Shuguang Cao, Shizi Luo, Tongjun Zheng, Zhuoneng Bi, Jiamei Mo, Lavrenty G. Gutsev, Nikita A. Emelianov, Victoria V. Ozerova, Nikita A. Slesarenko, Gennady L. Gutsev, Sergey M. Aldoshin, Fangyuan Sun, Yanqing Tian, Bala R. Ramachandran, Pavel A. Troshin, Xueqing Xu
Self-assembled molecules (SAMs) have been widely employed as hole transport layers (HTLs) in inverted perovskite solar cells (PSCs). However, the carbazole core of [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz) is insufficiently effective for passivating defects at the “bottom” of perovskite films, and the weak anchoring ability of phosphate groups toward the NiOx substrate appears to promote the formation of dimers, trimers, and higher-order oligomers, resulting in molecular accumulation. Herein, a novel technique is proposed to combine Me-4PACz with different thiol molecules to modify the buried interface of PSCs. Molecular dynamics simulations and infrared scattering-type scanning near-field optical microscopy (IR s-SNOM) results show that co-depositing Me-4PACz with thiol molecules forms hybrid SAMs that densely and uniformly cover the NiOx surface. The island-like structure of the hybrid SAMs serves as a template for forming the perovskite bulk heterojunction composed of interpenetrating networks of MA-rich and FA-rich domains, enabling efficient charge generation and suppressed bimolecular recombination. Particularly, (3-mercaptopropyl) trimethoxysilane (MPTMS) effectively prevents Me-4PACz aggregation by forming a multi-dentate anchor on the NiOx surface through hydrolytic condensation of ─OCH3 groups, while its ─SH groups passivate uncoordinated Pb2+ at the perovskite/HTL interface. Consequently, the resulting hybrid SAMs-modified PSC achieve a champion photoelectric conversion efficiency (PCE) of 25.4% and demonstrated better operational stability.
{"title":"Hybrid Self-Assembled Molecular Interlayers for Efficient and Stable Inverted Perovskite Solar Cells","authors":"Shuguang Cao, Shizi Luo, Tongjun Zheng, Zhuoneng Bi, Jiamei Mo, Lavrenty G. Gutsev, Nikita A. Emelianov, Victoria V. Ozerova, Nikita A. Slesarenko, Gennady L. Gutsev, Sergey M. Aldoshin, Fangyuan Sun, Yanqing Tian, Bala R. Ramachandran, Pavel A. Troshin, Xueqing Xu","doi":"10.1002/aenm.202405367","DOIUrl":"https://doi.org/10.1002/aenm.202405367","url":null,"abstract":"Self-assembled molecules (SAMs) have been widely employed as hole transport layers (HTLs) in inverted perovskite solar cells (PSCs). However, the carbazole core of [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz) is insufficiently effective for passivating defects at the “bottom” of perovskite films, and the weak anchoring ability of phosphate groups toward the NiO<i><sub>x</sub></i> substrate appears to promote the formation of dimers, trimers, and higher-order oligomers, resulting in molecular accumulation. Herein, a novel technique is proposed to combine Me-4PACz with different thiol molecules to modify the buried interface of PSCs. Molecular dynamics simulations and infrared scattering-type scanning near-field optical microscopy (IR s-SNOM) results show that co-depositing Me-4PACz with thiol molecules forms hybrid SAMs that densely and uniformly cover the NiO<i><sub>x</sub></i> surface. The island-like structure of the hybrid SAMs serves as a template for forming the perovskite bulk heterojunction composed of interpenetrating networks of MA-rich and FA-rich domains, enabling efficient charge generation and suppressed bimolecular recombination. Particularly, (3-mercaptopropyl) trimethoxysilane (MPTMS) effectively prevents Me-4PACz aggregation by forming a multi-dentate anchor on the NiO<i><sub>x</sub></i> surface through hydrolytic condensation of ─OCH<sub>3</sub> groups, while its ─SH groups passivate uncoordinated Pb<sup>2+</sup> at the perovskite/HTL interface. Consequently, the resulting hybrid SAMs-modified PSC achieve a champion photoelectric conversion efficiency (PCE) of 25.4% and demonstrated better operational stability.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"67 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463228","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}
Yiming Zhu, Jiaao Wang, Gregor Weiser, Malte Klingenhof, Toshinari Koketsu, Shangheng Liu, Yecan Pi, Graeme Henkelman, Xinyue Shi, Jiayi Li, Chih-Wen Pao, Min-Hsin Yeh, Wei-Hsiang Huang, Peter Strasser, Jiwei Ma
New anodic electrocatalysts with high performance and cost-effectiveness at large current densities help advance the emerging anion exchange membrane water electrolyzer (AEMWE) technology. To this end, a ruthenium (Ru) single atoms and sulfur (S) anions dual-doped NiFe layered double hydroxides (Ru-S-NiFe LDH) catalyst is reported with remarkably low alkaline oxygen evolution reaction (OER) overpotentials, high mass activities and prolonged stabilities at high current densities. Inspiringly, the AEMWE performance on Ru-S-NiFe LDH is also superior to the NiFe LDH. In-depth mechanism investigations reveal that Ru single atoms not only act as the highly active sites, but also facilitate the conductivity of NiFe LDH. Meanwhile, S anions accelerate the electrochemical reconstruction of NiFe LDH to OER-active NiFeOOH and alleviate the over-oxidation issue on Ru active sites. Benefiting from these, Ru-S-NiFe LDH shows significantly enhanced OER activity and stability. Theoretical calculations further validate the decreased OER free energy difference brought about by the Ru single atoms and S anions dual-doping. This study offers a proof-of-concept that the noble metal single atoms and anions dual-doping is a feasible strategy to construct the promising 3d transition metal-based electrocatalysts toward the practical alkaline water electrolyzer.
{"title":"Ru Single Atoms and Sulfur Anions Dual-Doped NiFe Layered Double Hydroxides for High-Current-Density Alkaline Oxygen Evolution Reaction","authors":"Yiming Zhu, Jiaao Wang, Gregor Weiser, Malte Klingenhof, Toshinari Koketsu, Shangheng Liu, Yecan Pi, Graeme Henkelman, Xinyue Shi, Jiayi Li, Chih-Wen Pao, Min-Hsin Yeh, Wei-Hsiang Huang, Peter Strasser, Jiwei Ma","doi":"10.1002/aenm.202500554","DOIUrl":"https://doi.org/10.1002/aenm.202500554","url":null,"abstract":"New anodic electrocatalysts with high performance and cost-effectiveness at large current densities help advance the emerging anion exchange membrane water electrolyzer (AEMWE) technology. To this end, a ruthenium (Ru) single atoms and sulfur (S) anions dual-doped NiFe layered double hydroxides (Ru-S-NiFe LDH) catalyst is reported with remarkably low alkaline oxygen evolution reaction (OER) overpotentials, high mass activities and prolonged stabilities at high current densities. Inspiringly, the AEMWE performance on Ru-S-NiFe LDH is also superior to the NiFe LDH. In-depth mechanism investigations reveal that Ru single atoms not only act as the highly active sites, but also facilitate the conductivity of NiFe LDH. Meanwhile, S anions accelerate the electrochemical reconstruction of NiFe LDH to OER-active NiFeOOH and alleviate the over-oxidation issue on Ru active sites. Benefiting from these, Ru-S-NiFe LDH shows significantly enhanced OER activity and stability. Theoretical calculations further validate the decreased OER free energy difference brought about by the Ru single atoms and S anions dual-doping. This study offers a proof-of-concept that the noble metal single atoms and anions dual-doping is a feasible strategy to construct the promising 3<i>d</i> transition metal-based electrocatalysts toward the practical alkaline water electrolyzer.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"29 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463243","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 inhomogeneous dendrite growth and parasitic side reactions of Zn anodes as well as its sluggish solvation/de‐solvation kinetics severely hinder the practicalization of fast charging Zn‐ion batteries. Regulating electric double layer (EDL) structure is an effective strategy to address these issues. Herein, a perovskite dielectric ZnTiO3 (ZTO) layer is designed on Zn anode to construct the autoregulative EDL for achieving fast charging capability. The ZTO layer can spontaneously generate the surface charge with external voltage to regulate the EDL structure, which results in an increased/decreased EDL capacitance under Zn plating/stripping potential respectively, leading to promoted Zn2+ solvation/de‐solvation for rapid reaction kinetics. Meanwhile, the H2O‐insufficient environment created by self‐regulated EDL and uniform electric field can prevent side reaction and dendrite growth during deposition process. Attributed to its EDL feature, ZTO@Zn exhibits an excellent cycle stability over 2850 h at 1 mA cm−2 in symmetrical cells. Even at high current density of 50 mA cm−2, it still exhibits a stable cycle for 230 h. Additionally, the as assembled ZTO@Zn//AC supercapacitor demonstrates ultralong lifetime of 140 000 cycles at 5 A g−1. This work provides an effective EDL regulation strategy to realize fast charging capability of metal anode for its practical application.
{"title":"Constructing Autoregulative Electric Double Layer Through Dielectric Effect Toward Fast Charging Zinc Metal Anode","authors":"Yuying Li, Boyu Ping, Junnan Qu, Jingxuan Ren, Cheng Lin, Jiahao Lei, Jinhao Chen, Jingyao Li, Renming Liu, Xintao Long, Xinli Guo, Dan Luo, Zhongwei Chen","doi":"10.1002/aenm.202405804","DOIUrl":"https://doi.org/10.1002/aenm.202405804","url":null,"abstract":"The inhomogeneous dendrite growth and parasitic side reactions of Zn anodes as well as its sluggish solvation/de‐solvation kinetics severely hinder the practicalization of fast charging Zn‐ion batteries. Regulating electric double layer (EDL) structure is an effective strategy to address these issues. Herein, a perovskite dielectric ZnTiO<jats:sub>3</jats:sub> (ZTO) layer is designed on Zn anode to construct the autoregulative EDL for achieving fast charging capability. The ZTO layer can spontaneously generate the surface charge with external voltage to regulate the EDL structure, which results in an increased/decreased EDL capacitance under Zn plating/stripping potential respectively, leading to promoted Zn<jats:sup>2+</jats:sup> solvation/de‐solvation for rapid reaction kinetics. Meanwhile, the H<jats:sub>2</jats:sub>O‐insufficient environment created by self‐regulated EDL and uniform electric field can prevent side reaction and dendrite growth during deposition process. Attributed to its EDL feature, ZTO@Zn exhibits an excellent cycle stability over 2850 h at 1 mA cm<jats:sup>−2</jats:sup> in symmetrical cells. Even at high current density of 50 mA cm<jats:sup>−2</jats:sup>, it still exhibits a stable cycle for 230 h. Additionally, the as assembled ZTO@Zn//AC supercapacitor demonstrates ultralong lifetime of 140 000 cycles at 5 A g<jats:sup>−1</jats:sup>. This work provides an effective EDL regulation strategy to realize fast charging capability of metal anode for its practical application.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"52 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452138","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}
Solid-state electrolytes (SSEs) hold significant potential for advancing lithium metal batteries (LMBs) by enhancing safety through the replacement of liquid electrolytes. However, challenges such as low ionic conductivity, limited electrochemical stability, and poor electrolyte/electrode interface compatibility hinder the development of high-energy-density LMBs. Herein, a strategy for designing SSEs is proposed using multiple-bridge engineered composite elastomer electrolytes (CEEs) that incorporate ion-rotating dipole interactions, ion-anchoring dipole interactions, and hydrogen bonding, along with a CEE-based composite elastomer cathode (CEC). This design combines a volume-adaptive elastomer matrix, a high-Li+ conducting deep eutectic electrolyte, and robust nanowires. The resultant CEE exhibits high ionic conductivity (1.7 × 10−3 S cm−1), a lithium transference number of 0.72, and a wide electrochemical stability window (up to 4.9 V) at 298 K. The engineered uniform Li+ flux also promotes stable Li plating/stripping for over 900 h at 0.1 mA cm−2. Furthermore, the LFP-based CEC|CEE|Li full cells deliver a reversible capacity of 133 mAh g−1 with 95% retention after 300 cycles in coin cells, and 129 mAh g−1 with 96% retention after 250 cycles in pouch cells at 1 C. This strategy presents a promising approach for designing solid-state polymer electrolytes to extend the lifespan of high-energy-density LMBs.
{"title":"Ion-Anchoring Dipole-Integrated Composite Elastomer Electrolyte and Cathode for High-Performance Lithium Metal Batteries via Multiple-Bridge Engineering","authors":"A Hyeon Cho, Ji Hyang Je, U Hyeok Choi","doi":"10.1002/aenm.202405312","DOIUrl":"https://doi.org/10.1002/aenm.202405312","url":null,"abstract":"Solid-state electrolytes (SSEs) hold significant potential for advancing lithium metal batteries (LMBs) by enhancing safety through the replacement of liquid electrolytes. However, challenges such as low ionic conductivity, limited electrochemical stability, and poor electrolyte/electrode interface compatibility hinder the development of high-energy-density LMBs. Herein, a strategy for designing SSEs is proposed using multiple-bridge engineered composite elastomer electrolytes (CEEs) that incorporate ion-rotating dipole interactions, ion-anchoring dipole interactions, and hydrogen bonding, along with a CEE-based composite elastomer cathode (CEC). This design combines a volume-adaptive elastomer matrix, a high-Li<sup>+</sup> conducting deep eutectic electrolyte, and robust nanowires. The resultant CEE exhibits high ionic conductivity (1.7 × 10<sup>−3</sup> S cm<sup>−1</sup>), a lithium transference number of 0.72, and a wide electrochemical stability window (up to 4.9 V) at 298 K. The engineered uniform Li<sup>+</sup> flux also promotes stable Li plating/stripping for over 900 h at 0.1 mA cm<sup>−2</sup>. Furthermore, the LFP-based CEC|CEE|Li full cells deliver a reversible capacity of 133 mAh g<sup>−1</sup> with 95% retention after 300 cycles in coin cells, and 129 mAh g<sup>−1</sup> with 96% retention after 250 cycles in pouch cells at 1 C. This strategy presents a promising approach for designing solid-state polymer electrolytes to extend the lifespan of high-energy-density LMBs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"25 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462393","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}
Lithium (Li) metal batteries offer high energy densities but suffer from uncontrolled lithium deposition, causing serious dendrite growth and volume fluctuation. Tailorable Li nucleation and uniform early-stage plating are essential for homogenous Li deposition. Herein, insertion type Li3VO4 is first demonstrated as efficient lithiophilic sites trapping Li+ ions for homogenous nucleation. By homogenizing the distribution of electric field and ions flux via an ingenious architecture design with Li3VO4 nanodots grown on the carbon fibers (LVO@CNFs), leveling Li metal deposition after nucleation is also realized. These, together, result in smooth and dendrite-free Li deposition on the LVO@CNFs via a trapping-and-leveling model, giving rise to unprecedented performance (highly stable Li plating/stripping exceeding 2500 h at 2 mA cm−2 under 3 mA h cm−2 capacity, high-capacity retention of 82.5% over 500 cycles in a Li@LVO@CNFs//LiFePO4 battery). The successful design of Li metal deposition host via insertion-type Li3VO4 may pave a new way for long lifespan Li metal batteries.
{"title":"Insertion Type Li3VO4 Lithiophilic Sites Boosting Dendrite-Free Lithium Deposition in Trapping-and-leveling Model","authors":"Bing Sun, Lingling Kuang, Meichun He, Qin Zhang, Yunfeng Guan, Chengzhi Zhang, Dongmei Zhang, Cunyuan Pei, Pengju Li, Shibing Ni","doi":"10.1002/aenm.202405307","DOIUrl":"https://doi.org/10.1002/aenm.202405307","url":null,"abstract":"Lithium (Li) metal batteries offer high energy densities but suffer from uncontrolled lithium deposition, causing serious dendrite growth and volume fluctuation. Tailorable Li nucleation and uniform early-stage plating are essential for homogenous Li deposition. Herein, insertion type Li<sub>3</sub>VO<sub>4</sub> is first demonstrated as efficient lithiophilic sites trapping Li<sup>+</sup> ions for homogenous nucleation. By homogenizing the distribution of electric field and ions flux via an ingenious architecture design with Li<sub>3</sub>VO<sub>4</sub> nanodots grown on the carbon fibers (LVO@CNFs), leveling Li metal deposition after nucleation is also realized. These, together, result in smooth and dendrite-free Li deposition on the LVO@CNFs via a trapping-and-leveling model, giving rise to unprecedented performance (highly stable Li plating/stripping exceeding 2500 h at 2 mA cm<sup>−2</sup> under 3 mA h cm<sup>−2</sup> capacity, high-capacity retention of 82.5% over 500 cycles in a Li@LVO@CNFs//LiFePO<sub>4</sub> battery). The successful design of Li metal deposition host via insertion-type Li<sub>3</sub>VO<sub>4</sub> may pave a new way for long lifespan Li metal batteries.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"81 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462394","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}
Jian Cui, Panpan Su, Wenxiu Li, Xiaoen Wang, Yongguang Zhang, Zuoyi Xiao, Qingda An, Zhongwei Chen
Hard carbon materials are regarded as the most promising negative electrode materials for commercial sodium‐ion batteries. As the most abundant bioresource in nature, cellulose has unique fiber structure and multifunctional groups, is considered to be appropriate precursor for the preparation for hard carbon. The present review comprehensively elaborates on the mechanism of sodium storage and different preparation methods of cellulose‐derived hard carbon, explores different microstructures of cellulose‐derived hard carbon for sodium storage and electrochemical performance in sodium ion batteries, proposes corresponding treatment methods to improve the electrochemical performance targeted at precursors of cellulose‐based materials. This review also presents an update on development of electrochemical performance for cellulose‐derived hard carbon in SIBs, figures out the achievements and shortcomings in the advanced study of cellulose‐derived hard carbon. Meanwhile, the relationship between electrochemical performance and microstructure of cellulose‐derived hard carbon obtained from different precursors and preparation methods is systematically summarized through theoretical calculations and characterization analyses. Additionally, the critical issues, challenges, and trends of cellulose‐derived hard carbon in SIBs for commercialization in future are discussed.
{"title":"Advanced Cellulose‐Derived Hard Carbon as Anode for Sodium‐Ion Batteries: Mechanisms, Optimization, and Challenges","authors":"Jian Cui, Panpan Su, Wenxiu Li, Xiaoen Wang, Yongguang Zhang, Zuoyi Xiao, Qingda An, Zhongwei Chen","doi":"10.1002/aenm.202404604","DOIUrl":"https://doi.org/10.1002/aenm.202404604","url":null,"abstract":"Hard carbon materials are regarded as the most promising negative electrode materials for commercial sodium‐ion batteries. As the most abundant bioresource in nature, cellulose has unique fiber structure and multifunctional groups, is considered to be appropriate precursor for the preparation for hard carbon. The present review comprehensively elaborates on the mechanism of sodium storage and different preparation methods of cellulose‐derived hard carbon, explores different microstructures of cellulose‐derived hard carbon for sodium storage and electrochemical performance in sodium ion batteries, proposes corresponding treatment methods to improve the electrochemical performance targeted at precursors of cellulose‐based materials. This review also presents an update on development of electrochemical performance for cellulose‐derived hard carbon in SIBs, figures out the achievements and shortcomings in the advanced study of cellulose‐derived hard carbon. Meanwhile, the relationship between electrochemical performance and microstructure of cellulose‐derived hard carbon obtained from different precursors and preparation methods is systematically summarized through theoretical calculations and characterization analyses. Additionally, the critical issues, challenges, and trends of cellulose‐derived hard carbon in SIBs for commercialization in future are discussed.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"25 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452162","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}
Sulfide‐based all‐solid‐state batteries (ASSBs) are widely recognized as one of the most promising next‐generation energy storage technologies. High‐mass‐loaded composite cathode is crucial for the electrochemical performance of ASSBs. However, the safety characteristics of practical composite cathodes have not been reported. Herein, the thermal runaway mechanisms of composite cathodes under different pressures are systematically revealed by employing pellet pressing of the LiNi0.8Co0.1Mn0.1O2 (NCM811) and Li6PS5Cl (LPSC). Completely different from conventional safety perceptions of powder, as the compaction density of the composite cathode increases, an inert P2Sx protective layer is generated in situ via the intensified the redox reactions at the interface, which inhibited exothermic reactions between the oxygen released from the NCM811 and LPSC. This work sheds light on the thermal runaway mechanisms of practical composite cathodes in sulfide‐based ASSBs, which can effectively build a bridge between academic and industrial research for the safety design of ASSBs.
{"title":"Thermal Runaway Mechanism of Composite Cathodes for All‐Solid‐State Batteries","authors":"Yu Wu, Wenjie Zhang, Xinyu Rui, Dongsheng Ren, Chengshan Xu, Xiang Liu, Xuning Feng, Zhuang Ma, Languang Lu, Minggao Ouyang","doi":"10.1002/aenm.202405183","DOIUrl":"https://doi.org/10.1002/aenm.202405183","url":null,"abstract":"Sulfide‐based all‐solid‐state batteries (ASSBs) are widely recognized as one of the most promising next‐generation energy storage technologies. High‐mass‐loaded composite cathode is crucial for the electrochemical performance of ASSBs. However, the safety characteristics of practical composite cathodes have not been reported. Herein, the thermal runaway mechanisms of composite cathodes under different pressures are systematically revealed by employing pellet pressing of the LiNi<jats:sub>0.8</jats:sub>Co<jats:sub>0.1</jats:sub>Mn<jats:sub>0.1</jats:sub>O<jats:sub>2</jats:sub> (NCM811) and Li<jats:sub>6</jats:sub>PS<jats:sub>5</jats:sub>Cl (LPSC). Completely different from conventional safety perceptions of powder, as the compaction density of the composite cathode increases, an inert P<jats:sub>2</jats:sub>S<jats:sub>x</jats:sub> protective layer is generated in situ via the intensified the redox reactions at the interface, which inhibited exothermic reactions between the oxygen released from the NCM811 and LPSC. This work sheds light on the thermal runaway mechanisms of practical composite cathodes in sulfide‐based ASSBs, which can effectively build a bridge between academic and industrial research for the safety design of ASSBs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"89 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452139","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}
Wenchao Yang, Catherine S. Pursglove De Castro, Safakath Karuthedath, Yuliar Firdaus, Nisreen Alshehri, Si Chen, Diego Rosas Villalva, Christopher E. Petoukhoff, Amr Dahman, Derya Baran, Thomas D. Anthopoulos, Frédéric Laquai, Julien Gorenflot
Long exciton diffusion length (LD) is key to maximizing excitation harvesting in organic solar cells, but contradicting values are reported for non-fullerene acceptors (NFA). To understand the factors enabling large LD, experimental observation of exciton decay by transient absorption spectroscopy (TAS) is combined with microscopic Kinetic Monte Carlo (KMC) simulations on 4 ITIC derivatives. Exciton decays are fitted considering singlet exciton-singlet exciton annihilation (SSA) and the intrinsic exciton's lifetime τ, resulting in LD from 20 to 70 nm. The critical importance of an independent estimate of τ is discussed and its measurements from pristine NFA films is found to be more relevant than from NFA molecules embedded in an inert polystyrene matrix. From experimental parameters, the microscopic Förster Resonant Energy Transfer hopping rate and the annihilation rate in a cubic lattice are determined, considering a Gaussian energetic disorder. KMC simulation of those rates are able to reproduce the experimental transients and LD, provided a lattice constant a close to the molecular π-π stacking distance is used. It is found that this tight packing and a low disorder are critical to reach large LD, and empirically relate linearly such that 40 meV more disorder can be compensated by 1 Angstrom tighter packing (shorter a).
{"title":"Determining Exciton Diffusion Length in Organic Semiconductors: Unifying Macro- and Microscopic Perspectives","authors":"Wenchao Yang, Catherine S. Pursglove De Castro, Safakath Karuthedath, Yuliar Firdaus, Nisreen Alshehri, Si Chen, Diego Rosas Villalva, Christopher E. Petoukhoff, Amr Dahman, Derya Baran, Thomas D. Anthopoulos, Frédéric Laquai, Julien Gorenflot","doi":"10.1002/aenm.202405322","DOIUrl":"https://doi.org/10.1002/aenm.202405322","url":null,"abstract":"Long exciton diffusion length (<i>L</i><sub><i>D</i></sub>) is key to maximizing excitation harvesting in organic solar cells, but contradicting values are reported for non-fullerene acceptors (NFA). To understand the factors enabling large <i>L</i><sub><i>D</i></sub>, experimental observation of exciton decay by transient absorption spectroscopy (TAS) is combined with microscopic Kinetic Monte Carlo (KMC) simulations on 4 ITIC derivatives. Exciton decays are fitted considering singlet exciton-singlet exciton annihilation (SSA) and the intrinsic exciton's lifetime <i>τ</i>, resulting in <i>L</i><sub><i>D</i></sub> from 20 to 70 nm. The critical importance of an independent estimate of <i>τ</i> is discussed and its measurements from pristine NFA films is found to be more relevant than from NFA molecules embedded in an inert polystyrene matrix. From experimental parameters, the microscopic Förster Resonant Energy Transfer hopping rate and the annihilation rate in a cubic lattice are determined, considering a Gaussian energetic disorder. KMC simulation of those rates are able to reproduce the experimental transients and <i>L</i><sub><i>D</i>,</sub> provided a lattice constant <i>a</i> close to the molecular <i>π-π</i> stacking distance is used. It is found that this tight packing and a low disorder are critical to reach large <i>L</i><sub><i>D</i></sub>, and empirically relate linearly such that 40 meV more disorder can be compensated by 1 Angstrom tighter packing (shorter <i>a</i>).","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"16 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462395","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}
Hua Li, Lei Jing, Guojiang Wen, Zhongfeng Ji, Chengye Ma, Xuewei Fu, Yu Wang, Wei Yang
The electrolytes for advanced lithium-metal batteries need to simultaneously achieve high-performances in ion-conductivity, lithium-ion transference number, elasticity and mechanical strength, and safety etc. Gel polymer electrolytes (GPEs) are promising, however, conventional GPEs find it challenging to achieve all these performances, mainly due to a poor control of the liquid plasticizer inside. Here, inspired by the animal skins that can perfectly overcome the trade-off between the mechanics and complex biofunctions via water-encapsulation inside cellular network, it is attempted to design and fabricate a type of skin-inspired nonflammable elastic GPE (SINE-GPE) to address this challenge. To do that, an anti-solvent induced self-assembly (ASISA) strategy is proposed to fabricate a porous vesicular membrane based on a triblock thermoplastic polyurethane (i.e., the SINE-skeleton). Then, nonflammable liquid electrolyte is encapsuled inside the SINE-skeleton to prepare the SINE-GPE. The resultant SINE-GPE achieves not only a high gel-strength of 2.0 ± 0.1 MPa, a recoverable strain of 90% and a high ionic conductivity of 1.2 × 10−3 S cm−1 at RT, but also selective lithium-ion transport (tLi+ = 0.82). Consequently, this SINE-GPE can effectively stabilize lithium-metal anode with a smooth solid-electrolyte-interphase, which is explained by a self-massaging mechanism of the SINE-GPE during lithium stripping and deposition.
{"title":"A Skin-Mimicked Polymer Gel Electrolyte for Stabilizing Lithium Metal Batteries","authors":"Hua Li, Lei Jing, Guojiang Wen, Zhongfeng Ji, Chengye Ma, Xuewei Fu, Yu Wang, Wei Yang","doi":"10.1002/aenm.202405365","DOIUrl":"https://doi.org/10.1002/aenm.202405365","url":null,"abstract":"The electrolytes for advanced lithium-metal batteries need to simultaneously achieve high-performances in ion-conductivity, lithium-ion transference number, elasticity and mechanical strength, and safety etc. Gel polymer electrolytes (GPEs) are promising, however, conventional GPEs find it challenging to achieve all these performances, mainly due to a poor control of the liquid plasticizer inside. Here, inspired by the animal skins that can perfectly overcome the trade-off between the mechanics and complex biofunctions via water-encapsulation inside cellular network, it is attempted to design and fabricate a type of skin-inspired nonflammable elastic GPE (SINE-GPE) to address this challenge. To do that, an anti-solvent induced self-assembly (ASISA) strategy is proposed to fabricate a porous vesicular membrane based on a triblock thermoplastic polyurethane (i.e., the SINE-skeleton). Then, nonflammable liquid electrolyte is encapsuled inside the SINE-skeleton to prepare the SINE-GPE. The resultant SINE-GPE achieves not only a high gel-strength of 2.0 ± 0.1 MPa, a recoverable strain of 90% and a high ionic conductivity of 1.2 × 10<sup>−3</sup> S cm<sup>−1</sup> at RT, but also selective lithium-ion transport (t<sub>Li+</sub> = 0.82). Consequently, this SINE-GPE can effectively stabilize lithium-metal anode with a smooth solid-electrolyte-interphase, which is explained by a self-massaging mechanism of the SINE-GPE during lithium stripping and deposition.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"16 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462462","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 seawater splitting for green hydrogen production is emerging as a key research focus for sustainable energy. Nevertheless, the inherent complexity of seawater, with its diverse ion composition – especially chloride ions, calcium ions, and magnesium ions – poses significant challenges in catalyst design. Designing highly active electrocatalysts that can resist chloride ion corrosion during seawater splitting is still a challenge. This article presents an overview of the fundamental mechanisms of seawater splitting and explores issues encountered at both the cathode and the anode electrode. The focus then shifts to chlorine corrosion at the anode, examining recent advances in preventing chlorine corrosion strategies. Notably, these design strategies, such as the anionic passivation layers, corrosion‐resistant metal doping, physical barrier layers, in situ phase transition‐driven seawater desalination, and decoupled seawater splitting, are comprehensively investigated, all of which aim to enhance the catalytic stability in seawater splitting. The review concludes with an outlook on the practical applications and challenges of producing green hydrogen through seawater splitting.
{"title":"Strategies for Designing Anti‐Chlorine Corrosion Catalysts in Seawater Splitting","authors":"Peng‐Jun Deng, Ruirui Xue, Jiajia Lu, Panagiotis Tsiakaras","doi":"10.1002/aenm.202405749","DOIUrl":"https://doi.org/10.1002/aenm.202405749","url":null,"abstract":"The seawater splitting for green hydrogen production is emerging as a key research focus for sustainable energy. Nevertheless, the inherent complexity of seawater, with its diverse ion composition – especially chloride ions, calcium ions, and magnesium ions – poses significant challenges in catalyst design. Designing highly active electrocatalysts that can resist chloride ion corrosion during seawater splitting is still a challenge. This article presents an overview of the fundamental mechanisms of seawater splitting and explores issues encountered at both the cathode and the anode electrode. The focus then shifts to chlorine corrosion at the anode, examining recent advances in preventing chlorine corrosion strategies. Notably, these design strategies, such as the anionic passivation layers, corrosion‐resistant metal doping, physical barrier layers, in situ phase transition‐driven seawater desalination, and decoupled seawater splitting, are comprehensively investigated, all of which aim to enhance the catalytic stability in seawater splitting. The review concludes with an outlook on the practical applications and challenges of producing green hydrogen through seawater splitting.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"92 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452163","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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