Even though hole-selective self-assembled monolayers (SAMs) are a key player for light management and carrier management in Pb- and Sn–Pb based perovskite solar cells (PSCs), they are markedly underdeveloped for Sn PSCs. Herein, we offer multifaceted approaches as a roadmap to tackle this challenge. We systematically reviewed recent publications on Sn PSCs utilizing hole-selective SAMs to identify underexplored approaches and suboptimal photovoltaic performance. We then examined state-of-the-art PSCs based on Pb and Sn–Pb perovskites to induce their success to arise from multifaceted approaches on the substrate, SAM, perovskite, and their interfaces. Additionally, we emphasized the unique underlying properties of Sn PSCs that warrant careful consideration. Finally, we proposed feasible approaches to improve the SAM-based Sn PSCs, in light of light management and carrier management, by leveraging the unique properties of Sn perovskites alongside the multifaceted approaches proven effective in other PSCs.
{"title":"Toward Maximizing Hole Selection with Self-Assembled Monolayers in Sn-Based Perovskite Solar Cells","authors":"Donghoon Song, Seung Wook Shin, Hui-Ping Wu, Eric Wei-Guang Diau, Juan-Pablo Correa-Baena","doi":"10.1021/acsenergylett.4c03228","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03228","url":null,"abstract":"Even though hole-selective self-assembled monolayers (SAMs) are a key player for light management and carrier management in Pb- and Sn–Pb based perovskite solar cells (PSCs), they are markedly underdeveloped for Sn PSCs. Herein, we offer multifaceted approaches as a roadmap to tackle this challenge. We systematically reviewed recent publications on Sn PSCs utilizing hole-selective SAMs to identify underexplored approaches and suboptimal photovoltaic performance. We then examined state-of-the-art PSCs based on Pb and Sn–Pb perovskites to induce their success to arise from multifaceted approaches on the substrate, SAM, perovskite, and their interfaces. Additionally, we emphasized the unique underlying properties of Sn PSCs that warrant careful consideration. Finally, we proposed feasible approaches to improve the SAM-based Sn PSCs, in light of light management and carrier management, by leveraging the unique properties of Sn perovskites alongside the multifaceted approaches proven effective in other PSCs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"24 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-17DOI: 10.1021/acsenergylett.5c00170
Jiwoo Yeop, Jae Hoon Son, Jin Uk Lee, Jina Roe, Jaehyeong Kim, Dongchan Lee, Nayoung Kim, Shinuk Cho, Jae Sung Lee, Han Young Woo, Jin Young Kim
Organic photoelectrochemical (OPEC) cells are efficient at generating photocurrents but face significant challenges in long-term stability due to the incompatibility of metal oxide charge transport layers with organic photoactive materials and their pH sensitivity. To overcome these issues, we developed an all-organic photoanode incorporating n-type self-assembled monolayers (SAMs) with imide core modifications, which optimize the work function of the ITO substrate, improving charge transfer and the onset potential (Vonset). The addition of a hole-transporting p-type conjugated polyelectrolyte (TPAFS-7TMA) further enhances hole transport and water wettability. This photoanode, designed for ascorbic acid oxidation, achieved a Vonset of 0.25 VRHE and a photocurrent density (Jph) of 7.92 mA cm–2 at oxidation potential and retained 90% of its initial Jph over 2 h under 1 sun irradiation. This all-organic design effectively addresses the limitations of conventional OPEC cells, providing a stable and efficient alternative for durable OPEC systems. We developed a stable and efficient all-organic photoanode for OPEC cells, utilizing imide-modified n-type SAMs and a p-type conjugated polyelectrolyte to enhance charge transfer, water wettability, and durability, achieving significant performance improvements.
{"title":"Realization of All-Organic Photoanodes for Photoelectrochemical Cells","authors":"Jiwoo Yeop, Jae Hoon Son, Jin Uk Lee, Jina Roe, Jaehyeong Kim, Dongchan Lee, Nayoung Kim, Shinuk Cho, Jae Sung Lee, Han Young Woo, Jin Young Kim","doi":"10.1021/acsenergylett.5c00170","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00170","url":null,"abstract":"Organic photoelectrochemical (OPEC) cells are efficient at generating photocurrents but face significant challenges in long-term stability due to the incompatibility of metal oxide charge transport layers with organic photoactive materials and their pH sensitivity. To overcome these issues, we developed an all-organic photoanode incorporating n-type self-assembled monolayers (SAMs) with imide core modifications, which optimize the work function of the ITO substrate, improving charge transfer and the onset potential (<i>V</i><sub>onset</sub>). The addition of a hole-transporting p-type conjugated polyelectrolyte (TPAFS-7TMA) further enhances hole transport and water wettability. This photoanode, designed for ascorbic acid oxidation, achieved a <i>V</i><sub>onset</sub> of 0.25 V<sub>RHE</sub> and a photocurrent density (<i>J</i><sub>ph</sub>) of 7.92 mA cm<sup>–2</sup> at oxidation potential and retained 90% of its initial <i>J</i><sub>ph</sub> over 2 h under 1 sun irradiation. This all-organic design effectively addresses the limitations of conventional OPEC cells, providing a stable and efficient alternative for durable OPEC systems. We developed a stable and efficient all-organic photoanode for OPEC cells, utilizing imide-modified n-type SAMs and a p-type conjugated polyelectrolyte to enhance charge transfer, water wettability, and durability, achieving significant performance improvements.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"14 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-17DOI: 10.1021/acsenergylett.5c00324
Nickil A. Shah, Galo J. Páez Fajardo, Hrishit Banerjee, Gaurav C. Pandey, Ashok S. Menon, Muhammad Ans, Veronika Majherova, Gerard Bree, Satish Bolloju, David C. Grinter, Pilar Ferrer, Pardeep K. Thakur, Tien-Lin Lee, Melanie J. Loveridge, Andrew J. Morris, Clare P. Grey, Louis F. J. Piper
In Ni-rich layered oxide cathodes, cycling above the oxygen-loss threshold voltage (∼4.3 V vs Li+/Li) promotes structural transformations at the cathode surface. These transformations can result in various thermodynamically favorable rocksalt-like (RSL) structures (NiO, NiOx, and/or LiyNizO) that have different Li+ transport properties. Elucidating the precise phase type in the RSL can help determine design strategies to improve Li+ kinetics and identify design rules to suppress capacity fade in Ni-rich cathodes. This study utilizes surface-sensitive X-ray absorption spectroscopy in combination with first-principles simulations and distinguishes the layered oxide spectroscopic features from those of surface-reduced layers of pure NiO and LixNi1–xO. The transport of lithium ions through this oxygen-loss-induced surface-reconstructed layer is studied with operando X-ray diffraction in a pouch cell as a function of cycling aging and constant voltage protocols.
{"title":"Nature of the Oxygen-Loss-Induced Rocksalt Layer and Its Impact on Capacity Fade in Ni-Rich Layered Oxide Cathodes","authors":"Nickil A. Shah, Galo J. Páez Fajardo, Hrishit Banerjee, Gaurav C. Pandey, Ashok S. Menon, Muhammad Ans, Veronika Majherova, Gerard Bree, Satish Bolloju, David C. Grinter, Pilar Ferrer, Pardeep K. Thakur, Tien-Lin Lee, Melanie J. Loveridge, Andrew J. Morris, Clare P. Grey, Louis F. J. Piper","doi":"10.1021/acsenergylett.5c00324","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00324","url":null,"abstract":"In Ni-rich layered oxide cathodes, cycling above the oxygen-loss threshold voltage (∼4.3 V vs Li<sup>+</sup>/Li) promotes structural transformations at the cathode surface. These transformations can result in various thermodynamically favorable rocksalt-like (RSL) structures (NiO, NiO<sub><i>x</i></sub>, and/or Li<sub><i>y</i></sub>Ni<sub><i>z</i></sub>O) that have different Li<sup>+</sup> transport properties. Elucidating the precise phase type in the RSL can help determine design strategies to improve Li<sup>+</sup> kinetics and identify design rules to suppress capacity fade in Ni-rich cathodes. This study utilizes surface-sensitive X-ray absorption spectroscopy in combination with first-principles simulations and distinguishes the layered oxide spectroscopic features from those of surface-reduced layers of pure NiO and Li<sub><i>x</i></sub>Ni<sub>1–<i>x</i></sub>O. The transport of lithium ions through this oxygen-loss-induced surface-reconstructed layer is studied with operando X-ray diffraction in a pouch cell as a function of cycling aging and constant voltage protocols.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"18 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-15DOI: 10.1021/acsenergylett.4c03269
Mengru Jin, Eugenia S. Vasileiadou, Ioannis Spanopoulos, Arushi Chaudhry, Mercouri G. Kanatzidis, Qing Tu
Our knowledge about dielectric breakdown of 2D hybrid organic–inorganic perovskites (HOIPs) is limited, although the breakdown is widely observed and harnessed for new device applications. Here, we investigate the out-of-plane breakdown of a benchmark 2D HOIP family, (BA)2MAn–1PbnI3n+1 (BA = butylammonium, MA = methylammonium, and n = 1–5), by conductive atomic force microscopy. Unlike conventional 2D materials, 2D HOIPs manifest milder breakdown morphologies, no clear trend of layer-by-layer damages, and stochastic characteristics of defect percolation, likely due to their low in-plane vs out-of-plane anisotropy. The influence of thickness, ramping rate, and n on the breakdown strength (EBD) is evaluated, which is on the order of 108 V/m, showing the intrinsic resilience of 2D HOIPs to breakdown and their potential as dielectric materials for 2D electronics. These results delineate the dielectric breakdown process in 2D HOIPs and provide indispensable insights into the electrical failure of 2D HOIPs in devices.
{"title":"Dielectric Breakdown of 2D Hybrid Organic–Inorganic Perovskites","authors":"Mengru Jin, Eugenia S. Vasileiadou, Ioannis Spanopoulos, Arushi Chaudhry, Mercouri G. Kanatzidis, Qing Tu","doi":"10.1021/acsenergylett.4c03269","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03269","url":null,"abstract":"Our knowledge about dielectric breakdown of 2D hybrid organic–inorganic perovskites (HOIPs) is limited, although the breakdown is widely observed and harnessed for new device applications. Here, we investigate the out-of-plane breakdown of a benchmark 2D HOIP family, (BA)<sub>2</sub>MA<sub><i>n</i>–1</sub>Pb<sub><i>n</i></sub>I<sub>3<i>n</i>+1</sub> (BA = butylammonium, MA = methylammonium, and <i>n</i> = 1–5), by conductive atomic force microscopy. Unlike conventional 2D materials, 2D HOIPs manifest milder breakdown morphologies, no clear trend of layer-by-layer damages, and stochastic characteristics of defect percolation, likely due to their low in-plane vs out-of-plane anisotropy. The influence of thickness, ramping rate, and <i>n</i> on the breakdown strength (<i>E</i><sub>BD</sub>) is evaluated, which is on the order of 10<sup>8</sup> V/m, showing the intrinsic resilience of 2D HOIPs to breakdown and their potential as dielectric materials for 2D electronics. These results delineate the dielectric breakdown process in 2D HOIPs and provide indispensable insights into the electrical failure of 2D HOIPs in devices.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"25 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418009","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-14DOI: 10.1021/acsenergylett.5c0012910.1021/acsenergylett.5c00129
Prashant V. Kamat*,
{"title":"“Highly Efficient and Stable” Perovskite Solar Cells: Hype Versus Reality","authors":"Prashant V. Kamat*, ","doi":"10.1021/acsenergylett.5c0012910.1021/acsenergylett.5c00129","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00129https://doi.org/10.1021/acsenergylett.5c00129","url":null,"abstract":"","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"10 2","pages":"896–897 896–897"},"PeriodicalIF":19.3,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-14DOI: 10.1021/acsenergylett.5c00129
Prashant V. Kamat
No doubt, in a short span of about 12 years, perovskite solar cells have made significant impacts both on fundamental research and in the development of photovoltaic (PV) technology. (1,2) The certified single-junction solar cell efficiency increased from 14.1% (2013) to 26.7% (2024), (2) although most of the recent champion solar cell efficiency gains were made through decreasing the area of the cell. (3) Si-perovskite tandem solar cells have attained a photoconversion efficiency (PCE) of 34.6%. The enthusiastic determination of the scientific community during the past decade was a key factor in turning academic research into practical reality. Efforts are now underway to produce large panels for solar PV installations in China and elsewhere. Despite this progress, one catchy phrase that we continue to see in the titles of scientific papers is “<i>efficient and stable</i>”, or even “<i>highly efficient and stable</i>”, or some variation thereof. In order to highlight a newly adopted procedure to formulate perovskite solar cells, authors often use such adjectives in the title of their paper. Since most research laboratories can now produce perovskite solar cells with ∼24% PCE, there is no need to claim high efficiency every time one reports a perovskite solar cell performance. Unless it is a record efficiency, any other claim of high efficiency appears to be an unnecessary hype. Looking back into the perovskite solar cell literature, the first reference to “<i>efficient and stable</i>” appeared in 2014. (4) Since then, this phrase has become a <i>mantra</i> for publishing perovskite papers, more noticeably even in “prominent” journals. Interestingly, its use in the title of perovskite solar cell articles is on the rise. Figure 1 shows the increased use of this phrase in journal titles during the last ten years. (Note: <i>ACS Energy Letters</i> has published ∼37 such articles during this period, mostly prior to 2021. We now discourage the use of nonquantifiable phrases in the title. (5)) Figure 1. Number of perovskite solar cells/photovoltaics papers (2014–2024) published with the phrase “efficient and stable” in the title in all journals. The entry for 2024 is partial data. Source: Web of Science, Clarivate Analytics, Dec 23, 2024. Many questions arise when one sees perovskite photovoltaics papers claiming “<i>Efficient</i>” or “<i>Highly Efficient</i>” in the title: Is this a real breakthrough or just another hyped claim? What makes the new “<i>highly efficient</i>” perovskite solar cell article distinctively different from the previous one published by the same group or in the same journal? Is it the chemical treatment that the authors employed or the new solar cell design that represents the scientific advance? Is the previous report, published by the same group six months earlier with a similar claim, now redundant? Unless one compares the record-breaking PV performance of a previously reported work, it is difficult to assess the merit of the
{"title":"“Highly Efficient and Stable” Perovskite Solar Cells: Hype Versus Reality","authors":"Prashant V. Kamat","doi":"10.1021/acsenergylett.5c00129","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00129","url":null,"abstract":"No doubt, in a short span of about 12 years, perovskite solar cells have made significant impacts both on fundamental research and in the development of photovoltaic (PV) technology. (1,2) The certified single-junction solar cell efficiency increased from 14.1% (2013) to 26.7% (2024), (2) although most of the recent champion solar cell efficiency gains were made through decreasing the area of the cell. (3) Si-perovskite tandem solar cells have attained a photoconversion efficiency (PCE) of 34.6%. The enthusiastic determination of the scientific community during the past decade was a key factor in turning academic research into practical reality. Efforts are now underway to produce large panels for solar PV installations in China and elsewhere. Despite this progress, one catchy phrase that we continue to see in the titles of scientific papers is “<i>efficient and stable</i>”, or even “<i>highly efficient and stable</i>”, or some variation thereof. In order to highlight a newly adopted procedure to formulate perovskite solar cells, authors often use such adjectives in the title of their paper. Since most research laboratories can now produce perovskite solar cells with ∼24% PCE, there is no need to claim high efficiency every time one reports a perovskite solar cell performance. Unless it is a record efficiency, any other claim of high efficiency appears to be an unnecessary hype. Looking back into the perovskite solar cell literature, the first reference to “<i>efficient and stable</i>” appeared in 2014. (4) Since then, this phrase has become a <i>mantra</i> for publishing perovskite papers, more noticeably even in “prominent” journals. Interestingly, its use in the title of perovskite solar cell articles is on the rise. Figure 1 shows the increased use of this phrase in journal titles during the last ten years. (Note: <i>ACS Energy Letters</i> has published ∼37 such articles during this period, mostly prior to 2021. We now discourage the use of nonquantifiable phrases in the title. (5)) Figure 1. Number of perovskite solar cells/photovoltaics papers (2014–2024) published with the phrase “efficient and stable” in the title in all journals. The entry for 2024 is partial data. Source: Web of Science, Clarivate Analytics, Dec 23, 2024. Many questions arise when one sees perovskite photovoltaics papers claiming “<i>Efficient</i>” or “<i>Highly Efficient</i>” in the title: Is this a real breakthrough or just another hyped claim? What makes the new “<i>highly efficient</i>” perovskite solar cell article distinctively different from the previous one published by the same group or in the same journal? Is it the chemical treatment that the authors employed or the new solar cell design that represents the scientific advance? Is the previous report, published by the same group six months earlier with a similar claim, now redundant? Unless one compares the record-breaking PV performance of a previously reported work, it is difficult to assess the merit of the","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"64 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418054","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Elevating the charge cutoff voltage of LiCoO2 (LCO) from 4.4 to 4.7 V can significantly boost energy density. However, conventional electrolyte strategies encountering the viscosity and wettability obstacles for high-voltage LCO cannot tackle the issues of severe electrolyte decomposition, electrode–electrolyte interface degradation, and irreversible phase-transitions simultaneously. Herein, we achieved stable operation of commercial LCO at 4.7 V using a superwettable low-concentration fluoroborate dual-salt electrolyte (LFE). Our elaborated LFE (0.5 M) features an anion-enriched solvation structure that creates ultrathin, stable yet fast ion/electron transfer electrode/electrolyte interphases, significantly alleviating electrolyte decomposition, interface degradation, and injurious lithium dendrites. Consequently, LFE enables LCO to deliver a record capacity retention of 89.5% after 200 cycles and rate capability, far surpassing state-of-the-art 4.7 V-charged Li||LCO batteries. We assembled 1.25 Ah-class graphite||LCO pouch cells using LFE, achieving 100% capacity retention after 300 cycles and showcasing practicality. This work inaugurates an innovative pathway to maximize energy storage devices performance.
{"title":"Unlocking 4.7 V LiCoO2 with a Counterintuitive Low-Concentration Fluoroborate Dual-Salt Electrolyte by Anion-Derived Interfacial Chemistry","authors":"Anping Zhang, Endian Yang, Zhihong Bi, Gongrui Wang, Shihao Liao, Xiaofeng Li, Yan Yu, Qi Liu, Xinhe Bao, Zhong-Shuai Wu","doi":"10.1021/acsenergylett.4c03117","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03117","url":null,"abstract":"Elevating the charge cutoff voltage of LiCoO<sub>2</sub> (LCO) from 4.4 to 4.7 V can significantly boost energy density. However, conventional electrolyte strategies encountering the viscosity and wettability obstacles for high-voltage LCO cannot tackle the issues of severe electrolyte decomposition, electrode–electrolyte interface degradation, and irreversible phase-transitions simultaneously. Herein, we achieved stable operation of commercial LCO at 4.7 V using a superwettable low-concentration fluoroborate dual-salt electrolyte (LFE). Our elaborated LFE (0.5 M) features an anion-enriched solvation structure that creates ultrathin, stable yet fast ion/electron transfer electrode/electrolyte interphases, significantly alleviating electrolyte decomposition, interface degradation, and injurious lithium dendrites. Consequently, LFE enables LCO to deliver a record capacity retention of 89.5% after 200 cycles and rate capability, far surpassing state-of-the-art 4.7 V-charged Li||LCO batteries. We assembled 1.25 Ah-class graphite||LCO pouch cells using LFE, achieving 100% capacity retention after 300 cycles and showcasing practicality. This work inaugurates an innovative pathway to maximize energy storage devices performance.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"10 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-12DOI: 10.1021/acsenergylett.4c03299
Debolina Mukherjee, Shyam Chand Pal, Yasaswini Oruganti, Byoung Gwan Lee, Arun K. Manna, Dae-Woon Lim, Madhab C. Das
Design of solid-state proton conductors (SSPCs) operating at low to intermediate temperatures (25–60 °C) is desirable to address the thermal-management issue in proton-exchange membrane fuel cells (PEMFCs). Among the various approaches in designing SSPCs, “orthophosphate coordination” is highly unexplored in MOFs. Herein, a new MOF: IITKGP-103 {[Ag(hmta)H2PO4]·2H2O}n with orthophosphate coordinated to Ag(I) center, is rationally designed. Synchronous alignments of two amphiprotic proton sources/carriers (H2PO4– and water) resulted in highly extended H-bonded networks that eased the fastest protonic relay (σ = 2.92 × 10–2 S cm–1) at intermediate temperature (60 °C) with smaller proton transfer (PT) energy barriers for both the identified conducting channels (∼5.6 kcal mol–1 for intralayer and ∼2.2 kcal mol–1 for interlayer), making MOF:IITKGP-103 the best performing intermediate temperature SSPC material. In contrast, nonsynchronous alignments of proton carriers in another orthophosphate coordinated framework Ag-bpy (1) resulted in 100 times lower conductivity with higher barriers (∼6.2 and ∼10.9 kcal mol–1) as validated through quantum-tunneling analysis.
{"title":"Intermediate Temperature Superprotonic Conductivity beyond 10–2 S cm–1 with Low Proton Transfer Energy Barrier in a Metal–Organic Framework","authors":"Debolina Mukherjee, Shyam Chand Pal, Yasaswini Oruganti, Byoung Gwan Lee, Arun K. Manna, Dae-Woon Lim, Madhab C. Das","doi":"10.1021/acsenergylett.4c03299","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03299","url":null,"abstract":"Design of solid-state proton conductors (SSPCs) operating at low to intermediate temperatures (25–60 °C) is desirable to address the thermal-management issue in proton-exchange membrane fuel cells (PEMFCs). Among the various approaches in designing SSPCs, “<i>orthophosphate coordination</i>” is highly unexplored in MOFs. Herein, a new <b>MOF</b>: <b>IITKGP-103</b> {[Ag(hmta)H<sub>2</sub>PO<sub>4</sub>]·2H<sub>2</sub>O}<sub><i>n</i></sub> with orthophosphate coordinated to Ag(I) center, is rationally designed. Synchronous alignments of two amphiprotic proton sources/carriers (H<sub>2</sub>PO<sub>4</sub><sup>–</sup> and water) resulted in highly extended H-bonded networks that eased the fastest protonic relay (σ = 2.92 × 10<sup>–2</sup> S cm<sup>–1</sup>) at intermediate temperature (60 °C) with smaller proton transfer (PT) energy barriers for both the identified conducting channels (∼5.6 kcal mol<sup>–1</sup> for <i>intralayer</i> and ∼2.2 kcal mol<sup>–1</sup> for <i>interlayer</i>), making <b>MOF:</b><b>IITKGP-103</b> the best performing intermediate temperature SSPC material. In contrast, nonsynchronous alignments of proton carriers in another orthophosphate coordinated framework <b>Ag-bpy (1)</b> resulted in 100 times lower conductivity with higher barriers (∼6.2 and ∼10.9 kcal mol<sup>–1</sup>) as validated through quantum-tunneling analysis.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"30 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143402015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-11DOI: 10.1021/acsenergylett.4c03315
Alexander Diercks, Julian Petry, Thomas Feeney, Roja Singh, Tonghan Zhao, Hang Hu, Yang Li, Ulrich W. Paetzold, Paul Fassl
Recent advances in sequential evaporation of perovskite solar cells (PSCs) have culminated in a rapid increase in reported power conversion efficiencies (PCEs), now on par with those of the best solution-processed counterparts. This development triggered vast interest from industry and academics. To date, however, very few studies addressed sequentially evaporated PSCs in the p-i-n architecture, and an in-depth process understanding is lacking. Here, we investigate the impact of the hole transport layer (HTL) on the formation of formamidinium lead triiodide (FAPI) perovskite thin films fabricated via an evaporated two-step process. We find that the crystal orientation of lead iodide (PbI2) changes significantly for different HTLs, thereby affecting the subsequent conversion and crystallization process. Adjusting the amount of deposited FAI reveals an unexpected correlation of the PbI2-to-perovskite X-ray diffraction peak intensity ratio to final PSC performance that depends on the employed HTL. Our approach enables PCEs of more than 17%, the highest reported for fully vacuum-processed pure FAPI PSCs in the p-i-n architecture.
{"title":"Sequential Evaporation of Inverted FAPbI3 Perovskite Solar Cells – Impact of Substrate on Crystallization and Film Formation","authors":"Alexander Diercks, Julian Petry, Thomas Feeney, Roja Singh, Tonghan Zhao, Hang Hu, Yang Li, Ulrich W. Paetzold, Paul Fassl","doi":"10.1021/acsenergylett.4c03315","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03315","url":null,"abstract":"Recent advances in sequential evaporation of perovskite solar cells (PSCs) have culminated in a rapid increase in reported power conversion efficiencies (PCEs), now on par with those of the best solution-processed counterparts. This development triggered vast interest from industry and academics. To date, however, very few studies addressed sequentially evaporated PSCs in the <i>p-i-n</i> architecture, and an in-depth process understanding is lacking. Here, we investigate the impact of the hole transport layer (HTL) on the formation of formamidinium lead triiodide (FAPI) perovskite thin films fabricated via an evaporated two-step process. We find that the crystal orientation of lead iodide (PbI<sub>2</sub>) changes significantly for different HTLs, thereby affecting the subsequent conversion and crystallization process. Adjusting the amount of deposited FAI reveals an unexpected correlation of the PbI<sub>2</sub>-to-perovskite X-ray diffraction peak intensity ratio to final PSC performance that depends on the employed HTL. Our approach enables PCEs of more than 17%, the highest reported for fully vacuum-processed pure FAPI PSCs in the <i>p-i-n</i> architecture.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"128 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Quasi-two-dimensional (quasi-2D) perovskites, interspersed with organic intercalating cations, demonstrate significant potential in blue perovskite light-emitting quasi-2D perovskites, with organic intercalating cations, and show potential in blue perovskite light-emitting diodes (PeLEDs). However, the broad distribution of quantum wells, especially low-n phases, hinders energy transfer and device performance. Additionally, imperfect crystal quality and rough film surfaces further limit the efficiency. This study demonstrates that quaternary ammonium halides, like betaine hydrochloride (betaine HCl), can control phase distribution, passivate defects, and enhance crystallization in perovskite films. The cation−π interaction between betaine HCl and phenylethylammonium (PEA+) reduces low-n phases, while interactions with the C═O group and Pb2+ reduce defects and regulate crystallization. These improvements result in an enhanced radiative recombination. The devices achieve a maximum external quantum efficiency (EQE) of 17.09% at 478 nm and 22.66% at 485 nm, one of the highest reported for blue PeLEDs. This work provides new insights into the phase distribution in quasi-2D perovskites.
{"title":"Multifunctional Additives with Cation−π Interactions Enable High-Performance Blue Perovskite Light-Emitting Diodes","authors":"Shuxin Wang, Zhiqiu Yu, Xiang-Feng Yang, Guoyi Chen, Chaomin Dong, Hua-Hua Fu, Weijun Ke, Guojia Fang","doi":"10.1021/acsenergylett.4c03551","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03551","url":null,"abstract":"Quasi-two-dimensional (quasi-2D) perovskites, interspersed with organic intercalating cations, demonstrate significant potential in blue perovskite light-emitting quasi-2D perovskites, with organic intercalating cations, and show potential in blue perovskite light-emitting diodes (PeLEDs). However, the broad distribution of quantum wells, especially low-<i>n</i> phases, hinders energy transfer and device performance. Additionally, imperfect crystal quality and rough film surfaces further limit the efficiency. This study demonstrates that quaternary ammonium halides, like betaine hydrochloride (betaine HCl), can control phase distribution, passivate defects, and enhance crystallization in perovskite films. The cation−π interaction between betaine HCl and phenylethylammonium (PEA<sup>+</sup>) reduces low-<i>n</i> phases, while interactions with the C═O group and Pb<sup>2+</sup> reduce defects and regulate crystallization. These improvements result in an enhanced radiative recombination. The devices achieve a maximum external quantum efficiency (EQE) of 17.09% at 478 nm and 22.66% at 485 nm, one of the highest reported for blue PeLEDs. This work provides new insights into the phase distribution in quasi-2D perovskites.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"35 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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