Research On The Application Of Phthalocyanine/porphyrin-based Microporous Polymer In Lithium/dual-ion Batteries

Lithium-ion batteries（LIBs）have been applied to various portable devices due to their unique advantages of high energy density and long cycling stability.Dual-ion batteries（DIBs）are more and more favored by scientists because they can provide higher voltages.Electrode materials play an important role in enhancing the performance of LIBs/DIBs.The application of inorganic materials has been limited in view of their limited capacity,limited resources and environmental problems.Organic electrode materials have been widely used as electrode materials due to their advantages of design flexibility,structure diversity,and easy availability of raw materials.Therefore,this thesis synthesized a series of phthalocyanine/porphyrin-based polymers and studied their electrochemical performance as electrode materials for LIBs/DIBs.The main contents and results are as follows:（1）Two phthalocyanine-based microporous polymers CuPcBE-CMP and CuPcBI-CMP were synthesized.By comparing their electrochemical performance as anode materials for LIBs,CuPcBI-CMP had better electrochemical performance than CuPcBE-CMP.When used as a cathode material for LIBs,CuPcBI-CMP could show a capacity of 190.8 m Ah·g^-1 in the voltage range of 1.5-4.5 V.When paired with lithium foil to form DIBs,the capacity presented an upward trend to 51.9 m Ah·g^-1 at 1 A g^-1.This capacity was maintained after 1,000 cycles.The cell revealed excellent cycle stability.When DIBs was constructed with graphite,it could provide a capacity of 466.9 m Ah·g^-1within a high voltage window of 3-4.8 V and the coulombic efficiency remained at 95%.（2）A microporous polymer of polycopper phthalocyanine（CuPPc）was synthesized.CuPPc shows a spherical morphology.As a cathode material for LIBs,it could provide a discharge capacity of 1376.7 m Ah·g^-1 at first-cycle.At a current density of 0.5 A g^-1,the capacity retention rate was 76.6%after 200 cycles.When paired with lithium foil to construct DIBs,it could provide a capacity of 145.9 m Ah·g^-1.Even at a current density of 2A g^-1,there was still a capacity of 22.8 m Ah·g^-1.When formed DIBs with graphite,it could provide a capacity of 438.2 m Ah·g^-1 within a high voltage window of 3-4.8 V.（3）A porphyrin-bridged microporous polymer（TAPPNA-CMP）containing carbonyl groups was designed and tested for LIBs/DIBs.When used as a cathode material for LIBs,it could provide a discharge capacity of 116.4 m Ah·g^-1at a current density of 0.05 A g^-1within a voltage window of 1.5-4.5 V.After constructing DIBs with lithium foil,it could provide a charge capacity of 129.3 m Ah·g^-1 at a current density of 0.05 A g^-1.In the rate test,the charge capacities of 74.3,62.5,38.1,23.9,17.6 and 73.4 m Ah·g^-1 were shown at current densities of 0.1,0.2,0.5,1.0,2 and 0.1 A g^-1,respectively.