Pub Date : 2024-12-28DOI: 10.1016/j.electacta.2024.145608
Zenonas Jusys, R. Jürgen Behm
We report results of a systematic study of the borohydride oxidation reaction (BOR) in borohydride containing 0.5 M NaOH electrolyte over Pt/C, Au/C and AuPt/C catalyst thin-film electrodes, performed under enforced mass transport conditions. Employing rotating disk electrode (RDE) and thin-layer flow cell differential electrochemical mass spectrometry (DEMS) measurements, we identify kinetic limitations over a wide range of transport conditions. Together with the highly sensitive detection of evolved hydrogen as a function of potential, due to the use of a cold trap at the mass spectrometer inlet, this allows us to separate changes in the reaction selectivity, from complete to incomplete borohydride oxidation, from other kinetic limitations. Evaluation of the (apparent) number of electrons transferred per borohydride ion, both from the RDE measurements via the Koutecky-Levich formalism and from the DEMS measurements via the H2 formation current, further supports the identification of complete borohydride oxidation (8 electron transfer) and incomplete oxidation (< 8 electrons transfer) reaction conditions. Using data on isotope labeled BD4- oxidation that we had published earlier, we identify weak secondary kinetic isotope effects for all catalysts, which indicate that B-H bond breaking does not represent the rate limiting step.
{"title":"Borohydride oxidation over Pt/C, Au/C and AuPt/C thin-film electrodes studied by rotating disk electrode and differential electrochemical mass spectrometry flow cell measurements","authors":"Zenonas Jusys, R. Jürgen Behm","doi":"10.1016/j.electacta.2024.145608","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145608","url":null,"abstract":"We report results of a systematic study of the borohydride oxidation reaction (BOR) in borohydride containing 0.5 M NaOH electrolyte over Pt/C, Au/C and AuPt/C catalyst thin-film electrodes, performed under enforced mass transport conditions. Employing rotating disk electrode (RDE) and thin-layer flow cell differential electrochemical mass spectrometry (DEMS) measurements, we identify kinetic limitations over a wide range of transport conditions. Together with the highly sensitive detection of evolved hydrogen as a function of potential, due to the use of a cold trap at the mass spectrometer inlet, this allows us to separate changes in the reaction selectivity, from complete to incomplete borohydride oxidation, from other kinetic limitations. Evaluation of the (apparent) number of electrons transferred per borohydride ion, both from the RDE measurements via the Koutecky-Levich formalism and from the DEMS measurements via the H<sub>2</sub> formation current, further supports the identification of complete borohydride oxidation (8 electron transfer) and incomplete oxidation (< 8 electrons transfer) reaction conditions. Using data on isotope labeled BD<sub>4</sub><sup>-</sup> oxidation that we had published earlier, we identify weak secondary kinetic isotope effects for all catalysts, which indicate that B-H bond breaking does not represent the rate limiting step.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"114 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888841","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 : 2024-12-28DOI: 10.1016/j.electacta.2024.145597
Umair Rashid, Muhammad Ismail, Abdul Naveed, Ali Haider, Tinglu Song, Xilan Ma, Youqi Zhu, Chuanbao Cao, Meishuai Zou
A unique strategy that employs synthesis of dandelion-like CoO nonostructure on nickel foam (NF) through a facile one step hydrothermal method is proposed. Each dandelion is further consisting of an array of nanograss self-supported on electrode. The self-supported CoO electrode exhibited excellent electrocatalytic properties in alkaline solutions, specifically in 1M KOH, with low overpotential of 258 and 162 mV at current density of 20 mA/cm2geo during the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. The exceptional catalytic activity is attributed to unique morphology which result in the formation of pinning and attachment sites that allow for the growth of nanograss and the creation of stable, self-supported structure. The hierarchical 3-dimensional fluffy structures and tight adhesion between active materials and the substrate results in the preparation of self-supported electrocatalyst which offer enhanced charge transfer, accelerated diffusion of electrolyte, a large surface area with multitude of active sites, effective catalytic components, and high conductivity during the electrocatalytic process presenting small Tafel slope of 68 and 123 mV/dec for OER and HER respectively. Furthermore, the developed overall electrolyzer enables efficient full water splitting at a low cell voltage of 1.33 V at 10 mA/cm2 current density. And demonstrates 100% endurance for up to 12 hours at 300 mA/cm2. When tested for supercapacitor performance, CoO@NF electrode demonstrates a high specific capacitance of 1592 F/g at a current density of 1 A/g in 2M KOH solution. Moreover, it displays a remarkable energy density of 48 Wh/Kg at a high power density of 500 W/Kg. The synthesized material exhibited impressive cyclic stability by sustaining 106% capacitance retention after 5000 cycles with columbic efficiency of 98.6%. This work proposes an innovative approach for the development of single material exhibiting both electrocatalytic and energy storage high-performance characteristics.
{"title":"Cobalt Oxide Nano Dandelions on Nickel Foam as Binder Free Bifunctional Electrocatalyst for Overall Water Splitting and Supercapacitance","authors":"Umair Rashid, Muhammad Ismail, Abdul Naveed, Ali Haider, Tinglu Song, Xilan Ma, Youqi Zhu, Chuanbao Cao, Meishuai Zou","doi":"10.1016/j.electacta.2024.145597","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145597","url":null,"abstract":"A unique strategy that employs synthesis of dandelion-like CoO nonostructure on nickel foam (NF) through a facile one step hydrothermal method is proposed. Each dandelion is further consisting of an array of nanograss self-supported on electrode. The self-supported CoO electrode exhibited excellent electrocatalytic properties in alkaline solutions, specifically in 1M KOH, with low overpotential of 258 and 162 mV at current density of 20 mA/cm<sup>2</sup><sub>geo</sub> during the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. The exceptional catalytic activity is attributed to unique morphology which result in the formation of pinning and attachment sites that allow for the growth of nanograss and the creation of stable, self-supported structure. The hierarchical 3-dimensional fluffy structures and tight adhesion between active materials and the substrate results in the preparation of self-supported electrocatalyst which offer enhanced charge transfer, accelerated diffusion of electrolyte, a large surface area with multitude of active sites, effective catalytic components, and high conductivity during the electrocatalytic process presenting small Tafel slope of 68 and 123 mV/dec for OER and HER respectively. Furthermore, the developed overall electrolyzer enables efficient full water splitting at a low cell voltage of 1.33 V at 10 mA/cm<sup>2</sup> current density. And demonstrates 100% endurance for up to 12 hours at 300 mA/cm<sup>2</sup>. When tested for supercapacitor performance, CoO@NF electrode demonstrates a high specific capacitance of 1592 F/g at a current density of 1 A/g in 2M KOH solution. Moreover, it displays a remarkable energy density of 48 Wh/Kg at a high power density of 500 W/Kg. The synthesized material exhibited impressive cyclic stability by sustaining 106% capacitance retention after 5000 cycles with columbic efficiency of 98.6%. This work proposes an innovative approach for the development of single material exhibiting both electrocatalytic and energy storage high-performance characteristics.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"80 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888847","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 : 2024-12-28DOI: 10.1016/j.electacta.2024.145575
Shayan Gul, Fatima Nasim, Muhammad Amtiaz Nadeem, Muhammad Imran, Amir Waseem, Muhammad Arif Nadeem
Electrocatalytic CO2 reduction reaction (eCO2RR) generates valuable chemical feedstocks but exhibits slow kinetics due to its proton-coupled electron transfer (PCET) process. Transition metal oxides, including iron oxides (FeO) and cobalt oxides (CoO), are economically feasible, non-toxic, and widely accessible materials for various electrochemical applications. Yet, they demonstrate near inactivity in eCO2RR. Our study reveals a notable boost in the activity and selectivity of FeO to reduce CO2 to CO when it is supported on cobalt oxide embedded nitrogen doped carbon nanotubes (CoO-NC). By varying the concentration of FeO, a series of FeO based electrocatalysts has been synthesized. The optimum ratio denoted as FeO/CoO-NC(0.16) exhibits a significant current density (j) of 38 mAcm-2 which is 3.8 times greater when FeO is deposited over commercial multiwalled carbon nanotubes (FeO/MWCNTs). Moreover, FeO/CoO-NC(0.16) shows a remarkably lower overpotential (η) of only 0.251 VRHE than FeO/MWCNTs (0.446 VRHE). The Faraday efficiency (FE) for electrocatalytic CO2 to CO conversion on the surface of FeO/CoO-NC(0.16) reaches ≈ 79% at −0.70 VRHE which is quantitively monitored by a GC-TCD. The present study offers a new avenue for the use of Fe as an efficient candidate for eCO2RR.
{"title":"Effective electrocatalytic conversion of CO2 to CO on CoO-NC supported iron oxide heterostructure","authors":"Shayan Gul, Fatima Nasim, Muhammad Amtiaz Nadeem, Muhammad Imran, Amir Waseem, Muhammad Arif Nadeem","doi":"10.1016/j.electacta.2024.145575","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145575","url":null,"abstract":"Electrocatalytic CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR) generates valuable chemical feedstocks but exhibits slow kinetics due to its proton-coupled electron transfer (PCET) process. Transition metal oxides, including iron oxides (FeO) and cobalt oxides (CoO), are economically feasible, non-toxic, and widely accessible materials for various electrochemical applications. Yet, they demonstrate near inactivity in eCO<sub>2</sub>RR. Our study reveals a notable boost in the activity and selectivity of FeO to reduce CO<sub>2</sub> to CO when it is supported on cobalt oxide embedded nitrogen doped carbon nanotubes (CoO-NC). By varying the concentration of FeO, a series of FeO based electrocatalysts has been synthesized. The optimum ratio denoted as FeO/CoO-NC(0.16) exhibits a significant current density (j) of 38 mAcm<sup>-2</sup> which is 3.8 times greater when FeO is deposited over commercial multiwalled carbon nanotubes (FeO/MWCNTs). Moreover, FeO/CoO-NC(0.16) shows a remarkably lower overpotential (η) of only 0.251 V<sub>RHE</sub> than FeO/MWCNTs (0.446 V<sub>RHE</sub>). The Faraday efficiency (FE) for electrocatalytic CO<sub>2</sub> to CO conversion on the surface of FeO/CoO-NC(0.16) reaches <span><span>≈</span><svg aria-label=\"Opens in new window\" focusable=\"false\" height=\"20\" viewbox=\"0 0 8 8\"><path d=\"M1.12949 2.1072V1H7V6.85795H5.89111V2.90281L0.784057 8L0 7.21635L5.11902 2.1072H1.12949Z\"></path></svg></span> 79% at −0.70 V<sub>RHE</sub> which is quantitively monitored by a GC-TCD. The present study offers a new avenue for the use of Fe as an efficient candidate for eCO<sub>2</sub>RR.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"114 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888720","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 : 2024-12-28DOI: 10.1016/j.electacta.2024.145605
Priyanka Chaluvachar, Mahesha G T, Vishnu G Nair, Dayananda K Pai, Sudhakar Y N
Energy storage technologies enable the efficient storage and release of energy, providing essential flexibility and stability to power grids worldwide. Supercapacitors are advanced energy storage systems capable of rapidly storing and releasing large amounts of electrical energy, offering long cycle life and high-power density. Herein, a carbon quantum dot (CQD) dispersed 2D graphitic carbon nitride (g-C3N4) nanocomposite was deposited with poly(3,4-ethylene dioxythiophene) (PEDOT) by an electrodeposition technique. The structural, morphological, functional group, and elemental characteristics of the synthesized materials were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). An electrochemical study of electrode materials named g-C3N4, g-C3N4-CQD and g-C3N4-CQD/PEDOT (GCP) composites was performed. The GCP electrode-based symmetric supercapacitor device exhibited a specific capacitance (Cs) of 109.5 F g−1 at a current density of 0.2 A g−1 in 1 M H2SO4. Herein, the prime novelty is the incorporation of CQDs as spacers between g-C3N4 layers, which substantially improved the surface area, providing potential benefits such as higher energy density and greater stability for supercapacitors. The supercapacitor device utilizing GCP demonstrated an energy density of 14.6 Wh kg−1 at a power density of 1.4 kW kg−1, operating at a current density of 0.2 A g−1. The improved electrochemical performance of the hybrid electrode materials is ascribed to the combined effect of the faradaic PEDOT and the non-faradaic CQDs incorporated into the g-C3N4 matrix.
{"title":"Graphitic carbon nitride supported metal-free heterostructure embedded with carbon quantum dots and PEDOT as electrodes for supercapacitors","authors":"Priyanka Chaluvachar, Mahesha G T, Vishnu G Nair, Dayananda K Pai, Sudhakar Y N","doi":"10.1016/j.electacta.2024.145605","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145605","url":null,"abstract":"Energy storage technologies enable the efficient storage and release of energy, providing essential flexibility and stability to power grids worldwide. Supercapacitors are advanced energy storage systems capable of rapidly storing and releasing large amounts of electrical energy, offering long cycle life and high-power density. Herein, a carbon quantum dot (CQD) dispersed 2D graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) nanocomposite was deposited with poly(3,4-ethylene dioxythiophene) (PEDOT) by an electrodeposition technique. The structural, morphological, functional group, and elemental characteristics of the synthesized materials were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). An electrochemical study of electrode materials named g-C<sub>3</sub>N<sub>4</sub>, g-C<sub>3</sub>N<sub>4</sub>-CQD and g-C<sub>3</sub>N<sub>4</sub>-CQD/PEDOT (GCP) composites was performed. The GCP electrode-based symmetric supercapacitor device exhibited a specific capacitance (C<sub>s</sub>) of 109.5 F g<sup>−1</sup> at a current density of 0.2 A g<sup>−1</sup> in 1 M H<sub>2</sub>SO<sub>4</sub>. Herein, the prime novelty is the incorporation of CQDs as spacers between g-C<sub>3</sub>N<sub>4</sub> layers, which substantially improved the surface area, providing potential benefits such as higher energy density and greater stability for supercapacitors. The supercapacitor device utilizing GCP demonstrated an energy density of 14.6 Wh kg<sup>−1</sup> at a power density of 1.4 kW kg<sup>−1</sup>, operating at a current density of 0.2 A g<sup>−1</sup>. The improved electrochemical performance of the hybrid electrode materials is ascribed to the combined effect of the faradaic PEDOT and the non-faradaic CQDs incorporated into the g-C<sub>3</sub>N<sub>4</sub> matrix.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"19 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888718","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 : 2024-12-28DOI: 10.1016/j.electacta.2024.145607
Wenchao Li, Qinglin Lian, Feifei Huang, Bo Zhang, Hongbo Zhang, Kangning Liu, Yankui Jia, Huaji Wang, Yuming Lai, Ying Jin
In this paper, we investigate the issue of droplet corrosion in carbon steel, employing both numerical simulations and experimental methodologies. We dissect the corrosion mechanism of carbon steel droplets, considering how droplet shape influences oxygen diffusion, movement of the corrosion interface, and the dynamic deposition of corrosion products to elucidate the corrosion dynamics. Both simulation and experiment results establish that at the droplet's edge, the density of corrosion products and the pH value are elevated compared to the central area, which, conversely, features more porous corrosion products and a lower pH value, leading to heightened anodic current density at the center. This disparity in porosity and pH values accentuates the difference in current densities and intensifies localized corrosion within the droplet. Structurally, the droplet's center functions as a local anode, while its edge serves as a cathode. Corrosion products in the central area primarily consist of green rust (Fe4(OH)8Cl), which exhibits higher porosity, whereas the edge is characterized by denser γ-FeOOH. Variations in the composition and protective attributes of these corrosion products further magnify the differences in current density. This autocatalytic progression instigates a stable internal anode-cathode reaction within the droplet, ultimately culminating in the development of a deeper corrosion pit at the central zone. Additionally, the numerical model in the paper can provide support for the prediction of atmospheric corrosion of carbon steel.
{"title":"Numerical simulation and experimental verification on the kinetics of droplet corrosion of carbon steel","authors":"Wenchao Li, Qinglin Lian, Feifei Huang, Bo Zhang, Hongbo Zhang, Kangning Liu, Yankui Jia, Huaji Wang, Yuming Lai, Ying Jin","doi":"10.1016/j.electacta.2024.145607","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145607","url":null,"abstract":"In this paper, we investigate the issue of droplet corrosion in carbon steel, employing both numerical simulations and experimental methodologies. We dissect the corrosion mechanism of carbon steel droplets, considering how droplet shape influences oxygen diffusion, movement of the corrosion interface, and the dynamic deposition of corrosion products to elucidate the corrosion dynamics. Both simulation and experiment results establish that at the droplet's edge, the density of corrosion products and the pH value are elevated compared to the central area, which, conversely, features more porous corrosion products and a lower pH value, leading to heightened anodic current density at the center. This disparity in porosity and pH values accentuates the difference in current densities and intensifies localized corrosion within the droplet. Structurally, the droplet's center functions as a local anode, while its edge serves as a cathode. Corrosion products in the central area primarily consist of green rust (Fe<sub>4</sub>(OH)<sub>8</sub>Cl), which exhibits higher porosity, whereas the edge is characterized by denser γ-FeOOH. Variations in the composition and protective attributes of these corrosion products further magnify the differences in current density. This autocatalytic progression instigates a stable internal anode-cathode reaction within the droplet, ultimately culminating in the development of a deeper corrosion pit at the central zone. Additionally, the numerical model in the paper can provide support for the prediction of atmospheric corrosion of carbon steel.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"9 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888846","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 : 2024-12-28DOI: 10.1016/j.electacta.2024.145606
Wenfeng Zhang, Yan Shan, Xuegang Yu, Kezheng Chen
In general, most flexible supercapacitors with excellent performance at room temperature cannot work properly at relatively low temperatures (such as 0 °C), mainly due to the poor cold resistance of the electrodes and electrolytes. In this paper, the carbon cloth was coated with positively charged Mn2+-doped Co(OH)2 coating by electrodeposition and then impregnated with negatively charged Ti3C2Tx nanosheets suspension (This electrode is named CC@Co(OH)2:Mn2+@Tx, Where x is the number of impregnation Ti3C2Tx.). The results show that the obtained electrode has a good supercapacitor performance with the specific capacitance of 22.13 F g-1 (the area specific capacitance of the sample is 202.5 mF cm-2), which is attributed to the synergistic effect of Ti3C2Tx and the flower microstructure of Mn2+-doped Co(OH)2 coating. Ti3C2Tx was introduced to polyvinyl alcohol/sodium alginate hydrogel electrolyte to obtain a new antifreezing organohydrogel and then a flexible asymmetric supercapacitor was assembled with CC@Co(OH)2:Mn2+@T3 as the positive electrode, CC@T3 as negative electrode, and the performance of the supercapacitor at 25 °C and at 0 °C were investigated. It was found the supercapacitor exhibited better performance at 0 °C instead of 25 °C. When the current density is 5 mA cm-2, the area specific capacitance of the supercapacitor at 0 °C reaches 52.02 mF cm-2. After 1000 cycles, the supercapacitor has a capacitance retention rate of 82.5% at 0 °C, which is much higher than that of 55.15% at 25 °C. The reason may be related to the Ti3C2Tx and the crosslinked networks structures of composite hydrogel. The results show that the supercapacitor has excellent working ability at 0 °C, which provides the possibility for the device to work normally in low temperature.
{"title":"A Ti3C2Tx-encapsulated Mn2+-doped Co(OH)2 nanosheets electrode grown on carbon cloth for low-temperature flexible supercapacitors","authors":"Wenfeng Zhang, Yan Shan, Xuegang Yu, Kezheng Chen","doi":"10.1016/j.electacta.2024.145606","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145606","url":null,"abstract":"In general, most flexible supercapacitors with excellent performance at room temperature cannot work properly at relatively low temperatures (such as 0 °C), mainly due to the poor cold resistance of the electrodes and electrolytes. In this paper, the carbon cloth was coated with positively charged Mn<sup>2+</sup>-doped Co(OH)<sub>2</sub> coating by electrodeposition and then impregnated with negatively charged Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> nanosheets suspension (This electrode is named CC@Co(OH)<sub>2</sub>:Mn<sup>2+</sup>@T<sub>x</sub>, Where x is the number of impregnation Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>.). The results show that the obtained electrode has a good supercapacitor performance with the specific capacitance of 22.13 F g<sup>-1</sup> (the area specific capacitance of the sample is 202.5 mF cm<sup>-2</sup>), which is attributed to the synergistic effect of Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> and the flower microstructure of Mn<sup>2+</sup>-doped Co(OH)<sub>2</sub> coating. Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> was introduced to polyvinyl alcohol/sodium alginate hydrogel electrolyte to obtain a new antifreezing organohydrogel and then a flexible asymmetric supercapacitor was assembled with CC@Co(OH)<sub>2</sub>:Mn<sup>2+</sup>@T<sub>3</sub> as the positive electrode, CC@T<sub>3</sub> as negative electrode, and the performance of the supercapacitor at 25 °C and at 0 °C were investigated. It was found the supercapacitor exhibited better performance at 0 °C instead of 25 °C. When the current density is 5 mA cm<sup>-2</sup>, the area specific capacitance of the supercapacitor at 0 °C reaches 52.02 mF cm<sup>-2</sup>. After 1000 cycles, the supercapacitor has a capacitance retention rate of 82.5% at 0 °C, which is much higher than that of 55.15% at 25 °C. The reason may be related to the Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> and the crosslinked networks structures of composite hydrogel. The results show that the supercapacitor has excellent working ability at 0 °C, which provides the possibility for the device to work normally in low temperature.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"91 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888719","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}
Efficient operation of electrochemical energy devices below freezing point poses a significant challenge for enhancing their environment adaptability. This issue is particularly critical for quasi-solid-state devices those utilize gel polymer electrolytes (GPEs), since low temperature could enhance polymer crystallization in GPEs, inducing external steric hindrance that impede ionic conductivity. Herein, we utilized polyhedral oligomeric silsesquioxanes (POSS) as the eight-armed cross-linking points in an in-situ photopolymerized network, thereby constructing low-temperature tolerance GPEs for dye-sensitized solar cells (DSSCs). Compared to conventional triple-armed cross-linking, POSS could increase the disorder of the polymer network and significantly lower the glass transition temperature of the GPE from -30°C to -48.7 °C. At an ultralow working temperature of -40 °C, the POSS-linked GPEs show a high ionic diffusion coefficient of 0.71 × 10-6 cm2 s-1 compare to that of liquid electrolyte, ensuring that the quasi-solid-state DSSCs successfully retained 36.3% of their room-temperature efficiency. Our work proved a design method for the low-temperature tolerance GPEs, which could enable the advanced electrochemical application in harsh climates, such as sensor, energy generation, and storage devices.
{"title":"POSS-Crosslinked Gel Polymer Electrolytes Enabling Low-Temperature Tolerant Dye-Sensitized Solar Cells","authors":"Jianfei Lin, Yanan Li, Yinglin Wang, Lingling Wang, Xintong Zhang","doi":"10.1016/j.electacta.2024.145596","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145596","url":null,"abstract":"Efficient operation of electrochemical energy devices below freezing point poses a significant challenge for enhancing their environment adaptability. This issue is particularly critical for quasi-solid-state devices those utilize gel polymer electrolytes (GPEs), since low temperature could enhance polymer crystallization in GPEs, inducing external steric hindrance that impede ionic conductivity. Herein, we utilized polyhedral oligomeric silsesquioxanes (POSS) as the eight-armed cross-linking points in an in-situ photopolymerized network, thereby constructing low-temperature tolerance GPEs for dye-sensitized solar cells (DSSCs). Compared to conventional triple-armed cross-linking, POSS could increase the disorder of the polymer network and significantly lower the glass transition temperature of the GPE from -30°C to -48.7 °C. At an ultralow working temperature of -40 °C, the POSS-linked GPEs show a high ionic diffusion coefficient of 0.71 × 10<sup>-6</sup> cm<sup>2</sup> s<sup>-1</sup> compare to that of liquid electrolyte, ensuring that the quasi-solid-state DSSCs successfully retained 36.3% of their room-temperature efficiency. Our work proved a design method for the low-temperature tolerance GPEs, which could enable the advanced electrochemical application in harsh climates, such as sensor, energy generation, and storage devices.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"23 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888729","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 : 2024-12-27DOI: 10.1016/j.electacta.2024.145598
Longxu Li, Wenxing Jiang, Qiqi Wan, Endao Zhang, Bang Li, Lei Yuan, Guangfu Li, Junbo Hou, Xiaodong Zhuang, Junliang Zhang, Changchun Ke
Anion Exchange Membrane Water Electrolysis (AEMWE), is considered as one of the most promising available green production technologies, due to its overall low cost and high performance. Porous transport layers (PTLs), are much important for the performance of AEMWE, providing effective electron transport channels and efficient removal of gas products. Stainless steel-based PTLs have been demonstrated to achieve better performance at a reduced cost compared to routine nickel-base PTLs. Herein, PTLs based on 316L stainless-steel with varying parameters (fiber diameter, thickness and porosity) are investigated from a production perspective to identify the optimal design. How these parameters impact the performance of water electrolysis is further analyzed by separating the ohmic, activation and mass transfer overpotentials. The results indicate that the fiber diameter and porosity are of greater significance than the thickness. The fiber diameter exerts the most substantial effect on the performance and polarization distribution for AEMWE. The PTL with a fiber diameter of 12 μm performs best, representing a compromise among electrochemical reaction, electrical conductivity and mass transfer. Furthermore, the ohmic resistance and mass transfer process are the main factors influencing the observed differences in performance with varying thicknesses and porosities. The optimum thickness and porosity are subsequently identified as 0.3 mm and 72%, respectively. In conclusion, this study presents an optimal structure for the anode PTL based on 316L stainless-steel felts in AEMWE, achieving the current density of 2.760 A/cm2 at 2.0 V.
{"title":"Production of the Porous Transport Layer Based on Stainless Steel Felt for Anion Exchange Membrane Water Electrolysis","authors":"Longxu Li, Wenxing Jiang, Qiqi Wan, Endao Zhang, Bang Li, Lei Yuan, Guangfu Li, Junbo Hou, Xiaodong Zhuang, Junliang Zhang, Changchun Ke","doi":"10.1016/j.electacta.2024.145598","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145598","url":null,"abstract":"Anion Exchange Membrane Water Electrolysis (AEMWE), is considered as one of the most promising available green production technologies, due to its overall low cost and high performance. Porous transport layers (PTLs), are much important for the performance of AEMWE, providing effective electron transport channels and efficient removal of gas products. Stainless steel-based PTLs have been demonstrated to achieve better performance at a reduced cost compared to routine nickel-base PTLs. Herein, PTLs based on 316L stainless-steel with varying parameters (fiber diameter, thickness and porosity) are investigated from a production perspective to identify the optimal design. How these parameters impact the performance of water electrolysis is further analyzed by separating the ohmic, activation and mass transfer overpotentials. The results indicate that the fiber diameter and porosity are of greater significance than the thickness. The fiber diameter exerts the most substantial effect on the performance and polarization distribution for AEMWE. The PTL with a fiber diameter of 12 μm performs best, representing a compromise among electrochemical reaction, electrical conductivity and mass transfer. Furthermore, the ohmic resistance and mass transfer process are the main factors influencing the observed differences in performance with varying thicknesses and porosities. The optimum thickness and porosity are subsequently identified as 0.3 mm and 72%, respectively. In conclusion, this study presents an optimal structure for the anode PTL based on 316L stainless-steel felts in AEMWE, achieving the current density of 2.760 A/cm<sup>2</sup> at 2.0 V.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"2 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888730","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 : 2024-12-27DOI: 10.1016/j.electacta.2024.145591
Liunan She, Yingqi Di, Le Zhai, Jie Cheng, Guofeng Pan, Yuhang Qi
This study investigates a novel slurry composition for the chemical mechanical polishing (CMP) of cobalt (Co) interconnects, addressing the critical demands of semiconductor device miniaturization to 10 nm feature sizes. Utilizing diethylene triamine penta methylene phosphonic acid (DTPMP) as a complexing agent and octyl hydroxamic acid (OHA) as an inhibitor, we demonstrate that the dual functionality of DTPMP and OHA optimizes Co removal rates while minimizing static etch rates, achieving a delicate balance between high removal rate and surface integrity. This interaction results in a controlled Co removal rate of up to 2078.2 Å/min, a dissolution rate as low as 19.2 Å/min at optimized concentrations, and a root mean square (RMS) roughness (Sq) of 0.744 nm. Experimental data and theoretical simulation studies reveal enhanced complexation due to the increased deprotonation of the phosphate group in DTPMP, laying a foundation for developing environmentally friendly and efficient CMP applications across various metal interconnects in advanced semiconductor devices.
{"title":"Dual functionality of DTPMP and OHA: Enhancement in removal rates and excellent surface quality of cobalt CMP","authors":"Liunan She, Yingqi Di, Le Zhai, Jie Cheng, Guofeng Pan, Yuhang Qi","doi":"10.1016/j.electacta.2024.145591","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145591","url":null,"abstract":"This study investigates a novel slurry composition for the chemical mechanical polishing (CMP) of cobalt (Co) interconnects, addressing the critical demands of semiconductor device miniaturization to 10 nm feature sizes. Utilizing diethylene triamine penta methylene phosphonic acid (DTPMP) as a complexing agent and octyl hydroxamic acid (OHA) as an inhibitor, we demonstrate that the dual functionality of DTPMP and OHA optimizes Co removal rates while minimizing static etch rates, achieving a delicate balance between high removal rate and surface integrity. This interaction results in a controlled Co removal rate of up to 2078.2 Å/min, a dissolution rate as low as 19.2 Å/min at optimized concentrations, and a root mean square (RMS) roughness (Sq) of 0.744 nm. Experimental data and theoretical simulation studies reveal enhanced complexation due to the increased deprotonation of the phosphate group in DTPMP, laying a foundation for developing environmentally friendly and efficient CMP applications across various metal interconnects in advanced semiconductor devices.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"41 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888843","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}
Based on the remediation challenges and practical needs of trichloroethylene (TCE)-contaminated groundwater, this study prepared an Ni-based composite electrode, Pd/Ni(OH)2/Ni foam (NF), and evaluates its electrocatalytic degradation effect on TCE in a groundwater environment. Under an applied voltage of –1.3 V versus Ag/AgCl, the TCE removal rate reaches 95% after 3 h of electrolysis. The introduction of Ni(OH)2 nanoarrays accelerates the electron transport process, shortens the ion transport distance, and significantly increases the electron density of Pd. Furthermore, TCE is rapidly reduced by adsorbed hydrogen radicals on the Pd surface, and the ethane conversion rate reaches 62%. The experimental results show that the electrode can maintain a strong electrocatalytic activity over a wide pH range (3–9) and that it is not affected by common anions, such as Ca2+, HCO3-, SO32-, or Cl-, in groundwater. Pd/Ni(OH)2/NF exhibits a high reactivity after six cycles of use. The remediation mechanism is studied by combining the microscopic characterization of materials, electrochemical activity testing, and process product identification, which provides an effective way of completely degrading chlorinated hydrocarbon pollutants in natural groundwater environment.
{"title":"Pd/Ni(OH)2/Ni foam: A nickel-based composite electrode for the electrochemical reductive remediation of trichloroethylene-contaminated groundwater","authors":"Liang Ding, Roujia Zhang, Peng Zhao, Changsheng Qu","doi":"10.1016/j.electacta.2024.145584","DOIUrl":"https://doi.org/10.1016/j.electacta.2024.145584","url":null,"abstract":"Based on the remediation challenges and practical needs of trichloroethylene (TCE)-contaminated groundwater, this study prepared an Ni-based composite electrode, Pd/Ni(OH)<sub>2</sub>/Ni foam (NF), and evaluates its electrocatalytic degradation effect on TCE in a groundwater environment. Under an applied voltage of –1.3 V versus Ag/AgCl, the TCE removal rate reaches 95% after 3 h of electrolysis. The introduction of Ni(OH)<sub>2</sub> nanoarrays accelerates the electron transport process, shortens the ion transport distance, and significantly increases the electron density of Pd. Furthermore, TCE is rapidly reduced by adsorbed hydrogen radicals on the Pd surface, and the ethane conversion rate reaches 62%. The experimental results show that the electrode can maintain a strong electrocatalytic activity over a wide pH range (3–9) and that it is not affected by common anions, such as Ca<sup>2+</sup>, HCO<sub>3</sub><sup>-</sup>, SO<sub>3</sub><sup>2-</sup>, or Cl<sup>-</sup>, in groundwater. Pd/Ni(OH)<sub>2</sub>/NF exhibits a high reactivity after six cycles of use. The remediation mechanism is studied by combining the microscopic characterization of materials, electrochemical activity testing, and process product identification, which provides an effective way of completely degrading chlorinated hydrocarbon pollutants in natural groundwater environment.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"83 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888728","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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