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Interfacial Zn^(2+)-solvation regulator towards reversible and stable Zn anode

Journal of Energy Chemistry 2025年第1期100卷 684-692页

作者： Miao Zhou Xiongbin Luo Hang Li Shan Guo Zhuang Tong Xiaotao Zhou Xu Li Zhaohui Hou Shuquan Liang Guozhao Fang College of Mechanical Engineering Key Laboratory of Hunan Province for Advanced Carbon-based Functional MaterialsHunan Institute of Science and TechnologyYueyang 414006HunanChina School of Materials Science and Engineering Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan ProvinceCentral South UniversityChangsha 410083HunanChina College of Materials and Metallurgy Guizhou UniversityGuiyang 550000GuizhouChina National Energy Metal Resources and New Materials Key Laboratory Central South UniversityChangsha 410083HunanChina

Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen ***,the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn^(2+)-solvation and deposition behavior demand comprehensive *** molecules endowed with special functional groups (such as hydroxyl,carboxyl,etc.) have the potential to significantly optimize the solvation structure of Zn^(2+)and regulate the interfacial electric double layer (EDL).By increasing nucleation overpotential and decreasing interfacial free energy,these functional groups facilitate a lower critical nucleation radius,thereby forming an asymptotic nucleation model to promote uniform Zn ***,this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense *** interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques,indicating that the H-Zn anode exhibits dendrite-free growth,no by-products,and weak hydrogen evolution,in sharp contrast to the bare ***,the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 ***,the H-Zn//NH_(4)V_(4)O^(10)(NVO) full battery showcases exceptional cycle stability,retaining 95.04%capacity retention after 400 cycles at a large current density of 5 A g^(-1).This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.

关键词： Aqueous zinc-ion batteries Zn^(2+)-solvation structure Interfacial reaction Asymptotic nucleation model Reversible and stable Zn anode

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Understanding the iodine electrochemical behaviors in aqueous zinc batteries

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Journal of Energy Chemistry 2025年第2期101卷 402-415,I0009页

作者： Xuefang Xie Xiaoxin Xu Shuquan Liang Guozhao Fang College of Physical Science and Technology Xinjiang UniversityUrumqi 830017XinjiangChina Xinjiang Key Laboratory of Solid State Physics and Devices Xinjiang UniversityUrumqi 830046XinjiangChina School of Materials Science&Engineering Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan ProvinceCentral South UniversityChangsha 41003 HunanChina National Energy Metal Resources and New Materials Key Laboratory Central South UniversityChangsha 410083HunanChina

Iodine is widely used in aqueous zinc batteries(ZBs)due to its abundant resources,low cost,and active redox *** addition to the active material in zinc-iodine batteries,iodine also plays an important role in other ZBs,such as regulating the electrochemical behavior of zinc ions,promoting the reaction kinetic and reversibility of other redox pairs,catalytic behaviors related to iodine reactions,coupling with other halogen ions,shuttle behaviors of polyiodides,***,there is currently a lack of comprehensive discussion on these ***,this review provides a comprehensive overview of the electrochemical behaviors of iodide in the aqueous *** effect of iodine ions on the Zn^(2+)desolvation behaviors and the interfacial behaviors of Zn anode was *** redox pairs boosting other redox pairs,such as MnO_(2)/Mn^(2+)redox pair and vanadium redox pair to obtain high reversibility and capacity was also ***,the catalytic behaviors related to iodine reactions in aqueous ZBs,synergistic reaction with other halogen ions and suppression of shuttle behaviors for high performance zinc-iodine batteries were systematically ***,future prospects for designing effective iodine electrochemical behaviors with practicability are proposed,which will provide scientific guidance for the practical application of iodine-related aqueous ZBs.

关键词： lodide ion Redox pairs Catalytic behavior Shuttle effect Zinc batteries

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Multi boron-doping effects in hard carbon toward enhanced sodium ion storage

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Journal of Energy Chemistry 2025年第1期100卷 730-738页

作者： Peng Zheng Wang Zhou Ying Mo Biao Zheng Miaomiao Han Qin Zhong Wenwen Yang Peng Gao Lezhi Yang Jilei Liu College of Materials Science and Engineering Hunan Joint International Laboratory of Advanced Materials and Technology for Clean EnergyHunan Province Key Laboratory for Advanced Carbon Materials and Applied TechnologyHunan UniversityChangsha 410082HunanChina Greater Bay Area Institute for Innovation Hunan UniversityGuangzhou 511300GuangdongChina Changsha Research Institute of Mining&Metallurgy Co. LTD.Changsha 410017HunanChina

Hard carbon (HC) has been considered as promising anode material for sodium-ion batteries (SIBs).The optimization of hard carbon’s microstructure and solid electrolyte interface (SEI) property are demonstrated effective in enhancing the Na+storage capability,however,a one-step regulation strategy to achieve simultaneous multi-scale structures optimization is highly ***,we have systematically investigated the effects of boron doping on hard carbon’s microstructure and interface chemistry.A variety of structure characterizations show that appropriate amount of boron doping can increase the size of closed pores via rearrangement of carbon layers with improved graphitization degree,which provides more Na+storage ***-situ Fourier transform infrared spectroscopy/electrochemical impedance spectroscopy (FTIR/EIS) and X-ray photoelectron spectroscopy (XPS) analysis demonstrate the presence of more BC3and less B–C–O structures that result in enhanced ion diffusion kinetics and the formation of inorganic rich and robust SEI,which leads to facilitated charge transfer and excellent rate *** a result,the hard carbon anode with optimized boron doping content exhibits enhanced rate and cycling *** general,this work unravels the critical role of boron doping in optimizing the pore structure,interface chemistry and diffusion kinetics of hard carbon,which enables rational design of sodium-ion battery anode with enhanced Na+storage performance.

关键词： Hard carbon Sodium-ion batteries Boron doping Pore structure Electrode/electrolyte interphases

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Tuning surface reactivity towards high-performance hard carbon in Li/Na/K-ion batteries

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Journal of Energy Chemistry 2025年第4期103卷 27-36页

作者： Wang Zhou Dan Wang Ying Mo Rui Tang Peng Gao Miaomiao Han Shi Chen Keigo Wakabayashi Takeharu Yoshii Hirotomo Nishihara Jilei Liu College of Materials Science and Engineering Hunan Joint International Laboratory of Advanced Materials and Technology of Clean EnergyHunan Province Key Laboratory for Advanced Carbon Materials and Applied TechnologyHunan UniversityChangsha 410082HunanChina The Key Laboratory of Micro-nano Energy Materials and Application Technologies University of Hunan Province&College of Physics and Electronic EngineeringHengyang Normal UniversityHengyang 421002HunanChina Joint Key Laboratory of the Ministry of Education Institute of Applied Physics and Materials EngineeringUniversity of MacaoMacao 999078China Institute of Multidisciplinary Research for Advanced Materials Tohoku University2-1-1 KatahiraAoba-kuSendaiMiyagi 980-8577Japan Advanced Institute for Materials Research(WPI-AIMR) Tohoku University2-1-1 KatahiraAoba-kuSendaiMiyagi 980-8577Japan

Controlling surface chemistry is critically important for improving the initial Coulombic efficiency(ICE)and adsorption capacity of hard carbon anode used in Li/Na/K-ion ***,accurately identifying the types and concentrations of hydrogen/oxygen terminated functional groups(HTFG/OTFGs)and distinguishing their functionalities remain ***,we quantitatively investigated the surface chemistry on hard carbon via ultra-high temperature programed desorption measurements,and uncovered the role of HTFG/OTFGs in influencing ICE and adsorption capacity in Li/Na/K-ions *** C-H group is found to be dominant species on the surface of hard carbon,and presents a positive correlation with ICE values and adsorption *** low reactivity of C-H group with both electrolyte salt and solvent results in the formation of thinner and highly conducive solid electrolyte interphase(SEI)layer,which benefit for the enhanced ICE and improved Li/Na/K-ions diffusion across SEI ***,the pimping trapping effect of C-H groups allows the adsorbed Li/Na/K-ions to migrate into graphitic interlayer quickly,enhancing the slope *** fabricating a C-H group-rich surface chemistry on hard carbon,a high ICE value and satisfactory specific capacity have been *** findings enrich our understanding of the surface chemistry-induced interfacial reaction,which effectively guides the rational design of high-performance hard carbon.

关键词： Hard carbon Surface chemistry C–H bond Initial coulombic efficiency Adsorption capacity

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Crystalline/Non-Crystalline Carbon Co-Modified Strategy to Construct N,S Co-Doped Carbon Layer Wrapped Fe_(0.95)S_(1.05)/Carbon Nanotubes for Enhanced Lithium Storage Property

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Acta Metallurgica Sinica(English Letters) 2025年第1期38卷 93-101页

作者： Liang Chen Lan−Yun Yang Li−Ting Zeng Xu Liu Xin−Rui Li Yu−Shan Tian Wei Wang Gang−Yong Li Chen−Xi Xu Zhao−Hui Hou Key Laboratory of Hunan Province for Advanced Carbon‒based Functional Materials School of Chemistry and Chemical EngineeringHunan Institute of Science and TechnologyYueyang414006China College of Materials Science and Engineering Central South University of Forestry and TechnologyChangsha410004China

Due to their high theoretical capacity and abundant resources,transition metal sulfides are regarded as a prospering alternative to replace the commercial graphite anode in lithium-ion batteries(LIBs),particularly for large-scale energy storage and conversion ***,low conductivity,easy agglomeration and obvious volume change greatly impede their practical *** this work,a novel crystalline/non-crystalline carbon co-modified strategy is proposed to fabricate N,S co-doped carbon(NSC)layer wrapped Fe_(0.95)S_(1.05)/carbon nanotubes(CNTs)composite(Fe_(0.95)S_(1.05)/CNTs@NSC)through a simple Fenton reaction followed by a sulfurization *** characterizations and analyses reveal that this strategy well combines the advantages of crystalline CNTs and non-crystalline NSC,ensuring good conductivity and a high contribution to capacity from the carbon ***,the joint encapsulation of Fe_(0.95)S_(1.05)by both CNTs and NSC can significantly mitigate the agglomeration and volume change of Fe_(0.95)S_(1.05)during the continuous charge/discharge *** from these advantageous features,the resultant Fe_(0.95)S_(1.05)/CNTs@NSC composite displays much improved cycling stability and rate capability when compared to the ***,our research offers a distinct and innovative approach to design and construct advanced transition metal sulfides/carbon composite anodes for LIBs.

关键词： Lithium-ion batteries Crystalline/non-crystalline carbon Joint encapsulation Fe_(0.95)S_(1.05)/CNTs@NSC Lithium storage property

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Construction of an artificial zinc alloy layer toward stable zinc-metal anode

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Green Energy & Environment 2025年第2期10卷 382-389页

作者： Long Jiang Yizhao Chai Dongdong Ji Liwei Li Le Li Bingan Lu Dongmin Li Jiang Zhou State Key Laboratory of Oil and Gas Equipment CNPC Tubular Goods Research InstituteXi'anShaanxi710077China School of Materials Science and Engineering Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan ProvinceCentral South UniversityChangsha410083China School of Physics and Electronics Hunan UniversityChangsha410082China

Aqueous zinc-ion batteries(AZIBs)present a promising option for next-generation batteries given their high safety,eco-friendliness,and resource ***,the practical application of zinc anodes is hindered by inevitable parasitic reactions and dendrite ***,zinc alloy layers(i.e.,ZnCo and ZnFe alloys)were rationally constructed on the zinc surface by chemical displacement *** alloying process exposes more(002)planes of the ZnCo anode to guide the preferential and dendrite-free zinc ***,the ZnCo alloy layer not only effectively inhibits water-induced side reactions but also accelerates electrode kinetics,enabling highly reversible zinc plating/*** a result,the ZnCo anode achieves a Coulombic efficiency of 99.2%over 1300 cycles,and the ZnCo symmetric cell exhibits a long cycle life of over 2000 h at 4.4 mA cm^(-2).Importantly,the ZnCo//NH_(4)V_(4)O_(10)full cell retains a high discharge capacity of 218.4 mAh g^(-1)after 800 ***,the ZnFe-based symmetric cell also displays excellent cycling stability over 2500 h at 1.77 mA cm^(-2).This strategy provides a facile anode modification approach toward high-performance AZIBs.

关键词： Zinc metal anode Zinc alloys Chemical displacement Aqueous zinc-ion batteries

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A small molecule based on dithieno[3,2-f:2′,3′-h]phthalimide enabling 19.22%efficiency by depressing non-radiative energy loss in ternary organic solar cells

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Journal of Energy Chemistry 2025年第5期104卷 194-201页

作者： Mengjie Li Youmei Qin Huanian Zhang Ji Wan Changhao Xiang Meihua Huang Jianqi Zhang Jie Min Linglong Ye Bin Zhao Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education College of ChemistryXiangtan UniversityXiangtan 411105HunanChina The Institute for Advanced Studies Wuhan UniversityWuhan 430072HubeiChina Key Laboratory for Green Organic Synthesis and Application of Hunan Province Key Laboratory of Polymeric Materials&Application Technology of Hunan ProvinceCollege of ChemistryXiangtan UniversityXiangtan 411105HunanChina CAS Key Laboratory of Nanosystem and Hierarchical Fabrication National Center for Nanoscience and TechnologyBeijing 100190China

Ternary blending as one of the most successful strategies has achieved continuous performance breakthroughs in organic solar cells(OSCs)over the past few ***,a small molecule featuring a dithieno[3,2-f:2′,3′-h]phthalimide derivative as the intermediate unit,named DTP-C8-R,is designed and utilized as the third component to construct ternary OSCs(TOSCs).The increased molecular packing of L8-BO as well as the charge transfer excitons between PM6 and DTP-C8-R lead to a very low nonradiative energy loss of 0.179 eV and a high open-circuit voltage(V_(OC))of 0.910 V in the TOSCs based on the PM6:L8-BO host ***,the DTP-C8-R:PM6:L8-BO film(0.05:0.95:1.2,w/w)possesses better fibrous nanophase separation and the enhancedπ-πstacking ordering of the acceptors with a larger crystal coherence length compared with the PM6:L8-BO blend film,so the TOSCs present more efficient exciton dissociation,longer carrier lifetime,faster carrier transport and less charge *** boosts the power conversion efficiency to 19.22%with a short-circuit current density of 27.10 mA cm^(-2).This work demonstrates that the small molecule based on a dithieno[3,2-f:2′,3′-h]phthalimide derivative as the minor component is an executable strategy to achieve high-performance TOSCs with high V_(OC).

关键词： Organic solar cells Small molecule Dithieno[3 2-f:2′ 3′-h]phthalimide derivative Low non-radiative energy loss High open-circuit voltage

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Time-dependent color-tunable room temperature phosphorescence from unusual conformational transitions in phenothiazine polymers under UV irradiation

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Science China Chemistry 2025年第3期68卷 1091-1098页

作者： Jiwen Lu Yifan Niu Chanjuan Jin Chengheng Wu Hanyu Wang Yan Guan Ping Wang Xinghe Fan Key Lab of Environment-Friendly Chemistry and Application of Ministry of Education Key Laboratory of Polymeric Materials and Application Technology of Hunan ProvinceKey Laboratory of Advanced Functional Polymer Materials of CollegesUniversities of Hunan ProvinceCollege of ChemistryXiangtan UniversityXiangtan 411105China Beijing National Laboratory for Molecular Sciences Key Laboratory of Polymer Chemistry and Physics of Ministry of EducationCenter for Soft Matter Science and EngineeringCollege of Chemistry and Molecular EngineeringPeking UniversityBeijing 100871China

Achieving color-tunable room-temperature phosphorescence(RTP),especially including blue RTP from a single-component polymer still faces a formidable ***,we wisely choose conformation-dependent phenothiazine with trifluoromethyl substituent as the side group of the phosphor monomer(Cz PT)and then copolymerize it with N-isopropylacrylamide(NIPAM)through photopolymerization to obtain polymers PPCz ***-dependent color-tunable phosphorescence from unusual quasi-equatorial(eq)to quasi-axial(ax)conformers are obtained,and the RTP color changes from orange(550 nm)to blue(470 nm)with phosphorescence lifetime up to 0.96 *** theoretical calculations confirm that the quasi-axial conformer is the preferred structure that facilitates the formation of intramolecular hydrogen bonds on the trifluoromethyl *** EPR spectra illustrate that the persistent UV irradiation generates radical cations to induce the conformational transitions first,followed by photopolymerization immobilizing the ax conformation in PPCz *** of data encryption and anti-counterfeiting are fabricated to show prompt and delayed multicolor *** work affords a simple and feasible avenue for two-dimensional color tunable room temperature phosphorescence from a single-component polymer.

关键词： polymeric room temperature phosphorescence color-tunable phosphorescence conformation-dependent time-dependent blue phosphorescence

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Experimental and numerical study on external explosions of cylindrical versus spherical charges at tunnel entrance

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Defence technology(防务技术) 2025年第4期46卷 227-243页

作者： Dan Luo Jinsheng Hu Anbao Wang Xiao Yu Mengmeng Zhang Meili Yao Chun Li Academy of Military Sciences PLABeijing 100850China Key Laboratory for Green&Advanced Civil Engineering Materials and Application Technology of Hunan Province College of Civil EngineeringHunan UniversityChangsha 410082China

Most of the existing studies on tunnel blast wave are based on spherical or grouped charges, however,conventional weapons are mostly cylindrical rather than spherical. In order to analyze the impact of cylindrical charges on the tunnel blast wave loads and to develop a quantitative calculation method, this study carried out experimental and numerical research. Initially, external explosion experiments were conducted using both 35 kg spherical charges and cylindrical charges with aspect ratio of 4.8 at two different distances from the tunnel entrance. Comparative analysis of the blast wave parameters in the tunnel revealed that the explosive equivalent of the cylindrical charges was significantly higher than that of the spherical charges. To address this, an equivalent coefficient κ based on the spherical charges was proposed for the cylindrical charges. Subsequently, numerical simulations were conducted for the experimental conditions, and the numerical simulation results match the experiments well. Through numerical calculations, the reliability of the equivalent coefficient κ under the experimental conditions was verified, and comparison analysis indicated that the explosion energy of cylindrical charges spreads more radially, resulting in more explosion energy entering the tunnel, which is the fundamental reason for the increase in tunnel blast wave loads. Additionally, analyzing the explosion energy ratio entering the tunnel is an effective method for calculating the equivalent coefficient κ. Finally, through more than one hundred sets of numerical calculation results, the impact of the proportional distance λ and the ratio of charge mass to the tunnel cross-section dimension φ on the equivalence coefficients κ was investigated. An empirical formula for the equivalence coefficient κ was derived through fitting, and the accuracy of the formula was validated through literature experimental results. The research findings of this paper will provide valuable guidance

关键词： Cylindrical charges Tunnel blast wave Equivalent coefficient Empirical formula Experiment and numerical simulation

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Achieving a large field-induced polarization and energy density in BaTiO_(3)films sputter-deposited on Si at 200℃ via a buffer-layer technique

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Journal of advanced Ceramics 2025年第3期14卷 69-78页

作者： Chao Liu Jun Ouyang Yuyao Zhao Hanfei Zhu Hongbu Cheng Zhenyan Liang Li Wang Institute of Advanced Energy Materials and Chemistry Jinan Engineering Laboratory for Multi-scale Functional MaterialsShandong Provincial Key Laboratory of Molecular EngineeringSchool of Chemistry and Chemical EngineeringQilu University of Technology(Shandong Academy of Sciences)Jinan 250353China Key Laboratory of Key Film Materials&Application for Equipments(Hunan Province) Hunan Provincial Key Laboratory of Thin Film Materials and DevicesSchool of Material Sciences and EngineeringXiangtan UniversityXiangtan 411105China Key Laboratory for Liquid–Solid Structure Evolution and Processing of Materials(Ministry of Education) School of Materials Science and EngineeringShandong UniversityJinan 250061China

Ferroelectric oxide films with a large field-induced polarization can be used in dielectric capacitors for charge or energy storage in microelectronic systems and hence have attracted intense research interest.A high processing temperature is usually required to produce a well-crystallized polar phase and hence a large polarization in the film,corresponding to a high charge or energy ***,high processing temperature not only reduces the charge‒discharge efficiency by producing a sizable remnant polarization but is also incompatible with the integration *** this study,we address this problem by creating a large field-induced polarization(~55.8μC/cm^(2))in BaTiO_(3)films sputter-deposited on Si at 200℃ via a buffer-layer *** large polarization led to a high energy density and efficiency(Wrec≈94.7 J/cm^(3),η≈78.2%@4 MV/cm).The thickness of LaNiO_(3)buffer layer was revealed to be the key factor determining the electric polarization(remnant and field-induced ones).A 50 nm LaNiO_(3)thickness,corresponding to the aforementioned polarization and energy storage performance,not only ensures proper crystallization in the BaTiO_(3)film,but also leads to an optimal combination of polycrystalline grains with a high dielectric *** latter accounts for the majority of the field-induced *** results revealed the key role of a buffer layer in tuning the microstructure of a low-temperature deposited ferroelectric oxide ***,the excellent charge/energy storage performance of these 200℃-deposited BaTiO_(3)films has provided many opportunities for this simple dielectric in microelectronics.

关键词： ferroelectric oxide films field-induced polarization BaTiO_(3) LaNiO3 energy density

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