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Emerging natural clay-based materials for stable and dendrite-free lithium metal anodes: A review

Chinese Chemical Letters 2025年第2期36卷 161-172页

作者： Haobo Wang Fei Wang Yong Liu Zhongxiu Liu Yingjie Miao Wanhong zhang Guangxin Wang Jiangtao Ji qiaobao zhang School of Materials Science and Engineering Provincial and Ministerial Co-construction of Collaborative Innovation Center for Non-ferrous Metal new Materials and Advanced Processing Technology Henan University of Science and Technology Faculty of Engineering Huanghe Science and Technology University Henan Key Laboratory of Non-Ferrous Materials Science & Processing Technology Henan University of Science and Technology College of Agricultural Equipment Engineering Henan University of Science and Technology State Key Laboratory of Physical Chemistry of Solid Surfaces College of Materials Xiamen University

Lithium metal is one of the most promising anodes for lithium batteries because of their high theoretical specific capacity and the low electrochemical potential. However, the commercialization of lithium metal anodes(LMAs) is facing significant obstacles, such as uncontrolled lithium dendrite growth and unstable solid electrolyte interface, leading to inferior Coulombic efficiency, unsatisfactory cycling stability and even serious safety issues. Introducing low-cost natural clay-based materials(NCBMs) in LMAs is deemed as one of the most effective methods to solve aforementioned issues. These NCBMs have received considerable attention for stabilizing LMAs due to their unique structure, large specific surface areas, abundant surface groups, high mechanical strength, excellent thermal stability, and environmental friendliness. Considering the rapidly growing research enthusiasm for this topic in the last several years, here, we review the recent progress on the application of NCBMs in stable and dendrite-free *** different structures and modification methods of natural clays are first summarized. In addition, the relationship between their modification methods and nano/microstructures, as well as their impact on the electrochemical properties of LMAs are systematically discussed. Finally, the current challenges and opportunities for application of NCBMs in stable LMAs are also proposed to facilitate their further development.

关键词： Aolid-state electrolyte Li metal anodes Natural clay-based materials Rechargeable batteries Surface modification

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Rational design of three-dimensional branched NiCo-P@CoNiMo-P core/shell nanowire heterostructures for high-performance hybrid supercapacitor

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Journal of Energy Chemistry 2021年第10期30卷 489-496,I0013页

作者： Yijing Huang Chong Luo qiaobao zhang Hehe zhang Ming-Sheng Wang State Key Lab of Physical Chemistry of Solid Surfaces College of MaterialsXiamen UniversityXiamen 361005FujianChina

Owing to the dramatically enhanced charge-mass transport and abundant electrochemically active sites,transition metal compound electrodes are increasingly attractive for achieving high-performance supercapacitors(SCs).Here,we report the fabrication of nickel foam supported three-dimensional(3 D)branched nickel-cobalt phosphides@tri-metal cobalt-nickel-molybdenum phosphides core/shell nanowire heterostructures(denoted as NiCo-P@CoNiMo-P)as high-performance electrode materials for hybrid *** presence of multiple valences of the cations in such NiCo-P@CoNiMo-P enables rich redox reactions and promoted synergy *** from their collective effects,the resulting electrode demonstrates high specific capacity of 1366 C g^(-1) at 2 A g^(-1)(2.03 C cm^(-2) at2 mA cm^(-2))and 922 C g^(-1) at 10 A g^(-1),as well as good cycling stability(retaining~94%of the initial capacity after 6000 cycles at 15 A g^(-1)).A hybrid SC using the NiCo-P@CoNiMo-P as the positive electrode and N-doped rGOs as the negative electrode exhibits a high energy density of 81.4 Wh kg^(-1) at a power density of 1213 W kg^(-1) and a capacity retention of 132%even after 6000 cycles at 10 A g^(-1).Our findings can facilitate the material design for boosting the performance of transition metal compounds based materials for fast energy storage.

关键词： Transition metal phosphides Branched nanowire heterostructures Electrode materials Hybird supercapacitors

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Lithiophilic N-doped carbon bowls induced Li deposition in layered graphene film for advanced lithium metal batteries

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Nano Research 2022年第1期15卷 352-360页

作者： Xiaoyu Feng Hong-Hui Wu Biao Gao Michai Swietostawski Xin He qiaobao zhang Department of Materials Science and Engineering College of MaterialsXiamen UniversityXiamen 361005China The State Key Laboratory of Refractories and Metallurgy and Institute of Advanced Materials and Nanotechnology Wuhan University oj Science and TechnologyWuhan 430081y China School of Materials Science and Engineering University of Science and Technology BeijingBeijing 100083China Faculty of Chemistry Jagiellonian Universityul.Gronostajowa 230-387 KrakowPoland School of Chemical Engineering Sichuan UniversityChengdu 610065China

Lithium(Li)metal with high theoretical capacity and low electrochemical potential is the most ideal anode for next-generation high-energy ***,the practical implementation of Li anode has been hindered by dendritic growth and volume expansion during cycling,which results in low Coulombic efficiency(CE),short lifespan,and safety ***,we report a highly stable and dendrite-free Li metal anode by utilizing N-doped hollow porous bowl-like hard carbon/reduced graphene nanosheets(CB@rGO)hybrids as three-dimensional(3D)conductive and lithiophilic scaffold *** lithiophilic carbon bowl(CB)mainly works as excellent guides during the Li plating process,whereas the rGO layer with high conductivity and mechanical stability maintains the integrity of the composite by confining the volume change in long-range order during ***,the local current density can be reduced due to the 3D conductive ***,CB@rGO presents a low lithium metal nucleation overpotential of 18 mV,high CE of 98%,and stable cycling without obvious voltage fluctuation for over 600 cycles at a current density of 1 mA cm^(-2).Our study not only provides a good CB@rGO host and pre-Lithiated CB@rGO composite anode electrode,but also brings a new strategy of designing 3D electrodes for those active materials suffering from severe volume expansion.

关键词： dendrite inhibition Li metal host lithium metal battery bowl-like carbon/reduced graphene nanosheets hybrids

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Leaf-inspired design of mesoporous Sb_(2)S_(3)/N-doped Ti_(3)C_(2)T_(x) composite towards fast sodium storage

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Science China Chemistry 2021年第6期64卷 964-973页

作者： Fengyi He Cheng Tang Guanjia Zhu Yadong Liu Aijun Du qiaobao zhang Minghong Wu Haijiao zhang Institute of Nanochemistry and Nanobiology Shanghai UniversityShanghai 200444China School of Environmental and Chemical Engineering Shanghai UniversityShanghai 200444China School of Chemistry Physics and Mechanical EngineeringScience and Engineering FacultyQueensland University of TechnologyBrisbane QLD 4001Australia Department of Materials Science and Engineering College of MaterialsXiamen UniversityXiamen 361005China

Owing to excellent conductivity and abundant surface terminals,MXene-based heterostructures have been intensively investigated as energy storage ***,elaborate design of the structure and composition of MXene-based hybrids towards superior electrochemical performance is still ***,we present an ingenious leaf-inspired design for preparing a unique Sb_(2)S_(3)/nitrogen-doped Ti_(3)C_(2)T_(x)MXene(L-Sb_(2)S_(3)/Ti_(3)C_(2))***-situ TEM observations reveal that the leaflike Sb_(2)S_(3)nanoparticles with numerous mesopores can well relieve the large volume changes via an inward pore filling mechanism with only 20%outward expansion,whereas highly conductive N-doped Ti_(3)C_(2)T_(x)nanosheets can serve as the robust mechanical support to reinforce the structural integrity of the *** from the structural and constituent merits,the L-Sb_(2)S_(3)/Ti_(3)C_(2)anode fabricated exhibits a fast sodium storage behavior in terms of outstanding rate capability(339.5 mA h g^(-1)at 2,000 mA g^(-1))and high reversible capacity at high current density(358.2 mA h g^(-1)at 1,000 mA g^(-1)after 100 cycles).Electrochemical kinetic tests and theoretical simulation further manifest that the boosted electrochemical performance mainly arises from such a unique leaf-like Sb_(2)S_(3)mesoporous nanostructure with abundant active sites,and enhanced Na^(+)adsorption energy on the heterojunction formed between Sb_(2)S_(3)nanoparticles and Ti_(3)C_2)matrix.

关键词： Sb_(2)S_(3) Ti_(3)C_(2)T_(x)MXene mesoporous structure anode materials sodium-ion batteries

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Highly integrated sulfur cathodes with strong sulfur/high-strength binder interactions enabling durable high-loading lithium-sulfur batteries

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Journal of Energy Chemistry 2020年第10期29卷 71-79页

作者： Arif Rashid Xingyu Zhu Gulian Wang Chengzhi Ke Sha Li Pengfei Sun Zhongli Hu qiaobao zhang Li zhang College of Energy Soochow Institute for Energy and Materials InnovationsSoochow UniversitySuzhou 215006JiangsuChina Department of Materials Science and Engineering College of MaterialsXiamen UniversityXiamen 361005FujianChina State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry College of Chemistry and Chemical EngineeringXiamen UniversityXiamen 361005FujianChina

The development of high-sulfur-loading Li-S batteries is a key prerequisite for their commercial *** requires to surmount the huge polarization,severe polysulfide shuttling and drastic volume change caused by electrode ***-strength polar binders are ideal for constructing robust and long-life high-loading sulfur cathodes but show very weak interfacial interaction with non-polar sulfur *** address this issue,this work devises a highly integrated sulfur@polydopamine/highstrength binder composite cathodes,targeting long-lasting and high-sulfur-loading Li-S *** super-adhesion polydopamine(PD)can form a uniform nano-coating over the graphene/sulfur(G-S)surface and provide strong affinity to the cross-linked polyacrylamide(c-PAM)binder,thus tightly integrating sulfur with the binder network and greatly boosting the overall mechanical strength/conductivity of the ***,the PD coating and c-PAM binder rich in polar groups can form two effective blockades against the effusion of soluble *** such,the 4.5 mg cm−2 sulfur-loaded G-S@PD-c-PAM cathode achieves a capacity of 480 mAh g−1 after 300 cycles at 1 C,while maintaining a capacity of 396 mAh g−1 after 50 cycles at 0.2 C when the sulfur loading rises to 9.1 mg cm−*** work provides a system-wide concept for constructing high-loading sulfur cathodes through integrated structural design.

关键词： Cross-linked high-strength polar binder Highly integrated electrode structure High-sulfur-loading Li-S battery Polydopamine nano-bonding layer Strong sulfur/binder interaction

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Atomic mechanisms of hexagonal close-packed Ni nanocrystallization revealed by in situ liquid cell transmission electron microscopy

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Nano Research 2022年第7期15卷 6772-6778页

作者： Junyu zhang Miao Li Zewen Kang Bensheng Xiao Haichen Lin Jingyu Lu Haodong Liu Xue zhang Dong-Liang Peng qiaobao zhang Instrumental Analysis Center Laboratory and Equipment Management DepartmentHuaqiao UniversityXiamen 361021China Department of Materials Science and Engineering College of MaterialsXiamen UniversityXiamen 361005China College of Chemical Engineering Huaqiao UniversityXiamen 361021China Center for Materials and Interfaces Shenzhen Institutes of Advanced TechnologyChinese Academy of Sciences1068 Xueyuan AvenueShenzhen 518055China Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM) Xiamen 361005China School of Science Harbin Institute of Technology(Shenzhen)Shenzhen 518055China Chemical Engineering University of California San DiegoLa JollaCA 92093USA

The fundamental understanding of the mechanism underlying the early stages of crystallization of hexagonal-close-packed(hcp)nanocrystals is crucial for their synthesis with desired properties,but it remains a significant ***,we report using in situ liquid cell transmission electron microscopy(TEM)to directly capture the dynamic nucleation process and track the real-time growth pathway of hcp Ni nanocrystals at the atomic *** is demonstrated that the growth of amorphous-phase-mediated hcp Ni nanocrystals is from the metal-rich liquid *** addition,the reshaped preatomic facet development of a single nanocrystal is also *** calculations further identify the non-classical features of hcp Ni *** discoveries could enrich the nucleation and growth model theory and provide useful information for the rational design of synthesis pathways of hcp nanocrystals.

关键词： hexagonal-close-packed(hcp)nanocrystals liquid cell transmission electron microscopy(TEM) amorphous-phasemediated reshape

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Deciphering the potassium storage phase conversion mechanism of phosphorus by combined solid-state NMR spectroscopy and density functional theory calculations

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Journal of Energy Chemistry 2023年第4期79卷 45-53页

作者： Huixin Chen Lingyi Meng Hongjun Yue Chengxin Peng qiaobao zhang Guiming Zhong Ding Chen State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body College of Mechanical and Vehicle EngineeringHunan UniversityChangsha 410082HunanChina CAS Key Laboratory of Design and Assembly of Functional Nanostructures and Fujian Provincial Key Laboratory of NanomaterialsFujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002FujianChina Laboratory of Advanced Spectro-electrochemistry and Li-ion Batteries Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023LiaoningChina Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Institute of Rare Earth MaterialsHaixi InstitutesChinese Academy of SciencesXiamen 361021FujianChina Department of Materials Science and Engineering College of MaterialsXiamen UniversityXiamen 361005FujianChina School of Materials Science and Chemistry University of Shanghai for Science and TechnologyShanghai 200093China

Phosphorus is the potential anode material for emerging potassium-ion batteries(PIBs)owing to the highest specific capacity and relatively low operation ***,the reversible delivered capacities of phosphorus-based anodes,in reality,are far from the theoretical capacity corresponding to the formation of K3P ***,their underlying potassium storage mechanisms remain poorly *** address this issue,for the first time,we perform high-resolution solid-state31P NMR combined with XRD measurements,and density functional theory calculations to yield a systemic quantitative understanding of(de)potassiation reaction mechanism of phosphorus *** explicitly reveal a previously unknown asymmetrical nanocrystalline-to-amorphous transition process via rP←→(K_(3)P_(11),K_(3)P_(7),beta-K_(4)P_(6))←→(alpha-K4P6)←→(K_(1-x)P,KP,K_(4-x)P3,K_(1+x)P)←→(amorphous K4P3,amorphous K3P)that are proceed along with the electrochemical potassiation/depotassiation ***,the corresponding KP alloys intermediates,such as the amorphous phases of K_(4)P_(3),K_(3)P,and the nonstoichiometric phases of“K_(1-x)P”,“K_(1+x)P”,“K_(4-x)P_(3)”are experimentally detected,which indicating various complicated K-P alloy species are coexisted and evolved with the sluggish electrochemical reaction kinetics,resulting in lower capacity of phosphorus-based *** findings offer some insights into the specific multi-phase evolution mechanism of alloying anodes that may be generally involved in conversion-type electrode materials for PIBs.

关键词： Red phosphorus Phase conversion Solid-state NMR Potassium ion batteries

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Understanding the growth mechanisms of metal-based core–shell nanostructures revealed by in situ liquid cell transmission electron microscopy

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Journal of Energy Chemistry 2022年第8期31卷 370-383,I0010页

作者： Junyu zhang Bensheng Xiao Junhui Zhao Miao Li Haichen Lin Zewen Kang Xianwen Wu Haodong Liu Dong-Liang Peng qiaobao zhang Instrumental Analysis Center Laboratory and Equipment Management DepartmentHuaqiao UniversityXiamen 361021FujianChina Department of Materials Science and Engineering College of MaterialsXiamen UniversityXiamen 361005FujianChina College of Materials Science and Engineering Huaqiao UniversityXiamen 361021FujianChina College of Chemical Engineering Huaqiao UniversityXiamen 361021FujianChina Chemical Engineering UC San DiegoLa JollaCA 92093United States School of Chemistry and Chemical Engineering Jishou UniversityJishou 416000HunanChina

Metal-based core-shell nanostructures have garnered enduring interest due to their unique properties and ***,their growth and transformation mechanisms in liquid media remain largely unknown because they lack direct observation of the dynamic growth process with high spatial and temporal *** the in situ liquid cell transmission electron microscopy(TEM)technique offers unprecedented real-time imaging and spectroscopy capabilities to directly track the evolution of structural and chemical transformation of metal-based core–shell nanostructures in liquid media under their working ***,this review highlights recent progress in utilizing in situ liquid cell TEM characterization technique in investigating the dynamic evolution of material structure and morphology of metal-based core–shell nanostructures at the nano/atomic scale in real-time.A brief introduction of the development of liquid cells for in situ TEM is first ***,recent advances in in situ liquid cell TEM for the fundamental study of growth mechanisms of metal based core–shell nanostructures are ***,the challenge and future developments of metalbased core–shell nanostructures for in situ liquid cell TEM are *** review is anticipated to inspire ongoing interest in revealing unseen growth dynamics of core–shell nanostructures by in situ liquid cell TEM technique.

关键词： In situ liquid cell TEM Metal-based core–shell nanostructures Growth mechanisms

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Advances in the structure design of substrate materials for zinc anode of aqueous zinc ion batteries

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Green Energy & Environment 2023年第6期8卷 1531-1552页

作者： Sinian Yang Hongxia Du Yuting Li Xiangsi Wu Bensheng Xiao zhangxing He qiaobao zhang Xianwen Wu School of Chemistry and Chemical Engineering Jishou UniversityJishou416000China School of Chemical Engineering North China University of Science and TechnologyTangshan063009China Department of Materials Science and Engineering College of MaterialsXiamen UniversityXiamen361005China Key Laboratory of High Performance Ceramics Fibers(Xiamen University) Ministry of EducationXiamen361005China

Aqueous zinc ion batteries(AZIBs) demonstrate tremendous competitiveness and application prospects because of their abundant resources,low cost, high safety, and environmental friendliness. Although the advanced electrochemical energy storage systems based on zinc ion batteries have been greatly developed, many severe problems associated with Zn anode impede its practical application, such as the dendrite formation,hydrogen evolution, corrosion and passivation phenomenon. To address these drawbacks, electrolytes, separators, zinc alloys, interfacial modification and structural design of Zn anode have been employed at present by scientists. Among them, the structural design for zinc anode is relatively mature, which is generally believed to enhance the electroactive surface area of zinc anode, reduce local current density, and promote the uniform distribution of zinc ions on the surface of anode. In order to explore new research directions, it is crucial to systematically summarize the structural design of anode materials. Herein, this review focuses on the challenges in Zn anode, modification strategies and the three-dimensional(3D) structure design of substrate materials for Zn anode including carbon substrate materials, metal substrate materials and other substrate materials. Finally, future directions and perspectives about the Zn anode are presented for developing high-performance AZIBs.

关键词： Zinc ion battery Structure design of substrate materials Dendrite-free 3D Zn anode

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Liquid-phase sintering enabling mixed ionic-electronic interphases and free-standing composite cathode architecture toward high energy solid-state battery

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Nano Research 2022年第7期15卷 6156-6167页

作者： Xiang Han Weijun Zhou Minfeng Chen Linshan Luo Lanhui Gu qiaobao zhang Jizhang Chen Bo Liu Songyan Chen Wenqing zhang College of Materials Science and Engineering Nanjing Forestry UniversityNanjing 210037China Department of Physics Xiamen UniversityXiamen 361005China College of Mathematics and Physics Jinggangshan UniversityJi’an 343009China Department of Materials Science and Engineering College of MaterialsXiamen 361005China Department of Physics Southern University of Science and TechnologyShenzhen 518055China

Solid-state batteries(SSBs)will potentially offer increased energy density and,more importantly,improved safety for next generation lithium-ion(Li-ion)*** enabling technology is solid-state composite cathodes with high operating voltage and area *** composite cathode manufacturing technologies,however,suffer from large interfacial resistance and low active mass loading that with excessive amounts of polymer electrolytes and conductive ***,we report a liquidphase sintering technology that offers mixed ionic-electronic interphases and free-standing electrode architecture design,which eventually contribute to high area capacity.A small amount(~4 wt.%)of lithium hydroxide(LiOH)and boric acid(H_(3)BO_(3))with low melting point are utilized as sintering additives that infiltrate into single-crystal Ni-rich LiNi_(0.8)Mn_(0.1)Co_(0.1)(NMC811)particles at a moderately elevated temperature(~350℃)in a liquid state,which not only enable intimate physical contact but also promote the densification *** addition,the liquid-phase additives react and transform to ionic-conductive lithium boron oxide,together with the indium tin oxide(ITO)nanoparticle coating,mixed ionic-electronic interphases of composite cathode are successfully ***,the liquid-phase sintering performed at high-temperature(~800℃)also enables the fabrication of highly dense and thick composite cathodes with a novel free-standing *** promising performance characteristics of such composite cathodes,for example,delivering an area capacity above 8 mAh·cm^(−2) within a wide voltage window up to 4.4 V,open new opportunities for SSBs with a high energy density of 500 Wh·kg^(−1) for safer portable electronic and electrical transport.

关键词： solid-state battery single-crystal Ni-rich LiNi_(0.8)Mn_(0.1)Co_(0.1) liquid-phase sintering mixed ionic-electronic interphases freestanding architecture

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