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An intermittent lithium deposition model based on CuMnbimetallic MOF derivatives for composite lithium anode with ultrahigh areal capacity and current densities

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Nano Research 2024年第4期17卷 2763-2769页

作者： Tao Wei Yanyan Zhou Cheng Sun Xingtong Guo Shoudong Xu Daifen Chen yongfu tang School of Energy and Power Jiangsu University of Science and TechnologyZhenjiang 212003China State Key Laboratory of Metastable Materials Science and Technology(MMST) Hebei Key Laboratory of Applied ChemistryYanshan UniversityQinhuangdao 066004China College of Materials Science and Engineering Taiyuan University of TechnologyTaiyuan 030024China

Recently,three-dimensional(3D)conductive frameworks have been chosen as the host for composite lithium(Li)metal anode because of their exceptional electrical conductivity and remarkable thermal and electrochemical ***,Li tends to accumulate on the top of the 3D frameworks with homogenous lithiophilicity and Li dendrite still *** work firstly designed a bimetallic metal-organic framework(MOF)(CuMn-MOF)derived Cu_(2)O and Mn_(3)O_(4) nanoparticles decorated carbon cloth(CC)substrates(CC@Cu_(2)O/Mn_(3)O_(4))to fabricate a composite Li *** to the synergistic effects of lithiophilic Cu_(2)O and Mn_(3)O_(4),the CC@Cu_(2)O/Mn_(3)O_(4)@Li symmetrical cell can afford a prolonged cycling lifespan(1400 h)under an ultrahigh current density and areal capacity(6 mA·cm^(-2)/6 mAh·cm^(-2)).When coupled with the LiFePO_(4)(LFP)cathode,the LFP||CC@Cu_(2)O/Mn_(3)O_(4)@Li full cell demonstrated a superior performance of 89.7 mAh·g^(-1) even at an extremely high current density(10 C).Furthermore,it can also be matched well with LiNi_(0.5)Co^(0).2Mn_(0.3)O_(2)(NCM523)***,to explain the excellent performances of the CC@Cu_(2)O/Mn_(3)O_(4)@Li composite anode,an intermittent model was also *** study offers a novel model that can enhance our comprehension of the Li deposition behavior and pave the way to attain stable and safe Li metal anodes by employing bimetallic MOF-derived materials to construct 3D frameworks.

关键词： lithium metal anode(LMA) three-dimensional(3D)frameworks intermittent lithiophilic model high areal capacity bimetallic metal-organic frameworks(MOFs)

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In-situ imaging the electrochemical reactions of Li-CO_(2) nanobatteries at high temperatures in an aberration corrected environmental transmission electron microscope

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Nano Research 2022年第1期15卷 542-550页

作者： Peng Jia Meiqi Yu Xuedong Zhang Tingting Yang Dingding Zhu Tongde Shen Liqiang Zhang yongfu tang Jianyu Huang Clean Nano Energy Center State Key Laboratory of Metastable Materials Science and TechnologyYanshan UniversityQinhuangdao 066004China Key Laboratory of Low Dimensional Materials and Application Technology of Ministry of Education School of Materials Science and EngineeringXiangtan UniversityXiangtan 411105China Hebei Key Laboratory of Applied Chemistry College of Environmental and Chemical EngineeringYanshan UniversityQinhuangdao 066004China

Rechargeable lithium-carbon dioxide(Li-CO_(2))batteries have attracted much attention due to their high theoretical energy densities and capture of C0_(2).However,the electrochemical reaction mechanisms of rechargeable Lo-CO_(2) batteries,particularly the decomposition mechanisms of the discharge product Li_(2)CO_(3) are still unclear,impeding their practical *** electrochemistry of Li_(2)CO_(3) is critical for improving the performance of Li-C0_(2) ***,in-situ environmental transmission electron microscopy(ETEM)technique was used to study electrochemistry of Li_(2)CO_(3) in Li-C0_(2) batteries during discharge and charge *** discharge,Li_(2)CO_(3) was nucleated and accumulated on the surface of the cathode media such as carbon nanotubes(CNTs)and Ag nanowires(Ag NWs),but it was hard to decompose during charging at room *** promote the decomposition of Li2C03,the charge reactions were conducted at high temperatures,during which Li_(2)CO_(3) was decomposed to lithium with release of *** functional theory(DFT)calculations revealed that the synergistic effect of temperature and biasing facilitates the decomposition of Li_(2)CO_(3).This study not only provides a fundamental understanding to the high temperature Li-C0_(2) nanobatteries,but also offers a valid technique,i.e.,discharging/charging at high temperatures,to improve the cyclability of Li-CO_(2) batteries for energy storage applications.

关键词： in-situ environmental transmission electron microscopy high temperature Li-C0_(2)nanobatteries electrochemistry Li2CO3

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In situ observation of electrochemical Ostwald ripening during sodium deposition

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Nano Research 2022年第3期15卷 2650-2654页

作者： Lin Geng Qiunan Liu Jingzhao Chen Peng Jia Hongjun Ye Jitong Yan Liqiang Zhang yongfu tang Jianyu Huang Clean Nano Energy Center State Key Laboratory of Metastable Materials Science and TechnologyYanshan UniversityQinhuangdao 066004China Key Laboratory of Low Dimensional Materials and Application Technology of Ministry of Education School of Materials Science and EngineeringXiangtan UniversityXiangtan 411105China Hebei Key Laboratory of Applied Chemistry College of Environmental and Chemical EngineeringYanshan UniversityQinhuangdao 066004China

Sodium(Na)metal batteries(SMBs)using Na anode are potential“beyond lithium”electrochemical technology for future energy storage ***,uncontrollable Na dendrite growth has plagued the application of *** Na deposition mechanisms,particularly the early stage of Na deposition kinetics,is critical to enable the *** this context,we conducted in situ observations of the early stage of electrochemical Na *** revealed an important electrochemical Ostwald ripening(EOR)phenomenon which dictated the early stage of Na ***,small Na nanocrystals were nucleated randomly,which then *** growth,smaller Na nanocrystals were contained by bigger ones via *** observed two types of EOR with one involving only electrochemical reaction driven by electrochemical potential difference between bigger and smaller nanocrystals;while the other being dominated by mass transport governed by surface energy *** results provide new understanding to the Na deposition mechanism,which may be useful for the development of SMB for energy storage applications.

关键词： in situ Na deposition electrochemical Ostwald ripening(EOR) Na nanocrystals

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Metal–organic framework-derived Co_(3)O_(4)modified nickel foam-based dendrite-free anode for robust lithium metal batteries

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Chinese Chemical Letters 2023年第8期34卷 382-386页

作者： Tao Wei Jiahao Lu Pan Zhang Guang Yang Cheng Sun Yanyan Zhou Quanchao Zhuang yongfu tang School of Energy and Power Jiangsu University of Science and TechnologyZhenjiang 212003China Hebei Key Laboratory of Applied Chemistry School of Environmental and Chemical EngineeringYanshan UniversityQinhuangdao 066004China Li-ion Batteries Lab School of Materials Science and EngineeringChina University of Mining and TechnologyXuzhou 221116China

For several decades,the promise of implementing of lithium(Li)metal anodes for Li batteries has been a"holy grail"for ***,we have proposed a facile design of a MOF-derived Co_(3)O_(4)nanoparticles modified nickel foam,i.e.,Co_(3)O_(4)-NF,as a 3D host to achieve a uniform infusion of the molten *** molten Li was uniformly absorbed on the Co_(3)O_(4)-NF host only in 10 s due to its high Li *** obtained Li-Co_(3)O_(4)-NF composite electrode shows high cycling stability in symmetric cells with low voltage hysteresis even at a high current density of 5 mA/*** full cells of Li-Co_(3)O_(4)-NF/LiFePO_(4)can cycle for more than 500 cycles at 2C without obvious capacity *** after cycling and in situ optical microscope results suggest that the unique 3D host structure of the Li-Co_(3)O_(4)-NF anode plays key roles on suppressing the dendrite growth and decreasing the local current *** believe this work might provide a new strategy for fabricating dendrite-free Li metal anodes and facilitate practical applications in Li batteries.

关键词： All solid-state lithium-ion batteries Metal-organic frameworks(MOFs) Lithium metal anodes Dendrite-free anode Three-dimensional anode

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Prestoring lithium into SnO_(2)coated 3D carbon fiber cloth framework as dendrite-free lithium metal anode

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Particuology 2024年第1期84卷 89-97页

作者： Tao Wei Yanyan Zhou Cheng Sun Lesheng Liu Sijia Wang Mengting Wang Ye Liu Qing Huang Quanchao Zhuang yongfu tang School of Energy and Power Jiangsu University of Science and TechnologyZhenjiang212003China College of Materials Science and Engineering Nanjing Forestry UniversityNanjing210037China Li-ion Batteries Lab School of Materials Science and EngineeringChina University of Mining and TechnologyXuzhouChina Hebei Key Laboratory of Applied Chemistry School of Environmental and Chemical EngineeringYanshan UniversityQinhuangdao066004China

For several decades,the promise of implementing of lithium(Li)metal anodes has been regarded as the"holy grail"for Li-based ***,we have proposed a facile design of a carbon fiber cloth(CFC)framework coated with SnO_(2)nanoparticles through a hydrothermal process,which served as a reliable host for prestoring molten Li to produce a CFC@SnO_(2)@Li composite ***,TEM,HRTEM,XPS and different electrochemical characterizations were carried *** to the synergetic effects of the 3D conductive CFC and the coated lithiophilic SnO_(2)nanoparticles,the designed CFC@SnO_(2)@Li electrodes can buffer the volume changes and reduce the local current density,thus suppress the Li dendrites during ***,the CFC@SnO_(2)electrodes showed a high and stable CE of 98.6%for 1000 cycles at a current density of 1 mA cm^(-2)(1 mAh cm^(-2)).What is more,at a high current density of 5 mA cm^(-2)and a high areal capacity of 5 mAh cm^(-2),the symmetric cell displayed relatively low overpotential and long cycling lifetime of 1600 *** results confirm its great potential as lithium metal anodes in practical battery applications.

关键词： Lithiophilic Lithium metal anodes SnO_(2) 3D anode Dendrite-free

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An intermittent lithium deposition model based on bimetallic MOFs derivatives for dendrite-free lithium anode with ultrahigh areal capacity

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Chinese Chemical Letters 2024年第8期35卷 520-525页

作者： Tao Wei Jiahao Lu Pan Zhang Qi Zhang Guang Yang Ruizhi Yang Daifen Chen Qian Wang yongfu tang School of Energy and Power Jiangsu University of Science and TechnologyZhenjiang 212003China State Key Laboratory of Metastable Materials Science and Technology(MMST) Hebei Key Laboratory of Applied ChemistryYanshan UniversityQinhuangdao 066004China College of Materials Science and Engineering Taiyuan University of TechnologyTaiyuan 030024China College of Energy Soochow UniversitySuzhou 215006China School of Low-carbon Energy and Power Engineering China University of Mining and TechnologyXuzhou 221116China

In the development of 3D conductive frameworks for lithium metal anode(LMA),two models have been proposed:top growth model and bottom-up growth ***,Li tends to accumulate on the top of these 3D frameworks with homogenous lithiophilicity(top growth)and Li dendrite still *** address this issue,some researchers have focused on developing 3D frameworks with gradient lithio-philicity,which realized bottom-up growth of ***,partial Li nucleation sites on the top of these frameworks were *** by the two models talked above,this work firstly proposed a novel intermittent lithiophilic model for lithium *** demonstrate the feasibility of this model,a bimetallic metal-organic frameworks derived ZnMn_(2)O_(4)-MnO nanoparticles were grown on carbon cloth for *** can cycle stably under ultra-high current and areal capacity(10 mA/cm^(2),10 mAh/cm^(2)).The in-situ optical microscopy(OM)was conducted to observe the Li deposition behavior,no dendrite was found during 80 h in ester-based electrolyte while the pure Li only cycled for *** is more,it can also be well-coupled with LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode and solid-state electrolyte,which further prove the advantages of the intermittent model for the development of LMAs with high safety and high energy density.

关键词： Intermittent lithiophilic model Lithium metal anode(LMA) Three-dimensional(3D)frameworks Lithiophilic Bimetallic metal-organic frameworks(MOFs)

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Synergy mechanism of defect engineering in MoS_(2)/FeS_(2)/C heterostructure for high-performance sodium-ion battery

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Journal of Energy Chemistry 2023年第7期82卷 268-276,I0006页

作者： Linlin Ma Xiaomei Zhou Jun Sun Pan Zhang Baoxiu Hou Shuaihua Zhang Ningzhao Shang Jianjun Song Hongjun Ye Hui Shao yongfu tang Xiaoxian Zhao Department of Chemistry College of ScienceHebei Agricultural UniversityBaoding 071001HebeiChina Hebei Key Laboratory of Applied Chemistry School of Environmental and Chemical EngineeringYanshan UniversityQinhuangdao 066004HebeiChina College of Chemistry Nankai UniversityTianjin 300071China Clean Nano Energy Center State Key Laboratory of Metastable Materials Science and TechnologyYanshan UniversityQinhuangdao 066004HebeiChina College of Physics Qingdao UniversityQingdao 266071HebeiChina CIRIMAT UniversitéPaul Sabatier31062 ToulouseFrance

MoS_(2) is a promising anode material in sodium-ion battery technologies for possessing high theoretical ***,the sluggish Na^(+) diffusion kinetics and low electronic conductivity hinder the ***,a unique MoS_(2)/FeS_(2)/C heterojunction with abundant defects and hollow structure(MFCHHS)was *** synergy of defect engineering in MoS_(2),FeS_(2),and the carbon layer of MFCHHS with a larger specific surface area provides multiple storage sites of Na^(+)corresponding to the surface-controlled *** MoS_(2)/FeS_(2)/C heterostructure and rich defects in MoS_(2) and carbon layer lower the Na^(+) diffusion energy ***,the construction of MoS_(2)/FeS_(2) heterojunction promotes electron transfer at the interface,accompanying with excellent conductivity of the carbon layer to facilitate reversible electrochemical *** abundant defects and mismatches at the interface of MoS_(2)/FeS_(2) and MoS_(2)/C heterojunctions could relieve lattice stress and volume change *** a result,the MFCHHS anode exhibits the high capacity of 613.1 mA h g^(-1)at 0.5 A g^(-1) and 306.1 mA h g^(-1) at 20 A g^(-1).The capacity retention of 85.0%after 1400 cycles at 5.0 A g^(-1) is *** density functional theory(DFT)calculation and in situ transmission electron microscope(TEM),Raman,ex-situ X-ray photon spectroscopy(XPS)studies confirm the low volume change during intercalation/deintercalation process and the efficient Na^(+)storage in the layered structure of MoS_(2) and carbon layer,as well as the defects and heterostructures in *** believe this work could provide an inspiration for constructing heterojunction with abundant defects to foster fast electron and Na^(+) diffusion kinetics,resulting in excellent rate capability and cycling stability.

关键词： Defect engineering Heterostructure Hollow structure Sodium-ion battery MoS_(2)/FeS_(2)

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Boosting the energy density of sulfide-based all-solid-state batteries at low temperatures by charging to high voltages up to 6 V

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Nano Research 2023年第8期16卷 10966-10975页

作者： Lun Zhang Xuedong Zhang Zhaoyu Rong Tao Wang Zhenyu Wang Zaifa Wang Longchen Zhang Qiao Huang Lingyun Zhu Liqiang Zhang yongfu tang Jianyu Huang Key Laboratory of Low Dimensional Materials and Application Technology of Ministry of Education School of Materials Science and EngineeringXiangtan UniversityXiangtan 411105China Clean Nano Energy Center State Key Laboratory of Metastable Materials Science and TechnologyYanshan UniversityQinhuangdao 066004China Guilin Electrical Equipment Scientific Research Institute Co. LtdGuilin 541004China GRINM(Guangdong)Institute for Advanced Materials and Technology Foshan 528000China Hebei Key Laboratory of Applied Chemistry College of Environmental and Chemical EngineeringYanshan UniversityQinhuangdao 066004China School of Materials Science&Engineering Anhui UniversityHefei 230601China

Sulfide electrolyte-based all-solid-state batteries(ASSBs)are potential next generation energy storage technology due to the high ionic conductivity of sulfide electrolytes and potentially improved energy density and ***,the performance of ASSBs at/below subzero temperatures has not been explored ***,low temperature(LT)performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)|Li_(9.54)Si_(1.74)P_(1.44)S11.7Cl_(0.3)(LiSPSCl)|Li_(4)Ti_(5)O_(12)(LTO)ASSBs was *** charging the ASSB to 6 V at−40℃,a capacity of 100.7 mAh∙g^(−1)at 20 mA∙g^(−1)was achieved,which is much higher than that charged to 4.3 V(4.6 mAh∙g^(−1))at−40℃.Moreover,atomic resolution microscopy revealed that the NCM811 remained almost intact even after being charged to 6 *** contrast,NCM811 was entirely destructed when charged to 6 V at room *** sharp difference arises from the large internal charge transfer resistance at LT which requires high voltage to ***,such high voltage is not harmful to the active material but beneficial to extracting most energy out of the ASSBs at *** also demonstrated that thinner electrolyte is favorable for LT operation of ASSBs due to the reduced ion transfer *** work provides new strategies to boost the capacity and energy density of sulfide-based ASSBs at LT for dedicated LT applications.

关键词： all-solid-state lithium batteries sulfide solid electrolyte low temperature Li_(4)Ti_(5)O_(12)(LTO)

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Tailoring lithium concentration in alloy anodes for long cycling and high areal capacity in sulfide-based all solid-state batteries

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eScience 2023年第1期3卷 71-79页

作者： Zaifa Wang Jun Zhao Xuedong Zhang Zhaoyu Rong yongfu tang Xinyu Liu Lingyun Zhu Liqiang Zhang Jianyu Huang Clean Nano Energy Center State Key Laboratory of Metastable Materials Science and TechnologyYanshan UniversityQinhuangdao 066004China Key Laboratory of Low Dimensional Materials and Application Technology of Ministry of Education School of Materials Science and EngineeringXiangtan UniversityXiangtanHunan 411105China Guilin Electrical Equipment Scientific Research Institute Co. LtdGuilin541004China Hebei Key Laboratory of Applied Chemistry College of Environmental and Chemical EngineeringYanshan UniversityQinhuangdao066004China School of Materials Science&Engineering Anhui UniversityHefei 230601PR China

Lithium–indium(Li-In)alloys are important anode materials for sulfide-based all-solid-state batteries(ASSBs),but how different Li concentrations in the alloy anodes impact the electrochemical performance of ASSBs remains *** paper systematically investigates the impact that different Li concentrations in Li-In anodes have on the performance of *** show that In with 1 wt%Li(LiIn-1)exhibits the best performance for ASSBs among all the tested Li-In *** essence,LiIn-1 not only provides sufficient Li to compensate for first-cycle capacity loss in the anode but also facilitates the formation of a LiIn alloy phase that has the best charge transfer kinetics among all the Li_(x) In alloy *** ASSB with a LiIn-1 anode and a LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2) cathode reached 3400 cycles at an initial capacity of 125 mAh/***,ASSBs with a high cathode active material(CAM)loading of 36 mg/cm 2 delivered a high areal capacity of 4.05 mAh/cm^(2) at high current density(4.8 mA/cm^(2)),with a capacity retention of 92% after 740 *** an ultra-high CAM loading of 55.3 mg/cm^(2),the ASSB achieved a stable areal capacity of 8.4 mAh/cm^(2) at current density of 1.7 mA/cm *** results bring us one step closer to the practical application of ASSBs.

关键词： All solid-state batteries Sulfide solid electrolyte Ni-rich cathode Li concentration

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Revealing alkali metal ions transport mechanism in the atomic channels of Au@a-MnO_(2)

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Journal of Energy Chemistry 2023年第7期82卷 350-358,I0008页

作者： Jingzhao Chen Yong Su Hongjun Ye Yushu tang Jitong Yan Zhiying Gao Dingding Zhu Jingming Yao Xuedong Zhang Tingting Yang Baiyu Guo Hui Li Qiushi Dai Yali Liang Jun Ma Bo Wang Haiming Sun Qiunan Liu Jing Wang Congcong Du Liqiang Zhang yongfu tang Jianyu Huang Clean Nano Energy Center State Key Laboratory of Metastable Materials Science and TechnologyYanshan UniversityQinhuangdao 066004HebeiChina School of Materials Science and Engineering Xiangtan UniversityXiangtan 411105HunanChina Hebei Key Laboratory of Applied Chemistry College of Environmental and Chemical EngineeringYanshan UniversityQinhuangdao 066004HebeiChina

Understanding alkali metal ions’(e.g.,Li^(+)/Na^(+)/K^(+))transport mechanism is challenging but critical to improving the performance of alkali metal *** using a-MnO_(2)nanowires as cathodes,the transport kinetics of Li^(+)/Na^(+)/K^(+)in the 2×2 channels of a-MnO_(2)with a growth direction of[001]is *** show that ion radius plays a decisive role in determining the ion transport and *** of the ion radii,Li^(+)/Na^(+)/K^(+)can all go through the 2×2 channels of a-MnO_(2),generating large stress and causing channel merging or ***,smaller ions such as Li^(+)and Na^(+)cannot only transport along the[001]direction but also migrate along thedirection to the nanowire surface;for large ion such as K^(+),diffusion along thedirection is *** different ion transport behavior has grand consequences in the electrochemistry of metal oxygen batteries(MOBs).For Li-O_(2)battery,Li^(+)transports uniformly to the nanowire surface,forming a uniform layer of oxide;Na^(+)also transports to the nanowire surface but may be clogged locally due to its larger radius,therefore sporadic pearl-like oxides form on the nanowire surface;K^(+)cannot transport to the nanowire surface due to its large radius,instead,it breaks the nanowire locally,causing local deposition of potassium *** study provides atomic scale understanding of the alkali metal ion transport mechanism which may be harnessed to improve the performance of MOBs.

关键词： Ion transport In-situ TEM STEM Metal oxygen batteries Metal ion batteries

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