| In recent years,the research and development of advanced battery materials have not only focused on capacity,cycle life,and charging and discharging performance,but also placed greater emphasis on their safety and environmental protection application needs.Organic electrode materials have highlighted enormous application potential.Especially,quinone cathode materials exhibit advantages such as excellent redox performance,easy structure design,and abundant raw material resources,which have attracted widespread attention from researchers.However,in the application of aqueous zinc ion batteries,the utilization efficiency of the redox active site of quinone cathode materials is relatively low,and the ion/electron transport kinetics is relatively poor.The relationship between the material structure and the electrochemical performance also needs more in-depth research.The insertion and extraction of zinc ions in quinone cathode materials are not entirely determined by active carbonyl groups,but also influenced by their microstructure and configuration.Developing new structured quinone cathode materials is an important way to solve these problems.This thesis takes quinone amine polymer cathode materials as the research object,and synthesizes a series of poly（quinone cyclohexanediamine）cathode materials,then systematically investigates their electrochemical performance in aqueous zinc ion batteries and explores the relationship between their structures and electrochemical performance.The main work of this article is as follows:（1）A novel organic quinone amine cathode material,poly（tetrachlorobenzoquinone1,2-cyclohexanediamine）（TC-12D）,was synthesized through polycondensation reaction using tetrachlorobenzoquinone and 1,2-cyclohexanediamine as raw materials.The structure of TC-12D was analyzed through FT-IR,Raman,SEM,XRD,and XPS characterization,and the effects of synthesis conditions including reaction temperature and solvent on the electrochemical performance of TC-12D were studied.The results showed that the synthesized TC-12D under the conditions of reaction temperature at 78℃and ethanol as solvent performed relatively superior capacity and cycling performance in aqueous zinc ion batteries.In detail,TC-12D exhibited an initial discharge capacity of 187.7 mAh·g-1 at a current density of 0.02 A·g-1.After 200 charge/discharge cycles,the capacity retention rate of TC-12D was 48%.At a current density of 0.1 A·g-1,the maximum discharge capacity of TC-12D was 64.2 mAh·g-1,and its capacity retention rate was 93.4%after 900 cycles.Both Coulombic efficiency were basically maintained at 100%.（2）A novel organic quinone amine cathode material poly（1,4-benzoquinone-1,2-cyclohexanediamine）（BQ-12D）was synthesized by 1,4-benzoquinone and 1,2-cyclohexanediamine through Michael oxidation addition reaction.The structure of BQ-12D was analyzed through FT-IR,Raman,SEM,XRD,and XPS characterization,and the effect of reaction temperature on its electrochemical performance was explored.The results showed that the synthesized BQ-12D under conditions of temperature 78℃in ethanol solvent performed relatively superior capacity and cycling performance.In detail,BQ-12D synthesized exhibited an initial discharge capacity of 146.2 mAh·g-1 at a current density of0.02 A·g-1,and a capacity retention rate of 53%after 200 charge/discharge cycles.At a high current density of 0.1 A·g-1,its first discharge specific capacity is 98.6 mAh·g-1,and the capacity retention rate after 250 cycles is 65.7%.（3）Poly（tetrachlorobenzoquinone-1,4-cyclohexanediamine）（TC-14D）,poly（1,4-benzoquinone-1,4-cyclohexanediamine）（BQ-14D）,and poly（chloroquinone-1,4-cyclohexanediamine）（CQCl-14D）cathode materials were synthesized by polymerization of tetrachlorobenzoquinone,1,4-benzoquinone,or chloroquinone acid with 1,4-cyclohexanediamine,respectively.The electrochemical performance of the series of poly（quinone 1,4-cyclohexanediamine）cathode materials was systematically investigated.The relationships between the structures of the polymerization position on cyclohexanediamine and substituted groups on quinone units with their electrochemical performance were preliminarily compared and explored.The results showed that the capacity and long cycle performance of the series of poly（quinone 1,2-cyclohexanediamine）cathode materials are generally superior to those of poly（quinone 1,4-cyclohexanediamine）cathode materials,indicating that poly（quinone 1,2-cyclohexanediamine）cathode materials polymerized via the ortho position of cyclohexanediamine are more conducive to the insertion and extraction of zinc ions;In the series of poly（quinone 1,4-cyclohexanediamine）cathode materials,the hydroxyl substituted on quinone CQCl-14D performed the best capacity and cycling performance,followed by the unsubstituted quinone BQ-14D,then the chlorine substituted on quinone TC-14D.In the series of poly（quinone 1,2-cyclohexanediamine）cathode materials,the opposite pattern is observed:the chlorine substituted on quinone TC-12D performed the best capacity and cycling performance,followed by the unsubstituted quinone BQ-12D,then the hydroxyl substituted on quinone TC-12D. |
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