{"title":"Vanadium-site multivalent cation doping strategy of fluorophosphate cathode for low self-discharge sodium-ion batteries","authors":"Xinyuan Wang, Qian Wang, Jiakai Zhang, Yuanzhen Ma, Miao Huang, Xiaojie Liu","doi":"10.1016/j.jechem.2024.11.003","DOIUrl":"10.1016/j.jechem.2024.11.003","url":null,"abstract":"<div><div>Na<sub>3</sub>V<sub>2</sub>O<sub>2</sub><em><sub>x</sub></em>(PO<sub>4</sub>)<sub>2</sub>F<sub>3−2</sub><em><sub>x</sub></em> (NVPOF) is considered one of the most promising cathode materials for sodium-ion batteries due to its favorable working potential and optimal theoretical specific capacity. However, its long-cycle and rate performance are significantly constrained by the low Na<sup>+</sup> electronic conductivity of NVPOF. Furthermore, the prevalent self-discharge phenomenon restricts its applicability in practical applications. In this paper, the cathode material Na<sub>3</sub>V<sub>1.84</sub>Fe<sub>0.16</sub>(PO<sub>4</sub>)<sub>2</sub>F<sub>3</sub> (<em>x =</em> 0.16) was synthesized by quantitatively introducing Fe<sup>3+</sup> into the V-site of NVPOF. The introduction of Fe<sup>3+</sup> significantly reduced the original bandgap and the energy barrier of NVPOF, as demonstrated through density functional theory calculations (DFT). When material <em>x</em> = 0.16 is employed as the cathode material for the sodium-ion battery, the Na<sup>+</sup> diffusion coefficient is significantly enhanced, exhibiting a lower activation energy of 42.93 kJ mol<sup>−1</sup>. Consequently, material <em>x</em> = 0.16 exhibits excellent electrochemical performance (rate capacity: 57.32 mA h g<sup>−1</sup> @10 C, cycling capacity: the specific capacity of 101.3 mA h g<sup>−1</sup> can be stably maintained after 1000 cycles at 1 C current density). It can also achieve a full charge state in only 2.39 min at a current density of 10 C while maintaining low energy loss across various stringent self-discharge tests. In addition, the sodium storage mechanism associated with the three-phase transition of Na<em><sub>X</sub></em>V<sub>1.84</sub>Fe<sub>0.16</sub>(PO<sub>4</sub>)<sub>2</sub>F<sub>3</sub> (<em>X =</em> 1, 2, 3) was elucidated by a series of experiments. In conclusion, this study presents a novel approach to multifunctional advanced sodium-ion battery cathode materials.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 365-376"},"PeriodicalIF":13.1,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sheraz Ahmed , Junjung Rohmat Sugiarto , Wonjoong Yoon , Muhammad Irshad , Heuntae Jo , Syeda Sidra Bibi , Soek Ki Kim , Muhammad Kashif Khan , Jaehoon Kim
{"title":"High-yield pentanes-plus production via hydrogenation of carbon dioxide: Revealing new roles of zirconia as promoter of iron catalyst with long-term stability","authors":"Sheraz Ahmed , Junjung Rohmat Sugiarto , Wonjoong Yoon , Muhammad Irshad , Heuntae Jo , Syeda Sidra Bibi , Soek Ki Kim , Muhammad Kashif Khan , Jaehoon Kim","doi":"10.1016/j.jechem.2024.11.010","DOIUrl":"10.1016/j.jechem.2024.11.010","url":null,"abstract":"<div><div>The metal oxide promoter decisively influences the overall performance of Fe catalysts in the direct hydrogenation of CO<sub>2</sub> to C<sub>5+</sub> hydrocarbons. However, the roles of metal oxide promoter for Fe catalysts, particularly ZrO<sub>2</sub>, have rarely been investigated. To plug this knowledge gap, a new Fe catalyst promoted with Na and partially reduced ZrO<em><sub>x</sub></em> (Na-FeZrO<em><sub>x</sub></em>-9) was developed in this study; the catalyst helped produce C<sub>5+</sub> hydrocarbons in remarkably high yield (26.3% at 360 °C). In contrast to ZrO<em><sub>x</sub></em>-free Fe-oxide, Na-FeZrO<em><sub>x</sub></em>-9 exhibited long-term stability for CO<sub>2</sub> hydrogenation (750 h on-stream). The findings revealed multiple roles of ZrO<em><sub>x</sub></em>. Notably, ZrO<em><sub>x</sub></em> decorated the Fe-oxide particles after calcination, thereby suppressing excess particle aggregation during the reaction, and acted as a “coke remover” to eliminate the carbon deposited on the catalyst surface. Additionally, oxygen vacancy (O<sub>v</sub>) sites in ZrO<em><sub>x</sub></em> and electron transfer from ZrO<em><sub>x</sub></em> to Fe sites facilitated the adsorption of CO<sub>2</sub> at the Zr-Fe interface.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 431-442"},"PeriodicalIF":13.1,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142757723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mengjie Hou , Lin Li , Ruisong Xu , Yunhua Lu , Jing Song , Zhongyi Jiang , Tonghua Wang , Xigao Jian
{"title":"Precursor-chemistry engineering toward ultrapermeable carbon molecular sieve membrane for CO2 capture","authors":"Mengjie Hou , Lin Li , Ruisong Xu , Yunhua Lu , Jing Song , Zhongyi Jiang , Tonghua Wang , Xigao Jian","doi":"10.1016/j.jechem.2024.11.006","DOIUrl":"10.1016/j.jechem.2024.11.006","url":null,"abstract":"<div><div>Carbon capture is an important strategy and is implemented to achieve the goals of CO<sub>2</sub> reduction and carbon neutrality. As a high energy-efficient technology, membrane-based separation plays a crucial role in CO<sub>2</sub> capture. It is urgently needed for membrane-based CO<sub>2</sub> capture to develop the high-performance membrane materials with high permeability, selectivity, and stability. Herein, ultrapermeable carbon molecular sieve (CMS) membranes are fabricated by pyrolyzing a finely-engineered benzoxazole-containing copolyimide precursor for efficient CO<sub>2</sub> capture. The microstructure of CMS membrane has been optimized by initially engineering the precursor-chemistry and subsequently tuning the pyrolysis process. Deep insights into the structure-property relationship of CMSs are provided in detail by a combination of experimental characterization and molecular simulations. We demonstrate that the intrinsically high free volume environment of the precursor, coupled with the steric hindrance of thermostable contorted fragments, promotes the formation of loosely packed and ultramicroporous carbon structures within the resultant CMS membrane, thereby enabling efficient CO<sub>2</sub> discrimination via size sieving and affinity. The membrane achieves an ultrahigh CO<sub>2</sub> permeability, good selectivity, and excellent stability. After one month of long-term operation, the CO<sub>2</sub> permeability in the mixed gas is maintained at 11,800 Barrer, with a CO<sub>2</sub>/N<sub>2</sub> selectivity exceeding 60. This study provides insights into the relationship between precursor-chemistry and CMS performance, and our ultrapermeable CMS membrane, which is scalable using thin film manufacturing, holds great potential for industrial CO<sub>2</sub> capture.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 421-430"},"PeriodicalIF":13.1,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142758923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yong Gang , Lu Xu , Silong Tu , Shusen Jiang , Yan Zhang , Hao Wang , Cheng Li , Xin Li
{"title":"Synergistic strain engineering of the perovskite films for improving flexible inverted perovskite solar cells under convex bending","authors":"Yong Gang , Lu Xu , Silong Tu , Shusen Jiang , Yan Zhang , Hao Wang , Cheng Li , Xin Li","doi":"10.1016/j.jechem.2024.11.008","DOIUrl":"10.1016/j.jechem.2024.11.008","url":null,"abstract":"<div><div>Flexible perovskite solar cells (fPSCs) have demonstrated commercial viability because of their promising lightness, flexibility, and low-cost advantages. However, in most applications, the fPSCs suffer from constant external stress, such as being kept at a convex bending state, imposing external stress on the brittle perovskite films and causing the fPSCs long-term stability problems. Overcoming these issues is vital. Herein, we propose an effective way to enhance the stability of the fPSCs under convex bending by modulating the residual stress of perovskite film for the first time. Specifically, we have carefully designed a synergistic strain engineering to toughen the perovskite films by introducing 1-butyl-3-methylimidazolium tetrafluoroborate, citric acid, and a novel cross-linker, 5-(1,2-dithiolan-3-yl) pentanoate into perovskite films simultaneously. Besides passivating the perovskite films, the multiple additives effectively convert the residual stress within the perovskite films from tensile to compressive type to alleviate the detrimental impact of bending on the flexible perovskite films. As a result, the optimal efficiencies of triple-additive modified fPSCs have achieved 22.19% (0.06 cm<sup>2</sup>) and 19.44% (1.02 cm<sup>2</sup>). More importantly, the strategy could significantly improve the stability of the perovskite films and fPSCs at a convex bending state. Our approach is inductive for the future practical field applications of high-performance fPSCs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 271-281"},"PeriodicalIF":13.1,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yating Huang , Jiajun Wang , Wei Zhao , Lujun Huang , Jinpeng Song , Yajie Song , Shaoshuai Liu , Bo Lu
{"title":"High-entropy sulfides enhancing adsorption and catalytic conversion of lithium polysulfides for lithium-sulfur batteries","authors":"Yating Huang , Jiajun Wang , Wei Zhao , Lujun Huang , Jinpeng Song , Yajie Song , Shaoshuai Liu , Bo Lu","doi":"10.1016/j.jechem.2024.11.002","DOIUrl":"10.1016/j.jechem.2024.11.002","url":null,"abstract":"<div><div>Lithium-sulfur (Li-S) batteries with high energy density suffer from the soluble lithium polysulfide species. Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commonly have limited catalytic abilities to improve battery performance. Herein, based on the Hume-Rothery rule and solvothermal method, the high-entropy sulfide NiCoCuTiVS<em><sub>x</sub></em> derived from Co<sub>9</sub>S<sub>8</sub> was designed and synthesized, to realize the combination of small local strain and excellent catalytic performance. With all five metal elements (Ni, Co, Cu, Ti, and V) capable of chemical interactions with soluble polysulfides, NiCoCuTiVS<em><sub>x</sub></em> exhibited strong chemical confinement of polysulfides and promoted fast kinetics for polysulfides conversion. Consequently, the S/NiCoCuTiVS<em><sub>x</sub></em> cathode can maintain a high discharge capacity of 968.9 mA h g<sup>−1</sup> after 200 cycles at 0.5 C and its capacity retention is 1.3 times higher than that of S/Co<sub>9</sub>S<sub>8</sub>. The improved cycle stability can be attributed to the synergistic effect originating from the multiple metal elements, coupled with the reduced nucleation and activation barriers of Li<sub>2</sub>S. The present work opens a path to explore novel electrocatalyst materials based on high entropy materials for the achievement of advanced Li-S batteries.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 263-270"},"PeriodicalIF":13.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yirong Xiao , Le Yang , Chaoyuan Zeng , Ze Hua , Shuangquan Qu , Niaz Ahmad , Ruiwen Shao , Wen Yang
{"title":"Suppressing high voltage chemo-mechanical degradation in single crystal nickel-rich cathodes for high-performance all-solid-state lithium batteries","authors":"Yirong Xiao , Le Yang , Chaoyuan Zeng , Ze Hua , Shuangquan Qu , Niaz Ahmad , Ruiwen Shao , Wen Yang","doi":"10.1016/j.jechem.2024.10.051","DOIUrl":"10.1016/j.jechem.2024.10.051","url":null,"abstract":"<div><div>Sulfide-based all-solid-state lithium batteries suffer from electrochemo-mechanical damage to Ni-rich oxide-based cathode active materials (CAMs), primarily caused by severe volume changes, results in significant stress and strain, causes micro-cracks and interfacial contact loss at potentials > 4.3 V(vs. Li/Li<sup>+</sup>). Quantifying micro-cracks and voids in CAMs can reveal the degradation mechanisms of Ni-rich oxide-based cathodes during electrochemical cycling. Nonetheless, the origin of electrochemical-mechanical damage remains unclear. Herein, We have developed a multifunctional PEG-based soft buffer layer (SBL) on the surface of carbon black (CB). This layer functions as a percolation network in the single crystal LiNi<sub>0.83</sub>Co<sub>0.07</sub>Mn<sub>0.1</sub>O<sub>2</sub> and Li<sub>6</sub>PS<sub>5</sub>Cl composite cathode layer, ensuring superior ionic conductivity, reducing void formation and particle cracking, and promoting uniform utilization of the cathode active material in all-solid-state lithium batteries (ASSLBs). High-angle annular dark-field STEM combined with nanoscale X-ray holo-tomography and plasma-focused ion beam scanning electron microscopy confirmed that the PEG-based SBL mitigated strain induced by reaction heterogeneity in the cathode. This strain produces lattice stretches, distortions, and curved transition metal oxide layers near the surface, contributing to structural degradation at elevated voltages. Consequently, ASSLBs with a LiNi<sub>0.83</sub>Co<sub>0.07</sub>Mn<sub>0.1</sub>O<sub>2</sub> cathode containing LCCB-10 (CB/PEG mass ratio: 100/10) demonstrate a high areal capacity (2.53 mAh g<sup>−1</sup>/0.32 mA g<sup>−1</sup>) and remarkable rate capability (0.58 mAh g<sup>−1</sup> at 1.4 mA g<sup>−1</sup>), with 88% capacity retention over 1000 cycles.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 377-385"},"PeriodicalIF":13.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anastasios I. Tsiotsias , Eleana Harkou , Nikolaos D. Charisiou , Victor Sebastian , Dhanaji R. Naikwadi , Bart van der Linden , Atul Bansode , Dragos Stoian , George Manos , Achilleas Constantinou , Maria A. Goula
{"title":"Very low Ru loadings boosting performance of Ni-based dual-function materials during the integrated CO2 capture and methanation process","authors":"Anastasios I. Tsiotsias , Eleana Harkou , Nikolaos D. Charisiou , Victor Sebastian , Dhanaji R. Naikwadi , Bart van der Linden , Atul Bansode , Dragos Stoian , George Manos , Achilleas Constantinou , Maria A. Goula","doi":"10.1016/j.jechem.2024.11.001","DOIUrl":"10.1016/j.jechem.2024.11.001","url":null,"abstract":"<div><div>Herein, the effect of the Ru:Ni bimetallic composition in dual-function materials (DFMs) for the integrated CO<sub>2</sub> capture and methanation process (ICCU-Methanation) is systematically evaluated and combined with a thorough material characterization, as well as a mechanistic (in-situ diffuse reflectance infrared fourier-transform spectroscopy (in-situ DRIFTS)) and computational (computational fluid dynamics (CFD) modelling) investigation, in order to improve the performance of Ni-based DFMs. The bimetallic DFMs are comprised of a main Ni active metallic phase (20 wt%) and are modified with low Ru loadings in the 0.1–1 wt% range (to keep the material cost low), supported on Na<sub>2</sub>O/Al<sub>2</sub>O<sub>3</sub>. It is shown that the addition of even a very low Ru loading (0.1–0.2 wt%) can drastically improve the material reducibility, exposing a significantly higher amount of surface-active metallic sites, with Ru being highly dispersed over the support and the Ni phase, while also forming some small Ru particles. This manifests in a significant enhancement in the CH<sub>4</sub> yield and the CH<sub>4</sub> production kinetics during ICCU-Methanation (which mainly proceeds via formate intermediates), with 0.2 wt% Ru addition leading to the best results. This bimetallic DFM also shows high stability and a relatively good performance under an oxidizing CO<sub>2</sub> capture atmosphere. The formation rate of CH<sub>4</sub> during hydrogenation is then further validated via CFD modelling and the developed model is subsequently applied in the prediction of the effect of other parameters, including the inlet H<sub>2</sub> concentration, inlet flow rate, dual-function material weight, and reactor internal diameter.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 309-328"},"PeriodicalIF":13.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhuohang Li , Ying Zhang , Xiang Li , Ruizhi Liang , Ye Tian , Ke Chu
{"title":"Construction of W1-Zn dinuclear sites to boost nitrite electroreduction to ammonia","authors":"Zhuohang Li , Ying Zhang , Xiang Li , Ruizhi Liang , Ye Tian , Ke Chu","doi":"10.1016/j.jechem.2024.10.054","DOIUrl":"10.1016/j.jechem.2024.10.054","url":null,"abstract":"<div><div>Electroreduction of nitrite to ammonia (NO<sub>2</sub>RR) is recognized as an appealing method for achieving renewable NH<sub>3</sub> production and waste NO<sub>2</sub><sup>−</sup> removal. Herein, monodispersed W-doped ZnO (W<sub>1</sub>-ZnO) is developed as an efficient NO<sub>2</sub>RR catalyst. Theoretical simulations and in situ spectroscopic measurements unravel that the enhanced NO<sub>2</sub>RR property of W<sub>1</sub>-ZnO originates from the creation of active W<sub>1</sub>-Zn dinuclear sites to selectively activate NO<sub>2</sub><sup>−</sup> and enhance the protonation energetics of NO<sub>2</sub><sup>−</sup>-to-NH<sub>3</sub> pathway, whilst repelling the competing H<sub>2</sub> evolution. Strikingly, W<sub>1</sub>-ZnO equipped in flow cell shows an impressive NO<sub>2</sub>RR performance with NH<sub>3</sub> yield rate of 970 μmol h<sup>−1</sup> cm<sup>−2</sup> and NH<sub>3</sub>-Faradaic efficiency of 94.5%.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 302-308"},"PeriodicalIF":13.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701603","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jia Zhang , Jianwei Li , Guofeng Jia , Huaiyou Wang , Min Wang
{"title":"Improving Na3V2(PO4)2F3 half-cell performance with NaBF4-enhanced sodium difluoro(oxalato)borate electrolyte","authors":"Jia Zhang , Jianwei Li , Guofeng Jia , Huaiyou Wang , Min Wang","doi":"10.1016/j.jechem.2024.10.053","DOIUrl":"10.1016/j.jechem.2024.10.053","url":null,"abstract":"<div><div>The global shift towards low-carbon energy storage has increased interest in sodium-ion batteries (SIBs) as a safer, cost-effective alternative to lithium-ion batteries. However, the commercial viability has been limited by compatibility issues between high-energy-density cathode materials, such as Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>F<sub>3</sub> (NVPF), and high-voltage electrolytes. Addressing the challenges, H-NaODFB (comprising 93.91% NaODFB and 5.85% NaBF<sub>4</sub>) electrolyte significantly improves the electrochemical performance and stability of NVPF cathodes. Na/NVPF half-cells using H-NaODFB electrolyte retained 92.4% capacity after 900 cycles, while Na/Na symmetric cells demonstrated a cycle life exceeding 600 h at 0.5 mA cm<sup>−2</sup>. The superior performance is attributed to improved Na<sup>+</sup> (de)intercalation reversibility, lower interfacial impedance (619.8 vs. 10,650.0 Ω), and faster reaction kinetics compared to NaODFB alone. Advanced time of flight-secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS) and aberration corrected transmission electron microscope (AC-TEM), combined with first-principles calculations, revealed that NaBF<sub>4</sub> in the H-NaODFB electrolyte plays a critical role in forming a stable cathode electrolyte interphase (CEI). The CEI consists of an initial inorganic and organic layer, followed by a fluoroborate layer, and finally a stable organic–inorganic polymeric layer, enhancing electrode stability and preventing over-oxidation. These findings provide valuable insights for designing high-performance electrolytes for SIBs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 340-352"},"PeriodicalIF":13.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748441","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mengyu Rong , Yifu Zhang , Xianfang Tan , Yang Wang , Na Gao , Chi Huang , Changgong Meng
{"title":"Breath inspired multifunctional low-cost inorganic colloidal electrolyte for stable zinc metal anode","authors":"Mengyu Rong , Yifu Zhang , Xianfang Tan , Yang Wang , Na Gao , Chi Huang , Changgong Meng","doi":"10.1016/j.jechem.2024.10.049","DOIUrl":"10.1016/j.jechem.2024.10.049","url":null,"abstract":"<div><div>The practical application of aqueous zinc-ion batteries (AZIBs) is primarily constrained by issues such as corrosion, zinc dendrite formation, and the hydrogen evolution reaction occurring at the zinc metal anode. To overcome these challenges, strategies for optimizing the electrolyte are crucial for enhancing the stability of the zinc anode. Inspired by the role of hemoglobin in blood cells, which facilitates oxygen transport during human respiration, an innovative inorganic colloidal electrolyte has been developed: calcium silicate-ZnSO<sub>4</sub> (denoted as CS-ZSO). This electrolyte operates in weak acidic environment and releases calcium ions, which participate in homotopic substitution with zinc ions, while the solvation environment of hydrated zinc ions in the electrolyte is regulated. The reduced energy barrier for the transfer of zinc ions and the energy barrier for the desolvation of hydrated ions imply faster ion transfer kinetics and accelerated desolvation processes, thus favoring the mass transfer process. Furthermore, the silicate colloidal particles act as lubricants, improving the transfer of zinc ions. Together, these factors contribute to the more uniform concentration of zinc ions at the electrode/electrolyte interface, effectively inhibiting zinc dendrite formation and reducing by-product accumulation. The Zn//CS-ZSO//Zn symmetric cell demonstrates stable operation for over 5000 h at 1 mA cm<sup>−2</sup>, representing 29-fold improvement compared to the Zn//ZSO//Zn symmetric cell, which lasts only 170 h. Additionally, the Zn//CS-ZSO//Cu asymmetric cell shows stable average Coulombic efficiency (CE) exceeding 99.6% over 2400 cycles, significantly surpassing the performance of the ZSO electrolyte. This modification strategy for electrolytes not only addresses key limitations associated with zinc anodes but also provides valuable insights into stabilizing anodes for the advancement of high-performance aqueous zinc-ion energy storage systems.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 218-229"},"PeriodicalIF":13.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}