oxidation. The theoretical screening of these materials reveals large effective masses for both electron and hole carriers, while the density of states (DOS) profiles indicate that only Fe and Cu tungstates show adequate features to be photoanodes. This agrees with experimental data showing that they yield the best photocurrents in the series. In fact, FeWO4 reaches over 0.04 mA cm-2 at 1.23 VRHE under one sun, a value 67% higher than the present record. The still low photoactivity is partly linked to the fact that the electrode deviates from the band edge pinning regime over a wide potential range. Under the same conditions, CuWO4 delivers a photocurrent over 0.3 mA cm-2, in line with the best results found in the literature. Overall, the exploratory analysis performed in this paper not only identifies the parameters that limit the photoelectrochemical response of a wide range of metal tungstates, but it enables the identification of iron and copper tungstates as promising photoanodes for solar water oxidation, whose performance may be enhanced by the implementation of some modification strategies.
实验和计算方法的结合提供了一种可靠的策略，不仅可以发现新材料，而且可以使其性能和内在局限性合理化。根据这一概念，四周期金属钨酸盐（RWO4, R = Mn, Fe, Co, Ni， Cu或Zn）已被探索用于太阳能水氧化的光阳极。这些材料的理论筛选表明，电子和空穴载流子的有效质量都很大，而态密度（DOS）谱表明，只有Fe和Cu钨酸盐具有足够的光阳极特征。这与实验数据一致，表明它们在该系列中产生最好的光电流。事实上，在一个太阳下，FeWO4在1.23 VRHE下达到0.04 mA cm-2以上，比目前的记录高67%。仍然较低的光活性部分与电极在宽电位范围内偏离带边缘钉住制度有关。在相同条件下，CuWO4提供超过0.3 mA cm-2的光电流，符合文献中发现的最佳结果。总的来说，本文进行的探索性分析不仅确定了限制各种金属钨酸盐光电反应的参数，而且还确定了铁和铜钨酸盐作为太阳能水氧化的有前途的光阳极，其性能可以通过实施一些改性策略来增强。
{"title":"Exploring the potential of transition metal tungstates for photoelectrochemical water oxidation: A combined experimental and computational approach","authors":"Ana Caravaca, Francisco J. Pastor, Andrés Parra-Puerto, Nathalia C. Verissimo, Néstor Guijarro, Teresa Lana-Villareal, Roberto Gómez","doi":"10.1039/d5ta08157b","DOIUrl":"https://doi.org/10.1039/d5ta08157b","url":null,"abstract":"The combination of experimental and computational methodologies offers a reliable strategy to not only discover new materials but also rationalize their performance and their intrinsic limitations. Following this concept, fourth-period metal tungstates (RWO4, R = Mn, Fe, Co, Ni, Cu or Zn) have been explored for their application as photoanodes for solar water oxidation. The theoretical screening of these materials reveals large effective masses for both electron and hole carriers, while the density of states (DOS) profiles indicate that only Fe and Cu tungstates show adequate features to be photoanodes. This agrees with experimental data showing that they yield the best photocurrents in the series. In fact, FeWO4 reaches over 0.04 mA cm-2 at 1.23 VRHE under one sun, a value 67% higher than the present record. The still low photoactivity is partly linked to the fact that the electrode deviates from the band edge pinning regime over a wide potential range. Under the same conditions, CuWO4 delivers a photocurrent over 0.3 mA cm-2, in line with the best results found in the literature. Overall, the exploratory analysis performed in this paper not only identifies the parameters that limit the photoelectrochemical response of a wide range of metal tungstates, but it enables the identification of iron and copper tungstates as promising photoanodes for solar water oxidation, whose performance may be enhanced by the implementation of some modification strategies.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"301 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Although perovskite solar cells (PSCs) have achieved impressive efficiency advancements, their surface-dominated defects and poor environmental robustness still restrict device performance and durability. Here, we develop a multifunctional morpholinium-based quaternary ammonium salt, 4-ethyl-4-methylmorpholinium bromide (EMMorBr), as an efficient posttreatment molecule to modulate the perovskite surface chemistry and interfacial energetics. Benefiting from its unique molecular configuration, EMMorBr enables dual-site defect passivation through the strong coordination between its electron-rich oxygen atoms and under-coordinated Pb 2+ , as well as electrostatic interactions between quaternary ammonium cations and halide vacancies. Meanwhile, hydrogen bonding interactions restrain organic cation vacancy formation, leading to suppressed non-radiative recombination and improved interfacial charge extraction. The resulting films exhibit enhanced crystallinity, reduced trap density, and more favorable energy-level alignment. As a consequence, the EMMorBr-modified inverted PSCs achieve a champion power conversion efficiency of 26.14% with negligible hysteresis. Moreover, the devices display remarkable environmental durability. This work offers a rational molecularengineering strategy toward high-efficiency and stable PSCs by leveraging quaternary onium salt chemistry.
{"title":"Quaternary Morpholinium-Mediated Defect Control in High-Performance Perovskite Solar Cells","authors":"Shengnan Wang, Ranran Xu, Fengqiao Xu, Weidong Lin, Yongbing Lou, Zhixiao Qin, Taiyang Zhang","doi":"10.1039/d5ta10578a","DOIUrl":"https://doi.org/10.1039/d5ta10578a","url":null,"abstract":"Although perovskite solar cells (PSCs) have achieved impressive efficiency advancements, their surface-dominated defects and poor environmental robustness still restrict device performance and durability. Here, we develop a multifunctional morpholinium-based quaternary ammonium salt, 4-ethyl-4-methylmorpholinium bromide (EMMorBr), as an efficient posttreatment molecule to modulate the perovskite surface chemistry and interfacial energetics. Benefiting from its unique molecular configuration, EMMorBr enables dual-site defect passivation through the strong coordination between its electron-rich oxygen atoms and under-coordinated Pb 2+ , as well as electrostatic interactions between quaternary ammonium cations and halide vacancies. Meanwhile, hydrogen bonding interactions restrain organic cation vacancy formation, leading to suppressed non-radiative recombination and improved interfacial charge extraction. The resulting films exhibit enhanced crystallinity, reduced trap density, and more favorable energy-level alignment. As a consequence, the EMMorBr-modified inverted PSCs achieve a champion power conversion efficiency of 26.14% with negligible hysteresis. Moreover, the devices display remarkable environmental durability. This work offers a rational molecularengineering strategy toward high-efficiency and stable PSCs by leveraging quaternary onium salt chemistry.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"41 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Luminescent solar concentrators (LSCs) are promising for building-integrated photovoltaics, where color tunability, form factor, and scalability are often more important than absolute efficiency. Here, a major challenge consists in developing eco-friendly luminophores with stable and controllable optical properties. Cu-doped Zn–In–Se (CZISe) quantum dots (QDs) are surface-passivated with trioctylphosphine (TOP), providing a model system to examine the role of ligand engineering in heavy-metal-free emitters. TOP modification increases the photoluminescence quantum yield from 22 ± 5% to 67 ± 5%, extends carrier lifetime, and induces a blue-shifted emission, reflecting improved surface passivation and altered excitonic dynamics. These changes nearly double the optical efficiency of laminated LSCs compared to devices with unmodified QDs. Importantly, this study reports flexible laminated LSCs fabricated with polyvinyl chloride (PVC) substrates, which maintain stable optical performance under mechanical deformation. This demonstration establishes ligand modification and flexible device architectures as complementary approaches for advancing the practical applicability of eco-friendly LSCs.
{"title":"Ligand-Engineered Cu–Zn–In–Se Quantum Dots for Flexible Laminated Luminescent Solar Concentrators","authors":"Xin Liu, Federico Rosei, Bing Luo, Lei Jin, Jiabin Liu, Daniele Benetti, Federico Rosei","doi":"10.1039/d5ta10030e","DOIUrl":"https://doi.org/10.1039/d5ta10030e","url":null,"abstract":"Luminescent solar concentrators (LSCs) are promising for building-integrated photovoltaics, where color tunability, form factor, and scalability are often more important than absolute efficiency. Here, a major challenge consists in developing eco-friendly luminophores with stable and controllable optical properties. Cu-doped Zn–In–Se (CZISe) quantum dots (QDs) are surface-passivated with trioctylphosphine (TOP), providing a model system to examine the role of ligand engineering in heavy-metal-free emitters. TOP modification increases the photoluminescence quantum yield from 22 ± 5% to 67 ± 5%, extends carrier lifetime, and induces a blue-shifted emission, reflecting improved surface passivation and altered excitonic dynamics. These changes nearly double the optical efficiency of laminated LSCs compared to devices with unmodified QDs. Importantly, this study reports flexible laminated LSCs fabricated with polyvinyl chloride (PVC) substrates, which maintain stable optical performance under mechanical deformation. This demonstration establishes ligand modification and flexible device architectures as complementary approaches for advancing the practical applicability of eco-friendly LSCs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"398 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrochromic materials exhibit electrically tunable optical properties and are widely applied in smart windows, optical switches, and photonic devices. However, the modulation amplitude of conventional electrochromic devices (ECDs) is fundamentally constrained by sluggish ion diffusion and incomplete redox reactions. Here, we report a high‐performance three-electrode electrochromic device (TRECD) incorporating a zinc auxiliary electrode that forms a capacitor-like “acceleration gate”. This structure, together with the Zn²⁺ dissolution–deposition reaction, synergistically accelerates ion transport, enabling full ion insertion/extraction within the electrochromic films. By optimizing the Li⁺/Zn²⁺ ratio in the electrolyte, the TRECD achieves substantially enhanced electrochemical and optical performance, including an 18-fold increase in areal capacitance, ultrafast response times (1.43 s for coloring, 2.72 s for bleaching), a record-high coloration efficiency of 603.37 cm² C⁻¹, and an exceptional optical modulation amplitude of 98.1%, reaching a minimum transmittance of 0.2%. This unprecedented contrast enables reversible switching between nearly full transparency and near-zero transmittance. Our results demonstrate that introducing an auxiliary Zn electrode and leveraging its coupled ion chemistry offers a powerful strategy for boosting the efficiency and functionality of electrochromic systems. This three-electrode structure opens new pathways for high‐contrast optical switches, tunable filters, smart windows, and reconfigurable photonic devices.
{"title":"High Performance Multifunctional Three Electrode Electrochromic Device Based on a Zn Auxiliary Electrode","authors":"Zinan Zhao, Menghan Tian, Yue Wang, Zelin Lu, Menghao Ma, Fan Wang, Xiaolan Zhong","doi":"10.1039/d5ta09759b","DOIUrl":"https://doi.org/10.1039/d5ta09759b","url":null,"abstract":"Electrochromic materials exhibit electrically tunable optical properties and are widely applied in smart windows, optical switches, and photonic devices. However, the modulation amplitude of conventional electrochromic devices (ECDs) is fundamentally constrained by sluggish ion diffusion and incomplete redox reactions. Here, we report a high‐performance three-electrode electrochromic device (TRECD) incorporating a zinc auxiliary electrode that forms a capacitor-like “acceleration gate”. This structure, together with the Zn²⁺ dissolution–deposition reaction, synergistically accelerates ion transport, enabling full ion insertion/extraction within the electrochromic films. By optimizing the Li⁺/Zn²⁺ ratio in the electrolyte, the TRECD achieves substantially enhanced electrochemical and optical performance, including an 18-fold increase in areal capacitance, ultrafast response times (1.43 s for coloring, 2.72 s for bleaching), a record-high coloration efficiency of 603.37 cm² C⁻¹, and an exceptional optical modulation amplitude of 98.1%, reaching a minimum transmittance of 0.2%. This unprecedented contrast enables reversible switching between nearly full transparency and near-zero transmittance. Our results demonstrate that introducing an auxiliary Zn electrode and leveraging its coupled ion chemistry offers a powerful strategy for boosting the efficiency and functionality of electrochromic systems. This three-electrode structure opens new pathways for high‐contrast optical switches, tunable filters, smart windows, and reconfigurable photonic devices.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"134 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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