Interpenetrated Structures for Enhancing Ion Diffusion Kinetics in Electrochemical Energy Storage Devices

The architectural design of electrodes offers new opportunities for next-generation electrochemical energy storage devices(EESDs)by increasing surface area,thickness,and active materials mass loading while maintaining good ion diffusion through optimized electrode tortuosity.However,conventional thick electrodes increase ion diffusion length and cause larger ion concentration gradients,limiting reaction kinetics.We demonstrate a strategy for building interpenetrated structures that shortens ion diffusion length and reduces ion concentration inhomogeneity.This free-standing device structure also avoids short-circuiting without needing a separator.The feature size and number of interpenetrated units can be adjusted during printing to balance surface area and ion diffusion.Starting with a 3D-printed interpenetrated polymer substrate,we metallize it to make it conductive.This substrate has two individually addressable electrodes,allowing selective electrodeposition of energy storage materials.Using a Zn//MnO_(2) battery as a model system,the interpenetrated device outperforms conventional separate electrode configurations,improving volumetric energy density by 221%and exhibiting a higher capacity retention rate of 49%compared to 35%at temperatures from 20 to 0℃.Our study introduces a new EESD architecture applicable to Li-ion,Na-ion batteries,supercapacitors,etc.

Synthesis, Crystal Structure and Gas Adsorption of a Two-fold Interpenetrated Three-dimensional Framework {[Cd(2-NO_2-BDC)(4,4？-DPA)]·(DMF)}_n

The reaction of Cd（NO_3）_2·4H_2O with 4,4？-dipyridylacetylene（4,4？-DPA） and 2-nitroterephthalic acid（2-NO_2-H_2BDC） in DMF/H_2O mixed solvent has afforded a compound {[Cd（2-NO_2-BDC）（4,4？-DPA）]·（DMF）}_n（1）. Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a = 12.1488（3）, b = 14.6689（3）, c = 13.1615（3） ？, β = 111.809（3）o, V = 2177.63（9） ？~3, Z = 4, C_（23）H_（18）N_4O_7 Cd, M_r = 574.81, D_c = 1.753 g/cm^3, μ = 8.523 mm^（-1）, F（000） = 1152, the final R = 0.0411 and wR = 0.1064 for 3589 observed reflections with I 〉 2s（I）. In compound 1, the Cd（Ⅱ） ions are linked by the carboxylate groups of 2-NO_2-BDC ligands to give a two-dimensional layered structure based on the centrosymmetric dinuclear Cd_2（COO）_2 units, which are further connected by the 4,4？-DPA ligands to produce a three-dimensional framework with pcu topology. Careful examination revealed that compound 1 is a 2-fold interpenetrating framework. Furthermore, the gas adsorption properties of 1 for N_2 and CO_2 have also been investigated.

A 3D Hydrogen-bonded 2-Fold Interpenetrated Supramolecular Structure of Cyclen Derivative

The title compound 1,4,7,10-tetrakis（2-（4-methoxyphenoxy）ethyl）-1,4,7,10-tetraazacyclododecane hydrobromide derivated from cyclen has been synthesized by 4-methoxyphenol via two steps and characterized by ^1H NMR and X-ray single-crystal diffraction. The crystal belongs to the orthorhombic system, space group Pbcn with a = 17.3174（15）, b = 12.9891（11）, c = 19.3379（17） A, V = 4349.8（7） ？3, Z = 4, Dc = 1.304 g/cm3, Mr = 853.87, F（000） = 1808, μ = 1.001 mm^-1, Mo Ka radiation（λ = 0.71073 A）, R = 0.0467 and w R = 0.1045 for 2774 observed reflections with I 〉 2σ（I）. X-ray structural analysis reveals that the molecular structure of the title compound is stabilized by intramolecular C–H···O and C–H···Br hydrogen-bonding interactions, and a 3D 2-fold interpenetrated supramolecular framework is constructed by intermolecular C–H···O and C–H···Br hydrogen-bonding interactions.

Helical Coordination Polymer with a 3-Fold Interpenetration Structure Based on 5-(Hydroxymethyl)isophthalic Acid

5-（Hydroxymethyl） isophthalic acid （H2HIA） as a novel organic ligand was prepared from 3,5-bis（methoxycarbonyl）benzoic acid by a two-step method. And then, a 3D helical coor- dination polymer with a 3-fold interpenetration structure, namely [Zn1/2（HIA）1/2（DPEE）1/2]n （1）, was hydrothermally synthesized at 160 ℃, using H2HIA ligands to assemble with DPEE ligands and Zn2＋ ions. Complex 1 crystalizes in orthorhombic system, space group Pnna, with a = 8.2118（5）, b = 17.1698（7）, c =14.9922（7） ？, V = 2113.82（18） ？3, μ = 1.194 mm-1, Z = 4 and S = 0.967. Moreover, some physical characteristics of complex 1, such as powder X-ray diffraction （PXRD）, thermogravimetry analyses （TGA） and photoluminescent properties, were also investigated.

Thermoreversible Thickening and Self-assembly Behaviors of pH/Temperature Dually Responsive Microgels with Interpenetrating Polymer Network Structure

The pH /temperature dually responsive microgels of interpenetrating polymer network( IPN) structure composed of poly( N-isopropylacrylamide)( PNIPAM) network and poly( acrylic acid)( PAA) network( PNIPAM /PAA IPN microgels) were synthesized by seed emulsion polymerization. The results obtained by dynamic laser light scattering( DLLS) show that the microgels have good pH /temperature dual sensitivities. The temperature sensitive component and the pH sensitive component inside the microgels have little interference with each other. The rheological properties of the concentrated PNIPAM /PAA IPN microgel dispersions as a function of temperature at pH 4. 0 or 7. 0 were investigated by viscometer,and the results displayed that only at pH 7. 0 the dispersions presented thermoreversible thickening behavior. Then the PNIPAM /PAA fibers were prepared by self-assembly of the PNIPAM /PAA IPN microgels in the ice-crystal templates formed by unidirectional liquid nitrogen freezing method. Field emission scanning electron microscopy( FESEM) images indicate that the PNIPAM /PAA fibers are rounded,randomly orientated and interweaved.

Interpenetrating structure for efficient Sb_(2)Se_(3) nanorod array solar cells loaded with CuInSe_(2) QDs sensitizer

The strong anisotropic electrical properties of one-dimensional(1 D) nanostructure semiconductors,especially the anisotropic carrier transport, have a negative and significant influence on the performance of solar cells if the nanostructures have random orientation. Considering the advantages of nanorod solar cells in carrier transport, we have achieved growth of vertically aligned Sb_(2)Se_(3) nanorod array with highly(hk1) orientation on Cd S substrate, and constructed superstrate nanorod solar cells for the first time. The Sb_(2)Se_(3) nanorod array solar cells exhibit the more efficient and long-range carrier transport in vertical direction. Furthermore, in order to suppress interface recombination, a CuInSe_(2) quantum dots(QDs) sensitizer has been applied to fill the volume between the nanorods completely, thus forming an interpenetrating nanocomposite structure. The CuInSe_(2) QDs can harvest additional light by absorption of visible light and contribute photocurrent. Meantime, the QDs function as a hole transport material and thus reduce the dependence of lateral transport. Consequently, the interpenetrating nanocomposite CuInSe_(2) / Sb_(2)Se_(3) solar cells display a power conversion efficiency of 7.54% with significant enhancements in the short-circuit current density and open-circuit voltage over pure Sb_(2)Se_(3) nanorod cells. This is the highest efficiency for superstrate solar cells based on Sb_(2)Se_(3) nanorod arrays.

ClO_4^--directed Assembly of Two Co^ⅡComplexes Based on Flexible N-donor Ligands:Syntheses,Crystal Structures and Magnetic Properties

The reaction of Co^II ions with 1,4-bis（imidazol）butane（bimb） or 1,4-bis（triazol）butane（bitb） in the presence of ClO4^-, respectively affords two CoII coordination complexes, namely {[Co（bimb）3]·2ClO4}n（I） and {[Co（bitb）3]·2ClO4}n（II）. Single-crystal X-ray analysis indicates that both complexes I and II show the same α-Po topological structures. However, complex I exhibits a 2-fold interpenetrating network, while complex II features a 3-fold interpenetrating network. In addition, solid-state properties such as thermal stabilities and magnetic properties of two complexes were also investigated.

Synthesis, Crystal Structure and Catalytic Properties of a Novel Ni(Ⅱ) MOF with a Rare [3+3+3] Nine Fold Interpenetrated Network

Metal-organic frameworks are a sort of rapid development crystal solids,which have greatly attracted a large amount of attention in recent decades.The construction of 3D[Ni(bcp)(bpp)]n(namely complex 1)displays a rare[3+3+3]nine-fold interpenetrated diamond topology,which can be successfully synthesized by a mixed strategy of 1,3-bis(4-carboxyphenoxy)propane(H2bcp)and 1,4-bis(4-pyridylmethyl)piperazine(bpp).The interpenetrated network may be ascribed to these flexible bridging linkers to facilitate the penetration degree.In addition,the resultant sample was adequately characterized by elemental analysis,single-crystal X-ray diffraction,powder X-ray diffraction,and thermal gravimetric analysis.Furthermore,the as-synthesized sample can be used as catalysis for chemical fixation of CO2 and epoxide to carbonate.