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Prussian Blue Nanocubes with an open framework structure Coated with PEDOT as High-Capacity Cathodes for Lithium-Sulfur Batteries

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ADVANCED MATERIALS 2017年第48期29卷 2017 Dec;29(48)页

作者： Su, Dawei Cortie, Michael Fan, Hongbo Wang, Guoxiu Univ Technol Sydney Fac Sci Sch Math & Phys Sci Ctr Clean Energy Technol Sydney NSW 2007 Australia Dongguan Univ Technol Sch Environm & Civil Engn Dongguan 523106 Guangdong Peoples R China

It is shown that Prussian blue analogues (PBAs) can be a very competitive sulfur host for lithium-sulfur (Li-S) batteries. Sulfur stored in the large interstitial sites of a PBA host can take advantage of reversible and efficient insertion/extraction of both Li+ and electrons, due to the well-trapped mobile dielectron redox centers in the well-defined host. It is demonstrated that Na2Fe[Fe(CN)(6)] has a large open framework, and as a cathode, it both stores sulfur and acts as a polysulfide diffusion inhibitor based on the Lewis acid-base bonding effect. The electrochemical testing shows that the S@Na2Fe[Fe(CN)(6)]@poly(3,4-ethylenedioxythiophene) composite achieves excellent reversibility, good stability, and fast kinetics. Its outstanding electrochemical properties should be ascribed to the internal transport of Li+/e-, maximizing the utilization of sulfur. Moreover, the open metal centers serve as the Lewis acid sites with high affinity to the negatively charged polysulfide anions, reducing the diffusion of polysulfides out of the cathode and minimizing the shuttling effect. The fundamental basis of these exceptional performance characteristics is explored through a detailed analysis of the structural and electrochemical behavior of the material. It is believed that the PBAs will have a useful role in ensuring more effective and stable Li-S batteries.

关键词： Lewis acid-base interaction lithium-sulfur batteries open framework structure sodium iron cyanide

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Room-temperature synthesis of layered open framework cathode for sodium-ion batteries

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Chinese Chemical Letters 2023年第5期34卷 576-579页

作者： Ruding Zhang Huixin Chen Hongjun Yue CAS Key Laboratory of Design and Assembly of Functional Nanostructures and Fujian Provincial Key Laboratory of NanomaterialsFujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Institute of Rare Earth MaterialsHaixi InstitutesChinese Academy of SciencesXiamen 361021China

The synthesis of active electrode materials at room temperature is one of the effective strategies to reduce the fabrication cost of sodium ion batteries(SIBs).Herein,a layered material(Na_(2)[(VO)_(2)(HPO_(4))_(2)C_(2)O_(4)]·2H_(2)O,abbreviated as NVPC followingly)with open-framework structures has been successfully prepared at room temperature under ambient conditions and is evaluated as a cathode for *** is revealed that NVPC cathode can deliver a maximum reversible capacity of ca.70 mAh/g at 10 mA/g,and exhibit superior rate capability and cycling performance:at 50 mA/g,maximum reversible capacity ca.50 m Ah/g with capacity retention of 88.4%over 250 cycles corresponds to only 0.046%capacity decay per cycle;at 100 mA/g,a maximum reversible capacity of 35 mAh/g with capacity retention of60.9%over 500 *** study demonstrates a practical example of a low-cost synthesis of the cathode materials for *** the same time,the systematic electrochemical research results also show promising prospects for long lifespan low-cost SIBs.

关键词： Room temperature solution synthesis open framework structure Cathode materials Sodium-ion batteries Full cell

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An open-framework structured Material: [Ni(en)2]3[Fe(CN)6]2 as a Cathode Material for Aqueous Sodium- and Potassium-Ion Batteries

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ACS APPLIED MATERIALS & INTERFACES 2022年第14期14卷 16197-16203页

作者： Zhang, Dapeng Sun, Lianhang Wang, Changhao Xue, Qing Feng, Jin Ran, Weiguang Yan, Tingjiang Qufu Normal Univ Sch Chem & Chem Engn Qufu 273165 Shandong Peoples R China

open-framework structured materials such as Prussian blue analogues and sodium superionic conductor (NASICON) materials have been regarded as promising electrode candidates for aqueous batteries. These materials exhibit outstanding long cycle stability and high rate capacity retention, due to their high ion diffusive rate in the crystal and the stable structure maintenance in the electrochemical reaction process. Herein, an open-framework structured material [Ni(en)(2)](3)[Fe(CN)(6)](2) (NienHCF) is prepared and first used as a cathode material for aqueous sodium- and potassium-ion batteries. The resultant material exhibits a high output potential and outstanding cycle performance (93.4% after 500 cycles at 1 A g(-1)) in K-ion batteries. Meanwhile, the electrochemical reaction mechanism is investigated. After coupling with the activated carbon anode, the K-ion full cell has 91.5% capacity retention at 5 A g(-1) and retains 77.2% after 1000 cycles at 0.5 A g(-1), exhibiting the potential as an electrode material for rechargeable aqueous K-ion and Na-ion batteries.

关键词： open framework structure Ni(en)(2)](3)[Fe(CN)(6)](2) cathode material aqueous sodium- and potassium-ion batteries electrochemical mechanism investigation

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Carbon-wrapped amorphous Ni-Co binary oxide nanosheet for high-performance pseudocapacitors

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APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING 2023年第1期129卷 1-8页

作者： Guo, Jialin Li, Wenjing Zheng, Peng Shang Luo Univ Coll Chem Engn & Modern Mat Shaanxi Key Lab Comprehens Utilizat Tailings Reso Shang Luo 726000 Shaanxi Peoples R China Xian Int Med Ctr Hosp Xian 710021 Shaanxi Peoples R China Shaanxi Univ Sci & Technol Sch Mat Sci & Engn Xian 710021 Shaanxi Peoples R China

The development of high-energy density supercapacitor demands that the electrode has the characteristic of good conductivity for electron and open framework structure and ion transfer. NiCo2O4 already exhibits superior electric conductivity among the multi-metal oxides. Here, carbon-wrapped amorphous Ni-Co oxide nanosheet is prepared by a hydrothermal method, followed by an annealing process in Ar atmosphere. The conductivity is further improved by carbon coating and it also has a more open structure, which is verified by extended X-ray absorption fine structure analysis. Owing to the advantage of its structure, the carbon-wrapped amorphous Ni-Co oxide shows large capacitance of 1775 F g(-1) at 1 A g(-1) in three-electrode aqueous system, high energy density of 73.5 Wh kg(-1) and power density of 806.7 W kg(-1) in asymmetric supercapacitors. The open framework feature of the amorphous would promote the wide exploration of amorphous Ni-Co oxide material as the electrode for energy storage devices.

关键词： Amorphous Ni-Co oxide Supercapacitor Cathode Nanosheet open framework structure

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Synthesis, structural determination and catalytic study of a new 2-D chloro-substituted zinc phosphate, (C8N2H20)[ZnCl(PO3(OH))]2

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JOURNAL OF MOLECULAR structure 2020年 1202卷 127216-000页

作者： Rayes, Ali Herrera, Raquel P. Moncer, Manel Ara, Irene Calestani, Gianluca Ayed, Brahim Mezzadri, Francesco Fac Sci Gabes UR11ES85 URCMEP Unite Rech Catalyse & Mat Environm & Proc Campus Univ Gabes 6072 Tunisia Univ Zaragoza Lab Organocatalisis Asimetr Dept Quim Organ ISQCHCSIC C Pedro Cerbuna 12 E-50009 Zaragoza Spain Univ Zaragoza ISQCH Dept Quim Organ CSIC C Pedro Cerbuna 12 E-50009 Zaragoza Spain Univ Parma Dept Chem Life Sci & Environm Sustainabil Parco Area Sci 17 I-43124 Parma Italy Univ Mounastir Fac Sci Mounastir Lab Mat Cristallochim & Thermodynam Monastir Tunisia Univ El Manar Fac Sci Tunis Lab Mat Cristallochim & Thermodynam Tunis Tunisia

A novel chloro-substituted zinc-phosphate, (C8N2H20)[ZnCl(PO3(OH))], has been synthesized by a slow evaporation method in the presence of 1,3-cyclohexanebis-(methylamine), which acts as a template. The structure consists of vertex linked ZnO3Cl and PO3(OH) tetrahedral, assembled into corrugated porous layers [ZnCl(PO3(OH))(2)](infinity) with (4.8(2)) topology. The optical properties were also investigated using Diffuse Reflecting Spectroscopy (DRS), showing that the title compound has semiconducting properties. In addition, the catalytic activity of (C8N2H20)[ZnCl(PO3(OH))](2) has been tested in the acetalisation reaction of aldehydes. The title compound displayed a high catalytic activity with practically total conversion in many examples using MeOD as solvent and as the sole source of acetalisation. More importantly, the reaction crudes are very clean and only the preferred products are found in the NMR spectra. (C) 2019 Elsevier B.V. All rights reserved.

关键词： Zinc-phosphate open framework structure Chloride-substitution X-ray diffraction Spectroscopic techniques Catalytic activity

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Topological aspects of lanthanide-adipate-aqua compounds: Close packed and open framework structures

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JOURNAL OF SOLID STATE CHEMISTRY 2013年 203卷 128-133页

作者： Chowdhuri, Durga Sankar Jana, Swapan Kumar Hazari, Debdoot Zangrando, Ennio Dalai, Sudipta Vidyasagar Univ Dept Chem & Chem Technol Midnapore 721102 W Bengal India Dept Chem & Pharmaceut Sci I-34127 Trieste Italy

A search in the Cambridge Structural Database (CSD) for lanthanide complexes with adipate [OOC(CH2)(4) COO](2-) and aqua ligands retrieved a fair number of compounds. To this dataset a new lanthanum metalorganic framework, {[La-2(adip)(3)(H2O)(2)] (1) (adipH(2)=adipic acid), synthesised and structurally characterized in these labs, was included. The crystal structures of these coordination polymers, of general formulation [Ln(2)(adip)(3)(H2O)], exhibit a variety of topologies and dimensionality, which were clustered in different classes and described in detail. It was explored that the majority of these evidences the presence of metal chains or dinuclear Ln2 entities (separated in both cases by 4.0-4.8 A), where lanthanide ions are differently connected by carboxylate groups with chelating or oxygen-bridging mode. The different amount of coordinated water molecules appear to affect the solid state networks. Moreover the crystal packing of these compounds shows peculiar aspects and examples were reported in the literature where the long alkyl chain of adipate connectors give rise to interpenetrated structures, or to porous material where lattice water or neutral larger molecules are clathrated. (C) 2013 Elsevier Inc. All rights reserved.

关键词： Lanthanide Adipate Close packed framework structure open framework structure

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Highly Reversible open framework Nanoscale Electrodes for Divalent Ion Batteries

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NANO LETTERS 2013年第11期13卷 5748-5752页

作者： Wang, Richard Y. Wessells, Colin D. Huggins, Robert A. Cui, Yi Stanford Univ Dept Mat Sci & Engn Stanford CA 94305 USA SLAC Natl Accelerator Lab Stanford Inst Mat & Energy Sci Menlo Pk CA 94025 USA

The reversible insertion of monovalent ions such as lithium into electrode materials has enabled the development of rechargeable batteries with high energy density. Reversible insertion of divalent ions such as magnesium would allow the creation of new battery chemistries that are potentially safer and cheaper than lithium-based batteries. Here we report that nanomaterials in the Prussian Blue family of open framework materials, such as nickel hexacyanoferrate, allow for the reversible insertion of aqueous alkaline earth divalent ions, including Mg2+, Ca2+, Sr2+, and Ba2+. We show unprecedented long cycle life and high rate performance for divalent ion insertion. Our results represent a step forward and pave the way for future development in divalent batteries.

关键词： Ion insertion magnesium ion batteries aqueous batteries Prussian Blue open framework structure nanomaterials

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CRYSTAL structure AND MAGNETIC PROPERTY OF SYNTHETIC GENGENBACHITE, KH₈(Fe_2.66Al_0.34)(PO₄)₆•6H₂O

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CANADIAN MINERALOGIST 2013年第2期51卷 223-232页

作者： Hu, Zhi-Biao Wang, Cheng-Xin Tong, Chang-Qing Huang, Ya-Xi Pan, Yuanming Mi, Jin-Xiao Longyan Univ Coll Chem & Mat Sci Longyan 364000 Fujian Peoples R China Xiamen Univ Coll Mat Fujian Prov Key Lab Adv Mat Dept Mat Sci & Engn Xiamen 361005 Peoples R China Univ Saskatchewan Dept Geol Sci Saskatoon SK S7N 5E2 Canada

Synthetic gengenbachite, KH8(Fe2.66Al0.34)(PO4)(6)center dot 6H(2)O, has been prepared hydrothermally at 423-393 K. Single-crystal X-ray structure refinements (R-1 = 0.035 for 1838 [I > 2 sigma(I)] unique reflections and wR(2) = 0.083 for all 1863 reflections) confirm that gengenbachite crystallizes in the trigonal space group P31c (No. 159) and is isotypic with synthetic (NH4) H8Fe33+(PO4)(6)center dot 6H(2)O. The crystal structure consists of [FeO6] octahedra and [PO4] tetrahedra forming a three-dimensional framework with eight-membered-ring channels running along the [100], [010], and [110] directions. All but one hydrogen atom have been located to allow description of the hydrogen bonds in gengenbachite. Magnetic susceptibility analysis of gengenbachite yielded the Curie constant C = 12.07 ***(-1) and the Weiss constant 0(P) = -58.9 K. The effective magnetic moment per Fe atom mu(eff) = 6.03 mu(B) provides further support for high-spin Fe3+ in octahedral coordination.

关键词： gengenbachite iron phosphate hydrothermal synthesis magnetic property open framework structure

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Two new zincophosphates, (H₃NCH₂CH₂NH₃)₂[Zn(μ-PO₄)₂] and (NH₄)[(H₃N)Zn{(μ-PO₄)Zn}₃]: Crystal structures and relationships to similar open framework zinco- and aluminophospates

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JOURNAL OF SOLID STATE CHEMISTRY 2011年第9期184卷 2506-2515页

作者： Karanovic, Ljiljana Poleti, Dejan Dordevic, Tamara Sutovic, Sabina Univ Belgrade Crystallog Lab Fac Min & Geol Belgrade 11000 Serbia Univ Belgrade Dept Gen & Inorgan Chem Fac Technol & Met Belgrade 11000 Serbia Univ Vienna Geozentrum Inst Mineral & Kristallog A-1090 Vienna Austria

Two new zincophosphates, bis(ethylenediammonim) catena-bis(mu-phosphato)zincate, (H3NCH2CH2NH3)(2) [Zn(mu-PO4)(2)] (1), and ammonium ammine-tris(mu-phosphato)tetrazincate, (NH4)I(H3N)Zn{(mu-PO4)Zn}(3)] (2), were synthesized under hydrothermal conditions and their crystal structures were determined by single-crystal X-ray diffraction analysis. The crystal structure of 1 consists of infinite macroanionic ZnP2O84- chains, running along the [0 0 1] direction, and diprotonated ethylenediammonium cations, H(2)en(2+). The crystal structure of 2 is built up from ZnO4, Zn(NH3)O-3 and PO4 vertex-sharing tetrahedra connected to form an open 3D framework. The ammonium groups, NH4,+ are located in the channels formed by 8M-rings extending along [1 0 0]. In order to study vibrational behavior of H(2)en(2+) and NH4+ cations, NH3 molecules in 1 and 2, single-crystal Raman spectra were obtained. Structural, chemical and topological similarities to the other open framework zinco- and aluminophosphates incorporating different guest species are discussed. (C) 2011 Elsevier Inc. All rights reserved.

关键词： Zincophosphate Inorganic-organic hybrid open framework structure Hydrogen bonding Hydrothermal synthesis

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Crystal structure and vibrational spectra of erbium bis(cyclotriphosphate) nonahydrate, ErNa₃(P₃O₉)₂ • trisodium 9H₂O

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JOURNAL OF CHEMICAL CRYSTALLOGRAPHY 2007年第9期37卷 601-608页

作者： Assaaoudi, Hassane Ijjaali, Mostafa Ennaciri, Abdelaziz Butler, Ian S. Kozinski, Janusz A. McGill Univ Dept Chem Montreal PQ H3A 2K6 Canada Tech Fes Saiss Fac Sci Fes Morocco Ibn Tofail Univ Dept Chem Spect Lab Kenitra Morocco Univ Saskatchewan Coll Engn Dept Chem Engn Saskatoon SK Canada

The cyclotriphosphate salt, ErNa3(P3O9)(2) center dot H2O, has been characterized by single-crystal X-ray diffraction [hexagonal, space group R(3) over bar c with unit cell parameters of a = b = 30.8451(14), c 12.8063(8) angstrom Z = 18]. The structure consists of alternating layers of [P3O9](3-) groups, ErO8 dodecahedra, Na(1)O-6 and Na(2)O-7 polyhedra linked together by water molecules. The P3O9 rings are grouped along the c-axis in a P3O9-ErO8 arrangement thereby producing broad, hexagonal channels of diameter of 6.65 angstrom with a side dimension of 3.907 angstrom. The absence of coincidences for the majority of the IR and Raman bands observed for the cyclotriphosphate salt is in accord with the centrosymmetric structure of the material. The vibrational spectra have been interpreted on the basis of factor group effects.

关键词： open framework structure crystal structure ErNa3(P3O9)(2) center dot 9H(2)O vibrational spectra

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