Pub Date : 2024-08-07DOI: 10.1149/1945-7111/ad69c8
Shamik Chakrabarti and A. K. Thakur
Electrochemical properties of Li2NiPO4F were studied using density functional theory. The obtained voltage, electronic band gap, capacity (∼ for 2 Li+ extraction) and energy density are achieved as 5.33 V, 4.0 eV, 287.3 mAh g−1 and 1531.31 Wh kg−1, respectively. Although, the electrochemical properties of Li2NiPO4F are promising, large electronic band gap would certainly pose a limitation for its commercial application. Nb is a transition metal and its electronegativity is 1.6 which is less than the electronegativity of 2.19 for P. This implies, less operating voltage would be obtained if we replace P in Li2NiPO4F by Nb to form Li2NiNbO4F. However, electronic configuration of Nb is [Kr] 4d45 s1 and the valance state of Nb in Li2NiNbO4F is +5, which in turn specify that, localized Nb d states will reside in conduction band of Li2NiNbO4F and hence the electronic band-gap would be less owing to this localized Nb-d states. Our speculation gets verified by the calculated properties of Li2NiNbO4F obtained through DFT as follows; Voltage, electronic band gap, capacity (∼ for 2 Li+ extraction) and energy density achieved, respectively, are 5.01 V, 3.64 eV (less than LiFePO4), 215.71 mAh g−1, 1080.71 Wh kg−1. Lower electronic band gap of Li2NiNbO4F makes it an alternative to Li2NiPO4F.
{"title":"Tuning of Band Gap of Cathode Li2NiPO4F by Replacing P to Nb and Forming Li2NiNbO4F for Application as 5 V Cathode in Lithium Ion Battery: A Density Functional Theory Study","authors":"Shamik Chakrabarti and A. K. Thakur","doi":"10.1149/1945-7111/ad69c8","DOIUrl":"https://doi.org/10.1149/1945-7111/ad69c8","url":null,"abstract":"Electrochemical properties of Li2NiPO4F were studied using density functional theory. The obtained voltage, electronic band gap, capacity (∼ for 2 Li+ extraction) and energy density are achieved as 5.33 V, 4.0 eV, 287.3 mAh g−1 and 1531.31 Wh kg−1, respectively. Although, the electrochemical properties of Li2NiPO4F are promising, large electronic band gap would certainly pose a limitation for its commercial application. Nb is a transition metal and its electronegativity is 1.6 which is less than the electronegativity of 2.19 for P. This implies, less operating voltage would be obtained if we replace P in Li2NiPO4F by Nb to form Li2NiNbO4F. However, electronic configuration of Nb is [Kr] 4d45 s1 and the valance state of Nb in Li2NiNbO4F is +5, which in turn specify that, localized Nb d states will reside in conduction band of Li2NiNbO4F and hence the electronic band-gap would be less owing to this localized Nb-d states. Our speculation gets verified by the calculated properties of Li2NiNbO4F obtained through DFT as follows; Voltage, electronic band gap, capacity (∼ for 2 Li+ extraction) and energy density achieved, respectively, are 5.01 V, 3.64 eV (less than LiFePO4), 215.71 mAh g−1, 1080.71 Wh kg−1. Lower electronic band gap of Li2NiNbO4F makes it an alternative to Li2NiPO4F.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"23 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-06DOI: 10.1149/1945-7111/ad6937
Divya Rathore, Harold Smith Perez, Ian Monchesky, Fanny Vain, Penghao Xiao, Chongyin Yang and J. R. Dahn
NMC640, a series of Li1+x(Ni0.6Mn0.4)1−xO2 materials, are important Co-free mid-Ni cathode materials for Li-ion batteries, offering high energy density and better cost-efficiency than Ni-rich counterparts. These materials require excess Li compared to stoichiometric composition to improve the electrochemical performance in terms of rate capability and cycling stability. Although lithium-to-transition metal ratios up to 1.15 can be used to optimize the performance, less than 80% of this lithium is electrochemically active during cycling up to a 4.4 V upper cut off. This study explores whether some percentage of the inactive Li can be replaced by sodium to make these materials more cost-effective and bring potential improvements in electrochemical performance. Various amounts of excess Li were substituted by sodium in the structure. The results show that sodium can be integrated into the layered oxide structure without forming any impurity phases and effectively decreases the cation mixing observed in these layered structures. However, this does compromise cycling stability and rate capability. Na tends to occupy Li sites rather than transition metal sites, resulting in electrochemical instability and capacity loss. Even though excess Li is not electrochemically active, it cannot be effectively replaced by sodium without compromising battery performance of Li1+x(Ni0.6Mn0.4)1−xO2 materials.
{"title":"Substituting Na for Excess Li in Li1+x(Ni0.6Mn0.4)1−xO2 Materials","authors":"Divya Rathore, Harold Smith Perez, Ian Monchesky, Fanny Vain, Penghao Xiao, Chongyin Yang and J. R. Dahn","doi":"10.1149/1945-7111/ad6937","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6937","url":null,"abstract":"NMC640, a series of Li1+x(Ni0.6Mn0.4)1−xO2 materials, are important Co-free mid-Ni cathode materials for Li-ion batteries, offering high energy density and better cost-efficiency than Ni-rich counterparts. These materials require excess Li compared to stoichiometric composition to improve the electrochemical performance in terms of rate capability and cycling stability. Although lithium-to-transition metal ratios up to 1.15 can be used to optimize the performance, less than 80% of this lithium is electrochemically active during cycling up to a 4.4 V upper cut off. This study explores whether some percentage of the inactive Li can be replaced by sodium to make these materials more cost-effective and bring potential improvements in electrochemical performance. Various amounts of excess Li were substituted by sodium in the structure. The results show that sodium can be integrated into the layered oxide structure without forming any impurity phases and effectively decreases the cation mixing observed in these layered structures. However, this does compromise cycling stability and rate capability. Na tends to occupy Li sites rather than transition metal sites, resulting in electrochemical instability and capacity loss. Even though excess Li is not electrochemically active, it cannot be effectively replaced by sodium without compromising battery performance of Li1+x(Ni0.6Mn0.4)1−xO2 materials.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"57 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942968","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-06DOI: 10.1149/1945-7111/ad6934
Wei He, Munaiah Yeddala, Leah Rynearson and Brett Lucht
The use of high-nickel NMC811 cathode and SiOx-Gr anode can greatly improve the overall energy densities of lithium-ion batteries. However, the unfavorable solid electrolyte interphase (SEI) layer generated from the decomposition of EC-based electrolytes lead to the poor cycling stability of NMC811||SiOx-Gr cells. Here we report an electrolyte design of 1.5 M LiPF6 dissolved in FEC/MA/BN 2:2:6 by volume, which can form thin, robust, and homogeneous SEI layer to greatly improve the charge transfer at the electrode-electrolyte interface. Importantly, the designed electrolyte shows an outstanding low temperature performance that it can deliver a capacity of 123.3 mAh g–1 after 50 cycles at −20 °C with a current density of 0.5 C, overwhelming the standard EC-based electrolyte (1.2 M LiPF6 EC/EMC 3:7 by volume) with a capacity of 35.7 mAh g–1. The electrolyte also has a superior rate performance that it achieves a capacity of 122.5 mAh g−1 at a high current density of 10 C. Moreover, the LTE electrolyte holds the great potential of extreme fast-charging ability because of the large part of CC contribution in the CCCV charging model at high charging current densities.
使用高镍 NMC811 正极和 SiOx-Gr 负极可以大大提高锂离子电池的整体能量密度。然而，基于 EC 的电解质在分解过程中会产生不利的固体电解质间相（SEI）层，导致 NMC811||SiOx-Gr 电池的循环稳定性较差。在此，我们报告了一种将 1.5 M LiPF6 按体积比 2:2:6 溶于 FEC/MA/BN 中的电解质设计，它可以形成薄、坚固、均匀的 SEI 层，从而大大改善电极-电解质界面的电荷转移。重要的是，所设计的电解液具有出色的低温性能，在零下 20 °C、电流密度为 0.5 C 的条件下循环 50 次后，其容量可达 123.3 mAh g-1，超过了容量为 35.7 mAh g-1 的标准 EC 型电解液（体积比为 1.2 M LiPF6 EC/EMC 3:7）。该电解液还具有卓越的速率性能，在 10 C 的高电流密度下可达到 122.5 mAh g-1 的容量。此外，由于在高充电电流密度下的 CCCV 充电模型中 CC 的贡献较大，因此 LTE 电解液具有极强的快速充电能力。
{"title":"Electrolyte Design for NMC811||SiOx-Gr Lithium-Ion Batteries with Excellent Low-Temperature and High-Rate Performance","authors":"Wei He, Munaiah Yeddala, Leah Rynearson and Brett Lucht","doi":"10.1149/1945-7111/ad6934","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6934","url":null,"abstract":"The use of high-nickel NMC811 cathode and SiOx-Gr anode can greatly improve the overall energy densities of lithium-ion batteries. However, the unfavorable solid electrolyte interphase (SEI) layer generated from the decomposition of EC-based electrolytes lead to the poor cycling stability of NMC811||SiOx-Gr cells. Here we report an electrolyte design of 1.5 M LiPF6 dissolved in FEC/MA/BN 2:2:6 by volume, which can form thin, robust, and homogeneous SEI layer to greatly improve the charge transfer at the electrode-electrolyte interface. Importantly, the designed electrolyte shows an outstanding low temperature performance that it can deliver a capacity of 123.3 mAh g–1 after 50 cycles at −20 °C with a current density of 0.5 C, overwhelming the standard EC-based electrolyte (1.2 M LiPF6 EC/EMC 3:7 by volume) with a capacity of 35.7 mAh g–1. The electrolyte also has a superior rate performance that it achieves a capacity of 122.5 mAh g−1 at a high current density of 10 C. Moreover, the LTE electrolyte holds the great potential of extreme fast-charging ability because of the large part of CC contribution in the CCCV charging model at high charging current densities.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"373 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942971","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
State-of-health (SOH) of lithium-ion batteries is an important indicator for measuring performance and remaining life. We propose an innovative prediction model that integrates variational mode decomposition (VMD), Dung Beetle optimizer (DBO), and support vector regression (SVR) algorithms. We extracted relevant features from the discharge characteristic curve and incremental capacity curve. We used Pearson and Spearman correlation coefficient methods for correlation analysis on the extracted health factors (HFs), selecting those that significantly impact SOH as input features. A DBO-SVR model was constructed to establish a nonlinear correlation between HFs and SOH, and the DBO algorithm was used to globally search and optimize the hyperparameters of the SVR model to improve its prediction accuracy. To reduce the impact of noise in battery signals on model performance, VMD technology was introduced to decompose battery signals into multiple intrinsic mode components, to extract useful features and remove noise to further improve prediction accuracy. The proposed method was validated using the NASA battery dataset and compared with other algorithm models. Results showed that the prediction model was significantly better than other models, with a maximum RMSE value of 0.84%, a maximum MAE value of 0.71%, and a stable prediction error value within 1%.
{"title":"State of Health Estimation of Lithium-Ion Battery for Electric Vehicle Based on VMD-DBO-SVR Model","authors":"Liang Tong, Minghui Gong, Yong Chen, Rao Kuang, Yonghong Xu, Hongguang Zhang, Baoying Peng, Fubin Yang, Jian Zhang and Yiyang Li","doi":"10.1149/1945-7111/ad6935","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6935","url":null,"abstract":"State-of-health (SOH) of lithium-ion batteries is an important indicator for measuring performance and remaining life. We propose an innovative prediction model that integrates variational mode decomposition (VMD), Dung Beetle optimizer (DBO), and support vector regression (SVR) algorithms. We extracted relevant features from the discharge characteristic curve and incremental capacity curve. We used Pearson and Spearman correlation coefficient methods for correlation analysis on the extracted health factors (HFs), selecting those that significantly impact SOH as input features. A DBO-SVR model was constructed to establish a nonlinear correlation between HFs and SOH, and the DBO algorithm was used to globally search and optimize the hyperparameters of the SVR model to improve its prediction accuracy. To reduce the impact of noise in battery signals on model performance, VMD technology was introduced to decompose battery signals into multiple intrinsic mode components, to extract useful features and remove noise to further improve prediction accuracy. The proposed method was validated using the NASA battery dataset and compared with other algorithm models. Results showed that the prediction model was significantly better than other models, with a maximum RMSE value of 0.84%, a maximum MAE value of 0.71%, and a stable prediction error value within 1%.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"10 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942907","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nanocomposite electrodes comprising LaSi2 and Si exhibit satisfactory charge–discharge cycling performances but their capacity is degraded after repeated cycles. A metallographic structure, in which the Si phase was finely dispersed in the LaSi2 matrix phase, was formed before cycling. The elastic LaSi2 relieved Si-generated stress and suppressed electrode disintegration. Contrarily, the LaSi2 phase in the metallographic structure was surrounded by the Si matrix phase after cycling. The positional relationship between the two phases was reversed, and LaSi2 could not relieve the stress. For a nanocomposite electrode containing CrSi2, which exhibits stiffness to withstand the Si-generated stress, the structural changes were suppressed after cycling, resulting in good cycling stability. Here, we considered that the addition of stiff silicides as a third phase to the LaSi2/Si composite could improve the cycle life. Thus, this study prepared nanocomposite electrodes containing elastic LaSi2, stiff MSi2 (where M = Cr, Mo, Nb, Ta, Ti, or W), and elemental Si and investigated their electrochemical performances. Reaction behaviors, such as the metallographic structure, electrode thickness, and phase transition, were also clarified. The LaSi2/NbSi2/Si electrode exhibited the best cycle life without changes in its metallographic structure owing to the synergistic effect of stiff and elastic silicides.
{"title":"Silicon-Based Nanocomposite Anodes with Excellent Cycle Life for Lithium-Ion Batteries Achieved by the Synergistic Effect of Two Silicides","authors":"Yasuhiro Domi, Hiroyuki Usui, Takumi Okasaka, Kei Nishikawa and Hiroki Sakaguchi","doi":"10.1149/1945-7111/ad69c6","DOIUrl":"https://doi.org/10.1149/1945-7111/ad69c6","url":null,"abstract":"Nanocomposite electrodes comprising LaSi2 and Si exhibit satisfactory charge–discharge cycling performances but their capacity is degraded after repeated cycles. A metallographic structure, in which the Si phase was finely dispersed in the LaSi2 matrix phase, was formed before cycling. The elastic LaSi2 relieved Si-generated stress and suppressed electrode disintegration. Contrarily, the LaSi2 phase in the metallographic structure was surrounded by the Si matrix phase after cycling. The positional relationship between the two phases was reversed, and LaSi2 could not relieve the stress. For a nanocomposite electrode containing CrSi2, which exhibits stiffness to withstand the Si-generated stress, the structural changes were suppressed after cycling, resulting in good cycling stability. Here, we considered that the addition of stiff silicides as a third phase to the LaSi2/Si composite could improve the cycle life. Thus, this study prepared nanocomposite electrodes containing elastic LaSi2, stiff MSi2 (where M = Cr, Mo, Nb, Ta, Ti, or W), and elemental Si and investigated their electrochemical performances. Reaction behaviors, such as the metallographic structure, electrode thickness, and phase transition, were also clarified. The LaSi2/NbSi2/Si electrode exhibited the best cycle life without changes in its metallographic structure owing to the synergistic effect of stiff and elastic silicides.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"41 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942969","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-06DOI: 10.1149/1945-7111/ad69ca
Jean-Luc Fattebert and Lorena Alzate-Vargas
We revisit a theoretical result by Okamoto (2013 Journal of The Electrochemical Society, 160, A404) who calculated the energy barrier for the decomposition of lithium hexafluorophosphate (LiPF6) into LiF + PF5 when solvated in Ethylene carbonate (EC)-based electrolyte. Using different numerical techniques to discretize the Density Functional Theory (DFT) equations, and different continuum solvation models with the same dielectric constant, our results largely confirm the original calculation. However, simulations with a higher dielectric permittivity value, closer to that of EC, show a lower energy barrier. More importantly, First-Principles simulations with an explicit solvent show a substantially lower energy barrier.
我们重温了 Okamoto（2013 Journal of The Electrochemical Society, 160, A404）的一项理论成果，他计算了六氟磷酸锂（LiPF6）在碳酸乙烯酯（EC）基电解质中溶解时分解为 LiF + PF5 的能障。我们使用不同的数值技术对密度泛函理论（DFT）方程进行离散化，并在相同介电常数下使用不同的连续介质溶解模型，结果在很大程度上证实了最初的计算结果。然而，介电常数值更高，更接近于导电率的模拟结果显示能垒更低。更重要的是，使用显式溶剂的第一性原理模拟显示出更低的能障。
{"title":"Communication—First-Principles Simulations of LiPF6 Decomposition in Ethylene Carbonate-Based Electrolytes","authors":"Jean-Luc Fattebert and Lorena Alzate-Vargas","doi":"10.1149/1945-7111/ad69ca","DOIUrl":"https://doi.org/10.1149/1945-7111/ad69ca","url":null,"abstract":"We revisit a theoretical result by Okamoto (2013 Journal of The Electrochemical Society, 160, A404) who calculated the energy barrier for the decomposition of lithium hexafluorophosphate (LiPF6) into LiF + PF5 when solvated in Ethylene carbonate (EC)-based electrolyte. Using different numerical techniques to discretize the Density Functional Theory (DFT) equations, and different continuum solvation models with the same dielectric constant, our results largely confirm the original calculation. However, simulations with a higher dielectric permittivity value, closer to that of EC, show a lower energy barrier. More importantly, First-Principles simulations with an explicit solvent show a substantially lower energy barrier.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"8 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942972","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-31DOI: 10.1149/1945-7111/ad6483
Taylor R. Garrick, Miguel A. Fernandez, Brian J. Koch, Erin Efimoff, Matthew Jones, Rafid Mollah, Hunter Teel, Xiaoniu Du, Sirivatch Shimpalee, Song-Yul Choe, Venkat R. Subramanian, Jason B. Siegel
Automotive manufacturers are working to improve individual cell, module, and overall pack design by increasing the performance, range, and durability, while reducing cost. One key piece to consider during the design process is the active material volume change, its linkage to the particle, electrode, and cell level volume changes, and the interplay with structural components in the rechargeable energy storage system. As the time from initial design to manufacture of electric vehicles decreases, design work needs to move to the virtual domain; therefore, a need for coupled electrochemical-mechanical models that take into account the active material volume change and the rate dependence of this volume change need to be considered. In this study, we illustrated the applicability of a coupled electrochemical-mechanical battery model considering multiple representative particles to capture experimentally measured rate dependent reversible volume change at the cell level through the use of an electrochemical-mechanical battery model that couples the particle, electrode, and cell level volume changes. By employing this coupled approach, the importance of considering multiple active material particle sizes representative of the distribution is demonstrated. The non-uniformity in utilization between two different size particles as well as the significant spatial non-uniformity in the radial direction of the larger particles is the primary driver of the rate dependent characteristics of the volume change at the electrode and cell level.
{"title":"Modeling Rate Dependent Volume Change in Porous Electrodes in Lithium-Ion Batteries","authors":"Taylor R. Garrick, Miguel A. Fernandez, Brian J. Koch, Erin Efimoff, Matthew Jones, Rafid Mollah, Hunter Teel, Xiaoniu Du, Sirivatch Shimpalee, Song-Yul Choe, Venkat R. Subramanian, Jason B. Siegel","doi":"10.1149/1945-7111/ad6483","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6483","url":null,"abstract":"Automotive manufacturers are working to improve individual cell, module, and overall pack design by increasing the performance, range, and durability, while reducing cost. One key piece to consider during the design process is the active material volume change, its linkage to the particle, electrode, and cell level volume changes, and the interplay with structural components in the rechargeable energy storage system. As the time from initial design to manufacture of electric vehicles decreases, design work needs to move to the virtual domain; therefore, a need for coupled electrochemical-mechanical models that take into account the active material volume change and the rate dependence of this volume change need to be considered. In this study, we illustrated the applicability of a coupled electrochemical-mechanical battery model considering multiple representative particles to capture experimentally measured rate dependent reversible volume change at the cell level through the use of an electrochemical-mechanical battery model that couples the particle, electrode, and cell level volume changes. By employing this coupled approach, the importance of considering multiple active material particle sizes representative of the distribution is demonstrated. The non-uniformity in utilization between two different size particles as well as the significant spatial non-uniformity in the radial direction of the larger particles is the primary driver of the rate dependent characteristics of the volume change at the electrode and cell level.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"292 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141868226","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-29DOI: 10.1149/1945-7111/ad650b
Tuyet Nhung Pham, Van Manh Tien, Van Hoang Ong, Nhat Trang Nguyen Le, Thuy Nguyen Linh Ho, Hoang Doan Tan Le, Nguyen Quang Hoa, Hoang Vinh Tran, Dinh Ngo Xuan, Huy Tran Quang, Lam Dinh Vu, Anh-Tuan Le
Silver (Ag) and gold (Au) nanoparticles (NPs) are incorporated into the zeolitic imidazolate framework-8 (ZIF-8) host matrix, which is successfully coated the screen-printed electrodes (SPEs) for the effective detection of chloramphenicol (CAP). The morphological and structural characteristics are examined using scanning electron microscope (SEM) and X-ray diffraction (XRD) analysis. Additionally, the electrochemical characteristics and sensing performance of CAP on the proposed electrodes are investigated in detail using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), chronoamperometry (CA), and differential pulse voltammetry (DPV) measurements, respectively. The results suggest the SPEs modified with Ag@ZIF-8 and Au@ZIF-8 exhibit impressive enhancements in sensitivity, linear concentration range, limits of detection (LODs), and repeatability. Under the optimum conditions, the proposed electrochemical sensors had a linear range of 0.25–50 μM for Ag@ZIF-8/SPE and 5–50 μM for Au@ZIF-8/SPE, corresponding to LODs of 0.16 and 0.404 μM, respectively. Notably, a series of kinetic parameters related to the redox reactions of both standard Fe(CN)63−/4− probe and CAP molecules in phosphate-buffered saline (PBS) buffer are determined. Furthermore, valuable insights into the influence mechanism nature of Ag@ZIF-8 and Au@ZIF-8 nanocomposites on the electrochemical behaviors are proposed, demonstrating the great potential of the developed sensors for CAP detection.
将银（Ag）和金（Au）纳米粒子（NPs）掺入到沸石咪唑啉框架-8（ZIF-8）主基质中，并成功涂覆到丝网印刷电极（SPEs）上，以有效检测氯霉素（CAP）。利用扫描电子显微镜（SEM）和 X 射线衍射（XRD）分析研究了其形态和结构特征。此外，还分别使用循环伏安法 (CV)、电化学阻抗谱 (EIS)、时变法 (CA) 和差分脉冲伏安法 (DPV) 测量方法详细研究了 CAP 在所提电极上的电化学特性和传感性能。结果表明，用 Ag@ZIF-8 和 Au@ZIF-8 修饰的固相萃取剂在灵敏度、线性浓度范围、检出限 (LOD) 和重复性方面都有显著提高。在最佳条件下，Ag@ZIF-8/SPE 的线性范围为 0.25-50 μM，Au@ZIF-8/SPE 的线性范围为 5-50 μM，相应的检测限分别为 0.16 和 0.404 μM。值得注意的是，测定了标准 Fe(CN)63-/4- 探针和 CAP 分子在磷酸盐缓冲盐水（PBS）缓冲液中氧化还原反应的一系列动力学参数。此外，还就 Ag@ZIF-8 和 Au@ZIF-8 纳米复合材料对电化学行为的影响机理性质提出了有价值的见解，证明了所开发的传感器在 CAP 检测方面的巨大潜力。
{"title":"Electrochemical Kinetic Behaviors and Sensing Performance of Au@ZIF-8 and Ag@ZIF-8 Nanocomposites-Based Platforms Towards Ultrasensitive Detection of Chloramphenicol","authors":"Tuyet Nhung Pham, Van Manh Tien, Van Hoang Ong, Nhat Trang Nguyen Le, Thuy Nguyen Linh Ho, Hoang Doan Tan Le, Nguyen Quang Hoa, Hoang Vinh Tran, Dinh Ngo Xuan, Huy Tran Quang, Lam Dinh Vu, Anh-Tuan Le","doi":"10.1149/1945-7111/ad650b","DOIUrl":"https://doi.org/10.1149/1945-7111/ad650b","url":null,"abstract":"Silver (Ag) and gold (Au) nanoparticles (NPs) are incorporated into the zeolitic imidazolate framework-8 (ZIF-8) host matrix, which is successfully coated the screen-printed electrodes (SPEs) for the effective detection of chloramphenicol (CAP). The morphological and structural characteristics are examined using scanning electron microscope (SEM) and X-ray diffraction (XRD) analysis. Additionally, the electrochemical characteristics and sensing performance of CAP on the proposed electrodes are investigated in detail using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), chronoamperometry (CA), and differential pulse voltammetry (DPV) measurements, respectively. The results suggest the SPEs modified with Ag@ZIF-8 and Au@ZIF-8 exhibit impressive enhancements in sensitivity, linear concentration range, limits of detection (LODs), and repeatability. Under the optimum conditions, the proposed electrochemical sensors had a linear range of 0.25–50 <italic toggle=\"yes\">μ</italic>M for Ag@ZIF-8/SPE and 5–50 <italic toggle=\"yes\">μ</italic>M for Au@ZIF-8/SPE, corresponding to LODs of 0.16 and 0.404 <italic toggle=\"yes\">μ</italic>M, respectively. Notably, a series of kinetic parameters related to the redox reactions of both standard Fe(CN)<sub>6</sub>\u0000<sup>3−/4−</sup> probe and CAP molecules in phosphate-buffered saline (PBS) buffer are determined. Furthermore, valuable insights into the influence mechanism nature of Ag@ZIF-8 and Au@ZIF-8 nanocomposites on the electrochemical behaviors are proposed, demonstrating the great potential of the developed sensors for CAP detection.<inline-formula>\u0000<inline-graphic xlink:href=\"jesad650b-ga.jpg\" xlink:type=\"simple\"></inline-graphic>\u0000</inline-formula>","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"25 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141868245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-25DOI: 10.1149/1945-7111/ad6508
Raluca-Ioana Stefan-van Staden, Damaris-Cristina Gheorghe and Ruxandra-Maria Ilie-Mihai
VSIG1 is a new biomarker member of the JAM family relevant in gastric cancer diagnostics. Due to its detection and quantification impact for fast and early diagnosis of gastric cancer, two types of intelligent miniplatforms based on stochastic sensors as detection tools, were designed and validated using real samples. A 3D stochastic microsensor based on Nitrogen and Sulfur dopped graphene paste modified with calix[4]arene-25,26,27,28-tetrol, and a 2D disposable screen-printed stochastic sensor based on thin film gold modified with calix[4]arene-25,26,27,28-tetrol were constructed and inserted as working sensors into the miniplatforms. The proposed intelligent miniplatforms shown sensitivities as high as 1.12 × 1010 s−1g−1ml, limits of determination of 1 × 10−23g ml−1, and working concentration ranges between 1 × 10−23 and 1 × 10−8 g ml−1. Recoveries higher than 99.30% with % RSD values lower than 0.05% were obtained when used for screening test of biological samples, for VSIG1.
{"title":"Molecular Recognition of VSIG1 in Biological Samples for Fast Diagnosis of Gastric Cancer","authors":"Raluca-Ioana Stefan-van Staden, Damaris-Cristina Gheorghe and Ruxandra-Maria Ilie-Mihai","doi":"10.1149/1945-7111/ad6508","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6508","url":null,"abstract":"VSIG1 is a new biomarker member of the JAM family relevant in gastric cancer diagnostics. Due to its detection and quantification impact for fast and early diagnosis of gastric cancer, two types of intelligent miniplatforms based on stochastic sensors as detection tools, were designed and validated using real samples. A 3D stochastic microsensor based on Nitrogen and Sulfur dopped graphene paste modified with calix[4]arene-25,26,27,28-tetrol, and a 2D disposable screen-printed stochastic sensor based on thin film gold modified with calix[4]arene-25,26,27,28-tetrol were constructed and inserted as working sensors into the miniplatforms. The proposed intelligent miniplatforms shown sensitivities as high as 1.12 × 1010 s−1g−1ml, limits of determination of 1 × 10−23g ml−1, and working concentration ranges between 1 × 10−23 and 1 × 10−8 g ml−1. Recoveries higher than 99.30% with % RSD values lower than 0.05% were obtained when used for screening test of biological samples, for VSIG1.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"3 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141776973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-25DOI: 10.1149/1945-7111/ad6482
Mohd. Sufiyan Khan, Anwesha Mukherjee, Pabitra Ghosh and Kumaresan R.
Ti2CrV alloy shows good hydrogen storage characteristics at room temperature and ambient pressure. The present study investigated the feasibility of direct electrochemical reduction of TiO2-Cr2O3-V3O5 to Ti2CrV in CaCl2 melt at 900 °C by the FFC Cambridge process. The electrolysis was conducted in a two-electrode assembly with the sintered mixed oxide cathode and HD graphite anode at a constant cell voltage of 3.1 V for different time intervals to elucidate the reduction mechanism of the metal oxide mixture. The obtained products were characterized by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy techniques. Cyclic voltammetry studies using metallic cavity electrode containing mixed metal oxide powder were also carried out to determine the electrochemical reduction behavior in CaCl2 melt at 900 °C. It was observed that the presence of pre-formed Cr and V metal in the vicinity of titanium oxide helped in its faster reduction. The complete metallization of the sintered mixed oxide pellet occurred after 15 h of electrolysis. The electrochemical reduction mechanism was observed to proceed through various intermediates such as chromium-rich Cr-V, vanadium-rich V-Cr, CaTiO3, TiO, Ti6O, Ti-V, and C15-TiCr2.
Ti2CrV 合金在室温和环境压力下具有良好的储氢特性。本研究探讨了在 900 °C 的 CaCl2 熔体中通过 FFC 剑桥工艺将 TiO2-Cr2O3-V3O5 直接电化学还原为 Ti2CrV 的可行性。电解在烧结混合氧化物阴极和 HD 石墨阳极的双电极组件中进行，在 3.1 V 恒定电池电压下进行不同时间间隔的电解，以阐明金属氧化物混合物的还原机制。获得的产物通过 X 射线衍射、扫描电子显微镜和能量色散 X 射线光谱技术进行了表征。此外，还使用含有混合金属氧化物粉末的金属空腔电极进行了循环伏安研究，以确定在 900 °C 下 CaCl2 熔体中的电化学还原行为。研究发现，在氧化钛附近存在预成形的铬和钒金属有助于加快其还原速度。烧结的混合氧化物颗粒在电解 15 小时后完全金属化。据观察，电化学还原机制是通过各种中间产物进行的，如富铬 Cr-V、富钒 V-Cr、CaTiO3、TiO、Ti6O、Ti-V 和 C15-TiCr2。
{"title":"Electrochemical Preparation of Ti2CrV Alloy in CaCl2 Melt","authors":"Mohd. Sufiyan Khan, Anwesha Mukherjee, Pabitra Ghosh and Kumaresan R.","doi":"10.1149/1945-7111/ad6482","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6482","url":null,"abstract":"Ti2CrV alloy shows good hydrogen storage characteristics at room temperature and ambient pressure. The present study investigated the feasibility of direct electrochemical reduction of TiO2-Cr2O3-V3O5 to Ti2CrV in CaCl2 melt at 900 °C by the FFC Cambridge process. The electrolysis was conducted in a two-electrode assembly with the sintered mixed oxide cathode and HD graphite anode at a constant cell voltage of 3.1 V for different time intervals to elucidate the reduction mechanism of the metal oxide mixture. The obtained products were characterized by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy techniques. Cyclic voltammetry studies using metallic cavity electrode containing mixed metal oxide powder were also carried out to determine the electrochemical reduction behavior in CaCl2 melt at 900 °C. It was observed that the presence of pre-formed Cr and V metal in the vicinity of titanium oxide helped in its faster reduction. The complete metallization of the sintered mixed oxide pellet occurred after 15 h of electrolysis. The electrochemical reduction mechanism was observed to proceed through various intermediates such as chromium-rich Cr-V, vanadium-rich V-Cr, CaTiO3, TiO, Ti6O, Ti-V, and C15-TiCr2.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"24 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141776881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","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：