Pub Date : 2024-10-22DOI: 10.1021/acsenergylett.4c02327
Wenjun Ding, Xinyi Shen, Ziyan Li, Zimin Fan, Zhiwei Chen, Juan Chen, Jun Luo, Wen Li, Yanzhong Pei
Urgent demand for a sustainable power supply for wearables promotes great efforts on the development of flexible thermoelectric devices. The elastic bendability allows the reservation of initial power and flexibility in inorganic thermoelectric films. The elasticity is related to the thickness engineeringly and the elastic strain scientifically, therefore guiding this work to focus on developing elastic thermoelectric generators using high-performing orthorhombic Ag2Se1–xSx films that thinned the bulks through multipass hot-rolling at ∼393 K. Such a plastic deformation enables a creation of dense dislocations and a refinement of grain and, thereby, a dramatic increase in the elastic strain, impressively securing a full recoverability in transport properties for the obtained films even after 100,000 times bending within a radius down to ∼3 mm. The resultant achievement of extraordinary specific power density of ∼5 μW/cm-K2 in a six-leg flexible device robustly demonstrates these alloys as a potentially sustainable power source for wearable electronics.
{"title":"Enhancing Recoverable Bendability in High-Performance Ag2Se-Based Thermoelectrics through Plastic Processing","authors":"Wenjun Ding, Xinyi Shen, Ziyan Li, Zimin Fan, Zhiwei Chen, Juan Chen, Jun Luo, Wen Li, Yanzhong Pei","doi":"10.1021/acsenergylett.4c02327","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02327","url":null,"abstract":"Urgent demand for a sustainable power supply for wearables promotes great efforts on the development of flexible thermoelectric devices. The elastic bendability allows the reservation of initial power and flexibility in inorganic thermoelectric films. The elasticity is related to the thickness engineeringly and the elastic strain scientifically, therefore guiding this work to focus on developing elastic thermoelectric generators using high-performing orthorhombic Ag<sub>2</sub>Se<sub>1–<i>x</i></sub>S<sub><i>x</i></sub> films that thinned the bulks through multipass hot-rolling at ∼393 K. Such a plastic deformation enables a creation of dense dislocations and a refinement of grain and, thereby, a dramatic increase in the elastic strain, impressively securing a full recoverability in transport properties for the obtained films even after 100,000 times bending within a radius down to ∼3 mm. The resultant achievement of extraordinary specific power density of ∼5 μW/cm-K<sup>2</sup> in a six-leg flexible device robustly demonstrates these alloys as a potentially sustainable power source for wearable electronics.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486598","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}
Pub Date : 2024-10-22DOI: 10.1021/acsenergylett.4c02709
Heng Liu, Huanhuan Niu, Wei-Hsiang Huang, Ting Shen, Changyuan Li, Chun-Chi Chang, Menghao Yang, Chenlong Gao, Long Yang, Quan Zong, Yanzhong Pei, Guozhong Cao, Chaofeng Liu
Layered vanadium-based materials have been extensively studied as promising cathode materials for aqueous zinc-ion batteries (AZIBs). However, challenges remain to achieve the desired high energy conversion efficiency and energy densities as well as long cycling stability requiring an in-depth understanding of the local and the electronic structure of a vanadium-based cathode, especially concerning the impacts on electrochemical potential and mass transfer in the electrochemical process. In this work, 1-butyl-1-methylpyrrolidinium cations are preintercalated into the layered hydrate vanadium pentoxide (V2O5·nH2O) and partially replace the electroneutral structural water, changing the local atomic environment. X-ray absorption spectroscopies demonstrate the V–O bond elongation and the distortion in the [VO6] octahedra, which alter the ligand field and brings the V 3d state to a lower energy level, ultimately leading to an increase in the electrochemical potential. It is also revealed that the preintercalated organic cations exert electrostatic interaction with lattice oxygen, stabilizing the layered structure and buffering lattice strain during cycling. Consequently, the modified cathode achieves a superior specific capacity of 412 mAh/g at 0.5 A/g and a capacity retention of 97% after 3000 cycles at 8 A/g. The unveiled correlation between local structure and electrochemical performance paves the way for optimizing the cathode materials by manipulating the local coordination environment.
层状钒基材料作为水性锌离子电池（AZIBs）的阴极材料，已经得到了广泛的研究。然而，要实现理想的高能量转换效率和能量密度以及长时间循环稳定性仍面临挑战，需要深入了解钒基阴极的局部和电子结构，特别是在电化学过程中对电化学势和传质的影响。在这项研究中，1-丁基-1-甲基吡咯烷鎓阳离子被预插层到层状水合物五氧化二钒（V2O5-nH2O）中，部分取代了电中性结构水，改变了局部原子环境。X 射线吸收光谱显示了 V-O 键的伸长和[VO6]八面体的畸变，这改变了配体场，使 V 3d 态处于较低能级，最终导致电化学势的增加。研究还发现，预烧结的有机阳离子与晶格氧产生了静电作用，从而稳定了层状结构，并在循环过程中缓冲了晶格应变。因此，改性阴极在 0.5 A/g 条件下的比容量达到了 412 mAh/g，在 8 A/g 条件下循环 3000 次后的容量保持率为 97%。局部结构与电化学性能之间的相关性得到了揭示，这为通过操纵局部配位环境来优化阴极材料铺平了道路。
{"title":"Unveiling the Local Structure and the Ligand Field of Organic Cation Preintercalated Vanadate Cathode for Aqueous Zinc-Ion Batteries","authors":"Heng Liu, Huanhuan Niu, Wei-Hsiang Huang, Ting Shen, Changyuan Li, Chun-Chi Chang, Menghao Yang, Chenlong Gao, Long Yang, Quan Zong, Yanzhong Pei, Guozhong Cao, Chaofeng Liu","doi":"10.1021/acsenergylett.4c02709","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02709","url":null,"abstract":"Layered vanadium-based materials have been extensively studied as promising cathode materials for aqueous zinc-ion batteries (AZIBs). However, challenges remain to achieve the desired high energy conversion efficiency and energy densities as well as long cycling stability requiring an in-depth understanding of the local and the electronic structure of a vanadium-based cathode, especially concerning the impacts on electrochemical potential and mass transfer in the electrochemical process. In this work, 1-butyl-1-methylpyrrolidinium cations are preintercalated into the layered hydrate vanadium pentoxide (V<sub>2</sub>O<sub>5</sub>·<i>n</i>H<sub>2</sub>O) and partially replace the electroneutral structural water, changing the local atomic environment. X-ray absorption spectroscopies demonstrate the V–O bond elongation and the distortion in the [VO<sub>6</sub>] octahedra, which alter the ligand field and brings the V 3<i>d</i> state to a lower energy level, ultimately leading to an increase in the electrochemical potential. It is also revealed that the preintercalated organic cations exert electrostatic interaction with lattice oxygen, stabilizing the layered structure and buffering lattice strain during cycling. Consequently, the modified cathode achieves a superior specific capacity of 412 mAh/g at 0.5 A/g and a capacity retention of 97% after 3000 cycles at 8 A/g. The unveiled correlation between local structure and electrochemical performance paves the way for optimizing the cathode materials by manipulating the local coordination environment.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486599","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}
Elucidating and regulating dynamic catalyst reconstruction are crucial for various electrocatalytic reactions. Here, we applied model fittings with operando characterizations to quantify the reconstruction activity (i.e., ability to reconstruct) of layered Co(OH)2 toward the oxygen evolution reaction (OER). By modulating the intercalation species into Co(OH)2, we governed distinct reconstruction thermodynamics and kinetics, with diverse mass changes and heterogeneous Co oxidation during the OER. We further established a volcano-type relationship between reconstruction activity and OER activity and identified that a moderate reconstruction activity, achieved by dual-anion intercalation, favored a high OER activity. This might result from its proper basal spacing that regulated the coupled ion (de)intercalation–electron transfer for reconstruction, leading to optimal Co for binding OER intermediates. The optimally reconstructed Co(OH)1.26Cl0.08(CO3)0.33·0.84 H2O delivered 1 A cm–2 at 1.78 V for anion-exchange membrane water electrolysis. This work laid the foundation for modulating reconstruction activities to benefit electrocatalysis.
阐明和调节催化剂的动态重构对各种电催化反应至关重要。在这里，我们应用模型拟合和操作表征来量化层状 Co（OH）2 在氧进化反应（OER）中的重构活性（即重构能力）。通过调节 Co（OH）2 中的插层物种，我们控制了不同的重构热力学和动力学，在 OER 过程中产生了不同的质量变化和异质 Co 氧化。我们进一步确定了重构活性与 OER 活性之间的火山型关系，并发现通过双阴离子插层实现的适度重构活性有利于提高 OER 活性。这可能是由于其适当的基底间距调节了离子（脱）插层-电子转移的耦合重构，从而获得了结合 OER 中间体的最佳 Co。最佳重构的 Co(OH)1.26Cl0.08(CO3)0.33-0.84 H2O 可在 1.78 V 电压下提供 1 A cm-2，用于阴离子交换膜电解水。这项工作为调节重构活性以促进电催化奠定了基础。
{"title":"Regulating Reconstruction Activity of Cobalt Electrode for Optimized Water Oxidation","authors":"Miao Wang, Ziyi Wang, Yunze Zhang, Yan Shi, Ting-Shan Chan, Shu-Chih Haw, Jian Wang, Hongsheng Wang, Siyuan Wang, Hao Fei, Ruoqi Liu, Tong Liu, Chang-Feng Yan, Jian Wang","doi":"10.1021/acsenergylett.4c02344","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02344","url":null,"abstract":"Elucidating and regulating dynamic catalyst reconstruction are crucial for various electrocatalytic reactions. Here, we applied model fittings with operando characterizations to quantify the reconstruction activity (i.e., ability to reconstruct) of layered Co(OH)<sub>2</sub> toward the oxygen evolution reaction (OER). By modulating the intercalation species into Co(OH)<sub>2</sub>, we governed distinct reconstruction thermodynamics and kinetics, with diverse mass changes and heterogeneous Co oxidation during the OER. We further established a volcano-type relationship between reconstruction activity and OER activity and identified that a moderate reconstruction activity, achieved by dual-anion intercalation, favored a high OER activity. This might result from its proper basal spacing that regulated the coupled ion (de)intercalation–electron transfer for reconstruction, leading to optimal Co for binding OER intermediates. The optimally reconstructed Co(OH)<sub>1.26</sub>Cl<sub>0.08</sub>(CO<sub>3</sub>)<sub>0.33</sub>·0.84 H<sub>2</sub>O delivered 1 A cm<sup>–2</sup> at 1.78 V for anion-exchange membrane water electrolysis. This work laid the foundation for modulating reconstruction activities to benefit electrocatalysis.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486600","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}
Pub Date : 2024-10-21DOI: 10.1021/acsenergylett.4c02376
Zhantao Liu, Guangxing Zhang, Jakub Pepas, Yifan Ma, Hailong Chen
Low-cost cathode materials with high energy density and good rate performance are critical for the development of next-generation solid-state Li-ion batteries (SSLIBs). Here, we report Li2FeCl4 as a cathode material for SSLIBs with highly reversible Li intercalation and deintercalation, a high operation voltage of 3.7 V vs Li+/Li, good rate capability, and good cycling stability with an 86% capacity retention after 6000 cycles. Operando synchrotron XRD reveals that the phase evolution of Li2FeCl4 during charge–discharge cycling involves both solid-solution and two-phase reactions, which maintains a very stable framework during Li insertion and extraction.
{"title":"Li2FeCl4 as a Cost-Effective and Durable Cathode for Solid-State Li-Ion Batteries","authors":"Zhantao Liu, Guangxing Zhang, Jakub Pepas, Yifan Ma, Hailong Chen","doi":"10.1021/acsenergylett.4c02376","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02376","url":null,"abstract":"Low-cost cathode materials with high energy density and good rate performance are critical for the development of next-generation solid-state Li-ion batteries (SSLIBs). Here, we report Li<sub>2</sub>FeCl<sub>4</sub> as a cathode material for SSLIBs with highly reversible Li intercalation and deintercalation, a high operation voltage of 3.7 V vs Li<sup>+</sup>/Li, good rate capability, and good cycling stability with an 86% capacity retention after 6000 cycles. Operando synchrotron XRD reveals that the phase evolution of Li<sub>2</sub>FeCl<sub>4</sub> during charge–discharge cycling involves both solid-solution and two-phase reactions, which maintains a very stable framework during Li insertion and extraction.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451956","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}
Molecular materials with high structure-design freedom are used as new interface passivators to reduce nonradiative recombination in inverted perovskite solar cells (PSCs). However, most molecular modifiers are unable to achieve a long-term passivation effect due to self-aggregation. Here, the molecular modifier 1-methyl-2-thiomethyl-1H-imidazole-5-carboxylate (SMC) with ester and thiol groups is carefully developed. The ester groups weaken self-aggregation triggered by intermolecular hydrogen bonds, making such aggregations easier to disassemble during heating to form a net-like insulating layer with random openings, which dramatically increase charge transport. More importantly, the electron transfer between thiol and disulfide can accelerate the elimination of Pb0 and I2 by redox reactions to prevent phase separation. Ultimately, the optimized inverted PSCs with bandgaps of 1.68 and 1.55 eV showed surprising fill factors of 84.83% and 86.18%, resulting in champion efficiencies of 23.45% (certified 22.98%, which is the highest to date for wide-bandgap) and 25.71% (certified 25.28%), respectively. Remarkably, both unencapsulated devices maintained over 94% of their initial efficiency under maximum power point tracking for 600 h (50 °C) and 1000 h (65 °C), respectively, confirming impressive long-term operational stability.
{"title":"Sustainable Molecular Passivation via Heat-Induced Disaggregation and Redox Reactions for Inverted Perovskite Solar Cells","authors":"Ziyi Li, Anxin Sun, Congcong Tian, Rongshan Zhuang, Yiting Zheng, Xiling Wu, Beilin Ouyang, Jiajun Du, Jingyu Cai, Jinling Chen, Teng Xue, Ran Li, Tiantian Cen, Yuyang Zhao, Kaibo Zhao, Qianwen Chen, Chun-Chao Chen","doi":"10.1021/acsenergylett.4c02220","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02220","url":null,"abstract":"Molecular materials with high structure-design freedom are used as new interface passivators to reduce nonradiative recombination in inverted perovskite solar cells (PSCs). However, most molecular modifiers are unable to achieve a long-term passivation effect due to self-aggregation. Here, the molecular modifier 1-methyl-2-thiomethyl-1<i>H</i>-imidazole-5-carboxylate (SMC) with ester and thiol groups is carefully developed. The ester groups weaken self-aggregation triggered by intermolecular hydrogen bonds, making such aggregations easier to disassemble during heating to form a net-like insulating layer with random openings, which dramatically increase charge transport. More importantly, the electron transfer between thiol and disulfide can accelerate the elimination of Pb<sub>0</sub> and I<sub>2</sub> by redox reactions to prevent phase separation. Ultimately, the optimized inverted PSCs with bandgaps of 1.68 and 1.55 eV showed surprising fill factors of 84.83% and 86.18%, resulting in champion efficiencies of 23.45% (certified 22.98%, which is the highest to date for wide-bandgap) and 25.71% (certified 25.28%), respectively. Remarkably, both unencapsulated devices maintained over 94% of their initial efficiency under maximum power point tracking for 600 h (50 °C) and 1000 h (65 °C), respectively, confirming impressive long-term operational stability.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452319","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}
Pub Date : 2024-10-18DOI: 10.1021/acsenergylett.4c02466
Chao Yang, Xing Zhou, Ruitao Sun, Wenxi Hu, Meilong Wang, Xiaoli Dong, Nan Piao, Jin Han, Wen Chen, Ya You
Employing a flame-retardant solvent (FRS) in the electrolyte has shown great potential for improving the safety of lithium-ion batteries (LIBs). Nevertheless, their poor compatibility with salts and commonly used solvents leads to the formation of a heterogeneous system, which drastically limits their concentration in the electrolyte and consequently deteriorates the safety performance. In this work, we employ a bridging solvent diethyl carbonate to raise the solubility of a highly effective FRS, ethoxy pentafluorocyclotriphosphonitrile (PFPN), to a concentration as high as 75 vol % in the electrolyte. The target electrolyte forms a stable N/P-rich cathode–electrolyte interface to protect the electrode from oxygen evolution and transition-metal ion dissolution, thereby enabling the LiCoO2 cathode to preserve 72% capacity retention over 500 cycles at 4.62 V. Moreover, this electrolyte can effectively delay occurrence time and improve the critical temperature of thermal runaway of 1 Ah LiCoO2||graphite pouch cells. Our work proposes a new direction for nonflammable electrolytes toward safe and high-energy LIBs.
{"title":"A Safe Electrolyte Enriched with Flame-Retardant Solvents for High-Voltage LiCoO2||Graphite Pouch Cells","authors":"Chao Yang, Xing Zhou, Ruitao Sun, Wenxi Hu, Meilong Wang, Xiaoli Dong, Nan Piao, Jin Han, Wen Chen, Ya You","doi":"10.1021/acsenergylett.4c02466","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02466","url":null,"abstract":"Employing a flame-retardant solvent (FRS) in the electrolyte has shown great potential for improving the safety of lithium-ion batteries (LIBs). Nevertheless, their poor compatibility with salts and commonly used solvents leads to the formation of a heterogeneous system, which drastically limits their concentration in the electrolyte and consequently deteriorates the safety performance. In this work, we employ a bridging solvent diethyl carbonate to raise the solubility of a highly effective FRS, ethoxy pentafluorocyclotriphosphonitrile (PFPN), to a concentration as high as 75 vol % in the electrolyte. The target electrolyte forms a stable N/P-rich cathode–electrolyte interface to protect the electrode from oxygen evolution and transition-metal ion dissolution, thereby enabling the LiCoO<sub>2</sub> cathode to preserve 72% capacity retention over 500 cycles at 4.62 V. Moreover, this electrolyte can effectively delay occurrence time and improve the critical temperature of thermal runaway of 1 Ah LiCoO<sub>2</sub>||graphite pouch cells. Our work proposes a new direction for nonflammable electrolytes toward safe and high-energy LIBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448897","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}
Pub Date : 2024-10-18DOI: 10.1021/acsenergylett.4c02592
Subham Das, Sudipa Aich, Aswathy M, Ranjani Viswanatha
This study explores vibrationally assisted delayed fluorescence (VADF) in Mn-doped CsPbBr3 nanocrystals using Förster resonance energy transfer (FRET). Mn doping enhances the FRET efficiency significantly due to an increase in host fluorescence efficiency, indicating an increase in the radiative pathways due to VADF. We observed that Mn facilitates efficient back-transfer of charge carriers, improving energy transfer to acceptor molecules such as Rhodamine 6G (R6G). The simplicity of tuning optical properties through Mn doping presents a promising method to enhance the energy efficiency in donor–acceptor systems for optoelectronic applications. However, further research on halide concentrations, acceptor molecules, and electron transfer mechanisms is necessary to optimize these systems for effective light energy harvesting.
{"title":"Harnessing Vibrationally Assisted Delayed Fluorescence for Enhanced Energy Transfer in Mn-Doped CsPbBr3 Nanocrystals","authors":"Subham Das, Sudipa Aich, Aswathy M, Ranjani Viswanatha","doi":"10.1021/acsenergylett.4c02592","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02592","url":null,"abstract":"This study explores vibrationally assisted delayed fluorescence (VADF) in Mn-doped CsPbBr<sub>3</sub> nanocrystals using Förster resonance energy transfer (FRET). Mn doping enhances the FRET efficiency significantly due to an increase in host fluorescence efficiency, indicating an increase in the radiative pathways due to VADF. We observed that Mn facilitates efficient back-transfer of charge carriers, improving energy transfer to acceptor molecules such as Rhodamine 6G (R6G). The simplicity of tuning optical properties through Mn doping presents a promising method to enhance the energy efficiency in donor–acceptor systems for optoelectronic applications. However, further research on halide concentrations, acceptor molecules, and electron transfer mechanisms is necessary to optimize these systems for effective light energy harvesting.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448903","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 development of high-energy 5 V-class LiNi0.5Mn1.5O4 batteries is severely limited by the instability of the cathode electrolyte interphase (CEI) at high temperature. Herein, we propose a nonflammable sulfone (SL)-based fluorinated hybrid electrolyte to form stable, uniform, and thin CEI layers, enabling Li||LiNi0.5Mn1.5O4 batteries to achieve elevated electrochemical performance at 60 °C. The formed highly stable inorganic-dominated CEI, comprising LixSOy, LixBOy, and LiF inorganic compositions, exhibits good thermal stability and mechanical strength. Moreover, the robust CEI layer effectively shields the LNMO particles from undesirable side-reactions and stabilizes the interface within the LiNi0.5Mn1.5O4 cathode during high-temperature cycling. In contrast to the conventional electrolyte, the Li||LiNi0.5Mn1.5O4 battery employing a nonflammable SL-based electrolyte exhibits a stable capacity retention of 88.5% after 100 cycles at 60 °C free from the risk of thermal runaway. This study reveals valuable insights into advanced electrolyte technology, paving the way for safer applications of Co-free high-energy batteries in the future.
正极电解质间相（CEI）在高温下的不稳定性严重限制了高能量 5 V 级 LiNi0.5Mn1.5O4 电池的发展。在此，我们提出了一种不易燃的基于砜（SL）的氟化混合电解质，以形成稳定、均匀和薄的 CEI 层，从而使锂离子电池在 60 °C下实现更高的电化学性能。由 LixSOy、LixBOy 和 LiF 等无机成分形成的高度稳定的无机主导 CEI 具有良好的热稳定性和机械强度。此外，在高温循环过程中，坚固的 CEI 层还能有效保护 LNMO 颗粒免受不良副反应的影响，并稳定 LiNi0.5Mn1.5O4 阴极内的界面。与传统电解液相比，采用不可燃 SL 型电解液的镍镉锰酸锂电池在 60 °C 下循环 100 次后，容量保持率稳定在 88.5%，且不会出现热失控风险。这项研究揭示了先进电解质技术的宝贵见解，为未来更安全地应用无钴高能电池铺平了道路。
{"title":"Nonflammable Sulfone-Based Electrolytes with Mechanically and Thermally Stable Interfaces Enabling LiNi0.5Mn1.5O4 to Operate at High Temperature","authors":"Tian-Ling Chen, Mengting Liu, Xin-Yu Fan, Yi-Hu Feng, Qiang Liu, Xue-Ru Liu, Hanshen Xin, Peng-Fei Wang","doi":"10.1021/acsenergylett.4c02458","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02458","url":null,"abstract":"The development of high-energy 5 V-class LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> batteries is severely limited by the instability of the cathode electrolyte interphase (CEI) at high temperature. Herein, we propose a nonflammable sulfone (SL)-based fluorinated hybrid electrolyte to form stable, uniform, and thin CEI layers, enabling Li||LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> batteries to achieve elevated electrochemical performance at 60 °C. The formed highly stable inorganic-dominated CEI, comprising Li<sub><i>x</i></sub>SO<sub><i>y</i></sub>, Li<sub><i>x</i></sub>BO<sub><i>y</i></sub>, and LiF inorganic compositions, exhibits good thermal stability and mechanical strength. Moreover, the robust CEI layer effectively shields the LNMO particles from undesirable side-reactions and stabilizes the interface within the LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> cathode during high-temperature cycling. In contrast to the conventional electrolyte, the Li||LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> battery employing a nonflammable SL-based electrolyte exhibits a stable capacity retention of 88.5% after 100 cycles at 60 °C free from the risk of thermal runaway. This study reveals valuable insights into advanced electrolyte technology, paving the way for safer applications of Co-free high-energy batteries in the future.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448171","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}
Pub Date : 2024-10-17DOI: 10.1021/acsenergylett.4c02580
Chaohui Li, Hyoungwon Park, Shudi Qiu, Fabian Streller, Kaicheng Zhang, Zijian Peng, Jiwon Byun, Jingjing Tian, Santanu Maiti, Zhiqiang Xie, Lirong Dong, Chao Liu, Vincent M. Le Corre, Ying Shang, Jianchang Wu, Jiyun Zhang, Mingjie Feng, Andreas Späth, Karen Forberich, Andres Osvet, Thomas Heumueller, Silke H. Christiansen, Marcus Halik, Rainer H. Fink, Tobias Unruh, Ning Li, Larry Lüer, Christoph J. Brabec
Formamidinium (FA)-based perovskites exhibit significant potential for highly efficient photovoltaics due to their promising optoelectronic properties and optimal bandgap. However, the undesired inactive phase arises from multiple crystal nucleation pathways formed by various intermediate phases during the film formation process, persistently accompanying it. FA-based perovskites frequently struggle to form uniform, highly crystalline films. This challenge complicates the development of reliable and highly reproducible crystallization processes for perovskites and the establishment of guidelines for controlling the α-phase formation. In this work, we investigate the role of poly(acrylonitril-co-methyl acrylate) (PAM) to simultaneously control nucleation and subsequent α-phase crystallization. This successfully demonstrates the regulation of oriented crystal growth through the creation of a PAM-PbI2 intermediate. Ultimately, PAM-modified p–i–n architecture devices obtain a promising power conversion efficiency (PCE) of 25.30%, with VOC (1.211 V), achieving 95% of the detailed balance limit. Additionally, PAM-modified devices maintain ≥90% of the initial efficiency for 1000 h under 1 sun and 65 °C operation.
{"title":"Controlling Intermediate Phase Formation to Enhance Photovoltaic Performance of Inverted FA-Based Perovskite Solar Cells","authors":"Chaohui Li, Hyoungwon Park, Shudi Qiu, Fabian Streller, Kaicheng Zhang, Zijian Peng, Jiwon Byun, Jingjing Tian, Santanu Maiti, Zhiqiang Xie, Lirong Dong, Chao Liu, Vincent M. Le Corre, Ying Shang, Jianchang Wu, Jiyun Zhang, Mingjie Feng, Andreas Späth, Karen Forberich, Andres Osvet, Thomas Heumueller, Silke H. Christiansen, Marcus Halik, Rainer H. Fink, Tobias Unruh, Ning Li, Larry Lüer, Christoph J. Brabec","doi":"10.1021/acsenergylett.4c02580","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02580","url":null,"abstract":"Formamidinium (FA)-based perovskites exhibit significant potential for highly efficient photovoltaics due to their promising optoelectronic properties and optimal bandgap. However, the undesired inactive phase arises from multiple crystal nucleation pathways formed by various intermediate phases during the film formation process, persistently accompanying it. FA-based perovskites frequently struggle to form uniform, highly crystalline films. This challenge complicates the development of reliable and highly reproducible crystallization processes for perovskites and the establishment of guidelines for controlling the α-phase formation. In this work, we investigate the role of poly(acrylonitril-<i>co</i>-methyl acrylate) (PAM) to simultaneously control nucleation and subsequent α-phase crystallization. This successfully demonstrates the regulation of oriented crystal growth through the creation of a PAM-PbI<sub>2</sub> intermediate. Ultimately, PAM-modified p–i–n architecture devices obtain a promising power conversion efficiency (PCE) of 25.30%, with <i>V</i><sub>OC</sub> (1.211 V), achieving 95% of the detailed balance limit. Additionally, PAM-modified devices maintain ≥90% of the initial efficiency for 1000 h under 1 sun and 65 °C operation.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444159","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}
Pub Date : 2024-10-17DOI: 10.1021/acsenergylett.4c02677
Fanxu Meng, Jiangzhou Qin, Qinghao Wu, Huiwang Dai, Pan Zhu, Tian Tang, Lixia Zhang, Zishuai Bill Zhang, Kuichang Zuo
Bipolar membranes (BPMs) are emerging options for kinetically accelerating water dissociation (WD) in electrochemical applications. Graphene oxide (GO) with abundant oxygenated functional groups is an efficient catalyst within BPMs to decrease the transmembrane potential. However, the dominant catalytic sites on GO for WD in BPMs have not been experimentally identified, and the reported simulative calculation results are controversial. Herein, we prepared carboxylated and partially hydroxylated GO-based BPMs, and for the first time quantitatively unraveled the correlativity between WD performance and carboxyl group content with tailor-designed experiments. By using a simple mechanical ball milling method, we further improved the bulk density of carboxyl on the GO catalyst, which achieved excellent WD performance during an operation of over 130 h operation. This study provides a subtle and facile strategy for catalyst design to advance BPM technologies.
双极性膜（BPM）是电化学应用中加速水解离（WD）的新兴选择。具有丰富含氧官能团的氧化石墨烯（GO）是双极膜中降低跨膜电位的高效催化剂。然而，GO 上用于 BPM 中 WD 的主要催化位点尚未通过实验确定，所报道的模拟计算结果也存在争议。在此，我们制备了羧基化和部分羟基化的基于 GO 的 BPM，并首次通过量身设计的实验定量地揭示了 WD 性能与羧基含量之间的相关性。通过使用简单的机械球磨方法，我们进一步提高了 GO 催化剂上羧基的体积密度，使其在超过 130 小时的操作过程中实现了优异的 WD 性能。这项研究为催化剂设计提供了一种微妙而简便的策略，从而推动了 BPM 技术的发展。
{"title":"Identifying the Critical Oxygenated Functional Groups on Graphene Oxide for Efficient Water Dissociation in Bipolar Membranes","authors":"Fanxu Meng, Jiangzhou Qin, Qinghao Wu, Huiwang Dai, Pan Zhu, Tian Tang, Lixia Zhang, Zishuai Bill Zhang, Kuichang Zuo","doi":"10.1021/acsenergylett.4c02677","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02677","url":null,"abstract":"Bipolar membranes (BPMs) are emerging options for kinetically accelerating water dissociation (WD) in electrochemical applications. Graphene oxide (GO) with abundant oxygenated functional groups is an efficient catalyst within BPMs to decrease the transmembrane potential. However, the dominant catalytic sites on GO for WD in BPMs have not been experimentally identified, and the reported simulative calculation results are controversial. Herein, we prepared carboxylated and partially hydroxylated GO-based BPMs, and for the first time quantitatively unraveled the correlativity between WD performance and carboxyl group content with tailor-designed experiments. By using a simple mechanical ball milling method, we further improved the bulk density of carboxyl on the GO catalyst, which achieved excellent WD performance during an operation of over 130 h operation. This study provides a subtle and facile strategy for catalyst design to advance BPM technologies.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444167","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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