A highly selective, stable and efficient non-precious metal catalyst is crucial for alkaline fuel cell applications. Recently, rare earth-based perovskite showed improved oxygen reduction reaction (ORR) which is analogous to commercial Pt/C. In this paper, strontium doped SmMnO3 (Sm1-xSrxMnO3 (x=0.1, 0.2, 0.3, and 0.4)) are synthesized by sol-gel route. The structure, valence state, and morphology of these samples were analyzed and oxygen adsorption behavior was investigated. Further, using the RRDE electrode (rotating ring disk electrode) the electro-catalytic behavior of the prepared catalyst toward ORR were investigated. The absorption of molecular oxygen by SmMnO3 catalyst was improved and the Mn valence state was tailored by doping Sr into the crystal lattice of SmMnO3. Sm1-xSrxMnO3 (x = 0.3) displayed highest ORR activity and stability among the synthesized electrocatalyst, with kinetic current density and onset potentials of 1.15 mA/cm2, and 0.92 V, respectively. High stability and electron transfer number around 4 makes the prepared electrocatalyst a viable alternate to commercial Pt/C for alkaline fuel cell application.
{"title":"Sm1-XSrxMnO3 (X = 0.1, 0.2, 0.3, and 0.4) Perovskite (SSM) with A-Site Doping Optimized as Oxygen Reduction Reaction (ORR) Electrocatalyst","authors":"Bibhuti Bhusan Nayak, Ipsha Hota, Siba Soren, Purnendu Parhi","doi":"10.1016/j.electacta.2024.145609","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145609","url":null,"abstract":"A highly selective, stable and efficient non-precious metal catalyst is crucial for alkaline fuel cell applications. Recently, rare earth-based perovskite showed improved oxygen reduction reaction (ORR) which is analogous to commercial Pt/C. In this paper, strontium doped SmMnO<sub>3</sub> (Sm<sub>1-x</sub>Sr<sub>x</sub>MnO<sub>3</sub> (x=0.1, 0.2, 0.3, and 0.4)) are synthesized by sol-gel route. The structure, valence state, and morphology of these samples were analyzed and oxygen adsorption behavior was investigated. Further, using the RRDE electrode (rotating ring disk electrode) the electro-catalytic behavior of the prepared catalyst toward ORR were investigated. The absorption of molecular oxygen by SmMnO<sub>3</sub> catalyst was improved and the Mn valence state was tailored by doping Sr into the crystal lattice of SmMnO<sub>3</sub>. Sm<sub>1-x</sub>Sr<sub>x</sub>MnO<sub>3</sub> (x = 0.3) displayed highest ORR activity and stability among the synthesized electrocatalyst, with kinetic current density and onset potentials of 1.15 mA/cm<sup>2</sup>, and 0.92 V, respectively. High stability and electron transfer number around 4 makes the prepared electrocatalyst a viable alternate to commercial Pt/C for alkaline fuel cell application.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"29 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142974599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-14DOI: 10.1016/j.electacta.2024.145539
Jan Witte, Philip Jordan, Thomas Turek
Anion exchange membrane water electrolysis (AEMWE) is an emerging technology combining the applicability of non-noble catalyst materials from traditional alkaline water electrolysis (AWE) with the low overpotentials and the compact design of proton exchange membrane water electrolysis (PEMWE). In the present work, different non-noble oxygen evolution reaction (OER) catalysts were studied and compared to the baseline reference catalyst at 25 °Celsius and 60 °Celsius, conditions usually applied in kinetic investigation (RDE setup) and in industrial scale electrolyzers, respectively. The catalysts were used as membrane electrode assembly (MEA) in a half-cell with flowing electrolyte at current densities of up to 1000 mA cm−2. The catalyst loading of the best performing catalyst was varied while the influence of the PTL type on the electrode performance was also investigated with this catalyst. It could be shown that an optimal catalyst loading reduced the overpotentials and that a lower porosity of PTL, which can enhance the interfacial contact between catalyst layer and PTL, also significantly improves the performance of the catalyst. Overall, this work shows a way towards further improvements of catalyst-coated PTLs for AEMWE.
{"title":"Experimental investigation of OER catalysts under real-life conditions in half-cell setup for Anion Exchange Membrane Water Electrolysis","authors":"Jan Witte, Philip Jordan, Thomas Turek","doi":"10.1016/j.electacta.2024.145539","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145539","url":null,"abstract":"Anion exchange membrane water electrolysis (AEMWE) is an emerging technology combining the applicability of non-noble catalyst materials from traditional alkaline water electrolysis (AWE) with the low overpotentials and the compact design of proton exchange membrane water electrolysis (PEMWE). In the present work, different non-noble oxygen evolution reaction (OER) catalysts were studied and compared to the baseline reference catalyst <figure><img alt=\"\" height=\"15\" src=\"https://ars.els-cdn.com/content/image/1-s2.0-S0013468624017754-fx1001.jpg\"/></figure> at 25 °Celsius and 60 °Celsius, conditions usually applied in kinetic investigation (RDE setup) and in industrial scale electrolyzers, respectively. The catalysts were used as membrane electrode assembly (MEA) in a half-cell with flowing electrolyte at current densities of up to 1000 mA cm<sup>−2</sup>. The catalyst loading of the best performing <figure><img alt=\"\" height=\"15\" src=\"https://ars.els-cdn.com/content/image/1-s2.0-S0013468624017754-fx1002.jpg\"/></figure> catalyst was varied while the influence of the PTL type on the electrode performance was also investigated with this catalyst. It could be shown that an optimal catalyst loading reduced the overpotentials and that a lower porosity of PTL, which can enhance the interfacial contact between catalyst layer and PTL, also significantly improves the performance of the catalyst. Overall, this work shows a way towards further improvements of catalyst-coated PTLs for AEMWE.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"36 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Diagnosis of breast cancer at its onset is crucial for the therapeutics so as to make the condition treatable, thereby increasing the patient survival rate. We report herein a simple and efficient electrochemical method using NiO thin film-based immunoelectrode to detect the proteins released by cancerous cells in human plasma (CA 15-3 polyclonal antibody). The raised polyclonal antibody is confirmed by Scanning Electron Microscope (SEM), Western blot and ouchterlony techniques. The developed immunoelectrode (CA 15-3/NiO/ITO/glass) has a low detection limit of 5 U/mL, sensitivity of 0.18 mA/(UmL-1) and fast response time of 2 s, which is comparable to that obtained with commercial ELISA kit. The testing of real samples of breast cancer was carried out using both the prepared immunoelectrode and CA 15-3 ELISA kit and the outcomes show strong correlation with one another. Interference studies with other diseases such as ovary cancer, lung cancer, asthma and tuberculosis were also analyzed by both techniques. The prepared immunoelectrode (CA 15-3/NiO/ITO/glass) was found to be highly sensitive and selective towards breast cancer detection and pave the way for the development of a simple, cost-effective and fast detection technique for breast cancer detection. We used an agent-based simulation model to evaluate the effects of targeting distinct cancer cell populations in breast cancer. Results showed that targeting cancer stem cells (CSCs) prevents tumor regrowth but harms other living cells, while targeting migratory cancer stem cells reduces metastasis with minimal impact on tumor mass. Targeting transitory cells lowered tumor burden without affecting metastasis. These findings suggest that a combined approach targeting CSCs, migratory stem cells, and transitory cells is crucial for effectively managing tumor growth and metastasis, offering a comprehensive strategy for breast cancer treatment.
{"title":"Electrochemical Immunosensor based on NiO for CA 15-3 detection and Agent-Based Modelling for Treatment Optimization","authors":"Kashima Arora, Vishal Gupta, Akshta Rajan, Lalit Kumar, Puja Munjal, Reena Jain, Anju Srivastava","doi":"10.1016/j.electacta.2025.145708","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.145708","url":null,"abstract":"Diagnosis of breast cancer at its onset is crucial for the therapeutics so as to make the condition treatable, thereby increasing the patient survival rate. We report herein a simple and efficient electrochemical method using NiO thin film-based immunoelectrode to detect the proteins released by cancerous cells in human plasma (CA 15-3 polyclonal antibody). The raised polyclonal antibody is confirmed by Scanning Electron Microscope (SEM), Western blot and ouchterlony techniques. The developed immunoelectrode (CA 15-3/NiO/ITO/glass) has a low detection limit of 5 U/mL, sensitivity of 0.18 mA/(UmL<sup>-1</sup>) and fast response time of 2 s, which is comparable to that obtained with commercial ELISA kit. The testing of real samples of breast cancer was carried out using both the prepared immunoelectrode and CA 15-3 ELISA kit and the outcomes show strong correlation with one another. Interference studies with other diseases such as ovary cancer, lung cancer, asthma and tuberculosis were also analyzed by both techniques. The prepared immunoelectrode (CA 15-3/NiO/ITO/glass) was found to be highly sensitive and selective towards breast cancer detection and pave the way for the development of a simple, cost-effective and fast detection technique for breast cancer detection. We used an agent-based simulation model to evaluate the effects of targeting distinct cancer cell populations in breast cancer. Results showed that targeting cancer stem cells (CSCs) prevents tumor regrowth but harms other living cells, while targeting migratory cancer stem cells reduces metastasis with minimal impact on tumor mass. Targeting transitory cells lowered tumor burden without affecting metastasis. These findings suggest that a combined approach targeting CSCs, migratory stem cells, and transitory cells is crucial for effectively managing tumor growth and metastasis, offering a comprehensive strategy for breast cancer treatment.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"118 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142974596","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
X-ray photoelectron spectroscopy (XPS) is a commonly used technique for investigating the surface properties and composition of catalysts used in polymer electrolyte membrane fuel cells and electrolyzers. XPS analysis of catalyst layers (CLs) is becoming increasingly utilized to provide greater understanding of CL properties and relationships between catalyst and support composition and structure, catalyst ink composition, CL fabrication methods and parameters, and their performance and durability. Characterization of Ir-based CLs is challenging due to several factors including interpretation of Ir 4f spectra, deconvolution of catalyst and ionomer species in O 1s spectra, and ionomer susceptibility to X-ray damage that leads to changes at the catalyst-ionomer interface often more significant than differences between samples. This study reports an approach for detailed XPS characterization of Ir-based CLs, establishes quantitative metrics and provides insights into the catalyst-ionomer interface that can be correlated to wide variety of processing and performance metrics. Specifically, we have evaluated surface compositional differences in CLs prepared with several common CL coating methods. We also investigated CLs prepared with different catalyst loadings and selected samples after electrochemical testing. In general, we found good agreements in trends observed from elemental ratios and those derived from detailed analysis of the O 1s spectra. Additionally, O 1s analysis revealed differences in the catalyst composition, addressing some of the challenges and limitations related to the interpretation of the Ir 4f spectra.
{"title":"X-ray Photoelectron Spectroscopy Investigation of Iridium Oxide Catalyst Layers: Insights into the Catalyst-Ionomer Interface","authors":"Jayson Foster, Xiang Lyu, Alexey Serov, Scott Mauger, Elliot Padgett, Svitlana Pylypenko","doi":"10.1016/j.electacta.2025.145705","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.145705","url":null,"abstract":"X-ray photoelectron spectroscopy (XPS) is a commonly used technique for investigating the surface properties and composition of catalysts used in polymer electrolyte membrane fuel cells and electrolyzers. XPS analysis of catalyst layers (CLs) is becoming increasingly utilized to provide greater understanding of CL properties and relationships between catalyst and support composition and structure, catalyst ink composition, CL fabrication methods and parameters, and their performance and durability. Characterization of Ir-based CLs is challenging due to several factors including interpretation of Ir 4f spectra, deconvolution of catalyst and ionomer species in O 1s spectra, and ionomer susceptibility to X-ray damage that leads to changes at the catalyst-ionomer interface often more significant than differences between samples. This study reports an approach for detailed XPS characterization of Ir-based CLs, establishes quantitative metrics and provides insights into the catalyst-ionomer interface that can be correlated to wide variety of processing and performance metrics. Specifically, we have evaluated surface compositional differences in CLs prepared with several common CL coating methods. We also investigated CLs prepared with different catalyst loadings and selected samples after electrochemical testing. In general, we found good agreements in trends observed from elemental ratios and those derived from detailed analysis of the O 1s spectra. Additionally, O 1s analysis revealed differences in the catalyst composition, addressing some of the challenges and limitations related to the interpretation of the Ir 4f spectra.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"7 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142974642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-14DOI: 10.1016/j.electacta.2025.145704
Romane Palluet, Marc Jeannin, Malo Duportal, Anne-Marie Grolleau, Philippe Refait
Carbon and low alloy steel structures immersed in seawater are commonly protected against corrosion by cathodic protection. In some complex structures, even though care is taken to avoid galvanic coupling, other metallic materials may be in contact with the protected carbon/low alloy steel and thus cathodically polarized too. The present study deals with complex structures that undergo immersion / emersion cycles. It is focused on the behavior of AISI 316L stainless steel parts affected by cathodic protection and aims to provide information about the electrochemical behavior of stainless steel during emersion periods. For that purpose, AISI 316L electrodes were polarized at -850 mV/Ag-AgCl-sw or -1050 mV/Ag-AgCl-sw during two months in natural seawater at 10°C and subsequently left at open circuit potential in a marine atmosphere for two weeks. µ-Raman spectroscopy analysis showed that the deposits were in any case mainly composed of aragonite CaCO3 but XRD analysis revealed the presence of brucite Mg(OH)2 at -1050 mV/Ag-AgCl-sw. Linear polarization resistance and electrochemical impedance spectroscopy measurements were carried out during the emersion period and showed that the calcareous deposit formed at -1050 mV/Ag-AgCl-sw retained more water during emersion than the deposit formed at -850 mV/Ag-AgCl-sw. Moreover, it delayed the increase in OCP associated with the interruption of cathodic protection. These differences are attributed to the underlying brucite film only present at -1050 mV/Ag-AgCl-sw that tends to dissolve when cathodic protection is interrupted, thus maintaining a higher pH at the metal/seawater interface.
{"title":"Electrochemical processes occurring on previously cathodically polarized AISI 316L stainless steel electrodes during emersion in marine atmosphere","authors":"Romane Palluet, Marc Jeannin, Malo Duportal, Anne-Marie Grolleau, Philippe Refait","doi":"10.1016/j.electacta.2025.145704","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.145704","url":null,"abstract":"Carbon and low alloy steel structures immersed in seawater are commonly protected against corrosion by cathodic protection. In some complex structures, even though care is taken to avoid galvanic coupling, other metallic materials may be in contact with the protected carbon/low alloy steel and thus cathodically polarized too. The present study deals with complex structures that undergo immersion / emersion cycles. It is focused on the behavior of AISI 316L stainless steel parts affected by cathodic protection and aims to provide information about the electrochemical behavior of stainless steel during emersion periods. For that purpose, AISI 316L electrodes were polarized at -850 mV/<sub>Ag-AgCl-sw</sub> or -1050 mV/<sub>Ag-AgCl-sw</sub> during two months in natural seawater at 10°C and subsequently left at open circuit potential in a marine atmosphere for two weeks. µ-Raman spectroscopy analysis showed that the deposits were in any case mainly composed of aragonite CaCO<sub>3</sub> but XRD analysis revealed the presence of brucite Mg(OH)<sub>2</sub> at -1050 mV/<sub>Ag-AgCl-sw.</sub> Linear polarization resistance and electrochemical impedance spectroscopy measurements were carried out during the emersion period and showed that the calcareous deposit formed at -1050 mV/<sub>Ag-AgCl-sw</sub> retained more water during emersion than the deposit formed at -850 mV/<sub>Ag-AgCl-sw</sub>. Moreover, it delayed the increase in OCP associated with the interruption of cathodic protection. These differences are attributed to the underlying brucite film only present at -1050 mV/<sub>Ag-AgCl-sw</sub> that tends to dissolve when cathodic protection is interrupted, thus maintaining a higher pH at the metal/seawater interface.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"29 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142974655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-12DOI: 10.1016/j.electacta.2025.145684
Feijie Wang, Dong Zhu, Cunman Zhang
To meet the increasing power demand of the application, a 200 kW fuel cell system with an alternating current impedance measuring system was installed on the test bench. The equivalent circuit model (ECM) and the essential equations for distribution of relaxation time (DRT) was been presented. The basic performance and operation parameters were tested using polarization curves. The impedance of the fuel cell was measured in the steady-state variable load condition, and the basic impedance loss of the stack was understood via ECM and DRT analyses. The impedance measurement, ECM, and DRT analyses were conducted by varying the cathode stoichiometric ratio, stack coolant temperature, and shutdown purge time, respectively. Results revealed that the total impedance of the stack decreased with the gradual increase in current density, and the relaxation time function <span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML"><mrow is="true"><mi is="true">γ</mi><mi is="true">l</mi><mi is="true">n</mi><mo is="true">(</mo><mi is="true">τ</mi><mo is="true">)</mo><mspace width="0.33em" is="true" /></mrow></math>' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="2.779ex" role="img" style="vertical-align: -0.812ex;" viewbox="0 -846.5 3069 1196.3" width="7.128ex" xmlns:xlink="http://www.w3.org/1999/xlink"><g fill="currentColor" stroke="currentColor" stroke-width="0" transform="matrix(1 0 0 -1 0 0)"><g is="true"><g is="true"><use xlink:href="#MJMATHI-3B3"></use></g><g is="true" transform="translate(543,0)"><use xlink:href="#MJMATHI-6C"></use></g><g is="true" transform="translate(842,0)"><use xlink:href="#MJMATHI-6E"></use></g><g is="true" transform="translate(1442,0)"><use xlink:href="#MJMAIN-28"></use></g><g is="true" transform="translate(1832,0)"><use xlink:href="#MJMATHI-3C4"></use></g><g is="true" transform="translate(2349,0)"><use xlink:href="#MJMAIN-29"></use></g><g is="true"></g></g></g></svg><span role="presentation"><math xmlns="http://www.w3.org/1998/Math/MathML"><mrow is="true"><mi is="true">γ</mi><mi is="true">l</mi><mi is="true">n</mi><mo is="true">(</mo><mi is="true">τ</mi><mo is="true">)</mo><mspace is="true" width="0.33em"></mspace></mrow></math></span></span><script type="math/mml"><math><mrow is="true"><mi is="true">γ</mi><mi is="true">l</mi><mi is="true">n</mi><mo is="true">(</mo><mi is="true">τ</mi><mo is="true">)</mo><mspace width="0.33em" is="true"></mspace></mrow></math></script></span>of the fuel cell was approximately 600–620 mΩ cm<sup>2</sup>. When the cathode stoichiometric ratio increased, mass transfer resistance significantly increased, while ohmic resistance (<em>R</em><sub>ohm</sub>), effective charge transfer resistance (<em>R</em><sub>act</sub>), and anode activation impedan
{"title":"Investigation of operating conditions for 200 kW fuel cell system based on electrochemical impedance spectroscopy","authors":"Feijie Wang, Dong Zhu, Cunman Zhang","doi":"10.1016/j.electacta.2025.145684","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.145684","url":null,"abstract":"To meet the increasing power demand of the application, a 200 kW fuel cell system with an alternating current impedance measuring system was installed on the test bench. The equivalent circuit model (ECM) and the essential equations for distribution of relaxation time (DRT) was been presented. The basic performance and operation parameters were tested using polarization curves. The impedance of the fuel cell was measured in the steady-state variable load condition, and the basic impedance loss of the stack was understood via ECM and DRT analyses. The impedance measurement, ECM, and DRT analyses were conducted by varying the cathode stoichiometric ratio, stack coolant temperature, and shutdown purge time, respectively. Results revealed that the total impedance of the stack decreased with the gradual increase in current density, and the relaxation time function <span><span style=\"\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow is=\"true\"><mi is=\"true\">&#x3B3;</mi><mi is=\"true\">l</mi><mi is=\"true\">n</mi><mo is=\"true\">(</mo><mi is=\"true\">&#x3C4;</mi><mo is=\"true\">)</mo><mspace width=\"0.33em\" is=\"true\" /></mrow></math>' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"><svg aria-hidden=\"true\" focusable=\"false\" height=\"2.779ex\" role=\"img\" style=\"vertical-align: -0.812ex;\" viewbox=\"0 -846.5 3069 1196.3\" width=\"7.128ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"><g fill=\"currentColor\" stroke=\"currentColor\" stroke-width=\"0\" transform=\"matrix(1 0 0 -1 0 0)\"><g is=\"true\"><g is=\"true\"><use xlink:href=\"#MJMATHI-3B3\"></use></g><g is=\"true\" transform=\"translate(543,0)\"><use xlink:href=\"#MJMATHI-6C\"></use></g><g is=\"true\" transform=\"translate(842,0)\"><use xlink:href=\"#MJMATHI-6E\"></use></g><g is=\"true\" transform=\"translate(1442,0)\"><use xlink:href=\"#MJMAIN-28\"></use></g><g is=\"true\" transform=\"translate(1832,0)\"><use xlink:href=\"#MJMATHI-3C4\"></use></g><g is=\"true\" transform=\"translate(2349,0)\"><use xlink:href=\"#MJMAIN-29\"></use></g><g is=\"true\"></g></g></g></svg><span role=\"presentation\"><math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow is=\"true\"><mi is=\"true\">γ</mi><mi is=\"true\">l</mi><mi is=\"true\">n</mi><mo is=\"true\">(</mo><mi is=\"true\">τ</mi><mo is=\"true\">)</mo><mspace is=\"true\" width=\"0.33em\"></mspace></mrow></math></span></span><script type=\"math/mml\"><math><mrow is=\"true\"><mi is=\"true\">γ</mi><mi is=\"true\">l</mi><mi is=\"true\">n</mi><mo is=\"true\">(</mo><mi is=\"true\">τ</mi><mo is=\"true\">)</mo><mspace width=\"0.33em\" is=\"true\"></mspace></mrow></math></script></span>of the fuel cell was approximately 600–620 mΩ cm<sup>2</sup>. When the cathode stoichiometric ratio increased, mass transfer resistance significantly increased, while ohmic resistance (<em>R</em><sub>ohm</sub>), effective charge transfer resistance (<em>R</em><sub>act</sub>), and anode activation impedan","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"36 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962728","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
As an alternative battery system, Cu–Zn battery is attractive because the raw materials are inexpensive and non-toxic. However, traditional Cu–Zn battery is not rechargeable due to the limited reversibility and low stability caused by the shuttling of Cu2+ ions to the Zn anode. In this study, we have constructed reversible Cu–Zn batteries with a cation-selective membrane in a common ZnSO4/Li2SO4 mixed electrolyte for both the catholyte and anolyte. The membrane allows the transfer of Li+ for the charge balance while suppressing the cross-over of Cu2+ ions, increasing the Coulombic efficiency of the battery. The effectiveness of the membrane and the stability of the battery are also found to be affected by the electrolyte concentration. Using 2 M ZnSO4/2 M Li2SO4 electrolyte, the Cu–Zn battery can be cycled for more than 4000 cycles with a capacity limitation of 0.1 mAh cm-2 at a current of 1 mA cm-2 with stable voltages and Coulombic efficiency of about 99.5%.
{"title":"Improving reversibility and reducing overpotential of Cu–Zn battery with electrolyte engineering and cation-selective membrane","authors":"Kaiming Xue, Qiaohui Duan, Koutarou Imaizumi, Hongfei Li, Denis Y.W. Yu","doi":"10.1016/j.electacta.2025.145690","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.145690","url":null,"abstract":"As an alternative battery system, Cu–Zn battery is attractive because the raw materials are inexpensive and non-toxic. However, traditional Cu–Zn battery is not rechargeable due to the limited reversibility and low stability caused by the shuttling of Cu<sup>2+</sup> ions to the Zn anode. In this study, we have constructed reversible Cu–Zn batteries with a cation-selective membrane in a common ZnSO<sub>4</sub>/Li<sub>2</sub>SO<sub>4</sub> mixed electrolyte for both the catholyte and anolyte. The membrane allows the transfer of Li<sup>+</sup> for the charge balance while suppressing the cross-over of Cu<sup>2+</sup> ions, increasing the Coulombic efficiency of the battery. The effectiveness of the membrane and the stability of the battery are also found to be affected by the electrolyte concentration. Using 2 M ZnSO<sub>4</sub>/2 M Li<sub>2</sub>SO<sub>4</sub> electrolyte, the Cu–Zn battery can be cycled for more than 4000 cycles with a capacity limitation of 0.1 mAh cm<sup>-2</sup> at a current of 1 mA cm<sup>-2</sup> with stable voltages and Coulombic efficiency of about 99.5%.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"26 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-12DOI: 10.1016/j.electacta.2025.145688
Hai-lin Ren, Yang Su, Shuai Zhao, Cheng-wei Li, Xiao-min Wang, Bo-han Li
SiOx (0 < x < 2) has been considered as one of the most promising anodes for lithium-ion batteries due to its high capacity and more stable cyclic charging and discharging performance, but it still has the drawbacks of lower intrinsic conductivity and larger volume expansion compared to graphite. For this purpose, Sn, a homologous element of Si, is selected in this paper, and the SiOx@SnO2 heterostructure is constructed on the SiOx surface using simple solvothermal and calcination methods. The combination of DFT analysis and experimental results shows that the heterogeneous structure enhances the Si-O bond strength in SiOx, and coupled with the localised stresses due to the lattice differences between SiOx and SnO2 alleviates the volume change of SiOx during lithiation /de-lithiation. The reversible capacity was 536.8 mAh g-1 after 300 cycles at 1C and 1152.4 mAh g-1 after 200 cycles at 0.5C. The construction of SiOx@SnO2 heterojunction will also bring the Fermi energy levels into the valence band, which makes the material exhibit some metallic properties and improves the electrical conductivity enhancing the Li+ diffusion.
{"title":"Construction of SiOx-SnO2 heterojunction and surface coating to achieve high-performance anode materials for lithium-ion batteries","authors":"Hai-lin Ren, Yang Su, Shuai Zhao, Cheng-wei Li, Xiao-min Wang, Bo-han Li","doi":"10.1016/j.electacta.2025.145688","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.145688","url":null,"abstract":"SiO<em><sub>x</sub></em> (0 < x < 2) has been considered as one of the most promising anodes for lithium-ion batteries due to its high capacity and more stable cyclic charging and discharging performance, but it still has the drawbacks of lower intrinsic conductivity and larger volume expansion compared to graphite. For this purpose, Sn, a homologous element of Si, is selected in this paper, and the SiO<em><sub>x</sub></em>@SnO<sub>2</sub> heterostructure is constructed on the SiO<em><sub>x</sub></em> surface using simple solvothermal and calcination methods. The combination of DFT analysis and experimental results shows that the heterogeneous structure enhances the Si-O bond strength in SiO<em><sub>x</sub></em>, and coupled with the localised stresses due to the lattice differences between SiO<em><sub>x</sub></em> and SnO<sub>2</sub> alleviates the volume change of SiO<em><sub>x</sub></em> during lithiation /de-lithiation. The reversible capacity was 536.8 mAh g<sup>-1</sup> after 300 cycles at 1C and 1152.4 mAh g<sup>-1</sup> after 200 cycles at 0.5C. The construction of SiO<em><sub>x</sub></em>@SnO<sub>2</sub> heterojunction will also bring the Fermi energy levels into the valence band, which makes the material exhibit some metallic properties and improves the electrical conductivity enhancing the Li<sup>+</sup> diffusion.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"11 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
On-chip micro-supercapacitors (MSCs) have great potential in applications like wireless sensor networks and portable electronic devices. Although a lot of researches have been done to show that transition metal nitride films, such as TiN, exhibit attractive performance, make good electrodes, their power and energy densities are still insufficient. This research reports the compositional optimization of TixMoyNz electrode films by magnetron co-sputtering on Si substrates utilizing a high-throughput technique, and the study of their electrochemical characteristics. This method can prepare multi-composition films in a single processing step, significantly reducing the time and costs compared with the traditional investigation method used for optimizing binary transition metal nitrides. At a power density of 15.8 W cm−3, the MSCs prepared using optimized TixMoyNz electrode on in-situ grown TiN current collector can sustain an energy density of 30.3 mWh cm−3 and maintain a 93% capacitance retention rate after 10,000 charge-discharge cycles.
{"title":"Titanium molybdenum nitride/titanium nitride laminated films prepared by a high-throughput method for on-chip microsupercapacitors","authors":"Bin Zhang, Mengxiao Wang, Jinyang Sui, Qidi Kou, Xiaokui Kang, Dayu Zhou","doi":"10.1016/j.electacta.2025.145687","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.145687","url":null,"abstract":"On-chip micro-supercapacitors (MSCs) have great potential in applications like wireless sensor networks and portable electronic devices. Although a lot of researches have been done to show that transition metal nitride films, such as TiN, exhibit attractive performance, make good electrodes, their power and energy densities are still insufficient. This research reports the compositional optimization of Ti<sub>x</sub>Mo<sub>y</sub>N<sub>z</sub> electrode films by magnetron co-sputtering on Si substrates utilizing a high-throughput technique, and the study of their electrochemical characteristics. This method can prepare multi-composition films in a single processing step, significantly reducing the time and costs compared with the traditional investigation method used for optimizing binary transition metal nitrides. At a power density of 15.8 W cm<sup>−3</sup>, the MSCs prepared using optimized Ti<sub>x</sub>Mo<sub>y</sub>N<sub>z</sub> electrode on in-situ grown TiN current collector can sustain an energy density of 30.3 mWh cm<sup>−3</sup> and maintain a 93% capacitance retention rate after 10,000 charge-discharge cycles.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"45 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-11DOI: 10.1016/j.electacta.2025.145686
Zhannur Myltykbayeva, José M. López Nieto, Beatriz M. Moreno-Torralbo, P. Concepción, Akerke Abylaikhan, Atıf Koca
Vanadyl octaethyl porphyrin (VOP) impregnated on SiO2 nanoparticles (SiO2@VOP) was investigated as an electrocatalyst for the water-splitting reaction for the cathodic hydrogen evolution reaction (HER). Multi-valent oxidation states of VO2+ center and multi-electron transfer properties of the porphyrin ring made this complex a potential candidate for the electrocatalytic processes. Altering the electrode modification protocol by changing the amount of the VOP, carbon black (CB), and Nafion (Nf) binder on the modification influenced the active sites, thus consequently enhancing the electrocatalytic activity of SiO2@VOP composites. Electrocatalytic HER measurements indicated excellent activity with low overpotential (108 mV), small Tafel slope (98 mV/dec), and high current density stability with the GCE/CB@SiO2@VOP(B) electrode.
{"title":"Optimizing the Electrocatalytic Hydrogen Production with Vanadyl Porphyrin Impregnated on Mesoporous SiO2 Nanoparticles","authors":"Zhannur Myltykbayeva, José M. López Nieto, Beatriz M. Moreno-Torralbo, P. Concepción, Akerke Abylaikhan, Atıf Koca","doi":"10.1016/j.electacta.2025.145686","DOIUrl":"https://doi.org/10.1016/j.electacta.2025.145686","url":null,"abstract":"Vanadyl octaethyl porphyrin (VOP) impregnated on SiO<sub>2</sub> nanoparticles (<strong>SiO<sub>2</sub>@VOP</strong>) was investigated as an electrocatalyst for the water-splitting reaction for the cathodic hydrogen evolution reaction (HER). Multi-valent oxidation states of VO<sup>2+</sup> center and multi-electron transfer properties of the porphyrin ring made this complex a potential candidate for the electrocatalytic processes. Altering the electrode modification protocol by changing the amount of the VOP, carbon black (CB), and Nafion (Nf) binder on the modification influenced the active sites, thus consequently enhancing the electrocatalytic activity of <strong>SiO<sub>2</sub>@VOP</strong> composites. Electrocatalytic HER measurements indicated excellent activity with low overpotential (108 mV), small Tafel slope (98 mV/dec), and high current density stability with the GCE/CB@<strong>SiO<sub>2</sub>@VOP(B)</strong> electrode.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"39 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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