Pub Date : 2024-11-23DOI: 10.1016/j.ssi.2024.116740
Haijing Cui , Changjiang Yang , Yankun Wang , Zehang Qin , Jun Chang
LiFePO4 batteries play a crucial role in energy storage and electric vehicles, with their precursor, FePO4, directly determining the electrochemical performance of LiFePO4. The key to preparing high-quality FePO4 is the precise regulation of crystal morphology. This study investigates the inter-ionic interaction of Fe3+ in a complex phosphate system to form monoclinic FePO4 with high crystallinity by precisely controlling process parameters such as pH and reaction temperature. The optimized process parameters are as follows: during the leaching stage, a P/Fe feeding ratio of 3:1 and a reaction temperature of 90 °C; during the oxidation stage, a 140 % excess of H2O2 and a reaction temperature of 50 °C; and during the crystallization stage, a pH of 1.5 and a reaction temperature of 90 °C, with an aging time of 1 h. The resulting FePO4 has a round cake morphology with a diameter of approximately 1.5 μm and a thickness of about 0.5 μm. The particle size distribution is narrow, with a D50 of 2.64 μm. The products exhibit consistent crystalline morphology, high crystallinity, an Fe content of 36.595 %, a P content of 20.676 %, and an Fe/P ratio of 0.981. The synthesized LiFePO4/C derived from this FePO4 shows a discharge capacity of 154 mAh/g at 0.2C. The proposed preparation mechanism has significant theoretical implications for the efficient and environmentally friendly production of FePO4 in the industry.
{"title":"Study on the mechanism of liquid-phase regulated preparation of battery-grade iron phosphate","authors":"Haijing Cui , Changjiang Yang , Yankun Wang , Zehang Qin , Jun Chang","doi":"10.1016/j.ssi.2024.116740","DOIUrl":"10.1016/j.ssi.2024.116740","url":null,"abstract":"<div><div>LiFePO<sub>4</sub> batteries play a crucial role in energy storage and electric vehicles, with their precursor, FePO<sub>4</sub>, directly determining the electrochemical performance of LiFePO<sub>4</sub>. The key to preparing high-quality FePO<sub>4</sub> is the precise regulation of crystal morphology. This study investigates the inter-ionic interaction of Fe<sup>3+</sup> in a complex phosphate system to form monoclinic FePO<sub>4</sub> with high crystallinity by precisely controlling process parameters such as pH and reaction temperature. The optimized process parameters are as follows: during the leaching stage, a P/Fe feeding ratio of 3:1 and a reaction temperature of 90 °C; during the oxidation stage, a 140 % excess of H<sub>2</sub>O<sub>2</sub> and a reaction temperature of 50 °C; and during the crystallization stage, a pH of 1.5 and a reaction temperature of 90 °C, with an aging time of 1 h. The resulting FePO<sub>4</sub> has a round cake morphology with a diameter of approximately 1.5 μm and a thickness of about 0.5 μm. The particle size distribution is narrow, with a D<sub>50</sub> of 2.64 μm. The products exhibit consistent crystalline morphology, high crystallinity, an Fe content of 36.595 %, a P content of 20.676 %, and an Fe/P ratio of 0.981. The synthesized LiFePO<sub>4</sub>/C derived from this FePO<sub>4</sub> shows a discharge capacity of 154 mAh/g at 0.2C. The proposed preparation mechanism has significant theoretical implications for the efficient and environmentally friendly production of FePO<sub>4</sub> in the industry.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"418 ","pages":"Article 116740"},"PeriodicalIF":3.0,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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 : 2024-11-22DOI: 10.1016/j.ssi.2024.116741
Yunfei Li , Qian Zhai , Chengyi Wen , Chunling Lu , Dongchao Qiu , Bingbing Niu , Biao Wang
Sm and Nb co-doping Sm1-xBaxFe0.9Nb0.1O3-δ (x= 0.05,0.10,0.15, abbreviated as SBFN05, SBFN10 and SBFN15) oxide was prepared and investigated as an electrode for symmetrical solid oxide fuel cells (SSOFCs). XRD results demonstrate that Sm1-xBaxFe0.9Nb0.1O3-δ samples form a stable cubic perovskite structure both in air and in H2 atmosphere. Among Sm1-xBaxFe0.9Nb0.1O3-δ samples, SBFN05 exhibits the lowest polarization resistance (Rp) at 600–800 °C. At 800 °C, the Rp of SBFN05 symmetrical electrode is 0.021 Ω cm2 in air and 0.2 Ω cm2 in H2, respectively. The Rp of SBFN05 electrode has good stability in air and in H2 during 100 h short-term test. At 850 °C, The maximum power density of single cell with SBFN05 symmetrical electrode feed with H2 fuel reaches 928.6 mWcm−2. Compared with BaFeO3-δ, SBFN05 has lower binding energy and its O 2P center is closer to Fermi energy, suggesting good structural stability and oxygen catalytic activity. The primary result suggests that SBFN05 is a potential candidate symmetrical electrode for IT-SOFCs.
制备了 Sm1-xBaxFe0.9Nb0.1O3-δ （x = 0.05、0.10、0.15，缩写为 SBFN05、SBFN10 和 SBFN15）氧化物，并将其作为对称固体氧化物燃料电池（SSOFC）的电极进行了研究。XRD 结果表明，Sm1-xBaxFe0.9Nb0.1O3-δ 样品在空气和 H2 大气中都形成了稳定的立方包晶结构。在 Sm1-xBaxFe0.9Nb0.1O3-δ 样品中，SBFN05 在 600-800 °C 时表现出最低的极化电阻（Rp）。在 800 °C 时，SBFN05 对称电极在空气中的 Rp 为 0.021 Ω cm2，在 H2 中的 Rp 为 0.2 Ω cm2。在 100 小时的短期试验中，SBFN05 电极在空气和 H2 中的 Rp 具有良好的稳定性。在 850 °C 时，使用 SBFN05 对称电极馈入 H2 燃料的单电池的最大功率密度达到 928.6 mWcm-2。与 BaFeO3-δ 相比，SBFN05 的结合能更低，其 O 2P 中心更接近费米能，这表明其具有良好的结构稳定性和氧催化活性。主要结果表明，SBFN05 是 IT-SOFCs 的潜在候选对称电极。
{"title":"Investigate the performance of Sm and Nb co-doping Sm1-xBaxFe0.9Nb0.1O3-δ symmetrical electrode for solid oxide fuel cells","authors":"Yunfei Li , Qian Zhai , Chengyi Wen , Chunling Lu , Dongchao Qiu , Bingbing Niu , Biao Wang","doi":"10.1016/j.ssi.2024.116741","DOIUrl":"10.1016/j.ssi.2024.116741","url":null,"abstract":"<div><div>Sm and Nb co-doping Sm<sub>1-<em>x</em></sub>Ba<sub><em>x</em></sub>Fe<sub>0.9</sub>Nb<sub>0.1</sub>O<sub>3-δ</sub> (<em>x</em> <em>=</em> 0.05,0.10,0.15, abbreviated as SBFN05, SBFN10 and SBFN15) oxide was prepared and investigated as an electrode for symmetrical solid oxide fuel cells (SSOFCs). XRD results demonstrate that Sm<sub>1-<em>x</em></sub>Ba<em><sub><sub>x</sub></sub></em>Fe<sub>0.9</sub>Nb<sub>0.1</sub>O<sub>3-δ</sub> samples form a stable cubic perovskite structure both in air and in H<sub>2</sub> atmosphere. Among Sm<sub>1-<em>x</em></sub>Ba<sub><em>x</em></sub>Fe<sub>0.9</sub>Nb<sub>0.1</sub>O<sub>3-δ</sub> samples, SBFN05 exhibits the lowest polarization resistance (Rp) at 600–800 °C. At 800 °C, the Rp of SBFN05 symmetrical electrode is 0.021 Ω cm<sup>2</sup> in air and 0.2 Ω cm<sup>2</sup> in H<sub>2</sub>, respectively. The Rp of SBFN05 electrode has good stability in air and in H<sub>2</sub> during 100 h short-term test. At 850 °C, The maximum power density of single cell with SBFN05 symmetrical electrode feed with H<sub>2</sub> fuel reaches 928.6 mWcm<sup>−2</sup>. Compared with BaFeO<sub>3-δ</sub>, SBFN05 has lower binding energy and its O 2P center is closer to Fermi energy, suggesting good structural stability and oxygen catalytic activity. The primary result suggests that SBFN05 is a potential candidate symmetrical electrode for IT-SOFCs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"418 ","pages":"Article 116741"},"PeriodicalIF":3.0,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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 : 2024-11-21DOI: 10.1016/j.ssi.2024.116742
Natalia V. Kireeva, Aslan Yu Tsivadze
Metal-air batteries are the target of the ever-growing interest as considering as the new “lead” technology among the most promising electrochemical energy storage solutions. The projected energy density of lithium-air batteries considered in this study exceeds current commercial lithium-ion batteries by more than three times. In this study, we consider the characteristics of MXenes, 2D layered phases with such attractive characteristics as a high specific surface area with the numerous active reaction centers, mechanical strength, the diverse functional characteristics and the perspectives of scalability of their production, which are of importance for the practical realization of Li-air batteries of different architecture. The formation of the phases of complex content and structure inherent to pseudomorphism at the interface, as it is actual for the objects of our study, allows one to conclude that it is necessary to consider the processes that occur at the interfaces of lithium-air battery cathodes in direct relation to the cathode material used. Machine learning methods were involved in model development for (i) MXenes predicting the electrochemical phase diagrams, Pourbaix diagrams, which circumscribe the stability window of MXenes of certain composition formed with synthesis-defined terminations as a function of pH and USHE for single and double MXenes and (ii) the elastic characteristics of MAX phases, precursors of MXenes, to assess the commensurability of the interface of MXene cathode materials and Li2O2 phase as well as the prospects of using target MXene compositions combined with the solid electrolyte materials of different families for employing in all-solid-state Li-air batteries. The obtained models demonstrate high predictive performance that argue on the possibility to use them for rational screening of new phases with desired functional characteristics.
{"title":"Using machine learning towards enhancement of electrochemical activity in OER/ORR half-reactions of MXene cathode materials for Li-air batteries","authors":"Natalia V. Kireeva, Aslan Yu Tsivadze","doi":"10.1016/j.ssi.2024.116742","DOIUrl":"10.1016/j.ssi.2024.116742","url":null,"abstract":"<div><div>Metal-air batteries are the target of the ever-growing interest as considering as the new “lead” technology among the most promising electrochemical energy storage solutions. The projected energy density of lithium-air batteries considered in this study exceeds current commercial lithium-ion batteries by more than three times. In this study, we consider the characteristics of MXenes, 2D layered phases with such attractive characteristics as a high specific surface area with the numerous active reaction centers, mechanical strength, the diverse functional characteristics and the perspectives of scalability of their production, which are of importance for the practical realization of Li-air batteries of different architecture. The formation of the phases of complex content and structure inherent to pseudomorphism at the interface, as it is actual for the objects of our study, allows one to conclude that it is necessary to consider the processes that occur at the interfaces of lithium-air battery cathodes in direct relation to the cathode material used. Machine learning methods were involved in model development for <em>(i)</em> MXenes predicting the electrochemical phase diagrams, Pourbaix diagrams, which circumscribe the stability window of MXenes of certain composition formed with synthesis-defined terminations as a function of pH and U<sub><em>SHE</em></sub> for single and double MXenes and <em>(ii)</em> the elastic characteristics of MAX phases, precursors of MXenes, to assess the commensurability of the interface of MXene cathode materials and Li<sub>2</sub>O<sub>2</sub> phase as well as the prospects of using target MXene compositions combined with the solid electrolyte materials of different families for employing in all-solid-state Li-air batteries. The obtained models demonstrate high predictive performance that argue on the possibility to use them for rational screening of new phases with desired functional characteristics.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"418 ","pages":"Article 116742"},"PeriodicalIF":3.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699685","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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 : 2024-11-21DOI: 10.1016/j.ssi.2024.116730
Michael C. Jollands , Shiyun Jin , Daniel C. Jones , Roland Stalder
The diffusivity of hydrogen, as protons, in Mg- and Be-doped corundum has been determined from 544 to 1007 °C, by annealing single crystals in CO2-H2 or N2-H2 mixes at ambient pressure. The addition of hydrogen leads to decolorization of the crystals, which is attributed to the associated removal of electron holes. Spatially resolved semi-quantitative profiles of hydrogen concentration versus distance were recorded using Fourier transform infrared spectroscopy, and/or Cr luminescence lifetime spectroscopy. These show hydrogen diffusion associated with trapping by Mg or Be, which leads to characteristic step shaped (broadly sigmoidal) forms of concentration-distance profiles. Numerical modelling of this diffusion-plus-trapping process allows hydrogen diffusion coefficients to be extracted, which are several orders of magnitude higher than any diffusion coefficients that have been previously determined in this system. This discrepancy is attributed to previous studies not taking trapping behaviour into account. Re-analysis of some published data, now considering trapping, can explain a ∼ 4-5 orders of magnitude discrepancy in calculated diffusion coefficients.
{"title":"H diffusion in Mg- and Be- doped ⍺Al2O3 (corundum) single crystals","authors":"Michael C. Jollands , Shiyun Jin , Daniel C. Jones , Roland Stalder","doi":"10.1016/j.ssi.2024.116730","DOIUrl":"10.1016/j.ssi.2024.116730","url":null,"abstract":"<div><div>The diffusivity of hydrogen, as protons, in Mg- and Be-doped corundum has been determined from 544 to 1007 °C, by annealing single crystals in CO<sub>2</sub>-H<sub>2</sub> or N<sub>2</sub>-H<sub>2</sub> mixes at ambient pressure. The addition of hydrogen leads to decolorization of the crystals, which is attributed to the associated removal of electron holes. Spatially resolved semi-quantitative profiles of hydrogen concentration versus distance were recorded using Fourier transform infrared spectroscopy, and/or Cr luminescence lifetime spectroscopy. These show hydrogen diffusion associated with trapping by Mg or Be, which leads to characteristic step shaped (broadly sigmoidal) forms of concentration-distance profiles. Numerical modelling of this diffusion-plus-trapping process allows hydrogen diffusion coefficients to be extracted, which are several orders of magnitude higher than any diffusion coefficients that have been previously determined in this system. This discrepancy is attributed to previous studies not taking trapping behaviour into account. <em>Re</em>-analysis of some published data, now considering trapping, can explain a ∼ 4-5 orders of magnitude discrepancy in calculated diffusion coefficients.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"418 ","pages":"Article 116730"},"PeriodicalIF":3.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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 : 2024-11-07DOI: 10.1016/j.ssi.2024.116723
Rafael Bianchini Nuernberg , Annie-Kim Landry , Frédéric Le Cras , Brigitte Pecquenard Le Cras
Currently, amorphous LiPON prepared by magnetron sputtering is the most employed thin film electrolyte due to its ionic conductivity (∼10−6 S.cm−1), negligible electronic conductivity, absence of grain boundaries and ability to passivate Li metal. Despite the outstanding cycling performance that this combination of properties enables, its moderate conductivity hinders the use microbatteries in Internet of Things applications due to the need for short but high current pulses during communication phases. To better meet this requirement, LiSiPON thin films with ionic conductivities more than ten times greater than that of LiPON have been synthesized, while encountering some challenges in controlling the composition and the reproducibility of the synthesis. Herein, we have synthesized LiSiPON thin films from a set of precursor targets having distinct lithium concentrations. The main results indicate that an increase in the lithium content in the target material significantly enhances its ionic conductivity. Curiously, the most conductive target results in lithium-deficient and poorly conductive thin films that are not particularly reproducible in terms of composition and electrical properties. Our results suggest that lithium migration away from the sputtered area (or racetrack), favored by the high ionic conductivity of the target, is the origin of the resulting Li-deficient films. Finally, we have succeeded in preparing LiSiPO targets with sufficiently low Li-ion conductivity that enable the reproducible deposition of highly conductive LiSiPON solid electrolytes.
{"title":"Enhancing ionic conductivity of LiSiPON thin films electrolytes: Overcoming synthesis challenges related to Li-migration in the precursor target","authors":"Rafael Bianchini Nuernberg , Annie-Kim Landry , Frédéric Le Cras , Brigitte Pecquenard Le Cras","doi":"10.1016/j.ssi.2024.116723","DOIUrl":"10.1016/j.ssi.2024.116723","url":null,"abstract":"<div><div>Currently, amorphous LiPON prepared by magnetron sputtering is the most employed thin film electrolyte due to its ionic conductivity (∼10<sup>−6</sup> S.cm<sup>−1</sup>), negligible electronic conductivity, absence of grain boundaries and ability to passivate Li metal. Despite the outstanding cycling performance that this combination of properties enables, its moderate conductivity hinders the use microbatteries in Internet of Things applications due to the need for short but high current pulses during communication phases. To better meet this requirement, LiSiPON thin films with ionic conductivities more than ten times greater than that of LiPON have been synthesized, while encountering some challenges in controlling the composition and the reproducibility of the synthesis. Herein, we have synthesized LiSiPON thin films from a set of precursor targets having distinct lithium concentrations. The main results indicate that an increase in the lithium content in the target material significantly enhances its ionic conductivity. Curiously, the most conductive target results in lithium-deficient and poorly conductive thin films that are not particularly reproducible in terms of composition and electrical properties. Our results suggest that lithium migration away from the sputtered area (or racetrack), favored by the high ionic conductivity of the target, is the origin of the resulting Li-deficient films. Finally, we have succeeded in preparing LiSiPO targets with sufficiently low Li-ion conductivity that enable the reproducible deposition of highly conductive LiSiPON solid electrolytes.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"418 ","pages":"Article 116723"},"PeriodicalIF":3.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142650883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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 : 2024-11-06DOI: 10.1016/j.ssi.2024.116709
{"title":"Preface \"Special Issue for the 21st International Conference on Solid State Protonic Conductors (SSPC-21)\"","authors":"","doi":"10.1016/j.ssi.2024.116709","DOIUrl":"10.1016/j.ssi.2024.116709","url":null,"abstract":"","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116709"},"PeriodicalIF":3.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142658761","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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.ssi.2024.116727
Ao Li , Yuxin Zheng , Yujia Zhang , Zhixiong Li , Liang Yin , Hong Li
Lithium-rich layered oxides (LROs), serving as high-energy cathode materials for lithium-ion batteries (LIBs), possess significant drawbacks that hinder their widespread use in practical applications. While surface modification can effectively shield LRO from structural degradation, precisely designing the surface structure remains a big challenge. This study focuses on the fabrication of uniform and thickness-controlled LiNbO3-coated nanostructures on the surface of LRO using the atomic layer deposition (ALD) technique. The LiNbO3 nanostructures on the cathode surface not only bolster the structural and interfacial stability but also facilitate Li+ diffusion, enhancing the cycling stability and the rate capability of LRO. Specifically, the LRO modified with a 3 nm thick LiNbO3 layer exhibited better capacity retention of 86.4 % after 200 cycles at 1C with a voltage decay rate of 2.86 mV per cycle, and a reversible discharge capacity of 88.1 mAh g−1 at 10C, underscoring the crucial role of surface nanostructures in enhancing electrochemical performance. This research sheds light on the strategic design of nanostructures at the grain surface of advanced cathode materials for high-performance LIBs.
{"title":"Enhancing cycling stability in Li-rich layered oxides by atomic layer deposition of LiNbO3 nanolayers","authors":"Ao Li , Yuxin Zheng , Yujia Zhang , Zhixiong Li , Liang Yin , Hong Li","doi":"10.1016/j.ssi.2024.116727","DOIUrl":"10.1016/j.ssi.2024.116727","url":null,"abstract":"<div><div>Lithium-rich layered oxides (LROs), serving as high-energy cathode materials for lithium-ion batteries (LIBs), possess significant drawbacks that hinder their widespread use in practical applications. While surface modification can effectively shield LRO from structural degradation, precisely designing the surface structure remains a big challenge. This study focuses on the fabrication of uniform and thickness-controlled LiNbO<sub>3</sub>-coated nanostructures on the surface of LRO using the atomic layer deposition (ALD) technique. The LiNbO<sub>3</sub> nanostructures on the cathode surface not only bolster the structural and interfacial stability but also facilitate Li<sup>+</sup> diffusion, enhancing the cycling stability and the rate capability of LRO. Specifically, the LRO modified with a 3 nm thick LiNbO<sub>3</sub> layer exhibited better capacity retention of 86.4 % after 200 cycles at 1C with a voltage decay rate of 2.86 mV per cycle, and a reversible discharge capacity of 88.1 mAh g<sup>−1</sup> at 10C, underscoring the crucial role of surface nanostructures in enhancing electrochemical performance. This research sheds light on the strategic design of nanostructures at the grain surface of advanced cathode materials for high-performance LIBs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116727"},"PeriodicalIF":3.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To reveal the ways and causes of conversion efficiency enhancement for quantum dot-sensitized solar cells (QDSSCs), chalcopyrite structure CuInS2 quantum dots (QDs) was synthesized in oil phase by the high temperature hot injection method. Then, QDs were transferred from oil phase to water phase with 3-mercaptopropionic acid as a ligand exchange reagent and loaded inducer of QDs. 3-mercaptopropionic acid coated QDs in water phase were sensitized on TiO2 nanocrystalline thin films to fabricate QDSSCs. The sensitization time of QDs and pH value in QDs solution are two important factors to affect the loading amounts of QDs and performance of the final assembled QDSSCs. Long-time sensitization of QDs on the TiO2 porous thin film will cause QDs to agglomerate and stack on the film. The pH of QDs aqueous solution influences the stable existence in solution of QDs and adsorption on the surface of TiO2. By balancing the influence of the above two factors, the optimal sensitization condition of CuInS2 QDs is adsorption in pH = 11 QDs solution for 2 h. In addition, the interface between QD-sensitized TiO2 porous thin film and FTO is another factor to affect the photoelectric conversion efficiency of QDSSCs. By adding Zn-doped TiO2 compact layer with high conductivity and electron mobility on QDSSCs to modify this interface, the photoelectric conversion efficiency of QDSSCs was further increased by 66.4 %.
{"title":"Performance improvement tactics of sensitized solar cells based on CuInS2 quantum dots prepared by high temperature hot injection","authors":"Yushan Li, Jiao Men, Guangyan Zhou, Yanhong Qiao, Jingbo Zhang","doi":"10.1016/j.ssi.2024.116731","DOIUrl":"10.1016/j.ssi.2024.116731","url":null,"abstract":"<div><div>To reveal the ways and causes of conversion efficiency enhancement for quantum dot-sensitized solar cells (QDSSCs), chalcopyrite structure CuInS<sub>2</sub> quantum dots (QDs) was synthesized in oil phase by the high temperature hot injection method. Then, QDs were transferred from oil phase to water phase with 3-mercaptopropionic acid as a ligand exchange reagent and loaded inducer of QDs. 3-mercaptopropionic acid coated QDs in water phase were sensitized on TiO<sub>2</sub> nanocrystalline thin films to fabricate QDSSCs. The sensitization time of QDs and pH value in QDs solution are two important factors to affect the loading amounts of QDs and performance of the final assembled QDSSCs. Long-time sensitization of QDs on the TiO<sub>2</sub> porous thin film will cause QDs to agglomerate and stack on the film. The pH of QDs aqueous solution influences the stable existence in solution of QDs and adsorption on the surface of TiO<sub>2</sub>. By balancing the influence of the above two factors, the optimal sensitization condition of CuInS<sub>2</sub> QDs is adsorption in pH = 11 QDs solution for 2 h. In addition, the interface between QD-sensitized TiO<sub>2</sub> porous thin film and FTO is another factor to affect the photoelectric conversion efficiency of QDSSCs. By adding Zn-doped TiO<sub>2</sub> compact layer with high conductivity and electron mobility on QDSSCs to modify this interface, the photoelectric conversion efficiency of QDSSCs was further increased by 66.4 %.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"418 ","pages":"Article 116731"},"PeriodicalIF":3.0,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142573454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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 : 2024-11-01DOI: 10.1016/j.ssi.2024.116725
Jeffy Jeffy, Nobuya Machida
The sulfide solid electrolyte xLiCl·(25-x)LiBr·75Li3PS4 was synthesized by a two-step glass-ceramic method. In the first step, amorphous precursors were obtained by a high-energy ball-milling method, and in the second step, the obtained precursors were heated up to a temperature in the range of 165 to 180 °C in order to obtain crystalline samples. The LGPS-like crystalline phase was precipitated in the heat-treated samples in the 0 < x < 12.5 composition range. The glass-ceramic samples showed high ion conductivities of 3 × 10−3 to 4 × 10−3 S cm−1 at 25 °C. A charge-discharge test was conducted on an all-solid-state test cell using the 7.5LiCl·17.5LiBr·75Li3PS4 (mol%) glass-ceramic sample as a separator. The cathode composite of the test cell was a mixture of LiNi1/3Mn1/3Co1/3O2 (NMC) active materials, the solid electrolyte, and acetylene black. The test cell exhibited high electrochemical stability and the electrochemical capacity based on NMC active materials was 145 mAhg−1.
{"title":"Synthesis and electrochemical properties of Li+-ion conducting solid electrolytes in the system xLiCl·(25-x)LiBr·75Li3PS4","authors":"Jeffy Jeffy, Nobuya Machida","doi":"10.1016/j.ssi.2024.116725","DOIUrl":"10.1016/j.ssi.2024.116725","url":null,"abstract":"<div><div>The sulfide solid electrolyte <em>x</em>LiCl·(25-<em>x</em>)LiBr·75Li<sub>3</sub>PS<sub>4</sub> was synthesized by a two-step glass-ceramic method. In the first step, amorphous precursors were obtained by a high-energy ball-milling method, and in the second step, the obtained precursors were heated up to a temperature in the range of 165 to 180 °C in order to obtain crystalline samples. The LGPS-like crystalline phase was precipitated in the heat-treated samples in the 0 < <em>x</em> < 12.5 composition range. The glass-ceramic samples showed high ion conductivities of 3 × 10<sup>−3</sup> to 4 × 10<sup>−3</sup> S cm<sup>−1</sup> at 25 °C. A charge-discharge test was conducted on an all-solid-state test cell using the 7.5LiCl·17.5LiBr·75Li<sub>3</sub>PS<sub>4</sub> (mol%) glass-ceramic sample as a separator. The cathode composite of the test cell was a mixture of LiNi<sub>1/3</sub>Mn<sub>1/3</sub>Co<sub>1/3</sub>O<sub>2</sub> (NMC) active materials, the solid electrolyte, and acetylene black. The test cell exhibited high electrochemical stability and the electrochemical capacity based on NMC active materials was 145 mAhg<sup>−1</sup>.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116725"},"PeriodicalIF":3.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571509","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
One method for enhancing the electrochemical performance of a solid oxide fuel cell (SOFC) cathode at low temperatures is to mix two oxides with dissimilar structures to form a composite electrode. To understand the enhancement factor of the composite electrode consisting of an ionic conducting oxide, Ce0.9Gd0.1O1.95 (GDC), and a mixed ionic and electronic conducting oxide, La0.6Sr0.4CoO3-δ (LSC), electrochemical measurements were performed as a function of composition ratio, temperature (673–1073 K), and oxygen partial pressure (p(O2), 1–10−4 bar). The area-specific conductivity (σE) that was obtained from the impedance spectra was enhanced at low temperature (T < 873 K) in the high p(O2) region (1–10−1 bar) for the samples that contained above 40 % of GDC. However, the enhancement was not significant at high temperatures (T > 873 K) under all measured p(O2) conditions. Although some LSC particles were replaced by GDC, the enhancement of the chemical capacitance of the composite electrode was observed. This indicates that GDC particles function as ionic conducting pathways in the composite electrode. To understand the enhancement mechanism, the experimental data of σE were compared with the calculated results using a one-dimensional transmission-line model (1-D TLM) considering only the contributions of surface resistivity and ionic resistivity. Results indicate that there is a discrepancy between the measured result of σE and the calculated result. Several plausible reasons for the discrepancy were discussed, where the contribution of the triple phase boundary reaction resistivity could not be ignored in the calculation of σE.
{"title":"Investigation of factors enhancing electrochemical properties of the porous La0.6Sr0.4CoO3-δ–Ce0.9Gd0.1O1.95 composite electrode for solid oxide fuel cell","authors":"Riyan Achmad Budiman , Junichi Sakuraba , Marika Sakai , Mina Yamaguchi , Shin-Ichi Hashimoto , Keiji Yashiro , Tatsuya Kawada","doi":"10.1016/j.ssi.2024.116724","DOIUrl":"10.1016/j.ssi.2024.116724","url":null,"abstract":"<div><div>One method for enhancing the electrochemical performance of a solid oxide fuel cell (SOFC) cathode at low temperatures is to mix two oxides with dissimilar structures to form a composite electrode. To understand the enhancement factor of the composite electrode consisting of an ionic conducting oxide, Ce<sub>0.9</sub>Gd<sub>0.1</sub>O<sub>1.95</sub> (GDC), and a mixed ionic and electronic conducting oxide, La<sub>0.6</sub>Sr<sub>0.4</sub>CoO<sub>3-<em>δ</em></sub> (LSC), electrochemical measurements were performed as a function of composition ratio, temperature (673–1073 K), and oxygen partial pressure (<em>p</em>(O<sub>2</sub>), 1–10<sup>−4</sup> bar). The area-specific conductivity (<em>σ</em><sub>E</sub>) that was obtained from the impedance spectra was enhanced at low temperature (<em>T</em> < 873 K) in the high <em>p</em>(O<sub>2</sub>) region (1–10<sup>−1</sup> bar) for the samples that contained above 40 % of GDC. However, the enhancement was not significant at high temperatures (<em>T</em> > 873 K) under all measured <em>p</em>(O<sub>2</sub>) conditions. Although some LSC particles were replaced by GDC, the enhancement of the chemical capacitance of the composite electrode was observed. This indicates that GDC particles function as ionic conducting pathways in the composite electrode. To understand the enhancement mechanism, the experimental data of <em>σ</em><sub>E</sub> were compared with the calculated results using a one-dimensional transmission-line model (1-D TLM) considering only the contributions of surface resistivity and ionic resistivity. Results indicate that there is a discrepancy between the measured result of <em>σ</em><sub>E</sub> and the calculated result. Several plausible reasons for the discrepancy were discussed, where the contribution of the triple phase boundary reaction resistivity could not be ignored in the calculation of <em>σ</em><sub>E</sub>.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"417 ","pages":"Article 116724"},"PeriodicalIF":3.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571510","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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