ACS Energy Letters 最新文献

{"title":"Beyond Conventional Methods for Evaluating Charge Transfer Kinetics in Aqueous Zinc-Ion Batteries: Insights from Ultramicroelectrode Voltammetry and Marcus–Hush Theory","authors":"Ziqing Wang, Kenta Kawashima, C. Buddie Mullins","doi":"10.1021/acsenergylett.5c02639","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c02639","url":null,"abstract":"Understanding intrinsic charge transfer kinetics is essential for aqueous zinc-ion batteries (AZIBs). In this work, we employ fast-scan cyclic voltammetry with ultramicroelectrodes (UMEs) to eliminate mass transfer limitations and accurately extract the exchange current density (<i>j</i>₀) and reorganization energy (<i>λ</i>) in representative zinc electrolytes: Zn(ClO₄)₂, ZnSO₄, Zn(TfO)₂, and ZnCl₂. While the Butler–Volmer model accurately describes kinetics at low overpotentials, it fails to capture the nonlinear Tafel behavior at higher overpotentials. In contrast, the Marcus–Hush model successfully accounts for these deviations while also providing physically meaningful kinetic parameters across a wider potential range. Additionally, electrolytes with larger anions and higher viscosities exhibit lower values for <i>j</i>₀ and higher values for <i>λ</i>, indicating that solvation structure and ion–solvent interactions contribute to interfacial kinetics. These findings highlight the limitations of the Butler–Volmer model and demonstrate that Marcus–Hush theory offers a more rigorous and accurate approach for evaluating charge transfer in AZIBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"88 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141037","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":"Steric Selectivity of Isomeric Ether Solvents for Fast-Charging and Low-Temperature SiOx Anodes","authors":"Yue Yin, Gaopan Liu, Dewei Xiao, Yu Peng, Gaohong Liu, Yonggang Wang, Xiaoli Dong, Yongyao Xia","doi":"10.1021/acsenergylett.5c02521","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c02521","url":null,"abstract":"SiO_<i>x</i> anodes promise high-energy-density batteries but suffer under fast-charging and low-temperature conditions because of an unstable SiO_<i>x</i>/electrolyte interphase and sluggish Li⁺ transport in the electrolyte. Given the importance of the electrolyte, we propose an isomer-specific steric-selective solvent strategy and screen the optimized solvent. The intricate relationship between solvent structure and electrochemical performance was explored based on two isomeric cyclic ethers with the same molecular formula (C₅H₁₀O): tetrahydropyran and 2-methyltetrahydrofuran (MTHF). The steric hindrance effect induced by −CH₃ in MTHF weakens the coordination between solvent and Li⁺, facilitating the formation of anion-derived solvation structures and a robust inorganic-rich interphase with high mechanical stability. Consequently, the MTHF-based electrolyte enables the LiFePO₄|SiO_<i>x</i> pouch cell with fast-charging capability (70%-capacity retention at 6 C) and low-temperature performance (46%-discharge-capacity retention under −50 °C). This isomeric steric-selective insight links molecular structure to interfacial chemistry and electrochemical performance, guiding electrolyte design for high-energy-density batteries under extreme conditions.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"18 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141040","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":"Heterodimensional Superlattice with Electron Spin-Polarization and Se-Vacancies for Superior Sodium-Ion Storage","authors":"Runze Fan, Chenyu Zhao, Renyuan Zhang, Yurong Cai","doi":"10.1021/acsenergylett.5c02025","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c02025","url":null,"abstract":"Transition metal dichalcogenides (TMDs) are remarkable in their high specific capacity, good electrical conductivity, and weak van der Waals force between adjacent layers in sodium-ion batteries (SIBs). However, TMD anodes are limited by sluggish reaction kinetics and significant volumetric change, which can lead to poor rate performance and cycle stability. Herein, we design a V₂Se₉/SnSe composite with a heterodimensional superlattice structure that offers contributions to reaction kinetics, electrical conductivity, and structural stability demonstrated by both experimental measurements and theoretical calculations. In addition, selenium vacancies (Se-vacancies) produce rich active sites, which can improve the specific capacity. Therefore, the as-prepared V₂Se₉/SnSe demonstrates an excellent rate capability of 648.5 mA h g^–1 at 10 A g^–1 and exceptional long-term cyclability of 653.2 mAh g^–1 after 2200 cycles at 4 A g^–1.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"102 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141031","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":"Building a High-Concentration Zn2+ Cation Reservoir of Zn Anode for Long-Cycling and High-Efficiency Zinc–Bromine Flow Batteries","authors":"Haichao Huang, Wenwen Cao, Jiayou Ren, Yichan Hu, Junzhi Huang, Chenxi Dong, Lei Wei, Guojin Liang, Hui-Ming Cheng","doi":"10.1021/acsenergylett.5c02492","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c02492","url":null,"abstract":"Zinc–bromine flow batteries (ZBFBs) are highly competitive for large-scale energy storage due to their safety and low cost. However, unstable Zn²⁺ distribution within the inner Helmholtz plane (IHP) of the Zn anode often leads to dendrite growth and severe polarization, especially under high-rate and long-duration conditions. In this work, we introduce MXene nanosheets with strong Zn²⁺ cation hosting capability onto carbon felt (MXene@CF), which form a “Zn²⁺ reservoir” at the electrode–electrolyte interface, stabilizing the IHP and preventing dendrite formation. The high electric conductivity, low activation energy barrier, and Zn²⁺-enriched IHP of the MXene@CF electrode collectively alleviate the Ohmic polarization, activation polarization, and concentration polarization, respectively, thus reducing overall voltage polarization and improving energy efficiency. ZBFBs with MXene@CF maintain stable cycling for over 1000 h at 20 mAh cm^–2 and 20 mA cm^–2 with an average energy efficiency of nearly 85%.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"21 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141039","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":"Controlled Energy Offloading via Self-Destructing Agents for Safer Li-Ion Batteries","authors":"Bowen Hou, Yong Peng, Yurui Hao, Liqi Zhao, Zhaoqiang Pei, Zheng Meng, Xinyu Rui, Zhenwei Wei, Junxian Hou, Xuning Feng, Li Wang, Minggao Ouyang, Xiangming He","doi":"10.1021/acsenergylett.5c01924","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c01924","url":null,"abstract":"Addressing the critical safety challenge of thermal runaway in lithium-ion batteries, we introduce a self-destruction strategy incorporating spatiotemporal electron capture agents. In LiNi_0.8Co_0.1Mn_0.1O₂ batteries, 7 of 14 tested agents, notably phloroglucinol, effectively modulated thermal runaway pathways, reducing heat release by up to 65% and reducing the peak temperature of 176.1 °C. Phloroglucinol demonstrated particularly positive performance (70% enthalpy reduction and 72% peak temperature-rise rate reduction). Conversely, lithium iron phosphate batteries required alternative approaches as thermal output increased. By correlating agent properties like water-binding energy and phenyl reactivity with performance, we provide actionable guidelines for designing safer battery chemistries, bridging fundamental research with practical applications to mitigate the safety-energy density dilemma.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"582 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141038","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":"Heterojunction-Coated Graphite Anode Enables Fast Charging via Built-In Electric Field-Regulated Interfacial Li-Ion Transport","authors":"Yeliang Sheng, Xinyang Yue, Wei Hao, Luoyi Ding, Jiyi Zhu, Zheng Liang","doi":"10.1021/acsenergylett.5c02653","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c02653","url":null,"abstract":"The sluggish Li-ion transport kinetics across anode interfaces remain a critical bottleneck limiting the fast-charging capability of lithium-ion batteries (LIBs). Herein, we design a lithiophilic Nb₂O₅/Zr₆Nb₂O₁₇ (N/ZN) heterojunction to regulate the Li-ion transport behavior across the graphite anode interface. The tailored work function difference between Nb₂O₅ and Zr₆Nb₂O₁₇ components establishes an internal built-in electric field that synergistically addresses the challenges: (i) accelerating interfacial Li ion (Li⁺) diffusion; (ii) optimizing Li intercalation/deintercalation kinetics; (iii) lowering the desolvation energy barrier. Therefore, the graphite anode with the N/ZN coating achieves 80.9% capacity retention at 6C-rate charging while effectively suppressing Li plating. This work demonstrates a heterojunction engineering strategy that concurrently enhances ionic transport and interfacial stability, offering a pathway for developing fast-charging anodes.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"152 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127949","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":"Growth of Tin Halide Perovskite Film on Two-Dimensional Hexagonal Boron Nitride via Thermal Evaporation","authors":"Taewan Roh, Youjin Reo, Seongmin Heo, Geonwoong Park, Wonryeol Yang, Beomjoo Ham, Jehyun An, Ju-Hyun Jung, Seung-Hwa Baek, Rock-Hyun Baek, Cheol-Joo Kim, Yong-Young Noh","doi":"10.1021/acsenergylett.5c02309","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c02309","url":null,"abstract":"Tin halide perovskites have served as channel materials for p-type transistors owing to their low hole effective mass and suitable hole density. However, they suffer from uncontrolled film crystallization, leading to excessive tin vacancies and self-p-doping. In this study, we report a facile way to grow three-dimensional (3D) tin halide perovskite films by thermal evaporation on a dangling-bond-free hexagonal boron nitride (hBN) surface. The hBN, transferred onto SiO₂ as a gate dielectric/channel interlayer, offers a hydrophobic surface that promotes the crystallization of CsSnI₃ films by reducing the nucleation site density, increasing the nuclei size, and promoting the formation of uniformly oriented enlarged grains. CsSnI₃ films grown on hBN exhibit reduced pinholes and grain boundaries, reducing the concentration of tin vacancies. Thin-film transistors using these films demonstrate accelerated charge transport with large current modulation without any additives. The proposed strategy can facilitate the engineering of defect-free perovskite channel layers for integrated perovskite electronics.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"13 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145133553","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":"Current Trends in Solid-State Electrochemical Energy Conversion and Storage Devices","authors":"Venkataraman Thangadurai","doi":"10.1021/acsenergylett.5c02456","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c02456","url":null,"abstract":"Published as part of &lt;i&gt;ACS Energy Letters&lt;/i&gt; special issue “The Evolving Landscape of Energy Research: Views from the Editorial Team”. Figure 1. (a) Schematic representation showing the operating principle of a solid oxide fuel cell (O-SOFC) and ceramic proton conducting H-SOFC. Unlike SOFC, there is no fuel dilution in proton conducting fuel cells since water is produced at the oxygen electrode (cathode). (b) Schematic representation showing a thermodynamically stable cell with proposed/desired energy levels of oxidant and reductant in an electrochemical cell. (c) Schematic representation showing typical polarization curves of “ideal”, high, moderate, and poor ceramic fuel cell performance. High oxide ion conductivity (about 10&lt;sup&gt;–2&lt;/sup&gt; S/cm) in the intermediate temperature regime (500–750 °C) without structural phase transition. Electrochemical stability window of at least 1.2 V against oxygen at operating temperature. Chemical stability in the working environment including reactions at electrode/electrolyte and reactant/electrolyte interfaces during the preparation and operation. Thermodynamic stability can be achieved only by placing the bottom of the electrolyte conduction band above the highest occupied molecular orbital (HOMO) of the cathode and the top of the electrolyte valence band below the lowest unoccupied molecular orbital (LUMO) of the anode (Figure 1b). (11) Negligible electronic conductivity (due to electrons and holes) over the entire range of oxygen partial pressures and temperatures. Capable of forming dense, gastight, pore-free thin-films (about 10–20 μm) with good adhesion to anode and cathode materials, with matching thermal expansion coefficients. Low interfacial and charge transfer resistances (0.1 Ω·cm&lt;sup&gt;2&lt;/sup&gt;) between the electrolyte and electrodes (cathode and anode) and low ohmic overpotential (Figure 1c). Low-cost, nontoxic, easily prepared, and chemically stable under ambient conditions, particularly in the presence of moisture and atmospheric CO&lt;sub&gt;2&lt;/sub&gt;. Figure 2. Idealized crystal structures of (a) fluorite-type (CeO&lt;sub&gt;2&lt;/sub&gt;/Y-doped ZrO&lt;sub&gt;2&lt;/sub&gt;) (oxide ion); (b) pyrochlore (Gd&lt;sub&gt;2&lt;/sub&gt;Ti&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;7&lt;/sub&gt;) (oxide ion); (c) perovskite-type (LaGaO&lt;sub&gt;3&lt;/sub&gt;) (oxide, proton, electrons); (d) brownmillerite (Ba&lt;sub&gt;2&lt;/sub&gt;In&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;) (oxide ion); (e) ordered double perovskite (Ba&lt;sub&gt;3&lt;/sub&gt;CaNb&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;9&lt;/sub&gt;) (proton, electrons), and (f) layered perovskite (Sr&lt;sub&gt;2&lt;/sub&gt;TiO&lt;sub&gt;4&lt;/sub&gt;) (oxide ion, electrons). Unit cell axis orientation is shown for noncubic structures only. Figure 3. Schematic diagram showing ion conduction pathways (vacancy and interstitial migrations) in typical solid-state electrolytes. Panels a and b show the position of ions and vacancies before and after ion migration, respectively. The dashed circle represents a vacant position after ion migration. Filled blue circles represent dopants. Filled yellow and red circles represent mobil","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"318 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116643","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":"Substrate-Independent and Antisolvent-Free Fabrication Method for Tin Perovskite Films via Imidazole-Complexed Intermediates","authors":"Fuyuki Harata, Ryuji Kaneko, Shuaifeng Hu, Noboru Ohashi, Tomoya Nakamura, Minh Anh Truong, Richard Murdey, Atsushi Wakamiya","doi":"10.1021/acsenergylett.5c02366","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c02366","url":null,"abstract":"The fabrication of metal halide perovskite thin films, particularly those containing Sn, relies heavily on the use of antisolvents. Film quality is strongly influenced by factors such as the choice of antisolvent, the primary precursor solvent, perovskite composition, and the size and wettability of the substrates. This complexity makes process optimization challenging and impedes the development of efficient tin perovskite solar cells (PSCs). In this work, we present a vacuum-quenching with crystal growth regulator (V-CGR) method, an antisolvent- and dimethyl sulfoxide (DMSO)-free, vacuum-assisted fabrication process for tin perovskite films whereby crystal growth could be regulated through the formation of intermediate films containing an amorphous [SnI₂–(1-vinylimidazole)] complex. The V-CGR method is compatible with diverse perovskite compositions and substrates, enabling the formation of uniform tin perovskite films up to 7.5 × 7.5 cm² and allowing device fabrication on hydrophobic hole-transporting monolayers such as MeO-2PACz and 2PACz.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"34 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145084072","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":"Dual-Site Mn-Doped Vanadate Cathodes Involving Vanadium and Manganese Dual Redox Chemistry for High-Energy Aqueous Zinc-Ion Batteries","authors":"Xinghe Xu, Tianhao Wang, Xudong Zhao, Xuanhui Qu, Lifang Jiao, Yongchang Liu","doi":"10.1021/acsenergylett.5c02376","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c02376","url":null,"abstract":"Popular vanadium-oxide and manganese-oxide based cathodes have garnered considerable attention for aqueous zinc-ion batteries (AZIBs) by virtue of their high discharge capacity and high working voltage, respectively. However, the low operating voltage of vanadium-oxide//Zn batteries and low specific capacity of manganese-oxide//Zn batteries significantly limit their practical applications. Herein, the V and Mn redox reactions are simultaneously activated in an intra-/interlayer dual-site Mn-doped Mn_0.4V_1.7O₅·0.5H₂O (MnVO) material to enhance the energy density. Specifically, the intralayer Mn-ions serve as redox centers to contribute capacity in the high-voltage region, while the interlayer Mn-ions mainly act as “pillars” to strengthen the layered structure. The combined spectroscopic/imaging analyses and theoretical computations elucidate the reversible V and Mn redox chemistry accompanied by H⁺/Zn²⁺ coinsertion/extraction in MnVO. Consequently, the tailored MnVO cathode achieves a significantly enhanced energy density (1.83 and 1.42 times those of vanadium-oxide and manganese-oxide, respectively) and an ultralong cycling durability (10000 cycles) in AZIBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"1 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089593","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}