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Fast thermal responsive separators toward long-life and safe lithium metal batteries

Nano Research 2024年第4期17卷 2746-2754页

作者： Pingan Li Zhifang Liu Yitong Peng Shanshan Yang Tao Meng Yunhuan Hu Yingjun Jiang Hao Sun Qi Li Xianluo Hu State Key Laboratory of Materials Processing and Die and Mould Technology School of Materials Science and EngineeringHuazhong University of Science and TechnologyWuhan 430074China

Lithium metal batteries(LMBs)have been extensively investigated during the past decades because of their ultrahigh energy densities.With the increasing demand for energy density,however,the safety issue of LMBs has become a significant challenge.In particular,localized areas of increased temperature(namely,hotspots)may be induced and even exacerbated within LMBs by uneven current distribution,internal short circuits,or inadequate heat dissipation,which significantly sacrifices battery safety and cycle life.Here,we report the rational design and fabrication of a fast thermal responsive separator capable of inhibiting the growth of lithium dendrites and mitigating thermal propagation,thereby reducing the risk of thermal runaway.The as-achieved separator comprises both an electrospun membrane using a phase change material with superior thermal-storage ability and a thermally conductive modification layer of hexagonal boron nitride nanosheets with a fast heat-transfer feature.It is demonstrated that such a unique integration of heat conduction and heat storage enables the functional separator with attractive abilities to mitigate hotspots and inhibit the growth of lithium dendrites upon the cycling of LMBs.Moreover,pouch cells with the thermal-responsive separator,as well as numerical simulations,verify much enhanced safety and cycle life of LMBs.This work may offer a new conceptual design of intelligent separators that acts as a functional unit encapsulated within a single cell to boost in-situ thermal management,which will help to develop high-safety and energy-dense LMBs.

关键词： lithium metal batteries separators hotspots safety thermal management

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Metal/covalent organic frameworks for aqueous rechargeable zinc-ion batteries

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Science China Chemistry 2024年第1期67卷 247-259页

作者： Hu Hong Xun Guo Jiaxiong Zhu Zhuoxi Wu Qing Li Chunyi Zhi Department of Materials Science and Engineering City University of Hong KongHong Kong 999077China

Lithium-ion batteries(LIBs)have become one of the most successful energy storage systems due to their high operating voltage,high energy density,and long cycle life.However,with the widespread use of LIBs in recent decades,lithium resources are at risk of being exhausted.Therefore,it is necessary to find a substitute for LIBs to meet the needs of future large-scale energy storage systems.Because of their competitiveness,low cost,and high safety,aqueous rechargeable zinc-ion batteries(ARZIBs)are regarded as promising components in the post-lithium-ion-battery era.Given the tunable composition,ordered porous channels,and controllable structure of metal-organic frameworks(MOFs)and covalent organic frameworks(COFs),these frameworks are viewed as potential materials for developing high-performance ARZIBs.In this review,we focus on the recent developments in the applications of MOF-/COF-based materials in ARZIBs,including in electrode materials,anode modifications,separators,and solid electrolytes.We then focus on the critical factors and optimization techniques of MOF-/COF-based materials that affect the performance of ARZIBs.Finally,we conclude with some projections for the expansion of ARZIBs containing MOF-/COF-based materials.

关键词： metal/covalent organic frameworks aqueous zinc-ion batteries electrode materials anode modifications separators electrolytes

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Metal-organic frameworks and their composites for advanced lithium-ion batteries:Synthesis,progress and prospects

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Journal of Energy Chemistry 2024年第2期89卷 449-470,I0011页

作者： Chengcai Liu Borong Wu Tao Liu Yuanxing Zhang Jingwen Cui Lingjun Huang Guoqiang Tan Ling Zhang Yuefeng Su Feng Wu School of Material Science and Engineering Beijing Institute of TechnologyBeijing 100081China Chonging Innovation Center Beijing Institute of TechnologyChongqing 401120China Collaborative Innovation Center of Electric Vehicles in Beijing Beijing 100081China

Metal-organic frameworks(MOFs)are among the most promising materials for lithium-ion batteries(LIBs)owing to their high surface area,periodic porosity,adjustable pore size,and controllable chemical composition.For instance,their unique porous structures promote electrolyte penetration,ions transport,and make them ideal for battery separators.Regulating the chemical composition of MOF can introduce more active sites for electrochemical reactions.Therefore,MOFs and their related composites have been extensively and thoroughly explored for LIBs.However,the reported reviews solely include the applications of MOFs in the electrode materials of LIBs and rarely involve other aspects.A systematic review of the application of MOFs in LIBs is essential for understanding the mechanism of MOFs and better designing related MOFs battery materials.This review systematically evaluates the latest developments in pristine MOFs and MOF composites for LIB applications,including MOFs as the main materials(anode,cathode,separators,and electrolytes)to auxiliary materials(coating layers and additives for electrodes).Furthermore,the synthesis,modification methods,challenges,and prospects for the application of MOFs in LIBs are discussed.

关键词： Metal-organic frameworks Electrodes Electrolytes separators Lithium-ion batteries

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Review on current development of polybenzimidazole membrane for lithium battery

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Journal of Energy Chemistry 2024年第4期91卷 579-608页

作者： Yonggui Deng Arshad Hussain Waseem Raza Xingke Cai Dongqing Liu Jun Shen College of Mechatronics and Control Engineering Shenzhen UniversityShenzhen 518060GuangdongChina Interdisciplinary Research Center for Hydrogen Technologies and Carbon Management(IRC-HTCM) King Fahd University of Petroleum&MineralsKFUPM Box 504031261 DhahranSaudi Arabia Institute for Advanced Study Shenzhen UniversityShenzhen 518060GuangdongChina

With the rapid development of portable technology,lithium batteries have emerged as potential candidates for high-performance energy storage systems owing to their high energy density and cycling stability.Among the key components of a lithium battery system,the separator plays a critical role as it directly influences the battery performance benchmark(cycling performance and safety).However,traditional polyolefin separators(polypropylene/polyethylene)are unable to meet the demands of highperformance and safer battery systems due to their poor electrolyte compatibility,thermal runaways,and ultimate growth of dendrites.In contrast,membranes fabricated using polybenzimidazole(PBI)exhibit excellent electrolyte wettability and outstanding thermal dimensional stability,thus holding great potential as separators for high-performance and high-safety batteries.In this paper,we present a comprehensive review of the general requirements for separators,synthesis technology for separators,and research trends focusing PBI membranes in lithium batteries to alleviate the current commercial challenges faced by conventional polyolefin separators.In addition,we discuss the future development direction for PBI battery separators by considering various factors such as production cost,ecological footprint,preparation technology,and battery component compatibility.By exploring these perspectives,we aim to promote the continued application and exploration of PBI-based materials to advance lithium battery technology.

关键词： Lithium batteries separators Porous separators Polybenzimidazole Membrane

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水系锌离子电池隔膜设计

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Science Bulletin 2024年第5期69卷 688-703页

作者：李斌曾友张炜松鲁兵安杨琪周江何章兴 School of Chemical Engineering North China University of Science and TechnologyTangshan 063009China State Key Laboratory of Chemical Resource Engineering College of Chemical EngineeringBeijing University of Chemical TechnologyBeijing 100029China School of Materials Science and Engineering Hunan Provincial Key Laboratory of Electronic Packaging and Advanced Functional MaterialsCentral South UniversityChangsha 410083China School of Physics and Electronics Hunan UniversityChangsha 410082China

Aqueous zinc-ion batteries(AZIBs)are attracting worldwide attention due to their multiple merits such as extreme safety,low cost,feasible assembly,and environmentally friendly enabled by water-based electrolytes.At present,AZIBs have experienced systematic advances in battery components including cathode,anode,and electrolyte,whereas research involving separators is insufficient.The separator is the crucial component of AZIBs through providing ion transport,forming contact with electrodes,serving as a container for electrolyte,and ensuring the efficient battery operation.Considering this great yet ignored significance,it is timely to present the latest advances in design strategies,the systematic classification and summary of separators.We summarize the separator optimization strategies mainly along two approaches including the modification of the frequently used glass fiber and the exploitation of new separators.The advantages and disadvantages of the two strategies are analyzed from the material types and the characteristics of different strategies.The effects and mechanisms of various materials on regulating the uniform migration and deposition of Zn2+,balancing the excessively concentrated nucleation points,inhibiting the growth of dendrites,and the occurrence of side reactions were discussed using confinement,electric field regulation,ion interaction force,desolvation,etc.Finally,potential directions for further improvement and development of AZIBs separators are proposed,aiming at providing helpful guidance for this booming field.

关键词： Aqueous zinc-ion batteries separators Dendrite Interface optimization Ion mass transfer

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Metal-Organic Frameworks Functionalized separators for Robust Aqueous Zinc-Ion Batteries

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Nano-Micro Letters 2022年第12期14卷 521-534页

作者： Yang Song Pengchao Ruan Caiwang Mao Yuxin Chang Ling Wang Lei Dai Peng Zhou Bingan Lu Jiang Zhou Zhangxing He School of Chemical Engineering North China University of Science and TechnologyTangshan 063009People’s Republic of China School of Materials Science and Engineering Hunan Provincial Key Laboratory of Electronic Packaging and Advanced Functional MaterialsCentral South UniversityChangsha 410083People’s Republic of China Hunan Provincial Key Defense Laboratory of High Temperature Wear-Resisting Materials and Preparation Technology Hunan University of Science and TechnologyXiangtan 411201People’s Republic of China School of Physics and Electronics Hunan UniversityChangsha 410082People’s Republic of China

Aqueous zinc-ion batteries(AZIBs)are one of the promising energy storage systems,which consist of electrode materials,electrolyte,and separator.The first two have been significantly received ample development,while the prominent role of the separators in manipulating the stability of the electrode has not attracted sufficient attention.In this work,a separator(UiO-66-GF)modified by Zr-based metal organic framework for robust AZIBs is proposed.UiO-66-GF effectively enhances the transport ability of charge carriers and demonstrates preferential orientation of(002)crystal plane,which is favorable for corrosion resistance and dendrite-free zinc deposition.Consequently,Zn|UiO-66-GF-2.2|Zn cells exhibit highly reversible plating/stripping behavior with long cycle life over 1650 h at 2.0 mA cm^(−2),and Zn|UiO-66-GF-2.2|MnO_(2) cells show excellent long-term stability with capacity retention of 85%after 1000 cycles.The reasonable design and application of multifunctional metal organic frameworks modified separators provide useful guidance for constructing durable AZIBs.

关键词： Aqueous zinc-ion batteries separators Metal-organic frameworks Ion transport Dendrite-free

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Status and Opportunities of Zinc Ion Hybrid Capacitors: Focus on Carbon Materials, Current Collectors, and separators

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纳微快报：英文版 2023年第6期15卷 73-111页

作者： Yanyan Wang Shirong Sun Xiaoliang Wu Hanfeng Liang Wenli Zhang College of Chemistry Chemical Engineering and Resource UtilizationNortheast Forestry University26 Hexing RoadHarbin 150040People’s Republic of China Guangdong Provincial Key Laboratory of Plant Resources Biorefinery School of Chemical Engineering and Light IndustryGuangdong University of Technology(GDUT)100 Waihuan Xi RoadPanyu DistrictGuangzhou 510006People’s Republic of China State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical EngineeringXiamen UniversityXiamen 361005People’s Republic of China Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory(Rongjiang Laboratory) Jieyang 515200People’s Republic of China School of Advanced Manufacturing Guangdong University of Technology(GDUT)Jieyang 522000People’s Republic of China

Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.

关键词： Zinc ion hybrid capacitors Carbon materials Carbon cathode Current collectors separators

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A Review of Nonaqueous Electrolytes,Binders,and separators for Lithium-Ion Batteries

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Electrochemical Energy Reviews 2022年第4期5卷 104-137页

作者： Jiale Xing Stoyan Bliznakov Leonard Bonville Miodrag Oljaca Radenka Maric Department of Chemical Engineering Center for Clean Energy EngineeringUniversity of ConnecticutStorrsCT 06269USA Growth and Technology KouraWalthamMA 02451USA

Lithium-ion batteries(LIBs)are the most important electrochemical energy storage devices due to their high energy den-sity,long cycle life,and low cost.During the past decades,many review papers outlining the advantages of state-of-the-art LIBs have been published,and extensive efforts have been devoted to improving their specific energy density and cycle life performance.These papers are primarily focused on the design and development of various advanced cathode and anode electrode materials,with less attention given to the other important components of the battery.The“nonelectroconductive”components are of equal importance to electrode active materials and can significantly affect the performance of LIBs.They could directly impact the capacity,safety,charging time,and cycle life of batteries and thus affect their commercial application.This review summarizes the recent progress in the development of nonaqueous electrolytes,binders,and separa-tors for LIBs and discusses their impact on the battery performance.In addition,the challenges and perspectives for future development of LIBs are discussed,and new avenues for state-of-the-art LIBs to reach their full potential for a wide range of practical applications are outlined.

关键词： Lithium-ion battery Electrolytes Binders separators

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Comparative study of different membranes as separators for rechargeable lithium-ion batteries

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International Journal of Minerals,Metallurgy and Materials 2013年第6期20卷 598-603页

作者： Hong-yan Guan Fang Lian Yan Ren Yan Wen Xiao-rong Pan Jia-lin Sun School of Materials Science and Engineering University of Science and Technology Beijing

Membranes of polypropylene （PP）, PP coated with nano-A1203, PP electrospun with polyvinylidene fluoride- hexafluoropropylene （PVdF-HFP）, and trilayer laminates of polypropylene-polyethylene-polypropylene （PP/PE/PP） were comparatively studied. Their physical properties were characterized by means of thermal shrinkage test, liquid electrolyte uptake, and field emission scanning electron microscopy （FESEM）. Results show that, for the different membranes as PP, PP coated with nanowA1203, PP electrospun with PVdF-HFP, and PP/PE/PP, the thermal shrinkages are 14%, 6%, 12.6%, and 13.3%, while the liquid electrolyte uptakes are 110%, 150%, 217%, and 129%, respectively. In addition, the effects on the performance of lithium-ion batteries （LiFePO4 and LiNil/3Col/3Mn1/302 as the cathode material） were investigated by AC impedance and galvanostatic charge/discharge test. It is found that PP coated with A1203 and PP electrospun with PVdF-HFP can effectively increase the wettability between the cathode material and liquid electrolyte, and therefore reduce the charge transfer resistance, which improves the capacity retention and battery performance.

关键词： lithium-ion batteries membranes separators thermal stability electrochemical properties

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Polyimide separators for rechargeable batteries

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Journal of Energy Chemistry 2021年第7期30卷 170-197页

作者： Ziheng Lu Fan Sui Yue-E Miao Guohua Liu Cheng Li Wei Dong Jiang Cui Tianxi Liu Junxiong Wu Chunlei Yang Shenzhen Institutes of Advanced Technology Chinese Academy of SciencesShenzhen 518055GuangdongChina College of Materials Science and Engineering Donghua UniversityShanghai 201620China Department of Materials Science and Engineering Clemson UniversityClemsonSC 29634USA Department of Mechanical Engineering The Hong Kong Polytechnic UniversityHong KongChina

separators are indispensable components of modern electrochemical energy storage devices such as lithium-ion batteries(LIBs).They perform the critical function of physically separating the electrodes to prevent short-circuits while permitting the ions to pass through.While conventional separators using polypropylene(PP) and polyethylene(PE) are prone to shrinkage and melting at relatively high temperatures(150℃ or above) causing short circuits and thermal runaway,separators made of thermally stable polyimides(PIs) are electrochemically stable and resistant to high temperatures,and possess good mechanical strength-making them a promising solution to the safety concerns of LIBs.In this review,the research progress on PI separators for use in LIBs is summarized with a special focus on molecular design and microstructural control.In view of the significant progress in advanced chemistries beyond LIBs,recent advances in PI-based membranes for applications in lithium-sulfur,lithium-metal,and solid-state batteries are also reviewed.Finally,practical issues are also discussed along with their prospects.

关键词： Polyimide Lithium-ion batteries separators Solid-state batteries Molecular design

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