Pub Date : 2024-09-17DOI: 10.1149/1945-7111/ad77f5
Wonseok Yang, Suhee Choi, Tae-Hong Park, Sungyeol Choi and Sang-Eun Bae
Understanding the redox reactions of fission products in molten salts is crucial for developing pyroprocessing techniques for used nuclear fuel. A rotating disk electrode is useful for investigating the electrochemical reactions with controlled mass transfer conditions, but its application has been limited in high-temperature corrosive molten salts. This study employs a tungsten (W) rotating disk electrode (RDE) to measure the electrochemical and kinetic properties of the Sm(III)/Sm(II) redox reaction in a LiCl-KCl eutectic molten salt. The properties of the Sm(III)/Sm(II) redox reaction, including diffusion coefficients, exchange current densities, charge transfer coefficients, activation energies, and Tafel slopes, were determined over a temperature range of 723–803 K using limiting currents in linear sweep voltammetry at various rotating speeds and mass transfer-corrected Tafel plots. The kinetic parameters obtained using the rotating disk electrode system can be useful for optimizing the design of pyroprocessing techniques.
了解熔盐中裂变产物的氧化还原反应对于开发废旧核燃料热处理技术至关重要。旋转盘电极可用于研究受控传质条件下的电化学反应，但其在高温腐蚀性熔盐中的应用一直受到限制。本研究采用钨（W）旋转盘电极（RDE）测量锂-氯化钾共晶熔盐中 Sm(III)/Sm(II) 氧化还原反应的电化学和动力学特性。在 723-803 K 的温度范围内，利用线性扫描伏安法在不同转速下的极限电流和传质校正塔菲尔图，测定了 Sm(III)/Sm(II) 氧化还原反应的特性，包括扩散系数、交换电流密度、电荷转移系数、活化能和塔菲尔斜率。使用旋转盘电极系统获得的动力学参数有助于优化热处理技术的设计。
{"title":"Rotating Disk Electrode Study of Sm(III)/Sm(II) in LiCl-KCl Eutectic Molten Salt","authors":"Wonseok Yang, Suhee Choi, Tae-Hong Park, Sungyeol Choi and Sang-Eun Bae","doi":"10.1149/1945-7111/ad77f5","DOIUrl":"https://doi.org/10.1149/1945-7111/ad77f5","url":null,"abstract":"Understanding the redox reactions of fission products in molten salts is crucial for developing pyroprocessing techniques for used nuclear fuel. A rotating disk electrode is useful for investigating the electrochemical reactions with controlled mass transfer conditions, but its application has been limited in high-temperature corrosive molten salts. This study employs a tungsten (W) rotating disk electrode (RDE) to measure the electrochemical and kinetic properties of the Sm(III)/Sm(II) redox reaction in a LiCl-KCl eutectic molten salt. The properties of the Sm(III)/Sm(II) redox reaction, including diffusion coefficients, exchange current densities, charge transfer coefficients, activation energies, and Tafel slopes, were determined over a temperature range of 723–803 K using limiting currents in linear sweep voltammetry at various rotating speeds and mass transfer-corrected Tafel plots. The kinetic parameters obtained using the rotating disk electrode system can be useful for optimizing the design of pyroprocessing techniques.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"11 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142263387","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 : 2024-09-17DOI: 10.1149/1945-7111/ad7987
Irina-Alina Chera-Anghel, Raluca-Ioana Stefan-van Staden, Catalina Cioates Negut and Jacobus Frederick van Staden
Ochratoxine A is a very stable mycotoxin which cannot be destroyed below 250°C. Found in grains, coffee, grapes, wine, milk, and meat, it can produce kidney damage and cancer. Therefore, a smartphone operated intellingent stochastic miniplatform was designed, characterised, and validated for the on-site screening of milk for fast determination of ochratoxine A. (Z)-N-[2-(4-hydroxyphenyl) ethyl]octadec-9-enamide was used as modifier of a gold matrix for a screen printed stochastic sensor used as sensing tool in the design of the miniplatform. A wide linear concentration range (1.0 × 10−15 − 1.0 × 10−7 mol l‒1) and a low limit of quantification of 1 fmol l‒1 were achieved for the assay of ochratoxin A. Recovery values higher than 99.00% were obtained for ochratoxine A, when the miniplatform was used for the screening of cow’s milk and vegetarian milk.
赭曲霉毒素 A 是一种非常稳定的霉菌毒素，在 250°C 以下无法被破坏。它存在于谷物、咖啡、葡萄、葡萄酒、牛奶和肉类中，可导致肾损伤和癌症。(Z)-N-[2-(4-羟基苯基)乙基]十八-9-烯酰胺被用作丝网印刷随机传感器的金基质改性剂，丝网印刷随机传感器被用作微型平台设计中的传感工具。赭曲霉毒素 A 的检测达到了较宽的线性浓度范围（1.0 × 10-15 - 1.0 × 10-7 mol l-1）和较低的定量限（1 fmol l-1）。
{"title":"A Smartphone Operated Intelligent Stochastic Miniplatform for On-Site Screening of Milk for Fast Determination of Ochratoxin A","authors":"Irina-Alina Chera-Anghel, Raluca-Ioana Stefan-van Staden, Catalina Cioates Negut and Jacobus Frederick van Staden","doi":"10.1149/1945-7111/ad7987","DOIUrl":"https://doi.org/10.1149/1945-7111/ad7987","url":null,"abstract":"Ochratoxine A is a very stable mycotoxin which cannot be destroyed below 250°C. Found in grains, coffee, grapes, wine, milk, and meat, it can produce kidney damage and cancer. Therefore, a smartphone operated intellingent stochastic miniplatform was designed, characterised, and validated for the on-site screening of milk for fast determination of ochratoxine A. (Z)-N-[2-(4-hydroxyphenyl) ethyl]octadec-9-enamide was used as modifier of a gold matrix for a screen printed stochastic sensor used as sensing tool in the design of the miniplatform. A wide linear concentration range (1.0 × 10−15 − 1.0 × 10−7 mol l‒1) and a low limit of quantification of 1 fmol l‒1 were achieved for the assay of ochratoxin A. Recovery values higher than 99.00% were obtained for ochratoxine A, when the miniplatform was used for the screening of cow’s milk and vegetarian milk.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"19 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142263582","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 : 2024-09-17DOI: 10.1149/1945-7111/ad7891
Yan Su, Ben Yang, Xinwei Xu, Maosheng Jing, Xinnian Meng and Yongming Tang
An approach to encapsulate zinc powder by in situ polymerization of aniline (PANI@Zn) is developed for Zn-rich epoxy coatings (ZRCs). With the application of PANI@Zn composites in the ZRCs, the encapsulated zinc particles are not activated due to the corrosion inhibition of PANI at the early stage of immersion, and physical shielding being mainly responsible for the protection of the steel substrate. At the stage of cathodic protection, the consumption of zinc powder is relatively uniform from the outer layer to the inner layer of the coating PANI@Zn coating, and the utilization rate of zinc powder is higher than that in the coating incorporated by the raw zinc powder. The required amount of zinc powder for achieving the same protective effect as the case of the raw zinc powder is reduced by ca. 20% after the application of the PANI@Zn composites.
{"title":"In Situ PANI Encapsulation of Zinc Powder Enhancing the Corrosion Resistance of Zinc-Rich Epoxy Coatings","authors":"Yan Su, Ben Yang, Xinwei Xu, Maosheng Jing, Xinnian Meng and Yongming Tang","doi":"10.1149/1945-7111/ad7891","DOIUrl":"https://doi.org/10.1149/1945-7111/ad7891","url":null,"abstract":"An approach to encapsulate zinc powder by in situ polymerization of aniline (PANI@Zn) is developed for Zn-rich epoxy coatings (ZRCs). With the application of PANI@Zn composites in the ZRCs, the encapsulated zinc particles are not activated due to the corrosion inhibition of PANI at the early stage of immersion, and physical shielding being mainly responsible for the protection of the steel substrate. At the stage of cathodic protection, the consumption of zinc powder is relatively uniform from the outer layer to the inner layer of the coating PANI@Zn coating, and the utilization rate of zinc powder is higher than that in the coating incorporated by the raw zinc powder. The required amount of zinc powder for achieving the same protective effect as the case of the raw zinc powder is reduced by ca. 20% after the application of the PANI@Zn composites.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"46 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142263583","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 : 2024-09-16DOI: 10.1149/1945-7111/ad76da
Alexander Karger, Simon E. J. O’Kane, Marcel Rogge, Cedric Kirst, Jan P. Singer, Monica Marinescu, Gregory J. Offer and Andreas Jossen
Degradation models are important tools for understanding and mitigating lithium-ion battery aging, yet a universal model that can predict degradation under all operating conditions remains elusive. One challenge is the coupled influence of calendar and cycle aging phases on degradation mechanisms, such as solid electrolyte interphase (SEI) formation. In this work, we identify and systematically compare three different SEI interaction theories found in the literature, and apply them to experimental degradation data from a commercial lithium-ion cell. In a step-by-step process, and after careful data selection, we show that SEI delamination without any cracking of the active particles, and SEI microcracking, where cycling only affects SEI growth during the cycle itself, are both unlikely candidates. Instead, the results indicate that upon cycling, both the SEI and the active particle crack, and we provide a simple, 4-parameter equation that can predict the particle crack rate. Contrary to the widely-accepted Paris’ law, the particle crack rate decreases with increasing cycles, potentially due to changing intercalation dynamics resulting from the increasing surface-to-volume ratio of the active particles. The proposed model predicts SEI formation accurately at different storage conditions, while simply adding the degradation from pure calendar and cycle aging underestimates the total degradation.
降解模型是了解和缓解锂离子电池老化的重要工具，然而，能够预测所有工作条件下降解情况的通用模型仍然遥不可及。其中一个挑战是日历和循环老化阶段对降解机制的耦合影响，例如固体电解质相（SEI）的形成。在这项工作中，我们确定并系统比较了文献中三种不同的 SEI 相互作用理论，并将它们应用到商用锂离子电池的实验降解数据中。经过一步步的研究和对数据的仔细筛选，我们发现，没有任何活性颗粒裂纹的 SEI 分层和 SEI 微裂纹（循环仅在循环过程中影响 SEI 的生长）都是不可能的候选理论。相反，结果表明，在循环过程中，SEI 和活性颗粒都会开裂，我们提供了一个简单的 4 参数方程，可以预测颗粒开裂率。与广为接受的帕里斯定律相反，颗粒开裂率会随着循环次数的增加而降低，这可能是由于活性颗粒的表面体积比不断增加，导致插层动力学发生了变化。所提出的模型可以准确预测不同存储条件下 SEI 的形成，而简单地将纯日历和循环老化产生的降解相加，则会低估总降解量。
{"title":"Modeling Particle Versus SEI Cracking in Lithium-Ion Battery Degradation: Why Calendar and Cycle Aging Cannot Simply be Added","authors":"Alexander Karger, Simon E. J. O’Kane, Marcel Rogge, Cedric Kirst, Jan P. Singer, Monica Marinescu, Gregory J. Offer and Andreas Jossen","doi":"10.1149/1945-7111/ad76da","DOIUrl":"https://doi.org/10.1149/1945-7111/ad76da","url":null,"abstract":"Degradation models are important tools for understanding and mitigating lithium-ion battery aging, yet a universal model that can predict degradation under all operating conditions remains elusive. One challenge is the coupled influence of calendar and cycle aging phases on degradation mechanisms, such as solid electrolyte interphase (SEI) formation. In this work, we identify and systematically compare three different SEI interaction theories found in the literature, and apply them to experimental degradation data from a commercial lithium-ion cell. In a step-by-step process, and after careful data selection, we show that SEI delamination without any cracking of the active particles, and SEI microcracking, where cycling only affects SEI growth during the cycle itself, are both unlikely candidates. Instead, the results indicate that upon cycling, both the SEI and the active particle crack, and we provide a simple, 4-parameter equation that can predict the particle crack rate. Contrary to the widely-accepted Paris’ law, the particle crack rate decreases with increasing cycles, potentially due to changing intercalation dynamics resulting from the increasing surface-to-volume ratio of the active particles. The proposed model predicts SEI formation accurately at different storage conditions, while simply adding the degradation from pure calendar and cycle aging underestimates the total degradation.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"94 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142263388","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 : 2024-09-15DOI: 10.1149/1945-7111/ad749f
Tim Dörenkamp, Mayank Sabharwal, Federica Marone, Felix N. Büchi, Thomas J. Schmidt and Jens Eller
Efficient removal of the electrochemically produced water from the gas diffusion layer (GDL) in polymer electrolyte fuel cells is crucial for reducing mass transport losses and improving the efficiency at high current densities. Understanding the relationship between the water percolation through the GDL and droplet formation in the gas channel will allow the design of advanced GDL materials, which provide optimal water management. In this study, a catalyst-coated membrane with 8 individual active areas (0.06 mm2 each) is investigated using operando X-ray tomographic microscopy to study the transient development and interaction of multiple percolating water clusters in a GDL and droplet formation in the channel. The 4D imaging results at a time resolution of 1 Hz showed transient instabilities in the developed percolating water networks at various frequencies associated with break-through and spontaneous water drainage.
{"title":"Investigation of Dynamic Water Cluster and Droplet Interactions in Polymer Electrolyte Fuel Cells using Operando X-ray Tomographic Microscopy","authors":"Tim Dörenkamp, Mayank Sabharwal, Federica Marone, Felix N. Büchi, Thomas J. Schmidt and Jens Eller","doi":"10.1149/1945-7111/ad749f","DOIUrl":"https://doi.org/10.1149/1945-7111/ad749f","url":null,"abstract":"Efficient removal of the electrochemically produced water from the gas diffusion layer (GDL) in polymer electrolyte fuel cells is crucial for reducing mass transport losses and improving the efficiency at high current densities. Understanding the relationship between the water percolation through the GDL and droplet formation in the gas channel will allow the design of advanced GDL materials, which provide optimal water management. In this study, a catalyst-coated membrane with 8 individual active areas (0.06 mm2 each) is investigated using operando X-ray tomographic microscopy to study the transient development and interaction of multiple percolating water clusters in a GDL and droplet formation in the channel. The 4D imaging results at a time resolution of 1 Hz showed transient instabilities in the developed percolating water networks at various frequencies associated with break-through and spontaneous water drainage.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"64 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142263581","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 : 2024-09-15DOI: 10.1149/1945-7111/ad778f
Ling Ran, Jie Li, Zhong Zou, Bo Zhang, Quanlin Li, Shuai Yang and Hongliang Zhang
Aluminum electrolysis cells (AECs) require effective thermal regulation to operate flexibly alongside renewable energy sources. Prior to implementing thermal regulation strategies, it is essential to predict the dynamic variations in the thermal field and ledge characteristics of a full-scale cell. This study introduces a transient electro-thermal-flow coupling model for a full-scale AEC, aimed at investigating the interactions between ledge distribution and various operational fields, including thermal, electric, and flow fields. The model facilitates the calculation and assessment of the dynamic properties of the ledge and thermal balance under ±15% flexible current variations. Results indicate that during a current increase, ledge melting predominantly occurs in the electrolyte layer, while ledge solidification is primarily observed in the metal layer during a current reduction. Regions with a thicker ledge and faster velocity tend to melt more during current increases and are less likely to return to their original shape and thickness during current reductions, complicating the rapid restoration of thermal equilibrium. To achieve uniform ledge distribution and real-time adaptation to flexible current variations, it is recommended to install distributed cooling devices on the sides of the AEC to enable differential ledge regulation at various locations.
{"title":"Fully-Coupled Electric-Thermal-Flow Modeling and Investigation of Dynamic Thermal-Ledge Behavior in Aluminum Electrolysis Cell","authors":"Ling Ran, Jie Li, Zhong Zou, Bo Zhang, Quanlin Li, Shuai Yang and Hongliang Zhang","doi":"10.1149/1945-7111/ad778f","DOIUrl":"https://doi.org/10.1149/1945-7111/ad778f","url":null,"abstract":"Aluminum electrolysis cells (AECs) require effective thermal regulation to operate flexibly alongside renewable energy sources. Prior to implementing thermal regulation strategies, it is essential to predict the dynamic variations in the thermal field and ledge characteristics of a full-scale cell. This study introduces a transient electro-thermal-flow coupling model for a full-scale AEC, aimed at investigating the interactions between ledge distribution and various operational fields, including thermal, electric, and flow fields. The model facilitates the calculation and assessment of the dynamic properties of the ledge and thermal balance under ±15% flexible current variations. Results indicate that during a current increase, ledge melting predominantly occurs in the electrolyte layer, while ledge solidification is primarily observed in the metal layer during a current reduction. Regions with a thicker ledge and faster velocity tend to melt more during current increases and are less likely to return to their original shape and thickness during current reductions, complicating the rapid restoration of thermal equilibrium. To achieve uniform ledge distribution and real-time adaptation to flexible current variations, it is recommended to install distributed cooling devices on the sides of the AEC to enable differential ledge regulation at various locations.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"30 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142263586","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 : 2024-09-15DOI: 10.1149/1945-7111/ad76de
Rankin Shum, Marah Cragun, Tyler Williams and Devin Rappleye
Residual water in molten CaCl2 reacts to form different byproducts, such as HCl, which can impact the corrosivity of the salt and efficiency of electrochemical operations, such as electrolytic oxide reduction and electrorefining. The ability to detect and quantify these byproducts electrochemically can provide feedback on the efficacy of vacuum drying and other purification methods, as well as the impact of these byproducts on process operations. An electrochemical signal’s association with the production of H2 is verified and characterized using cyclic voltammetry (CV) and residual gas analysis. CV estimated a 2-electron exchange process associated with H2 production. CV detected trace quantities of an oxidized species containing hydrogen in the salt on the order of 10 ppm. Different salt handling methods were compared for their impact on the hydrogen electrochemical signal. It was found that 30 min of exposure of CaCl2 in a beaker to low-humidity air (<20%) had minimal impact on the H2 production signal.
{"title":"Electrochemical Investigation of Moisture Byproducts in Molten Calcium Chloride","authors":"Rankin Shum, Marah Cragun, Tyler Williams and Devin Rappleye","doi":"10.1149/1945-7111/ad76de","DOIUrl":"https://doi.org/10.1149/1945-7111/ad76de","url":null,"abstract":"Residual water in molten CaCl2 reacts to form different byproducts, such as HCl, which can impact the corrosivity of the salt and efficiency of electrochemical operations, such as electrolytic oxide reduction and electrorefining. The ability to detect and quantify these byproducts electrochemically can provide feedback on the efficacy of vacuum drying and other purification methods, as well as the impact of these byproducts on process operations. An electrochemical signal’s association with the production of H2 is verified and characterized using cyclic voltammetry (CV) and residual gas analysis. CV estimated a 2-electron exchange process associated with H2 production. CV detected trace quantities of an oxidized species containing hydrogen in the salt on the order of 10 ppm. Different salt handling methods were compared for their impact on the hydrogen electrochemical signal. It was found that 30 min of exposure of CaCl2 in a beaker to low-humidity air (<20%) had minimal impact on the H2 production signal.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"3 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142263584","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 : 2024-09-15DOI: 10.1149/1945-7111/ad7764
Yiwei Sun, Fenjuan Shao, Yuting Luo, Haoxiang Wang, Yuyang He, Liying Sun and Dongpo Xu
An efficient molecularly-imprinted electrochemical sensor for the detection of ampicillin was prepared using polypyrrole tetracycline polymer modified with ZrO2 nanofibers. The ZrO2 nanofibers prepared by electrostatic spinning increased the surface area of the electrode with the binding sites of the electropolymerized membrane. The ampicillin sensor with polypyrrole as the functional monomer was able to specifically bind ampicillin molecules and detect ampicillin in various types of samples. In this study, cyclic voltammetry and differential pulse voltammetry were used to evaluate the electrochemical performance of ZrO2-MIP. Under the optimized conditions, the detection limit of this sensor was 0.397 nM, the detection range was 0.5 ∼ 500 nM, and the R2 reached 0.998. It has good selectivity, reproducibility, and stability, and achieves the AMP detection of the milk of the actual samples, which has a good prospect of application.
{"title":"ZrO2 Nanofiber-Based Molecular Imprinted Electrochemical Sensor for Detection of Ampicillin","authors":"Yiwei Sun, Fenjuan Shao, Yuting Luo, Haoxiang Wang, Yuyang He, Liying Sun and Dongpo Xu","doi":"10.1149/1945-7111/ad7764","DOIUrl":"https://doi.org/10.1149/1945-7111/ad7764","url":null,"abstract":"An efficient molecularly-imprinted electrochemical sensor for the detection of ampicillin was prepared using polypyrrole tetracycline polymer modified with ZrO2 nanofibers. The ZrO2 nanofibers prepared by electrostatic spinning increased the surface area of the electrode with the binding sites of the electropolymerized membrane. The ampicillin sensor with polypyrrole as the functional monomer was able to specifically bind ampicillin molecules and detect ampicillin in various types of samples. In this study, cyclic voltammetry and differential pulse voltammetry were used to evaluate the electrochemical performance of ZrO2-MIP. Under the optimized conditions, the detection limit of this sensor was 0.397 nM, the detection range was 0.5 ∼ 500 nM, and the R2 reached 0.998. It has good selectivity, reproducibility, and stability, and achieves the AMP detection of the milk of the actual samples, which has a good prospect of application.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"32 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142263585","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 : 2024-09-12DOI: 10.1149/1945-7111/ad75bd
Byeong-Su Kang, Se-Hyeon Jeon, Sang-Jun Park, Young-Woong Song, Jinsub Lim, YoungSun Hong, Min-Young Kim and Ho-Sung Kim
Sulfide-based solid electrolyte such as Li6PS5Cl (LPSCl) is unstable in contact with Li metal electrode due to decomposing to by-product resulting in poor performance. Therefore, the introduction of an interlayer to suppress reactivity is essential. In this study, instead of an interlayer, an oxide/polymer composite electrolyte was applied to suppress side reactions, while a sulfide-based electrolyte was used at the cathode to improve interfacial control between the cathode and the electrolyte. All-solid-state lithium batteries (ASLBs) were prepared by applying sulfide-based solid electrolyte (argyrodite, Li6PS5Cl) including NCM424, polyvinylidene fluoride (PVDF), and Super-P in a composite cathode layer, and a composite solid electrolyte (CSE) layer by mixing an oxide-based solid electrolyte (garnet, Al-doped Li7La3Zr2O12 (LLZO)), polymer (PEO, polyethylene oxide) and lithium metal as the anode. In this study, NCM424 powder was coated with LiNbO3 to prevent chemical reaction with the sulfide electrolyte. As the PVDF binder was applied to the cathode of the ASLB, the discharge capacity of the cell was approximately 163 mAh g−1 at 70 °C, 0.1 C, and 4.2 V cut-off and its capacity retention was 83% after 50 cycles. The effects of the PVDF were evaluated using both pouch-type cells. The capacity and cycle retention are greatly dependent on the PVDF content of the cathode materials and the drying temperature during the fabrication of the cathode. When the cathode with PVDF binder was dried at 130 °C, initial cycling was required for activation of the pouch cell, and it was possible to overcome this by adding a plasticizer. Highlights The composite cathode was prepared with LPSCl, NCM424, Super-P, and PVDF binder. The all-solid-state battery with the LPSCl composite cathode showed a discharge capacity of 163 mAh g−1 at 0.1 C. The cycling performance of the battery was improved by improving the properties of the active material particles.
硫化物固体电解质（如 Li6PS5Cl (LPSCl)）与锂金属电极接触时会分解成副产品，从而导致性能不稳定。因此，必须引入中间膜来抑制反应性。在这项研究中，采用氧化物/聚合物复合电解质代替中间层来抑制副反应，同时在阴极使用硫化物电解质来改善阴极与电解质之间的界面控制。通过在复合阴极层中使用包括 NCM424、聚偏二氟乙烯（PVDF）和 Super-P 在内的硫化物基固体电解质（霰石，Li6PS5Cl），制备了全固态锂电池（ASLB）、以及将氧化物基固体电解质（石榴石、掺铝的 Li7La3Zr2O12 (LLZO)）、聚合物（PEO，聚氧化乙烯）和金属锂混合作为阳极的复合固体电解质（CSE）层。在本研究中，NCM424 粉末表面涂有 LiNbO3，以防止与硫化物电解质发生化学反应。将 PVDF 粘合剂应用于 ASLB 的阴极时，在 70 °C、0.1 C 和 4.2 V 截断电压条件下，电池的放电容量约为 163 mAh g-1，循环 50 次后容量保持率为 83%。我们使用两种袋式电池对 PVDF 的效果进行了评估。容量和循环保持率在很大程度上取决于阴极材料中的 PVDF 含量和阴极制造过程中的干燥温度。当含有 PVDF 粘合剂的阴极在 130 °C 下干燥时，需要进行初始循环才能激活袋式电池，而通过添加增塑剂可以克服这一问题。亮点 使用 LPSCl、NCM424、Super-P 和 PVDF 粘合剂制备了复合阴极。使用 LPSCl 复合阴极的全固态电池在 0.1 C 时的放电容量为 163 mAh g-1。
{"title":"PVDF Binder in All-Solid-State Lithium Batteries with NCM/Sulfide/PVDF Cathode, Oxide/PEO SE Layer, and Li-metal Anode","authors":"Byeong-Su Kang, Se-Hyeon Jeon, Sang-Jun Park, Young-Woong Song, Jinsub Lim, YoungSun Hong, Min-Young Kim and Ho-Sung Kim","doi":"10.1149/1945-7111/ad75bd","DOIUrl":"https://doi.org/10.1149/1945-7111/ad75bd","url":null,"abstract":"Sulfide-based solid electrolyte such as Li6PS5Cl (LPSCl) is unstable in contact with Li metal electrode due to decomposing to by-product resulting in poor performance. Therefore, the introduction of an interlayer to suppress reactivity is essential. In this study, instead of an interlayer, an oxide/polymer composite electrolyte was applied to suppress side reactions, while a sulfide-based electrolyte was used at the cathode to improve interfacial control between the cathode and the electrolyte. All-solid-state lithium batteries (ASLBs) were prepared by applying sulfide-based solid electrolyte (argyrodite, Li6PS5Cl) including NCM424, polyvinylidene fluoride (PVDF), and Super-P in a composite cathode layer, and a composite solid electrolyte (CSE) layer by mixing an oxide-based solid electrolyte (garnet, Al-doped Li7La3Zr2O12 (LLZO)), polymer (PEO, polyethylene oxide) and lithium metal as the anode. In this study, NCM424 powder was coated with LiNbO3 to prevent chemical reaction with the sulfide electrolyte. As the PVDF binder was applied to the cathode of the ASLB, the discharge capacity of the cell was approximately 163 mAh g−1 at 70 °C, 0.1 C, and 4.2 V cut-off and its capacity retention was 83% after 50 cycles. The effects of the PVDF were evaluated using both pouch-type cells. The capacity and cycle retention are greatly dependent on the PVDF content of the cathode materials and the drying temperature during the fabrication of the cathode. When the cathode with PVDF binder was dried at 130 °C, initial cycling was required for activation of the pouch cell, and it was possible to overcome this by adding a plasticizer. Highlights The composite cathode was prepared with LPSCl, NCM424, Super-P, and PVDF binder. The all-solid-state battery with the LPSCl composite cathode showed a discharge capacity of 163 mAh g−1 at 0.1 C. The cycling performance of the battery was improved by improving the properties of the active material particles.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"12 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142263588","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 : 2024-09-12DOI: 10.1149/1945-7111/ad76db
KyuJung Jun, Yihan Xiao, Wenhao Sun, Young-Woon Byeon, Haegyeom Kim and Gerbrand Ceder
It is desirable to develop solid electrolytes that have both excellent reductive stability against lithium metal and oxidative stability against high-voltage cathodes. However, no inorganic superionic conductors reported thus far satisfy these criteria. Nitrides exhibit intrinsically superior stability against reduction but are often readily oxidized at voltages as low as 0.6 V. In this article, we investigated all nitride-based compounds to search for materials with improved oxidative stabilities over 2.0 V while retaining their intrinsic stability against Li metal. We found two compounds, LiPN2 and Li2CN2, with high oxidative stability > 2.0 V and low vacancy migration energies. Using fine-tuned CHGNet machine-learning interatomic potential, we found that upon introducing aliovalent dopants to introduce vacancies in Li2CN2, the dopant and vacancy strongly anchor with each other to result in trapped vacancies, which lowers ionic conductivity. In contrast, vacancies and dopants have minimal interactions in LiPN2, resulting in a high ionic conductivity. These two compounds were synthesized, but their ionic conductivities were not successfully measured because of the challenges in densification. With improved processing conditions, these compounds may serve as anode-side separators in dual-separator-type all-solid-state batteries or anode buffer layer materials interfaced with lithium metal.
{"title":"Nitride Lithium-ion Conductors with Enhanced Oxidative Stability","authors":"KyuJung Jun, Yihan Xiao, Wenhao Sun, Young-Woon Byeon, Haegyeom Kim and Gerbrand Ceder","doi":"10.1149/1945-7111/ad76db","DOIUrl":"https://doi.org/10.1149/1945-7111/ad76db","url":null,"abstract":"It is desirable to develop solid electrolytes that have both excellent reductive stability against lithium metal and oxidative stability against high-voltage cathodes. However, no inorganic superionic conductors reported thus far satisfy these criteria. Nitrides exhibit intrinsically superior stability against reduction but are often readily oxidized at voltages as low as 0.6 V. In this article, we investigated all nitride-based compounds to search for materials with improved oxidative stabilities over 2.0 V while retaining their intrinsic stability against Li metal. We found two compounds, LiPN2 and Li2CN2, with high oxidative stability > 2.0 V and low vacancy migration energies. Using fine-tuned CHGNet machine-learning interatomic potential, we found that upon introducing aliovalent dopants to introduce vacancies in Li2CN2, the dopant and vacancy strongly anchor with each other to result in trapped vacancies, which lowers ionic conductivity. In contrast, vacancies and dopants have minimal interactions in LiPN2, resulting in a high ionic conductivity. These two compounds were synthesized, but their ionic conductivities were not successfully measured because of the challenges in densification. With improved processing conditions, these compounds may serve as anode-side separators in dual-separator-type all-solid-state batteries or anode buffer layer materials interfaced with lithium metal.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"10 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222553","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}
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