A Solvent-Free Covalent Organic Framework Single-Ion Conductor Based on Ion-Dipole Interaction for All-Solid-State Lithium Organic Batteries

Single-ion conductors based on covalent organic frameworks(COFs)have garnered attention as a potential alternative to currently prevalent inorganic ion conductors owing to their structural uniqueness and chemical versatility.However,the sluggish Li+conduction has hindered their practical applications.Here,we present a class of solvent-free COF single-ion conductors(Li-COF@P)based on weak ion-dipole interaction as opposed to traditional strong ion-ion interaction.The ion(Li+from the COF)-dipole(oxygen from poly(ethylene glycol)diacrylate embedded in the COF pores)interaction in the Li-COF@P promotes ion dissociation and Li+migration via directional ionic channels.Driven by this single-ion transport behavior,the Li-COF@P enables reversible Li plating/stripping on Li-metal electrodes and stable cycling performance(88.3%after 2000 cycles)in organic batteries(Li metal anode||5,5’-dimethyl-2,2’-bis-p-benzoquinone(Me2BBQ)cathode)under ambient operating conditions,highlighting the electrochemical viability of the Li-COF@P for all-solid-state organic batteries.

A New One-dimensional Aluminium Fluorophosphate Templated by Organic Amine

A new one-dimensional aluminum fluorophosphate, AlP2O5（OH）3F·0.5[H2dien] （dien=diethylenetriamine）, was solvothermally synthesized by using organic amine as the structure directing agent, and its structure was determined by single-crystal X-ray diffraction. The complex inorganic architecture consists of trans-corner-sharing AlO4F2 octahedra chain decorated by phosphate tetrahedra along both sides of the -F-Al-F-Al-F- backbone displaying a series of Al2P three-membered rings, which will represent a new fundamental structural type in metal phosphates. The results of CHN elemental analysis, EDS, and TGA are also presented. Crystal data： C4H18Al2F2N3O16P4, monoclinic, space group P21/c with a=6.9107（14）, b=15.749（3）, c=8.9741（18） , β=109.829（2）o, V=918.8（3） 3, Z=2, Mr=580.05, Dc=2.097 g/cm3, μ=0.618 mm-1, S=1.022, F（000）=590, the final R=0.0510 and wR=0.1284 for 1607 observed reflections （I 〉 2σ（I））.

COF-based single Li^(+)solid electrolyte accelerates the ion diffusionandrestrains dendritegrowthin quasi-solid-state organic batteries

A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Among the various SSEs,the single Li-ion conductor has advantages in terms of enhancing the ion conductivity,eliminating interfacial side reactions,and broadening the electrochemical window.Covalent organic frameworks(COFs)are optimal platforms for achieving single Li-ion conduction behavior because of wellordered one-dimensional channels and precise chemical modification features.Herein,we study in depth three types of Li-carboxylate COFs(denoted LiOOC-COFn,n=1,2,and 3)as single Li-ion conducting SSEs.Benefiting from well-ordered directional ion channels,the single Li-ion conductor LiOOC-COF3 shows an exceptional ion conductivity of 1.36×10^(-5) S cm^(-1) at room temperature and a high transference number of 0.91.Moreover,it shows excellent electrochemical performance with long-term cycling,high-capacity output,and no dendrites in the quasi-solid-state organic battery,with the organic small molecule cyclohexanehexone(C_(6)O_(6))as the cathode and the Li metal as the anode,and enables effectively avoiding dissolution of the organic electrode by the liquid electrolyte.

Conductive Mechanism of Organic Conductor

Organic conductor is a kind of organic compound which has special electronic and magnetic properties. The research of the organic compounds has received considerable attention because of their potential applications in many areas. The molecular conductive units are theoretically investigated as well as their energy gap and charge distribution. The relationship of conductivity and micro mechanism is discussed.

Growth and Characterization of Doped CeO_2 Buffers on Ni-W Substrates for Coated Conductors Using Metal Organic Deposition Method

CeO2 and Ce0.8M0.2O2-d films （M = Mn, Y, Gd, Sm, Nd and La） with （00l） preferred orientation have been prepared on biaxially textured Ni-W substrates by metal organic decomposition （MOD） method. The factors influencing the formation of cracks on the surface of these CeO2 and doped CeO2 films on Ni-W substrates were explored by X-ray diffraction （XRD）, scanning electron microscopy （SEM） analysis, atomic force microscopy （AFM） and differential scanning calorimetry （DSC）. The results indicate that many factors, such as the change of the ionic radii of doping cations, the transformation of crystal structure and the formation of oxygen vacancies in lattices at high annealing temperature, may be related to the formation of cracks on the surface of these films. However, the crack formation shows no dependence on the crystal lattice mismatch degree of the films with Ni-W substrates. Moreover, the suppression of surface cracks is related to the change of intrinsic elasticity of CeO2 film with doping of cations with a larger radius. SEM and AFM investigations of Ce0.8M0.2O2-d （M = Y, Gd, Sm, Nd and La） films reveal the dense, smooth and crack-free microstructure, and their lattice parameters match well with that of YBCO, illuminating that they are potentially suitable to be as buffer layer, especially as cap layer in multi-layer architecture of buffer layer for coated conductors.

Roles of humidity and heat treatment temperatures on YBa_2Cu_3O_(7-x) coated conductors by trifluoroacetic acid-metal organic deposition process

YBa2Cu3O7-x(YBCO) films were fabricated on an LAO substrate using the trifluoroacetic acid-metal organic deposition(TFA-MOD) method and the effects of the humidity and heat treatment temperatures on the microstructure,degree of texture and critical properties of the films were evaluated.In order to understand the combined effects of the humidity and the calcining and firing temperatures on critical properties,heat-treatment was performed at various temperatures with the other processing variables fixed.The films were calcined at 400-430 ℃ and fired at 750-800 ℃ in a 0-12.1% humidified Ar-O2 atmosphere.The texture was determined by pole-figure analysis.The amount of the BaF2 phase was effectively reduced and a sharp and strong biaxial texture was formed under a humidified atmosphere,which led to increased critical properties.In addition,the microstructure varied significantly with firing temperature but changed little with calcining temperature.The highest IC of 40 A/cm-width,which corresponds to JC value of 1.8 MA/cm2,was obtained for the films fired at 775 ℃(in 12.1% humidity) after calcining at 400-430 ℃.It is likely that the highest IC value is due to the formation of a more pure YBCO phase,c-axis grains,and a denser microstructure.

One-dimensional(1D) micro/nanostructures of organic semiconductors for field-effect transistors

Organic semiconductors have gradually become the super stars on the stage of optoelectronic materials, due to their low cost, flexibility and solution processability. Numerous organic semiconductors, including small molecules and conjugated polymers, have been designed and synthesized to explore the potential of organic materials in optoelectronic industry. One-dimensional micro/nanostructures of organic semiconductors generally have more ordered packing structure with fewer defects compared with thin films, and are thus thought to show intrinsic carrier mobility of organic materials. Moreover, the packing structure in micro/nanostructures is clear and relatively easy to analyze, which makes these micro/nanostructures a good platform to study structure-property relationship. Therefore, design of suitable organic molecules to form micro-/nanostructures and methods to obtain ideal micro/nanostructures for functional devices will be fully discussed in this mini review. Finally, the perspective and opportunity of 1D micro/nanostructured organic materials based OFETs in the near future are also addressed.

Surface engineering of 1D nanocatalysts for value-added selective electrooxidation of organic chemicals

Electrolytic water splitting by renewable energy is a technology with great potential for producing hydrogen(H_(2))without carbon emission,but this technical route is hindered by its huge energy(electricity)cost,which is mainly wasted by the anode oxygen evolution reaction(OER)while the value of the anode product(oxygen)is very limited.Replacing the high-energy-cost OER with a selective organic compound electrooxidation carried out at a relatively lower potential can reduce the electricity cost while producing value-added chemicals.Currently,H_(2) generation coupled with synthesis of value-added organic compounds faces the challenge of low selectivity and slow generation rate of the anodic products.One-dimensional(1D)nanocatalysts with a unique morphology,well-defined active sites,and good electron conductivity have shown excellent performance in many electrocatalytic reactions.The rational design and regulation of 1D nanocatalysts through surface engineering can optimize the adsorption energy of intermediate molecules and improve the selectivity of organic electrooxidation reactions.Herein,we summarized the recent research progress of 1D nanocatalysts applied in different organic electrooxidation reactions and introduced several different fabrication strategies for surface engineering of 1D nanocatalysts.Then,we focused on the relationship between surface engineering and the selectivity of organic electrooxidation reaction products.Finally,future challenges and development prospects of 1D nanocatalysts in the coupled system consisting of organic electrooxidation and hydrogen evolution reactions are briefly outlined.

Polyimide covalent organic frameworks as efficient solid-state Li^(+) electrolytes

Covalent organic frameworks(COFs) are attractive porous crystalline materials with extremely high stability, easy functionalization, and open channels, which are expected to be unique ion conductors/transporters in lithium ion batteries(LIBs). Despite recent advances, low ion conductivity and low transference number, resulting in low charging/discharging rate, low energy density, and short battery life, are the main issues that limit their direct application as solid electrolytes in LIBs. Here, we designed and synthesized a novel polyimide COF, namely, TAPA-PDI-COF, with abundant C=O groups, which has been successfully employed as high-performance solid electrolytes by doping TAPA-PDI-COF and succinonitrile(SN). Both the well-defined nanochannels of COFs and SN confined in the well-aligned channels restricted the free migration of anions, while C=O on COFs and CN groups of SN enhanced Li^(+) transport, thus achieving a high ion conductivity of 0.102 m S cm^(-1)at 80 °C and a high lithium-ion transference number of 0.855 at room temperature. According to density functional theory(DFT)calculations, Li-ion migration mainly adopted in-plane transport rather than the axial pathway, which may be due to the shorter hopping distances in the planar pathway. The results suggest an effective strategy for the design and development of all-solidstate ionic conductors for achieving high-performance LIBs.

Amphoteric covalent organic framework as single Li+superionic conductor in all-solid-state

As a novel class of porous crystalline solids,covalent organic frameworks(COFs)based electrolyte can combine the advantages of both inorganic and polymer electrolytes,leading to such as higher structural stability to inhibit lithium dendrites and better processing facility for improving interfacial contact.However,the ionic components of Li salt tend to be closely associated in the form of ion pairs or even ionic aggregates in the channel of COFs due to strong coulombic interactions,thus resulting in slow ionic diffusion dynamics and low ionic conductivity.Herein,we successfully designed and synthesized a novel single-ion conducting nitrogen hybrid conjugated skeleton(NCS)as all solid electrolyte,whose backbone is consisted with triazine and piperazine rings.A loose bonding between the triazine rings and cations would lower the energy barrier during ions transfer,and electrostatic forces with piperazine rings could“anchor”anions to increase the selectivity during ions transfer.Thus,the NCSelectrolyte exhibits excellent room temperature lithium-ion conductivity up to 1.49 mS·cm−1 and high transference number of 0.84 without employing any solvent,which to the best of our knowledge is one of the highest COF-based electrolytes so far.Moreover,the fabricated all-solid-state lithium metal batteries demonstrate highly attractive properties with quite stable cycling performance over 100 cycles with 82%capacity reservation at 0.5 C.

Expanding the dimensionality of proton conduction enables ultrahigh anhydrous proton conductivity of phosphoric acid-doped covalent-organic frameworks

It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)through expanding the dimensionality of proton conduction.Three COF-based composites,COF-1@PA,COF-2@PA,and COF-3@PA(PA:phosphoric acid),are prepared by PA doping of three COFs with similar pore sizes but different amounts of hydrophilic groups.With the increase of hydrophilic groups,COFs can load more PA because of the enhanced hydrogen–bonding interactions between PA and the frameworks.powder X-ray diffraction(PXRD),scanning electron microscopy(SEM),and two-dimensional(2D)solid-state nuclear magnetic resonance(NMR)analyses show that PA can not only enter the channels of COF-3,but also insert into its 2D interlayers.This expands the proton conduction pathways from one-dimensional(1D)to three-dimensional(3D),which greatly improves the proton conductivity of COF-3.Meanwhile,the confinement effect of 1D channels and 2D layers of COF-3 also makes the hydrogen-bonded networks more orderly in COF-3@PA-30(30μL of PA loaded on COF-3).At 150℃,COF-3@PA-30 exhibits an ultrahigh anhydrous proton conductivity of 1.4 S·cm−1,which is a record of anhydrous proton conductivity reported to date.This work develops a new strategy for increasing the proton conductivity of 2D COF materials.

FAST ION CONDUCTORS BASED ON ORGANIC MONTMORILLONITE

Fast ion conductor is a kind of solid material possessing excellent character of translation ion at room temperature. Its translation ion power is almost the same as that of melt salt. In recent years, a few natural minerals with the open structure are found that they

酸浓度对苯胺聚合及所得产物的结构与性能的影响

本文研究了聚合溶液中酸浓度对苯胺的化学聚合行为及所得产物导电性能的影响。并用FTIR、元素分析及XPS等手段表征了不同条件下获得的聚合物分子链结构。

新型1,3-二硫杂戊烯衍生物的合成

首次合成了４ 个未见文献报道的１，３－二硫杂戊烯衍生物，用元素分析、ＩＲ、ＵＶ。

有机导体及超导体的回顾与展望

有机固体是一门多学科交叉的新型研究领域。主要研究具有磁性、光导、电导等特殊性质的分子体系的设计、合成与应用。本文在前人工作的基础上 ,对有机导体及有机超导体的发展历程、结构规律、导电性质作了总结 ;并对有机导体及超导体的单晶培养、晶体电导率的测量方法作了描述。目前 ,有机超导体的超导温度最高己达 12 .8K ,科学家除了改变不同的阴离子与现有的给体培养单晶外 ,还对现有的给体进行修饰和设计并合成了新的给体 ,本文对这一方面也进行了综述。同时对有机导体及超导体发展前景进行了展望。

基于有机电致发光显示的透明导电膜ITO

介绍了ITO作为OLED器件阳电极时,ITO各参数对OLED整体性能,如发光亮度、效率、寿命和稳定性的影响,并以溅射ITO工艺为例,分析了制备与处理环境对ITO的方阻、透过率、表面平整度及功函数的影响。针对其成因,提出了一些改进措施。对高性能平板显示OLED器件用透明导电阳极的研制具有一定的参考价值。

金属有机沉积法制备SrTiO_3薄膜

采用金属有机沉积(MOD)法制备了SrTiO3(STO)外延薄膜作为YBa2Cu3O7-δ涂层导体的缓冲层.以乙酸锶、钛酸丁酯为前驱物配制了Sr离子浓度为0.125 mol.L-1的SrTiO3前驱溶液.研究了950℃下不同烧结时间(90、120、150 min)对在双轴织构的Ni-W(200)金属基带上沉积STO外延薄膜晶体取向和微观形貌的影响.结果表明,在950℃氩氢混合气氛(Ar-4%H2)下适宜于STO薄膜外延生长的最佳烧结时间为120 min;STO缓冲层薄膜表面平整致密,无裂纹和孔洞,具有良好取向,可作为YBa2Cu3O7-δ涂层导体的缓冲层.

基于金属电极和有机半导体层的制备工艺对有机薄膜晶体管性能的研究

基于聚合物绝缘材料和半导体材料,采用溶液法旋涂工艺制作了有机薄膜晶体管(OTFT),通过不同方法制备有机半导体层、栅极和漏极,以提高有机薄膜晶体管的器件性能。结果表明,有机半导体层是否图形化以及不同金属电极的制备工艺对器件的接触电阻影响明显。有机半导体层图形化后,器件的开关比有较大的提升。采用lift-off工艺,先在聚合物绝缘层材料上对光刻胶图形化,然后利用真空蒸镀法将金属电极蒸镀到绝缘层材料上,最后将器件浸泡在70℃的NMP溶液中约30min,接触电阻约为4.8×107Ω;采用湿刻工艺对蒸镀在绝缘层材料上的金属电极进行处理,接触电阻有明显的下降,约为3.6×106Ω。

对我国行政听证主体制度完善之探讨

完整的行政听证主体制度的建立,有利于实现行政行为民主、公开、公正的要求,因此以行政听证主体为对象,通过与各国听证主体制度的比较,解析我国行政听证主体制度的不足,并通过借鉴美国等国家的做法及挖掘我国地方立法实践运作的创新举措来探讨我国行政听证主体制度的完善。

双—（二烷硫基四硫富瓦烯二硫）金属配合物的合成及性质研究

合成了三种未见文献报道的双-(二烷硫基四硫富瓦烯二硫)金属配合物和三种新的四硫富瓦烯(TTF)桥联的双金属配合物,测定了它们的电导率,讨论了含Ni配合物的电导率优于含Cu,Hg配合物的原因.