Pub Date : 2024-04-18DOI: 10.1088/2515-7655/ad405c
Julian Walker, E. D. Sødahl, Simon Scherre, Kenneth Marshall, Dmitry Chernyshov, Kristian Berland, T. Rojac
Ferroelectric plastic crystals are an emerging class of materials that combine room temperature ferroelectricity and piezoelectricity with a high temperature plastic mesophase prior to melting. These materials offer possibilities for accessing different property parameter spaces from the state-of-the-art metal oxide and polymer ferroelectrics. Tetraethylammonium bromotrichloroferrite, [(C2H5)4N][FeBrCl3], has a unipolar wurtzite-like structure and thus may have potential for small but stable piezoelectric coefficients like the iso-symmetrical AlN. In this study, density functional theory was used to compute elastic compliance, piezoelectric coefficients, and dielectric constant values. Single crystals grown from aqueous solutions were evaluated via single crystal synchrotron x-ray diffraction, impedance spectroscopy and high and weak-field electromechanical characterization. Diffraction studies revealed that the anion tetrahedra orientated preferentially so that the Br- ion had a 30% alignment with the polarization vector. Electromechanical measurements found piezoelectric coefficients in the 5 to 9 pCN-1 and pmV-1 range. The piezoelectric coefficient (d33) was most stable with 3.4% variation between 0.4 and 90 Hz and 0.5 and 3 V. Additional piezoelectric stability measurements were made as a function of DC bias field and temperature. Impedance measurements indicate contributions from either intrinsic effects unique to ionic plastic crystals, such as molecular rotation, or the extrinsic effect of electrode interfaces, both of which can play a role in the electromechanical response of the materials. The results show that [(C2H5)4N][FeBrCl3] has potential as a small signal piezoelectric that has a softer elastic moduli than AlN but a stiffer moduli than polyvinylidene fluoride, and thus occupies a unique parameter space.
{"title":"Electromechanical properties of uniaxial polar ionic plastic crystal [(C2H5)4N][FeBrCl3]","authors":"Julian Walker, E. D. Sødahl, Simon Scherre, Kenneth Marshall, Dmitry Chernyshov, Kristian Berland, T. Rojac","doi":"10.1088/2515-7655/ad405c","DOIUrl":"https://doi.org/10.1088/2515-7655/ad405c","url":null,"abstract":"\u0000 Ferroelectric plastic crystals are an emerging class of materials that combine room temperature ferroelectricity and piezoelectricity with a high temperature plastic mesophase prior to melting. These materials offer possibilities for accessing different property parameter spaces from the state-of-the-art metal oxide and polymer ferroelectrics. Tetraethylammonium bromotrichloroferrite, [(C2H5)4N][FeBrCl3], has a unipolar wurtzite-like structure and thus may have potential for small but stable piezoelectric coefficients like the iso-symmetrical AlN. In this study, density functional theory was used to compute elastic compliance, piezoelectric coefficients, and dielectric constant values. Single crystals grown from aqueous solutions were evaluated via single crystal synchrotron x-ray diffraction, impedance spectroscopy and high and weak-field electromechanical characterization. Diffraction studies revealed that the anion tetrahedra orientated preferentially so that the Br- ion had a 30% alignment with the polarization vector. Electromechanical measurements found piezoelectric coefficients in the 5 to 9 pCN-1 and pmV-1 range. The piezoelectric coefficient (d33) was most stable with 3.4% variation between 0.4 and 90 Hz and 0.5 and 3 V. Additional piezoelectric stability measurements were made as a function of DC bias field and temperature. Impedance measurements indicate contributions from either intrinsic effects unique to ionic plastic crystals, such as molecular rotation, or the extrinsic effect of electrode interfaces, both of which can play a role in the electromechanical response of the materials. The results show that [(C2H5)4N][FeBrCl3] has potential as a small signal piezoelectric that has a softer elastic moduli than AlN but a stiffer moduli than polyvinylidene fluoride, and thus occupies a unique parameter space.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":" 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140687845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-18DOI: 10.1088/2515-7655/ad405d
Yibing Zhu, Jonathan M Skelton, David J Lewis, Robert Freer
Strontium titanate (SrTiO3) is widely recognised as an environmentally-benign perovskite material with potential for thermoelectric applications. In this work we employ a systematic modelling approach to study the electronic structure and thermoelectric power factor of pure SrTiO3 and donor-doped Sr(Ti0.875M0.125)O3 (M = Cr, Mo, W, V, Nb, Ta). We find that the carrier concentration required to optimise the power factor of SrTiO3 is on the order of 1021 cm-3, in line with experimental studies. Substitution at the Ti (B) site with 12.5 mol% Nb or Ta is predicted to yield the best power factor among the six Group V/VI dopants examined, balancing the Seebeck coefficient and electrical conductivity, and doping with the more abundant Nb would likely give the best price/performance ratio. Although W doping can significantly improve the electrical conductivity, this is at the expense of a reduced Seebeck coefficient. The first-row elements V and Cr have a significantly different impact on the electrical properties compared to the other dopants, forming resonant levels or creating hole carriers and leading to poor thermoelectric performance compared to the second- and third-row dopants. However, the reduction in the bandgap due obtained with these dopants may make the materials suitable for other applications such as photovoltaics or photocatalysis. Our modelling reveals the critical carrier concentrations and best B-site dopants for optimising the electrical properties of SrTiO3, and our predictions are supported by good agreement with available experimental data. The work therefore highlights avenues for maximising the thermoelectric properties of this archetypal oxide material.
钛酸锶（SrTiO3）被广泛认为是一种对环境无害的包晶材料，具有热电应用潜力。在这项研究中，我们采用系统建模方法研究了纯 SrTiO3 和供体掺杂的 Sr(Ti0.875M0.125)O3（M = Cr、Mo、W、V、Nb、Ta）的电子结构和热电功率因数。我们发现，优化 SrTiO3 功率因数所需的载流子浓度约为 1021 cm-3，与实验研究结果一致。据预测，在所研究的六种 V/VI 族掺杂剂中，用 12.5 摩尔%的 Nb 或 Ta 取代 Ti (B) 位点可获得最佳功率因数，同时兼顾塞贝克系数和电导率。虽然掺杂 W 能显著提高导电性，但这是以降低塞贝克系数为代价的。与其他掺杂剂相比，第一排元素 V 和 Cr 对电性能的影响明显不同，它们会形成共振水平或产生空穴载流子，导致热电性能比第二排和第三排掺杂剂差。不过，这些掺杂剂导致的带隙减小可能会使材料适用于其他应用，如光伏或光催化。我们的建模揭示了优化 SrTiO3 电性能的临界载流子浓度和最佳 B 位掺杂剂，我们的预测与现有的实验数据非常吻合。因此，这项研究为最大限度地提高这种典型氧化物材料的热电特性指明了方向。
{"title":"Electronic transport and the thermoelectric properties of donor-doped SrTiO3","authors":"Yibing Zhu, Jonathan M Skelton, David J Lewis, Robert Freer","doi":"10.1088/2515-7655/ad405d","DOIUrl":"https://doi.org/10.1088/2515-7655/ad405d","url":null,"abstract":"\u0000 Strontium titanate (SrTiO3) is widely recognised as an environmentally-benign perovskite material with potential for thermoelectric applications. In this work we employ a systematic modelling approach to study the electronic structure and thermoelectric power factor of pure SrTiO3 and donor-doped Sr(Ti0.875M0.125)O3 (M = Cr, Mo, W, V, Nb, Ta). We find that the carrier concentration required to optimise the power factor of SrTiO3 is on the order of 1021 cm-3, in line with experimental studies. Substitution at the Ti (B) site with 12.5 mol% Nb or Ta is predicted to yield the best power factor among the six Group V/VI dopants examined, balancing the Seebeck coefficient and electrical conductivity, and doping with the more abundant Nb would likely give the best price/performance ratio. Although W doping can significantly improve the electrical conductivity, this is at the expense of a reduced Seebeck coefficient. The first-row elements V and Cr have a significantly different impact on the electrical properties compared to the other dopants, forming resonant levels or creating hole carriers and leading to poor thermoelectric performance compared to the second- and third-row dopants. However, the reduction in the bandgap due obtained with these dopants may make the materials suitable for other applications such as photovoltaics or photocatalysis. Our modelling reveals the critical carrier concentrations and best B-site dopants for optimising the electrical properties of SrTiO3, and our predictions are supported by good agreement with available experimental data. The work therefore highlights avenues for maximising the thermoelectric properties of this archetypal oxide material.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":" 12","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140687173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-10DOI: 10.1088/2515-7655/ad3d0b
Junhao Li, Soochan Kim, Lorenzo Mezzomo, Yvonne Chart, Jack Aspinall, Riccardo Ruffo, Mauro Pasta
Scalable processing of thin and robust solid-electrolyte separators is key for the commercialization of high-energy all-solid-state batteries (ASSBs). Herein, we report the preparation of Li6PS5Cl-based thin solid-electrolyte separators incorporating suitable binders for potential use in ASSBs by two scalable wet processing techniques: tape-casting with nitrile-butadiene rubber (NBR) and calendering with carboxylated nitrile butadiene rubber (XNBR). By means of tensile testing and electrochemical impedance spectroscopy, the influence of processing on the mechanical as well as the electrochemical properties of the resulting thin solid-electrolyte separators is investigated. A trade-off between the mechanical and electrochemical properties is observed, which is due to the inextricably linked microstructures (particle size, binder content and distribution, and porosity) induced by the two different processes. Thin solid-electrolyte separators prepared using the tape-casting method with the more well-distributed binder network demonstrate superior tensile mechanical properties compared to the ones prepared by the calendering method. The results provide insights into the processing-structure-property relationships of the thin solid-electrolyte separators, which will contribute to advancing the application of practical thin solid electrolytes in ASSBs.
{"title":"Processing-structure-property relationships in practical thin solid-electrolyte separators for all-solid-state batteries","authors":"Junhao Li, Soochan Kim, Lorenzo Mezzomo, Yvonne Chart, Jack Aspinall, Riccardo Ruffo, Mauro Pasta","doi":"10.1088/2515-7655/ad3d0b","DOIUrl":"https://doi.org/10.1088/2515-7655/ad3d0b","url":null,"abstract":"\u0000 Scalable processing of thin and robust solid-electrolyte separators is key for the commercialization of high-energy all-solid-state batteries (ASSBs). Herein, we report the preparation of Li6PS5Cl-based thin solid-electrolyte separators incorporating suitable binders for potential use in ASSBs by two scalable wet processing techniques: tape-casting with nitrile-butadiene rubber (NBR) and calendering with carboxylated nitrile butadiene rubber (XNBR). By means of tensile testing and electrochemical impedance spectroscopy, the influence of processing on the mechanical as well as the electrochemical properties of the resulting thin solid-electrolyte separators is investigated. A trade-off between the mechanical and electrochemical properties is observed, which is due to the inextricably linked microstructures (particle size, binder content and distribution, and porosity) induced by the two different processes. Thin solid-electrolyte separators prepared using the tape-casting method with the more well-distributed binder network demonstrate superior tensile mechanical properties compared to the ones prepared by the calendering method. The results provide insights into the processing-structure-property relationships of the thin solid-electrolyte separators, which will contribute to advancing the application of practical thin solid electrolytes in ASSBs.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"46 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140717313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-04DOI: 10.1088/2515-7655/ad3aa1
M. García‐Tecedor, I. Villar-García, Giulio Gorni, Marta Liras, V. A. de la Peña O'Shea, Mariam Barawi Moran
Vanadium doped TiO2 NCs stand out as a promising candidate for energy storage applications due to its high electrical conductivity and redox properties. However, the thermodynamical behavior of the material under working conditions has not been explored and the reasons for its superior performance remain unlocked. This study explores the use of a combination of advanced in situ spectroscopy techniques, including X-ray absorption spectroscopy (XAS), spectro-electrochemistry (SEC), and Electrochemical Impedance Spectroscopy (EIS) to provide unprecedented insights into the intricate electrochemical reaction mechanisms within these nanocrystals. Density functional theory calculations and EIS reveal the active role of substitutional V ions in the TiO2 anatase network as electron donors, enhancing surface charge and carrier density and improving pseudocapacitive properties. Cyclic voltammetry and in situ spectroelectrochemistry reveal that V-doped TiO2 NCs exhibit significantly improved charge storage capacities, particularly in the pseudo-capacitance storage mechanism. In situ SEC and XAS analyses indicate that a more effective reduction of Ti4+ ions occurs during the electrochemical process in doped NCs, leading to higher charge capacitance and faster processes. Furthermore, in situ XAS measurements of the V K-edge revealed that the vanadium ions, beyond improving the redox behavior of the host, also actively participate in the reduction process. The significant changes in the V K-edge XANES and EXAFS spectra observed under reduction conditions can be ascribed to a change in the structure and oxidation state of the vanadium ions during the electrochemical reaction.
掺钒二氧化钛氮氧化物具有高导电性和氧化还原性，是储能应用的理想候选材料。然而，该材料在工作条件下的热力学行为尚未得到研究，其卓越性能的原因也尚未揭晓。本研究结合使用先进的原位光谱技术，包括 X 射线吸收光谱 (XAS)、光谱-电化学 (SEC) 和电化学阻抗光谱 (EIS)，对这些纳米晶体内部错综复杂的电化学反应机制进行了前所未有的深入研究。密度泛函理论计算和电化学阻抗谱（EIS）揭示了二氧化钛锐钛矿网络中作为电子供体的取代型 V 离子的积极作用，它们增强了表面电荷和载流子密度，改善了伪电容特性。循环伏安法和原位光谱电化学分析表明，掺杂 V 离子的二氧化钛 NC 的电荷存储容量显著提高，尤其是在伪电容存储机制中。原位 SEC 和 XAS 分析表明，在掺杂 NC 的电化学过程中，Ti4+ 离子发生了更有效的还原，导致电荷电容更高，过程更快。此外，对 V K-edge 的原位 XAS 测量显示，钒离子除了改善宿主的氧化还原行为外，还积极参与了还原过程。在还原条件下观察到的 V K-edge XANES 和 EXAFS 光谱的明显变化可归因于电化学反应过程中钒离子结构和氧化态的变化。
{"title":"Unveiling the non-innocence of vanadium dopant in TiO2 nanocrystals for advanced energy storage and smart windows","authors":"M. García‐Tecedor, I. Villar-García, Giulio Gorni, Marta Liras, V. A. de la Peña O'Shea, Mariam Barawi Moran","doi":"10.1088/2515-7655/ad3aa1","DOIUrl":"https://doi.org/10.1088/2515-7655/ad3aa1","url":null,"abstract":"\u0000 Vanadium doped TiO2 NCs stand out as a promising candidate for energy storage applications due to its high electrical conductivity and redox properties. However, the thermodynamical behavior of the material under working conditions has not been explored and the reasons for its superior performance remain unlocked. This study explores the use of a combination of advanced in situ spectroscopy techniques, including X-ray absorption spectroscopy (XAS), spectro-electrochemistry (SEC), and Electrochemical Impedance Spectroscopy (EIS) to provide unprecedented insights into the intricate electrochemical reaction mechanisms within these nanocrystals. Density functional theory calculations and EIS reveal the active role of substitutional V ions in the TiO2 anatase network as electron donors, enhancing surface charge and carrier density and improving pseudocapacitive properties. Cyclic voltammetry and in situ spectroelectrochemistry reveal that V-doped TiO2 NCs exhibit significantly improved charge storage capacities, particularly in the pseudo-capacitance storage mechanism. In situ SEC and XAS analyses indicate that a more effective reduction of Ti4+ ions occurs during the electrochemical process in doped NCs, leading to higher charge capacitance and faster processes. Furthermore, in situ XAS measurements of the V K-edge revealed that the vanadium ions, beyond improving the redox behavior of the host, also actively participate in the reduction process. The significant changes in the V K-edge XANES and EXAFS spectra observed under reduction conditions can be ascribed to a change in the structure and oxidation state of the vanadium ions during the electrochemical reaction.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"45 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140743218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-03DOI: 10.1088/2515-7655/ad39dc
Osmar M Sousa, L. Assali, Milan V Lalic, C. M. Araujo, Olle Eriksson, H. Petrilli, A. Klautau
Zinc-ion batteries (ZIB) employing aqueous electrolytes have emerged as viable successors to the widely used lithium-ion batteries (LIBs), attributed to their cost-effectiveness, environmental friendliness, and intrinsic safety features. Despite these advantages, the performance of ZIBs is significantly hindered by the scarcity of suitable cathode materials, positioning manganese zinc oxide (ZnMn2O4) as a potential solution. In this study, we describe the ZnMn2O4 (ZMO) compound focusing on its properties variations during Zn extraction and potential battery applications. For the sake of comparison, we also analyze the same properties of the LiMn2O4 in its tetragonal phase (TLMO), for the first time, motivated by a recent discovery that the substitution of Zn ions by Li in ZMO forms isostructural TLMO compound at room temperature. The study was conducted within the density functional theory (DFT) framework, where the structural, electronic, magnetic, electrochemical, and spectroscopic properties of ZMO and TLMO are investigated under various conditions. Although both systems crystallize in tetragonal structures, they demonstrate distinct electronic and magnetic properties due todifferent oxidation states of the Mn. The TLMO exhibits a narrower band gap compared to ZMO, indicating enhanced electrical conductivity. In addition, TLMO presented a lower diffusion energy barrier than ZMO, indicating better ionic conductivity. To evaluate the potential application of these materials in battery technologies, we further explored their volume changes during charging/discharging cycles, simulating Zn or Li ions extraction. TLMO underwent a significant volume contraction of 5.8% upon complete Li removal, while ZMO experienced a more pronounced contraction of 12.5% with full Zn removal. By adjusting ion extraction levels, it is possible to reduce these contractions, thereby approaching more viable battery applications. Furthermore, spectroscopy results provide insights into the electronic transitions and validate the computational findings, consolidating our understanding of the intrinsic properties of ZMO and TLMO.
{"title":"Charging behavior of ZnMn2O4 and LiMn2O4 in a zinc- and lithium-ion battery: an ab initio study","authors":"Osmar M Sousa, L. Assali, Milan V Lalic, C. M. Araujo, Olle Eriksson, H. Petrilli, A. Klautau","doi":"10.1088/2515-7655/ad39dc","DOIUrl":"https://doi.org/10.1088/2515-7655/ad39dc","url":null,"abstract":"\u0000 Zinc-ion batteries (ZIB) employing aqueous electrolytes have emerged as viable successors to the widely used lithium-ion batteries (LIBs), attributed to their cost-effectiveness, environmental friendliness, and intrinsic safety features. Despite these advantages, the performance of ZIBs is significantly hindered by the scarcity of suitable cathode materials, positioning manganese zinc oxide (ZnMn2O4) as a potential solution. In this study, we describe the ZnMn2O4 (ZMO) compound focusing on its properties variations during Zn extraction and potential battery applications. For the sake of comparison, we also analyze the same properties of the LiMn2O4 in its tetragonal phase (TLMO), for the first time, motivated by a recent discovery that the substitution of Zn ions by Li in ZMO forms isostructural TLMO compound at room temperature. The study was conducted within the density functional theory (DFT) framework, where the structural, electronic, magnetic, electrochemical, and spectroscopic properties of ZMO and TLMO are investigated under various conditions. Although both systems crystallize in tetragonal structures, they demonstrate distinct electronic and magnetic properties due todifferent oxidation states of the Mn. The TLMO exhibits a narrower band gap compared to ZMO, indicating enhanced electrical conductivity. In addition, TLMO presented a lower diffusion energy barrier than ZMO, indicating better ionic conductivity. To evaluate the potential application of these materials in battery technologies, we further explored their volume changes during charging/discharging cycles, simulating Zn or Li ions extraction. TLMO underwent a significant volume contraction of 5.8% upon complete Li removal, while ZMO experienced a more pronounced contraction of 12.5% with full Zn removal. By adjusting ion extraction levels, it is possible to reduce these contractions, thereby approaching more viable battery applications. Furthermore, spectroscopy results provide insights into the electronic transitions and validate the computational findings, consolidating our understanding of the intrinsic properties of ZMO and TLMO.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"433 ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140750061","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-21DOI: 10.1088/2515-7655/ad3675
Adam M. Boyce, E. Martínez-Pañeda, P. Shearing
In the race to reduce global CO2 emissions and achieve net-zero, chemomechanics must play a critical role in the technological development of current and next-generation batteries to improve their energy storage capabilities and their lifetime. Many degradation processes arise through mechanics via the development of diffusion-induced stress and volumetric strains within the various constituent materials in a battery. From particle cracking in lithium-ion batteries to lithium dendrite-based fracture of solid electrolytes in solid-state batteries, it is clear that significant barriers exist in the development of these energy storage systems, where chemomechanics plays a central part. To accelerate technological and scientific advances in this area, multi-scale and highly coupled multiphysics modelling must be carried out that includes mechanics-based phenomena. In this perspective article, we provide an introduction to chemomechanical modelling, the various physical problems that it addresses, and the issues that need to be resolved in order to expand its use within the field of battery technology.
{"title":"The role of chemo-mechanical modelling in the development of battery technology – a perspective","authors":"Adam M. Boyce, E. Martínez-Pañeda, P. Shearing","doi":"10.1088/2515-7655/ad3675","DOIUrl":"https://doi.org/10.1088/2515-7655/ad3675","url":null,"abstract":"\u0000 In the race to reduce global CO2 emissions and achieve net-zero, chemomechanics must play a critical role in the technological development of current and next-generation batteries to improve their energy storage capabilities and their lifetime. Many degradation processes arise through mechanics via the development of diffusion-induced stress and volumetric strains within the various constituent materials in a battery. From particle cracking in lithium-ion batteries to lithium dendrite-based fracture of solid electrolytes in solid-state batteries, it is clear that significant barriers exist in the development of these energy storage systems, where chemomechanics plays a central part. To accelerate technological and scientific advances in this area, multi-scale and highly coupled multiphysics modelling must be carried out that includes mechanics-based phenomena. In this perspective article, we provide an introduction to chemomechanical modelling, the various physical problems that it addresses, and the issues that need to be resolved in order to expand its use within the field of battery technology.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"96 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140224090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-21DOI: 10.1088/2515-7655/ad3676
Poonam Yadav, Santosh Kumar, Nandhakumar Velankanni, Thomas D Kühne, Suresh Gosavi, R. Raghupathy, R. Bhosale, Georg Held, M. Shelke, Satishchandra B Ogale
Photocatalytic CO2 reduction is a sustainable pathway to produce syngas (H2 + CO) which is a key feed stock for the production of many important liquid fuels on the industrial scale. However, achieving appropriate tunable ratio of H2:CO in syngas for commercial purpose is a challenging task. In this work, we present a low cost and non-noble metal, phosphide based co-catalyst - Ni2P loaded CdS photocatalyst system for the photocatalytic CO2 reduction. Ni2P as a co-catalyst fosters efficient charge separation of photoexcited charges generated in CdS producing syngas. 3 wt.% CdS/Ni2P exhibited exceptional performance of 50.6 µmol/g/h of CO evolution rate and 115 µmol/g/h of H2 evolution rate with a syngas composition varying from 2 to 4 in H2:CO ratio. Further, the first-principles density functional theory (DFT) calculations were performed to study surface energetics of the catalyst system and the results are found to be consistent with our experimental findings. Indeed, they establish that the composite favors the CO2 photoreduction into syngas more efficiently as compared to pure surfaces.
{"title":"Photocatalytic CO2 reduction to syngas using nickel phosphide loaded CdS under visible light irradiation","authors":"Poonam Yadav, Santosh Kumar, Nandhakumar Velankanni, Thomas D Kühne, Suresh Gosavi, R. Raghupathy, R. Bhosale, Georg Held, M. Shelke, Satishchandra B Ogale","doi":"10.1088/2515-7655/ad3676","DOIUrl":"https://doi.org/10.1088/2515-7655/ad3676","url":null,"abstract":"\u0000 Photocatalytic CO2 reduction is a sustainable pathway to produce syngas (H2 + CO) which is a key feed stock for the production of many important liquid fuels on the industrial scale. However, achieving appropriate tunable ratio of H2:CO in syngas for commercial purpose is a challenging task. In this work, we present a low cost and non-noble metal, phosphide based co-catalyst - Ni2P loaded CdS photocatalyst system for the photocatalytic CO2 reduction. Ni2P as a co-catalyst fosters efficient charge separation of photoexcited charges generated in CdS producing syngas. 3 wt.% CdS/Ni2P exhibited exceptional performance of 50.6 µmol/g/h of CO evolution rate and 115 µmol/g/h of H2 evolution rate with a syngas composition varying from 2 to 4 in H2:CO ratio. Further, the first-principles density functional theory (DFT) calculations were performed to study surface energetics of the catalyst system and the results are found to be consistent with our experimental findings. Indeed, they establish that the composite favors the CO2 photoreduction into syngas more efficiently as compared to pure surfaces.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":" 17","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140221767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Carbon dots (CDs) are environmentally benign, strongly photoluminescent, metal free nanoparticles. Interfacing them with tailor-made organic semiconductors such as covalent organic frameworks (COFs) promises to yield multifunctional materials. In this study, microwave-derived CDs are successfully incorporated into the porous structure of COF in a one-pot method in which BDT-ETTA COF is synthesized by the amine and aldehyde condensation between 1,1,2,2-Tetra(p-aminophenyl)ethylene (ETTA) and Benzo[1,2-b:4,5-b’]dithiophene-2,6-dicarboxaldehyde (BDT) in the presence of CDs. A detailed structural and optoelectronic characterization of the COF/CDs composite reveals that upon tuning the CDs loadings encapsulated in COF the interaction between both components can be controlled allowing the switch between energy and charge transfer. At CDs loadings ≤ 20 wt%, strong binding of CDs to the COF enables charge transfer evinced from the quenched photoluminescence of both components and accelerated exciton decay kinetics of the COF. At CDs loadings ≥ 30 wt% Förster resonance energy transfer from CDs to COF prevails, leading to enhanced COF photoluminescence. Our study underlines the interaction mechanism in organic composites and provides the knowledge required for the design of novel functional materials with applications in photocatalysis, optoelectronics and sensing.
碳点（CD）是一种无害环境、强光致发光、不含金属的纳米粒子。将它们与共价有机框架（COFs）等量身定制的有机半导体结合有望产生多功能材料。本研究采用一锅法成功地将微波衍生的 CD 纳入到 COF 的多孔结构中，其中 BDT-ETTA COF 是在 CD 的存在下，通过 1,1,2,2-四（对氨基苯基）乙烯（ETTA）和苯并[1,2-b:4,5-b']二噻吩-2,6-二甲醛（BDT）之间的胺和醛缩合合成的。对 COF/CDs 复合材料的详细结构和光电特性分析表明，通过调节封装在 COF 中的 CD 的负载量，可以控制两种成分之间的相互作用，从而实现能量和电荷转移之间的转换。当 CD 的负载量≤ 20 wt% 时，CD 与 COF 的强结合可实现电荷转移，这一点可从两种成分的光致发光淬灭和 COF 的激子衰减动力学加速得到证明。当 CD 的负载量≥ 30 wt% 时，从 CD 到 COF 的佛斯特共振能量转移占主导地位，从而导致 COF 的光致发光增强。我们的研究强调了有机复合材料中的相互作用机制，并为设计新型功能材料提供了必要的知识，这些材料可应用于光催化、光电子学和传感领域。
{"title":"Synthetic control over the energy transfer and charge transfer between carbon dots and covalent organic framework","authors":"Julian Feijoo, Klaudija Paliušytė, Jenny Schneider","doi":"10.1088/2515-7655/ad3677","DOIUrl":"https://doi.org/10.1088/2515-7655/ad3677","url":null,"abstract":"\u0000 Carbon dots (CDs) are environmentally benign, strongly photoluminescent, metal free nanoparticles. Interfacing them with tailor-made organic semiconductors such as covalent organic frameworks (COFs) promises to yield multifunctional materials. In this study, microwave-derived CDs are successfully incorporated into the porous structure of COF in a one-pot method in which BDT-ETTA COF is synthesized by the amine and aldehyde condensation between 1,1,2,2-Tetra(p-aminophenyl)ethylene (ETTA) and Benzo[1,2-b:4,5-b’]dithiophene-2,6-dicarboxaldehyde (BDT) in the presence of CDs. A detailed structural and optoelectronic characterization of the COF/CDs composite reveals that upon tuning the CDs loadings encapsulated in COF the interaction between both components can be controlled allowing the switch between energy and charge transfer. At CDs loadings ≤ 20 wt%, strong binding of CDs to the COF enables charge transfer evinced from the quenched photoluminescence of both components and accelerated exciton decay kinetics of the COF. At CDs loadings ≥ 30 wt% Förster resonance energy transfer from CDs to COF prevails, leading to enhanced COF photoluminescence. Our study underlines the interaction mechanism in organic composites and provides the knowledge required for the design of novel functional materials with applications in photocatalysis, optoelectronics and sensing.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":" 11","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140220743","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-18DOI: 10.1088/2515-7655/ad34fc
M. R. Palacín, Patrik Johansson, R. Dominko, Ben Dlugatch, D. Aurbach, Zhenyou Li, Maximilian Fichtner, Olivera Lužanin, J. Bitenc, Zhixuan Wei, Clarissa Glaser, Jürgen Janek, Ana Fernández-Barquín, A. R. Mainar, O. Leonet, I. Urdampilleta, J. A. Blázquez, D. Tchitchekova, A. Ponrouch, P. Canepa, G. Gautam, Raúl San Román Gallego Casilda, C. Martinez-Cisneros, Nieves Ureña Torres, A. Várez, Jean-Yves Sanchez, K. Kravchyk, M. Kovalenko, Anastasia A. Teck, Huw Shiel, I. Stephens, M. P. Ryan, Eugen Zemlyanushin, Sonia Dsoke, Rebecca Grieco, Nagaraj Patil, Rebeca Marcilla, Xuan Gao, C. Carmalt, Guanjie He, M. Titirici
Battery technologies based in multivalent charge carriers with ideally two or three electrons transferred per ion exchanged between the electrodes have large promises in raw performance numbers, most often expressed as high energy density, and are also ideally based on raw materials that are widely abundant and less expensive. Yet, these are still globally in their infancy, with some concepts (e.g., Mg metal) being more technologically mature. The challenges to address are derived on one side from the highly polarizing nature of multivalent ions when compared to single valent concepts such as Li+ or Na+ present in Li-ion or Na-ion batteries, and on the other, from the difficulties in achieving efficient metal plating/stripping (which remains the holy grail for lithium). Nonetheless, research performed to date has given some fruits and a clearer view of the challenges ahead. These include technological topics (production of thin and ductile metal foil anodes) but also chemical aspects (electrolytes with high conductivity enabling efficient plating/stripping) or high-capacity cathodes with suitable kinetics (better inorganic hosts for intercalation of such highly polarisable multivalent ions). This roadmap provides an extensive review by experts in the different technologies, which exhibit similarities but also striking differences, of the current state of the art in 2023 and the research directions and strategies currently underway to develop multivalent batteries. The aim is to provide an opinion with respect to the current challenges, potential bottlenecks, and also emerging opportunities for their practical deployment.
{"title":"Roadmap on Multivalent Batteries","authors":"M. R. Palacín, Patrik Johansson, R. Dominko, Ben Dlugatch, D. Aurbach, Zhenyou Li, Maximilian Fichtner, Olivera Lužanin, J. Bitenc, Zhixuan Wei, Clarissa Glaser, Jürgen Janek, Ana Fernández-Barquín, A. R. Mainar, O. Leonet, I. Urdampilleta, J. A. Blázquez, D. Tchitchekova, A. Ponrouch, P. Canepa, G. Gautam, Raúl San Román Gallego Casilda, C. Martinez-Cisneros, Nieves Ureña Torres, A. Várez, Jean-Yves Sanchez, K. Kravchyk, M. Kovalenko, Anastasia A. Teck, Huw Shiel, I. Stephens, M. P. Ryan, Eugen Zemlyanushin, Sonia Dsoke, Rebecca Grieco, Nagaraj Patil, Rebeca Marcilla, Xuan Gao, C. Carmalt, Guanjie He, M. Titirici","doi":"10.1088/2515-7655/ad34fc","DOIUrl":"https://doi.org/10.1088/2515-7655/ad34fc","url":null,"abstract":"\u0000 Battery technologies based in multivalent charge carriers with ideally two or three electrons transferred per ion exchanged between the electrodes have large promises in raw performance numbers, most often expressed as high energy density, and are also ideally based on raw materials that are widely abundant and less expensive. Yet, these are still globally in their infancy, with some concepts (e.g., Mg metal) being more technologically mature. The challenges to address are derived on one side from the highly polarizing nature of multivalent ions when compared to single valent concepts such as Li+ or Na+ present in Li-ion or Na-ion batteries, and on the other, from the difficulties in achieving efficient metal plating/stripping (which remains the holy grail for lithium). Nonetheless, research performed to date has given some fruits and a clearer view of the challenges ahead. These include technological topics (production of thin and ductile metal foil anodes) but also chemical aspects (electrolytes with high conductivity enabling efficient plating/stripping) or high-capacity cathodes with suitable kinetics (better inorganic hosts for intercalation of such highly polarisable multivalent ions). This roadmap provides an extensive review by experts in the different technologies, which exhibit similarities but also striking differences, of the current state of the art in 2023 and the research directions and strategies currently underway to develop multivalent batteries. The aim is to provide an opinion with respect to the current challenges, potential bottlenecks, and also emerging opportunities for their practical deployment.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"42 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140234230","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-12DOI: 10.1088/2515-7655/ad331e
Ryan Foxall, H. Ishaq, Curran Crawford
This study proposes an off-grid direct air (carbon) capture (DAC) plant installed on the deck of an offshore floating wind turbine. The main objective is to understand detailed flow characteristics and CO2 dispersion around air contactors when placed in close proximity to one another. A solid sorbent DAC design is implemented using a commercially deployed air contactor configuration and sorbent. Computational fluid dynamics is used to determine the local conditions entering each unit based on varying wind speed and angle. Two-dimensional simulations were used to determine the pressure drop through a detailed air contactor design. Three dimensional simulations were used to model flow patterns and CO2 dispersion using passive scalars. A worst case scenario is analyzed for all DAC units in adsorption mode with fans running simultaneously. Two dimensional simulations show an under utilization of contactor length, and quantify pressure loss curves for four common sorbents. One commercially deployed sorbent is considered for further analysis; a pressure drop of 390.62 Pa is experienced for a flow velocity of 0.73m/s through a 1.5m x 1.5m x 1.5m contactor. Using three dimensional simulations, fan energy demands are computed based on flow velocities and applied pressure gradients. There is found to be a decrease in overall fan power demand as wind speed increases. High wind speeds can passively drive the adsorption process with fans shut off at certain wind directions. This occurs at an average contactor inlet velocity of 17.5m/s, correlating to a hub height (150m) wind speed of 24m/s. Thermal energy demands are computed based on inlet CO2 concentrations entering downstream units. Contactor arrangement, wind angles, and wind speeds have a significant impact on flow patterns experienced, and resulting CO2 dispersion. High wind speeds assist in CO2 dispersion, resulting in higher inlet concentrations to downstream DAC units and decreased thermal energy requirement.
{"title":"Ambient wind conditions impact on energy requirements of an offshore direct air capture plant","authors":"Ryan Foxall, H. Ishaq, Curran Crawford","doi":"10.1088/2515-7655/ad331e","DOIUrl":"https://doi.org/10.1088/2515-7655/ad331e","url":null,"abstract":"\u0000 This study proposes an off-grid direct air (carbon) capture (DAC) plant installed on the deck of an offshore floating wind turbine. The main objective is to understand detailed flow characteristics and CO2 dispersion around air contactors when placed in close proximity to one another. A solid sorbent DAC design is implemented using a commercially deployed air contactor configuration and sorbent. Computational fluid dynamics is used to determine the local conditions entering each unit based on varying wind speed and angle. Two-dimensional simulations were used to determine the pressure drop through a detailed air contactor design. Three dimensional simulations were used to model flow patterns and CO2 dispersion using passive scalars. A worst case scenario is analyzed for all DAC units in adsorption mode with fans running simultaneously. Two dimensional simulations show an under utilization of contactor length, and quantify pressure loss curves for four common sorbents. One commercially deployed sorbent is considered for further analysis; a pressure drop of 390.62 Pa is experienced for a flow velocity of 0.73m/s through a 1.5m x 1.5m x 1.5m contactor. Using three dimensional simulations, fan energy demands are computed based on flow velocities and applied pressure gradients. There is found to be a decrease in overall fan power demand as wind speed increases. High wind speeds can passively drive the adsorption process with fans shut off at certain wind directions. This occurs at an average contactor inlet velocity of 17.5m/s, correlating to a hub height (150m) wind speed of 24m/s. Thermal energy demands are computed based on inlet CO2 concentrations entering downstream units. Contactor arrangement, wind angles, and wind speeds have a significant impact on flow patterns experienced, and resulting CO2 dispersion. High wind speeds assist in CO2 dispersion, resulting in higher inlet concentrations to downstream DAC units and decreased thermal energy requirement.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"40 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140250874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","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：