Pub Date : 2025-03-17DOI: 10.1021/acsenergylett.5c00214
Shengnan Zhang, Leon Felix Mueller, Laurence Macray, Marnix Wagemaker, Lars J. Bannenberg, Swapna Ganapathy
Hybrid solid electrolytes (HSEs) leverage the benefits of their organic and inorganic components, yet optimizing ion transport and component compatibility requires a deeper understanding of their intricate ion transport mechanisms. Here, macroscopic charge transport is correlated with local lithium (Li)-ion diffusivity in HSEs, using poly(ethylene oxide) (PEO) as matrix and Li6PS5Cl as filler. Solvent- and dry-processing methods were evaluated for their morphological impact on Li-ion transport. Through multiscale solid-state nuclear magnetic resonance analysis, we reveal that the filler enhances local Li-ion diffusivity within the slow polymer segmental dynamics. Phase transitions indicate inhibited crystallization in HSEs, with reduced Li-ion diffusion barriers attributed to enhanced segmental motion and conductive polymer conformations. Relaxometry measurements identify a mobile component unique to the hybrid system at low temperatures, indicating Li-ion transport along polymer–filler interfaces. Comparative analysis shows solvent-processed HSEs exhibit better morphological uniformity and enhanced compatibility with Li-metal anodes via an inorganic-rich solid electrolyte interphase.
{"title":"Revealing Local Diffusion Dynamics in Hybrid Solid Electrolytes","authors":"Shengnan Zhang, Leon Felix Mueller, Laurence Macray, Marnix Wagemaker, Lars J. Bannenberg, Swapna Ganapathy","doi":"10.1021/acsenergylett.5c00214","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00214","url":null,"abstract":"Hybrid solid electrolytes (HSEs) leverage the benefits of their organic and inorganic components, yet optimizing ion transport and component compatibility requires a deeper understanding of their intricate ion transport mechanisms. Here, macroscopic charge transport is correlated with local lithium (Li)-ion diffusivity in HSEs, using poly(ethylene oxide) (PEO) as matrix and Li<sub>6</sub>PS<sub>5</sub>Cl as filler. Solvent- and dry-processing methods were evaluated for their morphological impact on Li-ion transport. Through multiscale solid-state nuclear magnetic resonance analysis, we reveal that the filler enhances local Li-ion diffusivity within the slow polymer segmental dynamics. Phase transitions indicate inhibited crystallization in HSEs, with reduced Li-ion diffusion barriers attributed to enhanced segmental motion and conductive polymer conformations. Relaxometry measurements identify a mobile component unique to the hybrid system at low temperatures, indicating Li-ion transport along polymer–filler interfaces. Comparative analysis shows solvent-processed HSEs exhibit better morphological uniformity and enhanced compatibility with Li-metal anodes via an inorganic-rich solid electrolyte interphase.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"33 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-17DOI: 10.1021/acsenergylett.5c00307
Lijie Wang, Yue Liu, Jie Yang, Xiangming Xu, Bingyao Shao, Hongwei Zhu, Haiting Cai, Tulai Sun, Jun Yin, Husam N. Alshareef, Osman M. Bakr, Yihan Zhu, Omar F. Mohammed
Two-dimensional (2D) materials hold great promise for next-generation optoelectronic devices, with photogenerated charge carrier transport being critical to their performance. However, the influence of photoexcitation-induced commensurate lattice thermal effects on surface charge carrier dynamics is poorly understood. Traditional photon-pump/photon-probe methods have constraints in capturing the subtle yet critical surface dynamics, especially for these ultrathin materials due to challenges in spatial resolution and penetration depth. In this study, we utilized scanning ultrafast electron microscopy (SUEM), a technique that offers unparalleled sensitivity to surface phenomena that are entirely inaccessible through other methods. Our findings reveal a ∼1.4% negative thermal expansion at elevated temperatures, inducing internal strain that modifies the electronic structure and significantly enhances surface carrier transport, resulting in an order-of-magnitude improvement in photodetection performance. Moreover, we demonstrate that photoinduced charge carrier diffusion occurs predominantly within the first tens of picoseconds after photoexcitation, a regime characterized by thermal excitation resulting from carrier–phonon interactions. These results establish a direct link among lattice thermal expansion, carrier dynamics, and optoelectronic performance.
{"title":"Lattice Expansion Enables Large Surface Carrier Diffusion in WS2 Monolayer","authors":"Lijie Wang, Yue Liu, Jie Yang, Xiangming Xu, Bingyao Shao, Hongwei Zhu, Haiting Cai, Tulai Sun, Jun Yin, Husam N. Alshareef, Osman M. Bakr, Yihan Zhu, Omar F. Mohammed","doi":"10.1021/acsenergylett.5c00307","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00307","url":null,"abstract":"Two-dimensional (2D) materials hold great promise for next-generation optoelectronic devices, with photogenerated charge carrier transport being critical to their performance. However, the influence of photoexcitation-induced commensurate lattice thermal effects on surface charge carrier dynamics is poorly understood. Traditional photon-pump/photon-probe methods have constraints in capturing the subtle yet critical surface dynamics, especially for these ultrathin materials due to challenges in spatial resolution and penetration depth. In this study, we utilized scanning ultrafast electron microscopy (SUEM), a technique that offers unparalleled sensitivity to surface phenomena that are entirely inaccessible through other methods. Our findings reveal a ∼1.4% negative thermal expansion at elevated temperatures, inducing internal strain that modifies the electronic structure and significantly enhances surface carrier transport, resulting in an order-of-magnitude improvement in photodetection performance. Moreover, we demonstrate that photoinduced charge carrier diffusion occurs predominantly within the first tens of picoseconds after photoexcitation, a regime characterized by thermal excitation resulting from carrier–phonon interactions. These results establish a direct link among lattice thermal expansion, carrier dynamics, and optoelectronic performance.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"55 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635408","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}
Garnet-type Li6.75La3Zr1.75Ta0.25O12 (LLZTO) holds significant potential as a solid-state electrolyte (SSE) comprising promising features such as high Li+ conductivity, wide electrochemical stability window, and compatibility with Li-metal. However, air exposure forms a thick Li2CO3 passivation layer (∼50 nm), which hinders storage, handling, and interfacial performance, especially for LLZTO nanoparticles (NPs) with a high surface area. This study introduces a scalable, green sonication-assisted method to control the Li2CO3 layer thickness (<10 nm), which enhances air stability without compromising ionic conduction. In-situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) further reveals the carbonate formation mechanism under atmospheric conditions. Electrochemical tests in ceramic-in-polymer (CIP) and polymer-in-ceramic (PIC) composite polymer electrolytes (CPEs) confirm that regulated Li2CO3 does not degrade the performance of passivated-LLZTO. The chemical-free, green approach suggested in this work maintains electrochemical properties, which enables scalable use of LLZTO-based SSEs for next-generation Li-metal batteries.
{"title":"Green Strategy for Li2CO3 Regulation in Garnet-Type Solid-State Electrolytes via Acoustic Cavitation","authors":"Pavitra Srivastava, Behrouz Bazri, Dheeraj Kumar Maurya, Yuan-Ting Hung, Da-Hua Wei, Ru-Shi Liu","doi":"10.1021/acsenergylett.5c00368","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00368","url":null,"abstract":"Garnet-type Li<sub>6.75</sub>La<sub>3</sub>Zr<sub>1.75</sub>Ta<sub>0.25</sub>O<sub>12</sub> (LLZTO) holds significant potential as a solid-state electrolyte (SSE) comprising promising features such as high Li<sup>+</sup> conductivity, wide electrochemical stability window, and compatibility with Li-metal. However, air exposure forms a thick Li<sub>2</sub>CO<sub>3</sub> passivation layer (∼50 nm), which hinders storage, handling, and interfacial performance, especially for LLZTO nanoparticles (NPs) with a high surface area. This study introduces a scalable, green sonication-assisted method to control the Li<sub>2</sub>CO<sub>3</sub> layer thickness (<10 nm), which enhances air stability without compromising ionic conduction. <i>In-situ</i> ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) further reveals the carbonate formation mechanism under atmospheric conditions. Electrochemical tests in ceramic-in-polymer (CIP) and polymer-in-ceramic (PIC) composite polymer electrolytes (CPEs) confirm that regulated Li<sub>2</sub>CO<sub>3</sub> does not degrade the performance of passivated-LLZTO. The chemical-free, green approach suggested in this work maintains electrochemical properties, which enables scalable use of LLZTO-based SSEs for next-generation Li-metal batteries.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"20 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-17DOI: 10.1021/acsenergylett.5c00155
Sofía Chozas-Barrientos, Abhyuday Paliwal, Federico Ventosinos, Cristina Roldán-Carmona, Lidón Gil-Escrig, Vladimir Held, Perrine Carroy, Delfina Muñoz, Henk J. Bolink
The use of commercial, Czochralski-grown silicon wafers as bottom cells in two-terminal perovskite/silicon tandem configurations often leads to defects in the top perovskite absorber due to their rough surfaces, featuring μm-sized pyramids and saw damages. Most recombination junctions in two-terminal tandem cells employ high conductive indium tin oxide which increases the effect of local shunts in the top cell by connecting them. We use Suns–VOC with selective illumination and external quantum efficiency measurements to identify these shunts. Additionally, we show that a molecular recombination junction composed of an n-doped C60 layer and a p-doped conjugated arylamine layer alleviates the effect of the shunts in the top cell, which we attribute to the lower lateral conductivity of the organic layers. This enables us to prepare two-terminal tandem devices using fully evaporated top cells on Czochralski textured silicon heterojunction cells with VOCs of up to 1.84 V and efficiencies above 22%.
{"title":"Molecular Recombination Junction for Vacuum-Deposited Perovskite/Silicon Two-Terminal Tandem Solar Cells","authors":"Sofía Chozas-Barrientos, Abhyuday Paliwal, Federico Ventosinos, Cristina Roldán-Carmona, Lidón Gil-Escrig, Vladimir Held, Perrine Carroy, Delfina Muñoz, Henk J. Bolink","doi":"10.1021/acsenergylett.5c00155","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00155","url":null,"abstract":"The use of commercial, Czochralski-grown silicon wafers as bottom cells in two-terminal perovskite/silicon tandem configurations often leads to defects in the top perovskite absorber due to their rough surfaces, featuring μm-sized pyramids and saw damages. Most recombination junctions in two-terminal tandem cells employ high conductive indium tin oxide which increases the effect of local shunts in the top cell by connecting them. We use Suns–<i>V</i><sub>OC</sub> with selective illumination and external quantum efficiency measurements to identify these shunts. Additionally, we show that a molecular recombination junction composed of an n-doped C<sub>60</sub> layer and a p-doped conjugated arylamine layer alleviates the effect of the shunts in the top cell, which we attribute to the lower lateral conductivity of the organic layers. This enables us to prepare two-terminal tandem devices using fully evaporated top cells on Czochralski textured silicon heterojunction cells with <i>V</i><sub>OC</sub>s of up to 1.84 V and efficiencies above 22%.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"24 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635389","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}
Prussian blue analogs (PBAs) are widely applicable as cathode materials due to their straightforward synthesis procedures, low cost, and considerable theoretical capacity. However, structural defects and low tap density pose substantial challenges to their commercial application. Herein, we propose a recrystallization-driven strategy to synthesize monoclinic binary hexacyanoferrate (CFHCF) with high crystallinity and a remarkably high tap density of 0.992 g cm–3. Moreover, the detailed process of quasi-spherical morphology evolution and defect repair is systematically investigated during recrystallization. Furthermore, various in situ and ex situ techniques are employed to reveal the origin of the high specific capacity and the structural evolution mechanism. Additionally, the designed CFHCF//HC pouch cell demonstrates satisfactory capacity retention over 250 cycles and successfully powers a toy platform for flag raising and lowering. Notably, this recrystallization-driven strategy offers valuable insights into the synthesis and commercial applications of highly crystallized PBAs.
{"title":"Recrystallization-Driven Quasi-Spherical Prussian Blue Analogs with High Tap Density and Crystallinity for Sodium-Ion Batteries","authors":"Siwei Fan, Yun Gao, Yang Liu, Li Li, Lingling Zhang, Zhiming Zhou, Shu-Lei Chou, Xueting Liu, Yue Shen, Yunhui Huang, Yun Qiao","doi":"10.1021/acsenergylett.5c00080","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00080","url":null,"abstract":"Prussian blue analogs (PBAs) are widely applicable as cathode materials due to their straightforward synthesis procedures, low cost, and considerable theoretical capacity. However, structural defects and low tap density pose substantial challenges to their commercial application. Herein, we propose a recrystallization-driven strategy to synthesize monoclinic binary hexacyanoferrate (CFHCF) with high crystallinity and a remarkably high tap density of 0.992 g cm<sup>–3</sup>. Moreover, the detailed process of quasi-spherical morphology evolution and defect repair is systematically investigated during recrystallization. Furthermore, various in situ and ex situ techniques are employed to reveal the origin of the high specific capacity and the structural evolution mechanism. Additionally, the designed CFHCF//HC pouch cell demonstrates satisfactory capacity retention over 250 cycles and successfully powers a toy platform for flag raising and lowering. Notably, this recrystallization-driven strategy offers valuable insights into the synthesis and commercial applications of highly crystallized PBAs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"183 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635407","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-16DOI: 10.1021/acsenergylett.5c00580
Henry M. Woolley, Martin Lange, Elina Nazmutdinova, Nella M. Vargas-Barbosa
After the final version of the manuscript was published, we (the authors) realized that Figure 4F–I did not render properly and the shaded regions corresponding the standard deviations (noted in the caption) were not visible. The new figure is below and the original caption remains unchanged. This article has not yet been cited by other publications.
{"title":"Correction to “Toward High-Capacity Li–S Solid-State Batteries: The Role of Partial Ionic Transport in the Catholyte”","authors":"Henry M. Woolley, Martin Lange, Elina Nazmutdinova, Nella M. Vargas-Barbosa","doi":"10.1021/acsenergylett.5c00580","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00580","url":null,"abstract":"After the final version of the manuscript was published, we (the authors) realized that Figure 4F–I did not render properly and the shaded regions corresponding the standard deviations (noted in the caption) were not visible. The new figure is below and the original caption remains unchanged. This article has not yet been cited by other publications.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"22 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-16DOI: 10.1021/acsenergylett.4c03307
Chi Ma, Chuankai Fu, Sheng Chang, Xing Xu, Guangxiang Zhang, Ziwei Liu, Hua Huo, Lishuang Fan, Geping Yin, Yulin Ma
Reinforced security and temperature tolerance are key prerequisites for the practical application of lithium metal batteries (LMBs). Achieving an optimal balance between maintaining a stable interface at a high temperature and ensuring rapid ion transport under a low temperature remains a critical challenge. Herein, an all-climate nonflammable electrolyte comprised of triethyl phosphate (TEP), lithium bis((trifluoromethyl)sulfonyl) azide (LiTFSI), and lithium nitrate (LiNO3) is proposed. The strong interaction between NO3– and TEP broadens the melting point of the electrolyte to −91.5 °C. A well-regulated lithium-ion solvation structure with low desolvation energy contributes to the formation of a durable inorganic–organic hybrid solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI), thereby enhancing the interfacial compatibility significantly. Consequently, the LMBs with the optimized TEP-based electrolyte demonstrate remarkable electrochemical performance in a wide temperature range of −60∼100 °C. The valuable insights gained from this work can offer theoretical guidance for developing wide-temperature electrolytes and high-performance LMBs.
{"title":"All-Climate and Nonflammable Electrolyte with a Strong Anion–Solvent Interaction for High-Performance Lithium Metal Batteries","authors":"Chi Ma, Chuankai Fu, Sheng Chang, Xing Xu, Guangxiang Zhang, Ziwei Liu, Hua Huo, Lishuang Fan, Geping Yin, Yulin Ma","doi":"10.1021/acsenergylett.4c03307","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03307","url":null,"abstract":"Reinforced security and temperature tolerance are key prerequisites for the practical application of lithium metal batteries (LMBs). Achieving an optimal balance between maintaining a stable interface at a high temperature and ensuring rapid ion transport under a low temperature remains a critical challenge. Herein, an all-climate nonflammable electrolyte comprised of triethyl phosphate (TEP), lithium bis((trifluoromethyl)sulfonyl) azide (LiTFSI), and lithium nitrate (LiNO<sub>3</sub>) is proposed. The strong interaction between NO<sub>3</sub><sup>–</sup> and TEP broadens the melting point of the electrolyte to −91.5 °C. A well-regulated lithium-ion solvation structure with low desolvation energy contributes to the formation of a durable inorganic–organic hybrid solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI), thereby enhancing the interfacial compatibility significantly. Consequently, the LMBs with the optimized TEP-based electrolyte demonstrate remarkable electrochemical performance in a wide temperature range of −60∼100 °C. The valuable insights gained from this work can offer theoretical guidance for developing wide-temperature electrolytes and high-performance LMBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"17 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635410","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-14DOI: 10.1021/acsenergylett.5c00631
Prashant V. Kamat
Figure 1. Rate constants (solid points) and theoretical fits (solid line) based on Marcus electron transfer expression. From ref (4). Copyright 2020 American Chemical Society. Figure 2. Examples of graphs showing causality between two variables. (A) Normalized incident photoconversion efficiency (IPCE) of 3D and 2D/3D perovskite solar cells in response to excitation wavelength. (B) The dependence of observed pseudo-first-order rate constant of biphenyl triplet decay (kobs) on the concentration of rubrene. From refs (5) and (6). Copyright 2022 and 2024 American Chemical Society. Figure 3. Examples of sample property comparison using (A) trend line and (B) column graph. Since there is neither correlation or causality between the two variables, the data is better presented using a column chart. From ref (8). Copyright 2024 American Chemical Society. I would like to thank Prof. Gregory H. Hartland for helpful discussions. This article references 8 other publications. This article has not yet been cited by other publications.
{"title":"Correlation, Causation and Comparison","authors":"Prashant V. Kamat","doi":"10.1021/acsenergylett.5c00631","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00631","url":null,"abstract":"Figure 1. Rate constants (solid points) and theoretical fits (solid line) based on Marcus electron transfer expression. From ref (4). Copyright 2020 American Chemical Society. Figure 2. Examples of graphs showing causality between two variables. (A) Normalized incident photoconversion efficiency (IPCE) of 3D and 2D/3D perovskite solar cells in response to excitation wavelength. (B) The dependence of observed pseudo-first-order rate constant of biphenyl triplet decay (<i>k</i><sub>obs</sub>) on the concentration of rubrene. From refs (5) and (6). Copyright 2022 and 2024 American Chemical Society. Figure 3. Examples of sample property comparison using (A) trend line and (B) column graph. Since there is neither correlation or causality between the two variables, the data is better presented using a column chart. From ref (8). Copyright 2024 American Chemical Society. I would like to thank Prof. Gregory H. Hartland for helpful discussions. This article references 8 other publications. This article has not yet been cited by other publications.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"18 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619061","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-14DOI: 10.1021/acsenergylett.5c00553
David Kumar Yesudoss, Bright Ngozichukwu, Ibrahima Gning, Balla D. Ngom, Abdoulaye Djire
This study explores the electrocatalytic nitrate reduction reaction (NO3–RR) using nitride-based two-dimensional Ti2NTx MXene (also known as MNene) synthesized via O2-assisted molten salt fluoride etching and its parent Ti2AlN MAX phase. Ti2NTx MNene achieved an ammonia (NH3) yield rate of ∼550 μmol h–1 g–1 with a Faradaic efficiency (FE) of ∼80%. Unexpectedly, the Ti2AlN MAX phase exhibited an even higher NH3 yield rate of ∼800 μmol h–1 g–1 at a comparable FE, despite its lower surface area and being traditionally considered a poor electrocatalyst. The enhanced performance of the MAX phase is likely due to −OH functionalization under alkaline conditions, leading to enhanced reaction kinetics. Postelectrolysis analyses, including Raman spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), confirmed no significant changes in crystallinity but indicated surface chemical changes. Control experiments with blank electrolytes and isotopically labelled 15NO3– substantiate that NH3 originates exclusively from nitrate reduction on the surface terminations. Time-resolved in situ spectroelectrochemical studies identified nitrite (NO2–) reduction to further intermediates as the rate-determining step. These findings not only challenge the conventional perception of MAX phases as poor electrocatalysts but also underscore the potential of nitride-based MAX and MXene materials as robust and efficient electrocatalysts for the NO3–RR.
{"title":"Time-Resolved Fourier Transform Infrared Spectroelectrochemical Investigation of Nitrate Reduction to Ammonia","authors":"David Kumar Yesudoss, Bright Ngozichukwu, Ibrahima Gning, Balla D. Ngom, Abdoulaye Djire","doi":"10.1021/acsenergylett.5c00553","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00553","url":null,"abstract":"This study explores the electrocatalytic nitrate reduction reaction (NO<sub>3</sub><sup>–</sup>RR) using nitride-based two-dimensional Ti<sub>2</sub>NT<i><sub><i>x</i></sub></i> MXene (also known as MNene) synthesized via O<sub>2</sub>-assisted molten salt fluoride etching and its parent Ti<sub>2</sub>AlN MAX phase. Ti<sub>2</sub>NT<i><sub><i>x</i></sub></i> MNene achieved an ammonia (NH<sub>3</sub>) yield rate of ∼550 μmol h<sup>–1</sup> g<sup>–1</sup> with a Faradaic efficiency (FE) of ∼80%. Unexpectedly, the Ti<sub>2</sub>AlN MAX phase exhibited an even higher NH<sub>3</sub> yield rate of ∼800 μmol h<sup>–1</sup> g<sup>–1</sup> at a comparable FE, despite its lower surface area and being traditionally considered a poor electrocatalyst. The enhanced performance of the MAX phase is likely due to −OH functionalization under alkaline conditions, leading to enhanced reaction kinetics. Postelectrolysis analyses, including Raman spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), confirmed no significant changes in crystallinity but indicated surface chemical changes. Control experiments with blank electrolytes and isotopically labelled <sup>15</sup>NO<sub>3</sub><sup>–</sup> substantiate that NH<sub>3</sub> originates exclusively from nitrate reduction on the surface terminations. Time-resolved <i>in situ</i> spectroelectrochemical studies identified nitrite (NO<sub>2</sub><sup>–</sup>) reduction to further intermediates as the rate-determining step. These findings not only challenge the conventional perception of MAX phases as poor electrocatalysts but also underscore the potential of nitride-based MAX and MXene materials as robust and efficient electrocatalysts for the NO<sub>3</sub><sup>–</sup>RR.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"10 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619054","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-14DOI: 10.1021/acsenergylett.5c00154
Jiahao He, Yang Zhou, Shibo Wu, Jingrui Cao, Bin Han, Zhiqiang Wang, Zaizai Tong, Muslum Demir, Pianpian Ma
The present study depicts innovative electrode and electrolyte designs to achieve advanced supercapacitor performance and stability. The mechanism of how the electronic structure of substitution ions impacts the phase structure and properties of SrCoO3−δ was in-depth elucidated, overcoming the inherent trade-off between specific capacity and cycle stability in perovskite materials. The as-prepared SrCo0.925Sc0.075O3−δ electrode achieves a high capacity of 467.7 C g–1 (129.92 mAh g–1) at 1 A g–1, with retention of 97.4% of its initial capacity after 10,000 cycles. Inspired by canopy structures, a “branch”-like dual-network 3D gel system was created and in situ integrated with the electrode as the “trunk”. This unique structure offers robust mechanical strength and flame retardancy, establishing an efficient conductive network. Devices featuring this design show electrochemical stability and flexibility, ensuring safe operation at extreme temperatures while balancing the stability and energy density. This research opens avenues for high-performance supercapacitors and quasi-solid-state gel batteries tailored applications.
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