CN-121975259-A - Intelligent response type semiconductor hydrogel electrolyte and preparation method thereof

CN121975259ACN 121975259 ACN121975259 ACN 121975259ACN-121975259-A

Abstract

The invention discloses an intelligent response type semiconductor hydrogel electrolyte and a preparation method thereof, which belong to the technical field of functional polymer materials and electrochemical energy storage, wherein the semiconductor hydrogel electrolyte comprises a three-dimensional network flexible gel skeleton, intelligent response materials, an electron transmission channel formed by semiconductor components and an ion transmission channel formed by ion conductors are distributed in the three-dimensional network flexible gel skeleton, the intelligent response materials comprise one or any combination of temperature sensitive materials, light response materials and pH sensitive materials, the intelligent response materials have a three-dimensional network structure with electronic conduction, ion conduction and multi-stimulus responsiveness, the ion conductivity is adjusted according to needs through phase change or molecular configuration change of an intelligent response unit, the limitation of static transmission of the traditional hydrogel electrolyte is broken through, and the problems that the traditional hydrogel electrolyte is poor in conductivity, difficult to cooperate with the semiconductor performance and lacks multi-stimulus responsiveness are solved.

Inventors

WEN NA
LIAN ZE
LIANG JIZHONG
YU HUA
Lu Haohe
LI BAOJIN
WANG XUAN
NIU SHU
LIU CHENG
XUE ZHIGANG

Assignees

国网山西省电力有限公司电力科学研究院

Dates

Publication Date: 20260505
Application Date: 20260119

Claims (10)

1. The intelligent response type semiconductor hydrogel electrolyte is characterized by comprising a three-dimensional network flexible gel skeleton, wherein intelligent response substances, an electron transmission channel formed by semiconductor components and an ion transmission channel formed by ion conductors are distributed in the three-dimensional network flexible gel skeleton, and the intelligent response substances comprise one or any combination of temperature sensitive materials, light response materials and pH sensitive materials.
2. The intelligent response type semiconductor hydrogel electrolyte according to claim 1, wherein the three-dimensional network flexible gel skeleton is a network structure formed by chemical crosslinking of one or more of acrylamide, polyacrylamide and polyvinyl alcohol.
3. The smart responsive semiconducting hydrogel electrolyte of claim 1, wherein the semiconducting component is an N-type semiconducting polymer P (PyV) or inorganic semiconducting nanoparticles.
4. The smart responsive semiconducting hydrogel electrolyte of claim 3, wherein the inorganic semiconducting nanoparticle is graphene oxide or Mxene.
5. The smart responsive semiconducting hydrogel electrolyte of claim 1 wherein the temperature sensitive material is poly N-isopropylacrylamide.
6. The smart responsive semiconducting hydrogel electrolyte of claim 1 wherein the light responsive material is a spiropyran and the pH sensitive material is an acrylic monomer.
7. The intelligent response type semiconductor hydrogel electrolyte according to claim 1, wherein the ionic conductor is lithium salt or [ EMIM ] [ TFSI ] ionic liquid.
8. The method for preparing the intelligent response type semiconductor hydrogel electrolyte according to any one of claims 1 to 7, comprising the following steps: step one, mixing and dissolving a flexible gel material, a semiconductor component and an intelligent response substance in water, and adding a photoinitiator and a crosslinking agent to prepare a precursor solution; Step two, polymerizing the precursor solution through photoinitiation to form crosslinked hydrogel; step three, soaking the crosslinked hydrogel in an ion conductor, introducing the ion conductor through solvent exchange, and simultaneously removing unreacted monomers; And fourthly, post-treatment, namely optimizing the pore structure through repeated operation of freezing-thawing cycle on the crosslinked hydrogel, or enhancing the mechanical strength through thermal annealing on the crosslinked hydrogel.
9. The preparation method of the intelligent response type semiconductor hydrogel electrolyte is characterized in that the mechanical property regulation and control of the hydrogel electrolyte are achieved through adjusting the content of semiconductor components and the concentration of a crosslinking agent, the electric conductivity regulation and control of the hydrogel electrolyte are achieved through adjusting the content of an ion conductor, and the temperature response, the pH response and the light response of the hydrogel electrolyte are adjusted through adjusting the content of an intelligent response substance.
10. The method for preparing the intelligent response type semiconductor hydrogel electrolyte according to claim 8, wherein the freezing-thawing is performed by freezing the crosslinked hydrogel at-20 ℃ for 10-14 hours and then thawing, and the thermal annealing is performed at 60 ℃ for 1-3 hours.

Description

Intelligent response type semiconductor hydrogel electrolyte and preparation method thereof Technical Field The invention belongs to the technical field of functional polymer materials and electrochemical energy storage, and particularly relates to an intelligent response type semiconductor hydrogel electrolyte and a preparation method thereof. Background The electrolyte is a key medium for realizing ion conduction in the battery or the capacitor, the shape and the components of the electrolyte are different according to application scenes, the electrolyte in the battery comprises a liquid electrolyte and a solid electrolyte, and the liquid electrolyte ‌ is a lithium battery electrolyte, consists of lithium salt (such as lithium hexafluorophosphate), an organic solvent (ethylene carbonate and the like) and an additive and is responsible for conducting lithium ions between a positive electrode and a negative electrode. Lead acid batteries use sulfuric acid as the electrolyte. The solid electrolyte ‌, which includes a polymer and an inorganic material (e.g., ceramic), is used for a solid-state battery with higher safety. The electrolyte in the capacitor is an electrolytic capacitor ‌, and the electrolyte is taken as a main part of a cathode to form a capacitor together with an oxide film (dielectric). The electrolyte of the aluminum electrolytic capacitor needs to have high conductivity, low vapor pressure and other characteristics, and is usually liquid or solid. Conventional electrolytes have certain limitations: The existing lithium ion battery and supercapacitor widely adopt liquid organic electrolyte or solid inorganic electrolyte, have the problems of liquid leakage risk, insufficient mechanical flexibility, poor compatibility with biological tissues and the like, and are difficult to meet the severe requirements of flexible electronic devices and implanted medical equipment on safety and flexibility. The hydrogel electrolyte is a semi-solid ion conductor in a battery or a capacitor, is formed by absorbing electrolyte-containing solution (such as zinc sulfate) by a polymer network (such as zinc alginate and polyacrylamide), and has flexibility and ion conductivity. The core function is to realize charge and discharge through ion transport, for example, in a zinc ion battery, zinc ions migrate between the anode and the cathode through an electrolyte. Although the common hydrogel electrolyte has high water content and flexibility, the ionic conductivity is generally lower than 10 mS/cm, and the intelligent responsiveness is lacking, so that the ion transmission behavior cannot be dynamically regulated according to environmental changes (such as temperature and pH), and the application of the common hydrogel electrolyte in an adaptive electronic system is limited. While the charge transmission efficiency can be improved by introducing semiconductor materials (such as conductive polymers and inorganic nano particles) into the hydrogel, the traditional compounding method is easy to cause semiconductor aggregation or mechanical property reduction, and the cooperative optimization of high conductivity and high flexibility is difficult to realize. And the existing hydrogel electrolyte lacks cooperative response capability to multiple stimuli, cannot realize advanced functions such as self-repairing, shape memory or ion release according to needs, and is difficult to meet the requirements of next-generation intelligent electronic devices. Disclosure of Invention The invention overcomes the defects of the prior art, provides an intelligent response type semiconductor hydrogel electrolyte and a preparation method thereof, and solves the problems that the existing hydrogel electrolyte is poor in conductivity, difficult to cooperate with the semiconductor performance in mechanical flexibility and lacks in multi-stimulus response. The invention is realized by the following technical scheme: an intelligent response type semiconductor hydrogel electrolyte comprises a three-dimensional network flexible gel skeleton, wherein intelligent response materials, an electron transmission channel formed by semiconductor components and an ion transmission channel formed by ion conductors are distributed in the three-dimensional network flexible gel skeleton, and the intelligent response materials comprise one or any combination of temperature sensitive materials, light response materials and pH sensitive materials. Preferably, the three-dimensional network flexible gel skeleton is a network structure formed by chemical crosslinking of one or more of acrylamide, polyacrylamide and polyvinyl alcohol. Preferably, the semiconductor component is an N-type semiconductor polymer P (PyV) or an inorganic semiconductor nanoparticle. Preferably, the inorganic semiconductor nanoparticle is graphene oxide or Mxene. Preferably, the temperature sensitive material is poly N-isopropyl acrylamide. Preferably, the light-responsive material is spiro