Although encouraging progress in spin-coated small-area organic solar cells (OSCs), reducing efficiency loss caused by differences in film uniformity and morphology when up-scaled to large-area modules through meniscus-guided coating is an important but unsolved issue. In this work, in-depth research is conducted on the influence of both liquid and solid additives on the film uniformity and morphology of active layer in blade-coated PM6:L8-BO binary system. The study reveals that high boiling point liquid additives like 1,8-diiodooctane (DIO) used in blade-coating not only delay the volatilization of the solvent but also trigger the Marangoni flow in the same direction as capillary flow, causing excessive aggregation of acceptors, therefore destroying device performance. On the contrary, the solid additive 2-Iododiphenyl ether (IDPE), which is first reported in this work, can preserve the mechanism for improving device performance while effectively suppressing the excessive aggregation of acceptors during the film-forming process in blade-coating from halogen-free solvent of toluene, resulting in highly homogeneous large-area active layer films. Consequently, organic solar modules with an impressive efficiency of 15.34% with a total module area of 18.90 cm2 via blade-coating based on PM6:L8-BO are achieved. This study not only provides a deep understanding on the effect of liquid and solid additives during blade-coating from the perspective of fluid mechanisms but also gives a pathway for the development of green solvent printed high-efficiency OSCs.
{"title":"Unravel the Distinctive Roles of Liquid and Solid Additives in Blade-Coated Active Layer for Organic Solar Cell Modules","authors":"Adiljan Wupur, Yaokai Li, Yongmin Luo, Tianyi Chen, Mengting Wang, Yiqing Zhang, Zhi-Xi Liu, Haotian Wu, Honglin Tan, Qing Zhang, Xiaokang Sun, Hanlin Hu, Xiong Li, Jiaying Wu, Weifei Fu, Weiming Qiu, Xi Yang, Hongzheng Chen","doi":"10.1002/aenm.202403132","DOIUrl":"https://doi.org/10.1002/aenm.202403132","url":null,"abstract":"Although encouraging progress in spin-coated small-area organic solar cells (OSCs), reducing efficiency loss caused by differences in film uniformity and morphology when up-scaled to large-area modules through meniscus-guided coating is an important but unsolved issue. In this work, in-depth research is conducted on the influence of both liquid and solid additives on the film uniformity and morphology of active layer in blade-coated PM6:L8-BO binary system. The study reveals that high boiling point liquid additives like 1,8-diiodooctane (DIO) used in blade-coating not only delay the volatilization of the solvent but also trigger the Marangoni flow in the same direction as capillary flow, causing excessive aggregation of acceptors, therefore destroying device performance. On the contrary, the solid additive 2-Iododiphenyl ether (IDPE), which is first reported in this work, can preserve the mechanism for improving device performance while effectively suppressing the excessive aggregation of acceptors during the film-forming process in blade-coating from halogen-free solvent of toluene, resulting in highly homogeneous large-area active layer films. Consequently, organic solar modules with an impressive efficiency of 15.34% with a total module area of 18.90 cm<sup>2</sup> via blade-coating based on PM6:L8-BO are achieved. This study not only provides a deep understanding on the effect of liquid and solid additives during blade-coating from the perspective of fluid mechanisms but also gives a pathway for the development of green solvent printed high-efficiency OSCs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317271","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}
Raimon Terricabres-Polo, Thomas A. de Bruin, Annanta Kaul, Wilfried G.J.H.M. van Sark, Celso de Mello Donega
Quantum dot (QD)-based luminescent solar concentrators (LSCs) promise to revolutionize solar energy technology by replacing building materials with energy-harvesting devices. However, QDs degrade under air, limiting the long-term performance of QD-LSCs. This study introduces an innovative approach to prevent QDs degradation by utilizing a photoactive polymer matrix (maleic anhydride-grafted poly(styrene-b-ethylene-co-butylene-b-styrene, SEBS-g-MA). This strategy has been tested outdoors over a 2-year period on five LSCs, followed by characterization of the weathered devices. The tested LSCs consist of three QD-LSCs (CuInS2/ZnS, InP/ZnSe/ZnS, CdSe/CdS/ZnS core/shell QDs), alongside a Lumogen dye-based LSC and a luminophore-free LSC. The study yields several findings: 1) SEBS-g-MA undergoes photochemistry outdoors, 2) SEBS-g-MA accelerates the photodegradation of Lumogen, 3) the power conversion efficiency of CdSe-based QD-LSC drops by 80% due to reduction of the photoluminescence quantum yield, and 4) under illumination SEBS-g-MA protects CuInS2 and InP-based QDs from degradation, ensuring a stable performance during the entire study. This work thus demonstrates for the first time that the interaction between the luminophores and the matrix is a critical determinant of the long-term success of LSCs. Leveraging on the fact that this is the longest outdoor study to date, we propose design rules for highly efficient and stable QD-LSCs.
{"title":"Durable Quantum Dot-Based Luminescent Solar Concentrators Enabled by a Photoactive Block Copolymer","authors":"Raimon Terricabres-Polo, Thomas A. de Bruin, Annanta Kaul, Wilfried G.J.H.M. van Sark, Celso de Mello Donega","doi":"10.1002/aenm.202402375","DOIUrl":"https://doi.org/10.1002/aenm.202402375","url":null,"abstract":"Quantum dot (QD)-based luminescent solar concentrators (LSCs) promise to revolutionize solar energy technology by replacing building materials with energy-harvesting devices. However, QDs degrade under air, limiting the long-term performance of QD-LSCs. This study introduces an innovative approach to prevent QDs degradation by utilizing a photoactive polymer matrix (maleic anhydride-grafted poly(styrene-b-ethylene-co-butylene-b-styrene, SEBS-g-MA). This strategy has been tested outdoors over a 2-year period on five LSCs, followed by characterization of the weathered devices. The tested LSCs consist of three QD-LSCs (CuInS<sub>2</sub>/ZnS, InP/ZnSe/ZnS, CdSe/CdS/ZnS core/shell QDs), alongside a Lumogen dye-based LSC and a luminophore-free LSC. The study yields several findings: 1) SEBS-g-MA undergoes photochemistry outdoors, 2) SEBS-g-MA accelerates the photodegradation of Lumogen, 3) the power conversion efficiency of CdSe-based QD-LSC drops by 80% due to reduction of the photoluminescence quantum yield, and 4) under illumination SEBS-g-MA protects CuInS<sub>2</sub> and InP-based QDs from degradation, ensuring a stable performance during the entire study. This work thus demonstrates for the first time that the interaction between the luminophores and the matrix is a critical determinant of the long-term success of LSCs. Leveraging on the fact that this is the longest outdoor study to date, we propose design rules for highly efficient and stable QD-LSCs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317268","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}
Huijing Liu, Zhiyu Zhang, Jia Xu, Huifang Han, Chenxu Zhao, Yao Fu, Kun Lang, Fan Shen, Pengchen Zou, Xuewei Liu, Ruifeng Shi, Zhenhuang Su, Xingyu Gao, Shengzhong Frank Liu, Jianxi Yao
All-inorganic cesium lead halide flexible perovskite solar cells (f-PSCs) exhibit superior thermal stability compared to their organic-inorganic hybrid counterparts. However, their flexibility and efficiency are still below-par for practical viability. This study presents an approach involving the introduction of multifunctional molecule ammonium benzenesulfonate (ABS) to selectively etch 0D-Cs4Pb(IBr)6 from the mixed-dimensional perovskite film surface, to attain more contact area between the perovskite and hole transport layer for improved hole extraction and transport. It is found that the ABS molecules bind to the perovskite lattice surface via O atoms and NH4+, effectively passivating surface defects and enhancing phase stability. The hydrophobic nature of the benzene ring in ABS further contributes to operational stability, leading to high cell efficiency of 15.00%, accompanied by enhanced operational stability. Even after undergoing 60 000 flexing cycles at a curvature radius of 5 mm, the ABS-treated f-PSC still retains over 98.5% of its initial efficiency. This multifunctional strategy for modifying typical mixed-dimensional perovskite compositions significantly enhances the photovoltaic performance and stability of flexible all-inorganic f-PSCs.
{"title":"Selective Chemical Etching to Remove 0D Cs4Pb(IBr)6 from Mixed-Dimensional Perovskite Surface Achieving High Efficiency Flexible All-Inorganic Perovskite Solar Cells with Superior Mechanical Durability","authors":"Huijing Liu, Zhiyu Zhang, Jia Xu, Huifang Han, Chenxu Zhao, Yao Fu, Kun Lang, Fan Shen, Pengchen Zou, Xuewei Liu, Ruifeng Shi, Zhenhuang Su, Xingyu Gao, Shengzhong Frank Liu, Jianxi Yao","doi":"10.1002/aenm.202402142","DOIUrl":"https://doi.org/10.1002/aenm.202402142","url":null,"abstract":"All-inorganic cesium lead halide flexible perovskite solar cells (f-PSCs) exhibit superior thermal stability compared to their organic-inorganic hybrid counterparts. However, their flexibility and efficiency are still below-par for practical viability. This study presents an approach involving the introduction of multifunctional molecule ammonium benzenesulfonate (ABS) to selectively etch 0D-Cs<sub>4</sub>Pb(IBr)<sub>6</sub> from the mixed-dimensional perovskite film surface, to attain more contact area between the perovskite and hole transport layer for improved hole extraction and transport. It is found that the ABS molecules bind to the perovskite lattice surface via O atoms and NH<sub>4</sub><sup>+</sup>, effectively passivating surface defects and enhancing phase stability. The hydrophobic nature of the benzene ring in ABS further contributes to operational stability, leading to high cell efficiency of 15.00%, accompanied by enhanced operational stability. Even after undergoing 60 000 flexing cycles at a curvature radius of 5 mm, the ABS-treated f-PSC still retains over 98.5% of its initial efficiency. This multifunctional strategy for modifying typical mixed-dimensional perovskite compositions significantly enhances the photovoltaic performance and stability of flexible all-inorganic f-PSCs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317267","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}
Phil Preikschas, Jie Zhang, Ranga Rohit Seemakurthi, Zan Lian, Antonio José Martín, Shibo Xi, Frank Krumeich, Haibin Ma, Yansong Zhou, Núria López, Boon Siang Yeo, Javier Pérez-Ramírez
Renewable-powered electrocatalytic CO2 conversion to long-chain hydrocarbons represents a sustainable path to produce chemicals and fuels. However, recently discovered systems still lack C–C coupling capabilities required to yield longer, more valuable carbon chains. This study reports cobalt catalysts with a focus on a Co3O4-derived material for the selective conversion of CO2 to C1–C7 hydrocarbons, following an Anderson–Schulz–Flory distribution. The obtained chain growth probability (α) of 0.54 substantially exceeds that of any other known electrocatalyst, which ranged from 0.2 to 0.4. Detailed in situ characterization and simulations indicated that Co-Co3O4 interfaces, formed in situ during CO2 electrolysis, are the active sites that promote enhanced chain growth. To prevent overreduction that causes the deactivation of these interfacial sites, the electrode is exposed to intermittent short reoxidation cycles during CO2 electrolysis. Consequently, the catalyst regained its oxidic phase and ability to form hydrocarbons. Overall, this study opens new frontiers in the one-step conversion of CO2 into multi-carbon products and suggests the exploration of metal–metal oxide interfaces as a promising strategy for further progress.
{"title":"CO2 Electroreduction to Long-Chain Hydrocarbons on Cobalt Catalysts","authors":"Phil Preikschas, Jie Zhang, Ranga Rohit Seemakurthi, Zan Lian, Antonio José Martín, Shibo Xi, Frank Krumeich, Haibin Ma, Yansong Zhou, Núria López, Boon Siang Yeo, Javier Pérez-Ramírez","doi":"10.1002/aenm.202401447","DOIUrl":"https://doi.org/10.1002/aenm.202401447","url":null,"abstract":"Renewable-powered electrocatalytic CO<sub>2</sub> conversion to long-chain hydrocarbons represents a sustainable path to produce chemicals and fuels. However, recently discovered systems still lack C–C coupling capabilities required to yield longer, more valuable carbon chains. This study reports cobalt catalysts with a focus on a Co<sub>3</sub>O<sub>4</sub>-derived material for the selective conversion of CO<sub>2</sub> to C<sub>1</sub>–C<sub>7</sub> hydrocarbons, following an Anderson–Schulz–Flory distribution. The obtained chain growth probability (<i>α</i>) of 0.54 substantially exceeds that of any other known electrocatalyst, which ranged from 0.2 to 0.4. Detailed in situ characterization and simulations indicated that Co-Co<sub>3</sub>O<sub>4</sub> interfaces, formed in situ during CO<sub>2</sub> electrolysis, are the active sites that promote enhanced chain growth. To prevent overreduction that causes the deactivation of these interfacial sites, the electrode is exposed to intermittent short reoxidation cycles during CO<sub>2</sub> electrolysis. Consequently, the catalyst regained its oxidic phase and ability to form hydrocarbons. Overall, this study opens new frontiers in the one-step conversion of CO<sub>2</sub> into multi-carbon products and suggests the exploration of metal–metal oxide interfaces as a promising strategy for further progress.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317269","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}
Siqi Wang, Minqiang Wu, Han Han, Ruxue Du, Zhengchuang Zhao, Wenjia Liu, Si Wu, Ruzhu Wang, Tingxian Li
Harvesting cold energy from the universe by radiative cooling (RC) is a promising zero-carbon route for green cooling. However, low power density and spatiotemporal energy mismatch of RC are great challenges for realizing efficient space cooling. Herein, a facile strategy for regulating cold energy from the universe by bifunctional phase change materials (PCM) for sustainable cooling is proposed. A bifunctional phase-change composite film (PCCF) by integrating RC coating with PCM for 24-h cold energy harvesting, storage, and utilization is demonstrated. The bifunctional PCCF can harvest cold energy from the universe and regulate the redundant cold energy generated by nighttime RC to compensate for the cold shortage of daytime RC, realizing flexible regulation of all-day RC and setting new records of cooling power up to 180 W m−2 with sub-ambient temperature drop of 11.95 °C. The work offers a promising strategy for zero-carbon sustainable cooling by maximizing RC with cold energy storage.
{"title":"Regulating Cold Energy from the Universe by Bifunctional Phase Change Materials for Sustainable Cooling","authors":"Siqi Wang, Minqiang Wu, Han Han, Ruxue Du, Zhengchuang Zhao, Wenjia Liu, Si Wu, Ruzhu Wang, Tingxian Li","doi":"10.1002/aenm.202402667","DOIUrl":"https://doi.org/10.1002/aenm.202402667","url":null,"abstract":"Harvesting cold energy from the universe by radiative cooling (RC) is a promising zero-carbon route for green cooling. However, low power density and spatiotemporal energy mismatch of RC are great challenges for realizing efficient space cooling. Herein, a facile strategy for regulating cold energy from the universe by bifunctional phase change materials (PCM) for sustainable cooling is proposed. A bifunctional phase-change composite film (PCCF) by integrating RC coating with PCM for 24-h cold energy harvesting, storage, and utilization is demonstrated. The bifunctional PCCF can harvest cold energy from the universe and regulate the redundant cold energy generated by nighttime RC to compensate for the cold shortage of daytime RC, realizing flexible regulation of all-day RC and setting new records of cooling power up to 180 W m<sup>−2</sup> with sub-ambient temperature drop of 11.95 °C. The work offers a promising strategy for zero-carbon sustainable cooling by maximizing RC with cold energy storage.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306322","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}
Intensity-modulated photocurrent and photovoltage spectroscopy (IMPS/IMVS) are powerful tools in optoelectronics such as photoelectrochemistry and photovoltaics, as they demonstrate distinct charge dynamic processes at different frequencies. Unlike the material characterization techniques, IMPS/IMVS offer an approach for investigating the dynamic behavior of charge carriers and ions from the device perspective. This review examines IMPS/IMVS from both theories and experiments to understand the intricate charge dynamics in solar cells with various materials and structures. To accommodate different types of cells, four primary theoretical models including the rate constant model, drift-diffusion model, equivalent circuit model, and distribution of relaxation times, are evaluated in detail. In the future, the incorporation of IMPS/IMVS with other time-domain and frequency-domain methods, along with imaging techniques, can significantly facilitate the characterization of charge dynamics with enhanced convenience, spatial dimensions, and accuracy.
{"title":"Intensity-Modulated Photocurrent and Photovoltage Spectroscopy for Characterizing Charge Dynamics in Solar Cells","authors":"Yanlong Wang, Haofeng Zheng, Jin Xiao, Yanan Liu, Qi Liu, Xuyu Ma, Jing Hu, Dechun Zou, Shaocong Hou","doi":"10.1002/aenm.202401585","DOIUrl":"https://doi.org/10.1002/aenm.202401585","url":null,"abstract":"Intensity-modulated photocurrent and photovoltage spectroscopy (IMPS/IMVS) are powerful tools in optoelectronics such as photoelectrochemistry and photovoltaics, as they demonstrate distinct charge dynamic processes at different frequencies. Unlike the material characterization techniques, IMPS/IMVS offer an approach for investigating the dynamic behavior of charge carriers and ions from the device perspective. This review examines IMPS/IMVS from both theories and experiments to understand the intricate charge dynamics in solar cells with various materials and structures. To accommodate different types of cells, four primary theoretical models including the rate constant model, drift-diffusion model, equivalent circuit model, and distribution of relaxation times, are evaluated in detail. In the future, the incorporation of IMPS/IMVS with other time-domain and frequency-domain methods, along with imaging techniques, can significantly facilitate the characterization of charge dynamics with enhanced convenience, spatial dimensions, and accuracy.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306321","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}
Birte Kressdorf, Jörg Hoffmann, Annika Dehning, Peter E. Blöchl, Michael Seibt, Christian Jooss
Strongly correlated manganites can be considered as model systems for the study of photovoltaic harvesting of hot polarons that can be excited from the electronically ordered ground state. In order to gain basic understanding of hot polaron harvesting, the deviations of the photovoltaic response of a heterojunction with polaronic absorber from a conventional semiconductor are analyzed. Specifically, the spectral and photon power density dependence of the open circuit voltage Uoc and the short circuit current density Jsc in heterojunctions consisting of orbital ordered Pr1-xCaxMnO3 (x = 0.1, PCMO) thin films epitaxially grown on single crystalline (100) SrTiO3 (STO) and Nb-doped (100) SrTiO3 (STNO) substrates are investigated. The observed behavior is fundamentally different from conventional solar cells, in which Uoc is limited by fast carrier relaxation to the band edges. Whereas the spectral and photon power dependence of Uoc of conventional semiconductor junctions is well described by the Shockley-Queisser (SQ) theory, the hot polaron junctions surprisingly show a scaling law behavior of Uoc. Such scaling laws otherwise apply to equilibrium order parameters in second-order phase transitions. It is concluded that its physical origin is the unique dependence of the quasi-Fermi level splitting on temperature, photon energy, and power density in a hot polaron system.
{"title":"Scaling Behavior in the Spectral and Power Density Dependent Photovoltaic Response of Hot Polaronic Heterojunctions","authors":"Birte Kressdorf, Jörg Hoffmann, Annika Dehning, Peter E. Blöchl, Michael Seibt, Christian Jooss","doi":"10.1002/aenm.202401189","DOIUrl":"https://doi.org/10.1002/aenm.202401189","url":null,"abstract":"Strongly correlated manganites can be considered as model systems for the study of photovoltaic harvesting of hot polarons that can be excited from the electronically ordered ground state. In order to gain basic understanding of hot polaron harvesting, the deviations of the photovoltaic response of a heterojunction with polaronic absorber from a conventional semiconductor are analyzed. Specifically, the spectral and photon power density dependence of the open circuit voltage <i>U<sub>oc</sub></i> and the short circuit current density <i>J<sub>sc</sub></i> in heterojunctions consisting of orbital ordered Pr<sub>1-x</sub>Ca<sub>x</sub>MnO<sub>3</sub> (<i>x = </i>0.1, PCMO) thin films epitaxially grown on single crystalline (100) SrTiO<sub>3</sub> (STO) and Nb-doped (100) SrTiO<sub>3</sub> (STNO) substrates are investigated. The observed behavior is fundamentally different from conventional solar cells, in which <i>U<sub>oc</sub></i> is limited by fast carrier relaxation to the band edges. Whereas the spectral and photon power dependence of <i>U<sub>oc</sub></i> of conventional semiconductor junctions is well described by the Shockley-Queisser (SQ) theory, the hot polaron junctions surprisingly show a scaling law behavior of <i>U<sub>oc</sub></i>. Such scaling laws otherwise apply to equilibrium order parameters in second-order phase transitions. It is concluded that its physical origin is the unique dependence of the quasi-Fermi level splitting on temperature, photon energy, and power density in a hot polaron system.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306325","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}
Victor Vanpeene, Lucas Huet, Julie Villanova, Margie Olbinado, Federica Marone, Eric Maire, Lionel Roué, Thomas Devic, Bernard Lestriez
The simple addition of a Zn(II) precursor to a preoptimized poly(carboxylic acid) binder solution enhances the electrochemical performance and cycle life of silicon-based electrodes. The binder/cation couple forms a cross-linked coordinated binder that plays a key role in enhancing the mechanical and chemical stability of the electrode microstructure. The impact of the addition of the Zn precursor on the microstructural evolution of the electrode during cycling is investigated at different scales (from cell/electrode to silicon particle scale) using complementary operando, in situ, and ex situ X-ray tomography techniques. Comparative analyses conducted on the reference and with Zn electrode formulations using operando and in situ X-ray micro-tomography allow for monitoring of the electrode morphological deformations along with the crack pattern formation and evolution during cycling. The benefits of the precursor addition include enhancing the mechanical stability of the electrode through a strengthened microstructure more apt to maintaining its integrity, as well as a better anchoring to the current collector leading to decreased electrical disconnections and capacity fade. Moreover, complementary ex situ X-ray nano-tomography measurements highlight the benefits of the precursor addition in terms of chemical stability with mitigated solid electrolyte interface (SEI) formation over the electrode cycling.
在预优化的聚（羧酸）粘合剂溶液中简单地添加锌（II）前体，就能提高硅基电极的电化学性能和循环寿命。粘合剂/阳离子耦合物形成了交联配位粘合剂，在增强电极微结构的机械和化学稳定性方面发挥了关键作用。利用互补的操作、原位和非原位 X 射线断层扫描技术，在不同尺度（从电池/电极到硅颗粒尺度）上研究了添加锌前驱体对循环过程中电极微观结构演变的影响。通过使用操作和原位 X 射线微断层扫描技术对参照物和锌电极配方进行比较分析，可以监测电极形态变形以及循环过程中裂纹的形成和演变。添加前驱体的好处包括：通过强化微观结构提高电极的机械稳定性，从而更有利于保持电极的完整性；更好地固定在集流器上，从而减少断电和容量衰减。此外，补充性原位 X 射线纳米层析成像测量也凸显了添加前驱体在化学稳定性方面的优势，在电极循环过程中减少了固体电解质界面（SEI）的形成。
{"title":"Deciphering the Benefits of Coordinated Binders in Si-Based Anodes by Combined Operando/In Situ and Ex Situ X-Ray Micro- and Nano-Tomographies","authors":"Victor Vanpeene, Lucas Huet, Julie Villanova, Margie Olbinado, Federica Marone, Eric Maire, Lionel Roué, Thomas Devic, Bernard Lestriez","doi":"10.1002/aenm.202403741","DOIUrl":"https://doi.org/10.1002/aenm.202403741","url":null,"abstract":"The simple addition of a Zn(II) precursor to a preoptimized poly(carboxylic acid) binder solution enhances the electrochemical performance and cycle life of silicon-based electrodes. The binder/cation couple forms a cross-linked coordinated binder that plays a key role in enhancing the mechanical and chemical stability of the electrode microstructure. The impact of the addition of the Zn precursor on the microstructural evolution of the electrode during cycling is investigated at different scales (from cell/electrode to silicon particle scale) using complementary operando, in situ, and ex situ X-ray tomography techniques. Comparative analyses conducted on the reference and with Zn electrode formulations using operando and in situ X-ray micro-tomography allow for monitoring of the electrode morphological deformations along with the crack pattern formation and evolution during cycling. The benefits of the precursor addition include enhancing the mechanical stability of the electrode through a strengthened microstructure more apt to maintaining its integrity, as well as a better anchoring to the current collector leading to decreased electrical disconnections and capacity fade. Moreover, complementary ex situ X-ray nano-tomography measurements highlight the benefits of the precursor addition in terms of chemical stability with mitigated solid electrolyte interface (SEI) formation over the electrode cycling.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306323","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}
Lynda Amichi, Haoran Yu, Amirkoushyar Ziabari, Obaidullah Rahman, David Arregui-Mena, Leiming Hu, K. C. Neyerlin, David A. Cullen
The loss of platinum (Pt) electrochemically active surface area (ECSA) is a critical degradation mode that often becomes a limiting factor for heavy-duty proton exchange membrane fuel cell vehicles. High surface area carbon supports have been shown to improve Pt dispersion and limit detrimental ionomer-electrocatalyst interactions due to their large interior pore volume. In this work, using automated scanning transmission electron tomography, the degradation of nanoparticles located on the interior versus exterior surfaces of the carbon support is compared following a catalyst-specific accelerated stress test (AST) of 90,000 voltage cycles between 0.6 V to 0.95 V. The results reveal a notable increase in median particle size for both interior and exterior Pt catalyst particles, with a slightly higher increase in particle size distribution and loss of specific surface area for the particles located on the exterior carbon surface. The fraction of Pt nanoparticles that reside within the interior of the carbon support also increased following the AST test, accompanied by evidence of an increase in average carbon mesopore size. The results shed light on the degradation mechanisms affecting electrochemical properties and the enhanced particle accessibility at lower relative humidity.
铂（Pt）电化学活性表面积（ECSA）的损失是一种关键的降解模式，通常成为重型质子交换膜燃料电池汽车的限制因素。高比表面积碳支撑物因其内部孔隙体积大，已被证明可改善铂的分散性并限制有害的离子体-电催化剂相互作用。在这项工作中，我们使用自动扫描透射电子断层扫描技术，比较了在 0.6 V 至 0.95 V 之间 90,000 次电压循环的催化剂特定加速应力测试 (AST) 之后，位于碳衬底内表面和外表面的纳米颗粒的降解情况。在进行 AST 试验后，位于碳载体内部的铂纳米颗粒的比例也有所增加，同时有证据表明碳中孔的平均尺寸也有所增加。这些结果揭示了影响电化学性质的降解机制，以及在相对湿度较低时颗粒可及性的增强。
{"title":"A 3D Nanoscale View of Electrocatalyst Degradation in Hydrogen Fuel Cells","authors":"Lynda Amichi, Haoran Yu, Amirkoushyar Ziabari, Obaidullah Rahman, David Arregui-Mena, Leiming Hu, K. C. Neyerlin, David A. Cullen","doi":"10.1002/aenm.202402310","DOIUrl":"https://doi.org/10.1002/aenm.202402310","url":null,"abstract":"The loss of platinum (Pt) electrochemically active surface area (ECSA) is a critical degradation mode that often becomes a limiting factor for heavy-duty proton exchange membrane fuel cell vehicles. High surface area carbon supports have been shown to improve Pt dispersion and limit detrimental ionomer-electrocatalyst interactions due to their large interior pore volume. In this work, using automated scanning transmission electron tomography, the degradation of nanoparticles located on the interior versus exterior surfaces of the carbon support is compared following a catalyst-specific accelerated stress test (AST) of 90,000 voltage cycles between 0.6 V to 0.95 V. The results reveal a notable increase in median particle size for both interior and exterior Pt catalyst particles, with a slightly higher increase in particle size distribution and loss of specific surface area for the particles located on the exterior carbon surface. The fraction of Pt nanoparticles that reside within the interior of the carbon support also increased following the AST test, accompanied by evidence of an increase in average carbon mesopore size. The results shed light on the degradation mechanisms affecting electrochemical properties and the enhanced particle accessibility at lower relative humidity.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aqueous Zn metal batteries show promise for large-scale energy storage but face challenges including dendrite formation, volume changes, and side reactions. This study introduces a novel anti-swelling supramolecule-crosslinked hydrogel (SCH) interphase to stabilize Zn metal anodes. The SCH, composed of cyclodextrin molecules crosslinked with polyvinyl alcohol, offers a multifaceted approach to enhance anode stability. It homogenizes ion flux and suppresses Zn dendrite growth by creating well-defined pathways for Zn2+ movement. The supramolecular structure selectively traps SO42− ions, effectively desolvating Zn2+ and enabling fast ion transportation. Additionally, by disrupting water cluster hydrogen bonds, SCH reduces free water activity, mitigating corrosion at the Zn surface. Electrochemical tests demonstrate the excellent performance of SCH-Zn, with symmetric cells achieve lifespans of 1800 h at 4 mA cm−2/2 mAh cm−2 and 1100 h at 10 mA cm−2/5 mAh cm−2. Zn||Cu half-cells maintain 99.7% Coulombic efficiency over 500 cycles, while full cells with polyaniline cathodes exhibit stable cycling for 1500 cycles at 5 A g−1 with no apparent capacity decay. These results highlight the effectiveness of the SCH in stabilizing Zn anodes. This study provides a new interfacial engineering strategy for high-performance aqueous Zn batteries, potentially accelerating their practical implementation in large-scale energy storage.
锌金属水电池有望用于大规模储能，但面临着枝晶形成、体积变化和副反应等挑战。本研究介绍了一种新型抗膨胀超分子交联水凝胶（SCH）中间相，用于稳定锌金属阳极。SCH 由与聚乙烯醇交联的环糊精分子组成，提供了一种增强阳极稳定性的多元方法。它通过创建明确的 Zn2+ 移动路径，使离子通量均匀化，并抑制 Zn 树枝的生长。超分子结构可选择性地捕获 SO42- 离子，有效地使 Zn2+ 脱溶，实现快速离子传输。此外，通过破坏水簇氢键，SCH 还能降低自由水的活性，减轻 Zn 表面的腐蚀。电化学测试证明了 SCH-Zn 的卓越性能，对称电池在 4 mA cm-2/2 mAh cm-2 条件下的寿命为 1800 小时，在 10 mA cm-2/5 mAh cm-2 条件下的寿命为 1100 小时。锌||铜半电池在 500 次循环中保持 99.7% 的库仑效率，而采用聚苯胺阴极的全电池在 5 A g-1 的条件下稳定循环 1500 次，且无明显容量衰减。这些结果凸显了 SCH 在稳定锌阳极方面的有效性。这项研究为高性能水性锌电池提供了一种新的界面工程策略，有可能加速其在大规模储能中的实际应用。
{"title":"Anti-Swelling Supramolecule-Crosslinked Hydrogel Interphase for Stable Zn Metal Anodes","authors":"Xuan Luo, Qingshun Nian, Qi Dong, Digen Ruan, Zhuangzhuang Cui, Zihong Wang, Bing-Qing Xiong, Xiaodi Ren","doi":"10.1002/aenm.202403187","DOIUrl":"https://doi.org/10.1002/aenm.202403187","url":null,"abstract":"Aqueous Zn metal batteries show promise for large-scale energy storage but face challenges including dendrite formation, volume changes, and side reactions. This study introduces a novel anti-swelling supramolecule-crosslinked hydrogel (SCH) interphase to stabilize Zn metal anodes. The SCH, composed of cyclodextrin molecules crosslinked with polyvinyl alcohol, offers a multifaceted approach to enhance anode stability. It homogenizes ion flux and suppresses Zn dendrite growth by creating well-defined pathways for Zn<sup>2+</sup> movement. The supramolecular structure selectively traps SO<sub>4</sub><sup>2−</sup> ions, effectively desolvating Zn<sup>2+</sup> and enabling fast ion transportation. Additionally, by disrupting water cluster hydrogen bonds, SCH reduces free water activity, mitigating corrosion at the Zn surface. Electrochemical tests demonstrate the excellent performance of SCH-Zn, with symmetric cells achieve lifespans of 1800 h at 4 mA cm<sup>−2</sup>/2 mAh cm<sup>−2</sup> and 1100 h at 10 mA cm<sup>−2</sup>/5 mAh cm<sup>−2</sup>. Zn||Cu half-cells maintain 99.7% Coulombic efficiency over 500 cycles, while full cells with polyaniline cathodes exhibit stable cycling for 1500 cycles at 5 A g<sup>−1</sup> with no apparent capacity decay. These results highlight the effectiveness of the SCH in stabilizing Zn anodes. This study provides a new interfacial engineering strategy for high-performance aqueous Zn batteries, potentially accelerating their practical implementation in large-scale energy storage.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306324","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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