Construction Of Co/Cu Coordination Polymers And Their Composite Film-based Triboelectric Nanogenerators And Their Performance Studies

There is widely distributed irregular micro-nano mechanical high entropy energy in nature,such as solar,water,wind,and mechanical energy.It will be an effective solution to alleviate the fossil fuel shortage and energy exhaustion if it can be utilized.With the increasing booming of the Internet of Things,there are a growing number of distributed electronics,followed by the demand for distributed energy.In the field of nanotechnology,triboelectric nanogenerator is of great significance in collecting mechanical energy from the environment and converting it into electrical energy.It generates electricity through contact electrification and the electrostatic coupling principle.The charge density is the major factor that affects the electrode’s output performance,which comes from the characteristics of the material itself.The current research on the triboelectric sequence of common materials is mostly limited to polymers,metal oxides and some metallic materials,while coordination polymers,as organic-inorganic hybrid materials,have the characteristics of easy modification,strong polarity controllability and variable structure that traditional materials do not have.In this paper,three new transition metal coordination polymers were constructed by selecting 4,4’,4’’tricarboxyltriphenylamine carboxylic acid as the main ligand and different N-containing organic ligands as the auxiliary ligands,ligated with cobalt（II）and copper（II）under solvothermal conditions,and the TENG devices were assembled using the coordination polymer powder and its binary/ternary component composite films prepared with organic polymers,and characterized their electrical properties.It not only broadens the TENG frictional electric sequence and nriches the regulation strategy of TENG electrode materials.The main studies are as follows:（1）4,4’,4’’-triphenylaminocarboxylic acid and 2,2’-bipyridine were selected as ligands to synthesize Co（II）coordination polymers（Co-CP）with a two-dimensional network structure.Firstly,the composite films were prepared by applying the flow casting/evaporation technique with different doping ratios of Co-CP as filler and quantitative polyvinylidene fluoride PVDF and assembled into a wear-resistant and stable TENG to investigate the optimal doping ratio（15%wt）of Co-CP when the output performance of Co-CP@PVDF-TENG was optimal.Then we further added the piezoelectric material Ba Ti O₃（BTO）to prepare the ternary component composite films(Co-CP_0.15@PVDF@BTO_0.05,Co-CP_0.15@PVDF@BTO_0.10)based on the preparation of Co-CP_0.15@PVDF composite film and assembled into TENG,which further improved the output performance of TENG.As a comparison,we also select the positive polar organic polymer ethyl cellulose（EC）instead of PVDF to prepare binary component composite membranes of different ratios of Co-CP and assembled into TENG(Co-CP_0.10@EC-TENG,Co-CP_0.15@EC-TENG).A series of electrical characterization results showed that the output performance of Co-CP_0.15@EC-TENG exceeds the Co-CP_0.15@PVDF-TENG and Co-CP_0.15@PVDF@BTO-TENG,which achieved a great enhancement of current and voltage.Finally,we applied the best output TENG(Co-CP_0.15@EC-TENG)to the electrochemical anti-corrosion system,which provided good protection to carbon steel.（2）4,4’,4’’-triphenylaminocarboxylic acid ligand and different N-containing organic ligands（2,2’-bipyridine and 2,4,6-tris（4-pyridine）1,3,5-triazine（TPT））were selected as ligands to synthesize two coordination polymers,one is Cu-BPY-CP,a one-dimensional chain with transition metal ions of Cu²⁺,another is Cu-TPT-CP with three-dimensional network structure.Spin-coated PVDF was used as the negative electrode material,and ligand polymers with different metal centers but the same ligand（Co-CP and Cu-BPY-CP）were powder coated to prepare the positive electrode and assembled into TENG,and the output of both applied to TENG,and it was concluded that Cu-BPY-CP has a larger TENG output performance,and then the ligand polymers with the same metal center ion(Cu²⁺)and different ligands were assembled into TENG to explore its output.The tests showed that Cu-BPY-CP-TENG had the largest output performance,followed by the output of Co-CP-TENG,and then the output of Cu-TPT-CP-TENG.