Pub Date : 2024-09-11DOI: 10.1149/1945-7111/ad7295
Carlos Tafara Mpupuni, Orynbassar Mukhan, Ji-Su Yun and Sung-Soo Kim
Lithium metal remains a promising candidate for high-energy-density rechargeable batteries due to its exceptional specific capacity and low reduction potential. However, practical implementation of lithium metal anodes faces challenges such as dendrite formation, limited cycle life, and safety concerns. This study introduces a novel approach to enhance the performance of lithium metal powder (LMP)-based electrodes by embedding a LiNO3-carbon composite interlayer between the LMP electrode and the copper foil current collector. The N-rich carbon interlayer acts as a reservoir for LiNO3, enabling its gradual release to maintain prolonged stability of the interfacial reactions of the Li-metal and providing additional Li nucleation sites. Our findings demonstrate that the LiNO3-carbon composite effectively suppresses dendrite formation, improves reversible capacity, and stabilizes the solid electrolyte interphase. Additionally, we validated the fast-charging capabilities of the Li/NCM622 half-cell employing the LiNO3-carbon-coated Cu foil with LMP electrodes. Our results highlight the significant synergistic effect of the LiNO3 additive and carbon interlayer in enhancing the performance of lithium metal-based batteries.
{"title":"A Bifunctional Carbon-LiNO3 Composite Interlayer for Stable Lithium Metal Powder Electrodes as High Energy Density Anode Material in Lithium Batteries","authors":"Carlos Tafara Mpupuni, Orynbassar Mukhan, Ji-Su Yun and Sung-Soo Kim","doi":"10.1149/1945-7111/ad7295","DOIUrl":"https://doi.org/10.1149/1945-7111/ad7295","url":null,"abstract":"Lithium metal remains a promising candidate for high-energy-density rechargeable batteries due to its exceptional specific capacity and low reduction potential. However, practical implementation of lithium metal anodes faces challenges such as dendrite formation, limited cycle life, and safety concerns. This study introduces a novel approach to enhance the performance of lithium metal powder (LMP)-based electrodes by embedding a LiNO3-carbon composite interlayer between the LMP electrode and the copper foil current collector. The N-rich carbon interlayer acts as a reservoir for LiNO3, enabling its gradual release to maintain prolonged stability of the interfacial reactions of the Li-metal and providing additional Li nucleation sites. Our findings demonstrate that the LiNO3-carbon composite effectively suppresses dendrite formation, improves reversible capacity, and stabilizes the solid electrolyte interphase. Additionally, we validated the fast-charging capabilities of the Li/NCM622 half-cell employing the LiNO3-carbon-coated Cu foil with LMP electrodes. Our results highlight the significant synergistic effect of the LiNO3 additive and carbon interlayer in enhancing the performance of lithium metal-based batteries.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"19 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222555","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 : 2024-09-11DOI: 10.1149/1945-7111/ad73a7
Marc Ayoub, Thomas Böhm, Markus Bierling, Simon Thiele and Matthew Brodt
During steady-state operation, the proton conduction profile and the concentration profiles of the reactants and products transported through catalyst layers are non-uniform in the in-plane and through-plane directions. It is, therefore, a reasonable hypothesis that the optimal arrangement of the constituents of the catalyst layers should also be non-uniform. One way to address the non-uniformity is through graded catalyst layers. This study elucidates the state-of-the-art for graded catalyst layers, which so far were primarily investigated for proton exchange membrane fuel cells (PEMFCs). We identify the most impactful types of gradients in the PEMFC cathode and highlight studies displaying their merits in terms of better conversion efficiencies and longer lifetimes. Furthermore, two critical issues that have received little attention so far are emphasized: on the one hand, industrially relevant manufacturing techniques must be developed and implemented. On the other hand, suitable techniques are needed to identify and characterize the gradients. In this study, guidance to navigate both of these challenges is offered.
{"title":"Review—Graded Catalyst Layers in Hydrogen Fuel Cells - A Pathway to Application-Tailored Cells","authors":"Marc Ayoub, Thomas Böhm, Markus Bierling, Simon Thiele and Matthew Brodt","doi":"10.1149/1945-7111/ad73a7","DOIUrl":"https://doi.org/10.1149/1945-7111/ad73a7","url":null,"abstract":"During steady-state operation, the proton conduction profile and the concentration profiles of the reactants and products transported through catalyst layers are non-uniform in the in-plane and through-plane directions. It is, therefore, a reasonable hypothesis that the optimal arrangement of the constituents of the catalyst layers should also be non-uniform. One way to address the non-uniformity is through graded catalyst layers. This study elucidates the state-of-the-art for graded catalyst layers, which so far were primarily investigated for proton exchange membrane fuel cells (PEMFCs). We identify the most impactful types of gradients in the PEMFC cathode and highlight studies displaying their merits in terms of better conversion efficiencies and longer lifetimes. Furthermore, two critical issues that have received little attention so far are emphasized: on the one hand, industrially relevant manufacturing techniques must be developed and implemented. On the other hand, suitable techniques are needed to identify and characterize the gradients. In this study, guidance to navigate both of these challenges is offered.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"9 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222556","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 : 2024-09-10DOI: 10.1149/1945-7111/ad7296
Raegan Chambers, Sajid Hussain, Jekaterina Kozlova, Kaupo Kukli, Peeter Ritslaid, Arvo Kikas, Vambola Kisand, Heiki Erikson and Kaido Tammeveski
Platinum nanoparticles (PtNPs) are attached to different single heteroatom-doped (N, S, P, and B) and dual heteroatom-doped (N, B and N, P) graphene nanosheets via electrochemical deposition using the chronoamperometric method, which allowed for strong attachment of the PtNPs onto the support surface. The effect of the support material on the electrocatalytic activity of the PtNPs on the oxygen reduction reaction (ORR) in acidic media is examined. The PtNPs supported on boron-doped graphene exhibit the highest specific activity (1.26 mA cm−2), and the PtNPs supported on nitrogen and boron dual heteroatom-doped graphene exhibit the highest mass activity (0.70 A mg−1) at 0.9 V vs reversible hydrogen electrode. The kinetics of the ORR vary significantly depending on the dopants, thus concluding that the heteroatom doping of the graphene support material affects the electrocatalytic activity of PtNPs toward the ORR.
利用计时沉积法，通过电化学沉积将铂纳米粒子（PtNPs）附着在不同的单杂原子掺杂（N、S、P 和 B）和双杂原子掺杂（N、B 和 N、P）石墨烯纳米片上，从而使 PtNPs 强力附着在支撑表面。研究了支撑材料对 PtNPs 在酸性介质中氧还原反应（ORR）电催化活性的影响。掺硼石墨烯支持的 PtNPs 表现出最高的比活性（1.26 mA cm-2），而氮和硼双杂原子掺杂石墨烯支持的 PtNPs 在 0.9 V 与可逆氢电极的电压下表现出最高的质量活性（0.70 A mg-1）。ORR 的动力学因掺杂剂的不同而有很大差异，因此得出结论：石墨烯支撑材料的杂原子掺杂会影响 PtNPs 对 ORR 的电催化活性。
{"title":"Pt Nanoparticles Electrochemically Deposited onto Heteroatom-Doped Graphene Supports as Electrocatalysts for ORR in Acid Media","authors":"Raegan Chambers, Sajid Hussain, Jekaterina Kozlova, Kaupo Kukli, Peeter Ritslaid, Arvo Kikas, Vambola Kisand, Heiki Erikson and Kaido Tammeveski","doi":"10.1149/1945-7111/ad7296","DOIUrl":"https://doi.org/10.1149/1945-7111/ad7296","url":null,"abstract":"Platinum nanoparticles (PtNPs) are attached to different single heteroatom-doped (N, S, P, and B) and dual heteroatom-doped (N, B and N, P) graphene nanosheets via electrochemical deposition using the chronoamperometric method, which allowed for strong attachment of the PtNPs onto the support surface. The effect of the support material on the electrocatalytic activity of the PtNPs on the oxygen reduction reaction (ORR) in acidic media is examined. The PtNPs supported on boron-doped graphene exhibit the highest specific activity (1.26 mA cm−2), and the PtNPs supported on nitrogen and boron dual heteroatom-doped graphene exhibit the highest mass activity (0.70 A mg−1) at 0.9 V vs reversible hydrogen electrode. The kinetics of the ORR vary significantly depending on the dopants, thus concluding that the heteroatom doping of the graphene support material affects the electrocatalytic activity of PtNPs toward the ORR.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"20 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222560","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 : 2024-09-10DOI: 10.1149/1945-7111/ad76df
Timothy Lichtenstein, Mark H. Schvaneveldt, Jarrod Gesualdi and Krista L. Hawthorne
Alternatives to the widely-used standard anodic decomposition reference electrodes in molten salts are necessary to enable more easily reproduced thermochemical and electrochemical data in molten salt electrolytes. The class of standard reference electrodes called cathodic decomposition electrodes (CDEs) are easily constructed and can be used to make thermochemical measurements in molten salts more directly compared to anodic decomposition electrodes. The lithium eutectic electrode (LEE) was chosen as a sample test case for validation and was applied to thermochemical measurements of electroactive species in molten LiCl-KCl eutectic. Transient measurements were made to measure the Li+/Li reduction potential at zero current in pure LiCl-KCl eutectic relative to a Li-alloy reference electrode to validate the reference potential of the LEE. Literature-reported electromotive force measurements against Li-alloy reference electrodes were used to generate a relationship between the LEE and the standard chlorine electrode and this relationship was used to evaluate measured and reported formal potential measurements for the LiCl-KCl-GdCl3 system. This work demonstrates the general framework for defining CDEs for any molten salt system and a method for calibrating external reference electrodes against a CDE standard reference electrode, improving the ease of obtaining thermochemical and electrochemical measurements in any molten salt system.
为了更容易地再现熔盐电解质中的热化学和电化学数据，有必要在熔盐中使用广泛使用的标准阳极分解参比电极之外，再使用其他参比电极。被称为阴极分解电极（CDE）的一类标准参比电极易于制造，与阳极分解电极相比，可以更直接地用于熔盐中的热化学测量。我们选择了锂共晶电极（LEE）作为验证样本，并将其应用于熔融锂盐-氯化钾共晶中电活性物种的热化学测量。进行了瞬态测量，测量纯 LiCl-KCl 共晶在零电流下相对于锂合金参比电极的 Li+/Li 还原电位，以验证 LEE 的参比电位。文献报道的针对锂合金参比电极的电动势测量值被用来生成 LEE 与标准氯电极之间的关系，这种关系被用来评估 LiCl-KCl-GdCl3 系统的测量值和报告的正式电势测量值。这项工作展示了为任何熔盐体系定义 CDE 的一般框架，以及根据 CDE 标准参比电极校准外部参比电极的方法，从而提高了在任何熔盐体系中获得热化学和电化学测量的便利性。
{"title":"Cathodic Decomposition Electrodes as Standard Reference Electrodes for Molten Salts: Example of the Lithium Eutectic Electrode for the LiCl-KCl Eutectic","authors":"Timothy Lichtenstein, Mark H. Schvaneveldt, Jarrod Gesualdi and Krista L. Hawthorne","doi":"10.1149/1945-7111/ad76df","DOIUrl":"https://doi.org/10.1149/1945-7111/ad76df","url":null,"abstract":"Alternatives to the widely-used standard anodic decomposition reference electrodes in molten salts are necessary to enable more easily reproduced thermochemical and electrochemical data in molten salt electrolytes. The class of standard reference electrodes called cathodic decomposition electrodes (CDEs) are easily constructed and can be used to make thermochemical measurements in molten salts more directly compared to anodic decomposition electrodes. The lithium eutectic electrode (LEE) was chosen as a sample test case for validation and was applied to thermochemical measurements of electroactive species in molten LiCl-KCl eutectic. Transient measurements were made to measure the Li+/Li reduction potential at zero current in pure LiCl-KCl eutectic relative to a Li-alloy reference electrode to validate the reference potential of the LEE. Literature-reported electromotive force measurements against Li-alloy reference electrodes were used to generate a relationship between the LEE and the standard chlorine electrode and this relationship was used to evaluate measured and reported formal potential measurements for the LiCl-KCl-GdCl3 system. This work demonstrates the general framework for defining CDEs for any molten salt system and a method for calibrating external reference electrodes against a CDE standard reference electrode, improving the ease of obtaining thermochemical and electrochemical measurements in any molten salt system.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"39 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222398","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 : 2024-09-10DOI: 10.1149/1945-7111/ad7533
Zhen Lei, Ksenya Mull and Nikolay Dimitrov
Cu-Ag alloy films were electrodeposited on Au substrates to serve as precursor alloys for synthesizing finely-structured nanoporous Ag (NPS) structures. Two innovative approaches, surface limited redox replacement (SLRR) and defect mediated growth (DMG) along with overpotential deposition (OPD), were comparatively utilized to fabricate Cu-Ag alloy films. The electrolyte for these novel approaches contained Pb2+ ions to serve either as a sacrificial metal to be replaced by the co-depositing Cu and Ag (in SLRR) or as mediating metal to facilitate the 2D growth of both alloy constituents (in DMG). The resulting alloy films from both approaches displayed superior uniformity and miscibility compared to the OPD alloy, as evidenced by electrochemical scanning electron microscopy (SEM) and X-ray diffraction characterization routines. In a subsequent step, NPS structures were generated through the de-alloying of as-deposited Cu-Ag alloys, as illustrated by SEM imaging that revealed ligament and pore sizes with a thickness in the ballpark of 40 nm. Also, surface area measurements done by a Pb underpotential deposition assay suggested a surface enhancement ratio nearly five times higher than that of flat Ag. Furthermore, various de-alloying potentials were assessed to determine the optimal de-alloying potential for the best outcome of the de-alloying process. Highlights Two new, kinetically mediated approaches were applied to electrodeposit CuAg alloys. Nanoporous Ag (NPS) was synthesized by dealloying of as-deposited CuAg alloys. The optimal dealloying potential range was identified by anodic polarization work. Overpotential growth of CuAg alloy was used as reference throughout the NPS synthesis. The interconnected-porosity NPS structures were studied by SEM and Pb UPD methods.
{"title":"New Electrochemical Approach for Synthesis of Nanoporous Silver","authors":"Zhen Lei, Ksenya Mull and Nikolay Dimitrov","doi":"10.1149/1945-7111/ad7533","DOIUrl":"https://doi.org/10.1149/1945-7111/ad7533","url":null,"abstract":"Cu-Ag alloy films were electrodeposited on Au substrates to serve as precursor alloys for synthesizing finely-structured nanoporous Ag (NPS) structures. Two innovative approaches, surface limited redox replacement (SLRR) and defect mediated growth (DMG) along with overpotential deposition (OPD), were comparatively utilized to fabricate Cu-Ag alloy films. The electrolyte for these novel approaches contained Pb2+ ions to serve either as a sacrificial metal to be replaced by the co-depositing Cu and Ag (in SLRR) or as mediating metal to facilitate the 2D growth of both alloy constituents (in DMG). The resulting alloy films from both approaches displayed superior uniformity and miscibility compared to the OPD alloy, as evidenced by electrochemical scanning electron microscopy (SEM) and X-ray diffraction characterization routines. In a subsequent step, NPS structures were generated through the de-alloying of as-deposited Cu-Ag alloys, as illustrated by SEM imaging that revealed ligament and pore sizes with a thickness in the ballpark of 40 nm. Also, surface area measurements done by a Pb underpotential deposition assay suggested a surface enhancement ratio nearly five times higher than that of flat Ag. Furthermore, various de-alloying potentials were assessed to determine the optimal de-alloying potential for the best outcome of the de-alloying process. Highlights Two new, kinetically mediated approaches were applied to electrodeposit CuAg alloys. Nanoporous Ag (NPS) was synthesized by dealloying of as-deposited CuAg alloys. The optimal dealloying potential range was identified by anodic polarization work. Overpotential growth of CuAg alloy was used as reference throughout the NPS synthesis. The interconnected-porosity NPS structures were studied by SEM and Pb UPD methods.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"26 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222559","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 : 2024-09-10DOI: 10.1149/1945-7111/ad75be
Allan Lebreton, Jérémy Barbé, Christophe Lethien, Jonathan N. Coleman and Thierry Brousse
Vanadium nitride is a highly promising material for micro-pseudocapacitors when used as a bifunctional thin film, i.e. an electrode material and a current collector, owing to its remarkable electrical and electrochemical properties. However, the specific limitations associated with high-rate cycling remain unclear. In this study, we evaluate how the characteristic time associated with charge/discharge of vanadium nitride films is modified with the film thicknesses using electrochemical impedance spectroscopy and cyclic voltammetry measurements coupled to a semi-empirical model commonly utilized to assess the high-rate behaviour of battery electrodes. Both methodologies are in good agreement and revealed that rate capability of this bi-functional material is limited by the VN electrical conductivity. To confirm this finding, VN thin films were sputtered on platinum current collectors, leading to a six-fold reduction in the characteristic time associated with charge/discharge of the current collectors/electrode material. This underscores the importance of using current collectors even for highly conductive electrode materials.
{"title":"Tuning Deposition Conditions for VN Thin Films Electrodes for Microsupercapacitors: Influence of the Thickness","authors":"Allan Lebreton, Jérémy Barbé, Christophe Lethien, Jonathan N. Coleman and Thierry Brousse","doi":"10.1149/1945-7111/ad75be","DOIUrl":"https://doi.org/10.1149/1945-7111/ad75be","url":null,"abstract":"Vanadium nitride is a highly promising material for micro-pseudocapacitors when used as a bifunctional thin film, i.e. an electrode material and a current collector, owing to its remarkable electrical and electrochemical properties. However, the specific limitations associated with high-rate cycling remain unclear. In this study, we evaluate how the characteristic time associated with charge/discharge of vanadium nitride films is modified with the film thicknesses using electrochemical impedance spectroscopy and cyclic voltammetry measurements coupled to a semi-empirical model commonly utilized to assess the high-rate behaviour of battery electrodes. Both methodologies are in good agreement and revealed that rate capability of this bi-functional material is limited by the VN electrical conductivity. To confirm this finding, VN thin films were sputtered on platinum current collectors, leading to a six-fold reduction in the characteristic time associated with charge/discharge of the current collectors/electrode material. This underscores the importance of using current collectors even for highly conductive electrode materials.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"99 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222561","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 : 2024-09-10DOI: 10.1149/1945-7111/ad7534
Zhefei Zhao, Linlin Zhang, Minghao Chen, Ruopeng Yu, Xuyao Yao, Yinghua Xu, Youqun Chu, Xinbiao Mao and Huajun Zheng
Electrochemical selective dechlorination can be regarded as one of the most promising strategies for generating high-valued chemicals. In the electrochemical dechlorination process of 2-chloro-5-trichloromethylpyridine (TCMP), except the anticipated dechlorination products involving 2-chloro-5-dichloromethylpyridine (DCMP), 2-chloro-5-chloromethylpyridine (CCMP), and 2-chloro-5-methylpyridine (CMP), some unexpected oxygen-incorporated products (6-chloronicotinic acid (CNA) and 6-chloronicotinoyl methyl ester (MCN)) can be obtained. Consequently, understanding the electrochemical dechlorination behavior of TCMP is crucial. Our research revealed that the activated Ag electrodes in halide ion solution exhibit enhanced electrochemical activities for electrochemical dechlorination of TCMP, compared with the pure Ag owing to the increased active specific surface areas and charge transfer. Second, oxygen participation in the reaction is a necessary condition for the formation of oxygen-incorporated products. A 100% selectivity of oxygen-incorporated products can be obtained at the potential of −0.6 V vs Ag/AgCl. Conversely, insufficient oxygen may lead to the potential becoming the determining condition that affects the reaction pathways. A more negative potential (−1.2 V vs Ag/AgCl) is conducive to the formation of dechlorination products with 94.2% conversion and 100% selectivity. This study, for the first time, elucidates the electrocatalyst, atmosphere, and potential-dependent activity and selectivity for the two dechlorination pathways of TCMP.
电化学选择性脱氯可以说是生成高价值化学品的最有前途的策略之一。在 2-氯-5-三氯甲基吡啶（TCMP）的电化学脱氯过程中，除了涉及 2-氯-5-二氯甲基吡啶（DCMP）的预期脱氯产物外，2-氯-5-二氯甲基吡啶（CCMP）和 2-氯-5-三氯甲基吡啶（TCMP）的电化学选择性脱氯产物均可作为高附加值化学品、（CCMP）和 2-氯-5-甲基吡啶（CMP）外，还可以得到一些意想不到的氧掺杂产物（6-氯烟酸（CNA）和 6-氯烟酸甲酯（MCN））。因此，了解 TCMP 的电化学脱氯行为至关重要。我们的研究发现，与纯银相比，在卤化离子溶液中的活化银电极在 TCMP 的电化学脱氯过程中表现出更强的电化学活性，这是由于活性比表面积和电荷转移增加所致。其次，氧参与反应是形成氧结合产物的必要条件。与 Ag/AgCl 相比，在电位为 -0.6 V 时，氧结合产物的选择性为 100%。相反，氧气不足可能导致电位成为影响反应途径的决定性条件。更负的电位（-1.2 V vs Ag/AgCl）有利于形成脱氯产物，转化率为 94.2%，选择性为 100%。这项研究首次阐明了 TCMP 两种脱氯途径中的电催化剂、气氛以及电势对活性和选择性的影响。
{"title":"Oxygen-Controlled Electrocatalysis for Selective Dechlorination of 2-Chloro-5-Trichloromethyl Pyridine on Activated Ag Electrode","authors":"Zhefei Zhao, Linlin Zhang, Minghao Chen, Ruopeng Yu, Xuyao Yao, Yinghua Xu, Youqun Chu, Xinbiao Mao and Huajun Zheng","doi":"10.1149/1945-7111/ad7534","DOIUrl":"https://doi.org/10.1149/1945-7111/ad7534","url":null,"abstract":"Electrochemical selective dechlorination can be regarded as one of the most promising strategies for generating high-valued chemicals. In the electrochemical dechlorination process of 2-chloro-5-trichloromethylpyridine (TCMP), except the anticipated dechlorination products involving 2-chloro-5-dichloromethylpyridine (DCMP), 2-chloro-5-chloromethylpyridine (CCMP), and 2-chloro-5-methylpyridine (CMP), some unexpected oxygen-incorporated products (6-chloronicotinic acid (CNA) and 6-chloronicotinoyl methyl ester (MCN)) can be obtained. Consequently, understanding the electrochemical dechlorination behavior of TCMP is crucial. Our research revealed that the activated Ag electrodes in halide ion solution exhibit enhanced electrochemical activities for electrochemical dechlorination of TCMP, compared with the pure Ag owing to the increased active specific surface areas and charge transfer. Second, oxygen participation in the reaction is a necessary condition for the formation of oxygen-incorporated products. A 100% selectivity of oxygen-incorporated products can be obtained at the potential of −0.6 V vs Ag/AgCl. Conversely, insufficient oxygen may lead to the potential becoming the determining condition that affects the reaction pathways. A more negative potential (−1.2 V vs Ag/AgCl) is conducive to the formation of dechlorination products with 94.2% conversion and 100% selectivity. This study, for the first time, elucidates the electrocatalyst, atmosphere, and potential-dependent activity and selectivity for the two dechlorination pathways of TCMP.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"7 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222400","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 : 2024-09-09DOI: 10.1149/1945-7111/ad7406
D. Nienhues, L. Müller and M. Nowottnick
This paper evaluates the electrochemical properties of aluminum (0.5 w%) copper alloy metallized test chip surfaces with interdigital structures and distances between 3 and 20 μm, regarding sodium chloride and potassium fluoride contamination in the range of 1011–1016 ions per cm2 at high humidity (85%) and high temperature (85 °C). These accelerated tests result in leakage currents and impedance values which show a significant change above a contamination limit value of 1014 ions per cm2 for both salts i.e., the leakage current starts to increase well above a few pico amperes, and the impedance decreases significantly. This contamination level can be seen as a turning point, after which devices can undergo for example signal shifts or corroded metal tracks over lifetime. But not only the start point of an increase in leakage current decides about the harmfulness of the contamination, other important influences are deliquescence and how high the leakage current gets at its maximum. Therefore, even with the same starting point, the risk evaluation is not the same for sodium chloride and potassium fluoride.
{"title":"Influence of Sodium Chloride and Potassium Fluoride on Electrochemical Properties of Aluminum Copper Interdigital Structures","authors":"D. Nienhues, L. Müller and M. Nowottnick","doi":"10.1149/1945-7111/ad7406","DOIUrl":"https://doi.org/10.1149/1945-7111/ad7406","url":null,"abstract":"This paper evaluates the electrochemical properties of aluminum (0.5 w%) copper alloy metallized test chip surfaces with interdigital structures and distances between 3 and 20 μm, regarding sodium chloride and potassium fluoride contamination in the range of 1011–1016 ions per cm2 at high humidity (85%) and high temperature (85 °C). These accelerated tests result in leakage currents and impedance values which show a significant change above a contamination limit value of 1014 ions per cm2 for both salts i.e., the leakage current starts to increase well above a few pico amperes, and the impedance decreases significantly. This contamination level can be seen as a turning point, after which devices can undergo for example signal shifts or corroded metal tracks over lifetime. But not only the start point of an increase in leakage current decides about the harmfulness of the contamination, other important influences are deliquescence and how high the leakage current gets at its maximum. Therefore, even with the same starting point, the risk evaluation is not the same for sodium chloride and potassium fluoride.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"32 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222402","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 : 2024-09-09DOI: 10.1149/1945-7111/ad75bb
Xin Li, Yangwanhao Song and Hengqi Ren
An accurate estimation of the lithium battery’s state of charge (SOC) is critical. The article proposes a dual fractional order multi-innovations cubature Kalman filter (DFOMICKF) algorithm for estimating lithium battery SOC. The algorithm adopts the idea of multiple time scales, where one of the FOMICKF is used to identify the circuit model parameters online in the macro time scale. Another FOMICKF is used to estimate the SOC in the micro time scale, and the circuit parameters updated online in real-time are passed into the estimation of the SOC filter to form an online joint estimation method of SOC and circuit parameters. Finally, multiple algorithms of DFOMICKF, FOMICKF, FOCKF, and CKF are compared and experimented under different working conditions to compare and analyze the estimated SOC errors. It is verified that the proposed algorithm can solve the problems of inaccuracy, poor convergence, and poor robustness of the traditional Kalman filtering algorithm for estimating SOC, which has good research value.
{"title":"State of Charge Estimation of Lithium-Ion Batteries Based on Fractional-Order Model with Mul-ti-Innovations Dual Cubature Kalman Filter Method","authors":"Xin Li, Yangwanhao Song and Hengqi Ren","doi":"10.1149/1945-7111/ad75bb","DOIUrl":"https://doi.org/10.1149/1945-7111/ad75bb","url":null,"abstract":"An accurate estimation of the lithium battery’s state of charge (SOC) is critical. The article proposes a dual fractional order multi-innovations cubature Kalman filter (DFOMICKF) algorithm for estimating lithium battery SOC. The algorithm adopts the idea of multiple time scales, where one of the FOMICKF is used to identify the circuit model parameters online in the macro time scale. Another FOMICKF is used to estimate the SOC in the micro time scale, and the circuit parameters updated online in real-time are passed into the estimation of the SOC filter to form an online joint estimation method of SOC and circuit parameters. Finally, multiple algorithms of DFOMICKF, FOMICKF, FOCKF, and CKF are compared and experimented under different working conditions to compare and analyze the estimated SOC errors. It is verified that the proposed algorithm can solve the problems of inaccuracy, poor convergence, and poor robustness of the traditional Kalman filtering algorithm for estimating SOC, which has good research value.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"3 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222399","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 : 2024-09-09DOI: 10.1149/1945-7111/ad73a6
Rémy Rouxhet, Maxime Loudeche, Ronny Santoro and Joris Proost
Lime holds considerable potential in diverse environmental applications. However, its current production remains highly carbon-intensive, emitting more than one ton of CO2 per ton of lime. To address this issue, recent studies have explored the concept of electrifying the decarbonation of limestone to produce hydrated lime. In this work, a two-compartment electrolysis cell capable of producing Ca(OH)2 has been tested at different currents. Precise pH and Ca2+ concentration measurements demonstrate that the electrolysis setup is able to dissolve CaCO3 and precipitate Ca(OH)2 with near-perfect efficiencies. Notably, it highlights that Faraday’s law and the concept of transport number can be applied to predict both the equilibrium and kinetic behavior of each step of the process in each of the two cell compartments. Moreover, the use of controlled batch additions of CaCO3 in the system, as opposed to one-time excess addition, was assessed to mitigate the fouling of the cationic exchange membrane used to separate the compartments. Finally, based on the experimental findings, key guidelines are proposed to achieve a perfect reaction stoichiometry for each step. These findings pave the way for a more sustainable and environmentally friendly approach to lime production.
{"title":"Low-Temperature Water Electrolysis Under a Sustained pH-Gradient for Electrochemically-Induced Decarbonation of Limestone into Hydrated Lime","authors":"Rémy Rouxhet, Maxime Loudeche, Ronny Santoro and Joris Proost","doi":"10.1149/1945-7111/ad73a6","DOIUrl":"https://doi.org/10.1149/1945-7111/ad73a6","url":null,"abstract":"Lime holds considerable potential in diverse environmental applications. However, its current production remains highly carbon-intensive, emitting more than one ton of CO2 per ton of lime. To address this issue, recent studies have explored the concept of electrifying the decarbonation of limestone to produce hydrated lime. In this work, a two-compartment electrolysis cell capable of producing Ca(OH)2 has been tested at different currents. Precise pH and Ca2+ concentration measurements demonstrate that the electrolysis setup is able to dissolve CaCO3 and precipitate Ca(OH)2 with near-perfect efficiencies. Notably, it highlights that Faraday’s law and the concept of transport number can be applied to predict both the equilibrium and kinetic behavior of each step of the process in each of the two cell compartments. Moreover, the use of controlled batch additions of CaCO3 in the system, as opposed to one-time excess addition, was assessed to mitigate the fouling of the cationic exchange membrane used to separate the compartments. Finally, based on the experimental findings, key guidelines are proposed to achieve a perfect reaction stoichiometry for each step. These findings pave the way for a more sustainable and environmentally friendly approach to lime production.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"10 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222401","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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