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in situ xrd and electrochemical investigation on a new intercalation-type anode for high-rate lithium ion capacitor

Journal of Energy Chemistry 2021年第6期30卷 109-117,I0004页

作者： Bobo Zou Ting Wang Shengyuan Li Rong Kang Guochun Li Sherif AEl-Khodary Dickon HLNg Xianhu Liu Jingxia Qiu Yan Zhao Jiabiao Lian Huaming Li Institute for Energy Research Jiangsu UniversityZhenjiang 212013JiangsuChina Nanyang Environment and Water Research Institute(NEWRI) Interdisciplinary Graduate School(IGS)Nanyang Technological University50 Nanyang Avenue639798Singapore Department of Physics The Chinese University of Hong KongShatinHong KongChina Key Laboratory of Materials Processing&Mold(Zhengzhou University) Ministry of EducationZhengzhou UniversityZhengzhou 450002HenanChina

A new intercalation-type anode material is reported herein to improve the lithium storage kinetics for high-rate lithium ion capacitors.The crystal structure of orthorhombic NaNbO3 indicates two possible tunnels for lithium ions insertion into NaNbO3 host along theanddirections.Moreover,in situ xrd is conducted to investigate the lithium storage mechanism and structural evolution of the NaNb O_(3) anode,demonstrating its intercalation behavior through(101)and(141)planes.Furthermore,the rGO nanosheets are introduced to facilitate the charge transfer,which also effectively prevent the aggregation of NaNbO3 nanocubes.As expected,the NaNbO_(3)/rGO nanocomposites possess remarkable reversible capacity(465 mA h g^(-1) at 0.1 A g^(-1)),superior rate capability(325 mA h g^(-1) at 1.0 A g^(-1))and cycling stability,attributed to their synergistic effect and high Li+diffusion coefficient DLi[D(NaNbO_(3)/rGO)/D(NaNbO_(3))≈31.54].Remarkably,the NaNbO3/rGO-based LIC delivers a high energy density of 166.7 W h kg^(-1) at 112.4 W kg^(-1) and remains 24.1 W h kg^(-1) at an ultrahigh power density of26621.2 W kg^(-1),with an outstanding cycling durability(90%retention over 3000 cycles at 1.0 A g^(-1)).This study provides new insights on novel intercalation-type anode material to enrich the materials system of LICs.

关键词： Lithium ion capacitor Intercalation-type anode NaNbO3 nanocubes in situ xrd High energy/power densities

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Hierarchical intercalation of tetrafluoroborate anion into graphite electrode from sulfolane

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Journal of Energy Chemistry 2022年第12期75卷 378-382,I0010页

作者： Yunju Wang Hongyu Wang State Key Laboratory of Electroanalytical Chemistry Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022JilinChina School of Applied Chemistry and Engineering University of Science and Technology of ChinaHefei 230026AnhuiChina

The anion storage behavior of graphite positive electrode in a dual-ion battery is closely related to the solvation of anion in the corresponding electrolyte solution.The classical electrolyte solutions of Li BF_(4)^(-)sulfolane(SL)have long been recognized in the community of lithium batteries and still appear promising in dual-ion batteries.Nevertheless,the solvation of BF_(4)^(-)by SL has seldom been addressed before.In this study,the solvation states of SL-BF_(4)^(-)are adjusted by varying LiBF_(4)concentration or introducing auxiliary salts of LiPF_6or SBPBF_(4)(SBP:spiro-(1,1')-bipyrrolidinium)in the electrolyte solutions of Li/graphite dualion cells.The electrochemical storage processes of SL-BF_(4)^(-)anions in graphite electrodes are investigated through in situ X-ray diffraction measurements.Two kinds of graphite intercalation compounds(GICs)with contrastive intercalation gallery heights(IGHs)have been discovered,which are ascribed to the storage of different kinds of SL-BF_(4)^(-)anions in graphite electrode.The interactions between ions and SL in the electrolyte solutions are characterized by Fourier transform infrared spectroscopy and then correlated with the performance of Li/graphite cells.

关键词： Dual-ion batteries Lithium tetrafluoroborate Sulfolane in situ xrd Highly concentrated solutions

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Negative thermal expansion and phase transition of low-temperature Mg_(2)NiH_(4)

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Journal of Magnesium and Alloys 2023年第9期11卷 3338-3349页

作者： Qun Luo Qi Cai Qinfen Gu Yu Shi Bin Liu Xuan Quy Tran Syo Matsumura Tong-Yi Zhang Kazuhiro Nogita Tao Lyu Qian Li Fusheng Pan State Key Laboratory of Advanced Special Steel&Shanghai Key Laboratory of Advanced Ferrometallurgy&School of Materials Science and Engineering Shanghai UniversityShanghai 200444China Materials Genome Institute Shanghai UniversityShanghai 200444China Australian Synchrotron ANSTO800 Blackburn RoadClaytonVictoria 3168Australia Department of Applied Quantum Physics and Nuclear Engineering Kyushu UniversityFukuoka 819-0395Japan Nihon Superior Centre for the Manufacture of Electronic Materials(NS CMEM) School of Mechanical and Mining EngineeringThe University of QueenslandBrisbaneQueensland 4072Australia National Engineering Research Center for Magnesium Alloy Chongqing UniversityChongqing 400044China

The negative thermal expansion(NTE) phenomenon is of great significance in fabricating zero thermal expansion(ZTE) materials to avoid thermal shock during heating and cooling. NTE is observed in limited groups of materials, e.g., metal cyanides, oxometallates, and metalorganic frameworks, but has not been reported in the family of metal hydrides. Herein, a colossal and continuous negative thermal expansion is firstly developed in the low-temperature phases of LT1-and LT2-Mg_(2)NiH_(4) between 488 K and 733 K from in-situ transmission electron microscope(TEM) video, with the volume contraction reaching 18.7% and 11.3%, respectively. The mechanisms for volume contraction of LT1 and LT2 phases are elucidated from the viewpoints of phase transformation, magnetic transition, and dehydrogenation, which is different from common NTE materials containing flexible polyhedra units in the structure. The linear volume shrinkage of LT2 in the temperature of 488-553 K corresponds to the phase transition of LT2→HT with a thermal expansion coefficient of -799.7 × 10^(-6) K^(-1) revealed by in-situ synchrotron powder X-ray diffraction. The sudden volume contraction in LT1 between 488 and 493 K may be caused by the rapid dehydrogenation of LT1 to Mg_(2)Ni. The revealed phenomenon in single composite material with different structures would be significant for preparing zero thermal expansion materials by tuning the fraction of LT1 and LT2 phases.

关键词： Negative thermal expansion Mg_(2)NiH_(4) Phase transformation In situ TEM in situ xrd

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Bi nanoparticles in situ encapsulated by carbon film as high-performance anode materials for Li-ion batteries

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Journal of Energy Chemistry 2022年第6期31卷 524-530,I0015页

作者： Jun Yang Jiahui Xian Qinglin Liu Yamei Sun Guangqin Li MOE Laboratory of Bioinorganic and Synthetic Chemistry Lehn Institute of Functional MaterialsSchool of ChemistrySun Yat-Sen UniversityGuangzhou 510006GuangdongChina

Bismuth (Bi) has indeed inspired great interests in lithium-ion batteries (LIBs) due to the high capacity,but was still limited by the low electrical conductivity and large volume variation.Herein,a composite material based on Bi nanoparticles in situ encapsulated by carbon film (Bi@CF) is prepared successfully through a facile metal–organic framework (MOF)-engaged approach.As anode materials for LIBs,the Bi@CF composites achieved high reversible capacities of 705 and 538 mAh g^(-1)at 0.2 and 0.5 A g^(-1) after200 cycles,and long cycling performance with a stable capacity of 306 mAh g^(-1)at 1.0 A g^(-1) even after 900 cycles.In situ X-ray diffraction (xrd) measurements clearly revealed the conversion between Bi and Li_(3)Bi during the alloying/dealloying process,confirming the good electrochemical reversibility of Bi@CF for Li-storage.The reaction kinetics of this Bi@CF composite was further studied by galvanostatic intermittent titration technique (GITT).This work may provide an inspiration for the elaborate design and facile preparation of alloy-type anode materials for high-performance rechargeable batteries.

关键词： Bi nanoparticles Carbon film Anode materials Lithium-ion batteries in situ xrd

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Intercalation behavior of spiro-bipyrrolidinium cation into graphite electrodes from ethylene carbonate

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Chinese Chemical Letters 2023年第4期34卷 605-607页

作者： Jiaxing Qi Jichao Gao Ying Wang Masaki Yoshio Hongyu Wang State Key Laboratory of Electroanalytical Chemistry Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China School of Applied Chemistry and Engineering University of Science and Technology of ChinaHefei 230026China School of Chemistry and Chemical Engineering Linyi UniversityLinyi 276000China State Key Laboratory of Rare Earth Resource Utilization Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China Advanced Research Center Saga University1341 Yoga-machiSaga 840-0047Japan

The intercalation behavior of spiro-(1,1)-bipyrrolidinium cation(SBP+) into graphite electrode from spiro-(1,1)-bipyrrolidinium tetrafluoroborate-ethylene carbonate(SBPBF4-EC) solutions is investigated by conventional electrochemical tests and in situ X-ray diffraction measurements. Two kinds of graphite intercalation compounds(GICs) with discrete characteristic intercalated gallery heights(IGHs)(ca. 0.95 and0.75 nm) can be obtained with varying the salt concentration. The effect of graphite type is also addressed.

关键词： Spiro-(1,1)-bipyrrolidinium Ethylene carbonate Graphite intercalation compounds Intercalated gallery height Solvation in situ xrd

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Dimensional Gradient Structure of CoSe2@CNTs-MXene Anode Assisted by Ether for High-Capacity,Stable Sodium Storage

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Nano-Micro Letters 2021年第2期13卷 377-390页

作者： Enze Xu Pengcheng Li Junjie Quan Hanwen Zhu Li Wang Yajing Chang Zhenjie Sun Lei Chen Dabin Yu Yang Jiang School of Materials Science and Engineering Hefei University of TechnologyHefei 230009People’s Republic of China School of Chemistry and Chemical Engineering Hefei University of TechnologyHefei 230009People’s Republic of China State Key Laboratory of Pulsed Power Laser Technology National University of Defense TechnologyHefei 230037People’s Republic of China

Recently,abundant resources,low-cost sodium-ion batteries are deemed to the new-generation battery in the field of largescale energy storage.Nevertheless,poor active reaction dynamics,dissolution of intermediates and electrolyte matching problems are significant challenges that need to be solved.Herein,dimensional gradient structure of sheet-tube-dots is constructed with CoSe2@CNTs-MXene.Gradient structure is conducive to fast migration of electrons and ions with the association of ether electrolyte.For half-cell,CoSe2@CNTs-MXene exhibits high initial coulomb efficiency(81.7%)and excellent cycling performance(400 mAh g^-1 cycling for 200 times in 2 Ag^−1).Phase transformation pathway from crystalline CoSe2-Na2Se with Co and then amorphous CoSe2 in the discharge/charge process is also explored by in situ X-ray diffraction.Density functional theory study discloses the CoSe2@CNTs-MXene in ether electrolyte system which contributes to stable sodium storage performance owing to the strong adsorption force from hierarchical structure and weak interaction between electrolyte and electrode interface.For full cell,CoSe2@CNTs-MXene//Na3V2(PO4)3/C full battery can also afford a competitively reversible capacity of 280 mAh g^−1 over 50 cycles.Concisely,profiting from dimensional gradient structure and matched electrolyte of CoSe2@CNTs-MXene hold great application potential for stable sodium storage.

关键词： CoSe2@CNTs-MXene Ether electrolyte in situ xrd DFT calculation Sodium-ion full battery

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Mo_(3)Nb_(14)O_(44): A New Li^(+) Container for High-Performance Electrochemical Energy Storage

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Energy & Environmental Materials 2021年第1期4卷 65-71页

作者： Renjie Li Guisheng Liang Xiangzhen Zhu Qingfeng Fu Yongjun Chen Lijie Luo Chunfu Lin Institute of Materials for Energy and Environment School of Materials Science and EngineeringQingdao UniversityQingdao 266071China School of Materials Science and Engineering Hainan UniversityHaikou 570228China Songshan Lake Materials Laboratory Dongguan 523808China

Intercalating Nb-based oxides are promising anode compounds for lithiumion batteries since they have both good safety and large capacities.However,the research in this field is still limited.Here,Mo_(3)Nb_(14)O_(44)with a large theoretical capacity of 398 mAh g^(–1)(Mo^(64)←→Mo^(4+)and Nb^(5+)←→Nb^(3+))is exploited as a new Nb-based oxide anode compound,and Mo_(3)Nb_(14)O_(44)micron-sized particles(Mo_(3)Nb_(14)O_(44)-M)and Mo3Nb14O44 nanowires(Mo_(3)Nb_(14)O_(44)-N)are demonstrated.Mo3Nb14O44 owns a tetragonal shear ReO_(3)crystal structure(high-symmetric 14 space group)constructed by 4×4×∞(Mo,Nb)O_(6)octahedron blocks linked by Mo O4 tetrahedra,forming an A–B–A layered structure with a large interlayer spacing.This interesting structure allows fast Li+storage within the interlayers and significant intercalation-pseudocapacitive behavior,leading to the high rate performance of Mo_(3)Nb_(14)O_(44)-M/Mo_(3)Nb_(14)O_(44)-N with a large 10 C versus 0.1 C capacity retention percentage of 38.1/54.2%.Mo_(3)Nb_(14)O_(44)-M/Mo_(3)Nb_(14)O_(44)-N further exhibits a safe operating potential of 1.72/1.68 V,large reversible capacity of 323/321 m Ah g^(–1)at 0.1 C,high initial coulombic efficiency of 92.2/90.0%,and good cycling stability with 71.8/75.8%capacity retention after 1000 cycles at10 C.Additionally,a Li Mn_(2)O_(4)/Mo_(3)Nb_(14)O_(44)-N full cell also performs well.Therefore,Mo_(3)Nb_(14)O_(44)holds great promise as a fast-charging,safe,largecapacity,high-efficient,and long-life Li^(+)anode container.

关键词： anode in situ xrd Li^(+)storage Mo3Nb14O44 shear ReO3 crystal structure

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Mechanism of Lithium and Cobalt Recovery from Spent Lithium-ion Batteries by Sulfation Roasting Process

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Chemical Research in Chinese Universities 2020年第5期36卷 908-914页

作者： YU Yucshan WANG Dahui CHEN Huaijing ZHANG Xiaodong XU Li YANG Lixin State Key Laboratory of Advance Processing and Recycling of Nonferrous Metals Lanzhou University TechnologyLanzhou 730050P.R.China College of Science Lanzhou University TechnologyLanzhou 730050P.R.China

Diflerent from the traditional pyTometallurgical recovery process of Li and Co from spent lithium-ion batteries,a new recovery method for Li and Co was established by converting LiCoO2 into water-soluble metal sul-fates by roasting a mixture of LiCoO2 and NaHSO4-H2O.The evolution law of the mixture with increased roasting temperature was investigated by thennogravimetry-diflerential scamiing calorimetry(TG-DSC),in situ X-ray diflrac-tion(xrd),xrd,and X-ray photoelectron spectroscopy(XPS).The results show that the phase transition of LiCoO2 mixed with NaHSO4 H2O with increased temperature proceeded as follows:LiCoO2,NaHSO4 H2O→LiCo02,NaHSO4→Lil-xCo02,LiNaSO4,Na2S2O7,Na2SO4→Li1-xCoCO2,Co3O4,LiNaSO4,Na2SO4→Co3O4,LiNaSO4.The reaction mechanism of this roasting process may be as follows:LiCoO2+NaHSO4-H2O→l/2Li2SO4+l/2Na2SO4+l/3Co3O4+l/12O2+3/2H2O,Li2SO4+Na2SO4=2LiNaSO4.

关键词： LiCoO2 Chemical evolution Roasting in situ xrd

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Co-Al Nanocomposites as Highly Active and Stable Catalysts for Ammonia Decomposition

Co-Al Nanocomposites as Highly Active and Stable Catalysts f...

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中国化学会第九届全国无机化学学术会议

作者： Ying-Qiu Gu Chun-Jiang Jia Xin-Pu Fu Pei-Pei Du Zhao Jin Rui Si School of Chemistry and Chemical Engineering Shandong University Shanghai Institute of Applied Physics Chinese Academy of Sciences

Co-Al nanocomposite catalysts have been synthesized by a one-pot evaporation-induced self-assembly method.The catalysts were characterized by various techniques including powder X-ray diffraction(xrd),X-ray absorption fine structure(XAFS),N adsorption/desorption,transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In addition,in situ xrd under catalytic reaction conditions and H-TPR in combination with in situ synchrotron xrd were performed.For the ammonia decomposition reaction,about 93%NH-conversion and 37 mmolgminH-formation rate were achieved over the 90 at.%Co-Al catalyst at 600 ℃using a space velocity of 36,000 cmghNH.Based on the in situ xrd results we found that besides metallic Co,CoO cannot be excluded to be an active phase for the ammonia decomposition reaction;the introduction of alumina can significantly suppress the agglomeration of the active metallic Co phase,and thus maintain the high activity of the cobalt catalyst.

关键词： Co-Al catalysts ammonia decomposition in situ xrd active phase

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