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Local charge homogenization strategy enables ultra-high voltage tolerance of polyether electrolytes for 4.7 V lithium metal batteries

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National science Review 2025年第2期12卷 219-229页

作者： Yuanlong Wu Piao Luo Kexin Su Mao Yu Xin Song Lianzhan Huang Shaocong Zhang Huiyu Song Li Du Weishu Liu Zhiming Cui Guangdong Provincial Key Laboratory of Fuel Cell Technology School of Chemistry and Chemical EngineeringSouth China University of Technology Department of Materials Science and Engineering Southern University of Science and Technology Guangdong Provincial Key Laboratory of Advanced Energy Storage Materials School of Materials Science and Engineering South China University of Technology School of Software Engineering South China University of Technology

In-situ fabricated polyether electrolytes have been regarded as one of the most promising solid electrolyte systems. Nevertheless, they cannot match high-voltage cathodes over 4.3 V due to their poor oxidative stability. Herein, we propose an effective local charge homogenization strategy based on the triglycidyl isocyanurate（TGIC） crosslinker, achieving ultra-high-voltage electrochemical stability of polyether electrolytes（viz. PTIDOL） at cutoff voltages up to 4.7 V. The introduction of TGIC optimizes the Li+solvation environment, thereby homogenizing the charge distribution at ether oxygen（EO） sites, resulting in significantly enhanced oxidative stability of the polyether main chain. Consequently, the Li|PTIDOL|LiNi0.6Co0.2Mn0.2O2（NCM622） cell achieves long-term operation at an ultra-high cutoff voltage with a capacity retention of 81.8% after 400 cycles, one of the best results reported for polyether electrolytes to date. This work provides significant insights for the development of polyether electrolytes with high-voltage tolerance and the advancement of high-energy-density batteries.

关键词： lithium metal batteries solid polymer electrolytes polymerization high voltage local charge homogenization

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Decomposition of pre-existing Au-P clusters induced in situ a-Fe grains uniformization in Fe-P-based nanocrystalline alloys

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Rare Metals 2024年第10期43卷 5242-5255页

作者： Min-Hao Han Cheng Sun Guo-Guo Xi Yang Meng Qiang Luo Xue-Qian Yu Wen-Feng Zhang Hao Liu Hong-Jie Xu Tao Zhang Key Laboratory of Aerospace Materials and Performance(Ministry of Education) School of Materials Science and EngineeringBeihang UniversityBeijing 100191China Laboratory of Functional Fiber Materials Institute of Bast Fiber CropsChinese Academy of Agricultural ScienceChangsha 410205China School of Materials Science and Engineering Jiangsu Key Laboratory for Advanced Metallic MaterialsSoutheast UniversityNanjing 211189China Institute for Advanced Materials North China Electric Power UniversityBeijing 102206China Center for Advanced Analysis and Computational Science Zhengzhou UniversityZhengzhou 450001China

In Fe-based amorphous-/nanocrystalline ribbons,the uniformization and refinement of a-Fe grains are key aspects for optimizing their soft magnetic and mechanical ***,the Fe-P-C-B nanocrystalline alloy system was selected for *** produced as-spun ribbons with pre-existing nanocrystals through melt-quenching and then obtained a well-distributed a-Fe nanocrystalline structure through annealing below the first crystallization onset temperature(633 K)resulting in excellent magnetic properties(saturation magnetization of 1.65 T and coercivity of 1.6 A·m^(-1))ultra-wide annealing temperature window(from 613 to 733 K),and extremely high annealing stability(up to 480 min at 633 K).Furthermore,we propose a new in situ two-step mechanism for the uniformization of a-Fe nanocrystals,which is separately induced by the decomposition of the Au-P clusters and the pre-existing a-Fe nanocrystals during *** work underscores the crucial significance of micro-alloying via metastable clusters primarily influenced by metal-phosphide interactions in the process of refining a-Fe ***,i introduces a new principle for optimizing the comprehensive properties of Fe-based amorphous/nanocrystalline alloys.

关键词： Fe-based nanocrystalline alloys Soft magnetic property In-situ nano-crystallization Microalloying

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interface engineering strategy via electron-defect trimethyl borate additive toward 4.7 V ultrahigh-nickel LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)battery

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Journal of Energy Chemistry 2024年第5期92卷 639-647页

作者： Yilin Zhang Yuqing Chen Qiu He Jinlong Ke Wei Wang Jian-Fang Wu Peng Gao Yanhua Li 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 College of Materials Science and Engineering Sichuan UniversityChengdu 610065SichuanChina School of Materials Science and Engineering Hunan Institute of TechnologyHengyang 421002HunanChina

The Li metal battery with ultrahigh-nickel cathode(LiNi_(x)M_(1-x)O_(2),M=Mn,Co,and x≥0.9)under high-voltage is regarded as one of the most promising approaches to fulfill the ambitious target of 400 Wh/***,the practical application is impeded by the instability of electrode/electrolyte interface and Ni-rich cathode *** we proposed an electron-defect electrolyte additive trimethyl borate(TMB)which is paired with the commercial carbonate electrolyte to construct highly conductive fluorine-and boron-rich cathode electrolyte interface(CEI)on LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90)surface and solid electrolyte interphase(SEI)on lithium metal *** modified CEI effectively mitigates the structural transformation from layered to disordered rock-salt phase,and consequently alleviate the dissolution of transition metal ions(TMs)and its“cross-talk”effect,while the enhanced SEI enables stable lithium plating/striping and thus demonstrated good compatibility between electrolyte and lithium metal *** a result,the common electrolyte with 1 wt%TMB enables 4.7 V NCM90/Li cell cycle stably over 100 cycles with 70%capacity *** work highlights the significance of the electron-defect boron compounds for designing desirable interfacial chemistries to achieve high performance NCM90/Li battery under high voltage operation.

关键词： NCM90 batteries Electrolyte additive Trimethyl borate

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Immobilizing Triphenylamine with Photoredox Inert Sr^(2+)Forming Sr-MOF with Controlled Electron Migration for Photocatalytic Oxidation of Thiols to Disulfides

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Chinese Journal of Chemistry 2024年第10期42卷 1093-1099页

作者： Ying-Xia Wang Fang Zheng Dong-Xia Song Bao-Yue Niu Lu-Qian Deng Xian-Ming Zhang Key Laboratory of Magnetic Molecules and Magnetic Information Materials(Ministry of Education) Schoolof Chemistry and Materials ScienceShanxi Normal UniversityTaiyuanShanxi 030006China Key Laboratory of Interface Science and Engineering in Advanced Material(Ministry of Education) College of ChemistryTaiyuan University of TechnologyTaiyuanShanxi 030024China

The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the *** and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy polymerization and difficult *** overcome these obstacles while controlling the photogenerated electrons transfer directly to target substrates,herein,we constructed one TPA-based metal-organic framework(MOF),(Me_(2)NH_(2))[Sr(TCBPA)]·DMA·3H_(2)O(1),by direct self-assembly of tris(4′-carboxybiphenyl)amine(H_(3)TCBPA)and photoredox inert strontium ion(Sr^(2+)).DFT calculations revealed that the valence band maximum(VBM)and the conduction band minimum(CBM)are mainly located on TCBPA^(3-),successfully inhibiting the undesirable electron migration to metal *** results indicated that 1 displays superior performance than homogeneous H_(3)TCBPA,which may result from the abundant π…π and C—H…π interactions between the well-arranged TCBPA^(3-)and the build-in electric field between the anionic framework and the Me_(2)NH^(2+).This work highlights that immobilizing TPAs into MOFs is one promising approach to designing heterogeneous photocatalysts for the synthesis of disulfides by oxidative coupling of thiols.

关键词： Triphenylamine Metal-organic frameworks Strontium Photooxidation Thiols Disulfides

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High-temperature creep rupture behavior of dissimilar welded joints of RAFM steel and 316L steel by friction stir welding

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Journal of Iron and Steel Research International 2024年第10期31卷 2438-2447页

作者： Xin Ji Bin He Wei Guan Chen-xi Liu Hui-jun Li Lei Cui Yong-chang Liu Tianjin Key Laboratory of Advanced Joining Technology School of Materials Science and EngineeringTianjin UniversityTianjin300354China State Key Lab of Hydraulic Engineering Simulation and Safety School of Materials Science and EngineeringTianjin UniversityTianjin300350China

Creep rupture of the reduced activation ferritic/martensitic(RAFM)steel and 316L steel dissimilar joint by friction stir welding was *** creep rupture time of the dissimilar joint was 1941 h at 600℃/100 MPa and 120 h at 650℃/100 *** creep fracture occurred in heat affect zone(HAZ)of RAFM steel side where coarse Laves phase was *** formation and coarsening of the Laves phase particles in HAZ of RAFM steel side were the main reasons that caused the creep fracture of the dissimilar *** Laves phase particles nucleated adjacent to the large M_(23)C_(6) particles at the grain boundaries where W element segregated and grew fast during creep *** large Laves phase would deteriorate the pinning effect of M_(23)C_(6) carbides and weaken the solid solution strengthening ***,the size of the Laves phase in HAZ of RAFM steel side was bigger than that in stir zone of RAFM steel *** reasons explain the creep fracture in HAZ of RAFM steel side of dissimilar joint.

关键词： Creep behavior Dissimilar joint Friction stir welding Laves phase M23C6 carbide

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Lightweight and large-scale rGO reinforced SiBCN aerogels with hierarchical cellular structures exposed to high-temperature environments

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Journal of materials science & Technology 2024年第12期179卷 145-154页

作者： Huijie Wang Zhiwei Chen Dong Su Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of Education School of Materials Science and EngineeringTianjin UniversityTianjin 300350China

SiBCN ceramic aerogel is an ideal potential candidate for ultra-high temperature thermal insulation due to its unique microscopic pore structure combined with the excellent thermal stability of SiBCN ***,reduced graphene oxide(rGO)modified SiBCN aerogels(rGO/SiBCN)were prepared through solvothermal,freeze-casting and pyrolysis,and the dimension of the aerogel is up toΦ130 mm×28 *** density of the rGO/SiBCN aerogel is as low as 0.024 g/cm^(3) and the microstructural regulation is achieved by controlling the rGO content in the *** hierarchical cellular structure endows the aerogel with a high specific surface area(148.6 m^(2)/g)and low thermal conductivity(0.057 W m^(-1) K^(-1)).The 10 mm-thick sample exhibits excellent thermal insulation and ablation resistance,as evidenced by its ability to reduce the temperature from~1100℃to~180℃under the intense heat of a butane ***,benefiting from the ultrahigh-temperature stability of SiBCN,the rGO/SiBCN aerogel exhibits good thermal stability up to 1200℃in argon and short-oxidation resistance at 800℃in ***-fore,the rGO/SiBCN aerogel with superior overall performance could expand its practical application in high-temperature thermal insulation under extreme environments.

关键词： rGO/SiBCN Lightweight Large size Hierarchical cellular structure Thermal insulation

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Ultrafast micro/nano-manufacturing of metastable materials for energy

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National science Review 2024年第4期11卷 283-298页

作者： Xiaoya Cui Yanchang Liu Yanan Chen School of Materials Science and Engineering Key Laboratory of Advanced Ceramics and Machining Technology(Ministry of Education) and Tianjin Key Laboratory of Composite and Functional MaterialsTianjin University Ministry of Education Key Laboratory of Protein Sciences School of Life SciencesTsinghua University

The structural engineering of metastable nanomaterials with abundant defects has attracted much attention in energy-related fields. The high-temperature shock(HTS) technique, as a rapidly developing and advanced synthesis strategy, offers significant potential for the rational design and fabrication of high-quality nanocatalysts in an ultrafast, scalable, controllable and eco-friendly way. In this review, we provide an overview of various metastable micro-and nanomaterials synthesized via HTS, including single metallic and bimetallic nanostructures, high entropy alloys, metal compounds(e.g. metal oxides) and carbon nanomaterials. Note that HTS provides a new research dimension for nanostructures, i.e. kinetic modulation. Furthermore, we summarize the application of HTS—as supporting films for transmission electron microscopy grids—in the structural engineering of 2D materials, which is vital for the direct imaging of metastable materials. Finally, we discuss the potential future applications of high-throughput and liquid-phase HTS strategies for non-equilibrium micro/nano-manufacturing beyond energy-related *** is believed that this emerging research field will bring new opportunities to the development of nanoscience and nanotechnology in both fundamental and practical aspects.

关键词： high-temperature shock technique defect engineering metastable phase kinetic modulation non-equilibrium micro/nano-manufacturing

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In situ observation of the electrochemical behavior of Li–CO_(2)/O_(2)batteries in an environmental transmission electron microscope

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Carbon Energy 2024年第4期6卷 244-255页

作者： Peng Jia Yunna Guo Dongliang Chen Jingming Yao Xuedong Zhang Jianguo Lu Yuqing Qiao Liqiang Zhang Hebei Key Laboratory of Applied Chemistry College of Environmental and Chemical EngineeringYanshan UniversityQinhuangdaoChina State Key Laboratory of Metastable Materials Science and Technology Clean Nano Energy CenterYanshan UniversityQinhuangdaoChina State Key Laboratory of Silicon and Advanced Semiconductor Materials School of Materials Science and EngineeringZhejiang UniversityHangzhouChina Key Laboratory of Low Dimensional Materials and Application Technology of Ministry of Education School of Materials Science and EngineeringXiangtan UniversityXiangtanChina

Li–CO_(2)/O_(2)batteries,a promising energy storage technology,not only provide ultrahigh discharge capacity but also capture CO_(2)and turn it into renewable *** electrochemical reaction pathways'ambiguity,however,creates a hurdle for their practical *** study used copper selenide(CuSe)nanosheets as the air cathode medium in an environmental transmission electron microscope to in situ study Li–CO_(2)/O_(2)(mix CO_(2)as well as O_(2)at a volume ratio of 1:1)and Li–O_(2)batteries as well as Li–CO_(2)*** discharge reactions take place successively in the Li–CO_(2)/O_(2)–CuSe nanobattery:(I)4Li^(+)+O_(2)+4e^(−)→2Li_(2)O;(II)Li_(2)O+CO_(2)→Li_(2)CO_(3).The charge reaction proceeded via(III)2Li_(2)CO_(3)→4Li^(+)+2CO_(2)+O_(2)+4e^(−).However,Li–O_(2)and Li–CO_(2)nanobatteries showed poor cycling stability,suggesting the difficulty in the direct decomposition of the discharge *** fluctuations of the Li–CO_(2)/O_(2)battery's electrochemistry were also shown to depend heavily on O_(2).The CuSe‐based Li–CO_(2)/O_(2)battery showed exceptional electrochemical *** Li^–CO_(2)/O_(2)battery offered a discharge capacity apex of 15,492 mAh g^(−1) and stable cycling 60 times at 100 mA g^(−1).Our research offers crucial insight into the electrochemical behavior of Li–CO_(2)/O_(2),Li–O_(2),and Li–CO_(2)nanobatteries,which may help the creation of high‐performance Li–CO_(2)/O_(2)batteries for energy storage applications.

关键词： CuSe nanosheets electrochemical reaction in situ environmental transmission electron microscopy Li-CO_(2)battery Li-CO_(2)/O_(2)battery Li-O_(2)battery

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Low sintering shrinkage porous ceramics: Principles, progress, and perspectives

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Journal of advanced Ceramics 2025年第2期14卷 1-36页

作者： Jie Xu Yueqi Shao Xiaoying Feng Xiaoyan Zhang Hao Li Jinlong Yang Feng Gao State Key Laboratory of Solidification Processing MIIT Key Laboratory of Radiation Detection Materials and DevicesSchool of Materials Science and EngineeringNorthwestern Polytechnical UniversityXi’an 710072China Institute for Advanced Materials and Technology University of Science and Technology BeijingBeijing 100083China State Key Lab of New Ceramics and Fine Processing School of Materials Science and EngineeringTsinghua UniversityBeijing 100084China

Porous ceramics are lightweight materials with diverse pore structures and are widely applied in areas such as thermal insulation, sound absorption, filtration, catalysis, and energy storage. However, excessive shrinkage during the sintering process of porous ceramics leads to cracking and deterioration, posing significant challenges for achieving complex shapes. Despite its importance, the field of low sintering shrinkage porous ceramics has not received sufficient attention. This review systematically discusses the principles and progress in the development of low sintering shrinkage porous ceramics. First, we introduce the characteristics of various preparation methods, including partial sintering, particle-stabilized foaming, gel-casting, foam-gelcasting, and additive manufacturing (AM). We then explain three primary principles of low sintering shrinkage from the perspectives of the volume effect and mass transfer processes. This review focuses on the properties and applications of typical low sintering shrinkage ceramics such as mullite and alumina, particularly their mechanical properties and thermal conductivity as thermal insulation and ceramic cores. Finally, we summarize the current state and present future perspectives on low sintering shrinkage porous ceramics.

关键词： porous ceramics low sintering shrinkage volume expansion mass transfer process pore structure properties

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A donor-acceptor conjugated bipolar polymer with multielectron redox sites for long-cycle-life and high-rate aqueous zinc dual-ion batteries

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Journal of Energy Chemistry 2025年第3期102卷 144-150页

作者： Lian-Wei Luo Siteng Zhu Wen Yan Ma Dan Li Chong Zhang Jia-Xing Jiang Key Laboratory of Optoelectronic Chemical Materials and Devices(Ministry of Education) School of Optoelectronic Materials&TechnologyJianghan UniversityWuhan 430056HubeiChina Key Laboratory for Macromolecular Science of Shaanxi Province Shaanxi Engineering Laboratory for Advanced Energy TechnologySchool of Materials Science and EngineeringShaanxi Normal UniversityXi'an 710062ShaanxiChina

Aqueous zinc-ion batteries(AZIBs)have hugely latent advantages in large-scale energy storage due to its innate safety,reasonable price,and ***,most AZIB cathode materials suffer from short cycling life and poor rate ***,a bipolar donor-acceptor(D-A)conjugated microporous polymer(PTZ-BDTB),consisting of electron-withdrawing benzo[1,2-b:4,5-b']dithiophene-4,8-dio ne(BDTB)units and electron-donating phenothiazine(PTZ)units,is developed as the cathode material of aqueous zinc dual-ion batteries(AZDIBs).The D-A type structure design could reduce the band gap,thus promoting electron transfer in the polymer ***,the PTZ-BDTB cathode in a30 mol/kg(m)ZnCl_(2)water-in-salt electrolyte exhibits a high reversible capacity of 202 mA h g^(-1)at0.05 A g^(-1)with excellent rate performance(109 mA h g^(-1)at 15 A g^(-1)),which is far superior to its counterpart polymers PPTZ and ***,PTZ-BDTB shows ultra-stable cycle performance with capacity retention ratios of 76.2%after 460 cycles at 0.05 A g^(-1)and 96%after 27000 cycles at 5 A g^(-1).PTZBDTB also exhibits a low self-discharge ability with capacity retention about 76.4%after resting the battery for 28 *** results demonstrate that D-A type structural design is a promising strategy for constructing high performance cathode materials for AZDIBs.

关键词： Conjugated microporous polymer Donor-acceptor structure Bipolar organic cathode material Aqueous zinc dual-ion batteries

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