Development And Electrochemical Properties Of Materials For Proton Conducting With Thermal Response And Thermally Chargeable Supercapacitors

In human society and natural environment,the existence of thermal energy is extensive and diverse,so any practice of thermal energy management can significantly benefit the society.On the one hand,based on the utilization of ambient heat or artificial heating,temperature remote control,gate control and early warning monitoring technologies are widely used in drug release,thermal control brake and other fields;On the other hand,for the recovery of heat energy,especially low-grade heat,thermoelectric technology can convert heat energy into electricity based on temperature difference and output,which can help alleviate global energy crisis or enable wearable electronics integration applications.In order to promote the richness and practicability of the thermal energy management system,this paper will develop the materials and study the electrochemical properties of the thermal response proton conduction and ionic thermally chargeable supercapacitors.The thermochromic compound HBABSA transforms its structure from keto to enol-type under thermal stimulation,which can dissociate more free protons.The composite material with the function of thermal response proton conduction switch was prepared by loading HBABSA into the cavity of MOF-808.The proton conduction switching ratio of the composite reaches 16 at 57%RH.In addition,a series of HBABSA@MOF-808/PP-X hybrid membranes with different filler contents were prepared by doping the composite into the PAMPS/PVA substrate.The results show that the hybrid membrane filled with 25%HBABSA@MOF-808 has a switching ratio of 5.4 at 57%RH and a conductivity of 5.57×10^-3 S/cm at 353 K.Using PAMPS/PAA based hydrogel doped with g-C₃N₄ as solid electrolyte and2D NH₂-Ni/Co-BDC MOF@Ti₃C₂T_x MXene composite material as electrode,the flexible ionic thermally chargeable supercapacitor has the ability to directly convert low-grade heat into electric and store electric energy.It can provide power support for flexible electronic integrated systems.The assembled device produces a thermal voltage of 55.68 m V,a Seeback coefficient of 18.56 m V/K,and an energy conversion efficiency of 0.65%atΔT of 3 K.In addition,the device has a low resistance of 20.5Ω,and demonstrates excellent cyclic thermal recharging performance and the ability to drive electronics,demonstrating the utility of the device.With P（AM-AMPS-AYP K⁺）hydrogel with the property of self-healing as solid electrolyte and Ti₃C₂T_x MXene@PPy composite film with strong photothermal properties as flexible electrode,the flexible symmetric thermally chargeable supercapacitor assembled has the functions of thermoelectric conversion based on ion Soret effect and energy storage based on Faraday pseudocapacitor.Therefore,thermal power generation and electricity storage can be realized under the action of temperature difference.Based on the Ti₃C₂T_x MXene-based composite electrode’s photothermal conversion and high thermal conductivity,the device can be attached to the surface of human skin and adapt to different scenes of thermal generation.AtΔT=1.8K,the thermally chargeable supercapacitor achieved a high ionic thermal voltage of43 m V,which produced a Seebeck coefficient of 23.89 m V/K and a high energy exchange efficiency of 1.7%,respectively.In addition,the integrated multifunctional sensing system with the device as the power supply has potential applications for real-time monitoring of human health and motion,as well as mechanical learning for hand-electronic recognition.