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In-plane grain boundary induced defect state in hierarchical NiCo-LDH and effect on battery-type charge storage

Nano Research 2023年第4期16卷 4908-4916页

作者： Jinjin Ban Xiaohan Wen Honghong Lei Guoqin Cao Xinhong Liu Chunyao Niu Guosheng Shao Junhua Hu School of Materials Science and Engineering Industrial Technology Research Institute of Resource and Materials of Henan ProvinceZhengzhou UniversityZhengzhou 450001China State Center for International Cooperation on Designer Low-carbon&Environmental Materials(CDLCEM) Zhengzhou University100 Kexue AvenueZhengzhou 450001China Henan Provincial Key Laboratory for Metal Fuel Battery Foguang Power Generation Equipment Co.Ltd50 Holly StreetZhengzhou 450000China International laboratory for Quantum Functional Materials of henan School of Physics and MicroelectronicsZhengzhou UniversityZhengzhou 450001China

Domain boundaries are regarded as the effective active sites for electrochemical energy storage materials due to defects enrichment therein.However,layered double hydroxides(LDHs)tend to grow into single crystalline nano sheets due to their unique two-dimentional(2D)lattice structure.Previously,much efforts were made on the designing hierarchical structure to provide more exposed electroactive sites as well as accelerate the mass transfer.Herein,we demonstrate a strategy to introduce low angle grain boundary(LAGB)in the flakes of Ni/Co layered double hydroxides(NiCo-LDHs).These defect-rich nano flakes were self-assembled into hydrangea-like spheres that further constructed hollow cage structure.Both the formation of hierarchical structure and grain boundaries are interpreted with the synergistic effect of Ni2+/Co2+ratio in an“etching-growth”process.The domain boundary defect also results in the preferential formation of oxygen vacancy(Vo).Additionally,density functional theory(DFT)calculation reveals that Co substitution is a critical factor for the formation of adjacent lattice defects,which contributes to the formation of domains boundary.The fabricated battery-type Faradaic NiCo-LDH-2 electrode material exhibits significantly enhanced specific capacitance of 899 C·g^(−1)at a current density of 1 A·g^(−1).NiCo-LDH-2//AC asymmetric capacitor shows a maximum energy density of 101.1 Wh·kg^(−1)at the power density of 1.5 kW·kg^(−1).

关键词： sacrificial template grain boundary oxygen vacancy(Vo) hierarchical structure

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Recent advances based on Mg anodes and their interfacial modulation in Mg batteries

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Journal of Magnesium and Alloys 2022年第10期10卷 2699-2716页

作者： Fanfan Liu Guoqin Cao Jinjin Ban Honghong Lei Yan Zhang Guosheng Shao Aiguo Zhou Li zhen Fan Junhua Hu School of Materials Science and Engineering Industrial Technology Research Institute of Resource and Materials of Henan ProvinceZhengzhou UniversityZhengzhou 450001China State Center for International Cooperation on Designer Low-carbon and Environmental Materials(CDLCEM) Zhengzhou UniversityZhengzhou 450001China Henan Provincial Key Laboratory for Metal Fuel Battery Foguang Power Generation Equipment Co.Ltd50 Holly StreetZhengzhou 450000China School of Materials Science and Engineering Nanjing Institute of TechnologyNanjing 211167China henan key laboratory of Materials on Deep-Earth Engineering School of Materials Science and EngineeringHenan Polytechnic UniversityJiaozuo 454000China Beijing Advanced Innovation Center for Materials Genome Engineering Institute of Advanced Materials and TechnologyUniversity of Science and Technology BeijingBeijing 100083China

Magnesium(Mg)batteries(MBs),as post-lithium-ion batteries,have received great attention in recent years due to their advantages of high energy density,low cost,and safety insurance.However,the formation of passivation layers on the surface of Mg metal anode and the poor compatibility between Mg metal and conventional electrolytes during charge-discharge cycles seriously affect the performance of MBs.The great possibility of generating Mg dendrites has also caused controversy among researchers.Moreover,the regulation of Mg deposition and the enhancement of battery cycle stability is largely limited by interfacial stability between Mg metal anode and electrolyte.In this review,recent advances in interfacial science and engineering of MBs are summarized and discussed.Special attention is given to interfacial chemistry including passivation layer formation,incompatibilities,ion transport,and dendrite growth.Strategies for building stable electrode/interfaces,such as anode designing and electrolyte modification,construction of artificial solid electrolyte interphase(SEI)layers,and development of solid-state electrolytes to improve interfacial contacts and inhibit Mg dendrite and passivation layer formation,are reviewed.Innovative approaches,representative examples,and challenges in developing high-performance anodes are described in detail.Based on the review of these strategies,reference is provided for future research to improve the performance of MBs,especially in terms of interface and anode design.

关键词： Magnesium anode Dendrite Passivation layers Interfacial engineering Solid electrolyte interphase

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A strategy based on water soluble coal tar pitches to construct MnO_(2)@C composite materials with high electrochemical performance

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Science China(Technological Sciences) 2024年第1期67卷 311-320页

作者： LIU Bo WANG Kun GUO ZhaoQi HAN BeiBei XU GuiYing JU DongYing AN BaiGang LI YongCheng NI ZhenYong ZHOU WeiMin key laboratory of Energy Materials and Electrochemistry Research Liaoning Province University of Science and Technology LiaoningAnshan 114051China Advanced Science Research laboratory Saitama Institute of TechnologyFusaiji 1690Japan Liaoning Starry Sky Sodium battery Co. Ltd.Anshan 114051China Sinosteel Anshan Research Institute of Thermo-Energy Co. Ltd.Anshan 114051China State key laboratory of Marine Resource Utilization in South China Sea Hainan Provincial Key Lab of Fine ChemistrySchool of Chemical Engineering and TechnologyHainan UniversityHaikou 570228China key laboratory of Advanced fuel Cells and Electrolyzers Technology of Zhejiang Province Ningbo Institute of Materials Technology and EngineeringChinese Academy of SciencesNingbo 315201China

The water soluble coal tar pitches(WS-CTPs)were successfully prepared and used to construct the MnO_(2)@C composite materials by a hydrothermal method.It is interestingly observed that the structures and morphologies of MnO_(2)@C materials can be controlled by controlling the dosages of WS-CTPs and KMnO4.Meanwhile,it is aware that MnO_(2)exists in the MnO_(2)@C materials in an amorphous state.Compared with MnO_(2),MnO_(2)@C materials output a remarkable improvement in electrochemical performance.For instance,MnO_(2)@C-0.3 shows the storage capacity at 965.7 mA h g^(−1)after 300 cycles at a current density of 0.1 A g^(−1).In addition,after 600 cycles at a current density of 1.0 A g^(−1),the storage capacity of MnO_(2)@C-0.3 still keeps 450.3 mA h g^(−1),indicating that MnO_(2)@C-0.3 owns tremendous cycle stability at a high current density.In view of the fact that the coal tar pitches possess great cost advantages,the strategy of using WS-CTPs as a carbon source to cover the metal oxides is a competitive way to expand the application of metal oxides in the fabrication of electrodes of LIBs.

关键词： water soluble coal tar pitches MnO_(2) composite materials lithium ion batteries(LIBs) energy storage systems(ESSs) coal tar pitches

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Urea-induced interfacial engineering enabling highly reversible aqueous zinc-ion battery

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Rare metals 2024年第4期43卷 1599-1609页

作者： Bin-Rui Xu Quan-An Li Yong Liu Guang-Bin Wang Zi-He Zhang Feng-Zhang Ren School of Material Science and Engineering Henan University of Science and Technology School of Information Engineering Henan University of Science and Technology Longmen laboratory provincial and Ministerial Co-Construction of Collaborative Innovation Center for Non-Ferrous metal New Materials and Advanced Processing Technology

Aqueous zinc-ion batteries(AZIBs) have been regarded as prospective rechargeable energy storage devices because of the high theoretical capacity and low redox potential of Zn metal.However,the uncontrollable formation of dendrites and the water-induced side reactions at the Zn/electrolyte interface,and the poor reversibility under a high current density(> 2 mA·cm-2) and large area capacity(>2 mAh·cm-2) still limit the practical applications of AZIBs.Therefore,a strategy that can overcome these difficulties is urgently needed.Here,we introduce an environmentally friendly and low-cost additive,namely urea,to the electrolyte of AZIBs to induce uniform Zn deposition and suppress the side reactions.Measurements of the adsorption behavior,electrochemical characterization,and observations of the morphology revealed the interfacial modification induced by urea on the Zn/electrolyte interface,demonstrating its huge potential in AZIBs.Consequently,the long-term cycling stability(over2100 h) of a Zn/Zn symmetric cell under a high current density of 5 mA·cm-2and a capacity of 5 mAh·cm-2was achieved with a 1 mol·L-1ZnSO4electrolyte with the urea additive.Additionally,the assembled Zn/NH4V4O10full cell with urea exhibited excellent cycling performance and an outstanding average Coulombic efficiency of 99.98%.These results indicate that this is a low-cost and effective additive strategy for realizing highly reversible AZIBs.

关键词： Zn anode Urea additive Interface engineering Dendrite growth Side reaction

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Synthesis and application of single-atom catalysts in sulfur cathode for high-performance lithium–sulfur batteries

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Chinese Chemical Letters 2023年第1期34卷 73-83页

作者： Yingjie Miao Yufan Zheng Feng Tao Zhijun Chen Yi Xiong Fengzhang Ren Yong Liu provincial and Ministerial Co-Construction of Collaborative Innovation Center for Non-Ferrous metal New Materials and Advanced Processing Technology Henan Key Laboratory of Non-Ferrous Materials Science and Processing TechnologySchool of Materials Science and EngineeringHenan University of Science and TechnologyLuoyang 471023China School of Intelligent Manufacturing Ecosystem Xi’an Jiaotong–Liverpool UniversitySuzhou 215123China Luoyang Bearing Research Institute Co. Ltd.Luoyang 471039China

Lithium–sulfur(Li-S)batteries are regarded as one of the most promising energy storage devices because of their low cost,high energy density,and environmental friendliness.However,Li-S batteries suffer from sluggish reaction kinetics and serious“shuttle effect”of lithium polysulfides(LiPSs),which causes rapid decay of battery capacity and prevent their practical application.To address these problems,introducing single-atom catalysts(SACs)is an effective method to improve the electrochemical performance of Li-S batteries,due to their high catalytic efficiency and definite active sites for LiPSs.In this paper,we summarized the latest developments in enhancing the electrochemical performance of cathode for Li-S batteries through introducing different SACs.Furthermore,we briefly introduced the catalytic mechanism of SACs and discussed the strategies of synthesizing SACs,including the spatial confinement strategy and the coordination design strategy.Finally,the challenges and prospects in this field are proposed.We believe that this review would help to design and fabricate high-performance Li-S batteries via introducing SACs and boost their practical application.

关键词： Single-atom catalysts Lithium-sulfur batteries Sulfur cathode Synthesis and application Polysulfide conversion Shuttle effect

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Synthesis of metal Oxides@C(metal=Ni,Fe) Based Prussian Blue Analogs as a High-performance Anode Material for Lithium-ion battery

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Acta metallurgica Sinica(English Letters) 2021年第3期34卷 435-443页

作者： Wei Yang Xiaoxian Pang Zhao Xue Jinhao Ye Haosen Fan Ting Shu Wenzhi Zheng Shengzhou Chen School of Chemistry and Chemical Engineering Guangzhou UniversityGuangzhou 510006China Patent Examination Cooperation(henan)Center of the Patent Office Zhengzhou 450046China key laboratory of fuel Cell Technology of Guangdong Province Guangzhou 510640China

Ni3[Fe(CN)6]2 nano-cubic precursors were prepared by chemical coprecipitation at room temperature with nickel acetate and potas sium ferricyanide as raw materials.The corresponding NiFe2O4-NiO@C composites with excellent crystallization were prepared by two-stage oxidation at low temperature.The microstructure and electrochemical behavior of the materials showed that the Prussian blue analog was transformed into metal oxide while the carbon coating was maintained in the twostage oxidation at low temperature.The existence of the carbon coating reduces the charge transfer impedance to 31.5 Ω.At the current density of 500 mA/g,the reversible capacity of 632.7 mAh/g is maintained after 500 cycles.At the same time,carbon cladding can also enhance the role of pseudocapacitance in the material.At the scanning rate of 0.1 mV/s,the pseudocapacitance account for 54.4% of the total discharge capacity,which is significantly higher than that of uncoated materials.

关键词： Lithium-ion battery Anode materials metal oxide Prussian blue

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A strategy based on water soluble coal tar pitches to construct MnO@C composite materials with high electrochemical performance

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Science China Technological Sciences 2023年

作者： LIU Bo WANG Kun GUO ZhaoQi HAN BeiBei XU GuiYing JU DongYing AN BaiGang LI YongCheng NI ZhenYong ZHOU WeiMin Sinosteel Anshan Research Institute of Thermo-Energy Co. Ltd. Advanced Science Research laboratory Saitama Institute of Technology State key laboratory of Marine Resource Utilization in South China Sea Hainan Provincial Key Lab of Fine Chemistry School of Chemical Engineering and Technology Hainan University key laboratory of Advanced fuel Cells and Electrolyzers Technology of Zhejiang Province Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences key laboratory of Energy Materials and Electrochemistry Research Liaoning Province University of Science and Technology Liaoning Liaoning Starry Sky Sodium battery Co. Ltd.

The water soluble coal tar pitches (WS-CTPs) were successfully prepared and used to construct the MnO2@C composite materials by a hydrothermal method.It is interestingly observed that the structures and morphologies of MnO2@C materials can be controlled by controlling the dosages of WS-CTPs and KMnO4.Meanwhile,it is aware that MnO2exists in the MnO2@C materials in an amorphous state.Compared with MnO2,MnO2@C materials output a remarkable improvement in electrochemical performance.For instance,MnO2@C-0.3 shows the storage capacity at 965.7 mA h g-1after 300 cycles at a current density of 0.1 A g-1.In addition,after 600 cycles at a current density of 1.0 A g-1,the storage capacity of MnO2@C-0.3 still keeps 450.3 mA h g-1,indicating that MnO2@C-0.3 owns tremendous cycle stability at a high current density.In view of the fact that the coal tar pitches possess great cost advantages,the strategy of using WS-CTPs as a carbon source to cover the metal oxides is a competitive way to expand the application of metal oxides in the fabrication of electrodes of LIBs.

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Intrinsically zincophobic protective layer for dendrite-free zinc metal anode

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Chinese Chemical Letters 2022年第5期33卷 2653-2657页

作者： Chunlin Xie Qi Zhang Zefang Yang Huimin Ji Yihu Li Huanhuan Li Liang Fu Dan Huang Yougen Tang Haiyan Wang Hunan provincial key laboratory of Chemical Power Sources College of Chemistry and Chemical EngineeringCentral South UniversityChangsha 410083China School of Chemistry and Chemical Engineering Henan Normal UniversityXinxiang 453007China College of Materials Science and Engineering Chongqing UniversityChongqing 400045China Guangxi Novel battery Materials Research Center of Engineering Technology School of Physical Science and TechnologyGuangxi UniversityNanning 530004China

Aqueous zinc anodes have attracted the attention of many researchers owing to their high safety,low cost,and high theoretical specific capacity.However,its practical application is severely limited by the dendrite growth on zinc anode.Herein,we develop an intrinsically zincophobic barium-titanate protective layer with a porous structure to suppress the zinc dendrite formation by homogenizing the ion distribution on the anode surface,increasing the nucleation sites,and limiting the irregular zinc growth.Based on these synergistic effects,the coated zinc anode can exhibit long cycle life(840 h at 0.5 mA/cm^(2) for 0.5 mAh/cm^(2))and low voltage hysteresis(36 mV).This work can provide a feasible direction for the design of intrinsically zincophobic coating materials to uniformize the zinc stripping and plating.

关键词： Zinc metal anode Zinc dendrites Barium-titanate Protective layer Intrinsically zincophobicity

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Nitric oxide assists nitrogen reduction reaction on 2D MBene: A theoretical study

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Chinese Chemical Letters 2024年第5期35卷 428-433页

作者： Chaozheng He Jia Wang Ling Fu Wei Wei henan Engineering Center of New Energy battery Materials College of Chemistry and Chemical EngineeringShangqiu Normal UniversityShangqiu 476000China School of Chemistry and Chemical Engineering Shandong Provincial Key Laboratory/Collaborative Innovation Center of Chemical Energy Storage&Novel Cell TechnologyLiaocheng UniversityLiaocheng 252059China Institute of Environment and Energy Catalysis Shaanxi Key Laboratory of Optoelectronic Functional Materials and DevicesSchool of Materials Science and Chemical EngineeringXi’an Technological UniversityXi’an 710021China College of Resources and Environmental Engineering Tianshui Normal UniversityTianshui 741001China

Electrocatalytic synthesis of ammonia as an environment-friendly and sustainable development method has received widespread attention in recent years.Two-dimensional(2D)materials are a promising catalyst for ammonia synthesis due to their large surface area.In this work,we have constructed a series of 2D metal borides(MBenes)with transition metal(TM)defects(TMd-MBenes)and comprehensively calculated the reactivity of electrocatalytic synthesis of ammonia-based on density functional theory.The results have demonstrated that the TMd-MBenes can effectively activate nitrogen oxide(NO)and nitrogen(N2)molecules thermodynamically.Particularly interesting,the co-chemisorption of O atoms,dissociated from NO,can facilitate the spilled of the inert N2 molecules into single N atoms,which can further hydrogenate into ammonia easily with an ultralow limiting potential of 0.59 V on TMd-MnB.Our research has not only provided clues for catalyst design for experimental study but also paved the way for the industrial application of electrocatalytic ammonia synthesis.

关键词： 2D mbenes Nitrogen electro-reduction DFT N_(2)activation Ammonia synthesis

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Novel fusiform core-shell-MOF derived in tact metal@carb on composite:An efficient cathode catalyst for aqueous and solid-state Zn-air batteries

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Journal of Energy Chemistry 2022年第1期31卷 385-394,I0011页

作者： Di Zhou Hongquan Fu Jilan Long Kui Shen Xinglong Gou Chemical Synthesis and Pollution Control key laboratory of Sichuan Province College of Chemistry and Chemical EngineeringChina West Normal UniversityNanchong 637000SichuanChina key laboratory of fuel Cell Technology of Guangdong Province School of Chemistry and Chemical EngineeringSouth China University of TechnologyGuangzhou 510640GuangdongChina

Owing to the varied mechanisms of ORR/OER,exploiting cost-effective bifunctional catalysts with robust ORR/OER activities and excellent performances in Zn-air batteries is still a challenge.In this work,the Co/CoO@NSC bifunctional catalyst is obtained by using Zn-MOF@Co-MOF as self-template.The Co/CoO@NSC composite has interconnected porous architecture with in tact metal@carb on structure,exhibiting superior electrocatalytic activities toward ORR and OER that can be comparable with the Pt/C and RuO_(2) catalysts,respectively.The Co/CoO@NSC-based aqueous Zn-air battery achieves a high specific capacity(759.7 mAh/g)and energy density(990.5 Wh/kg),and ultra-long rechargeable property(more than 400 h/1200 cycles).The Co/CoO@NSC-based solid-state Zn-air battery also delivers an excellent performance with a long cycle life(more than 143 h/858 cycles).Most importantly,the newly synthesized and recharged Co/CoO@NSC-based solid-state Zn-air battery can be used to light up a 2 V LED lamp for more than 28 h,demonstrating the superior practicability as rechargeable power source.

关键词： Core-shell structure metal organic framework Aqueous Zn-air battery Solid-state Zn-air battery Ultra long cycle life

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