Iman Pinnock, Yujia Fan, Yijia Zhu, Bastola Narayan, Tianlei Wang, Ivan P. Parkin, Buddha Deka Boruah
Aqueous zinc-ion batteries (AZIBs) have gained attention for their intrinsic characteristics, driven by key advantages such as cost-effectiveness, widespread availability of zinc, and reduced environmental impact and make AZIBs a promising alternative to lithium-based batteries, with potential applications in mini-grid and mini off-grid energy systems. However, achieving high capacity is crucial for AZIBs, driving research focus towards developing advanced cathode materials. Vanadium dioxide (VO2(B)) has emerged as a promising cathode material for AZIBs, owing to its large tunnel-like framework, which accommodates Zn²⁺ ions for enhanced capacity. The overall performance of cathode materials depends not only on their inherent properties, but also on synthesis methods, electrode processing techniques, and achieving ultra-high mass loading for 3D electrodes. In this study, we explore the optimization of VO2(B) cathodes through refined synthesis approaches, various electrode processing methods, and the development of 3D electrodes with ultrahigh mass loading. As a result, we achieved significant improvements in specific capacity, from 310 mAh g-1 to 500 mAh g-1, through parameter tuning. Additionally, our optimized cathodes demonstrated a stable capacity retention of 71.5% after 1000 cycles. We also developed ultra-high mass loading cathodes of 24 g cm-², achieving areal capacity of 4.6 mAh cm-2, with a stability of 81.5% after 1000 cycles. This work provides a comprehensive approach to obtaining high-capacity cathodes, contributing to the advancement of reliable and high-performance AZIBs.
锌离子水电池（AZIBs）因其固有特性而备受关注，其主要优势包括成本效益高、锌的广泛供应以及对环境的影响较小，这些优势使 AZIBs 成为锂电池的理想替代品，并有望应用于微型电网和小型离网能源系统。然而，实现高容量对 AZIBs 至关重要，这促使研究重点转向开发先进的阴极材料。二氧化钒（VO2(B)）因其大型隧道状框架可容纳 Zn²⁺ 离子以增强容量，已成为一种很有前途的 AZIB 阴极材料。阴极材料的整体性能不仅取决于其固有特性，还取决于合成方法、电极加工技术以及实现三维电极的超高质量负载。在本研究中，我们通过精细合成方法、各种电极加工方法和超高质量负载三维电极的开发，探索了 VO2(B) 阴极的优化方法。结果，通过参数调整，我们显著提高了比容量，从 310 mAh g-1 提高到 500 mAh g-1。此外，我们优化的阴极在 1000 次循环后显示出 71.5% 的稳定容量保持率。我们还开发出了 24 g cm-² 的超高质量负载阴极，实现了 4.6 mAh cm-2 的等面积容量，1000 次循环后的稳定性达到 81.5%。这项工作为获得高容量阴极提供了一种全面的方法，有助于开发可靠的高性能 AZIB。
{"title":"Advancing High Capacity 3D VO2(B) Cathodes for Improved Zinc-ion Battery Performance","authors":"Iman Pinnock, Yujia Fan, Yijia Zhu, Bastola Narayan, Tianlei Wang, Ivan P. Parkin, Buddha Deka Boruah","doi":"10.1039/d4ta06572g","DOIUrl":"https://doi.org/10.1039/d4ta06572g","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) have gained attention for their intrinsic characteristics, driven by key advantages such as cost-effectiveness, widespread availability of zinc, and reduced environmental impact and make AZIBs a promising alternative to lithium-based batteries, with potential applications in mini-grid and mini off-grid energy systems. However, achieving high capacity is crucial for AZIBs, driving research focus towards developing advanced cathode materials. Vanadium dioxide (VO2(B)) has emerged as a promising cathode material for AZIBs, owing to its large tunnel-like framework, which accommodates Zn²⁺ ions for enhanced capacity. The overall performance of cathode materials depends not only on their inherent properties, but also on synthesis methods, electrode processing techniques, and achieving ultra-high mass loading for 3D electrodes. In this study, we explore the optimization of VO2(B) cathodes through refined synthesis approaches, various electrode processing methods, and the development of 3D electrodes with ultrahigh mass loading. As a result, we achieved significant improvements in specific capacity, from 310 mAh g-1 to 500 mAh g-1, through parameter tuning. Additionally, our optimized cathodes demonstrated a stable capacity retention of 71.5% after 1000 cycles. We also developed ultra-high mass loading cathodes of 24 g cm-², achieving areal capacity of 4.6 mAh cm-2, with a stability of 81.5% after 1000 cycles. This work provides a comprehensive approach to obtaining high-capacity cathodes, contributing to the advancement of reliable and high-performance AZIBs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"254 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing efficient oxygen evolution reaction (OER) catalysts was urgent for producing clean hydrogen energy. High-entropy oxides (HEOs) have become a focus of interest, were widely used for OER. HEOs would provide multiple degrees of freedom, allowing modification of the composition and atomic arrangement to fine-tune the electronic structure or active sites to optimize catalytic activity in OER. However, achieving multi-ion crystallization in HEOs while maintaining porous or nanostructured morphology still remained a challenge. In this work, (Ni0.2Co0.2Zn0.2Cu0.2Mg0.2)Fe2O4 nanofibers were prepared by the electrospinning method. (Ni0.2Co0.2Zn0.2Cu0.2Mg0.2)Fe2O4 exhibited enhanced OER activity (η10 =286 mV, Tafel slope =136 mV dec-1) and strong catalytic stability compared with single, binary, ternary, and quaternary oxides. The oxygen vacancies generated during the OER were confirmed by EPR experiments. XPS, TEM and In situ Raman spectroscopy confirmed the self-reconstruction of (Ni0.2Co0.2Zn0.2Cu0.2Mg0.2)Fe2O4 during the OER. DFT calculations revealed that the high entropy structure would promote the shift of the D-band center towards the Fermi level and reduce the ΔGmax, which were consistent with the catalytic performance results. This research demonstrated the significant importance of high-entropy concept to boost the performance of high entropy materials for electrochemical application.
开发高效的氧进化反应（OER）催化剂是生产清洁氢能的当务之急。高熵氧化物（HEOs）已成为人们关注的焦点，并被广泛用于氧进化反应。高熵氧化物具有多个自由度，可通过改变成分和原子排列来微调电子结构或活性位点，从而优化 OER 的催化活性。然而，在 HEOs 中实现多离子结晶，同时保持多孔或纳米结构形态仍然是一个挑战。本研究采用电纺丝方法制备了（Ni0.2Co0.2Zn0.2Cu0.2Mg0.2）Fe2O4 纳米纤维。(与单氧化物、二元氧化物、三元氧化物和四元氧化物相比，(Ni0.2Co0.2Zn0.2Cu0.2Mg0.2)Fe2O4 表现出更高的 OER 活性（η10 =286 mV，Tafel 斜坡 =136 mV dec-1）和更强的催化稳定性。EPR 实验证实了 OER 过程中产生的氧空位。XPS、TEM 和原位拉曼光谱证实了(Ni0.2Co0.2Zn0.2Cu0.2Mg0.2)Fe2O4 在 OER 过程中的自重构。DFT 计算表明，高熵结构会促进 D 波段中心向费米级移动并降低 ΔGmax，这与催化性能结果是一致的。这项研究表明，高熵概念对于提高高熵材料的电化学应用性能具有重要意义。
{"title":"High entropy spinel oxide (Ni0.2Co0.2Zn0.2Cu0.2Mg0.2)Fe2O4 nanofibers for efficient oxygen evolution reaction","authors":"Mengyuan Zhang, Xuanyu Zhou, Kongliang Luo, Yaning Fan, Chuandong He, Qiang Niu, Junjun Zhang, Pengfei Zhang, Sheng Dai","doi":"10.1039/d4ta06051b","DOIUrl":"https://doi.org/10.1039/d4ta06051b","url":null,"abstract":"Developing efficient oxygen evolution reaction (OER) catalysts was urgent for producing clean hydrogen energy. High-entropy oxides (HEOs) have become a focus of interest, were widely used for OER. HEOs would provide multiple degrees of freedom, allowing modification of the composition and atomic arrangement to fine-tune the electronic structure or active sites to optimize catalytic activity in OER. However, achieving multi-ion crystallization in HEOs while maintaining porous or nanostructured morphology still remained a challenge. In this work, (Ni0.2Co0.2Zn0.2Cu0.2Mg0.2)Fe2O4 nanofibers were prepared by the electrospinning method. (Ni0.2Co0.2Zn0.2Cu0.2Mg0.2)Fe2O4 exhibited enhanced OER activity (η10 =286 mV, Tafel slope =136 mV dec-1) and strong catalytic stability compared with single, binary, ternary, and quaternary oxides. The oxygen vacancies generated during the OER were confirmed by EPR experiments. XPS, TEM and In situ Raman spectroscopy confirmed the self-reconstruction of (Ni0.2Co0.2Zn0.2Cu0.2Mg0.2)Fe2O4 during the OER. DFT calculations revealed that the high entropy structure would promote the shift of the D-band center towards the Fermi level and reduce the ΔGmax, which were consistent with the catalytic performance results. This research demonstrated the significant importance of high-entropy concept to boost the performance of high entropy materials for electrochemical application.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"1 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohasin Tarek, Ferdous Yasmeen, Mohammed Abdul Basith
Aqueous supercapacitors (SCs) are often constrained by low operational voltage and energy density due to the low decomposition voltage of water. In this work, we address these limitations by fabricating symmetric SCs using nanoporous Dysprosium Orthoferrite (DyFeO3) electrodes in dilute, neutral aqueous electrolytes. The nanoporous architecture of the DyFeO3 electrode material, with an average pore size of 3.41 nm, was confirmed using Brunauer–Emmett–Teller analysis and comprehensively characterized through XRD, FESEM, TEM, XPS, Raman spectroscopy, EPR, and zeta potential measurements. The fabricated SC, operating in a 0.5 M Na2SO4 aqueous electrolyte, exhibited a high working voltage of 2.5 V, delivering an energy density of 41.81 W h kg-1 at a power density of 1250 W kg-1, with 90% capacitance retention after 10,000 cycles. Furthermore, the addition of 20% acetonitrile (AN) to the 0.5 M Na2SO4 electrolyte extended the potential window to 3.1 V, increasing the energy density to 84.43 W h kg-1 at a power density of 1550 W kg-1. The fabricated symmetric SC demonstrated excellent long-term stability, retaining approximately 99% capacitance and Coulombic efficiency after a 600-hour float voltage test. These findings, for the first time, reveal the potential of nanoporous DyFeO3 as electrode material in a 0.5 M Na2SO4(aq.)/20%AN electrolyte for advancing symmetric SCs, featuring an unprecedented ultra-wide electrochemical stability window along with significantly enhanced energy and power densities.
由于水的分解电压较低，水性超级电容器（SC）通常受制于较低的工作电压和能量密度。在这项工作中，我们利用纳米多孔镝正铁（DyFeO3）电极在稀释的中性水电解质中制造出了对称超级电容器，从而解决了这些限制。DyFeO3 电极材料的纳米多孔结构（平均孔径为 3.41 nm）已通过布鲁瑙尔-艾美特-泰勒分析法得到证实，并通过 XRD、FESEM、TEM、XPS、拉曼光谱、EPR 和 zeta 电位测量法进行了全面表征。在 0.5 M Na2SO4 水基电解液中工作时，所制备的 SC 显示出 2.5 V 的高工作电压，在功率密度为 1250 W kg-1 时可提供 41.81 W h kg-1 的能量密度，在 10,000 次循环后电容保持率为 90%。此外，在 0.5 M Na2SO4 电解液中加入 20% 的乙腈 (AN) 可将电位窗口扩展到 3.1 V，在功率密度为 1550 W kg-1 时，能量密度增至 84.43 W h kg-1。制造出的对称 SC 具有出色的长期稳定性，在经过 600 小时的浮动电压测试后，仍能保持约 99% 的电容和库仑效率。这些发现首次揭示了纳米多孔 DyFeO3 作为电极材料在 0.5 M Na2SO4（aq.）/20%AN 电解液中推动对称 SC 发展的潜力，其特点是具有前所未有的超宽电化学稳定性窗口以及显著增强的能量和功率密度。
{"title":"High-voltage Symmetric Supercapacitors Developed by Engineering DyFeO3 Electrodes and Aqueous Electrolytes","authors":"Mohasin Tarek, Ferdous Yasmeen, Mohammed Abdul Basith","doi":"10.1039/d4ta06769j","DOIUrl":"https://doi.org/10.1039/d4ta06769j","url":null,"abstract":"Aqueous supercapacitors (SCs) are often constrained by low operational voltage and energy density due to the low decomposition voltage of water. In this work, we address these limitations by fabricating symmetric SCs using nanoporous Dysprosium Orthoferrite (DyFeO<small><sub>3</sub></small>) electrodes in dilute, neutral aqueous electrolytes. The nanoporous architecture of the DyFeO<small><sub>3</sub></small> electrode material, with an average pore size of 3.41 nm, was confirmed using Brunauer–Emmett–Teller analysis and comprehensively characterized through XRD, FESEM, TEM, XPS, Raman spectroscopy, EPR, and zeta potential measurements. The fabricated SC, operating in a 0.5 M Na<small><sub>2</sub></small>SO<small><sub>4</sub></small> aqueous electrolyte, exhibited a high working voltage of 2.5 V, delivering an energy density of 41.81 W h kg<small><sup>-1</sup></small> at a power density of 1250 W kg<small><sup>-1</sup></small>, with 90% capacitance retention after 10,000 cycles. Furthermore, the addition of 20% acetonitrile (AN) to the 0.5 M Na<small><sub>2</sub></small>SO<small><sub>4</sub></small> electrolyte extended the potential window to 3.1 V, increasing the energy density to 84.43 W h kg<small><sup>-1</sup></small> at a power density of 1550 W kg<small><sup>-1</sup></small>. The fabricated symmetric SC demonstrated excellent long-term stability, retaining approximately 99% capacitance and Coulombic efficiency after a 600-hour float voltage test. These findings, for the first time, reveal the potential of nanoporous DyFeO<small><sub>3</sub></small> as electrode material in a 0.5 M Na<small><sub>2</sub></small>SO<small><sub>4</sub></small>(aq.)/20%AN electrolyte for advancing symmetric SCs, featuring an unprecedented ultra-wide electrochemical stability window along with significantly enhanced energy and power densities.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"6 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685063","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Joana Ferreira Machado, Jeremy Gérard Hieulle, Aline Vanderhaegen, Alex Redinger
Light-induced degradation of tin-based organic inorganic halide perovskites (Sn-HOIP) absorbers is a major barrier for their deployment in photovoltaic applications. Sn-HOIP are believed to intrinsically degrade due to the tendency of tin to change the oxidation state from (2+) to (4+). So far, most studies have been performed on absorbers that were synthesized with solvent-based techniques. The solvents themselves have been associated with Sn-HOIP degradation. Here, we show that in solvent-free coevaporated methylammonium tin iodide (MASI) films exposed to white light, no Sn(4+) could be detected, even after almost 100,h of exposure. To understand the degradation mechanism, the chemical composition at the surface of MASI was measured by X-ray photoelectron spectroscopy after different illumination intervals. The measurements showed that MASI decomposed into tin iodide (SnI$_2$) and a minimal amount of metallic tin. The SnI$_2$ phase at the surface increases as a function of light exposure. Despite the strong degradation, light-induced decomposition was not accompanied by the formation of Sn(4+). In addition, the stability of SnI$_2$ under illumination was studied and compared to that of PbI$_2$. Here, SnI$_2$ did not show any degradation, contrarily to PbI$_2$ which degraded into metallic lead. Our results show that the tendency of tin to be in multiple oxidation states is not triggered by light. Instead, the critical point is the choice of an organic component (methylammonium) that leaves the perovskite crystal during illumination. These results show that it is essential to retain the organic component in the perovskite lattice, either by including additives or by replacing the organic component.
{"title":"Light-induced degradation of methylammonium tin iodide absorber layers","authors":"Joana Ferreira Machado, Jeremy Gérard Hieulle, Aline Vanderhaegen, Alex Redinger","doi":"10.1039/d4ta06361a","DOIUrl":"https://doi.org/10.1039/d4ta06361a","url":null,"abstract":"Light-induced degradation of tin-based organic inorganic halide perovskites (Sn-HOIP) absorbers is a major barrier for their deployment in photovoltaic applications. Sn-HOIP are believed to intrinsically degrade due to the tendency of tin to change the oxidation state from (2+) to (4+). So far, most studies have been performed on absorbers that were synthesized with solvent-based techniques. The solvents themselves have been associated with Sn-HOIP degradation. Here, we show that in solvent-free coevaporated methylammonium tin iodide (MASI) films exposed to white light, no Sn(4+) could be detected, even after almost 100,h of exposure. To understand the degradation mechanism, the chemical composition at the surface of MASI was measured by X-ray photoelectron spectroscopy after different illumination intervals. The measurements showed that MASI decomposed into tin iodide (SnI$_2$) and a minimal amount of metallic tin. The SnI$_2$ phase at the surface increases as a function of light exposure. Despite the strong degradation, light-induced decomposition was not accompanied by the formation of Sn(4+). In addition, the stability of SnI$_2$ under illumination was studied and compared to that of PbI$_2$. Here, SnI$_2$ did not show any degradation, contrarily to PbI$_2$ which degraded into metallic lead. Our results show that the tendency of tin to be in multiple oxidation states is not triggered by light. Instead, the critical point is the choice of an organic component (methylammonium) that leaves the perovskite crystal during illumination. These results show that it is essential to retain the organic component in the perovskite lattice, either by including additives or by replacing the organic component.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"23 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685062","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Addressing the urgent need for innovative solutions to combat climate change, this study introduces a groundbreaking approach to the selective separation of carbon dioxide (CO2) from the industrial flue and biogas streams. By leveraging the unique properties of Metal-Organic Frameworks (MOFs) and the versatility of polydimethylsiloxane (PDMS), we developed a hybrid membrane that stands at the forefront of CO2 separation technology. At the core of our innovation is the strategic incorporation of a moisture-stable, Zn(II) (aminoiosphtalic)(4,4',4″-(1H-imidazole-2,4,5-triyl)tripyridine) MOF into a cross-linked polymethylsiloxane layer. This composite membrane, with a thickness of up to 25 µm, is fabricated over asymmetric polysulfone hollow fibers, resulting in a robust platform that showcases exceptional selectivity and efficiency in CO2 separation. This hybrid membrane distinguishes itself from other adsorbents by demonstrating CO2 flux values ranging from 50 to 240 Gas Permeation Unit under gauge pressures of 10-100 kPa, and achieving unparalleled selectivity ratios of CO2/N2 ~ 249 and CO2/CH4 ~199 at the minimal pressure of 10 kPa. The membrane's exceptional recyclable performance, coupled with the simplicity of fabrication marks a significant advancement in the field of gas separation. The present findings pave the way for next-generation carbon capture technologies and align with the global imperative for cleaner industrial processes.
{"title":"Unlocking Advanced CO2 Separation via Scalable and Nitrogen-rich MOF- Cross-linked Polydimethylsiloxane Hollow Fiber Hybrid Membrane","authors":"Nayan Nandha, Partha Pratim Pratim Mondal, Utpal Thummar, Ranadip Goswami, Pranay Kumar, Subhadip Neogi, Puyam Sobhindro S. Singh","doi":"10.1039/d4ta05319b","DOIUrl":"https://doi.org/10.1039/d4ta05319b","url":null,"abstract":"Addressing the urgent need for innovative solutions to combat climate change, this study introduces a groundbreaking approach to the selective separation of carbon dioxide (CO2) from the industrial flue and biogas streams. By leveraging the unique properties of Metal-Organic Frameworks (MOFs) and the versatility of polydimethylsiloxane (PDMS), we developed a hybrid membrane that stands at the forefront of CO2 separation technology. At the core of our innovation is the strategic incorporation of a moisture-stable, Zn(II) (aminoiosphtalic)(4,4',4″-(1H-imidazole-2,4,5-triyl)tripyridine) MOF into a cross-linked polymethylsiloxane layer. This composite membrane, with a thickness of up to 25 µm, is fabricated over asymmetric polysulfone hollow fibers, resulting in a robust platform that showcases exceptional selectivity and efficiency in CO2 separation. This hybrid membrane distinguishes itself from other adsorbents by demonstrating CO2 flux values ranging from 50 to 240 Gas Permeation Unit under gauge pressures of 10-100 kPa, and achieving unparalleled selectivity ratios of CO2/N2 ~ 249 and CO2/CH4 ~199 at the minimal pressure of 10 kPa. The membrane's exceptional recyclable performance, coupled with the simplicity of fabrication marks a significant advancement in the field of gas separation. The present findings pave the way for next-generation carbon capture technologies and align with the global imperative for cleaner industrial processes.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"13 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Raquel Dantas Campos, Shivam Singh, Herman Heffner, Markus Löffler, Fabian Paulus, Yana Vaynzof
Lead sulfide quantum dot solar cells have been largely studied only in the n–i–p architecture, with very few reports on the inverted p–i–n structure. Although the p–i–n structure provides several advantages, such as low-temperature processing and is generally compatible with tandem applications, the realization of p–i–n PbS solar cells has been hindered by the absence of suitable hole transport layers. That led to the necessity of introducing a 1,2-ethanedithiol (EDT) passivated PbS layer, which, while improving hole extraction, significantly hinders device reproducibility and stability. Here, we demonstrate PbS quantum dot solar cells based on carbazole- and dibenzothiophene-based self-assembled molecules as hole transport layers for the first time. We show that the properties of the organic interlayer influence the formation of the PbS quantum dot active layer and, consequently, the device performance. Among the studied self-assembled molecules, the best photovoltaic performance was obtained for Br-2EPT, reaching power conversion efficiencies of up to 6.3%, among the highest for p–i–n devices that are not based on the use of EDT-PbS. These results underline the great potential of self-assembled molecules as hole transport layers in inverted p–i–n PbS quantum dot solar cells.
{"title":"Self-assembled molecules for hole extraction in efficient inverted PbS quantum dot solar cells","authors":"Raquel Dantas Campos, Shivam Singh, Herman Heffner, Markus Löffler, Fabian Paulus, Yana Vaynzof","doi":"10.1039/d4ta04791e","DOIUrl":"https://doi.org/10.1039/d4ta04791e","url":null,"abstract":"Lead sulfide quantum dot solar cells have been largely studied only in the n–i–p architecture, with very few reports on the inverted p–i–n structure. Although the p–i–n structure provides several advantages, such as low-temperature processing and is generally compatible with tandem applications, the realization of p–i–n PbS solar cells has been hindered by the absence of suitable hole transport layers. That led to the necessity of introducing a 1,2-ethanedithiol (EDT) passivated PbS layer, which, while improving hole extraction, significantly hinders device reproducibility and stability. Here, we demonstrate PbS quantum dot solar cells based on carbazole- and dibenzothiophene-based self-assembled molecules as hole transport layers for the first time. We show that the properties of the organic interlayer influence the formation of the PbS quantum dot active layer and, consequently, the device performance. Among the studied self-assembled molecules, the best photovoltaic performance was obtained for Br-2EPT, reaching power conversion efficiencies of up to 6.3%, among the highest for p–i–n devices that are not based on the use of EDT-PbS. These results underline the great potential of self-assembled molecules as hole transport layers in inverted p–i–n PbS quantum dot solar cells.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"70 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Meisheng Han, Kunxiong Zheng, Jie Liu, Zhiyu Zou, Yongbiao Mu, Hengyuan Hu, Fenghua Yu, Wenjia Li, Lei Wei, Lin Zeng, Tianshou Zhao
Conversion-type transition-metal compounds (C-TMCs) are widely used as lithium-ion-battery (LIB) anodes due to their high theoretical capacity. However, their significant discrepancy in lithium storage capacity is observed across a wide temperature range, a comprehensive understanding of the underlying mechanism remains exclusive. Herein, we propose a methodology to clarify the capacity discrepancy mechanisms by choosing Fe1-xS anode as a representation. Specifically, we demonstrate lithium storage three stages of Fe1-xS across a wide temperature range, involving insertion, conversion, and space charge. Furthermore, we reveal that the capacity discrepancy mechanisms of Fe1-xS across a wide temperature range are basically from the differences in the amount of spin-polarized electrons injection into Fe, which induces different storage amount of lithium ions into Li2S during the space charge lithium storage by in-situ magnetometry as a dominant technology. Higher operation temperatures of batteries benefit for more storage of ions and electrons in Li2S and Fe, respectively. Our work clarifies the importance of space charge on the improvement of capacity for C-TMCs in a wide temperature range, which can provide a guidance for developing high-capacity anodes applicable to wide-temperature-range LIBs.
转化型过渡金属化合物（C-TMC）因其理论容量高而被广泛用作锂离子电池（LIB）阳极。然而，由于它们的锂存储容量在很宽的温度范围内都存在显著差异，因此对其潜在机理的全面了解仍是空白。在此，我们提出了一种以 Fe1-xS 阳极为代表来阐明容量差异机制的方法。具体而言，我们展示了 Fe1-xS 在宽温度范围内的三个储锂阶段，涉及插入、转换和空间电荷。此外，我们还揭示了 Fe1-xS 在宽温度范围内的容量差异机制主要来自注入 Fe 的自旋极化电子量的不同，从而在以原位磁力计为主导技术的空间充电锂存储过程中，诱导锂离子进入 Li2S 的存储量不同。电池的工作温度越高，离子和电子在 Li2S 和 Fe 中的存储量就越大。我们的研究阐明了空间电荷对 C-TMCs 在宽温度范围内提高容量的重要性，为开发适用于宽温度范围锂电池的高容量阳极提供了指导。
{"title":"Mechanistic insights into capacity discrepancies of conversion-type transition-metal compounds in wide-temperature-range lithium-ion batteries","authors":"Meisheng Han, Kunxiong Zheng, Jie Liu, Zhiyu Zou, Yongbiao Mu, Hengyuan Hu, Fenghua Yu, Wenjia Li, Lei Wei, Lin Zeng, Tianshou Zhao","doi":"10.1039/d4ta06381c","DOIUrl":"https://doi.org/10.1039/d4ta06381c","url":null,"abstract":"Conversion-type transition-metal compounds (C-TMCs) are widely used as lithium-ion-battery (LIB) anodes due to their high theoretical capacity. However, their significant discrepancy in lithium storage capacity is observed across a wide temperature range, a comprehensive understanding of the underlying mechanism remains exclusive. Herein, we propose a methodology to clarify the capacity discrepancy mechanisms by choosing Fe1-xS anode as a representation. Specifically, we demonstrate lithium storage three stages of Fe1-xS across a wide temperature range, involving insertion, conversion, and space charge. Furthermore, we reveal that the capacity discrepancy mechanisms of Fe1-xS across a wide temperature range are basically from the differences in the amount of spin-polarized electrons injection into Fe, which induces different storage amount of lithium ions into Li2S during the space charge lithium storage by in-situ magnetometry as a dominant technology. Higher operation temperatures of batteries benefit for more storage of ions and electrons in Li2S and Fe, respectively. Our work clarifies the importance of space charge on the improvement of capacity for C-TMCs in a wide temperature range, which can provide a guidance for developing high-capacity anodes applicable to wide-temperature-range LIBs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"23 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The increasing demand for high-efficiency heat engines, along with advancements in the power generation and aerospace industries, necessitates the development of high-temperature (HT) alloys with superior mechanical properties, as well as enhanced oxidation and corrosion resistance. This review comprehensively examines the potential of complex concentrated alloys (CCAs) to meet these demands. Beginning with an overview of the extensively studied Cantor alloy systems, it explores the effects of elemental additions and substitutions-such as Al, Nb, Cu, and Si-on the oxidation behavior of CCAs. The review delves into the mechanisms of oxide scale formation and design strategies for enhancing oxidation resistance. Additionally, it emphasizes the integration of advanced computational techniques and machine learning for alloy development. By synthesizing existing research, this review identifies key knowledge gaps and offers a solid foundation for future CCA research, guiding the intelligent design of next-generation HT alloys.
随着发电和航空航天工业的发展，人们对高效热机的需求日益增长，因此有必要开发具有优异机械性能、更强抗氧化性和耐腐蚀性的高温（HT）合金。本综述全面探讨了复合浓缩合金 (CCA) 在满足这些需求方面的潜力。文章首先概述了经过广泛研究的康托合金体系，然后探讨了元素添加和替代（如铝、铌、铜和硅）对 CCA 氧化行为的影响。综述深入探讨了氧化鳞形成的机理以及增强抗氧化性的设计策略。此外，它还强调了先进计算技术和机器学习在合金开发中的应用。通过综合现有研究，本综述找出了关键的知识差距，为未来的 CCA 研究奠定了坚实的基础，为下一代 HT 合金的智能设计提供了指导。
{"title":"High-temperature oxidation behavior of transition metal complex concentrated alloys (TM-CCAs): a comprehensive review","authors":"Haofei Sun, Emily Seto, Meifeng Li, Jing Liu","doi":"10.1039/d4ta06071g","DOIUrl":"https://doi.org/10.1039/d4ta06071g","url":null,"abstract":"The increasing demand for high-efficiency heat engines, along with advancements in the power generation and aerospace industries, necessitates the development of high-temperature (HT) alloys with superior mechanical properties, as well as enhanced oxidation and corrosion resistance. This review comprehensively examines the potential of complex concentrated alloys (CCAs) to meet these demands. Beginning with an overview of the extensively studied Cantor alloy systems, it explores the effects of elemental additions and substitutions-such as Al, Nb, Cu, and Si-on the oxidation behavior of CCAs. The review delves into the mechanisms of oxide scale formation and design strategies for enhancing oxidation resistance. Additionally, it emphasizes the integration of advanced computational techniques and machine learning for alloy development. By synthesizing existing research, this review identifies key knowledge gaps and offers a solid foundation for future CCA research, guiding the intelligent design of next-generation HT alloys.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"4 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hengwei Lou, Yikai Yang, Xiuming Bu, Haoxin Fan, Duo Weng, Jian Zhang, Wei Gao, Dan Wen
Using the thermodynamically favorable glucose oxidation reaction (GOR) to replace oxygen evolution reaction (OER) not only enables energy-efficient hydrogen production but also yields high-value products for water electrolysis. Herein, self-supported nickel phosphide nanowire arrays on Ni foam (Ni-P@NF) were facilely synthesized for GOR-assisted hydrogen production. Ni-P@NF can provide a current density of 100 mA cm-2 for GOR at 1.32 V (vs. RHE) and yield formic acid as the main product with the Faraday efficiency up to 97 %. The partial reconstruction of Ni-P into NiOOH on the surface during the GOR was recognized to comprehend the GOR catalytic mechanism. By coupling GOR and HER with Ni-P@NF as the electrodes, a low voltage of 1.43 V is required to drive the current density of 10 mA cm-2 for stable hydrogen generation and glucose conversion simultaneously. Thus, this work achieved energy-efficient hydrogen production and formic acid generation, providing of the well-aligned Ni-P nanowire arrays as the bifunctional catalysts for biomass oxidation-assisted water splitting.
利用热力学上有利的葡萄糖氧化反应（GOR）来取代氧进化反应（OER），不仅能实现高效制氢，还能产生高价值的电解水产品。本文在镍泡沫上简便地合成了自支撑磷化镍纳米线阵列（Ni-P@NF），用于 GOR 辅助制氢。Ni-P@NF 可在 1.32 V（相对于 RHE）电压下为 GOR 提供 100 mA cm-2 的电流密度，并以甲酸为主要产物，法拉第效率高达 97%。在 GOR 过程中，Ni-P 在表面部分重构为 NiOOH，从而理解了 GOR 的催化机理。通过以 Ni-P@NF 为电极耦合 GOR 和 HER，只需 1.43 V 的低电压即可驱动 10 mA cm-2 的电流密度，从而同时实现稳定的制氢和葡萄糖转化。因此，这项工作实现了高能效制氢和甲酸生成，为生物质氧化辅助水分离提供了排列整齐的 Ni-P 纳米线阵列双功能催化剂。
{"title":"Efficient electrocatalytic glucose oxidation coupled water electrolysis driven by the Ni-foam supported Ni-P nanowire arrays","authors":"Hengwei Lou, Yikai Yang, Xiuming Bu, Haoxin Fan, Duo Weng, Jian Zhang, Wei Gao, Dan Wen","doi":"10.1039/d4ta06649a","DOIUrl":"https://doi.org/10.1039/d4ta06649a","url":null,"abstract":"Using the thermodynamically favorable glucose oxidation reaction (GOR) to replace oxygen evolution reaction (OER) not only enables energy-efficient hydrogen production but also yields high-value products for water electrolysis. Herein, self-supported nickel phosphide nanowire arrays on Ni foam (Ni-P@NF) were facilely synthesized for GOR-assisted hydrogen production. Ni-P@NF can provide a current density of 100 mA cm-2 for GOR at 1.32 V (vs. RHE) and yield formic acid as the main product with the Faraday efficiency up to 97 %. The partial reconstruction of Ni-P into NiOOH on the surface during the GOR was recognized to comprehend the GOR catalytic mechanism. By coupling GOR and HER with Ni-P@NF as the electrodes, a low voltage of 1.43 V is required to drive the current density of 10 mA cm-2 for stable hydrogen generation and glucose conversion simultaneously. Thus, this work achieved energy-efficient hydrogen production and formic acid generation, providing of the well-aligned Ni-P nanowire arrays as the bifunctional catalysts for biomass oxidation-assisted water splitting.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"14 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Grant M Musgrave, Eden Y Yau, Huang Sijia, Caleb Reese, Chen Wang
Bio-based carboxylic acids are some of the most available renewable chemicals, but since they are solids with high melting temperatures, they cannot be directly used as liquid resins. To this end, we report the formation of supramolecular complexes between an amino methacrylate and various solid carboxylic acids. The ionically bonded methacrylates exhibit low viscosities and rapid reaction kinetics for free-radical mediated polymerization, showing quantitative methacrylate conversions within one minute of irradiation at 5 mW/cm2 405nm light. We demonstrate the implementation of these acid-base complexes as a neat resin system that comprises orthogonal polymerization reactions (free-radical methacrylate polymerization and epoxy-acid polymerization reactions), which yields high-strength network polymer materials.
{"title":"Solventless, Rapid-polymerizable Liquid Resins from Solid Carboxylic Acids through Low-viscosity Acid/Base Complexes","authors":"Grant M Musgrave, Eden Y Yau, Huang Sijia, Caleb Reese, Chen Wang","doi":"10.1039/d4ta05417b","DOIUrl":"https://doi.org/10.1039/d4ta05417b","url":null,"abstract":"Bio-based carboxylic acids are some of the most available renewable chemicals, but since they are solids with high melting temperatures, they cannot be directly used as liquid resins. To this end, we report the formation of supramolecular complexes between an amino methacrylate and various solid carboxylic acids. The ionically bonded methacrylates exhibit low viscosities and rapid reaction kinetics for free-radical mediated polymerization, showing quantitative methacrylate conversions within one minute of irradiation at 5 mW/cm2 405nm light. We demonstrate the implementation of these acid-base complexes as a neat resin system that comprises orthogonal polymerization reactions (free-radical methacrylate polymerization and epoxy-acid polymerization reactions), which yields high-strength network polymer materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"18 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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