Xiaoming Liu, Zhengwu Fang, Yubin Zhang, Yan Wang, W. Beck Andrews, Katsuyo Thornton, Neil P. Dasgupta, Miaofang Chi
{"title":"Unraveling the Origin of Grain Boundary Lithium Deficiency in Ceramic Solid Electrolytes","authors":"Xiaoming Liu, Zhengwu Fang, Yubin Zhang, Yan Wang, W. Beck Andrews, Katsuyo Thornton, Neil P. Dasgupta, Miaofang Chi","doi":"10.1021/acsenergylett.5c00117","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00117","url":null,"abstract":"Realizing solid electrolytes with low grain-boundary (GB) resistance is critical for advancing all-solid-state batteries. High GB resistance in SEs is often attributed to deficiencies in mobile ions at these boundaries; yet, when and how these deficiencies form during synthesis remain unclear. Here, we use a unique in situ scanning transmission electron microscopy setup to guide solid electrolyte crystallization during annealing, enabling real-time observation of GB formation at the atomic scale, with Li<sub>0.33</sub>La<sub>0.56</sub>TiO<sub>3</sub> as a model SE. We reveal an ultrathin, less than 1.5 nm thick, lithium-deficient layer that emerges at the crystallization front upon crystallization and persists as two adjacent crystals fuse to form a GB. We offer two hypotheses for the origin of the lithium-deficient layer, one based on thermodynamic stabilization and the other on kinetic constraints. Our results provide guidelines for designing synthesis strategies to reduce GB resistance in solid electrolytes.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"21 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695829","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}
Qingxia Hu, Mengjiao Sun, Yunchun Zha, Guiquan Zhao, Hanlin Tang, Li Yang, Mou Yang, Bohuai Pang, Yongjiang Sun, Hong Guo
{"title":"Ti Substitution Strategy Improves Electrochemical Performance of Na3V2(PO4)2F3 Cathode","authors":"Qingxia Hu, Mengjiao Sun, Yunchun Zha, Guiquan Zhao, Hanlin Tang, Li Yang, Mou Yang, Bohuai Pang, Yongjiang Sun, Hong Guo","doi":"10.1021/acsenergylett.5c00315","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00315","url":null,"abstract":"NASICON-type Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>F<sub>3</sub> (NVPF) is a promising cathode for sodium-ion batteries (SIBs), but its performance is hindered by Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP) impurities and intrinsic limitations. To overcome these challenges, Ti-substituted NVPF cathodes are successfully synthesized using the sol–gel method in this study. Theoretical calculations and advanced analyses confirm that substituting Ti ions for V in the NVPF lattice effectively eliminates NVP impurities, mitigates the low-voltage plateau issue, and enhances both electronic conductivity and sodium-ion diffusion kinetics. Hence, the optimized Na<sub>3</sub>V<sub>1</sub>.<sub>95</sub>Ti<sub>0</sub>.<sub>05</sub>(PO<sub>4</sub>)<sub>2</sub>F<sub>3</sub> cathode demonstrated a high initial capacity of 129.10 mAh g<sup>–1</sup> at 0.2 C. Notably, it exhibited excellent cycling stability, with capacity retentions of 91.98% after 500 cycles at 5 C and 81.14% after 6000 cycles at 30 C, significantly outperforming the unsubstituted NVPF sample. This study provides a practical new approach for the development of high-performance cathode materials for SIBs and is expected to accelerate the commercialization process of SIBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"183 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672299","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":"Elucidating Charge Carrier Solvation in Biredox Eutectic Electrolytes for Nonaqueous Symmetrical Organic Redox Flow Batteries","authors":"Chengxin Peng, Yunjie Cao, Wanghao Li, Yue Liu, Zhou Zhang, Liang Wang, Wenjing Tang, Ting Yi, Shixue Dou, Yu Zhao","doi":"10.1021/acsenergylett.5c00150","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00150","url":null,"abstract":"Charge carrier solvation is crucial for mass transfer rates and redox kinetics of redox couples in organic redox flow batteries (ORFBs), yet it remains underexplored. This study employs molecular dynamics simulations to investigate charge carrier solvation in biredox eutectic electrolytes (BEEs) under diverse solvent and salt conditions. Results demonstrate that acetonitrile (ACN) molecules preferentially occupy the primary solvation shell of the bis(trifluoromethanesulfonimide) anions (TFSI<sup>–</sup>) in the catholyte and the tetrabutylammonium cations (TBA<sup>+</sup>) in the anolyte, forming charge carrier solvation, thus decoupling the molecular interactions within the BEEs and accelerating the redox kinetics in ORFBs. With an optimized ACN-TBATFSI electrolyte, a prototype symmetrical flow cell can achieve a high output voltage of 2.35 V, high material utilization of 93%, and stable cyclability with a capacity retention rate of 99.97% per cycle after 1200 cycles. This work highlights the potential of modulating the charge carrier solvation to enhance the electrochemical performance of ORFBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"15 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672298","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":"Bismuth Confined in Thick Nitrogen-Doped Carbon for Durable Low-Temperature Potassium-Ion Batteries","authors":"Guanghai Chen, Biao Feng, Gengchen Xu, Qinghua Gong, Lijie Yan, Changkai Zhou, Jietao Jiang, Lijun Yang, Qiang Wu, Xizhang Wang, Zheng Hu","doi":"10.1021/acsenergylett.4c03489","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03489","url":null,"abstract":"Bismuth is an alloying-type anode for potassium-ion batteries (PIBs) but faces the challenges of large volume expansion and sluggish potassiation/depotassiation kinetics. Herein, a composite of Bi nanoparticles confined in 10 nm-thick nitrogen-doped carbon layer (Bi@NC) exhibits notable rate capability (333 mAh g<sup>–1</sup>@30 A g<sup>–1</sup>) and cycling stability (290 mAh g<sup>–1</sup>@10 A g<sup>–1</sup> after 2000 cycles) in K-storage. The high performance of Bi@NC is mainly ascribed to the encapsulation of Bi with thick N-doped carbon and a partial K<sup>+</sup>-solvent co-intercalation mechanism in the ether-based electrolyte, which enable the formation of a conductive c-K<sub>3</sub>Bi discharge product and stable solid electrolyte interphase, ensuring loss-free pulverization while avoiding high energy-consuming desolvation, leading to fast charge transfer kinetics even at low temperature. Accordingly, the PIB assembled with the Bi@NC anode and TiS<sub>2</sub> cathode exhibits exceptional rate and cycling performance especially at −40 °C. This study provides an advanced Bi@NC anode for PIBs with exceptional low-temperature performance.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"90 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660830","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}
Mingyu Ma, Gang Ye, Soyeong Jang, Yazhuo Kuang, Linlong Zhang, Shuyan Shao, L. Jan Anton Koster, Derya Baran, Jian Liu
{"title":"Realizing an N-Type Organic Thermoelectric ZT of 0.46","authors":"Mingyu Ma, Gang Ye, Soyeong Jang, Yazhuo Kuang, Linlong Zhang, Shuyan Shao, L. Jan Anton Koster, Derya Baran, Jian Liu","doi":"10.1021/acsenergylett.4c03590","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03590","url":null,"abstract":"The performance of n-type organic thermoelectric materials is significantly limited by a lack of a deep understanding of the structure–property relationship. In this study, we aim to establish a connection between the molecular structure and the density of states (DOS) profile related to thermoelectric performance. We synthesized three new diketopyrrolopyrrole-based polymers, each functionalized with amphipathic side chains. The only difference among these polymers is the number of sp<sup>2</sup>-N substitutions. Our findings indicate that as the number of substitutions increases, the DOS profile widens and intensifies, creating new peaks that extend toward the bandgap. This enables more efficient doping and coherent charge transport. Consequently, we achieved a high electrical conductivity of 63.8 S cm<sup>–1</sup>, a power factor of 111.8 μW m<sup>–1</sup> K<sup>–2</sup>, and a ZT of 0.46, representing a significant advancement in n-type organic thermoelectrics. This work provides valuable guidelines for designing high-performance thermoelectric materials by rationally tailoring the DOS profile.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"70 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654118","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}
Muhammad Irfan Ullah, Xiaobo Ding, Yang Liu, Yuquan Zou, Qura Tul Ain, Lin Yuan, Haotian Gao, Yu Yin, Ihsan Ullah, Guozheng Shi, Xiangqiang Pan, Zeke Liu, Wanli Ma
{"title":"Surface Configuration Enables PbSe Quantum Dot Solar Cells with Efficiency beyond 12%","authors":"Muhammad Irfan Ullah, Xiaobo Ding, Yang Liu, Yuquan Zou, Qura Tul Ain, Lin Yuan, Haotian Gao, Yu Yin, Ihsan Ullah, Guozheng Shi, Xiangqiang Pan, Zeke Liu, Wanli Ma","doi":"10.1021/acsenergylett.4c03326","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03326","url":null,"abstract":"Lead selenide (PbSe) quantum dots (QDs) are promising materials for optoelectronic devices owing to their strong confinement and high multiple exciton generation. Nevertheless, their full potential remains unrealized, hampered by the challenges of complex synthesis and insufficient passivation. Here, we have devised an optimized surface configuration strategy based on a directly synthesized semiconductive QD ink system. By integrating tailored passivation through a bifunctional molecule, we significantly improved both the optoelectronic properties and the colloidal stability of the QD inks. Consequently, the photovoltaic devices attained a power conversion efficiency (PCE) of 12.07%, marking the highest reported value among all PbSe QD solar cells. Additionally, the QD inks exhibit colloidal stability for over two months, demonstrating outstanding long-term performance. These results emphasize the efficacy of this method in producing high-performance, enduring PbSe QDs for optoelectronic applications.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"214 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654119","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}
Advay Shirwalkar, Manjodh Kaur, Sichen Zhong, Max Pupucevski, Keda Hu, Yushan Yan, Judith Lattimer, James McKone
{"title":"Comparing Intrinsic Catalytic Activity and Practical Performance of Ni- and Pt-Based Alkaline Anion Exchange Membrane Water Electrolyzer Cathodes","authors":"Advay Shirwalkar, Manjodh Kaur, Sichen Zhong, Max Pupucevski, Keda Hu, Yushan Yan, Judith Lattimer, James McKone","doi":"10.1021/acsenergylett.5c00439","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00439","url":null,"abstract":"The stringent cost and performance requirements of renewable hydrogen production systems dictate that electrolyzers benefit from the use of nonprecious catalysts only if they deliver the same level of activity and durability as their precious metal counterparts. Here we report on recent work to understand interrelationships between the intrinsic activity of Ni- and Pt-based electrolyzer cathode catalysts and their performance in zero-gap alkaline water electrolyzer assemblies. Our results suggest that nanoparticulate Ni–Mo exhibits HER activity that is roughly 10-fold lower than Pt–Ru on the basis of turnover frequency under low (≤100 mV) polarization conditions. We further found that the HER activity of Ni–Mo/C cathodes is inhibited by aryl piperidinium anion-exchange ionomers bearing bicarbonate counter-anions. After addressing this poisoning effect, we produced electrolyzer assemblies based on Ni–Mo/C cathodes that delivered indistinguishable current density vs cell potential relationships compared to otherwise identical assemblies with Pt–Ru cathodes. This result indicates that the contribution of the cathode to the total cell polarization is small, even for the less active Ni–Mo/C catalyst, and further implies that Pt-based cathodes can indeed be replaced by nonprecious alternatives with no loss in performance.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"95 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640187","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":"Achieving Safe and Stable Lithium-Based Batteries via Molecular Dipole Interactions","authors":"Siru He, Peide Zhu, Zhixin Liu, Lida Wang, Zhitong Li, Yuejiao Chen, Libao Chen, Xingzhu Wang, Baomin Xu","doi":"10.1021/acsenergylett.5c00710","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00710","url":null,"abstract":"The lithium metal battery technology, utilizing a lithium metal anode and high-voltage cathodes, offers high power density, but faces challenges such as dendrite growth, dead lithium, and poor interfacial dynamics. Here, a nonflammable electrolyte is proposed based on dipole interactions between HTFP and DME solvents, enhancing Li<sup>+</sup>-FSI<sup>–</sup> coordination and reducing Li<sup>+</sup> desolvation energy. The dipole interaction lowers the LUMO energy of solvated FSI<sup>–</sup>, promoting the formation of a stable interfacial phase and efficient lithium deposition and stripping. Consequently, Li||NCM811 cells exhibit ∼90% capacity retention over 500 cycles with >99.5% Coulombic efficiency and also perform well at −30 °C. In addition, commercial graphite||NCM523 pouch cells achieve 90% capacity retention after 500 cycles and high safety.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"34 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654120","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}
Chaozheng Liu, Bo Lin, Zhenglin Li, Chuhang Liu, Yao Wang, Weimin Chen, Wangwang Xu, Mei-Chun Li, Shu Hong, Lei Zhang, Pei Yang, Min Wang, Kangning Zhao, Changtong Mei
{"title":"A Janus Membrane with Asymmetrical Proton Transport for Cross-Communication Harmony for an Extreme Lean Electrolyte Zn–V Battery","authors":"Chaozheng Liu, Bo Lin, Zhenglin Li, Chuhang Liu, Yao Wang, Weimin Chen, Wangwang Xu, Mei-Chun Li, Shu Hong, Lei Zhang, Pei Yang, Min Wang, Kangning Zhao, Changtong Mei","doi":"10.1021/acsenergylett.5c00369","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c00369","url":null,"abstract":"The Zn metal anode demands a reduction in water activity and proton concentration to prevent undesirable side reactions, while the V-based cathode necessitates water as a “lubricant” and protons as intercalation guests, presenting a challenge in balancing these needs. Herein, we report a Janus membrane with asymmetrical proton transport for cross-communication harmony in Zn–V batteries, designed to harmonize these contrasting requirements. The MXene-rich phase blocks the proton/water transport through the F-termination site and effectively suppresses dendrite formation through epitaxial growth. Meanwhile, the proton selective cellulose-rich phase (H<sup>+</sup>/Zn<sup>2+</sup> selectivity of over 21) stabilizes the cathode/electrolyte interface by capturing dissolved vanadium and enhancing proton intercalation into the cathode. This designed Janus membrane enables a practical Zn–V full battery at a high depth of discharge of 66.7% and extreme lean electrolyte (1 g/Ah) conditions, enabling the high energy zinc battery (214.8 Wh/kg<sub>electrode</sub>). Our approach introduces a sustainable separator for long-lasting, high-performance zinc metal batteries.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"183 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654121","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":"Machine Learning Prediction of Organic–Inorganic Halide Perovskite Solar Cell Performance from Optical Properties","authors":"Ruiqi Zhang, Brandon Motes, Shaun Tan, Yongli Lu, Meng-Chen Shih, Yilun Hao, Karen Yang, Shreyas Srinivasan, Moungi G. Bawendi, Vladimir Bulović","doi":"10.1021/acsenergylett.4c03592","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c03592","url":null,"abstract":"Numerical toolsets have the potential to enable accelerated development of hybrid organic–inorganic halide perovskite (HOIP) solar cells. In the present study, we develop a machine learning (ML) approach that accurately predicts the current–voltage behavior of 3D/2D-structured (FAMA)Pb(IBr)<sub>3</sub>/OABr HOIP solar cells under AM1.5 illumination. Using measured responses from 368 devices, we train a neural network (NN) with three optical inputs of constituent HOIP films (transmission, spectrally resolved photoluminescence, and time-resolved photoluminescence) to predict the solar cell’s open-circuit voltage (Voc), short-circuit current (Jsc), and fill factors (FF). The model achieves 91%, 94%, and 89% accuracy for 95% of Voc, Jsc, and FF predictions, with coefficient of determination (R<sup>2</sup>) values of 0.47, 0.77, and 0.58, respectively. By linking ML predictions to extracted physical parameters from the measured HOIP films optical properties, we identify key factors influencing the prediction results. Furthermore, we develop separate ML-classification algorithms that identify degraded solar cells with >90% accuracies using the same optical data. This work demonstrates an efficient, nondestructive approach for HOIP solar cell assessment that can assist in accelerating the next generation of perovskite solar cell developments.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"17 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635388","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}