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CN-121975106-A - High-flexibility aryl polymer and preparation method and application thereof

CN121975106ACN 121975106 ACN121975106 ACN 121975106ACN-121975106-A

Abstract

The invention discloses a high-flexibility aryl polymer, a preparation method and application thereof, wherein the high-flexibility aryl polymer replaces the traditional polyethylene oxide, and the solid electrolyte prepared by the high-flexibility aryl polymer has high room temperature ion conductivity, good flexibility and high voltage resistance. The invention develops a novel polymer matrix material, fundamentally solves the problems of low ionic conductivity, intolerance to high voltage, poor flexibility and the like of the conventional polymer electrolyte at room temperature, and breaks through the key technical bottleneck in the current solid-state battery field.

Inventors

  • LI MING
  • MOU HONGLI
  • LIU JUNYU

Assignees

  • 武汉立膜科技有限公司

Dates

Publication Date
20260505
Application Date
20251218

Claims (10)

  1. 1. A highly flexible aryl polymer characterized by comprising structural units of the formula: , wherein A is selected from at least one of the groups shown in the following structural formula: , wherein Ar 1 、Ar 2 is independently selected from aromatic groups having 3 to 20 carbon atoms; G 0 is selected from at least one of the groups shown in the following structural formula: Wherein R 1 、R 2 、R 3 is independently selected from hydrogen, alkyl having 1-20 carbon atoms, or aryl having 6-20 carbon atoms, or is independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, carbonyl, halogen substituted alkyl having 1-20 carbon atoms, or is independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, carbonyl, halogen substituted aryl having 6-20 carbon atoms; The ring substituent is at least one of aliphatic carbocycle substituent, polycyclic aromatic ring substituent and heterocyclic substituent with 3-20 carbon atoms, m is a natural number not more than 10; e is selected from J, or a combination of J and K, wherein J is selected from at least one of dihaloaromatic ring radical containing at least one strong electron withdrawing group, dihaloaromatic ring radical containing at least one N atom and aryl radical containing two halomethyl groups, and K is selected from at least one of aryl radical containing two acyl halide groups and dihaloalkyl radical having 1 to 20 carbon atoms; Each G 1 、G 2 is independently selected from any one of O, S, NR 4 , wherein R 4 is selected from hydrogen, alkyl with 1-20 carbon atoms or aryl with 6-20 carbon atoms, or is independently selected from carboxyl, hydroxyl, amino, sulfhydryl, nitro, halogen substituted alkyl with 1-20 carbon atoms, or is independently selected from carboxyl, hydroxyl, amino, sulfhydryl, nitro, halogen substituted aryl with 6-20 carbon atoms.
  2. 2. A method of preparing the highly flexible aryl polymer of claim 1, comprising the steps of: in the presence of alkali, monomer G and monomer M are subjected to polymerization reaction to generate the high-flexibility aryl polymer; or in the presence of alkali, the monomer G, the monomer M and the cross-linking agent monomer are subjected to polymerization reaction to generate the high-flexibility aryl polymer; The structural general formula of the monomer G is as follows: , The monomer M is selected from Q or a combination of Q and P, wherein Q is selected from at least one of dihalogenated aromatic ring hydrocarbon containing at least one strong electron withdrawing group, dihalogenated aromatic ring hydrocarbon containing at least one N atom and aromatic hydrocarbon containing two halogenated methyl groups, and P is selected from at least one of aromatic hydrocarbon containing two acyl halide groups and dihaloalkane containing 1-20 carbon atoms; The cross-linking agent monomer is selected from aromatic hydrocarbon compounds containing three or more hydroxyl groups, mercapto groups, amino groups or halogens, or selected from alkane containing three or more halogens and nitrogen-containing heterocyclic compounds containing a plurality of active groups; the base is selected from at least one of an alkali metal hydroxide or an alkali metal carbonate.
  3. 3. An aryl polymer containing aliphatic ether chains, characterized by comprising structural units of the formula: , wherein B is a fatty ether chain, the polymerization degree of the fatty ether chain is more than or equal to 1, and G 0 is at least one of the groups shown in the following structural formula: , And B is attached to R 1 、R 2 or R 3 of G 0 , or B is attached to a ring of G 0 ; b is at least one selected from the groups shown in the following structural formulas: Wherein n is the degree of polymerization.
  4. 4. A process for the preparation of an aryl polymer containing aliphatic ether chains, characterized by the steps of: when the high-flexibility aryl polymer of claim 1 contains active hydrogen, the high-flexibility aryl polymer of claim 1 is polymerized with at least one of ethylene oxide, propylene oxide, tetrahydrofuran, chloroether, epichlorohydrin and oxetane in the presence of an initiator to generate the aryl polymer containing aliphatic ether chains; The initiator is at least one selected from alkali metal alkoxide, hydroxide, metalloporphyrin compound, double metal cyanide complex, strong protonic acid and Lewis acid.
  5. 5. An aryl polymer containing sulfonic acid groups, characterized by comprising structural units of the general formula: , wherein, C is sulfonic acid group, and G 0 is selected from at least one of the groups shown in the following structural formula: , And C is attached to R 1 、R 2 or R 3 of G 0 , or C is attached to a ring of G 0 .
  6. 6. A method for preparing an aryl polymer containing sulfonic acid groups, which is characterized by comprising the following steps: When the high-flexibility aryl polymer of claim 1 contains active hydrogen, the high-flexibility aryl polymer of claim 1 is polymerized with cyclic sulfonate or halogenated alkyl sulfonic acid containing 3-10 carbon atoms in the presence of alkali to generate the aryl polymer containing sulfonic acid groups; the alkali is at least one selected from alkali metal alkoxide and hydroxide.
  7. 7. The preparation method of the aryl polymer film is characterized by comprising the following steps: Dissolving at least one of the high-flexibility aryl polymer of claim 1, the aryl polymer containing fatty ether chains of claim 3 and the aryl polymer containing sulfonic acid groups of claim 5 in an organic solvent to obtain a polymer solution, casting or die casting the polymer solution into a film, and drying to obtain the aryl compound film; the organic solvent is one or the combination of a plurality of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, methylene dichloride, toluene, ethylbenzene, dimethylbenzene and ethyl acetate.
  8. 8. A method for preparing an aryl polymer solid electrolyte, which is characterized by comprising the following steps: Uniformly mixing at least one of the high-flexibility aryl polymer gold of claim 1 and the aryl polymer containing fatty ether chains of claim 3 with any one or more of polyether, polyester, polynitrile, fluorine-containing polymer, single-ion conductor polymer, lithium salt, sodium salt, potassium salt, acid and nano filler, and pressing the obtained mixture into a film to obtain the aryl polymer solid electrolyte membrane; or uniformly mixing at least one of the high-flexibility aryl polymer gold of claim 1 and the aryl polymer containing the aliphatic ether chain of claim 3 with any one or more of polyether, polyester, polynitrile, fluorine-containing polymer, single-ion conductor polymer, lithium salt, sodium salt, potassium salt, acid, nano filler and solvent, and coating the obtained mixed solution on a substrate to prepare the film, thereby obtaining the aryl polymer solid electrolyte film.
  9. 9. The method for producing an aryl polymer solid electrolyte according to claim 8, characterized in that: the polyether is at least one selected from polyethylene oxide and polypropylene oxide; The polyester is at least one selected from polypropylene carbonate and poly-epsilon-caprolactone; The polynitrile is at least one selected from polyacrylonitrile and polybutylece nitrile; The fluorine-containing polymer is at least one selected from polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene copolymer; the single ion conductor polymer is selected from polymers containing crown ether, hole ether and nitrogen heterocycle, metal organic framework compounds and covalent organic framework materials; The lithium salt is at least one selected from lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium tetrafluoroborate, lithium dioxalate borate and lithium oxalato difluoroborate; The sodium salt is at least one selected from sodium hexafluorophosphate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium bisfluorosulfonyl imide, sodium bistrifluoromethanesulfonyl imide, sodium tetrafluoroborate, sodium dioxalate borate and sodium oxalyldifluoroborate; the potassium salt is at least one selected from potassium hexafluorophosphate, potassium perchlorate, potassium trifluoromethane sulfonate, potassium difluorosulfimide, potassium bistrifluoromethylsulfonimide, potassium tetrafluoroborate, potassium dioxalate borate and potassium oxalate difluoroborate; the acid is at least one selected from phosphoric acid, sulfuric acid, trifluoromethane sulfonic acid and solid acid; The nano filler is at least one selected from aluminum oxide, silicon oxide, titanium oxide, oxide solid electrolyte, sulfide solid electrolyte and chloride solid electrolyte; The solvent is at least one selected from dimethyl sulfoxide, dimethyl carbonate, acetonitrile, N-methylpyrrolidone and N, N-dimethylformamide; the substrate is at least one selected from polypropylene porous membrane, polyethylene porous membrane, polyimide porous membrane and ceramic porous membrane.
  10. 10. Use of the highly flexible aryl polymer of claim 1, the fatty ether chain-containing aryl polymer of claim 3 or the sulfonic acid group-containing aryl polymer of claim 5 for the preparation of a solid electrolyte, electrode material binder for a battery.

Description

High-flexibility aryl polymer and preparation method and application thereof Technical Field The invention relates to the technical field of solid electrolytes, in particular to a high-flexibility aryl polymer and a preparation method and application thereof. Background With the rapid development of portable electronic devices and new energy automobiles, there is an increasing demand for batteries with high energy density, high safety and long cycle life. The traditional lithium ion battery generally adopts liquid organic electrolyte, has potential safety hazards of easy leakage, inflammability, explosiveness and the like, and severely restricts the safety performance of the battery. The solid electrolyte is expected to fundamentally solve the safety problem because of the advantages of non-volatilization, non-leakage, good thermal stability and the like, and becomes an important development direction of the next-generation battery technology. The polymer solid electrolyte has light weight, good flexibility and easy processing and forming, can realize tight interface contact with electrode materials, and has wide application prospect in flexible electronic devices and high-energy-density batteries. Among them, polyethylene oxide (PEO) -based polymer electrolytes are one of the most widely studied systems at present. However, PEO-based electrolytes have high crystallinity at room temperature, resulting in difficult ion migration, and generally low room temperature ionic conductivity (typically below 10 -4 S/cm), which is far from meeting practical application requirements. Furthermore, PEO is not resistant to high voltages and at greater than 4 Vvs. Li/Li + may decompose. To improve PEO properties, researchers modify by blending, block copolymerization, crosslinking, addition of plasticizers or inorganic fillers, etc., but these methods often compromise mechanical strength or thermal stability at the expense of high ionic conductivity, high mechanical strength, and excellent flexibility. Therefore, the development of a novel polymer matrix material fundamentally solves the problems of low ionic conductivity, intolerance to high voltage, poor flexibility and the like of the conventional polymer electrolyte at room temperature, and becomes a key technical bottleneck to be broken through in the current solid-state battery field. Disclosure of Invention In order to solve the problems in the prior art, the invention provides a high-flexibility aryl polymer, a preparation method and application thereof, wherein the high-flexibility aryl polymer replaces the traditional polyethylene oxide, and the solid electrolyte prepared by using the high-flexibility aryl polymer has high room temperature ion conductivity, good flexibility and high voltage resistance. The technical scheme adopted for achieving the purposes of the invention is as follows: A highly flexible aryl polymer characterized by comprising structural units of the formula: , wherein A is selected from at least one of the groups shown in the following structural formula: , wherein Ar 1、Ar2 is independently selected from aromatic groups having 3 to 20 carbon atoms; G 0 is selected from at least one of the groups shown in the following structural formula: , Wherein R 1、R2、R3 is independently selected from hydrogen, alkyl having 1-20 carbon atoms, or aryl having 6-20 carbon atoms, or is independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, carbonyl, halogen substituted alkyl having 1-20 carbon atoms, or is independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, carbonyl, halogen substituted aryl having 6-20 carbon atoms; the ring substituent is at least one of aliphatic carbocycle substituent, polycyclic aromatic ring substituent and heterocyclic substituent with 3-20 carbon atoms, m is a natural number not more than 10; Further, A is selected from at least one of the groups represented by the following structural formulas: e is selected from J, or a combination of J and K, wherein J is selected from at least one of a dihaloaromatic ring containing at least one strong electron withdrawing group, a dihaloaromatic ring containing at least one N atom, and an aryl group containing two halomethyl groups, K is selected from at least one of an aryl group containing two acyl halides and a dihaloalkyl group having 1 to 20 carbon atoms; Further, A is selected from at least one of the groups represented by the following structural formulas: Each G 1、G2 is independently selected from any one of O, S, NR 4, wherein R 4 is selected from hydrogen, alkyl with 1-20 carbon atoms or aryl with 6-20 carbon atoms, or is independently selected from carboxyl, hydroxyl, amino, sulfhydryl, nitro, halogen substituted alkyl with 1-20 carbon atoms, or is independently selected from carboxyl, hydroxyl, amino, sulfhydryl, nitro, halogen substituted aryl with 6-20 carbon atoms. Further, G1 and G2 are each independently selected from O, S, NMe, NH, NPh. A meth