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Accurate identification of glass crystallization helps in selecting high electronic conductivity materials

Progress in Natural Science:Materials International 2024年第3期34卷 503-511页

作者： Fanhou Kong Shuli Li Suoqi Zhao Huiwen Li Lin Li Zhenting Zang Rui Zhang Hongrui Liu Lehan Wang Changjiu Li Keng H.Chung Dongying Key Laboratory of New Energy Materials and Devices & School of Chemical Engineering Shandong Institute of Petroleum and Chemical Technology Special Glass Key Lab of Hainan Province & State Key Laboratory of Marine Resource Utilization in South China Sea Hainan University

Though the current research on vanadium-based glass electrodes has made great progress, the conductivity theory of V-based glasses has not been obviously improved and crystals cannot be positioned precisely. The changes in the valence state of V3+, V4+and V5+are regulated by the strong reducing agent Fe2P to realize valence bond transformation of the amorphous electrode, explore the redox process of multi-electron reactions and further optimize the conductivity of electrode materials. VPFe2 and VPFe3 precipitate VO2crystals and VPFe4 precipitates VO2and V6O11crystals. Electron back-scattered diffraction was used to accurately identify the distribution and specific positions of both types of crystals. V6O11crystals exhibit a strong texture according to pole figure and inverse pole figure. XPS reveals that Fe2P and V2O5, undergo a redox reaction during the hightemperature melting process, where V5+is reduced to V4+and V3+and V4+renders a positive influence on conductivity. The addition of Fe2P increases the content of V4+in the glass and VPFe3 glass contains the highest content of V4+, leading to the highest electronic conductivity. V2O5transforms into VO2crystals and VO2transforms into V6O11with the increase of Fe2P content. The type of nanocrystal precipitation in glass affects electronic conductivity.

关键词： Electron back-scattered diffraction electronic conductivity Glass crystallization Multi-electron reactions V2O5

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Effect of ZrO_2 (9mol% Y_2O_3) coating thickness on the electronic conductivity of Mg-PSZ oxygen sensors

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Journal of University of Science and Technology Beijing 2005年第2期12卷 160-165页

作者： ChangheGao HaileiZhao QingguoLiu WeijiangWu WeihuaQiu MaterialsScienceandEngineeringSchool.UniversityofScienceandTechnologyBeijing Beijing100083China

The ZrO2 (9mol% Y2O3) coating was prepared evenly on the surface of MgO partially stabilized zirconia (Mg-PSZ) tube (oxygen sensor probe) by dipping the green Mg-PSZ tube in a ZrO2 (9mol% Y2O3) slurry and then co-firing at 1750°C for 8 h. The double-cell method was employed to measure the electronic conductivity parameter and exam the reproducibility of the coated Mg- PSZ tube. The experimental results indicate that the good thermal shock resistance of the Mg-PSZ tube can be retained when the coating thickness is not more than 3.4 μm. The ZrO2 (9mol% Y2O3) coating reduces the electronic conductivity parameter remarka- bly, probably due to the lower electronic conductivity of Y2O,-stabilized ZrO2 than that of MgO-stabilized ZrO2. Moreover, the ZrO2 (9mol% Y2O3) coating can improve the reproducibility and accuracy of the Mg-PSZ tube significantly in the low oxygen measure- ment. The smooth surface feature and lower electronic conductivity of the coated Mg-PSZ tube should be responsible for this im- provement.

关键词： oxygen sensor stabilized ZrO2 solid electrolyte coating electronic conductivity

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Experimental measurement of proton conductivity and electronic conductivity of membrane electrode assembly for proton exchange membrane fuel cells

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Progress in Natural Science:Materials International 2020年第6期30卷 912-917页

作者： Ruili Sun Zhangxun Xia Congrong Yang Fenning Jing Suli Wang Gongquan Sun Division of Fuel Cells and Battery Dalian National Laboratory for Clean Energy Dalian Institute of Chemical Physics Chinese Academy of Sciences Key Laboratory of Fuel Cells & Hybrid Power Sources Chinese Academy of Sciences University of Chinese Academy of Sciences

Charge transport processes involving the proton migration and electron transfer for different parts of membrane electrode assemble(MEA) play an essential role for developing the novel electrode and enhancing the electrochemical performance towards proton exchange membrane fuel cells(PEMFCs). However, the coupled charge transport processes make it difficult for evaluating proton conductivity and electronic conductivity of different parts in MEAs under operation conditions of fuel cells. Here in this work, we propose an experiment approach for separating the electronic conductivity and proton conductivity of different components of MEA at the operating conditions of PEMFCs. This approach involves two different measuring devices, which both consist of electron or proton conducting layers, sealing layers and sample layer, followed by tailoring the thickness of sample layers and via electrochemical impedance spectroscopy(EIS) to quantity the electronic conductivity and proton conductivity of different layers. These experiment results show the great potential in the development of different components of MEA.

关键词： Proton exchange membrane fuel cells Membrane electrode assembly Proton conductivity electronic conductivity

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Ionic/electronic conductivity regulation of n-type polyoxadiazole lithium sulfonate conductive polymer binders for high-performance silicon microparticle anodes

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Chinese Chemical Letters 2021年第1期32卷 203-209页

作者： Yuanyuan Yu Huihui Gao Jiadeng Zhu Dazhe Li Fengxia Wang Chunhui Jiang Tianhaoyue Zhong Shuheng Liang Mengjin Jiang College of Polymer Science and Engineering Sichuan UniversityChengdu 610065China Chemical Sciences Division Oak Ridge National LaboratoryOak RidgeTN 37831United States

Low-cost silicon microparticles(SiMP),as a substitute for nanostructured silicon,easily suffer from cracks and fractured during the electrochemical cycle.A novel n-type conductive polymer binder with excellent electronic and ionic conductivities as well as good adhesion,has been successfully designed and applied for high-performance SiMP anodes in lithium-ion batteries to address this problem.Its unique features are attributed to the stro ng electron-withdrawing oxadiazole ring structure with sulfonate polar groups.The combination of rigid and flexible components in the polymer ensures its good mechanical strength and ductility,which is beneficial to suppress the expansion and contraction of SiMP s during the charge/discharge process.By fine-tuning the monomer ratio,the conjugation and sulfonation degrees of the polymer can be precisely controlled to regulate its ionic and electronic conductivities,which has been systematically analyzed with the help of an electrochemical test method,filling in the gap on the conductivity measurement of the polymer in the doping state.The experimental results indicate that the cell with the developed n-type polymer binder and SiMP(~0.5 μm) anodes achieves much better cycling performance than traditional non-conductive binders.It has been considered that the initial capacity of the SiMP anode is controlled by the synergetic effect of ionic and electronic conductivity of the binder,and the capacity retention mainly depends on its electronic conductivity when the ionic conductivity is sufficient.It is worth noting that the fundamental research of this wo rk is also applicable to other battery systems using conductive polymers in order to achieve high energy density,broadening their practical applications.

关键词： n-Doping Conductive binder electronic conductivity Ionic conductivity High-performance silicon microparticle anodes

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Study on electronic conductivity of CaO-SiO2-Al2O3-FeOx Slag System

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Journal of Iron and Steel Research(International) 2000年第1期7卷 9-13页

作者： LU Xiong-gang LI Fu-shen LI Li-fen CHOU Kou-chih University of Science and Technology Beijing Shanghai University

A study on electronic conductivity of CaO-SiO2-Al2O3-FeOxslag system with Wagner polarization technique was carried out.The experimental data show that electronic conductivity is consisted of free electron conductivity and electron hole conductivity and both are related to the content of Fe3+and Fe2+.Free electron conductivity is decreasing and electron hole conductivity is increasing while Fe3+changes to Fe2+.There is a maximum electronic conductivity at some ratio of ferric ions Fe3+to total ion content.Under the experimental conditions,the electronic conductivity is in the range of 10-4—10-2S/cm.

关键词： smelt slag electron hole electronic conductivity

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Investigating Stability Properties for Transition Metal Carbonate Precursors Using Universal Cluster Expansion Technique(UNCLE)as Cathodes for Li-Ion Batteries

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材料科学与工程（中英文A版） 2024年第1期14卷 26-33页

作者： Mogahabo Tebogo Morukuladi N.L.Lethole M.C.Masedi N.N.Ngoepe P.E.Ngoepe Materials Modelling Centre University of LimpopoPrivate Bag x1106Sovenga 0727South Africa Department of Physics University of Fort HareAlice 5700South Africa

The universal cluster expansion technique was used in this study to determine the binary phase diagrams for the transition metal carbonate precursors MCO3(M:Mn,Ni,Co).The use of mixed cathode materials in lithium-ion batteries such as NMC(Ni,Mn and Co)formulations,is a strategic approach to optimize performance,enhance safety and address cost and environmental considerations in the rapidly evolving field of energy storage.This study focuses on the cost issue related to lithium ion batteries by investigating the manganese rich NMC since manganese is more abundant and cost-effective.We doped MnCO3 with nickel and doped MnCO3 with cobalt then ran cluster expansion calculations to generate binary phases.The binary phase diagrams generated indicated that doping MnCO3 with nickel favours the Mn-rich side,while doping MnCO3 with cobalt favours 50%Mn-rich and 50%Co-rich.We further extracted the most stable structures from both binary diagrams and determined their electronic,mechanical and vibrational stabilities using DFT(density functional theory)calculations within the LDA(local gradient approximation)with Hubbard parameter(U).The electronic properties revealed that both materials are semiconductors due to their narrow energy band gap obtained while the mechanical properties showed that structures are mechanically stable since their necessary conditions for trigonal and triclinic systems were satisfied.

关键词： Binary phase diagrams mechanical properties electronic conductivity phonon dispersion curves.

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A Janus heteroatom-doped carbon electrocatalyst for hydrazine oxidation

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National Science Review 2023年第3期10卷 152-162页

作者： Jieting Ding Hao-Fan Wang Xianfeng Yang Wenbo Ju Kui Shen Liyu Chen Yingwei Li School of Chemistry and Chemical Engineering South China University of Technology Analytical and Testing Centre South China University of Technology School of Physics and Optoelectronics South China University of Technology

The trade-off between the intrinsic activity and electronic conductivity of carbon materials is a major barrier for electrocatalysis.We report a Janus-type carbon material combining electrically conductive nitrogen-doped carbon(NC) and catalytically active boron,nitrogen co-doped carbon(BNC).The integration of NC with BNC can not only ensure high electronic conductivity of the hybrid,but also achieve an enhancement in the intrinsic activity of the BNC side due to the electron redistribution on their coupling interfaces.In the electro catalytic hydrazine oxidation reaction(HzOR),the Janus carbon electrocatalyst exhibits superior activity than their single counterparts and simple physical mixtures.D ensity functional theory calculations reve al that the NC/BNC interfaces simultaneously promote efficient electron transport and decrease the free energy of the rate-determining step in the HzOR process.

关键词： electronic conductivity heteroatom-doped carbon hydrazine oxidation reaction intrinsic activity metal–organic frameworks

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High-temperature transport properties of BaSn_(1−x)Sc_(x)O_(3−δ) ceramic materials as promising electrolytes for protonic ceramic fuel cells

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Journal of Advanced Ceramics 2022年第7期11卷 1131-1143页

作者： Inna A.ZVONAREVA AlexeyМ.MINEEV Natalia A.TARASOVA Xian-Zhu FU Dmitry A.MEDVEDEV Institute of High Temperature Electrochemistry Ural Branch of the Russian Academy of SciencesYekaterinburg 620066Russia Ural Federal University Yekaterinburg 620002Russia Boreskov Institute of Catalysis Novosibirsk 630090Russia College of Materials Science and Engineering Shenzhen UniversityShenzhen 518060China

Protonic ceramic fuel cells(PCFCs)offer a convenient means for electrochemical conversion of chemical energy into electricity at intermediate temperatures with very high efficiency.Although BaCeO_(3)-and BaZrO_(3)-based complex oxides have been positioned as the most promising PCFC electrolytes,the design of new protonic conductors with improved properties is of paramount importance.Within the present work,we studied transport properties of scandium-doped barium stannate(Sc-doped BaSnO_(3)).Our analysis included the fabrication of porous and dense BaSn_(1−x)Sc_(x)O_(3−δ)ceramic materials(0≤x≤0.37),as well as a comprehensive analysis of their total,ionic,and electronic conductivities across all the experimental conditions realized under the PCFC operation:both air and hydrogen atmospheres with various water vapor partial pressures(p(H2O)),and a temperature range of 500–900℃.This work reports on electrolyte domain boundaries of the undoped and doped BaSnO_(3)for the first time,revealing that pure BaSnO_(3)exhibits mixed ionic–electronic conduction behavior under both oxidizing and reducing conditions,while the Sc-doping results in the gradual improvement of ionic(including protonic)conductivity,extending the electrolyte domain boundaries towards reduced atmospheres.This latter property makes the heavilydoped BaSnO_(3)representatives attractive for PCFC applications.

关键词： BaSnO_(3) protonic ceramic fuel cells(PCFCs) proton transport perovskite hydration electronic conductivity

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High-rate performance magnesium batteries achieved by direct growth of honeycomb-like V_(2)O_(5)electrodes with rich oxygen vacancies

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Nano Research 2023年第4期16卷 4880-4887页

作者： Dongzheng Wu Yichao Zhuang Fei Wang Yang Yang Jing Zeng Jinbao Zhao College of Chemistry and Chemical Engineering State-Province Joint Engineering Laboratory of Power Source Technology for New Energy VehicleState Key Laboratory of Physical Chemistry of Solid SurfacesEngineering Research Center of Electrochemical TechnologyMinistry of EducationCollaborative Innovation Center of Chemistry for Energy MaterialsXiamen UniversityXiamen 361005China School of Chemical Engineering and Light Industry Guangdong University of TechnologyGuangzhou 510006China

Rechargeable magnesium batteries(RMBs)have emerged as a promising next-generation electrochemical energy storage technology due to their superiority of low price and high safety.However,the practical applications of RMBs are severely limited by immature electrode materials.Especially,the high-rate cathode materials are highly desired.Herein,we propose a dualfunctional design of V_(2)O_(5)electrode with rational honeycomb-like structure and rich oxygen vacancies to enhance the kinetics synergistically.The result demonstrates that oxygen vacancies can not only boost the intrinsic electronic conductivity of V_(2)O_(5),but also enhance the Mg^(2+)diffusion kinetics inside the cathode,leading to the good high-rate performance.Moreover,ex-situ X-ray diffraction(XRD),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS)characterizations reveal that Mg^(2+)is mainly intercalated from the(101)plane of V_(2)O_(5)−X based on the insertion-type electrochemical mechanism;meanwhile,the highly reversible structure evolution during Mg^(2+)insertion/extraction is also verified.This work proposes that the dual-functional design of electrode has a great influence in enhancing the electrochemical performance of cathode materials for RMBs.

关键词： V2O5 rechargeable magnesium batteries oxygen vacancies kinetics electronic conductivity

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High-performance Ta-doped Li_(7)La_(3)Zr_(2)O_(12) garnet oxides with AlN additive

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Journal of Advanced Ceramics 2022年第10期11卷 1530-1541页

作者： Chang ZHANG Xiangchen HU Zhiwei NIE Cong WU Nan ZHENG Shaojie CHEN Yihang YANG Ran WEI Jiameng YU Nan YANG Yi YU Wei LIU School of Physical Science and Technology ShanghaiTech UniversityShanghai 201210China Shanghai Key Laboratory of High-resolution Electron Microscopy ShanghaiTech UniversityShanghai 201210China

Garnet-type oxide is one of the most promising solid-state electrolytes(SSEs)for solid-state lithium-metal batteries(SSLMBs).However,the Li dendrite formation in garnet oxides obstructs the further development of the SSLMBs seriously.Here,we report a high-performance garnet oxide by using AlN as a sintering additive and Li as an anode interface layer.AlN with high thermal conductivity can promote the sintering activity of the garnet oxides,resulting in larger particle size and higher relative density.Moreover,Li3N with high ionic conductivity formed at grain boundaries and interface can also improve Li-ion transport kinetics.As a result,the garnet oxide electrolytes with AlN show enhanced thermal conductivity,improved ionic conductivity,reduced electronic conductivity,and increased critical current density(CCD),compared with the counterpart using Al_(2)O_(3) sintering aid.In addition,Li symmetric cells and Li|LiFePO_(4)(Li|LFP)half cells using the garnet electrolyte with the AlN additive exhibit good electrochemical performances.This work provides a simple and effective strategy for high-performance SSEs.

关键词： solid-state lithium-metal battery(SSLMB) garnet oxide thermal conductivity electronic conductivity critical current density(CCD)

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