Long Yang, Ramesh Poonchi Sivasankaran, Mee Kyung Song, Amol Uttam Pawar, Don Keun Lee, Young Soo Kang
Photocatalytic (PC) CO2 reduction reaction (CO2RR) into value-added oxygenated products is one of the most promising ways of solving climate warming change and energy crisis simultaneously. To reach higher selectivity and productivity of fuel products, it still remains great challenge in controlling both simultaneous sequential multi-electron/proton shuttling through different transporting pathway, which determines the intermediates and final products. Consequently, a multifunctional nickel-perylene-carbon nitride nanosheet (NS-P-g-C3N4-Ni) are constructed rationally to strengthen the electron and proton transfer via different pathway at the same time through molecule-level carbon backbone with excellent conductivity/charge capacity and proton transport via pendant functional group of -NH2 from water oxidation sites of Ni metal cluster on perylene skeleton. CO2 adsorption is enhanced and reduction energy is reduced by the complexation of N-atom site of NS-P-g-C3N4-Ni and adjustment of co-planarity, optimizing conduction band and band gap with energy controllable techniques. In situ FT-IR/Raman/EPR spectra identified and verified the transformation of active intermediates (*CO2•−, *COOH and H*COO−) adsorbed on the NS-P-g-C3N4-Ni by complexation and highly selective production of formic acid (60%) is achieved. This work sheds light on the construction of effective well-structured sites in photocatalytic CO2 reduction to produce value-added products with higher selectivity and productivity.
光催化（PC）将二氧化碳还原反应（CO2RR）转化为高附加值含氧产品，是同时解决气候变暖和能源危机的最有前途的方法之一。为了获得更高的燃料产品选择性和生产率，控制多电子/质子通过不同传输途径的同时顺序穿梭仍是一项巨大挑战，这决定了中间产物和最终产品。因此，我们合理地构建了一种多功能过烯碳氮化镍纳米片（NS-P-g-C3N4-Ni），通过分子级碳骨架加强电子和质子同时通过不同途径的传输，具有优异的导电性/电荷容量，并通过过烯骨架上镍金属簇的水氧化位点的-NH2悬垂官能团进行质子传输。通过络合 NS-P-g-C3N4-Ni 的 N 原子位点和调整共平面度，提高了对 CO2 的吸附能力并降低了还原能，利用能量可控技术优化了导带和带隙。原位 FT-IR/Raman/EPR 光谱确定并验证了吸附在 NS-P-g-C3N4-Ni 上的活性中间体（*CO2--、*COOH 和 H*COO--）通过络合发生了转变，并实现了甲酸（60%）的高选择性生产。这项工作揭示了如何在光催化二氧化碳还原过程中构建有效的结构良好的位点，以生产具有更高选择性和生产率的增值产品。
{"title":"Highly Selective Solar CO2 Conversion into Formic Acid in Nickel-Perylene-C3N4 Semiconductor Photocatalyst","authors":"Long Yang, Ramesh Poonchi Sivasankaran, Mee Kyung Song, Amol Uttam Pawar, Don Keun Lee, Young Soo Kang","doi":"10.1002/aenm.202402798","DOIUrl":"https://doi.org/10.1002/aenm.202402798","url":null,"abstract":"Photocatalytic (PC) CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) into value-added oxygenated products is one of the most promising ways of solving climate warming change and energy crisis simultaneously. To reach higher selectivity and productivity of fuel products, it still remains great challenge in controlling both simultaneous sequential multi-electron/proton shuttling through different transporting pathway, which determines the intermediates and final products. Consequently, a multifunctional nickel-perylene-carbon nitride nanosheet (NS-P-g-C<sub>3</sub>N<sub>4</sub>-Ni) are constructed rationally to strengthen the electron and proton transfer via different pathway at the same time through molecule-level carbon backbone with excellent conductivity/charge capacity and proton transport via pendant functional group of -NH<sub>2</sub> from water oxidation sites of Ni metal cluster on perylene skeleton. CO<sub>2</sub> adsorption is enhanced and reduction energy is reduced by the complexation of N-atom site of NS-P-g-C<sub>3</sub>N<sub>4</sub>-Ni and adjustment of co-planarity, optimizing conduction band and band gap with energy controllable techniques. In situ FT-IR/Raman/EPR spectra identified and verified the transformation of active intermediates (<sup>*</sup>CO<sub>2</sub><sup>•−</sup>, <sup>*</sup>COOH and H<sup>*</sup>COO<sup>−</sup>) adsorbed on the NS-P-g-C<sub>3</sub>N<sub>4</sub>-Ni by complexation and highly selective production of formic acid (60%) is achieved. This work sheds light on the construction of effective well-structured sites in photocatalytic CO<sub>2</sub> reduction to produce value-added products with higher selectivity and productivity.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142171471","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 binder's choice holds immense significance in the quest for robust electrochemical performances of lithium/sodium-ion battery's (LIB/SIB) electrodes. Conventional PVDF binder is a passive polymer lacking the ability to transport Li+/Na+ and facilitate ion kinetics. This limitation poses constraints in achieving high specific capacity, fast charging, and long cycle life. Herein, a novel water-soluble concentrated imidazolium functionalized poly(ionic liquid), poly(oxycarbonylmethylene 1-allyl-3-methyimidazolium) (PMAI) is synthesized, and evaluated it as binder in LIB/SIB. PMAI-based anodic-half cell exhibits excellent electrochemical performance, achieving higher capacities (297 mAhg−1 at 1C for LIBs and 250 mAhg−1 at 60 mAg−1 for SIBs) and good cycle stability (80 % capacity retention after 750 cycles for LIBs; 96% capacity retention after 200 cycles for SIBs), compared to PVDF binder. In addition, PMAI/Gr delivers a higher discharge capacity of 85 mAhg−1 than PVDF/Gr with 47 mAhg−1 at 5C. PMAI-containing electrodes show better rate capability at different current densities than PVDF binder in LIB/SIB. The enhanced ion diffusion coefficient, lower resistance and decreased activation energy of desolvation, are ascribed to densely polar ionic liquid groups along the polymer and formation of a functionalized SEI via binder reduction. The novel PMAI binder's design and full-cell examination confirm its potential in secondary-ion battery applications.
{"title":"Densely Imidazolium Functionalized Water Soluble Poly(Ionic Liquid) Binder for Enhanced Performance of Carbon Anode in Lithium/Sodium-Ion Batteries","authors":"Amarshi Patra, Noriyoshi Matsumi","doi":"10.1002/aenm.202403071","DOIUrl":"https://doi.org/10.1002/aenm.202403071","url":null,"abstract":"The binder's choice holds immense significance in the quest for robust electrochemical performances of lithium/sodium-ion battery's (LIB/SIB) electrodes. Conventional PVDF binder is a passive polymer lacking the ability to transport Li<sup>+</sup>/Na<sup>+</sup> and facilitate ion kinetics. This limitation poses constraints in achieving high specific capacity, fast charging, and long cycle life. Herein, a novel water-soluble concentrated imidazolium functionalized poly(ionic liquid), poly(oxycarbonylmethylene 1-allyl-3-methyimidazolium) (PMAI) is synthesized, and evaluated it as binder in LIB/SIB. PMAI-based anodic-half cell exhibits excellent electrochemical performance, achieving higher capacities (297 mAhg<sup>−1</sup> at 1C for LIBs and 250 mAhg<sup>−1</sup> at 60 mAg<sup>−1</sup> for SIBs) and good cycle stability (80 % capacity retention after 750 cycles for LIBs; 96% capacity retention after 200 cycles for SIBs), compared to PVDF binder. In addition, PMAI/Gr delivers a higher discharge capacity of 85 mAhg<sup>−1</sup> than PVDF/Gr with 47 mAhg<sup>−1</sup> at 5C. PMAI-containing electrodes show better rate capability at different current densities than PVDF binder in LIB/SIB. The enhanced ion diffusion coefficient, lower resistance and decreased activation energy of desolvation, are ascribed to densely polar ionic liquid groups along the polymer and formation of a functionalized SEI via binder reduction. The novel PMAI binder's design and full-cell examination confirm its potential in secondary-ion battery applications.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142171472","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}
Constructing an all-in-one wearable electronic system integrated with an energy-harvesting, an energy-storing, and a working unit can fundamentally solve the problems of sustainable energy supply, miniaturization, and lightweight for further commercialization. Here, an all-in-one wearable system consisting of solar cell, cathode-free zinc ion micro-battery (ZIMB) and piezoresistive pressure sensor is proposed, achieving an ultralong and stable power supply. Under the action of photocurrent, this integrated system is stimulated to in situ generate MnO2 on the initial cathode-free substrate, meanwhile converts into chemical energy for powering the sensor, which eliminates prepreparation and treatment of the cathode for energy storage units. The facial cathode-free ZIMB combining the all-in-one design enhances matching degree between different units and improves the integration. The working mechanism of the cathode-free ZIMB is analyzed systematically through multiple ex situ characterizations and density functional theory (DFT) simulation. And the integrated sensing system illuminating for 12.0 h realizes the ultralong energy supply of the pressure sensor up to 150 000 cycles. As a concept, the integrated wearable electronic is used to detect human physiological signals, showcasing potential applications in activity monitoring, intelligent robotics, human–computer interaction, and other related fields.
{"title":"Cathode-Free Aqueous Micro-battery for an All-in-One Wearable System with Ultralong Stability","authors":"Tao Huang, Bowen Gao, Mingfeng Li, Xin Zhou, Wenbin He, Jinfeng Yan, Xiao Luo, Wei Lai, Jian Li, Shijun Luo, Yang Yue, Yanan Ma, Yihua Gao","doi":"10.1002/aenm.202402871","DOIUrl":"https://doi.org/10.1002/aenm.202402871","url":null,"abstract":"Constructing an all-in-one wearable electronic system integrated with an energy-harvesting, an energy-storing, and a working unit can fundamentally solve the problems of sustainable energy supply, miniaturization, and lightweight for further commercialization. Here, an all-in-one wearable system consisting of solar cell, cathode-free zinc ion micro-battery (ZIMB) and piezoresistive pressure sensor is proposed, achieving an ultralong and stable power supply. Under the action of photocurrent, this integrated system is stimulated to in situ generate MnO<sub>2</sub> on the initial cathode-free substrate, meanwhile converts into chemical energy for powering the sensor, which eliminates prepreparation and treatment of the cathode for energy storage units. The facial cathode-free ZIMB combining the all-in-one design enhances matching degree between different units and improves the integration. The working mechanism of the cathode-free ZIMB is analyzed systematically through multiple ex situ characterizations and density functional theory (DFT) simulation. And the integrated sensing system illuminating for 12.0 h realizes the ultralong energy supply of the pressure sensor up to 150 000 cycles. As a concept, the integrated wearable electronic is used to detect human physiological signals, showcasing potential applications in activity monitoring, intelligent robotics, human–computer interaction, and other related fields.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142171142","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}
Xuemin Wang, Ming Liu, Na Li, Zhigang Li, Cui Zhang, Shuangxi Liu
Monitoring the dynamic behavior of active species and modulating their electronic architecture are crucial for the development of efficient catalysts. Here, a 3D ordered multi-level porous Ni2P/CeO2 heterojunction catalyst with a “self-optimization effect” is strategically synthesized for efficient oxygen evolution reaction (OER). This catalyst exhibits a low overpotential of 235 mV at 20 mA cm−2 in 1.0 m KOH. During the OER process, the heterojunction catalyst specifically undergoes a unique phase transition involving the leaching of the P element, which triggers the formation of the PO43−-NiOOH/CeO2 catalyst with PO43− adsorbed on the surface of the reconstructed product NiOOH/CeO2. Density functional theory calculations reveal that the CeO2 and adsorbed-PO43− in the self-optimized structure are essential and minor factors for enhancing catalytic activity, respectively. They collaborate to promote the redistribution of electron density in surface Ni and O, increasing the d/p-band center difference. This phenomenon results in optimized adsorption/desorption of the key intermediates such as *OOH and improved catalytic performance. Overall, this research highlights the potential of d/p-band modulation for the rational design of cost-effective and high-efficiency electrocatalysts.
监测活性物种的动态行为并调节其电子结构对于开发高效催化剂至关重要。本文战略性地合成了一种具有 "自我优化效应 "的三维有序多孔 Ni2P/CeO2 异质结催化剂，用于高效氧进化反应（OER）。这种催化剂在 1.0 m KOH 中 20 mA cm-2 的过电位很低，仅为 235 mV。在 OER 过程中，异质结催化剂经历了一个独特的相变过程，其中涉及 P 元素的浸出，这引发了 PO43--NiOOH/CeO2 催化剂的形成，PO43- 吸附在重构产物 NiOOH/CeO2 的表面。密度泛函理论计算表明，自我优化结构中的 CeO2 和吸附的 PO43- 分别是提高催化活性的关键和次要因素。它们共同促进了表面 Ni 和 O 中电子密度的重新分布，增加了 d/p 带中心差。这一现象优化了*OOH 等关键中间产物的吸附/解吸，提高了催化性能。总之，这项研究凸显了 d/p 带调制在合理设计经济高效的电催化剂方面的潜力。
{"title":"Swelling the d/p-Band Center Difference Induced by Heterostructure Self-Optimization Engineering for Enhanced Water Oxidation","authors":"Xuemin Wang, Ming Liu, Na Li, Zhigang Li, Cui Zhang, Shuangxi Liu","doi":"10.1002/aenm.202402923","DOIUrl":"https://doi.org/10.1002/aenm.202402923","url":null,"abstract":"Monitoring the dynamic behavior of active species and modulating their electronic architecture are crucial for the development of efficient catalysts. Here, a 3D ordered multi-level porous Ni<sub>2</sub>P/CeO<sub>2</sub> heterojunction catalyst with a “self-optimization effect” is strategically synthesized for efficient oxygen evolution reaction (OER). This catalyst exhibits a low overpotential of 235 mV at 20 mA cm<sup>−2</sup> in 1.0 <span>m</span> KOH. During the OER process, the heterojunction catalyst specifically undergoes a unique phase transition involving the leaching of the P element, which triggers the formation of the PO<sub>4</sub><sup>3−</sup>-NiOOH/CeO<sub>2</sub> catalyst with PO<sub>4</sub><sup>3−</sup> adsorbed on the surface of the reconstructed product NiOOH/CeO<sub>2</sub>. Density functional theory calculations reveal that the CeO<sub>2</sub> and adsorbed-PO<sub>4</sub><sup>3−</sup> in the self-optimized structure are essential and minor factors for enhancing catalytic activity, respectively. They collaborate to promote the redistribution of electron density in surface Ni and O, increasing the <i>d</i>/<i>p</i>-band center difference. This phenomenon results in optimized adsorption/desorption of the key intermediates such as *OOH and improved catalytic performance. Overall, this research highlights the potential of <i>d</i>/<i>p</i>-band modulation for the rational design of cost-effective and high-efficiency electrocatalysts.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142171140","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}
Xuefeng Wang, Zijian Li, Haeseong Jang, Changsheng Chen, Shangguo Liu, Liu Wang, Min Gyu Kim, Jaephil Cho, Qing Qin, Xien Liu
Ruthenium Dioxide (RuO2), as one of the most promising alternatives to IrO2, suffers from the severe dissolution and overoxidation of Ru active sites during the acidic oxygen evolution reaction (OER), which hinders its practical application. Herein, the study constructs a short-range ordered tantalum single atoms-doped RuO2 catalyst (Ta-RuO2) with asymmetric Ru-O-Ta(-O-Ta) active units for the enhanced acidic OER. The Ta-RuO2 catalyst exhibits superior catalytic activity with an overpotential of 201 mV at 10 mA cm−2 and a long-lasting stability of 280 h. Physical characterizations combined with electrochemical tests reveal that the incorporation of atomically arranged Ta atoms induces significant tensile strain, effectively optimizing the adsorption strength of oxygen-containing intermediates by regulating the Ru d-band center and weakening the Ru-O covalency, thus boosting the catalytic activity. Furthermore, the formed Ru-O-Ta(-O-Ta) active local structure is well maintained during the OER process owing to the synergy of strong corrosion resistance of Ta-O bonds and the electron transfers from Ta to Ru via oxygen bridge stabilizing the Ru sites, contributing to the enhanced stability. This study provides a novel method via incorporation of corrosion-resistant and short-range ordered single atoms to significantly enhance the acidic OER stability and activity of cost-effective catalysts.
二氧化钌（RuO2）作为二氧化铱（IrO2）最有前途的替代品之一，在酸性氧进化反应（OER）过程中存在严重的 Ru 活性位点溶解和过氧化问题，阻碍了其实际应用。本研究构建了一种具有不对称 Ru-O-Ta(-O-Ta) 活性单元的短程有序掺杂钽单原子 RuO2 催化剂（Ta-RuO2），用于增强酸性 OER。物理表征结合电化学测试表明，原子排列整齐的 Ta 原子可产生显著的拉伸应变，通过调节 Ru d 带中心和削弱 Ru-O 共价，有效优化含氧中间产物的吸附强度，从而提高催化活性。此外，在 OER 过程中，由于 Ta-O 键具有很强的耐腐蚀性，而电子通过氧桥从 Ta 转移到 Ru 又稳定了 Ru 位点，因此形成的 Ru-O-Ta(-O-Ta) 活性局部结构得以很好地保持，从而提高了稳定性。这项研究提供了一种新方法，即通过加入抗腐蚀和短程有序单原子来显著提高具有成本效益的催化剂的酸性 OER 稳定性和活性。
{"title":"RuO2 with Short-Range Ordered Tantalum Single Atoms for Enhanced Acidic Oxygen Evolution Reaction","authors":"Xuefeng Wang, Zijian Li, Haeseong Jang, Changsheng Chen, Shangguo Liu, Liu Wang, Min Gyu Kim, Jaephil Cho, Qing Qin, Xien Liu","doi":"10.1002/aenm.202403388","DOIUrl":"https://doi.org/10.1002/aenm.202403388","url":null,"abstract":"Ruthenium Dioxide (RuO<sub>2</sub>), as one of the most promising alternatives to IrO<sub>2</sub>, suffers from the severe dissolution and overoxidation of Ru active sites during the acidic oxygen evolution reaction (OER), which hinders its practical application. Herein, the study constructs a short-range ordered tantalum single atoms-doped RuO<sub>2</sub> catalyst (Ta-RuO<sub>2</sub>) with asymmetric Ru-O-Ta(-O-Ta) active units for the enhanced acidic OER. The Ta-RuO<sub>2</sub> catalyst exhibits superior catalytic activity with an overpotential of 201 mV at 10 mA cm<sup>−2</sup> and a long-lasting stability of 280 h. Physical characterizations combined with electrochemical tests reveal that the incorporation of atomically arranged Ta atoms induces significant tensile strain, effectively optimizing the adsorption strength of oxygen-containing intermediates by regulating the Ru <i>d</i>-band center and weakening the Ru-O covalency, thus boosting the catalytic activity. Furthermore, the formed Ru-O-Ta(-O-Ta) active local structure is well maintained during the OER process owing to the synergy of strong corrosion resistance of Ta-O bonds and the electron transfers from Ta to Ru via oxygen bridge stabilizing the Ru sites, contributing to the enhanced stability. This study provides a novel method via incorporation of corrosion-resistant and short-range ordered single atoms to significantly enhance the acidic OER stability and activity of cost-effective catalysts.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142171480","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}
Ye Yuan, Genghua Yan, Chris Dreessen, Thomas Kirchartz
Transient photoluminescence is a frequently used method in the field of halide perovskite photovoltaics to quantify recombination by determining the characteristic decay time of an exponential decay. This decay time is often considered to be a single value for a certain perovskite film. However, there are many mechanisms that lead to non-exponential decays. Here, it is shown that photoluminescence decays in many lead-halide perovskites are non-exponential and follow a power-law relation between PL intensity and time that is caused by shallow defects. Decay times therefore vary continuously as a function of time and injection level. In situations where recombination is bimolecular and decays follow a power law, the differential decay time equals the time delay after the laser pulse for long time delays and therefore completely lacks quantitative information about the recombination rate. Quantifying recombination using transient PL measurements, therefore, requires analyzing the lifetime as a function of injection level rather than time. As an alternative to the continuously varying decay time, a bimolecular recombination coefficient can also be determined, which correlates with the photoluminescence quantum efficiency. Finally, the influence of the repetition rate and the background subtraction method on the analysis of power-law type PL decays is discussed.
{"title":"Understanding Power-Law Photoluminescence Decays and Bimolecular Recombination in Lead-Halide Perovskites","authors":"Ye Yuan, Genghua Yan, Chris Dreessen, Thomas Kirchartz","doi":"10.1002/aenm.202403279","DOIUrl":"https://doi.org/10.1002/aenm.202403279","url":null,"abstract":"Transient photoluminescence is a frequently used method in the field of halide perovskite photovoltaics to quantify recombination by determining the characteristic decay time of an exponential decay. This decay time is often considered to be a single value for a certain perovskite film. However, there are many mechanisms that lead to non-exponential decays. Here, it is shown that photoluminescence decays in many lead-halide perovskites are non-exponential and follow a power-law relation between PL intensity and time that is caused by shallow defects. Decay times therefore vary continuously as a function of time and injection level. In situations where recombination is bimolecular and decays follow a power law, the differential decay time equals the time delay after the laser pulse for long time delays and therefore completely lacks quantitative information about the recombination rate. Quantifying recombination using transient PL measurements, therefore, requires analyzing the lifetime as a function of injection level rather than time. As an alternative to the continuously varying decay time, a bimolecular recombination coefficient can also be determined, which correlates with the photoluminescence quantum efficiency. Finally, the influence of the repetition rate and the background subtraction method on the analysis of power-law type PL decays is discussed.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166628","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}
Hongmin Liu, Xinran Gao, Yitao Lou, Hua Kun Liu, Shi Xue Dou, Zhongchao Bai, Nana Wang
Solar rechargeable batteries (SRBs), as an emerging technology for harnessing solar energy, integrate the advantages of photochemical devices and redox batteries to synergistically couple dual-functional materials capable of both light harvesting and redox activity. This enables direct solar-to-electrochemical energy storage within a single system. However, the mismatch in energy levels between coupled photochemical storage materials (PSMs) and the occurrence of side reactions with liquid electrolytes during charge-discharge cycles lead to a decrease in solar energy conversion efficiency. This impedes the advancement of SRBs. This review comprehensively discusses of the latest advancements in PSMs, which are crucial for designing advanced SRBs. It delves into an extensive discussion of the design criteria for dual-functional photochemical storage cathodes (PSCs) and elucidates the operational mechanism of SRBs. Additionally, it further discusses the performance, efficiency, and long-term cycle stability of SRBs in relation to photoelectronic and photothermal mechanisms. Finally, an outlook on primary challenges and prospects that SRBs will encounter is provided to offer novel insights for their technological advancement.
{"title":"Coupled Photochemical Storage Materials in Solar Rechargeable Batteries: Progress, Challenges, and Prospects","authors":"Hongmin Liu, Xinran Gao, Yitao Lou, Hua Kun Liu, Shi Xue Dou, Zhongchao Bai, Nana Wang","doi":"10.1002/aenm.202402381","DOIUrl":"https://doi.org/10.1002/aenm.202402381","url":null,"abstract":"Solar rechargeable batteries (SRBs), as an emerging technology for harnessing solar energy, integrate the advantages of photochemical devices and redox batteries to synergistically couple dual-functional materials capable of both light harvesting and redox activity. This enables direct solar-to-electrochemical energy storage within a single system. However, the mismatch in energy levels between coupled photochemical storage materials (PSMs) and the occurrence of side reactions with liquid electrolytes during charge-discharge cycles lead to a decrease in solar energy conversion efficiency. This impedes the advancement of SRBs. This review comprehensively discusses of the latest advancements in PSMs, which are crucial for designing advanced SRBs. It delves into an extensive discussion of the design criteria for dual-functional photochemical storage cathodes (PSCs) and elucidates the operational mechanism of SRBs. Additionally, it further discusses the performance, efficiency, and long-term cycle stability of SRBs in relation to photoelectronic and photothermal mechanisms. Finally, an outlook on primary challenges and prospects that SRBs will encounter is provided to offer novel insights for their technological advancement.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166619","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 activation of lattice oxygen oxidation mechanism (LOM) will endow iridium-based electrocatalysts with desired acid-available water oxidation activity, compared to the conventional adsorbate evolution mechanism (AEM). However, the inherent symmetric [IrO6] octahedra of commercial Ir-based catalysts generally thermodynamically favor the AEM pathway contributing to the moderate water oxidation performance. Here, based on typical layered Ca2IrO4 (CIO) modeled materials, the d-orbitals electron repulsion strategy is demonstrated, via constructing asymmetrically polarized Ir‒O‒Ru configuration in Ru-CIO, to effectively activate the lattice oxygen participating in water oxidation process for decent oxygen-related electrocatalytic activity. Specifically, a great increase of ≈700-fold and ≈170-fold in mass activity and turnover frequency, respectively, has been realized for the optimal Ru-CIO electrocatalyst in an acid medium relative to the commercial IrO2 electrocatalysts, where a small overpotential of only 175 mV is required for achieving 10 mA cmgeo‒2. In situ X-ray fine structure spectroscopies combined with in situ 18O- isotope-labeled differential electrochemical mass spectrometry analyses reveal that desirable LOM has been boosted by the activated lattice oxygen and the flexible Ir(3+δ)+ active sites of asymmetric [IrO6] octahedra, which results in superior OER kinetics for Ir-based oxide catalysts.
与传统的吸附剂进化机制（AEM）相比，激活晶格氧氧化机制（LOM）将赋予铱基电催化剂理想的酸性水氧化活性。然而，商用铱基催化剂固有的对称[IrO6]八面体通常在热力学上倾向于 AEM 途径，从而导致水氧化性能一般。本文以典型的层状 Ca2IrO4（CIO）模型材料为基础，通过在 Ru-CIO 中构建不对称极化的 Ir-O-Ru 构型，证明了 d 轨道电子排斥策略可有效激活参与水氧化过程的晶格氧，从而提高与氧相关的电催化活性。具体来说，与商用二氧化铱电催化剂相比，最佳 Ru-CIO 电催化剂在酸性介质中的质量活性和翻转频率分别提高了≈700 倍和≈170 倍。原位 X 射线精细结构光谱与原位 18O- 同位素标记的差分电化学质谱分析相结合，揭示了活化的晶格氧和不对称[IrO6]八面体的柔性 Ir(3+δ)+ 活性位点提高了理想的 LOM，从而为基于 Ir 的氧化物催化剂带来了卓越的 OER 动力学。
{"title":"Activating Lattice Oxygen Oxidation Mechanism in Asymmetric [IrO6] Octahedra of Ir-Based Oxides Toward Superior Acidic Electrochemical Water Oxidation","authors":"Yuying Liu, Ziyi Liu, Na Li, Chao Wang, Huijuan Wang, Qianqian Ji, Fengchun Hu, Hao Tan, Chaocheng Liu, Chenglong Liu, Zhi Li, Sihua Feng, Bing Tang, Ruiqi Liu, Liyang Lv, Weiren Cheng, Wensheng Yan","doi":"10.1002/aenm.202402902","DOIUrl":"https://doi.org/10.1002/aenm.202402902","url":null,"abstract":"The activation of lattice oxygen oxidation mechanism (LOM) will endow iridium-based electrocatalysts with desired acid-available water oxidation activity, compared to the conventional adsorbate evolution mechanism (AEM). However, the inherent symmetric [IrO<sub>6</sub>] octahedra of commercial Ir-based catalysts generally thermodynamically favor the AEM pathway contributing to the moderate water oxidation performance. Here, based on typical layered Ca<sub>2</sub>IrO<sub>4</sub> (CIO) modeled materials, the <i>d</i>-orbitals electron repulsion strategy is demonstrated, via constructing asymmetrically polarized Ir‒O‒Ru configuration in Ru-CIO, to effectively activate the lattice oxygen participating in water oxidation process for decent oxygen-related electrocatalytic activity. Specifically, a great increase of ≈700-fold and ≈170-fold in mass activity and turnover frequency, respectively, has been realized for the optimal Ru-CIO electrocatalyst in an acid medium relative to the commercial IrO<sub>2</sub> electrocatalysts, where a small overpotential of only 175 mV is required for achieving 10 mA cm<sub>geo</sub><sup>‒2</sup>. In situ X-ray fine structure spectroscopies combined with in situ <sup>18</sup>O- isotope-labeled differential electrochemical mass spectrometry analyses reveal that desirable LOM has been boosted by the activated lattice oxygen and the flexible Ir<sup>(3+δ)+</sup> active sites of asymmetric [IrO<sub>6</sub>] octahedra, which results in superior OER kinetics for Ir-based oxide catalysts.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166650","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}
Xu Gao, Biao Li, Gwenaëlle Rousse, Anatolii V. Morozov, Michaël Deschamps, Erik Elkaïm, Leiting Zhang, Kurt Kummer, Artem M. Abakumov, Jean-Marie Tarascon
Creating high-energy-density cathodes is crucial for building next-generation lithium-ion batteries. However, materials exploration along two main directions, namely Li-rich or Ni-rich oxides, has encountered bottlenecks. To get rid of the impasse, here a “Li-rich Ni-rich” route is consolidated by designing a new family of Li1+yNi(3-5y)/3W2y/3O2 oxides with high-voltage cycling stability up to 4.5 V and high capacities over 230 mAh g−1. It is discovered that W6+ is largely incorporated into the LiNiO2 lattice, forming W/Ni(Li) inverse honeycomb-ordered nano-domains. These Li-rich domains enable reversible anionic redox, clearly demonstrated by X-ray absorption spectroscopy, resonant inelastic X-ray scattering, transmission electron microscopy, and nuclear magnetic resonance, which is linked to improved electrochemical performance. Furthermore, the incorporation of W6+ into the lattice proves to be the key to generating electrochemically active Li-rich domains irrespective of Li stoichiometry given that a similar local structure is found in W-substituted non-Li-rich oxides. This therefore implies the underestimated role of high-valence cations in tuning the structure and electrochemistry of Ni-rich oxides. These results underline the necessity of a Li-rich composition in the request for reversible high capacity, reinforcing the promise of a “Li-rich Ni-rich” avenue for developing advanced cathodes.
创造高能量密度阴极对于制造下一代锂离子电池至关重要。然而，沿着富锂或富镍氧化物这两个主要方向进行的材料探索遇到了瓶颈。为了摆脱这一僵局，本文通过设计一系列新的 Li1+yNi(3-5y)/3W2y/3O2 氧化物，巩固了 "富锂-富镍 "路线，这些氧化物具有高达 4.5 V 的高压循环稳定性和超过 230 mAh g-1 的高容量。研究发现，W6+在很大程度上融入了 LiNiO2 晶格，形成了 W/Ni(Li)反蜂巢有序纳米域。X 射线吸收光谱、共振非弹性 X 射线散射、透射电子显微镜和核磁共振都清楚地表明，这些富含锂的结构域能够实现可逆的阴离子氧化还原，这与电化学性能的改善息息相关。此外，鉴于在 W 取代的非富锂氧化物中也发现了类似的局部结构，因此无论锂的化学计量如何，W6+ 加入晶格都被证明是产生电化学活性富锂畴的关键。因此，这意味着高价阳离子在调整富镍氧化物结构和电化学方面的作用被低估了。这些结果凸显了富锂离子成分在实现可逆高容量方面的必要性，加强了开发先进阴极的 "富锂镍 "途径的前景。
{"title":"Achieving High-Voltage Stability in Li-Rich Ni-Rich Oxides with Local W/Ni(Li) Superstructure","authors":"Xu Gao, Biao Li, Gwenaëlle Rousse, Anatolii V. Morozov, Michaël Deschamps, Erik Elkaïm, Leiting Zhang, Kurt Kummer, Artem M. Abakumov, Jean-Marie Tarascon","doi":"10.1002/aenm.202402793","DOIUrl":"https://doi.org/10.1002/aenm.202402793","url":null,"abstract":"Creating high-energy-density cathodes is crucial for building next-generation lithium-ion batteries. However, materials exploration along two main directions, namely Li-rich or Ni-rich oxides, has encountered bottlenecks. To get rid of the impasse, here a “Li-rich Ni-rich” route is consolidated by designing a new family of Li<sub>1+</sub><i><sub>y</sub></i>Ni<sub>(3-5</sub><i><sub>y</sub></i><sub>)/3</sub>W<sub>2</sub><i><sub>y</sub></i><sub>/3</sub>O<sub>2</sub> oxides with high-voltage cycling stability up to 4.5 V and high capacities over 230 mAh g<sup>−1</sup>. It is discovered that W<sup>6+</sup> is largely incorporated into the LiNiO<sub>2</sub> lattice, forming W/Ni(Li) inverse honeycomb-ordered nano-domains. These Li-rich domains enable reversible anionic redox, clearly demonstrated by X-ray absorption spectroscopy, resonant inelastic X-ray scattering, transmission electron microscopy, and nuclear magnetic resonance, which is linked to improved electrochemical performance. Furthermore, the incorporation of W<sup>6+</sup> into the lattice proves to be the key to generating electrochemically active Li-rich domains irrespective of Li stoichiometry given that a similar local structure is found in W-substituted non-Li-rich oxides. This therefore implies the underestimated role of high-valence cations in tuning the structure and electrochemistry of Ni-rich oxides. These results underline the necessity of a Li-rich composition in the request for reversible high capacity, reinforcing the promise of a “Li-rich Ni-rich” avenue for developing advanced cathodes.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142161169","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}
Yayu Guo, Kai Liu, Cheng Li, Dawei Song, Hongzhou Zhang, Zhenyu Wang, Yufen Yan, Lianqi Zhang, Sheng Dai
Sulfide-based superionic conductors present great promise to achieve high energy density and safety for all-solid-state sodium batteries (ASSSBs). However, the poor electrolyte/electrode interface compatibility and humid air stability seriously hinder their deployment in ASSSBs. Herein, a series of high-performance Na3-□Sb1-4x(SnWCaTi)xS4 sulfide-based solid electrolytes (SSEs) are reported by coupling the vacancy effect with configurational entropy, which displays an excellent interface stability against sodium metal and an extraordinary tolerance toward the moist atmosphere, even for water. The optimized electrolyte effectively inhibits the detrimental mixed ion-electron conducting interphase formation, achieving the ultra-stable operation of Na–Na symmetric cell up to 1000 h. Furthermore, the Na+ diffusion kinetics is obviously enhanced by increasing the Na sites local anisotropy and Na vacancies. Eventually, the assembled TiS2//Na5Sn ASSSBs deliver a remarkable reversible capacity of 211.6 mAh g−1 at 0.5C with a long-term cycling performance of 450 cycles at room temperature. More importantly, it achieves a steady running up to 100 cycles at 1C even if this electrolyte is placed in the air with a dew temperature of 13.8 °C for 30 min, the highest values in the state-of-the-art sulfide-based ASSSBs. The well-designed SSEs open a new avenue for realizing the advanced and powerful ASSSBs.
硫化物基超离子导体在实现全固态钠电池（ASSSB）的高能量密度和安全性方面大有可为。然而，电解质/电极界面兼容性差以及在潮湿空气中的稳定性严重阻碍了它们在全固态钠电池中的应用。本文报告了一系列高性能 Na3-□Sb1-4x(SnWCaTi)xS4 硫化物基固体电解质（SSEs），该电解质将空位效应与构型熵耦合在一起，对金属钠具有极佳的界面稳定性，对潮湿空气具有超强的耐受性，甚至对水也是如此。此外，通过增加 Na 位点的局部各向异性和 Na 空位，Na+ 扩散动力学明显增强。最终，组装好的 TiS2/Na5Sn ASSSB 在 0.5C 温度下可提供 211.6 mAh g-1 的显著可逆容量，在室温下可长期循环 450 次。更重要的是，即使将这种电解质放在露水温度为 13.8 °C 的空气中 30 分钟，它也能在 1C 温度下稳定运行 100 个循环。精心设计的 SSE 为实现先进、功能强大的 ASSSB 开辟了一条新途径。
{"title":"A Sulfide-Based Solid Electrolyte With High Humid Air Tolerance for Long Lifespan All-Solid-State Sodium Batteries","authors":"Yayu Guo, Kai Liu, Cheng Li, Dawei Song, Hongzhou Zhang, Zhenyu Wang, Yufen Yan, Lianqi Zhang, Sheng Dai","doi":"10.1002/aenm.202401504","DOIUrl":"https://doi.org/10.1002/aenm.202401504","url":null,"abstract":"Sulfide-based superionic conductors present great promise to achieve high energy density and safety for all-solid-state sodium batteries (ASSSBs). However, the poor electrolyte/electrode interface compatibility and humid air stability seriously hinder their deployment in ASSSBs. Herein, a series of high-performance Na<sub>3-□</sub>Sb<sub>1-4x</sub>(SnWCaTi)<sub>x</sub>S<sub>4</sub> sulfide-based solid electrolytes (SSEs) are reported by coupling the vacancy effect with configurational entropy, which displays an excellent interface stability against sodium metal and an extraordinary tolerance toward the moist atmosphere, even for water. The optimized electrolyte effectively inhibits the detrimental mixed ion-electron conducting interphase formation, achieving the ultra-stable operation of Na–Na symmetric cell up to 1000 h. Furthermore, the Na<sup>+</sup> diffusion kinetics is obviously enhanced by increasing the Na sites local anisotropy and Na vacancies. Eventually, the assembled TiS<sub>2</sub>//Na<sub>5</sub>Sn ASSSBs deliver a remarkable reversible capacity of 211.6 mAh g<sup>−1</sup> at 0.5C with a long-term cycling performance of 450 cycles at room temperature. More importantly, it achieves a steady running up to 100 cycles at 1C even if this electrolyte is placed in the air with a dew temperature of 13.8 °C for 30 min, the highest values in the state-of-the-art sulfide-based ASSSBs. The well-designed SSEs open a new avenue for realizing the advanced and powerful ASSSBs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":null,"pages":null},"PeriodicalIF":27.8,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142161182","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：