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Boosting the performance of liNi_(0.90)Co_(0.06)Mn_(0.04)O_(2) electrode by uniform li_(3)PO_(4) coating via atomic layer deposition

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Chinese Chemical Letters 2024年第5期35卷 499-503页

作者： Mingjiao Lu Zhixing Wang Gui Luo Huajun Guo Xinhai li Guochun Yan Qihou li Xianglin li Ding Wang Jiexi Wang School of Metallurgy and Environment Central South UniversityChangsha 410083China BASF ShanShan Battery Materials Co. Ltd.Changsha 410006China Engineering Research Center of the Ministry of Education for Advanced Battery Materials Central South UniversityChangsha 410083China Hunan Provincial Key Laboratory of Nonferrous Value-Added Metallurgy Central South UniversityChangsha 410083China School of Physics and Chemistry Hunan First Normal UniversityChangsha 410205China National and Local Joint Engineering Laboratory for lithium-ion Batteries and Materials Preparation Technology Key Laboratory of Advanced Battery Materials of Yunnan ProvinceFaculty of Metallurgical and Energy EngineeringKunming University of Science and TechnologyKunming 650093China

Ultra-high nickel material is considered to be a promising cathode ***,with the increase of nickel content,the interfacial side reactions between the cathode and electrolyte become increasingly ***,an atomically controllable ionic conductor li_(3)PO_(4)(LPO)coating is deposited on the liNi_(0.90)Co_(0.06)Mn_(0.04)O_(2)(NCM9064)based electrode by the atomic layer deposition *** results shows that the LPO coating is uniformly and densely covered on the surface of secondary particles of NCM9064,helping to prevent the direct contact between the electrolyte and cathode during the chargingdischarging *** addition,the coating layer is electrochemically *** a result,the interfacial side reactions during the long cycle are effectively suppressed,and the solid electrolyte interphase layer at the interface is *** electrode with 20 layers of LPO deposition(ALD-LPO-20)exhibits an excellent capacity retention of 81%after 200 cycles in 2.8-4.3 V at 25℃,which is 18%higher than the unmodified material(ALD-LPO-0).Besides,the moderate LPO coating improves the rate capability and high temperature cycling performance of *** study provides a method for the modification of ultra-high nickel cathode materials and corresponding electrodes.

关键词： Ultra-high nickel material liNi_(0.90)Co_(0.06)Mn_(0.04)O_(2) Atomic layer deposition li_(3)PO_(4) Ionic conductor

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Hard-carbon hybrid li-ion/metal anode enabled by preferred mesoporous uniform lithium growth mechanism

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Journal of Energy Chemistry 2024年第1期88卷 252-259,I0006页

作者： Fang Yan Yan liu Yuan li Yan Wang Zicen Deng Meng li Zhenwei Zhu Aohan Zhou Ting li Jingyi Qiu Gaoping Cao Shaobo Huang Biyan Wang Hao Zhang School of Chemistry and Biological Engineering University of Science and TechnologyBeijing 100083China Research Institute of Chemical Defense Beijing 100191China College of Physics and Engineering Henan University of Science and TechnologyLuoyang 471023HenanChina National Base for International Science&Technology Cooperation School of ChemistryXiangtan UniversityXiangtan 411105HunanChina Materials and Manufacturing Department Beijing University of TechnologyBeijing 100124China

To achieve high energy density in lithium batteries,the construction of lithium-ion/metal hybrid anodes is a promising *** particular,because of the anisotropy of graphite,hybrid anode formed by graphite/li metal has low transport kinetics and is easy to causes the growth of lithium dendrites and accumulation of dead li,which seriously affects the cycle life of batteries and even causes safety ***,by comparing graphite with two types of hard carbon,it was found that hybrid anode formed by hard carbon and lithium metal,possessing more disordered mesoporous structure and lithophilic groups,presents better *** indicate that the mesoporous structure provides abundant active site and storage space for dead *** the synergistic effect of this structure and lithophilic functional groups(–COOH),the reversibility of hard carbon/lithium metal hybrid anode is maintained,promoting uniform deposition of lithium metal and alleviating formation of lithium *** hybrid anode maintains a 99.5%Coulombic efficiency(CE)after 260 cycles at a specific capacity of 500 m Ah/*** work provides new insights into the hybrid anodes formed by carbon-based materials and lithium metal with high specific energy and fast charging ability.

关键词： Hard carbon/li metal hybrid anode Mesoporous structure Surface oxygen functional group Fast charging lithium batteries

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Layered niobium carbide enabling excellent kinetics and cycling stability of li-Mg-B-H hydrogen storage material Layered niobium carbide enabling excellent kinetics

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Rare Metals 2024年第3期43卷 1153-1166页

作者： li-Wen Lu Hui Luo Guang-Xu li Yun li Xin-Hua Wang Cun-Ke Huang Zhi-QiangLan Wen-Zheng Zhou Jin Guo Mohammad Ismail Hai-Zhen liu Guangxi Novel Battery Materials Research Center of Engineering Technology Guangxi Colleges and Universities Key Laboratory of Blue Energy and Systems IntegrationSchool of Physical Science and TechnologyGuangxi UniversityNanning530004China State Key Laboratory of Featured Metal Materials and life-Cycle Safety for Composite Structures Nanning530004China School of Mechanical and Electrical Engineering Quzhou College of TechnologyQuzhou324000China Department of Materials Science and Engineering Zhejiang UniversityHangzhou310027China Faculty of Ocean Engineering Technology and Informatics Universiti Malaysia Terengganu21030Kuala NerusTerengganuMalaysia Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) Nankai UniversityTianjin300071China

The li-Mg-B-H composite(2liBH_(4)+MgH_(2))has a high capacity of 11.4 wt%as a hydrogen storage ***,the slow kinetics and poor cycling stability severely restrict its practical *** this work,a layered Nb_(2)C MXene was first synthesized and then introduced to tailor the kinetics and cycling stability of the li-Mg-B-H *** milled 2liH+MgB_(2)composites were initially hydrogenated to obtain the 2liBH_(4)+MgH_(2)*** 2liBH_(4)+MgH_(2)+5wt%Nb_(2)C can release 9.0 wt%H_(2)in 30 min at 400℃,while it is only 2.7 wt%for the undoped 2liBH_(4)+MgH_(2).The dehydrogenation activation energies of MgH_(2)and liBH_(4)are 123 and 154 kJ·mol^(-1)respectively for the 5 wt%Nb_(2)C-doped composite,lower than the undoped composite(164 and 165 kJ·mol^(-1)).The 2liBH_(4)+MgH_(2)+5 wt%Nb_(2)C possesses excellent cycling stability,with the reversible capacity only slightly reduced from 9.4 wt%for the 1st cycle to 9.3 wt%for the 20th ***_(2)C keeps stable in the composite and acts as an efficient catalyst for the li-Mg-B-H *** is believed that both the layered structure and the active Nb element contribu te to the enhanced hydrogen storage performances of the li-Mg-B-H *** work confirms that the Nb_(2)C MXene with layered stru cture has a significant enhancing impact on the li-Mg-B-H hydrogen storage materials,which is different from the bulk NbC.

关键词： Hydrogen storage lithium borohydride Magnesium hydride Nb_(2)C MXene

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新型苯酚类茂金属配合物的合成及表征

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石油化工 2020年第9期49卷 841-845页

作者：李昊坤韩书亮金钊宋文波中国石化北京化工研究院北京100013

利用Sonogashira偶联反应合成了一系列邻位双炔基取代的苯酚类配体,通过配位反应,得到一种新型的苯酚类茂金属配合物。通过1H NMR,13C NMR,HRMS谱图及单晶X射线衍射对配合物及其配体进行了结构表征。实验结果表明,通过保护基的引入,反... 详细信息

利用Sonogashira偶联反应合成了一系列邻位双炔基取代的苯酚类配体,通过配位反应,得到一种新型的苯酚类茂金属配合物。通过1H NMR,13C NMR,HRMS谱图及单晶X射线衍射对配合物及其配体进行了结构表征。实验结果表明,通过保护基的引入,反应过程得到优化,在保证反应简洁性的前提下,大大提高了配合物合成效率。通过改变苯酚类配体炔基上的取代基,合成一系列带有不同取代基的苯酚类配体,进而影响配合物金属中心周围的电子云密度和空间位阻效应,得到一系列不同性能的配合物,为开发新型茂金属催化剂奠定基础,促进聚烯烃工业的发展。

关键词：茂金属苯酚合成催化剂

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Catalytic anode surface enabling in situ polymerization of gel polymer electrolyte for stable li metal batteries

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Nano Research 2024年第6期17卷 5216-5223页

作者： Guocheng li Kang liang Yuanjian li Xiangrui Duan lin Fu Zhao Cai Zhaofu Zhang Jiangnan Dai Yongming Sun Wuhan National Laboratory for Optoelectronics Huazhong University of Science and TechnologyWuhan 430074China The Institute of Technological Sciences Wuhan UniversityWuhan 430074China Faculty of Materials Science and Chemistry China University of Geoscience(Wuhan)Wuhan 430074China

Employing quasi-solid-state gel polymer electrolyte(GPE)instead of the liquid counterpart has been regarded as a promising strategy for improving the electrochemical performance of li metal ***,the poor and uneven interfacial contact between li metal anode and GPE could cause large interfacial resistance and electrochemical li stripping/plating inhomogeneity,deteriorating the electrochemical ***,we proposed that the functional component of composite anode could work as the catalyst to promote the in situ polymerization reaction,and we experimentally realized the integration of polymerized-dioxolane electrolyte and li/li_(22)Sn_(5)/liF composite electrode with low interfacial resistance and good stability by in situ catalyzation ***,the reaction kinetics and stability of metallic li anode were significantly *** a demonstration,symmetric cell using such a GPE-li/li_(22)Sn_(5)/liF integration achieved stable cycling beyond 250 cycles with small potential hysteresis of 25 mV at 1 mA·cm^(−2)and 1 mAh·cm^(−2),far outperforming the counterpart regular GPE on pure *** with liNi0.5Co0.3Mn0.2O2,the full cell with the GPE-li/li_(22)Sn_(5)/liF integration maintained 85.7%of the original capacity after 100 cycles at 0.5 C(1 C=200 mA·g^(−1)).Our research provides a promising strategy for reducing the resistance between GPE and li metal anode,and realizes li metal batteries with enhance electrochemical performance.

关键词： catalyzation polymerization interface resistance interfacial stability li metal batteries electrochemical performance

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Enhanced electrochemical performance of li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3) solid electrolyte by anion doping

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Nano Research 2024年第3期17卷 1465-1472页

作者： Jingrui Kang Xu Guo Rui Gu Honglei Hao Yi Tang Jiahui Wang li Jin Hongfei li Xiaoyong Wei Electronic Materials Research Laboratory Key Laboratory of the Ministry of Education&International Center for Dielectric ResearchSchool of Electronic and Information EngineeringXi’an Jiaotong UniversityXi’an 710049China School of Energy and Materials Shanghai Key Laboratory of Engineering Materials Application and EvaluationShanghai Polytechnic UniversityShanghai 201209China

Nowadays,the majority of the studies on the substitution are focused on cations(such as Y^(3+),Ti^(4+),P^(5+),etc.)in li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),while there are few studies on the substitution of anion O^(2-).In this work,the modified LATP with a series of liCl(LATPClx,x=0.1,0.2,0.3,0.4)additives is prepared to enhance ionic *** successful introduction of Cl-makes the length of the c axis decrease from 20.822(2)to 20.792(1)Å,and the bulk conductivity of 2.13×10^(-3) S·cm^(-1) is achieved in LATPCl_(0.3).Moreover,the Al/Ti-O1/Cl1 and Al/Ti-O_(2)/Cl_(2) distance decrease,while the li1-O_(2)/Cl_(2) distance *** ions migrate more easily in the nanochannel of *** addition,the liCl additive increases the relative density and the grain boundary conductivity of LATPClx ***,a higher ionic conductivity of 2.12×10^(–4) S·cm^(-1) and a low activation energy of 0.30 eV are obtained in LATPCl_(0.3).Correspondingly,the symmetric cell exhibits a low overpotential of±50 mV for over 200 h in LATPCl_(0.3).The solid-state li|LATPCl_(0.3)|NCM811(NCM811=liNi0.8Co0.1Mn0.1O_(2))battery exhibits high initial capacity 185.1 mAh·g^(-1) with a capacity retention rate of 95.4%after 100 cycles at 0.5 *** result suggests that liCl additive is an effective strategy to promote electrochemical properties of LATP solid electrolyte and can be considered for reference to other inorganic solid electrolytes systems.

关键词： li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)solid electrolyte anion doping ionic conductivity cyclic performance

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Vinyltrimethylsilane as a novel electrolyte additive for improving interfacial stability of li-rich cathode working in high voltage

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Chinese Chemical Letters 2024年第2期35卷 534-538页

作者： Bing Jiang Hao li Bi Luo Lehao liu lihua Chu Qiaobao Zhang Meicheng li State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources School of New EnergyNorth China Electric Power UniversityBeijing 102206China State Key Laboratory of Physical Chemistry of Solid Surfaces College of MaterialsXiamen UniversityXiamen 361005China

Boosting the interfacial stability between electrolyte and li-rich cathode material at high operating voltage is vital important to enhance the cycling stability of li-rich cathode materials for high-performance li-ion *** this work,vinyltrimethylsilane as a new type of organic silicon electrolyte additive is studied to address the interfacial instability of li-rich cathode material at high operating *** cells using vinyltrimethylsilane additive shows the high capacity retention of 73.9%after 300 cycles at 1 C,whereas the cells without this kind of additive only have the capacity retention of 58.9%.The improvement of stability is mainly attributed to the additive helping to form a more stable surface film for li-rich cathode material,thus avoiding direct contact between the electrolyte and the cathode material,slowing down the dissolution of metal ions and the decomposition of the electrolyte under high operating *** findings in this work shed some light on the design of stable cycling performance of li-rich cathode toward advanced li-ion batteries.

关键词： Vinyltrimethylsilane Electrolyte additive li-rich cathode Interfacial stability Capacity retention

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Congener-derived template to construct lithiophilic organic-inorganic layer/interphase for high volumetric capacity dendrite-free li metal batteries

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Chinese Chemical Letters 2024年第3期35卷 453-460页

作者： Kang Yang Long li Yuanbin Xiao Qiaoli Zhang Chenpeng Xi Borong li Yan Yu Chengkai Yang Key Laboratory of Advanced Materials Technologies International(HongKong Macao and Taiwan)Joint Laboratory on Advanced Materials TechnologiesCollege of Materials Science and EngineeringFuzhou UniversityFuzhou 350108China

The development of lithium-metal batteries(LMBs)is seriously restricted by the out-of-control dendrites growth and infinite volume ***,a pervasive organic-inorganic layer construction strategy is reported for the composite lithium metal anode with congener-derived organic-inorganic solid electrolyte interphase(SEI).In this strategy,the organic-inorganic Ag@polydopamine(Ag@PDA)layer is coated on the arbitrary substrates by a simple two-step *** thin and stable congener-derived SEI is insitu formed with fewer inorganic components and more organic components during charging/*** polydopamine with sufficient adhesion groups and lithiophilic Ag layer realize near-zero nucleation overpotential during lithium *** low interface resistance and stable lithium deposition are ***,the practical areal and volumetric capacities of the composite anode with three-dimensional copper(3DCu)as the substrate are 10 mAh/cm^(2)and 1538 mAh/cm^3(*** mass of anode).The symmetrical cell shows very low polarization voltage(10 mV)and more than 2500 h cycles life at 1 mA/cm^(2)(1 mAh/cm^(2)).The liNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)-based full cells show improved capacity retention(82%)after 100 cycles at 0.5 *** modified lithiophilic anode with congener-derived interphase provides a promising strategy to realize the next-generation dendrite-free LMBs.

关键词： lithium metal anode Congener-derived lithiophilicity Volumetric capacity Organic-inorganic interphase

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Anion competition for li^(+)solvated coordination environments in poly(1,3 dioxolane)electrolyte to enable high-voltage lithium metal solid-state batteries

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Journal of Energy Chemistry 2024年第9期96卷 633-641页

作者： Qiujun Wang Yanqiang Ma Xiaomeng Jia Di Zhang Zhaojin li Huilan Sun Qujiang Sun Bo Wang li-Zhen Fan Hebei Key Laboratory of Flexible Functional Materials School of Materials Science and EngineeringHebei University of Science and TechnologyShijiazhuang 050000HebeiChina Beijing Advanced Innovation Center for Materials Genome Engineering Institute of Advanced Materials and TechnologyUniversity of Science and Technology BeijingBeijing 100083China

Gel-based polymer electrolytes are limited by the polarity of the residual solvent,which restricts the coupling-breaking behaviour during li^(+)conduction,resulting in the li^(+)transport kinetics being greatly ***,we designed anion competitive gel polymer electrolyte(ACPE)by introducing lithium difluoro(oxalato)borate(liDFOB)anion into the 1,3-dioxolane(DOL)in situ polymerisation *** enhances the ionic dipole interaction between li^(+)and the solvent molecules and synergizes with li^(+)across the solvation site of the polymer ethylene oxide(EO)unit,combination that greatly improves the li^(+)transport *** a result,ACPE exhibits 1.12 mS cm^(−1)ionic conductivity and 0.75 li^(+)transfer number at room ***,this intra-polymer solvation sheath allows preferential desolvation of DFOB−,which contributes to the formation of kinetically stable anion-derived interphase and effectively mitigates side *** results demonstrate that the assembled li||NCM622 solid-state battery exhibits lifespan of over 300 cycles with average Coulombic efficiency of 98.8%and capacity retention of 80.3%.This study introduces a novel approach for ion migration and interface design,paving the way for high-safety and high-energy-density batteries.

关键词： li-metal batteries Poly(1,3-dioxolane) In situ polymerization Solid-state polymer electrolytes Anion competition

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Polyimide covalent organic frameworks as efficient solid-state li^(+) electrolytes

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Science China Chemistry 2024年第5期67卷 1647-1652页

作者： Xu liu Shi Wang Siqi liu Chengfang liu Xiangchun li Jian Wu Dazhi li Shihao Xu Chongyang liu Wen-Yong Lai State Key Laboratory of Organic Electronics and Information Displays(SKLOEID) Institute of Advanced Materials(IAM)School of Chemistry and Life SciencesNanjing University of Posts&TelecommunicationsNanjing 210023China

Covalent organic frameworks(COFs) are attractive porous crystalline materials with extremely high stability, easy functionalization, and open channels, which are expected to be unique ion conductors/transporters in lithium ion batteries(liBs). Despite recent advances, low ion conductivity and low transference number, resulting in low charging/discharging rate, low energy density, and short battery life, are the main issues that limit their direct application as solid electrolytes in liBs. Here, we designed and synthesized a novel polyimide COF, namely, TAPA-PDI-COF, with abundant C=O groups, which has been successfully employed as high-performance solid electrolytes by doping TAPA-PDI-COF and succinonitrile(SN). Both the well-defined nanochannels of COFs and SN confined in the well-aligned channels restricted the free migration of anions, while C=O on COFs and CN groups of SN enhanced li^(+) transport, thus achieving a high ion conductivity of 0.102 m S cm^(-1)at 80 °C and a high lithium-ion transference number of 0.855 at room temperature. According to density functional theory(DFT)calculations, li-ion migration mainly adopted in-plane transport rather than the axial pathway, which may be due to the shorter hopping distances in the planar pathway. The results suggest an effective strategy for the design and development of all-solidstate ionic conductors for achieving high-performance liBs.

关键词： lithium ion batteries(liBs) covalent organic frameworks(COFs) solid-state ion conductors solid-state electrolytes ion conductivity

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