Soft Template-directed Synthesis Of Porous Conjugated Polymers And Their Electrochemical Properties

?-conjugated polymers(?-CPs)are characterized by delocalized electrons,high room temperature conductivity,adjustable polar functional groups,easy preparation and doping,which have unique attractions in the fields of adsorption,energy conversion,catalysis and biomedicine.Furthermore,the creation of regular mesoporous structures for?-CPs can endow it a large specific surface area,exposed active sites,adjustable pore size and unique mesoscopic structure,which can greatly improve its performance and application potential in different fields.However,the synthesis of porous?-CPs is usually limited to microporous or small mesoporous structures and involves strict reaction conditions,resulting in a low mass transfer rate,which greatly limits its application.In this paper,spherical micelles formed by block copolymers were used as templates to guide the polymerization growth of conjugated molecules under mild conditions,controlled synthesize novel mesoporous?-CPs materials with specific nanoarchitectures,and further explore their electrochemical properties.The main research contents and results are as follows:1.Preparation of mesoporous poly(1,3,5-tris(4-aminophenyl)benzene)and the investigation on their lithium ion storage propertiesa series of 1,3,5-tris(4-aminophenyl)benzene(TAPB)-based mesoporous?-conjugated polymers are constructed by one-pot nanoemulsion induced interfacial self-assembly strategy.The pore size and structure can be controlled by regulating the amount of toluene in the system.In addition,two-dimensional hierarchical GO@m PTAPB composite nanosheets are synthesized by introducing two-dimensional monolayer graphene oxide(GO)and inducing co-assembly and in-situ polymerization of micelle emulsion at the GO interface.Benefiting from rich redox-active functional groups,ordered mesoporous structure,excellent electron conductivity and 2D conjugated framework,GO@m PTAPB exhibits high capability of accommodating Li⁺anions(up to 382 m Ah g^-1 at 0.2 A g^-1)and outstanding electrochemical stability(87.6%capacity retention after 1000 cycles).In addition,the ex-situ Raman and impedance spectrum are further applied to reveal the lithium ion storage mechanism of the materials.2.Preparation of mesoporous poly(4,4',4'',4'''-pyrene-1,3,6,8-tetrayl)tetraaniline)and its application in lithium sulfur battery separatorBy controlling the bottom-up self-assembly of pyrene-based organic small molecules and their co-assembly with external micelles,a core-shell fibrous m PPy TTA materials are obtained from the in-situ polymerization of supramolecular nano-assemblies and directed polymerization of composite micelles of Py TTA monomer.By adjusting the reaction conditions,the morphological evolution mechanism of pyrene-based?-conjugated mesoporous polymer is further confirmed,and the growth mechanism of m PPy TTA-NF is proposed and discussed.Density Functional Theory(DFT)calculations shows that pyrene-based?-conjugated mesoporous polymers can anchor and catalyze polysulfide conversion due to strong adsorption between them.Pyrene-based isomeric m PPy TTA-NF has unique physical and chemical properties such as highly ordered mesoporous structure,?-conjugated framework and abundant polar chemical groups,can greatly promote the chemical adsorption and catalytic conversion of polysulfide,thus achieving rapid ion/electron transport.As a novel interlayer material for lithium-sulfur batteries,it shows high discharge specific capacity(up to 1274 m Ah g^-1 at 2.0 C),long cycle stability(74.2%capacity retention rate after 200 cycles)and excellent rate performance(up to 876.3m Ah g^-1 at 4.0 C).