{"title":"Rationalizing Light-Induced Phase Segregation Reversal by Halide Oxidation and Diffusion in Mixed Halide Perovskites","authors":"Nuerbiya Aihemaiti, Siying Peng","doi":"10.1021/acsenergylett.4c03073","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03073","url":null,"abstract":"Lead halide perovskites are one of the most promising materials as active layers of optoelectronic devices. Phase segregation under illumination in mixed halide perovskites is one of the major issues in stable device operation. Herein, we rationalize illumination power dependent phase segregation phenomena, including two thresholds between which phase segregation occurs, and the reversal of phase segregation. Our experimental observation combining confocal photoluminescence mapping with in situ Raman spectroscopy supports the halide oxidation model. We observed phase segregation beyond the illuminated area, while the illuminated area remained mixed. Reversal of phase segregation under illumination was also observed. We propose that the spatial distribution of phase segregation is driven by halide oxidation and diffusion of the products through mass flow, as verified by light- and spatial-dependent lattice halide vibrations. Our insights into phase segregation may provide new perspectives for manipulating phase segregation by local light intensity for dynamically tunable optoelectronics.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"28 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143019995","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}
{"title":"Electrochemical Grain Refinement Enables High-Performance Lithium–Aluminum-Anode-Based All-Solid-State Batteries","authors":"Lun Zhang, Xuedong Zhang, Baiyu Guo, Zhaoyu Rong, Zhihao Yan, Bo Wang, Menglin Li, Zhenyu Wang, Lingyun Zhu, Qiao Huang, Yongfu Tang, Jianyu Huang","doi":"10.1021/acsenergylett.4c03250","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03250","url":null,"abstract":"Lithium–aluminum (Li<sub><i>x</i></sub>Al, <i>x</i> = the molar ratio of Li to Al), an important alloy anode with a specific capacity over 2 times higher than that of the carbon anode used in commercial liquid electrolyte lithium-ion batteries (LELIBs), has been proven to be a failure in LELIBs due to the notorious pulverization phenomenon. However, whether or not such pulverization persists in all solid state lithium batteries (ASSLBs) remains unclear. Herein, we show that pulverization of the Li<sub><i>x</i></sub>Al anode is mitigated in ASSLBs due to the applied external stack pressure, thus preventing the mechanical failure of the Li<sub><i>x</i></sub>Al anode in ASSLBs. Moreover, electron microscopy investigation reveals that, instead of pulverization, electrochemomechanical stress induces 2 orders of magnitude grain size reduction from a few tens of microns to a few hundred nanometers. The grain-refined Li<sub><i>x</i></sub>Al anode facilitates lithium ion transport, which improves the rate performance and specific capacity of the Li<sub><i>x</i></sub>Al anode. Consequently, the assembled single-crystal LiNi<sub>0.83</sub>Co<sub>0.12</sub>Mn<sub>0.05</sub>O<sub>2</sub>|Li<sub>10</sub>Si<sub>0.3</sub>PS<sub>6.7</sub>Cl<sub>1.8</sub>|Li<sub>0.4</sub>Al ASSLBs reach 2000 cycles with a capacity retention of 100% at 3C (13.9 mA/cm<sup>2</sup>, room temperature), at a high areal capacity of 2.1 mAh/cm<sup>2</sup>. The all-solid pouch cell with a Li<sub><i>x</i></sub>Al anode can reach an energy density of 219 Wh kg<sup>–1</sup> based on the total mass of the cell. These results demonstrate the prospect of implementing the Al-based anode in ASSLBs for practical energy storage applications.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"49 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143019996","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}
Haoran Zhou, Md Aftabuzzaman, Masud, Sung Ho Kang, Hwan Kyu Kim
{"title":"Key Materials and Fabrication Strategies for High-Performance Dye-Sensitized Solar Cells: Comprehensive Comparison and Perspective","authors":"Haoran Zhou, Md Aftabuzzaman, Masud, Sung Ho Kang, Hwan Kyu Kim","doi":"10.1021/acsenergylett.4c03579","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03579","url":null,"abstract":"For more than three decades, dye-sensitized solar cells (DSSCs) have attracted numerous researchers as viable alternatives in photovoltaic technology. It offers several advantages, such as using eco-friendly materials, inexpensive processing techniques, indoor photovoltaic potentials, and integrating photovoltaics into building applications. Nevertheless, DSSCs will require further development in manufacturing methods and materials to remain competitive with other thin-film solar technologies that offer high photovoltaic efficiency. It is essential to give an overview of the latest developments in this area and highlight the primary elements required for realizing high-performance technologies, such as photoanode modification, dye formulation, and electrolyte optimization. Recent advancements have shown promising improvements in DSSCs with copper-based electrolytes, and integrating new interface materials like preadsorbents or postadsorbents has also opened new possibilities for DSSCs. Here, we comprehensively compare and discuss the key materials and device fabrication processes for high-performance DSSCs and present future research perspectives.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"50 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143019998","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}
Yunya Zhang, Wurigumula Bao, Ethan Jeffs, Bin Liu, Bing Han, Weijie Mai, Xinyu Li, Weikang Li, Yun Xu, Bhargav Bhamwala, Alex Liu, Louis Ah, Kun Ryu, Ying Shirley Meng, Hong Gan
{"title":"Unveiling the Impacts of Charge/Discharge Rate on the Cycling Performance of Li-Metal Batteries","authors":"Yunya Zhang, Wurigumula Bao, Ethan Jeffs, Bin Liu, Bing Han, Weijie Mai, Xinyu Li, Weikang Li, Yun Xu, Bhargav Bhamwala, Alex Liu, Louis Ah, Kun Ryu, Ying Shirley Meng, Hong Gan","doi":"10.1021/acsenergylett.4c03215","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03215","url":null,"abstract":"Lithium metal batteries (LMBs) offer superior energy density and power capability but face challenges in cycle stability and safety. This study introduces a strategic approach to improving LMB cycle stability by optimizing charge/discharge rates. Our results show that slow charging (0.2C) and fast discharging (3C) significantly improve performance, with a multilayer LMB retaining over 80% capacity after 1000 cycles. Fast discharge rates promote lithium plating beneath the SEI layer, suppressing its growth and improving Coulombic efficiency, whereas slow discharge rates facilitate lithium plating above the SEI, leading to SEI accumulation. We propose a rational hypothesis linking SEI conductivity and cycling conditions and introduce an intermittent pulse discharge protocol to emulate electric vehicle applications, further improving the stability. These optimized cycling strategies enhance the LMB lifespan, utility, and safety, paving the way for broader market adoption in the years ahead.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"33 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992560","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}
{"title":"Unlocking Ultrafast Diagnosis of Retired Batteries via Interpretable Machine Learning and Optical Fiber Sensors","authors":"Taolue Zhang, Ruifeng Tan, Pinxi Zhu, Tong-Yi Zhang, Jiaqiang Huang","doi":"10.1021/acsenergylett.4c03054","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03054","url":null,"abstract":"Retired batteries are of great economic and environmental importance, which are indispensable considerations in the life cycle of lithium-ion batteries. However, existing methods for evaluating retired batteries are time- and resource-consuming, hindering efficient screening for later recycling or reuse. Herein, combining optical fiber sensors and interpretable machine learning (ML), we establish a data-driven framework for retired battery datasets with 265 cells of different chemistries (LiFePO<sub>4</sub>/graphite, LiMn<sub>2</sub>O<sub>4</sub>/graphite) and achieve ultrafast state of health diagnosis within 3 min, offering mean absolute errors of 1.17% and 2.78%, respectively. The proposed data-driven framework identifies the salient regions in the time-resolved multivariable data and helps to uncover underlying thermodynamic/kinetic aging mechanisms. We also demonstrate the incorporated thermal information obtained via optical fibers complements voltage signals by improving prediction accuracy and antinoise ability. This work not only showcases the potential of battery sensing in retired battery diagnosis but also unlocks the unexplored synergy between sensing and interpretable ML for diverse battery applications.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"71 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990757","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}
{"title":"A Conversion Aluminum Fluoride Nanowire Interlayer for Stable Lithium Metal Batteries","authors":"Wenbin Fu, Kaixi Chen, Fujia Wang, Yice Wang, Evan Wilson, Vismay Chandra, Doyoub Kim, Gleb Yushin","doi":"10.1021/acsenergylett.4c03216","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03216","url":null,"abstract":"The use of a lithium metal anode enables batteries with significantly higher energy density, but at the expense of the growth of lithium dendrites that trigger internal short circuits, induce safety risks, and reduce cycle stability. To address this challenge, here, we report the design of an aluminum fluoride nanowire membrane as a conversion interlayer to regulate lithium deposition for significantly more stable and safe lithium metal batteries. The interlayer generates a LiF-rich solid electrolyte interphase and alloy nanoparticles in contact with lithium to offer active sites guiding lithium nucleation, regulating lithium deposition, and increasing Coulombic efficiencies. With such an interlayer, lithium metal full cells show significantly improved stability compared to those with bare Cu, when paired with a LiFePO<sub>4</sub> or LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> cathode. Our results indicate that using an aluminum fluoride interlayer can be a promising strategy in realizing lithium metal batteries with high specific energy density.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"30 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990758","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}
Olivia T. Vulpin, James B. Mitchell, Lihaokun Chen, Jeonghoon Lim, Sayantan Sasmal, Nathan G. Price, Sam R. Jarvis, Shannon W. Boettcher
{"title":"Comparing Advanced Bipolar Membranes for High-Current Electrodialysis and Membrane Electrolysis","authors":"Olivia T. Vulpin, James B. Mitchell, Lihaokun Chen, Jeonghoon Lim, Sayantan Sasmal, Nathan G. Price, Sam R. Jarvis, Shannon W. Boettcher","doi":"10.1021/acsenergylett.4c03538","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03538","url":null,"abstract":"Advanced bipolar membranes (BPMs) with low water-dissociation overpotential (η<sub>wd</sub>) may enable new electrochemical technologies for electrolysis, fuel cells, acid–base synthesis, brine remediation, lithium-battery recycling, and cement production. However, these advanced BPMs have only been demonstrated in BPM water electrolysis (BPMWE) configurations where the BPM is under static compression by the porous-transport layers. It is important to study these BPMs in applications like electrodialysis where large degrees of static compression are not possible. We present a BPM electrodialysis (BPMED) platform to measure water-dissociation overpotential (η<sub>wd</sub>) and compare BPMWE and BPMED systems. We show advanced BPMs with half the η<sub>wd</sub> compared to commercial BPMs for BPMED while maintaining ∼90% current efficiency from 0.05–0.5 A cm<sup>–2</sup>. The BPMED η<sub>wd</sub> values are, however, about 0.2 V higher at 0.5 A cm<sup>–2</sup> than those for BPMWE. Regardless, these results show that BPMs developed and optimized in BPMWE applications are well-suited for next-generation high-current-density BPMED technologies.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"30 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989007","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}
{"title":"Uniform Sub-5 nm Crystalline Nickel-Based Heterojunctions for Overall Water Splitting Electrocatalysis","authors":"Yuanyuan Wang, Rui Yin, Lei Yuan, Xingmei Guo, Xiangjun Zheng, Qianqian Fan, Zhongyao Duan, Yuanjun Liu, Junhao Zhang, Shenglin Xiong","doi":"10.1021/acsenergylett.4c03097","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03097","url":null,"abstract":"Exploring a general method for constructing uniform heterostructures with sub-5 nm crystallites and dense interfaces is crucial yet challenging for advancing water electrocatalysis. Herein, a bottom-up cocrystallization strategy, involving in situ transformation of amorphous Ni–P through gas–solid reactions, is proposed to synthesize a series of nickel-based heterojunctions on carbon cloth (CC). Thereinto, interface-wealthy NiS<sub>2</sub>-Ni<sub>2</sub>P/CC with densely packed 3–4 nm crystallites demonstrates superb catalytic performance for both hydrogen and oxygen evolution. The electrolyzer merely requires cell voltages of 1.79 and 1.89 V to propel overall water splitting currents of 200 and 400 mA cm<sup>–2</sup>, respectively, outperforming the vast majority of reported nickel-based heterojunctions. Theoretical calculations reveal that charge redistribution and electronic structure modulation optimize the hydrogen and oxygen evolution pathways at the NiS<sub>2</sub> and Ni<sub>2</sub>P sides of the interfaces, respectively. Moreover, uniform hybridization with densely distributed heterointerfaces offers abundant active sites for electrocatalysis, pioneering an extendable approach for constructing advanced heterojunction catalysts for green hydrogen production.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"27 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989008","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}
Jaeyong Lee, Zach J. Hoffman, Saheli Chakraborty, Vivaan Patel, Nitash P. Balsara
{"title":"Toward Optimization of Polymer Electrolytes by Electrochemical Characterization: Poly(pentyl malonate) versus Poly(ethylene oxide)","authors":"Jaeyong Lee, Zach J. Hoffman, Saheli Chakraborty, Vivaan Patel, Nitash P. Balsara","doi":"10.1021/acsenergylett.4c03525","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03525","url":null,"abstract":"Ion transport in two polymer electrolytes, poly(ethylene oxide) (PEO) and poly(pentyl malonate) (PPM), mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is studied in the vicinity of the limiting current. The experimental measurements are in quantitative agreement with theoretical predictions based on the concentrated solution theory. The properties of two electrolytes are compared using a new plot wherein the length-normalized limiting current, <i>i</i><sub>lim</sub><i>L</i>, is plotted as a function of the length-normalized potential drop, Φ<sub>lim</sub>/<i>L</i>, in symmetric cells with electrolyte thickness, <i>L</i>. We propose that electrolyte design should aim to obtain the largest values of <i>i</i><sub>lim</sub><i>L</i> and the smallest values of Φ<sub>lim</sub>/<i>L</i>. Using this criterion, PPM/LiTFSI is a better polymer electrolyte than PEO/LiTFSI. We hope that PPM/LiTFSI will serve as a benchmark for developing next-generation polymer electrolytes.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"127 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986222","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}
Tae-Ung Wi, Zachary H Levell, Shaoyun Hao, Ahmad Elgazzar, Peng Zhu, Yuge Feng, Feng-Yang Chen, Wei Ping Lam, Mohsen Shakouri, Yuanyue Liu, Haotian Wang
{"title":"Selective and Stable Ethanol Synthesis via Electrochemical CO2 Reduction in a Solid Electrolyte Reactor","authors":"Tae-Ung Wi, Zachary H Levell, Shaoyun Hao, Ahmad Elgazzar, Peng Zhu, Yuge Feng, Feng-Yang Chen, Wei Ping Lam, Mohsen Shakouri, Yuanyue Liu, Haotian Wang","doi":"10.1021/acsenergylett.4c03091","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03091","url":null,"abstract":"Electrochemical CO<sub>2</sub> reduction to ethanol faces challenges such as low selectivity, a product mixture with liquid electrolyte, and poor catalyst/reactor stability. Here, we developed a grain-rich zinc-doped Cu<sub>2</sub>O precatalyst that presented a high ethanol Faradaic efficiency of over 40% under a current density of 350 mA·cm<sup>–2</sup>. Our density functional theory (DFT) simulation suggested that Zn atoms inside the structure have a greater carbophilicity than the Cu atoms to help facilitate *CHCHO formation, a key reaction intermediate toward ethanol instead of other C<sub>2</sub> products. A high Faradaic efficiency ratio between ethanol and ethylene (FE<sub>EtOH</sub>/FE<sub>C2H4</sub>) reached 2.34 in the zinc-doped Cu<sub>2</sub>O precatalyst, representing an over 4-fold improvement compared to bare Cu<sub>2</sub>O precatalyst. By integrating this Cu-based catalyst into a porous solid electrolyte (PSE) reactor with a salt-managing design, we achieved stable ethanol production for over 180 h under a current density of 250 mA·cm<sup>–2</sup> while maintaining ethanol selectivity at ∼30%.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"106 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981170","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}