Improvement in durability is one of the important subjects for utilizing solid oxide electrolyzer cell (SOEC) systems widely. In SOEC stacks, separators are exposed to complexed dual atmosphere (i.e. hydrogen - steam mixed gases and oxygen rich air are on each side). In this study, the degradation phenomena of separator materials (SUS430, ZMG232G10, Crofer22APU) in SOEC dual atmosphere were investigated. The samples were exposed in SOEC dual and simple atmospheres at 700 °C for 500 h. Then, their cross sections were analyzed by X-ray diffraction and scanning electron microscopy/energy-dispersive X-ray analysis. The degradation mechanisms of the separator materials in the SOEC stack operating conditions were discussed. ZMG232G10 and Crofer22APU with high Cr content showed thin oxide layer under both the dual or single atmosphere, while SUS430 with low Cr content showed significant oxidation in the H2-steam atmosphere and on the air side under the dual atmosphere condition. The significant oxidation on the air side of the dual atmosphere of SUS430 observed in this study is a unique phenomenon under the dual atmosphere condition and not observed in a single air atmosphere.
{"title":"Accelerated High-Temperature Oxidation Behavior of Ferritic Stainless Steel under Air/H2+H2O Dual Atmosphere","authors":"Riko Inuzuka, Norikazu Osada, Kiyoshi Imai, Tsuneji Kameda, Tatsumi Ishihara","doi":"10.1149/1945-7111/ad6bc4","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6bc4","url":null,"abstract":"Improvement in durability is one of the important subjects for utilizing solid oxide electrolyzer cell (SOEC) systems widely. In SOEC stacks, separators are exposed to complexed dual atmosphere (i.e. hydrogen - steam mixed gases and oxygen rich air are on each side). In this study, the degradation phenomena of separator materials (SUS430, ZMG232G10, Crofer22APU) in SOEC dual atmosphere were investigated. The samples were exposed in SOEC dual and simple atmospheres at 700 °C for 500 h. Then, their cross sections were analyzed by X-ray diffraction and scanning electron microscopy/energy-dispersive X-ray analysis. The degradation mechanisms of the separator materials in the SOEC stack operating conditions were discussed. ZMG232G10 and Crofer22APU with high Cr content showed thin oxide layer under both the dual or single atmosphere, while SUS430 with low Cr content showed significant oxidation in the H2-steam atmosphere and on the air side under the dual atmosphere condition. The significant oxidation on the air side of the dual atmosphere of SUS430 observed in this study is a unique phenomenon under the dual atmosphere condition and not observed in a single air atmosphere.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"60 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222461","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 : 2024-08-28DOI: 10.1149/1945-7111/ad6eba
Qingliang Zhang, Ningsong Qu
Copper alloys, such as ZCuPb10Sn10, have been widely applied to friction pairs in various products. Surface texture, such as micro-dimple array has attracted significant attention from researchers worldwide to improve tribological performance. To generate micro-dimple array on ZCuPb10Sn10 alloy by electrochemical machining, it is essential to investigate the electrochemical dissolution behavior of ZCuPb10Sn10 in NaNO3 solution. In this paper, the electrochemical dissolution behavior of ZCuPb10Sn10 alloy in NaNO3 solution is investigated through experimental tests. Anodic polarization, Tafel polarization, and electrochemical impedance spectroscopy were conducted to investigate its passive and corrosion behavior. The microstructure and composition of the dissolved surfaces were analyzed under various conditions. Additionally, a model was proposed to explain the electrochemical dissolution process of ZCuPb10Sn10 alloy in NaNO3 solution under high pressure hydrostatic conditions. Ultimately, a NaNO3 solution with 10% in concentration and 20 °C in temperature was selected as the electrolyte and a micro-dimple array with an average diameter of 119.7 μm and a depth of 7.4 μm was successfully generated with through-mask electrochemical micromachining on the surface of ZCuPb10Sn10 alloy.
{"title":"Electrochemical Dissolution Behavior of ZCuPb10Sn10 Alloy in NaNO3 Solution","authors":"Qingliang Zhang, Ningsong Qu","doi":"10.1149/1945-7111/ad6eba","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6eba","url":null,"abstract":"Copper alloys, such as ZCuPb10Sn10, have been widely applied to friction pairs in various products. Surface texture, such as micro-dimple array has attracted significant attention from researchers worldwide to improve tribological performance. To generate micro-dimple array on ZCuPb10Sn10 alloy by electrochemical machining, it is essential to investigate the electrochemical dissolution behavior of ZCuPb10Sn10 in NaNO<sub>3</sub> solution. In this paper, the electrochemical dissolution behavior of ZCuPb10Sn10 alloy in NaNO<sub>3</sub> solution is investigated through experimental tests. Anodic polarization, Tafel polarization, and electrochemical impedance spectroscopy were conducted to investigate its passive and corrosion behavior. The microstructure and composition of the dissolved surfaces were analyzed under various conditions. Additionally, a model was proposed to explain the electrochemical dissolution process of ZCuPb10Sn10 alloy in NaNO<sub>3</sub> solution under high pressure hydrostatic conditions. Ultimately, a NaNO<sub>3</sub> solution with 10% in concentration and 20 °C in temperature was selected as the electrolyte and a micro-dimple array with an average diameter of 119.7 μm and a depth of 7.4 μm was successfully generated with through-mask electrochemical micromachining on the surface of ZCuPb10Sn10 alloy.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"176 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222464","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 : 2024-08-28DOI: 10.1149/1945-7111/ad6fd7
Monsuru Dauda, John Hendershot, Mustapha Bello, Junghyun Park, Alvaro Loaiza Orduz, Orhan Kizilkaya, Phillip Sprunger, Anthony Engler, Koffi Yao, Craig Plaisance, John Flake
In this study Cu, Sn, and bimetallic CuSnx nanoparticles were synthesized and evaluated as electrocatalysts for CO2 reduction using zero gap membrane electrode assemblies. Results show bimetallic electrocatalysts with Sn contents above 10% yield formate as a primary product with Faradaic Efficiencies near 70% at 350 mA cm−2. Cu-Snx electrocatalysts with less than 10% Sn yield CO at current densities below 350 mA cm−2 and relatively lower cell potentials. When the low-Sn content bimetallic electrocatalysts were evaluated in alkaline anolytes at 350 mA cm−2, ethanol was recorded as the primary product (FE = 48.5% at Ecell ≥ 3.0 V). We propose enhanced C2 activity and selectivity originate from Cu dimers adjacent to Sn atoms for bimetallic electrocatalyst with low-Sn content. The C2 active sites are lost when the surface Sn content exceeds 25%–38%.
本研究合成了铜、锡和双金属 CuSnx 纳米粒子，并将其作为使用零间隙膜电极组件进行二氧化碳还原的电催化剂进行了评估。结果表明，Sn 含量高于 10% 的双金属电催化剂在 350 mA cm-2 电流条件下，主要产物甲酸的法拉第效率接近 70%。锡含量低于 10%的铜锡双金属电催化剂在电流密度低于 350 mA cm-2 和电池电位相对较低的条件下产生 CO。在 350 mA cm-2 的碱性溶液中评估低锡含量的双金属电催化剂时，乙醇被记录为主要产物（Ecell ≥ 3.0 V 时 FE = 48.5%）。我们认为，C2 活性和选择性的增强源于低锡含量双金属电催化剂中与锡原子相邻的铜二聚体。当表面锡含量超过 25%-38% 时，C2 活性位点就会消失。
{"title":"Activity and Selectivity in the Electrochemical Reduction of CO2 at CuSnx Electrocatalysts Using a Zero-Gap Membrane Electrode Assembly","authors":"Monsuru Dauda, John Hendershot, Mustapha Bello, Junghyun Park, Alvaro Loaiza Orduz, Orhan Kizilkaya, Phillip Sprunger, Anthony Engler, Koffi Yao, Craig Plaisance, John Flake","doi":"10.1149/1945-7111/ad6fd7","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6fd7","url":null,"abstract":"In this study Cu, Sn, and bimetallic CuSn<sub>x</sub> nanoparticles were synthesized and evaluated as electrocatalysts for CO<sub>2</sub> reduction using zero gap membrane electrode assemblies. Results show bimetallic electrocatalysts with Sn contents above 10% yield formate as a primary product with Faradaic Efficiencies near 70% at 350 mA cm<sup>−2</sup>. Cu-Sn<sub>x</sub> electrocatalysts with less than 10% Sn yield CO at current densities below 350 mA cm<sup>−2</sup> and relatively lower cell potentials. When the low-Sn content bimetallic electrocatalysts were evaluated in alkaline anolytes at 350 mA cm<sup>−2</sup>, ethanol was recorded as the primary product (FE = 48.5% at E<sub>cell</sub> ≥ 3.0 V). We propose enhanced C<sub>2</sub> activity and selectivity originate from Cu dimers adjacent to Sn atoms for bimetallic electrocatalyst with low-Sn content. The C<sub>2</sub> active sites are lost when the surface Sn content exceeds 25%–38%.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"2 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222466","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}
To meet the industrial production needs for high-quality and precisely controllable structured high-end nickel foils, rare Earth compounds are added as additives in complex industrial electrolytes to improve the quality of the nickel deposition layer. This study investigates the effects of adding rare Earth compounds to the existing industrial production electrolytes (which already contain various organic and inorganic additives in a mixed acid solution) on the surface microstructure, cerium content, grain size, and crystal orientation of the nickel deposition layer. Using direct current electrodeposition, different concentrations of rare Earth compounds were added to the industrial electrolyte, and the cerium content, grain size, and crystal orientation were characterized. The results show that adding 0.8 g·l−1 CeCl3 accelerates the nucleation rate and shortens the nucleation relaxation time. The addition of rare Earth elements promotes multi-directional preferential growth, resulting in uniform and fine grain size, improved grain structure of the deposition layer, and reduced surface roughness of the nickel plating layer. Therefore, rare Earth elements can be used to regulate the structure, microstructure, and grain refinement of the nickel deposition layer without affecting its composition.
{"title":"The Effect of the Rare Earth Element Cerium on the Electrocrystallization and Microstructure of Nickel Electrodeposits in Industrial Electrolytes","authors":"Yang-Tao Xu, Yan-Hong Li, Yin Peng, Zhi-Qiang Zhong","doi":"10.1149/1945-7111/ad70da","DOIUrl":"https://doi.org/10.1149/1945-7111/ad70da","url":null,"abstract":"To meet the industrial production needs for high-quality and precisely controllable structured high-end nickel foils, rare Earth compounds are added as additives in complex industrial electrolytes to improve the quality of the nickel deposition layer. This study investigates the effects of adding rare Earth compounds to the existing industrial production electrolytes (which already contain various organic and inorganic additives in a mixed acid solution) on the surface microstructure, cerium content, grain size, and crystal orientation of the nickel deposition layer. Using direct current electrodeposition, different concentrations of rare Earth compounds were added to the industrial electrolyte, and the cerium content, grain size, and crystal orientation were characterized. The results show that adding 0.8 g·l<sup>−1</sup> CeCl<sub>3</sub> accelerates the nucleation rate and shortens the nucleation relaxation time. The addition of rare Earth elements promotes multi-directional preferential growth, resulting in uniform and fine grain size, improved grain structure of the deposition layer, and reduced surface roughness of the nickel plating layer. Therefore, rare Earth elements can be used to regulate the structure, microstructure, and grain refinement of the nickel deposition layer without affecting its composition.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"20 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222482","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 : 2024-08-28DOI: 10.1149/1945-7111/ad6ef6
Si-Qi Jiao, Yu-Feng Liu, Xiao-Hong Zheng, Cheng Zhang, Xiao-Rui Wang
Compared to gas sensors based on single metal oxide, gas sensors based on binary metal oxide semiconductors (MOS) offer a rich variety of structural types and hold great potential for excellent selectivity. Inspired by this, we synthesized BiVO4 powder through a stepwise reaction combining calcination with hydrothermal bath and investigated the influence of different calcination temperatures on its gas sensitivity performance. Our study revealed that BiVO4-600 exhibited optimal TEA gas sensing behavior at 225 °C, showing high response values (Ra/Rg = 43.4) and fast response/recovery times (15 s/52 s). Additionally, the sensor displayed high stability, repeatability, and exceptional selectivity. Preliminary research indicates that calcination temperature induces changes in the oxygen vacancy content of BiVO4, thus affecting its sensing performance.
{"title":"Controlling Oxygen Vacancy Content by Varying Calcination Temperature to Enhance the Gas Sensing Performance of BiVO4 Material","authors":"Si-Qi Jiao, Yu-Feng Liu, Xiao-Hong Zheng, Cheng Zhang, Xiao-Rui Wang","doi":"10.1149/1945-7111/ad6ef6","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6ef6","url":null,"abstract":"Compared to gas sensors based on single metal oxide, gas sensors based on binary metal oxide semiconductors (MOS) offer a rich variety of structural types and hold great potential for excellent selectivity. Inspired by this, we synthesized BiVO<sub>4</sub> powder through a stepwise reaction combining calcination with hydrothermal bath and investigated the influence of different calcination temperatures on its gas sensitivity performance. Our study revealed that BiVO<sub>4</sub>-600 exhibited optimal TEA gas sensing behavior at 225 °C, showing high response values (R<sub>a</sub>/R<sub>g</sub> = 43.4) and fast response/recovery times (15 s/52 s). Additionally, the sensor displayed high stability, repeatability, and exceptional selectivity. Preliminary research indicates that calcination temperature induces changes in the oxygen vacancy content of BiVO<sub>4</sub>, thus affecting its sensing performance.<inline-formula>\u0000<inline-graphic xlink:href=\"jesad6ef6-ga.jpg\" xlink:type=\"simple\"></inline-graphic>\u0000</inline-formula>","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"70 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222465","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}
Lithium-air batteries (LABs) are gaining attention as a promising energy storage solution. Their theoretical energy density of 3,505 Whkg−1 exceeds that of conventional lithium-ion batteries (500–800 Whkg−1). The commercial viability and widespread adoption of lithium-air batteries face challenges such as poor cycling stability, limited lifespan, and unresolved side reactions. In this study, we synthesized spinel CoFe2O4-decorated on bio-based poly(2,5-benzimidazole) derived N-doped carbon for electrocatalysts. Notably, strong metal-substrate interaction (SMSI) was observed through various characterizations. The bifunctional electrocatalytic activity and stability toward oxygen reduction reaction and oxygen evolution reaction were significantly enhanced by the SMSI, The LAB demonstrated a high discharge capacity of 18,356 mAhg−1 at a current density of 200 mAg−1, maintaining a remarkable discharge capacity of 1,000 mAhg−1 even at a high current density of 400 mAg−1 for 200 cycles. CoFe2O4-decorated on bio-derived ABPBI holds promise as a practical air-breathing electrode for high-capacity rechargeable LABs.
{"title":"CoFe2O4 Nanoparticles on Bio-Based Polymer Derived Nitrogen Doped Carbon as Bifunctional Electrocatalyst for Li-Air Battery","authors":"Pirapath Arkasalerks, Amarshi Patra, Kottisa Sumala Patnaik, Koichi Higashimine, Noriyoshi Matsumi","doi":"10.1149/1945-7111/ad69c9","DOIUrl":"https://doi.org/10.1149/1945-7111/ad69c9","url":null,"abstract":"Lithium-air batteries (LABs) are gaining attention as a promising energy storage solution. Their theoretical energy density of 3,505 Whkg<sup>−1</sup> exceeds that of conventional lithium-ion batteries (500–800 Whkg<sup>−1</sup>). The commercial viability and widespread adoption of lithium-air batteries face challenges such as poor cycling stability, limited lifespan, and unresolved side reactions. In this study, we synthesized spinel CoFe<sub>2</sub>O<sub>4</sub>-decorated on bio-based poly(2,5-benzimidazole) derived N-doped carbon for electrocatalysts. Notably, strong metal-substrate interaction (SMSI) was observed through various characterizations. The bifunctional electrocatalytic activity and stability toward oxygen reduction reaction and oxygen evolution reaction were significantly enhanced by the SMSI, The LAB demonstrated a high discharge capacity of 18,356 mAhg<sup>−1</sup> at a current density of 200 mAg<sup>−1</sup>, maintaining a remarkable discharge capacity of 1,000 mAhg<sup>−1</sup> even at a high current density of 400 mAg<sup>−1</sup> for 200 cycles. CoFe<sub>2</sub>O<sub>4</sub>-decorated on bio-derived ABPBI holds promise as a practical air-breathing electrode for high-capacity rechargeable LABs.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"23 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222469","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}
In this study, a 3D-prinited solution-flow type microdroplet cell (SF-MDC) is employed as a new technique for the fabrication of porous anodic aluminum oxide (AAO) layer using oxalic acid electrolyte on aluminum. The surface morphology of the porous AAO film was characterized by a scanning electron microscope. The aim of this study was to fabricate a through-hole porous alumina layer in a single step anodizing process and to investigate the influence of anodized voltages and scanning speeds on the thickness and pore structure of alumina layer. The results showed that the pore diameter and interpore distance were directly proportional to the anodizing voltage. The thicknesses of formed AAO films were found to be 35.5, 50.7, and 81.6 μm at scanning speeds of 10, 5, and 2.5 μms−1, respectively. Through-hole porous AAO was successfully fabricated at room temperature without chemical etching. The SF-MDC fabrication technique is proposed as an environmentally attractive and suitable process for the fabrication of porous AAO layers.
{"title":"Formation of Through-Hole Porous Anodic Aluminum Oxide Layer Locally with 3D Printed Solution Flow Type Microdroplet Cell","authors":"Adane Adugna Ayalew, Xiaole Han, Yoganandan Govindaraj, Masatoshi Sakairi","doi":"10.1149/1945-7111/ad6fd6","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6fd6","url":null,"abstract":"In this study, a 3D-prinited solution-flow type microdroplet cell (SF-MDC) is employed as a new technique for the fabrication of porous anodic aluminum oxide (AAO) layer using oxalic acid electrolyte on aluminum. The surface morphology of the porous AAO film was characterized by a scanning electron microscope. The aim of this study was to fabricate a through-hole porous alumina layer in a single step anodizing process and to investigate the influence of anodized voltages and scanning speeds on the thickness and pore structure of alumina layer. The results showed that the pore diameter and interpore distance were directly proportional to the anodizing voltage. The thicknesses of formed AAO films were found to be 35.5, 50.7, and 81.6 μm at scanning speeds of 10, 5, and 2.5 μms<sup>−1</sup>, respectively. Through-hole porous AAO was successfully fabricated at room temperature without chemical etching. The SF-MDC fabrication technique is proposed as an environmentally attractive and suitable process for the fabrication of porous AAO layers.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"46 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222470","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 : 2024-08-27DOI: 10.1149/1945-7111/ad6eb9
Igor Mele, Klemen Zelič, Marko Firm, Jože Moškon, Miran Gaberšček, Tomaž Katrašnik
Electrochemical impedance spectroscopy (EIS) is essential for non-invasive battery characterization. This paper addresses the challenge of adequate interpretation of EIS spectra, which are often complicated by overlapping internal phenomena occurring on similar time scales. We present, for the first time, a high-fidelity numerical time-domain electrochemical model that can virtually replicate experimental EIS spectra with three superimposed high-frequency semicircles, a transition to the diffusion tail at elevated imaginary values, and a tilted diffusion tail at low frequencies. These advanced features were made possible by extending state-of-the-art porous electrode model with innovative sub-models for the double layer phenomenon at the carbon black/electrolyte and metal Li-anode/electrolyte interfaces, and transport phenomena of charged species through the solid electrolyte interphase at the Li-anode interface. Additionally, we modelled the diffusion tail inclination by introducing representative active particles of varying sizes. Results from custom-made half-cells confirm the model’s ability to decipher EIS spectra more accurately compared to existing models. Moreover, innovative physics-based battery model that is capable of accurately modelling intra-cell phenomena can reveal internal states and physical parameters of batteries using measured EIS spectra. The model, therefore, also enables functionality of an advanced virtual sensor, which is an important diagnostics feature in next-generation battery management systems.
电化学阻抗光谱（EIS）对于非侵入式电池特性分析至关重要。本文探讨了如何充分解释 EIS 光谱的难题，因为在相似的时间尺度上发生的重叠内部现象通常会使 EIS 光谱变得复杂。我们首次提出了一种高保真数值时域电化学模型，该模型可以几乎复制实验 EIS 光谱，其中包括三个叠加的高频半圆、虚值升高时向扩散尾部的过渡以及低频时倾斜的扩散尾部。这些先进特性是通过扩展最先进的多孔电极模型实现的，该模型具有创新的子模型，可用于模拟炭黑/电解质和金属锂阳极/电解质界面的双层现象，以及带电物种通过锂阳极界面上的固体电解质相间层的传输现象。此外，我们还通过引入不同尺寸的代表性活性颗粒来模拟扩散尾部的倾斜度。定制半电池的结果证实，与现有模型相比，该模型能够更准确地解读 EIS 光谱。此外，基于物理学的创新电池模型能够准确模拟电池内部现象，利用测量的 EIS 光谱揭示电池的内部状态和物理参数。因此，该模型还能实现先进虚拟传感器的功能，而这正是下一代电池管理系统的重要诊断功能。
{"title":"Enhanced Porous Electrode Theory Based Electrochemical Model for Higher Fidelity Modelling and Deciphering of the EIS Spectra","authors":"Igor Mele, Klemen Zelič, Marko Firm, Jože Moškon, Miran Gaberšček, Tomaž Katrašnik","doi":"10.1149/1945-7111/ad6eb9","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6eb9","url":null,"abstract":"Electrochemical impedance spectroscopy (EIS) is essential for non-invasive battery characterization. This paper addresses the challenge of adequate interpretation of EIS spectra, which are often complicated by overlapping internal phenomena occurring on similar time scales. We present, for the first time, a high-fidelity numerical time-domain electrochemical model that can virtually replicate experimental EIS spectra with three superimposed high-frequency semicircles, a transition to the diffusion tail at elevated imaginary values, and a tilted diffusion tail at low frequencies. These advanced features were made possible by extending state-of-the-art porous electrode model with innovative sub-models for the double layer phenomenon at the carbon black/electrolyte and metal Li-anode/electrolyte interfaces, and transport phenomena of charged species through the solid electrolyte interphase at the Li-anode interface. Additionally, we modelled the diffusion tail inclination by introducing representative active particles of varying sizes. Results from custom-made half-cells confirm the model’s ability to decipher EIS spectra more accurately compared to existing models. Moreover, innovative physics-based battery model that is capable of accurately modelling intra-cell phenomena can reveal internal states and physical parameters of batteries using measured EIS spectra. The model, therefore, also enables functionality of an advanced virtual sensor, which is an important diagnostics feature in next-generation battery management systems.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"9 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222468","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 : 2024-08-27DOI: 10.1149/1945-7111/ad6b46
Samaneh Shahsavarifar, Morteza Rezapour, Mehdi Mehrpooya, Hermann Ehrlich, Teofil Jesionowski, Mohammad Reza Ganjali, Rafael Luque, Mehdi Rahimi-Nasrabadi
Polyoxometalates (POMs) are inorganic nanoclusters that consist of oxygen and transition metals. These nanoclusters serve as excellent precursors for creating electrode materials that contain transition metals. Additionally, the interaction between POMs and carbon substrates produces positive synergistic effects. There has been considerable attention on employing POMs and carbon nanostructures (for example carbon nanotubes, graphene, and mesoporous carbon) in composite materials for diverse purposes including catalysis, transformation, storage of energy, molecular detection, and electrical detection. By combining the reactive nature of POMs with the exceptional electrical properties of carbon nanostructures, highly desirable composite features can be achieved. This review delves into the extensive use of POM/nanocarbon materials for constructing rechargeable lithium-ion batteries, providing an in-depth analysis of the characteristics of POMs and the techniques employed for binding carbon.
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Pub Date : 2024-08-26DOI: 10.1149/1945-7111/ad6b48
Eric D. Rus, Eduardo L. Corrêa, Cindi L. Dennis, Thomas P. Moffat
The effects of potential and the presence of B(OH)3 on Pt1-xCox alloy electrodeposition from aqueous chloride-based solutions on Ru substrates was investigated. Films deposited at potentials more reducing than −0.65 V vs SCE were hexagonal close packed and greater than 90% Co (mole basis), and films deposited at potentials more oxidizing than −0.65 V were face centered cubic and showed a monotonic decrease in cobalt content as the potential increased. The composition and structure-potential dependences were not strongly affected by the presence of B(OH)3. Structural change coincided with a distinct knee-like feature in the composition-potential relationship, along with a prominent narrow voltammetric peak associated with Co deposition, possibly related to nucleation and growth of the hcp phase. The presence of B(OH)3 produced a sharp minimum in both Coulombic efficiency and deposition rate at potentials near −0.65 V and almost entirely suppressed the voltammetric feature. This may be associated with a combination of B(OH)3-derived proton reduction and inhibition of metal deposition by adsorbed B(OH)3 or B(OH)3-derived species. The presence of B(OH)3 affected the magnetic behavior of films deposited at potentials more oxidizing than −0.55 V (i.e., those with compositions less than about 40% Co) only weakly, but resulted in generally smaller maximum magnetizations for films deposited at more reducing potentials, and notably a much lower magnetization for films deposited at −0.65 V.
研究了电位和 B(OH)3 的存在对 Pt1-xCox 合金在 Ru 基底上从氯化物水溶液中电沉积的影响。在相对于 SCE 的还原电位高于 -0.65 V 时沉积的薄膜为六方紧密堆积，钴含量超过 90%（摩尔基）；而在相对于 SCE 的氧化电位高于 -0.65 V 时沉积的薄膜为面中心立方体，并且随着电位的升高，钴含量呈单调下降趋势。结构变化与成分-电位关系中明显的膝状特征以及与钴沉积有关的突出窄伏安峰相吻合，这可能与 hcp 相的成核和生长有关。在电位接近 -0.65 V 时，B(OH)3 的存在会使库仑效率和沉积速率急剧下降，并几乎完全抑制了伏安特性。这可能与 B(OH)3 衍生的质子还原以及吸附的 B(OH)3 或 B(OH)3 衍生物种对金属沉积的抑制作用有关。B(OH)3 的存在对在氧化性比 -0.55 V 更强的电位下沉积的薄膜（即钴含量低于 40% 的薄膜）的磁性行为影响较弱，但对在还原性更强的电位下沉积的薄膜的最大磁化率普遍较小，尤其是在 -0.65 V 下沉积的薄膜的磁化率更低。
{"title":"Influence of Potential and the Presence of Boric Acid on Pt1-xCox Alloy Electrodeposition and Magnetic Properties","authors":"Eric D. Rus, Eduardo L. Corrêa, Cindi L. Dennis, Thomas P. Moffat","doi":"10.1149/1945-7111/ad6b48","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6b48","url":null,"abstract":"The effects of potential and the presence of B(OH)<sub>3</sub> on Pt<sub>1-x</sub>Co<sub>x</sub> alloy electrodeposition from aqueous chloride-based solutions on Ru substrates was investigated. Films deposited at potentials more reducing than −0.65 V vs SCE were hexagonal close packed and greater than 90% Co (mole basis), and films deposited at potentials more oxidizing than −0.65 V were face centered cubic and showed a monotonic decrease in cobalt content as the potential increased. The composition and structure-potential dependences were not strongly affected by the presence of B(OH)<sub>3</sub>. Structural change coincided with a distinct knee-like feature in the composition-potential relationship, along with a prominent narrow voltammetric peak associated with Co deposition, possibly related to nucleation and growth of the hcp phase. The presence of B(OH)<sub>3</sub> produced a sharp minimum in both Coulombic efficiency and deposition rate at potentials near −0.65 V and almost entirely suppressed the voltammetric feature. This may be associated with a combination of B(OH)<sub>3</sub>-derived proton reduction and inhibition of metal deposition by adsorbed B(OH)<sub>3</sub> or B(OH)<sub>3</sub>-derived species. The presence of B(OH)<sub>3</sub> affected the magnetic behavior of films deposited at potentials more oxidizing than −0.55 V (i.e., those with compositions less than about 40% Co) only weakly, but resulted in generally smaller maximum magnetizations for films deposited at more reducing potentials, and notably a much lower magnetization for films deposited at −0.65 V.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"5 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222478","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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