Pub Date : 2024-07-24DOI: 10.1088/2515-7655/ad670f
Rodrigo Rodriguez, L. Deiner, Bang-Hung Tsao, Joseph Fellner
Thick lithium-iron phosphate (LFP) cathodes (31 mg cm-2) with rationally engineered pore structure and tortuosity were manufactured with an aerosol jet (AJ) printer. Cathode pore structuring was tuned by controlling the rate at which the printed ink dried. Slow-drying prints yielded smoother cathodes while fast-drying prints resulted in mesoscale structuring with substantial surface roughness. X-ray tomography further revealed that the rapid drying of AJ printed LFP cathodes produced low-tortuosity pore channels which were preserved after calendering. Full cells comprised of AJ print optimized LFP cathodes, with 30 mg cm-2 active material loadings, and capacity-matched, AJ printed lithium titanate anodes were assembled and electrochemically tested. Performance of the AJ printed full cells was compared to tape-cast (TC) full cells. At equivalent electrode loadings, compositions, and thicknesses, the AJ full cells outperformed the TC cells, averaging approximately 14% greater capacity per cycle after 100 cycles at a C/2 rate. Furthermore, at 1C, the AJ printed full cells realized a near two-fold increase in discharge capacity over the TC cells.
{"title":"Enhanced rate capability and capacity of LIB full cells achieved through aerosol jet printing","authors":"Rodrigo Rodriguez, L. Deiner, Bang-Hung Tsao, Joseph Fellner","doi":"10.1088/2515-7655/ad670f","DOIUrl":"https://doi.org/10.1088/2515-7655/ad670f","url":null,"abstract":"\u0000 Thick lithium-iron phosphate (LFP) cathodes (31 mg cm-2) with rationally engineered pore structure and tortuosity were manufactured with an aerosol jet (AJ) printer. Cathode pore structuring was tuned by controlling the rate at which the printed ink dried. Slow-drying prints yielded smoother cathodes while fast-drying prints resulted in mesoscale structuring with substantial surface roughness. X-ray tomography further revealed that the rapid drying of AJ printed LFP cathodes produced low-tortuosity pore channels which were preserved after calendering. Full cells comprised of AJ print optimized LFP cathodes, with 30 mg cm-2 active material loadings, and capacity-matched, AJ printed lithium titanate anodes were assembled and electrochemically tested. Performance of the AJ printed full cells was compared to tape-cast (TC) full cells. At equivalent electrode loadings, compositions, and thicknesses, the AJ full cells outperformed the TC cells, averaging approximately 14% greater capacity per cycle after 100 cycles at a C/2 rate. Furthermore, at 1C, the AJ printed full cells realized a near two-fold increase in discharge capacity over the TC cells.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"3 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141807466","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-19DOI: 10.1088/2515-7655/ad658d
Megh N. Khanal, Vincent R Whiteside, Mritunjaya Parashar, T. Merckx, Mohin Sharma, Y. Kuang, Aranzazu Aguirre, H. Afshari, Sarallah Hamtaei, Tom Aernouts, Bart Vermang, Bibhudutta Rout, I. R. Sellers
Here, the radiation hardness of metal halide perovskite solar cells exposed to space conditions versus the effects of environmental degradation are assessed. The relative response of the constituent layers of the architecture to radiation is analyzed, revealing a general resilience of the structure when assessed across varying proton energy levels and fluences. However, despite the tolerance of the structure to irradiation, sensitivity to environmental degradation is observed during the transit of the device between the radiation and characterization facilities. Experimental evidence suggests the NiOx/perovskite interface is particularly sensitive to the effects of humidity and/or temperature exposure but the irradiation of the devices appears to induce thermally activated annealing improving the solar cells upon radiation exposure.
{"title":"Radiation versus environmental degradation in unencapsulated metal halide perovskite solar cells","authors":"Megh N. Khanal, Vincent R Whiteside, Mritunjaya Parashar, T. Merckx, Mohin Sharma, Y. Kuang, Aranzazu Aguirre, H. Afshari, Sarallah Hamtaei, Tom Aernouts, Bart Vermang, Bibhudutta Rout, I. R. Sellers","doi":"10.1088/2515-7655/ad658d","DOIUrl":"https://doi.org/10.1088/2515-7655/ad658d","url":null,"abstract":"\u0000 Here, the radiation hardness of metal halide perovskite solar cells exposed to space conditions versus the effects of environmental degradation are assessed. The relative response of the constituent layers of the architecture to radiation is analyzed, revealing a general resilience of the structure when assessed across varying proton energy levels and fluences. However, despite the tolerance of the structure to irradiation, sensitivity to environmental degradation is observed during the transit of the device between the radiation and characterization facilities. Experimental evidence suggests the NiOx/perovskite interface is particularly sensitive to the effects of humidity and/or temperature exposure but the irradiation of the devices appears to induce thermally activated annealing improving the solar cells upon radiation exposure.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"122 16","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141821948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-09DOI: 10.1088/2515-7655/ad6104
S. Gharabeiki, Muhammad Uzair Farooq, Taowen Wang, Mohit Sood, M. Melchiorre, Christian Kaufmann, A. Redinger, S. Siebentritt
The presence of Urbach tails in Cu(In,Ga)Se2 (CIGSe) absorbers has been identified as a limiting factor for the performance of the CIGSe solar cells. The tail states contribute to both radiative and non-radiative recombination processes, ultimately leading to a reduction in the open-circuit voltage (VOC) and, consequently, decreasing the overall efficiency of CIGSe devices. Urbach tails result from structural and thermal disorders. The Urbach tails can be characterized by the Urbach energy, which is associated with the magnitude of the tail states. Within polycrystalline CIGSe absorbers, grain boundaries can be considered as structural disorder and, therefore, can potentially contribute to the Urbach tails. In fact, it has been proposed that the band bending at grain boundaries contribute significantly to the tail states. This study focuses on examining the correlation between Urbach tails and the band bending at the grain boundaries. The Urbach energies of the CIGSe samples are extracted from photoluminescence (PL) measurements, which reveal that the introduction of Sodium (Na) into the material can lead to a reduction in the Urbach energy, and an even further decrease can be achieved through the RbF post-deposition treatment (PDT). The band bending at the grain boundaries is investigated by Kelvin probe force microscopy (KPFM) measurements. A thorough statistical analysis of more than 340 grain boundaries does not show any correlation between Urbach tails and grain boundaries. We measure small band bending values at the grain boundaries, in the range of the thermal energy (26meV at room temperature). Furthermore, our intensity dependent PL measurements indicate that Urbach tails are, at least in part, a result of electrostatic potential fluctuations. This supports the model that the introduction of alkali elements mainly decreases the magnitude of electrostatic potential fluctuations, resulting in a subsequent reduction in the Urbach energy.
{"title":"Grain boundaries are not the source of Urbach tails in Cu(In,Ga)Se2 absorbers","authors":"S. Gharabeiki, Muhammad Uzair Farooq, Taowen Wang, Mohit Sood, M. Melchiorre, Christian Kaufmann, A. Redinger, S. Siebentritt","doi":"10.1088/2515-7655/ad6104","DOIUrl":"https://doi.org/10.1088/2515-7655/ad6104","url":null,"abstract":"\u0000 The presence of Urbach tails in Cu(In,Ga)Se2 (CIGSe) absorbers has been identified as a limiting factor for the performance of the CIGSe solar cells. The tail states contribute to both radiative and non-radiative recombination processes, ultimately leading to a reduction in the open-circuit voltage (VOC) and, consequently, decreasing the overall efficiency of CIGSe devices. Urbach tails result from structural and thermal disorders. The Urbach tails can be characterized by the Urbach energy, which is associated with the magnitude of the tail states. Within polycrystalline CIGSe absorbers, grain boundaries can be considered as structural disorder and, therefore, can potentially contribute to the Urbach tails. In fact, it has been proposed that the band bending at grain boundaries contribute significantly to the tail states. This study focuses on examining the correlation between Urbach tails and the band bending at the grain boundaries. The Urbach energies of the CIGSe samples are extracted from photoluminescence (PL) measurements, which reveal that the introduction of Sodium (Na) into the material can lead to a reduction in the Urbach energy, and an even further decrease can be achieved through the RbF post-deposition treatment (PDT). The band bending at the grain boundaries is investigated by Kelvin probe force microscopy (KPFM) measurements. A thorough statistical analysis of more than 340 grain boundaries does not show any correlation between Urbach tails and grain boundaries. We measure small band bending values at the grain boundaries, in the range of the thermal energy (26meV at room temperature). Furthermore, our intensity dependent PL measurements indicate that Urbach tails are, at least in part, a result of electrostatic potential fluctuations. This supports the model that the introduction of alkali elements mainly decreases the magnitude of electrostatic potential fluctuations, resulting in a subsequent reduction in the Urbach energy.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"63 18","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141663185","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-05DOI: 10.1088/2515-7655/ad5fbb
Chanho Kim, Inyoung Jang
As the urgency to address global warming increases, the demand for clean energy generation systems that can mitigate greenhouse gases is intensifying. Solid oxide cells (SOCs) have emerged as a key technology for clean energy conversion, offering the benefits of power generation without submission of any pollutants including greenhouse gases. As the consumption of energy rises, the electrochemical performance of SOCs must be enhanced to meet the future energy demand. With the advent of 3D printing technology, the fabrication of SOCs has undergone a transformative shift, enabling precise structural control beyond the capabilities of traditional ceramic processes. This technology facilitates the creation of complex geometries, optimizing functionality through structural innovation and maximizing the electrochemical performance by enhancing reaction sites. Our review covers the brief outlook and the profound impact of 3D printing technology on SOC fabrication, highlighting its role in surpassing the structural constraints of conventional SOCs and paving the way for advanced applications like metal supported SOCs and integrated stack modules. Through the review, it is evident that continued, in-depth research into 3D printing for SOCs is crucial for maximizing their role as a sustainable energy resource in the future.
随着解决全球变暖问题的紧迫性增加，对能够减少温室气体排放的清洁能源发电系统的需求也在不断增加。固体氧化物电池（SOC）已成为清洁能源转换的一项关键技术，它具有发电而不排放任何污染物（包括温室气体）的优点。随着能源消耗的增加，必须提高固体氧化物电池的电化学性能，以满足未来的能源需求。随着 3D 打印技术的出现，SOC 的制造发生了变革性的转变，实现了超出传统陶瓷工艺能力的精确结构控制。这项技术有助于创造复杂的几何形状，通过结构创新优化功能，并通过增强反应位点最大限度地提高电化学性能。我们的综述涵盖了 3D 打印技术的简要展望和对 SOC 制造的深远影响，强调了它在超越传统 SOC 结构限制方面的作用，并为金属支撑 SOC 和集成堆栈模块等先进应用铺平了道路。通过综述，我们可以清楚地看到，继续深入研究用于 SOC 的 3D 打印技术对于最大限度地发挥其作为未来可持续能源资源的作用至关重要。
{"title":"Comprehensive review and future perspectives: 3D printing technology for all types of solid oxide cells","authors":"Chanho Kim, Inyoung Jang","doi":"10.1088/2515-7655/ad5fbb","DOIUrl":"https://doi.org/10.1088/2515-7655/ad5fbb","url":null,"abstract":"\u0000 As the urgency to address global warming increases, the demand for clean energy generation systems that can mitigate greenhouse gases is intensifying. Solid oxide cells (SOCs) have emerged as a key technology for clean energy conversion, offering the benefits of power generation without submission of any pollutants including greenhouse gases. As the consumption of energy rises, the electrochemical performance of SOCs must be enhanced to meet the future energy demand. With the advent of 3D printing technology, the fabrication of SOCs has undergone a transformative shift, enabling precise structural control beyond the capabilities of traditional ceramic processes. This technology facilitates the creation of complex geometries, optimizing functionality through structural innovation and maximizing the electrochemical performance by enhancing reaction sites. Our review covers the brief outlook and the profound impact of 3D printing technology on SOC fabrication, highlighting its role in surpassing the structural constraints of conventional SOCs and paving the way for advanced applications like metal supported SOCs and integrated stack modules. Through the review, it is evident that continued, in-depth research into 3D printing for SOCs is crucial for maximizing their role as a sustainable energy resource in the future.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":" 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141674813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-04DOI: 10.1088/2515-7655/ad5f54
Jens Nissen, Jan-Peter Boye, J. Schwämmlein, Markus Hölzle
Fuel gross starvation in a polymer electrolyte membrane fuel cell is an error state, during which the supplied amount of fuel is insufficient to sustain the requested electrical current. A novel experimental technique was developed to intentionally provoke well-controlled fuel starvation situations of one single cell in a multi-cell fuel cell stack. This modification was implemented in a 20-cell stack of automotive-sized cell geometry and carbon composite bipolar plates. The intentional fuel starvation situation was analyzed using a printed circuit board to measure the current density distribution in addition to a multipoint cell voltage monitoring to measure local cell voltages. The provoked detrimental subsidiary reactions of the anode were found to take place spatially separated from the normal hydrogen oxidation reaction. It was therefore possible to determine and intentionally vary the hydrogen stoichiometry of the fuel starved cell. This error state caused intense distortions of the starved cells current density distribution and local cell voltages. The maximum difference obtained between outlet and inlet voltage of the modified cell was 1.4 V. Compared to the average current density, a more than 4-times higher maximum local current density was measured in the affected cell. Adjacent cells were also affected via electric cell-to-cell interaction. Characteristic patterns therefore became visible in the cell voltage distribution, measured by the inlet and outlet cell voltage monitoring. The use of carbon composite bipolar plates is favoring the occurrence of these patterns due to their relatively high electric sheet resistance. Using the new hardware setup, we could investigate the relation between the hydrogen stoichiometry of the affected cell during fuel gross starvation and the observed irregular redistribution of current density and local cell voltages.
{"title":"Fuel starvation in automotive PEMFC stacks: hydrogen stoichiometry and electric cell-to-cell interaction","authors":"Jens Nissen, Jan-Peter Boye, J. Schwämmlein, Markus Hölzle","doi":"10.1088/2515-7655/ad5f54","DOIUrl":"https://doi.org/10.1088/2515-7655/ad5f54","url":null,"abstract":"\u0000 Fuel gross starvation in a polymer electrolyte membrane fuel cell is an error state, during which the supplied amount of fuel is insufficient to sustain the requested electrical current. A novel experimental technique was developed to intentionally provoke well-controlled fuel starvation situations of one single cell in a multi-cell fuel cell stack. This modification was implemented in a 20-cell stack of automotive-sized cell geometry and carbon composite bipolar plates. The intentional fuel starvation situation was analyzed using a printed circuit board to measure the current density distribution in addition to a multipoint cell voltage monitoring to measure local cell voltages. The provoked detrimental subsidiary reactions of the anode were found to take place spatially separated from the normal hydrogen oxidation reaction. It was therefore possible to determine and intentionally vary the hydrogen stoichiometry of the fuel starved cell. This error state caused intense distortions of the starved cells current density distribution and local cell voltages. The maximum difference obtained between outlet and inlet voltage of the modified cell was 1.4 V. Compared to the average current density, a more than 4-times higher maximum local current density was measured in the affected cell. Adjacent cells were also affected via electric cell-to-cell interaction. Characteristic patterns therefore became visible in the cell voltage distribution, measured by the inlet and outlet cell voltage monitoring. The use of carbon composite bipolar plates is favoring the occurrence of these patterns due to their relatively high electric sheet resistance. Using the new hardware setup, we could investigate the relation between the hydrogen stoichiometry of the affected cell during fuel gross starvation and the observed irregular redistribution of current density and local cell voltages.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":" 30","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141679125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-12DOI: 10.1088/2515-7655/ad5760
Youdong Kim, InHo Kim, C. Meisel, C. Herradón, Peter Rand, Jayoon Yang, Hyun Sik Kim, Neal Sullivan, R. O’Hayre
Protonic ceramic fuel cells (PCFCs) are emerging as a promising technology for reduced temperature ceramic energy conversion devices. The BaCe0.4Zr0.4Y0.1Yb0.1O3−δ (BCZYYb4411) electrolyte is notable for its high proton conductivity. However, the tendency of barium to volatilize in BCZYYb4411 during high-temperature sintering compromises its chemical stability and performance. This study investigates the effects of intentionally incorporating excess barium into BCZYYb4411, formulated as Ba1+xCe0.4Zr0.4Y0.1Yb0.1O3−δ (where x = 0, 0.1, 0.2, and 0.3), with the aim of compensating barium evaporation and enhancing the physical and chemical properties. We find that excess barium results in a greater shrinkage rate, facilitating a denser electrolyte structure. This barium-enriched electrolyte demonstrates improved electrochemical performance by effectively counteracting the deleterious effects of barium evaporation. Applying this strategy to tubular PCFCs, we achieved a peak power density of 480 mW/cm² at 600 °C. This unique approach provides a simple, tunable, and easy-to-implement processing modification to achieve high-performance tubular PCFC.
质子陶瓷燃料电池（PCFCs）是一种新兴的降温陶瓷能源转换设备技术，具有广阔的发展前景。BaCe0.4Zr0.4Y0.1Yb0.1O3-δ（BCZYYb4411）电解质以其高质子传导性而著称。然而，在高温烧结过程中，BCZYYb4411 中的钡易挥发，影响了其化学稳定性和性能。本研究调查了有意在 BCZYYb4411（配方为 Ba1+xCe0.4Zr0.4Y0.1Yb0.1O3-δ，其中 x = 0、0.1、0.2 和 0.3）中加入过量钡的影响，目的是补偿钡的挥发并提高其物理和化学特性。我们发现，过量的钡会导致更大的收缩率，从而使电解质结构更加致密。这种富钡电解质通过有效抵消钡蒸发的有害影响，改善了电化学性能。将这一策略应用于管状 PCFC，我们在 600 °C 时实现了 480 mW/cm² 的峰值功率密度。这种独特的方法为实现高性能管状 PCFC 提供了一种简单、可调且易于实施的加工改性方法。
{"title":"Improving tubular protonic ceramic fuel cell performance by compensating Ba evaporation via a Ba-excess optimized proton conducting electrolyte synthesis strategy","authors":"Youdong Kim, InHo Kim, C. Meisel, C. Herradón, Peter Rand, Jayoon Yang, Hyun Sik Kim, Neal Sullivan, R. O’Hayre","doi":"10.1088/2515-7655/ad5760","DOIUrl":"https://doi.org/10.1088/2515-7655/ad5760","url":null,"abstract":"\u0000 Protonic ceramic fuel cells (PCFCs) are emerging as a promising technology for reduced temperature ceramic energy conversion devices. The BaCe0.4Zr0.4Y0.1Yb0.1O3−δ (BCZYYb4411) electrolyte is notable for its high proton conductivity. However, the tendency of barium to volatilize in BCZYYb4411 during high-temperature sintering compromises its chemical stability and performance. This study investigates the effects of intentionally incorporating excess barium into BCZYYb4411, formulated as Ba1+xCe0.4Zr0.4Y0.1Yb0.1O3−δ (where x = 0, 0.1, 0.2, and 0.3), with the aim of compensating barium evaporation and enhancing the physical and chemical properties. We find that excess barium results in a greater shrinkage rate, facilitating a denser electrolyte structure. This barium-enriched electrolyte demonstrates improved electrochemical performance by effectively counteracting the deleterious effects of barium evaporation. Applying this strategy to tubular PCFCs, we achieved a peak power density of 480 mW/cm² at 600 °C. This unique approach provides a simple, tunable, and easy-to-implement processing modification to achieve high-performance tubular PCFC.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"108 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141352381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-06DOI: 10.1088/2515-7655/ad54ee
Santosh Kumar, James J C Counter, D. Grinter, M. V. van Spronsen, Pilar Ferrer-Escorihuela, Alex Large, Marcin W Orzech, Pawel Jerzy Wojcik, Georg Held
Suitable reaction cells are critical for operando near ambient pressure (NAP) soft X-ray photoelectron spectroscopy (XPS) and Near-edge X-ray absorption fine structure (NEXAFS) studies. They enable tracking the chemical state and structural properties of catalytically active materials under realistic reaction conditions, and thus allow a better understanding of charge transfer at the liquid-solid interface, activation of reactant molecules, and surface intermediate species. In order to facilitate such studies, we have developed a top-side illuminated operando spectro-electrochemical flow cell for synchrotron-based NAP-XPS and NEXAFS studies. Our modular design uses a non-metal (PEEK) body, and replaceable membranes which can be either of X-ray transparent silicon nitride (SiNx) or of water permeable polymer membrane materials (e.g., NafionTM). The design allows rapid sample exchange and simultaneous measurements of total electron yield (TEY), Auger electron yield (AEY) and fluorescence-yield (TFY). The developed system is highly modular and can be used in the laboratory or directly at the beamline for operando XPS/ X-ray absorption spectroscopy (XAS) investigations of surfaces and interfaces. We present examples to demonstrate the capabilities of the cell. These include an operando NEXAFS study of the Cu-redox chemistry using a SiNx membrane/Ti-Au/ Cu working electrode assembly (WEA) and a NAP-XPS and -NEXAFS study of water adsorption on a NafionTM polymer membrane based working electrode assembly (NafionTM/C/IrOx catalyst).
合适的反应池对于近环境压力（NAP）软 X 射线光电子能谱（XPS）和近边 X 射线吸收精细结构（NEXAFS）研究至关重要。它们能够跟踪催化活性材料在实际反应条件下的化学状态和结构特性，从而更好地了解液固界面的电荷转移、反应物分子的活化以及表面中间物种。为了促进此类研究，我们开发了一种顶部照明的操作光谱电化学流动池，用于基于同步辐射的 NAP-XPS 和 NEXAFS 研究。我们的模块化设计采用非金属（PEEK）主体和可更换膜，这些膜既可以是 X 射线透明的氮化硅（SiNx），也可以是透水性聚合物膜材料（如 NafionTM）。这种设计可以快速交换样品，并同时测量总电子产率（TEY）、奥杰电子产率（AEY）和荧光产率（TFY）。所开发的系统具有高度模块化的特点，可用于实验室或直接在光束线对表面和界面进行操作性 XPS/ X 射线吸收光谱（XAS）研究。我们将举例说明该单元的功能。其中包括使用 SiNx 膜/钛金/铜工作电极组件 (WEA) 对铜氧化还原化学进行的操作性 NEXAFS 研究，以及对基于 NafionTM 聚合物膜的工作电极组件（NafionTM/C/IrOx 催化剂）上的水吸附进行的 NAP-XPS 和 -NEXAFS 研究。
{"title":"An electrochemical flow cell for operando XPS and NEXAFS investigation of solid-liquid interfaces","authors":"Santosh Kumar, James J C Counter, D. Grinter, M. V. van Spronsen, Pilar Ferrer-Escorihuela, Alex Large, Marcin W Orzech, Pawel Jerzy Wojcik, Georg Held","doi":"10.1088/2515-7655/ad54ee","DOIUrl":"https://doi.org/10.1088/2515-7655/ad54ee","url":null,"abstract":"\u0000 Suitable reaction cells are critical for operando near ambient pressure (NAP) soft X-ray photoelectron spectroscopy (XPS) and Near-edge X-ray absorption fine structure (NEXAFS) studies. They enable tracking the chemical state and structural properties of catalytically active materials under realistic reaction conditions, and thus allow a better understanding of charge transfer at the liquid-solid interface, activation of reactant molecules, and surface intermediate species. In order to facilitate such studies, we have developed a top-side illuminated operando spectro-electrochemical flow cell for synchrotron-based NAP-XPS and NEXAFS studies. Our modular design uses a non-metal (PEEK) body, and replaceable membranes which can be either of X-ray transparent silicon nitride (SiNx) or of water permeable polymer membrane materials (e.g., NafionTM). The design allows rapid sample exchange and simultaneous measurements of total electron yield (TEY), Auger electron yield (AEY) and fluorescence-yield (TFY). The developed system is highly modular and can be used in the laboratory or directly at the beamline for operando XPS/ X-ray absorption spectroscopy (XAS) investigations of surfaces and interfaces. We present examples to demonstrate the capabilities of the cell. These include an operando NEXAFS study of the Cu-redox chemistry using a SiNx membrane/Ti-Au/ Cu working electrode assembly (WEA) and a NAP-XPS and -NEXAFS study of water adsorption on a NafionTM polymer membrane based working electrode assembly (NafionTM/C/IrOx catalyst).","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"18 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141377953","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-05-22DOI: 10.1088/2515-7655/ad4f15
Matthew Labbe, Douglas G Ivey
The air electrode of a Zn-air battery facilitates the O2 reduction and evolution reactions during battery discharge and charge, respectively. These reactions are kinetically sluggish and appropriate catalysts are essential at the air electrode to increase battery efficiency. Precious metals are traditionally used, but increasingly attention has shifted towards non-precious metal catalysts to decrease the cost and increase the practicality of Zn-air batteries. However, loading of the catalyst onto the air electrode is equally as important as catalyst selection. Several methods can be used to deposit catalysts, each with their own advantages and disadvantages. Example methods include spray-coating, electrodeposition, and impregnation. These can be categorized as indirect, direct, and hybrid catalyst loading techniques, respectively. Direct and hybrid loading methods generally provide better depth of loading than indirect methods, which is an important consideration for the porous, air-breathing electrode of a Zn-air battery. Furthermore, direct methods are free from ancillary materials such as a binder, required by indirect and hybrid methods, which translates into better cycling stability. This review examines the various techniques for fabricating catalyst-enhanced air electrodes with an emphasis on their contributions to battery performance and durability. More durable Zn-air battery air electrodes directly translate to longer operational lifetimes for practical Zn-air batteries, which is an important consideration for the future implementation of electrochemical energy storage in energy systems and technologies. Generally, direct catalyst loading techniques, which integrate catalyst material directly onto the air electrode structure, provide superior cycling performance to indirect catalyst loading techniques, which distribute an ex-situ synthesized material onto the top layer of the air electrode. Hybrid catalyst loading techniques, which grow catalyst material directly onto nanostructured supports and then integrate them throughout the air electrode architecture, offer a compromise between direct and indirect methods.
{"title":"Catalyst integration within the air electrode in secondary Zn-air batteries","authors":"Matthew Labbe, Douglas G Ivey","doi":"10.1088/2515-7655/ad4f15","DOIUrl":"https://doi.org/10.1088/2515-7655/ad4f15","url":null,"abstract":"\u0000 The air electrode of a Zn-air battery facilitates the O2 reduction and evolution reactions during battery discharge and charge, respectively. These reactions are kinetically sluggish and appropriate catalysts are essential at the air electrode to increase battery efficiency. Precious metals are traditionally used, but increasingly attention has shifted towards non-precious metal catalysts to decrease the cost and increase the practicality of Zn-air batteries. However, loading of the catalyst onto the air electrode is equally as important as catalyst selection. Several methods can be used to deposit catalysts, each with their own advantages and disadvantages. Example methods include spray-coating, electrodeposition, and impregnation. These can be categorized as indirect, direct, and hybrid catalyst loading techniques, respectively. Direct and hybrid loading methods generally provide better depth of loading than indirect methods, which is an important consideration for the porous, air-breathing electrode of a Zn-air battery. Furthermore, direct methods are free from ancillary materials such as a binder, required by indirect and hybrid methods, which translates into better cycling stability. This review examines the various techniques for fabricating catalyst-enhanced air electrodes with an emphasis on their contributions to battery performance and durability. More durable Zn-air battery air electrodes directly translate to longer operational lifetimes for practical Zn-air batteries, which is an important consideration for the future implementation of electrochemical energy storage in energy systems and technologies. Generally, direct catalyst loading techniques, which integrate catalyst material directly onto the air electrode structure, provide superior cycling performance to indirect catalyst loading techniques, which distribute an ex-situ synthesized material onto the top layer of the air electrode. Hybrid catalyst loading techniques, which grow catalyst material directly onto nanostructured supports and then integrate them throughout the air electrode architecture, offer a compromise between direct and indirect methods.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"27 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141112200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-23DOI: 10.1088/2515-7655/ad423c
Mohana V Kante, A. R. Lakshmi Nilayam, Kosova Kreka, Horst Hahn, S. S. Bhattacharya, L. Velasco, A. Tarancón, Christian Kübel, Simon Schweidler, M. Botros
Fluorite-type ceria-based ceramics are well established as oxygen ion conductors due to their high conductivity superseding state-of-the-art electrolytes like yttria-stabilized zirconia. However, at specific temperature and oxygen partial pressure, they occasionally exhibit electronic conduction attributed to polaron hopping via multivalent cations (e.g. Pr and Ce). (Ce, La, Sm, Pr, Y)O2-δ is a high-entropy oxide with a fluorite-type structure, featuring low concentrations of multivalent cations which could potentially mitigate polaron hopping. However, (Ce, La, Sm, Pr, Y)O2-δ undergoes a structural transition to the bixbyite-type structure above 1000 °C. In this study, we introduce Zr doping into (Ce, La, Pr, Sm, Y)O2-δ to hinder the structural transition at elevated temperatures. Indeed, fluorite structure at elevated temperatures is stabilized at approximately 10 at.% Zr doping. The total conductivity initially increases with doping, peaking at 5 at.% Zr doping, and subsequently decreases with further doping. Interestingly, electronic conductivity in (Ce, La, Pr, Sm, Y)1-xZrxO2-δ under oxidizing atmospheres is not significant and is lowest at 8 at.% Zr. These results suggest that ceria-based high entropy oxides can serve as oxygen ion conductors with significantly reduced electronic contribution. This work paves the way for new compositionally complex electrolytes as well as protective coatings for solid oxide fuel cells.
{"title":"Influence of Zr-doping on structure and transport properties of rare earth high entropy oxides","authors":"Mohana V Kante, A. R. Lakshmi Nilayam, Kosova Kreka, Horst Hahn, S. S. Bhattacharya, L. Velasco, A. Tarancón, Christian Kübel, Simon Schweidler, M. Botros","doi":"10.1088/2515-7655/ad423c","DOIUrl":"https://doi.org/10.1088/2515-7655/ad423c","url":null,"abstract":"\u0000 Fluorite-type ceria-based ceramics are well established as oxygen ion conductors due to their high conductivity superseding state-of-the-art electrolytes like yttria-stabilized zirconia. However, at specific temperature and oxygen partial pressure, they occasionally exhibit electronic conduction attributed to polaron hopping via multivalent cations (e.g. Pr and Ce). (Ce, La, Sm, Pr, Y)O2-δ is a high-entropy oxide with a fluorite-type structure, featuring low concentrations of multivalent cations which could potentially mitigate polaron hopping. However, (Ce, La, Sm, Pr, Y)O2-δ undergoes a structural transition to the bixbyite-type structure above 1000 °C. In this study, we introduce Zr doping into (Ce, La, Pr, Sm, Y)O2-δ to hinder the structural transition at elevated temperatures. Indeed, fluorite structure at elevated temperatures is stabilized at approximately 10 at.% Zr doping. The total conductivity initially increases with doping, peaking at 5 at.% Zr doping, and subsequently decreases with further doping. Interestingly, electronic conductivity in (Ce, La, Pr, Sm, Y)1-xZrxO2-δ under oxidizing atmospheres is not significant and is lowest at 8 at.% Zr. These results suggest that ceria-based high entropy oxides can serve as oxygen ion conductors with significantly reduced electronic contribution. This work paves the way for new compositionally complex electrolytes as well as protective coatings for solid oxide fuel cells.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":"121 31","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140669311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-18DOI: 10.1088/2515-7655/ad405b
Chirantan Shee, Swagata Banerjee, Satyaranjan Bairagi, Aiswarya Baburaj, N. Kumar S K, Akshaya Kumar Aliyana, Daniel M. Mulvihill, R. Alagirusamy, S. W. Ali
In the recent era of energy crisis, piezoelectric and triboelectric effects are surfacing out of several research topics. Polyvinylidene fluoride (PVDF) and its copolymers are well known piezoelectric polymers due to their high piezoelectricity and widely used in flexible devices. PVDF is greatly utilized in preparation of triboelectric layer also due to its higher electronegative nature amongst common polymers. On the other hand, zinc oxide (ZnO) has been studied widely to investigate its multifunctional properties including piezoelectricity, pyroelectricity and antibacterial activity. This versatile material can be prepared, using low cost and environmental friendly routes, in various morphologies. Various research is already performed to capture the synergistic effect of reinforcing ZnO within PVDF polymeric matrix. This work firstly describes the basic principles of piezoelectric and triboelectric effects. Thereafter, piezoelectric and triboelectric performances of PVDF and ZnO based materials are briefly depicted based on their structures. Finally, challenges and future scopes, associated with the mechanical energy harvesting from such materials, are highlighted.
{"title":"A critical review on polyvinylidene fluoride (PVDF)/zinc oxide (ZnO) based piezoelectric and triboelectric nanogenerators","authors":"Chirantan Shee, Swagata Banerjee, Satyaranjan Bairagi, Aiswarya Baburaj, N. Kumar S K, Akshaya Kumar Aliyana, Daniel M. Mulvihill, R. Alagirusamy, S. W. Ali","doi":"10.1088/2515-7655/ad405b","DOIUrl":"https://doi.org/10.1088/2515-7655/ad405b","url":null,"abstract":"\u0000 In the recent era of energy crisis, piezoelectric and triboelectric effects are surfacing out of several research topics. Polyvinylidene fluoride (PVDF) and its copolymers are well known piezoelectric polymers due to their high piezoelectricity and widely used in flexible devices. PVDF is greatly utilized in preparation of triboelectric layer also due to its higher electronegative nature amongst common polymers. On the other hand, zinc oxide (ZnO) has been studied widely to investigate its multifunctional properties including piezoelectricity, pyroelectricity and antibacterial activity. This versatile material can be prepared, using low cost and environmental friendly routes, in various morphologies. Various research is already performed to capture the synergistic effect of reinforcing ZnO within PVDF polymeric matrix. This work firstly describes the basic principles of piezoelectric and triboelectric effects. Thereafter, piezoelectric and triboelectric performances of PVDF and ZnO based materials are briefly depicted based on their structures. Finally, challenges and future scopes, associated with the mechanical energy harvesting from such materials, are highlighted.","PeriodicalId":509250,"journal":{"name":"Journal of Physics: Energy","volume":" 7","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140686456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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