Preparation And Properties Of Metal Phthalocyanine (Porphyrin) Based Organic Framework/CNT

As a new type of energy storage system between traditional capacitors and batteries,supercapacitors（SCs）have the advantages of high-power density,fast charging and discharging processes,good cycling stability and environmental friendliness,which have promising applications in many fields and great economic value.The performance of supercapacitors is primarily determined by the electrode materials,and how to develop high-performance electrode material is of great concern to researchers.The combination of different kinds of electrode materials by physical or chemical methods can improve the shortcomings of single electrode materials in terms of power density,energy density and the large-scale commercial application,which can not only achieve a reasonable balance of material structure and performance,but also help to optimize the comprehensive performance of supercapacitors（such as specific capacitance and cycling stability）,which become the main trend of the development of electrode materials for supercapacitors.Metal organic polymer/carbon-based composites are characterized by easily tunable structure,adjustable pore size,diverse central coordination atoms and excellent thermal/chemical stability.As the electrode materials for supercapacitor,it is expected to break through the bottleneck of practical application of high-performance supercapacitor and accelerate its industrial application.However,metal phthalocyanine（porphyrin）-based organic frameworks have metal centers and nitrogen active sites,resulting in redox reactions,which are not sufficient to enhance specific capacitance due to their weak conductivity and redox activity.Combining with carbon-based materials is expected to improve the performance of supercapacitors.Based on this,this thesis realized the composite of phthalocyanine（porphyrin）-based conjugated microporous polymers（CMP）with carbon nanotubes（CNT）through the functional design of organic framework structures and the combination of carbon-based materials.Then,a series of metal phthalocyanine（porphyrin）-based organic framework/CNT composites were prepared with the advantages of porous organic materials and phthalocyanine（porphyrin）-based compounds.The electrochemical properties of these composites as electrode materials for supercapacitor have been investigated.The main research contents and results are as follows:（1）Polymetallic phthalocyanine conjugated microporous polymer/single-walled carbon nanotube composites（PMPc-CMP/SWCNT,M=Fe and Co）were successfully prepared by a facile one-pot microwave assisted synthesis technology using 1,2,4,5-tetracyanobenzene,metal salts,and single-walled carbon nanotubes（SWCNT）as raw materials.On this basis,the PMPc-CMP/SWCNT electrode was obtained by the conventional grinding method.The PFe Pc-CMP/SWCNT-2 composite material of PFe Pc-CMP and SWCNT with a weight ratio of 1:1 was used as the electrode material for supercapacitor,the specific capacitance was 257.0 F g^-1at a current density of 1 A g^-1and could be cycled for 1300 cycles at a high current density of 10 A g^-1.The good electrochemical performance can be attributed to the synergistic effect between the pseudocapacitance mechanism of PFe Pc-CMP and the double-layer capacitance mechanism of SWCNT.（2）Terephthalaldehyde linked metal phthalocyanine conjugated microporous polymer（MPc-CMP）was successfully prepared by a fast microwave-assisted synthesis technology using terephthalaldehyde and metal phthalocyanine（M=Co and Fe）as raw materials and then compounded with multi-walled carbon nanotubes（MWCNT）to generate independent flexible films（MPc-CMP/MWCNT）without covalent bonding.The Co Pc-CMP/MWCNT-2 flexible electrode of Co Pc-CMP and MWCNT with a weight ratio of 1:3 was used as the electrode material of the supercapacitor.Benefiting from the synergistic effect and strong interactions between Co Pc-CMP and MWCNT,the flexible Co Pc-CMP/MWCNT-2 electrode had a high specific capacitance of 289.1 F g^-1at a current density of 1 A g^-1and good capacity retention of 82.4%after 1350 cycles at a high current density of 10 A g^-1.（3）Triphenylamine aldehyde linked cobalt phthalocyanine conjugated microporous polymer（NC-CMP）with a three-dimensional network structure were successfully synthesized by a fast microwave-assisted synthesis technology using triphenylamine aldehyde and cobalt phthalocyanines.The NC-CMP was combined with highly conductive MWCNT by vacuum filtration method to obtain non-covalent bonded flexible films（NC-CMP/MWCNT）.The NC-CMP/MWCNT-3 of NC-CMP and MWCNT with a weight ratio of 1:3 was used as self-supporting binder-free flexible electrodes for supercapacitors.NC-CMP/MWCNT-3 exhibited the specific capacitance of was 213.4 F g^-1at a current density of 0.5 A g^-1and a capacity retention of 85.3%after 1750 cycles at a current density of 20 A g^-1.（4）Pyromellitic dianhydride linked copper porphyrin conjugated microporous polymer（CuTAPP-CMP）were successfully synthesized by polycondensation reactions using pyromellitic dianhydride and copper porphyrin as raw materials.Then,CuTAPP-CMP was then combined with MWCNT with good electrical conductivity by a simple vacuum filtration strategy.The CuTAPP-CMP/MWCNT composite fims show the flexible properties.The CuTAPP-CMP/MWCNT-3 of CuTAPP-CMP and MWCNT with a weight ratio of 1:3 was used as a flexible electrode for supercapacitor,which exhibited a specific capacitance of 207.8 F g^-1at a current density of 1 A g^-1and the good electrochemical performance at 20 A g^-1over 3700 cycles.