Pub Date : 2024-11-06DOI: 10.1016/j.electacta.2024.145313
M.A. Deyab , Q. Mohsen
The battery's high energy density, economical price, and ecological sustainability of the Zn-air battery make it a bright future battery technology. However, parasitic reactions, which can diminish the battery's life cycle and efficacy, are the key challenges for potential development of Zn-air batteries. Glycyrrhiza glabra roots extract (GGRE) has been investigated as an alternative hydrogen gas evolution and corrosion inhibitor for Zn-air batteries in order to mitigate the parasitic reaction. The results obtained reveal that the inhibition capacity of the GGRE extract increases with concentration and reaches its highest level (75.6 %) around 350 mg l-1 of GGRE extract. GGRE extract is a mixed type inhibitor with a predominately cathodic effect based on the polarization data. The GGRE extract adsorption on the Zn surface complies with Freundlich isotherm. In comparison to the blank Zn-KOH (354 mAh g-1), the battery containing 350 mg l-1 GGRE extract has the highest discharge capacity (533 mAh g-1) and the best cyclability (92.9 % retention after 500 cycles). Overall, GGRE extract can significantly optimize the performance of Zn-air batteries.
{"title":"Effect of plant extract additives on the parasitic reaction in alkaline Zn-air batteries","authors":"M.A. Deyab , Q. Mohsen","doi":"10.1016/j.electacta.2024.145313","DOIUrl":"10.1016/j.electacta.2024.145313","url":null,"abstract":"<div><div>The battery's high energy density, economical price, and ecological sustainability of the Zn-air battery make it a bright future battery technology. However, parasitic reactions, which can diminish the battery's life cycle and efficacy, are the key challenges for potential development of Zn-air batteries. Glycyrrhiza glabra roots extract (GGRE) has been investigated as an alternative hydrogen gas evolution and corrosion inhibitor for Zn-air batteries in order to mitigate the parasitic reaction. The results obtained reveal that the inhibition capacity of the GGRE extract increases with concentration and reaches its highest level (75.6 %) around 350 mg l<sup>-1</sup> of GGRE extract. GGRE extract is a mixed type inhibitor with a predominately cathodic effect based on the polarization data. The GGRE extract adsorption on the Zn surface complies with Freundlich isotherm. In comparison to the blank Zn-KOH (354 mAh g<sup>-1</sup>), the battery containing 350 mg l<sup>-1</sup> GGRE extract has the highest discharge capacity (533 mAh g<sup>-1</sup>) and the best cyclability (92.9 % retention after 500 cycles). Overall, GGRE extract can significantly optimize the performance of Zn-air batteries.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145313"},"PeriodicalIF":5.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588406","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 : 2024-11-05DOI: 10.1016/j.electacta.2024.145314
Abhishek A, Naveenkumar N, Ramesh V
Supercapacitors or electrochemical capacitors are known for their supporting pulse power because of their high-power density compared to the battery. In this work, Al and Zn doped SnSb, i.e., Sn0.95SbZn0.05, Sn0.9SbZn0.1, Sn0.95SbAl0.05, and Sn0.9SbAl0.1 have been synthesized through chemical co-precipitation method. The powder X-ray diffraction, Raman spectroscopy, and UV–visible spectroscopy are intensely scrutinised to infer the phase formation, vibrational, and optical properties of the synthesized materials. Furthermore, the SEM, TEM, and X-ray photoelectron spectroscopy are used to study the material's morphology, chemical, and oxidation state; the Zn-doped SnSb alone focused because of their better electrochemical performance than the Al-doped SnSb. Using a three-electrode setup, the electrochemical performance of the following Sn0.95SbZn0.05, Sn0.9SbZn0.1, Sn0.95SbAl0.05, and Sn0.9SbAl0.1 are evaluated in that Sn0.95SbZn0.05 has recorded higher specific capacitance of 588 F/g at 1A/g than the other. Then, the electrochemical analysis is further proceeded with the fabrication of an asymmetric device based on Swagelok assembly in which activated carbon acts as the negative electrode and Sn0.95SbZn0.05 as the positive electrode and has recorded the maximum power and energy density value of 4266 W/Kg and energy density of 8.57 Wh/Kg. It also has shown outstanding cyclic stability for 5000 charge-discharge cycles at 10 A/g.
{"title":"Electrochemical properties of Zn and Al-doped SnSb for asymmetric supercapacitor application","authors":"Abhishek A, Naveenkumar N, Ramesh V","doi":"10.1016/j.electacta.2024.145314","DOIUrl":"10.1016/j.electacta.2024.145314","url":null,"abstract":"<div><div>Supercapacitors or electrochemical capacitors are known for their supporting pulse power because of their high-power density compared to the battery. In this work, Al and Zn doped SnSb, i.e., Sn<sub>0.95</sub>SbZn<sub>0.05</sub>, Sn<sub>0.9</sub>SbZn<sub>0.1</sub>, Sn<sub>0.95</sub>SbAl<sub>0.05,</sub> and Sn<sub>0.9</sub>SbAl<sub>0.1</sub> have been synthesized through chemical co-precipitation method. The powder X-ray diffraction, Raman spectroscopy, and UV–visible spectroscopy are intensely scrutinised to infer the phase formation, vibrational, and optical properties of the synthesized materials. Furthermore, the SEM, TEM, and X-ray photoelectron spectroscopy are used to study the material's morphology, chemical, and oxidation state; the Zn-doped SnSb alone focused because of their better electrochemical performance than the Al-doped SnSb. Using a three-electrode setup, the electrochemical performance of the following Sn<sub>0.95</sub>SbZn<sub>0.05</sub>, Sn<sub>0.9</sub>SbZn<sub>0.1</sub>, Sn<sub>0.95</sub>SbAl<sub>0.05,</sub> and Sn<sub>0.9</sub>SbAl<sub>0.1</sub> are evaluated in that Sn<sub>0.95</sub>SbZn<sub>0.05</sub> has recorded higher specific capacitance of 588 F/g at 1A/g than the other. Then, the electrochemical analysis is further proceeded with the fabrication of an asymmetric device based on Swagelok assembly in which activated carbon acts as the negative electrode and Sn<sub>0.95</sub>SbZn<sub>0.05</sub> as the positive electrode and has recorded the maximum power and energy density value of 4266 W/Kg and energy density of 8.57 Wh/Kg. It also has shown outstanding cyclic stability for 5000 charge-discharge cycles at 10 A/g.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145314"},"PeriodicalIF":5.5,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580233","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 : 2024-11-05DOI: 10.1016/j.electacta.2024.145317
Dezhong Hu , Jingbo Wen , Zhibin Pei , Dong Xiang , Xiongwu Kang
Electrochemical reduction of carbon dioxide (CO2RR) into value-added multi-carbon (C2) products utilizing renewable energy is a promising way to reduce carbon emission and achieve carbon neutrality. However, rational design of catalysts towards high C2 products selectivity remains a formidable task. Herein, fluorine modified copper catalyst was synthesised by thermal anneal in the presence of ammonium fluoride and sequential annealing in argon atmosphere. The charge distribution and coordination environment on copper surface were adjusted by doped fluorine atoms, which enables the formation of key intermediates and their sequential evolution into ethylene. The catalyst achieves a remarkable Faradaic efficiency (FE) of 40.6 % for eCO2RR to ethylene and remains stable over 13 h. Density functional theory calculations indicates that the excellent CO2RR performance can be attributed to the suppressed hydrogen evolution on fluorine-doped copper catalyst. Our work brings a potential modification strategy of Cu-based catalyst for electrolytic CO2-to-C2 pathway.
{"title":"Fluorine-regulated Cu catalyst boosts electrochemical reduction of CO2 towards ethylene production","authors":"Dezhong Hu , Jingbo Wen , Zhibin Pei , Dong Xiang , Xiongwu Kang","doi":"10.1016/j.electacta.2024.145317","DOIUrl":"10.1016/j.electacta.2024.145317","url":null,"abstract":"<div><div>Electrochemical reduction of carbon dioxide (CO<sub>2</sub>RR) into value-added multi-carbon (C<sub>2</sub>) products utilizing renewable energy is a promising way to reduce carbon emission and achieve carbon neutrality. However, rational design of catalysts towards high C<sub>2</sub> products selectivity remains a formidable task. Herein, fluorine modified copper catalyst was synthesised by thermal anneal in the presence of ammonium fluoride and sequential annealing in argon atmosphere. The charge distribution and coordination environment on copper surface were adjusted by doped fluorine atoms, which enables the formation of key intermediates and their sequential evolution into ethylene. The catalyst achieves a remarkable Faradaic efficiency (FE) of 40.6 % for eCO<sub>2</sub>RR to ethylene and remains stable over 13 h. Density functional theory calculations indicates that the excellent CO<sub>2</sub>RR performance can be attributed to the suppressed hydrogen evolution on fluorine-doped copper catalyst. Our work brings a potential modification strategy of Cu-based catalyst for electrolytic CO<sub>2</sub>-to-C<sub>2</sub> pathway.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145317"},"PeriodicalIF":5.5,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580080","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 : 2024-11-05DOI: 10.1016/j.electacta.2024.145305
Zyun Siroma, Kentaro Kuratani
A new method for graphing electrical impedance values named a “differentiation-based Bode plot” is proposed. This method facilitates the analysis procedure and reduces the arbitrariness of the interpretation of electrochemical impedance spectroscopy (EIS) data. Among the various methods for graphing impedance values, Nyquist plots are commonly adopted (primarily in the field of EIS) because of the apparent correlation between their shape and the corresponding equivalent circuit. However, because Nyquist plots do not contain frequency information, Bode phase and magnitude plots are frequently utilized. Although such plots are suitable for determining the absolute magnitude and phase of the impedance, they are not always useful for selecting the structure of an equivalent circuit, which is a hypothetical model for electrochemical cells. In the proposed method, instead of the real (Z’) and imaginary (Z’’) parts, two functions of the impedance derivatives with respect to frequency, i.e., dZ’/d(log f) and dZ’’/d(log f), are plotted. As substitutions for the Bode phase and magnitude plots, arctan{dZ’’/d(log f) ÷ dZ’/d(log f)} and log[sqrt{(dZ’/d(log f))2 + (dZ’’/d(log f))2}] are plotted against log f. Unlike the classical Bode plot, the differentiation-based Bode plot is independent of the lateral shift in the Nyquist plot, which is advantageous for determining an equivalent circuit. To demonstrate this advantage, the impedance values of typical equivalent circuits used in electrochemistry are calculated and plotted to compare differentiation-based Bode plots with Nyquist and classical Bode plots.
{"title":"New method for graphing impedance values as an analytical tool suitable for electrochemical impedance spectroscopy","authors":"Zyun Siroma, Kentaro Kuratani","doi":"10.1016/j.electacta.2024.145305","DOIUrl":"10.1016/j.electacta.2024.145305","url":null,"abstract":"<div><div>A new method for graphing electrical impedance values named a “differentiation-based Bode plot” is proposed. This method facilitates the analysis procedure and reduces the arbitrariness of the interpretation of electrochemical impedance spectroscopy (EIS) data. Among the various methods for graphing impedance values, Nyquist plots are commonly adopted (primarily in the field of EIS) because of the apparent correlation between their shape and the corresponding equivalent circuit. However, because Nyquist plots do not contain frequency information, Bode phase and magnitude plots are frequently utilized. Although such plots are suitable for determining the absolute magnitude and phase of the impedance, they are not always useful for selecting the structure of an equivalent circuit, which is a hypothetical model for electrochemical cells. In the proposed method, instead of the real (<em>Z’</em>) and imaginary (<em>Z’’</em>) parts, two functions of the impedance derivatives with respect to frequency, i.e., <em>dZ’</em>/<em>d</em>(log <em>f</em>) and <em>dZ’’</em>/<em>d</em>(log <em>f</em>), are plotted. As substitutions for the Bode phase and magnitude plots, arctan{<em>dZ’’</em>/<em>d</em>(log <em>f</em>) ÷ <em>dZ’</em>/<em>d</em>(log <em>f</em>)} and log[sqrt{(<em>dZ’</em>/<em>d</em>(log <em>f</em>))<sup>2</sup> + (<em>dZ’’</em>/<em>d</em>(log <em>f</em>))<sup>2</sup>}] are plotted against log <em>f</em>. Unlike the classical Bode plot, the differentiation-based Bode plot is independent of the lateral shift in the Nyquist plot, which is advantageous for determining an equivalent circuit. To demonstrate this advantage, the impedance values of typical equivalent circuits used in electrochemistry are calculated and plotted to compare differentiation-based Bode plots with Nyquist and classical Bode plots.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145305"},"PeriodicalIF":5.5,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580099","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 : 2024-11-04DOI: 10.1016/j.electacta.2024.145316
Antonio Gomes dos Santos Neto , Jose Antonio de Oliveira Junior , Glaucio Régis Nagurniak , Shuai Zhang , Marcelo Eduardo Huguenin Maia da Costa , Liying Liu , Marco Aurélio Suller Garcia , Sergio Yesid Gómez González , Maurício Jeomar Piotrowski , Cristiane Luisa Jost
We introduce an innovative electrochemical sensing method for the sensitive detection of Baicalein (BAI), emphasizing a simple surface modification process. The study encompasses both practical and theoretical investigations into the electrochemical behavior of nanoporous gold. Our theoretical analysis, based on advanced quantum-mechanical calculations, demonstrates that the adsorption of BAI molecule on gold-based substrates is energetically favorable, with adsorption energy increasing from an unmodified surface to a more porous substrate. BAI physisorbs on unmodified regions in a horizontal alignment, while it chemisorbs more strongly on nanoporous regions by penetrating the pores. On less modified surfaces, interaction energy predominates, whereas on heavily modified surfaces, distortion energies become more significant due to increased substrate reactivity. These results align with physicochemical characterizations, which reveal that nanoscale modifications, induced by different anodization times, explain the variations in electrode performance. Experimentally, cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were employed using both a gold electrode (GE) and a nanoporous gold electrode (NPGE). The GE was subjected to surface treatment by immersion in H2SO4 and potential control at ca. +2.0 V for 40 seconds, resulting in a nanoporous configuration. Following optimizations, Adsorptive Stripping Voltammetry (AdSV) was used to determine BAI. The method achieved detection (LOD) and quantification (LOQ) limits of 0.015 µmol L-1 and 0.045 µmol L-1, respectively (Edeposition=-0.25 V; tdeposition=50 s). Additionally, the standard addition method was applied to the NPGE for recovering BAI from spiked synthetic human plasma and urine, with success rates ranging from 93.4% to 106%. This approach exhibited excellent stability, precision, and accuracy, with minimal interference from other substances. Moreover, the theoretical findings provided deeper insights into the selective electrochemical detection of BAI on nanoporous gold surfaces, offering new perspectives on this field.
{"title":"Integrating theoretical and experimental insights into nanoporous gold electrochemistry for enhanced baicalein sensing performance","authors":"Antonio Gomes dos Santos Neto , Jose Antonio de Oliveira Junior , Glaucio Régis Nagurniak , Shuai Zhang , Marcelo Eduardo Huguenin Maia da Costa , Liying Liu , Marco Aurélio Suller Garcia , Sergio Yesid Gómez González , Maurício Jeomar Piotrowski , Cristiane Luisa Jost","doi":"10.1016/j.electacta.2024.145316","DOIUrl":"10.1016/j.electacta.2024.145316","url":null,"abstract":"<div><div>We introduce an innovative electrochemical sensing method for the sensitive detection of Baicalein (BAI), emphasizing a simple surface modification process. The study encompasses both practical and theoretical investigations into the electrochemical behavior of nanoporous gold. Our theoretical analysis, based on advanced quantum-mechanical calculations, demonstrates that the adsorption of BAI molecule on gold-based substrates is energetically favorable, with adsorption energy increasing from an unmodified surface to a more porous substrate. BAI physisorbs on unmodified regions in a horizontal alignment, while it chemisorbs more strongly on nanoporous regions by penetrating the pores. On less modified surfaces, interaction energy predominates, whereas on heavily modified surfaces, distortion energies become more significant due to increased substrate reactivity. These results align with physicochemical characterizations, which reveal that nanoscale modifications, induced by different anodization times, explain the variations in electrode performance. Experimentally, cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were employed using both a gold electrode (GE) and a nanoporous gold electrode (NPGE). The GE was subjected to surface treatment by immersion in H<sub>2</sub>SO<sub>4</sub> and potential control at ca. +2.0 V for 40 seconds, resulting in a nanoporous configuration. Following optimizations, Adsorptive Stripping Voltammetry (AdSV) was used to determine BAI. The method achieved detection (LOD) and quantification (LOQ) limits of 0.015 µmol L<sup>-1</sup> and 0.045 µmol L<sup>-1</sup>, respectively (E<sub>deposition</sub>=-0.25 V; t<sub>deposition</sub>=50 s). Additionally, the standard addition method was applied to the NPGE for recovering BAI from spiked synthetic human plasma and urine, with success rates ranging from 93.4% to 106%. This approach exhibited excellent stability, precision, and accuracy, with minimal interference from other substances. Moreover, the theoretical findings provided deeper insights into the selective electrochemical detection of BAI on nanoporous gold surfaces, offering new perspectives on this field.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145316"},"PeriodicalIF":5.5,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580081","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 : 2024-11-03DOI: 10.1016/j.electacta.2024.145293
Jiafei Liu, Marc Secanell
Electrode composition optimization is critical to achieving high and stable anion exchange membrane fuel cell (AEMFC) performance. In this article, inkjet printing is pioneered as a method to fabricate AEMFC electrodes with varying and graded cathode ionomer loading in order to assess its impact on electrode electrochemical properties, cell performance and stability. Inkjet printed catalyst layers (CLs) exhibited decreasing porosity with increasing ionomer content, maintaining a constant active area at 50 under fully humidified conditions. The increase in active area and ionic conductivity with increasing ionomer content was detectable only at higher temperatures. At 60 with 90% relative humidity inlet gases, the AEMFCs with cathode electrodes with optimal 20 wt% uniform ionomer content achieved a highly repeatable and stable performance of 0.53 with a total loading of 0.3 . Grading the cathode ionomer content, with higher concentration near the membrane and lower near the gas diffusion layer (GDL), does not improve cell performance, indicating neither cathode conductivity nor mass transport limits performance. When tested at 80 , AEMFCs with a graded cathode ionomer structure (30 wt% near the membrane and 20 wt% near the GDL) demonstrated improved stability compared to those with a uniform 20 wt% ionomer content. This stability improvement is attributed to better water retention with more cathode ionomer content, as evidenced by the cell’s ability to maintain low resistance.
{"title":"Exploring the impact of ionomer content and distribution on inkjet printed cathodes for anion exchange membrane fuel cells","authors":"Jiafei Liu, Marc Secanell","doi":"10.1016/j.electacta.2024.145293","DOIUrl":"10.1016/j.electacta.2024.145293","url":null,"abstract":"<div><div>Electrode composition optimization is critical to achieving high and stable anion exchange membrane fuel cell (AEMFC) performance. In this article, inkjet printing is pioneered as a method to fabricate AEMFC electrodes with varying and graded cathode ionomer loading in order to assess its impact on electrode electrochemical properties, cell performance and stability. Inkjet printed catalyst layers (CLs) exhibited decreasing porosity with increasing ionomer content, maintaining a constant active area at 50 <span><math><mrow><mo>°</mo><mi>C</mi></mrow></math></span> under fully humidified conditions. The increase in active area and ionic conductivity with increasing ionomer content was detectable only at higher temperatures. At 60 <span><math><mrow><mo>°</mo><mi>C</mi></mrow></math></span> with 90% relative humidity inlet gases, the AEMFCs with cathode electrodes with optimal 20 wt% uniform ionomer content achieved a highly repeatable and stable performance of 0.53 <span><math><mrow><mtext>W</mtext><mo>/</mo><msup><mrow><mtext>cm</mtext></mrow><mrow><mn>2</mn></mrow></msup></mrow></math></span> with a total loading of 0.3 <span><math><mrow><msub><mrow><mtext>mg</mtext></mrow><mrow><mtext>Pt</mtext></mrow></msub><mo>/</mo><msubsup><mrow><mtext>cm</mtext></mrow><mrow><mtext>CL</mtext></mrow><mrow><mn>2</mn></mrow></msubsup></mrow></math></span>. Grading the cathode ionomer content, with higher concentration near the membrane and lower near the gas diffusion layer (GDL), does not improve cell performance, indicating neither cathode conductivity nor mass transport limits performance. When tested at 80 <span><math><mrow><mo>°</mo><mi>C</mi></mrow></math></span>, AEMFCs with a graded cathode ionomer structure (30 wt% near the membrane and 20 wt% near the GDL) demonstrated improved stability compared to those with a uniform 20 wt% ionomer content. This stability improvement is attributed to better water retention with more cathode ionomer content, as evidenced by the cell’s ability to maintain low resistance.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145293"},"PeriodicalIF":5.5,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566145","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-03DOI: 10.1016/j.electacta.2024.145315
Vijay Srinivasan Murugesan , Michael Ruby Raj , Hock Beng Lee , Neetesh Kumar
The design of donor-acceptor (D-A)-based random copolymers-type hole transporting materials (HTMs) are important for achieving superior performance of perovskite solar cells (PSCs) with high durability. In this work, a 2-alkylthienyl-substituted benzodithiophene (BDTT)-based random copolymer (denoted as RCP-BDTTPD), containing 2-ethylhexylthiophene-substituted benzo[1,2-b:4,5-b′]dithiophene (BDTT as an electron-donor; M1) and two different side-chain functionalized thieno[3,4-c]-pyrrole-4,6‑dione as the electron-acceptors (M2 and M3), is prepared and applied as an efficient interfacial HTM for PSCs. The optical, electrochemical, and electronic properties of RCP-BDTTPD are shown to be structurally and energetically viable to serve as HTM for PSCs. The RCP-BDTTPD has deeper highest occupied molecular orbitals (HOMO; −5.53 eV) and lowest unoccupied molecular orbitals (LUMO; −3.57 eV) energy levels. This is shown to be energetically suitable for realizing better compatibility with Cs-containing formamidinium/methylammonium (FAMA) mixed-cation perovskite as light absorber having HOMO energy level (−5.85 eV). The RCP-BDTTPD possessing gradient band alignment with perovskite, which is shown to be highly significant for the extraction of charge carriers, resulting in higher hole mobility of PSCs. RCP-BDTTPD delivered a reasonably good Voc of 1.10 V and higher Jsc of 19.01 mAcm−2 and, champion power conversion efficiency (PCE) up to 15.30 % with hole mobility (1.34×10−3 cm2V−1s−1) and high durability (Encapsulated cell retention of its PCE about 98 % over 16 h under harsh environment: Temp. ∼85 °C, RH∼85 %). This work demonstrating a potential application of RCP-BDTTPD based HTMs for the fabrication of high-performance PSCs with high durability as well as low cost.
{"title":"Fabrication of high-efficiency perovskite solar cells using benzodithiophene-based random copolymeric hole transport material","authors":"Vijay Srinivasan Murugesan , Michael Ruby Raj , Hock Beng Lee , Neetesh Kumar","doi":"10.1016/j.electacta.2024.145315","DOIUrl":"10.1016/j.electacta.2024.145315","url":null,"abstract":"<div><div>The design of donor-acceptor (D-A)-based random copolymers-type hole transporting materials (HTMs) are important for achieving superior performance of perovskite solar cells (PSCs) with high durability. In this work, a 2-alkylthienyl-substituted benzodithiophene (BDTT)-based random copolymer (denoted as <strong>RCP-BDTTPD</strong>), containing 2-ethylhexylthiophene-substituted benzo[1,2-b:4,5-b′]dithiophene (BDTT as an electron-donor; M1) and two different side-chain functionalized thieno[3,4-c]-pyrrole-4,6‑dione as the electron-acceptors (<strong>M2</strong> and <strong>M3</strong>), is prepared and applied as an efficient interfacial HTM for PSCs. The optical, electrochemical, and electronic properties of <strong>RCP-BDTTPD</strong> are shown to be structurally and energetically viable to serve as HTM for PSCs. The <strong>RCP-BDTTPD</strong> has deeper highest occupied molecular orbitals (HOMO; −5.53 eV) and lowest unoccupied molecular orbitals (LUMO; −3.57 eV) energy levels. This is shown to be energetically suitable for realizing better compatibility with Cs-containing formamidinium/methylammonium (FAMA) mixed-cation perovskite as light absorber having HOMO energy level (−5.85 eV). The <strong>RCP-BDTTPD</strong> possessing gradient band alignment with perovskite, which is shown to be highly significant for the extraction of charge carriers, resulting in higher hole mobility of PSCs. <strong>RCP-BDTTPD</strong> delivered a reasonably good V<sub>oc</sub> of 1.10 V and higher <em>J</em><sub>sc</sub> of 19.01 mAcm<sup>−2</sup> and, champion power conversion efficiency (PCE) up to 15.30 % with hole mobility (1.34×10<sup>−3</sup> cm<sup>2</sup>V<sup>−1</sup>s<sup>−1</sup>) and high durability (Encapsulated cell retention of its PCE about 98 % over 16 h under harsh environment: Temp. ∼85 °C, RH∼85 %). This work demonstrating a potential application of <strong>RCP-BDTTPD</strong> based HTMs for the fabrication of high-performance PSCs with high durability as well as low cost.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145315"},"PeriodicalIF":5.5,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566070","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}
Ni@Au electrodes are prepared by galvanic replacement of Ni atoms of a commercial Ni foam by Au atoms. The physicochemical characterizations indicate gold atomic ratios of ca. 6 %, independently on the galvanic replacement time (1, 2 and 3 min), but differences in the structure of the deposited gold layers. The shapes of the cyclic voltammograms recorded in a 0.1 M NaOH aqueous electrolyte indicate that both Au and Ni sites are accessible. In the presence of 0.1 M glucose, the same oxidation onset potential of ca. 0.3 V vs RHE and a comparable activity in terms of achieved geometric current densities were recorded for all the Ni@Au electrodes. The long term electrolyses of 0.1 M glucose in 0.1 M aqueous KOH electrolyte on the Ni@Au electrodes performed at cell voltages corresponding to anode potentials of 0.575 V, 0.675 V and 0.775 V vs RHE show a surprising excellent stability over 5 h, which is explained by the presence of a Ni(OH)2 layer on the surface of the Ni foam in contact with the deposited gold layers. Conversions up to 60 % are obtained after 5 h electrolyses with the Ni-Au electrode obtained after 3 min deposition, with 100 % selectivity and faradaic efficiency towards gluconic acid for all the electrodes and for the lower potential of 0.575 V vs RHE. Increasing the glucose and KOH initial concentrations decreases the conversion rate, selectivity and faradaic efficiency.
Ni@Au 电极是通过金原子电化学置换商用泡沫镍中的镍原子而制备的。理化特性表明，金原子比率约为 6%，与电化学置换时间（1、2 和 3 分钟）无关，但沉积金层的结构存在差异。在 0.1 M NaOH 水溶液电解液中记录的循环伏安图的形状表明，金和镍的位点都是可接触的。在 0.1 M 葡萄糖存在下，所有 Ni@Au 电极都记录到了相同的氧化起始电位（与 RHE 相比约为 0.3 V），在达到的几何电流密度方面也具有相似的活性。在 Ni@Au 电极上对 0.1 M KOH 电解液中的 0.1 M 葡萄糖进行长期电解，电解槽电压分别为 0.575 V、0.675 V 和 0.775 V（相对于 RHE），结果表明在 5 小时内具有令人惊讶的出色稳定性，这是因为在与沉积金层接触的镍泡沫表面存在镍（OH）2 层。在 3 分钟沉积后获得的镍金电极上进行 5 小时电解后，转化率高达 60%，所有电极和 0.575 V 对 RHE 的较低电位对葡萄糖酸的选择性和远红外效率均为 100%。增加葡萄糖和 KOH 的初始浓度会降低转化率、选择性和法拉第效率。
{"title":"Selective electrooxidation of glucose towards gluconic acid on Ni@Au foam electrodes","authors":"Erwann Ginoux , Thibault Rafaïdeen , Patrick Cognet , Laure Latapie , Christophe Coutanceau","doi":"10.1016/j.electacta.2024.145307","DOIUrl":"10.1016/j.electacta.2024.145307","url":null,"abstract":"<div><div>Ni@Au electrodes are prepared by galvanic replacement of Ni atoms of a commercial Ni foam by Au atoms. The physicochemical characterizations indicate gold atomic ratios of ca. 6 %, independently on the galvanic replacement time (1, 2 and 3 min), but differences in the structure of the deposited gold layers. The shapes of the cyclic voltammograms recorded in a 0.1 M NaOH aqueous electrolyte indicate that both Au and Ni sites are accessible. In the presence of 0.1 M glucose, the same oxidation onset potential of ca. 0.3 V vs RHE and a comparable activity in terms of achieved geometric current densities were recorded for all the Ni@Au electrodes. The long term electrolyses of 0.1 M glucose in 0.1 M aqueous KOH electrolyte on the Ni@Au electrodes performed at cell voltages corresponding to anode potentials of 0.575 V, 0.675 V and 0.775 V vs RHE show a surprising excellent stability over 5 h, which is explained by the presence of a Ni(OH)<sub>2</sub> layer on the surface of the Ni foam in contact with the deposited gold layers. Conversions up to 60 % are obtained after 5 h electrolyses with the Ni-Au electrode obtained after 3 min deposition, with 100 % selectivity and faradaic efficiency towards gluconic acid for all the electrodes and for the lower potential of 0.575 V vs RHE. Increasing the glucose and KOH initial concentrations decreases the conversion rate, selectivity and faradaic efficiency.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145307"},"PeriodicalIF":5.5,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563172","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}
Electrochemical CO2 fixation is vital for sustainability in the chemical industry, yet the selective synthesis of multi-carbon products remains challenging. Organic electrosynthesis offers promise by enabling precise control over reaction conditions and facilitating novel reactivity patterns. One such technique, electrochemical carboxylation, involves coupling CO2 with organic molecules to produce carboxylic acids. Specifically, electro-carboxylation of acetophenone yields atrolactic acid, a valuable precursor for nonsteroidal anti-inflammatory drugs, providing a greener alternative to traditional production methods. This study focuses on the synthesis and characterization of boron-doped diamond (BDD) films using the microwave plasma-assisted chemical vapor deposition (MP-CVD) method and synthesized BDD electrodes were then used for the electrolytic carboxylation of acetophenone. Various analytical techniques, including X-ray diffraction (XRD), Raman spectroscopy, and laser microscopy, etc. were employed to characterize the BDD films. Various BDD films synthesized for different durations were utilized in the electrolytic carboxylation of acetophenone, with the highest yield of atrolactic acid (25 %) achieved using a BDD film synthesized over 6 h. Also, the effect of BDD surface modification i.e. oxygen and hydrogen terminated BDD on the synthesis of atrolactic acid was studied. Additionally, different electrolytes were employed in the synthesis process of atrolactic acid. A comparative study between Pt and BDD electrodes for the electrolytic carboxylation of acetophenone was conducted, and a mechanism for the formation of atrolactic acid was proposed.
{"title":"Electrochemical carboxylation: Green synthesis of atrolactic acid using boron-doped diamond electrodes","authors":"Yuvaraj M. Hunge , Toya Inaba , Keizo Ishihara , Kai Takagi , Ryoya Okamura , Hiroshi Uetsuka , Chiaki Terashima","doi":"10.1016/j.electacta.2024.145310","DOIUrl":"10.1016/j.electacta.2024.145310","url":null,"abstract":"<div><div>Electrochemical CO<sub>2</sub> fixation is vital for sustainability in the chemical industry, yet the selective synthesis of multi-carbon products remains challenging. Organic electrosynthesis offers promise by enabling precise control over reaction conditions and facilitating novel reactivity patterns. One such technique, electrochemical carboxylation, involves coupling CO<sub>2</sub> with organic molecules to produce carboxylic acids. Specifically, electro-carboxylation of acetophenone yields atrolactic acid, a valuable precursor for nonsteroidal anti-inflammatory drugs, providing a greener alternative to traditional production methods. This study focuses on the synthesis and characterization of boron-doped diamond (BDD) films using the microwave plasma-assisted chemical vapor deposition (MP-CVD) method and synthesized BDD electrodes were then used for the electrolytic carboxylation of acetophenone. Various analytical techniques, including X-ray diffraction (XRD), Raman spectroscopy, and laser microscopy, etc. were employed to characterize the BDD films. Various BDD films synthesized for different durations were utilized in the electrolytic carboxylation of acetophenone, with the highest yield of atrolactic acid (25 %) achieved using a BDD film synthesized over 6 h. Also, the effect of BDD surface modification i.e. oxygen and hydrogen terminated BDD on the synthesis of atrolactic acid was studied. Additionally, different electrolytes were employed in the synthesis process of atrolactic acid. A comparative study between Pt and BDD electrodes for the electrolytic carboxylation of acetophenone was conducted, and a mechanism for the formation of atrolactic acid was proposed.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145310"},"PeriodicalIF":5.5,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563170","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 : 2024-11-02DOI: 10.1016/j.electacta.2024.145308
Alan M.P. Sakita, Edson A. Ticianelli
Cation exchange membranes are considered a suitable option for zero-gap CO2 electrolysis due to their potential to avoid carbonation and improve carbon efficiency. However, the use of acidic anolytes remains an issue due to high hydrogen production. This study investigates Nafion® membranes (111, 112, 115, 211, and 212) with different thicknesses produced by extrusion or solution-cast processes in a zero-gap cell with an acidic anolyte containing K2SO4. Faradaic efficiencies for CO production (FECO) are higher with thinner membranes, regardless of the manufacturing process, reaching FECO around 75 % at 50 mA cm⁻². Additionally, membranes with similar thicknesses (∼50.8 µm) but produced in different ways displayed flow field carbonation after 3 h of electrolysis at 30 °C and 50 mA cm⁻². Linear sweep voltammetry (LSV) in full and half-cell configurations shows limiting diffusion current (iL) relative to proton transport for all the employed membranes, no matter the thickness. In contrast, the iL for Nafion® 115, the thicker membrane, is suppressed, indicating that proton depletion is fast and the electrode surface alkalinization primarily results from water reduction in this case. A mechanistic analysis was performed to explain the behavior of the limiting currents in the cell with Ar- and CO2-feed, indicating that CO2 reduction aids in the consumption of H+ provided by the membrane, increasing the local pH at less negative potentials. Overall, thinner membranes exhibited higher values of FECO and energy efficiency for CO (EE%CO). However, solution-cast membranes are more prone to provide K+, leading to better performance than those prepared by extrusion.
由于阳离子交换膜具有避免碳化和提高碳效率的潜力，因此被认为是零间隙二氧化碳电解的合适选择。然而，由于制氢量高，使用酸性溶液仍是一个问题。本研究调查了在含有 K2SO4 的酸性溶液的零间隙电池中，通过挤压或溶液浇铸工艺生产的不同厚度的 Nafion® 膜（111、112、115、211 和 212）。无论生产工艺如何，较薄的膜产生二氧化碳的法拉第效率（FECO）较高，在 50 mA cm-² 的条件下，FECO 达到 75% 左右。此外，在 30°C 和 50 mA cm-² 条件下电解 3 小时后，厚度相似（50.8 µm）但制造方法不同的膜会出现流场碳化现象。全电池和半电池配置下的线性扫描伏安法（LSV）显示，无论膜的厚度如何，所有采用的膜都具有相对于质子传输的极限扩散电流（iL）。相比之下，较厚的 Nafion® 115 膜的 iL 被抑制，这表明质子耗竭速度很快，在这种情况下，电极表面碱化主要是由水还原造成的。为解释氩气和二氧化碳馈入电池中的极限电流行为，进行了机理分析，结果表明二氧化碳还原有助于消耗膜提供的 H+，在负电位较低时提高局部 pH 值。总体而言，较薄的膜表现出较高的 FECO 值和 CO 能量效率（EE%CO）。然而，溶液浇铸膜更容易提供 K+，因此比挤压制备的膜性能更好。
{"title":"The role of cation exchange membrane characteristics in CO2 electrolysis to CO using acid anolyte","authors":"Alan M.P. Sakita, Edson A. Ticianelli","doi":"10.1016/j.electacta.2024.145308","DOIUrl":"10.1016/j.electacta.2024.145308","url":null,"abstract":"<div><div>Cation exchange membranes are considered a suitable option for zero-gap CO<sub>2</sub> electrolysis due to their potential to avoid carbonation and improve carbon efficiency. However, the use of acidic anolytes remains an issue due to high hydrogen production. This study investigates Nafion® membranes (111, 112, 115, 211, and 212) with different thicknesses produced by extrusion or solution-cast processes in a zero-gap cell with an acidic anolyte containing K<sub>2</sub>SO<sub>4</sub>. Faradaic efficiencies for CO production (FE<sub>CO</sub>) are higher with thinner membranes, regardless of the manufacturing process, reaching FE<sub>CO</sub> around 75 % at 50 mA cm⁻². Additionally, membranes with similar thicknesses (∼50.8 µm) but produced in different ways displayed flow field carbonation after 3 h of electrolysis at 30 °C and 50 mA cm⁻². Linear sweep voltammetry (LSV) in full and half-cell configurations shows limiting diffusion current (i<sub>L</sub>) relative to proton transport for all the employed membranes, no matter the thickness. In contrast, the i<sub>L</sub> for Nafion® 115, the thicker membrane, is suppressed, indicating that proton depletion is fast and the electrode surface alkalinization primarily results from water reduction in this case. A mechanistic analysis was performed to explain the behavior of the limiting currents in the cell with Ar- and CO<sub>2</sub>-feed, indicating that CO<sub>2</sub> reduction aids in the consumption of <em>H</em><sup>+</sup> provided by the membrane, increasing the local pH at less negative potentials. Overall, thinner membranes exhibited higher values of FE<sub>CO</sub> and energy efficiency for CO (EE<sup>%</sup><sub>CO</sub>). However, solution-cast membranes are more prone to provide <em>K</em><sup>+</sup>, leading to better performance than those prepared by extrusion.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"509 ","pages":"Article 145308"},"PeriodicalIF":5.5,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563280","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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