High-flexibility aryl polymer as well as preparation method and application thereof

Abstract

The invention discloses a high-flexibility aryl polymer and a preparation method and application thereof.The high-flexibility aryl polymer replaces traditional polyoxyethylene, and a solid electrolyte prepared from the high-flexibility aryl polymer is high in room-temperature ionic conductivity, good in flexibility and resistant to high voltage. A novel polymer matrix material is developed, the problems that an existing polymer electrolyte is low in room-temperature ionic conductivity, not resistant to high voltage, poor in flexibility and the like are fundamentally solved, and the key technical bottleneck in the current solid-state battery field is broken through.

Description

Technical Field

[0001] This invention relates to the field of solid electrolyte technology, specifically to a highly flexible aryl polymer, its preparation method, and its applications. Background Technology

[0002] With the booming development of portable electronic devices and new energy vehicles, the demand for batteries with high energy density, high safety, and long cycle life is becoming increasingly urgent. Traditional lithium-ion batteries generally use liquid organic electrolytes, which pose safety hazards such as easy leakage, flammability, and explosion, seriously restricting the safety performance of batteries. Solid electrolytes, due to their advantages such as non-volatility, non-leakage, and good thermal stability, are expected to fundamentally solve the above safety problems and become an important development direction for next-generation battery technology.

[0003] Polymer solid electrolytes, due to their light weight, high flexibility, ease of processing and molding, and ability to achieve close interfacial contact with electrode materials, have broad application prospects 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.

[0004] However, PEO-based electrolytes have high crystallinity at room temperature, which makes ion migration difficult and results in generally low room temperature ionic conductivity (typically below 10). -4 The voltage ratio (S / cm) is far from meeting the needs of practical applications. Furthermore, PEO is not resistant to high voltages, exceeding 4V compared to Li / Li. + It will decompose. To improve the performance of PEO, researchers have modified it by blending, block copolymerization, crosslinking, adding plasticizers or inorganic fillers, etc. However, these methods often come at the cost of sacrificing mechanical strength or thermal stability, and it is difficult to simultaneously achieve high ionic conductivity, high mechanical strength and excellent flexibility.

[0005] Therefore, developing novel polymer matrix materials to fundamentally solve the problems of low room-temperature ionic conductivity, poor high-voltage tolerance, and poor flexibility of existing polymer electrolytes has become a key technological bottleneck that urgently needs to be overcome in the field of solid-state batteries. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a highly flexible aryl polymer, its preparation method, and its application. The highly flexible aryl polymer of this invention replaces traditional polyethylene oxide. The solid electrolyte prepared using the highly flexible aryl polymer of this invention has high room temperature ionic conductivity, good flexibility, and high voltage resistance.

[0007] The technical solution adopted to achieve the above-mentioned objectives of this invention is as follows: A highly flexible aryl polymer, characterized by comprising structural units of the following general formula: , Wherein, A is selected from at least one of the groups shown in the following structural formulas: , Ar1 and Ar2 are each independently selected from aromatic groups having 3-20 carbon atoms; G0 is selected from at least one of the groups shown in the following structural formulas: , R1, R2, and R3 are each independently selected from hydrogen, alkyl groups having 1-20 carbon atoms, or aryl groups having 6-20 carbon atoms, or are each independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, carbonyl, or halogen-substituted alkyl groups having 1-20 carbon atoms, or are each independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, carbonyl, or halogen-substituted aryl groups having 6-20 carbon atoms; The cyclic substituent is selected from at least one of aliphatic carbocyclic substituents, polycyclic aromatic ring substituents, and heterocyclic substituents having 3-20 carbon atoms; m is a natural number not greater than 10; Furthermore, A is selected from at least one of the groups shown in the following structural formulas: E is selected from J, or from a combination of J and K; wherein J is selected from at least one of a dihaloaromatic ring containing at least one electron-withdrawing group, a dihaloaromatic ring containing at least one N atom, and an aryl group containing two halomethyl groups, and K is selected from at least one of an aryl group containing two acyl halide groups and a dihaloalkyl group having 1-20 carbon atoms. Furthermore, A is selected from at least one of the groups shown in the following structural formulas: G1 and G2 are each independently selected from any one of O, S, and NR4, wherein R4 is selected from hydrogen, an alkyl group having 1-20 carbon atoms, or an aryl group having 6-20 carbon atoms, or independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, or halogen-substituted alkyl group having 1-20 carbon atoms, or independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, or halogen-substituted aryl group having 6-20 carbon atoms.

[0008] Furthermore, G1 and G2 are independently selected from O, S, NMe, NH, and NPh, respectively.

[0009] A method for preparing a highly flexible aryl polymer includes the following steps: Under alkaline conditions, monomers G and M undergo a polymerization reaction to generate the highly flexible aryl polymer described above. Alternatively, in the presence of an alkali, monomers G, M, and crosslinking agent monomers undergo a polymerization reaction to generate the highly flexible aryl polymer described above. The general structural formula of the monomer G is as follows: , Furthermore, the monomer G is selected from at least one of the compounds shown in the following structural formulas: The monomer M is selected from Q, or a combination of Q and P; wherein Q is selected from at least one of a dihaloaromatic hydrocarbon containing at least one strong electron-withdrawing group, a dihaloaromatic hydrocarbon containing at least one N atom, and an aromatic hydrocarbon containing two halomethyl groups, and P is selected from at least one of an aromatic hydrocarbon containing two acyl halide groups and a dihaloalkane having 1-20 carbon atoms. Furthermore, the monomer M is selected from at least one of the compounds shown in the following structural formulas: Among them, X1 and X2 are independently selected from nitro, cyano, carbonyl, ester, hydroxyl and halogen, respectively; The crosslinking agent monomer is selected from aromatic compounds containing three or more hydroxyl groups, mercapto groups, amino groups or halogens, or from alkanes containing three or more halogens, or nitrogen-containing heterocyclic compounds containing multiple active groups (such as amino groups or halogens). The molar ratio of monomer G, monomer M, and crosslinking agent monomer is 1:0.7-1.3:0-0.3.

[0010] The base is selected from at least one of alkali metal hydroxides or alkali metal carbonates; Furthermore, the alkali is selected from at least one of potassium carbonate, sodium carbonate, lithium carbonate, potassium hydroxide, sodium hydroxide, and lithium hydroxide.

[0011] An aryl polymer containing aliphatic ether chains, comprising structural units of the following general formula: , Wherein, B is an aliphatic ether chain with a degree of polymerization not greater than 10000, and G0 is selected from at least one of the groups shown in the following structural formulas: , And B is connected to R1, R2 or R3 of G0, or B is connected to the ring of G0; B is selected from at least one of the groups shown in the following structural formulas: Where n is the degree of aggregation, 1≤n≤8000.

[0012] A method for preparing an aryl polymer containing aliphatic ether chains includes the following steps: When the highly flexible aryl polymer contains active hydrogen, in the presence of an initiator, the highly flexible aryl polymer is polymerized with at least one of ethylene oxide, propylene oxide, tetrahydrofuran, chloro ether, epichlorohydrin and oxetane to generate the aryl polymer containing aliphatic ether chains. The initiator is selected from at least one of the following: alkali metal alkoxides (such as sodium methoxide, potassium tert-butoxide), hydroxides (KOH, NaOH), metal porphyrin compounds (such as tetraphenylporphyrin iron, tetramethylporphyrin zinc), bimetallic cyanide complexes (such as zinc hexacyanocobalt(III) acid, cobalt hexacyanoferrate(III) acid), strong protic acids (such as perchloric acid, trifluoromethanesulfonic acid), and Lewis acids (such as antimony pentachloride, boron trifluoride ethers).

[0013] An aryl polymer containing sulfonic acid groups, comprising structural units of the following general formula: , Wherein, C is a sulfonic acid group, and G0 is selected from at least one of the groups shown in the following structural formulas: , Furthermore, C is connected to R1, R2, or R3 of G0, or C is connected to the ring of G0.

[0014] A method for preparing an aryl polymer containing sulfonic acid groups includes the following steps: When the highly flexible aryl polymer contains active hydrogen, in the presence of an alkali, the highly flexible aryl polymer is polymerized with a cyclosulfonate or haloalkylsulfonic acid containing 3-10 carbon atoms to generate the aryl polymer containing sulfonic acid groups. The alkali is selected from at least one of alkali metal alkoxides (such as sodium methoxide, potassium tert-butoxide) and hydroxides (KOH, NaOH).

[0015] A method for preparing aryl polymer thin films, comprising the following steps: At least one of the highly flexible aryl polymer, the aryl polymer containing aliphatic ether chains, and the aryl polymer containing sulfonic acid groups is dissolved in an organic solvent to obtain a polymer solution. The polymer solution is then cast or die-cast into a film and dried to obtain the aryl compound film. The organic solvent is one or a combination of several of the following: dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

[0016] A method for preparing an aryl polymer solid electrolyte includes the following steps: At least one of the highly flexible aryl polymer and the aryl polymer containing aliphatic ether chains is mixed uniformly with any one or more of polyether, polyester, polyacrylonitrile, fluoropolymer, single-ion conductor polymer, lithium salt, sodium salt, potassium salt, acid and nanofiller, and the resulting mixture is pressed into a membrane to obtain the aryl polymer solid electrolyte membrane. Alternatively, at least one of the highly flexible aryl polymer gold of claim 1 and the aryl polymer containing aliphatic ether chains of claim 3 can be mixed uniformly with any one or more of polyether, polyester, polyacrylonitrile, fluoropolymer, single-ion conductor polymer, lithium salt, sodium salt, potassium salt, acid, nanofiller and solvent, and the resulting mixed solution can be coated on a substrate to prepare a film, thereby obtaining the aryl polymer solid electrolyte membrane.

[0017] Furthermore, the polyether is selected from at least one of polyethylene oxide and polypropylene oxide; The polyester is selected from at least one of polypropylene carbonate and poly-ε-caprolactone; The polyacrylonitrile is selected from at least one of polyacrylonitrile and polybutadiene nitrile; The fluoropolymer is selected from at least one of polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene copolymer; The single-ion conductor polymer is selected from carboxylic acid type (-COO) - -), sulfonic acid type (-SO3) - -), sulfonylimide type (-SO2 N( - SO2-) and borate type (-BO4) - -), such as a hyperbranched single-ion conductive solid polymer electrolyte (HPCPEG) rich in continuous ether oxygen bonds at carboxyl centers, lithium sulfonated polyoxadiazole (Li-SPOD) electrolyte, PBI-g-LiPSTFSI, P(PEGDA-co-LiBMAB)@PVDF-HFP; The lithium salt is selected from at least one of lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bisfluorosulfonylimide, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate, lithium dioxalateborate, and lithium difluoroborate oxalate. The sodium salt is selected from at least one of sodium hexafluorophosphate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium difluorosulfonamide, sodium ditrifluoromethanesulfonamide, sodium tetrafluoroborate, sodium dioxalate borate, and sodium difluoroborate oxalate. The potassium salt is selected from at least one of potassium hexafluorophosphate, potassium perchlorate, potassium trifluoromethanesulfonate, potassium difluorosulfonamide, potassium ditrifluoromethanesulfonamide, potassium tetrafluoroborate, potassium dioxalate borate, and potassium difluoroborate oxalate. The acid is selected from at least one of phosphoric acid, sulfuric acid, trifluoromethanesulfonic acid, and solid acids; The nanofillers are selected from alumina, silicon dioxide, titanium dioxide, and oxide solid electrolytes (such as LLZO, LLTO, Li3OX, Na3Zr2Si2PO). 12 At least one of the following: sulfide solid electrolytes (LGPS, Li6PS5X, Li2S-P2S5), and chloride solid electrolytes; The solvent is selected from at least one of dimethyl sulfoxide, dimethyl carbonate, acetonitrile, N-methylpyrrolidone, and N,N-dimethylformamide; The substrate is selected from at least one of polypropylene porous membrane, polyethylene porous membrane, polyimide porous membrane and ceramic porous membrane.

[0018] The application of the aforementioned highly flexible aryl polymer, the aforementioned aryl polymer containing aliphatic ether chains, or the aryl polymer containing sulfonic acid groups in the preparation of battery solid electrolytes and electrode material binders.

[0019] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows: Testing revealed that the highly flexible aryl polymer of this invention exhibits excellent flexibility, with an elongation at break as high as 900%, and also demonstrates good flexibility at -2 to 7V vs. Li / Li. + No redox reaction occurs within the electrochemical window, indicating that it has good high-voltage resistance. Therefore, preparing a solid electrolyte from the highly flexible aryl polymer of this invention can significantly improve the flexibility and high-voltage resistance of the solid electrolyte. Tests have shown that the ionic conductivity of the prepared solid electrolyte is greater than 0.58 S / cm, which is much higher than the ionic conductivity of PEO-based solid electrolytes at room temperature. Attached Figure Description

[0020] Figure 1 The polyarylene ether P1 prepared in Example 1 1 H-NMR spectrum.

[0021] Figure 2 This is a physical image of the polymer film M1a prepared in Example 1.

[0022] Figure 3 This is a physical image of the polymer film M6a prepared in Example 6.

[0023] Figure 4 The polyarylene ether P7 prepared in Example 7 1 H-NMR spectrum.

[0024] Figure 5 This is a physical image of the polymer film M8a prepared in Example 8.

[0025] Figure 6 The polyarylene ether P9 prepared in Example 9 1H-NMR spectrum. Detailed Implementation

[0026] The present invention will now be described in detail with reference to specific embodiments, but these embodiments are not to be construed as limiting the scope of protection of the present invention in any sense.

[0027] Example 1 1. Dissolve 192.00 g (1 mol) of 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 228.29 g (1 mol) of bisphenol A (CAS No.: 80-05-7) and 117.82 g (2.1 mol) of potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 38 h. After the reaction is complete, a viscous solution is obtained.

[0028] 2. When the viscous solution was added dropwise to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 307.42 g of polyarylether P1 (yield 88.5%).

[0029] Polyarylether P1 1 H-NMR spectrum as shown Figure 1 As shown, the specific chemical shift data are as follows: 1 HNMR (400 MHz, DMSO-d6, ppm) δH =1.51-1.64, 6.62-6.68, 6.95-7.02, 7.08-7.13, 7.22-7.29, 7.66-7.70, 8.12-8.14.

[0030] 3. Take 200g of polyarylether P1 and 1L of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution onto a glass substrate and bake at 100℃ for 10 hours to obtain a polymer film M1a, as shown below. Figure 2 As shown. The elongation at break of M1a is 1500%. At -2 to 7V vs. Li / Li + No redox reaction occurs inside the electrochemical window, indicating that M1a can withstand high voltage.

[0031] 4. Mix 1g of polyarylether P1 and 0.3g of lithium hexafluorophosphate evenly and press into a dense, smooth sheet M1b. Place M1b into a test mold and clamp it tightly on both sides with stainless steel electrode blocks to ensure good contact. The test shows that the ionic conductivity of M1b at room temperature is 1.1mS / cm.

[0032] Example 2 1. Dissolve 192.00 g (1 mol) of 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 268.36 g (1 mol) of bisphenol Z (CAS No.: 843-55-0) and 117.82 g (2.1 mol) of potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 40 h. After the reaction is complete, a viscous solution is obtained.

[0033] 2. When the viscous solution was dropped into water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 332.03 g of polyarylether P2 (yield 85.7%).

[0034] 1 HNMR (400 MHz, DMSO-d6, ppm) δH =1.42-1.55, 2.02-2.06, 6.64-6.67, 7.08-7.13, 7.66-7.70, 8.12-8.14.

[0035] 3. A polymer solution was obtained by mixing 200g of polyarylether P2 and 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100℃ for 10 hours to obtain polymer film M2a. The elongation at break of M2a was 900%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-7V vs Li / Li...) + No redox reaction occurs inside the electrochemical window, indicating that M2a can withstand high voltage.

[0036] 4. Mix 1g of polyarylene ether P2 and 0.3g of lithium bis(fluorosulfonyl)imide evenly and press them into a membrane M2a. Tests show that the ionic conductivity of M2a is 1.2mS / cm at room temperature.

[0037] Example 3 1. Dissolve 192.00 g (1 mol) of 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 250.28 g (1 mol) of bisphenol S (CAS No.: 80-09-1) and 117.82 g (2.1 mol) of potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 43 h. After the reaction is complete, a viscous solution is obtained.

[0038] 2. When the viscous solution was dropped into water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 333.90 g of polyarylether P3 (yield 90.4%).

[0039] 1HNMR (400 MHz, DMSO-d6, ppm) δH =6.75-7.01, 7.07-7.09,7.62-7.83,8.08-8.10.

[0040] 3. A polymer solution was obtained by mixing 200g of polyarylether P3 and 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100℃ for 10 hours to obtain polymer film M3a. The elongation at break of M3a was 1100%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-7V vs Li / Li.) + No redox reaction occurs inside the electrochemical window, indicating that M3a can withstand high voltage.

[0041] 4. Mix 1g of polyarylene ether P3 and 0.3g of lithium bis(fluorosulfonyl)imide evenly and press them into a membrane M3b. Tests show that the ionic conductivity of M3b is 0.85mS / cm at room temperature.

[0042] Example 4 1. Dissolve 192.00 g (1 mol) of 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 218.28 g (1 mol) of 4,4'-dihydroxydiphenyl sulfide (CAS No.: 2664-63-3) and 117.82 g (2.1 mol) of potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 48 h. After the reaction is complete, a viscous solution is obtained.

[0043] 2. When the viscous solution was dropped into water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 300.92 g of polyarylether P4 (yield 89.2%).

[0044] 1 HNMR (400 MHz, DMSO-d6, ppm) δH =6.62-6.83,7.06-7.08, 7.12-7.25,7.62-7.66, 8.08-8.10.

[0045] 3. A polymer solution was obtained by mixing 200g of polyarylether P4 and 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100℃ for 10 hours to obtain polymer film M4a. The elongation at break of M4a was 1200%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-6V vs Li / Li.) + No redox reaction occurs inside the electrochemical window, indicating that M4a can withstand high voltage.

[0046] 4. Add 1g of polyarylether P4, 0.1g of PEO, and 0.2g of LLZO (Li7La3Zr2O) 12 0.1 g of lithium bis(fluorosulfonyl)imide was mixed evenly and pressed into a membrane M4b. Tests showed that the ionic conductivity of M4b at room temperature was 1.5 mS / cm.

[0047] Example 5 1. Place the three-necked flask on an ice-salt bath at 0°C. Add 432.00 g (1.5 mol) of 1-naphthol (CAS No.: 90-15-3) to the flask, then slowly add 300 mL of concentrated sulfuric acid dropwise over approximately half an hour, maintaining the internal temperature ≤ 5°C during the addition. After the addition is complete, the flask contains a pale red, clear liquid. Then, quickly add 109.5 mL of acetone to the flask in one go, immediately resulting in a deep red turbidity. Continue stirring the reaction at 0°C for 30 min; at this point, the color no longer deepens significantly. Remove the ice-salt bath and continue stirring the reaction at room temperature for 60 min. After the reaction is complete as monitored by TLC, slowly pour the resulting mixture into crushed ice while stirring; a large amount of orange-yellow solid precipitates. After complete precipitation, filter the mixture and wash the filter cake twice with ice water. The washed filter cake was recrystallized with 95 v / v% ethanol, the crystals were collected by filtration, and dried under vacuum at 60 °C for 20 min to obtain 339.53 g of orange-yellow needle-like powder (yield 68.9%).

[0048] 2. Dissolve 192.00 g (1 mol) of 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 328.43 g (1 mol) of orange-yellow needle-like powder and 117.82 g (2.1 mol) of potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 48 h. After the reaction is complete, a viscous solution is obtained.

[0049] 3. When the viscous solution was added dropwise to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 387.54 g of polyarylether P5 (yield 86.6%).

[0050] 1 HNMR (400 MHz, DMSO-d6, ppm) δH =6.87-6.95,7.07-7.09, 7.28-7.34,7.41-7.59, 7.62-7.63,7.64-7.71, 8.08-8.10.

[0051] 4. Take 200g of polyarylene ether P5 and 1L of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution onto a PET substrate using a casting method and bake at 100℃ for 10 hours to obtain polymer film M5a. The elongation at break of M5a is 1300%. (In -2-7V vs Li / Li) + No redox reaction occurs inside the electrochemical window, indicating that M5a can withstand high voltage.

[0052] 5. Add 1g of polyarylether P5, 0.2g of polyacrylonitrile, and 0.1g of LGPS (Li 10 GeP2S 12 The mixture was homogenized with 0.1 g of lithium hexafluorophosphate and 0.1 g of lithium difluorosulfonylimide, and then pressed into a membrane M5b. Tests showed that the ionic conductivity of M5b at room temperature was 2.8 mS / cm.

[0053] Example 6 1. Dissolve 192.00 g (1 mol) 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 114.15 g (0.5 mol) bisphenol A (CAS No.: 80-05-7), 134.18 g (0.5 mol) bisphenol Z (CAS No.: 843-55-0) and 117.82 g (2.1 mol) potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 50 h. After the reaction is complete, a viscous solution is obtained.

[0054] 2. When the viscous solution was added dropwise to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 318.91g of polyarylether P6 (yield 86.8%).

[0055] 1 HNMR (400 MHz, DMSO-d6, ppm) δH =1.42-1.64,2.02-2.06, 6.61-6.67,6.95-7.02,7.08-7.19,7.22-7.24,7.66-7.71,8.12-8.15.

[0056] 3. Take 200g of polyarylether P6 and 1L of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution onto a glass substrate and bake at 100℃ for 10 hours to obtain a polymer film M6a. Figure 3 As shown, the elongation at break of M6a is 1300%. (At -2-7V vs Li / Li) + No redox reaction occurs inside the electrochemical window, indicating that M6a can withstand high voltage.

[0057] 4. Mix 1g of polyarylene ether P6, 0.3g of lithium bis(fluorosulfonyl)imide, and 2mL of DMSO until homogeneous. Then, coat the resulting mixture onto a porous polypropylene membrane and dry it to obtain film M6b. Tests show that the ionic conductivity of M6b at room temperature is 0.58mS / cm.

[0058] Example 7 1. Dissolve 192.00 g (1 mol) 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 114.15 g (0.5 mol) bisphenol A (CAS No.: 80-05-7), 175.21 g (0.5 mol) 9,9-bis(4-hydroxyphenyl)fluorene (CAS No.: 3236-71-3) and 117.82 g (2.1 mol) potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at a constant temperature of 90 °C for 72 h. After the reaction is complete, a viscous solution is obtained.

[0059] 2. When the viscous solution was added dropwise to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 341.86.91 g of polyarylether P7 (yield 83.7%).

[0060] Polyarylether P7 1 H-NMR spectrum as shown Figure 4 As shown, the specific chemical shift data are as follows: 1 HNMR (400 MHz, DMSO-d6, ppm) δH =1.51-1.64, 6.61-6.68, 6.88-6.93, 6.95-7.02, 7.08-7.19, 7.22-7.47, 7.66-7.71, 7.83-7.93, 8.12-8.15.

[0061] 3. A polymer solution was obtained by mixing 200g of polyarylether P7 and 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100℃ for 10 hours to obtain polymer film M7a. The elongation at break of M7a was 1050%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-7V vs Li / Li.) + No redox reaction occurs inside the electrochemical window, indicating that M7a can withstand high voltage.

[0062] 4. Mix 1g of polyarylene ether P7, 0.1g of PEO, and 0.3g of sodium bis(fluorosulfonyl)imide evenly and press them into a membrane M7b. Tests show that the ionic conductivity of M7b is 0.89 mS / cm at room temperature.

[0063] Example 8 1. Dissolve 96.00 g (0.5 mol) 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 228.30 g (1 mol) bisphenol A (CAS No.: 80-05-7), 87.53 g (0.5 mol) 1,4-p-dichlorobenzyl (CAS No.: 623-25-6) and 117.82 g (2.1 mol) potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 24 h. After the reaction is complete, a viscous solution is obtained.

[0064] 2. When the viscous solution was added to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 290.61 g of polyarylether P8 (yield 90.6%).

[0065] 1 HNMR (400MHz, DMSO-d6, ppm) δH=1.51-1.64,4.59-4.61,6.62-6.67,6.95-7.02,7.08-7.13,7.20-7.29,7.66-7.71,8.12-8.15.

[0066] 3. Take 200g of polyarylether P8 and 1L of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution onto a glass substrate and bake at 100℃ for 10 hours to obtain a polymer film M8a. Figure 5 As shown, the elongation at break of M8a is 900%. (At -2-7V vs Li / Li) + No redox reaction occurs inside the electrochemical window, indicating that M8a can withstand high voltage.

[0067] 4. Mix 1g of polyarylene ether P8 and 0.3g of lithium bis(trifluoromethanesulfonyl)imide evenly and press them into a membrane M8b. Tests show that the ionic conductivity of M8b is 0.95mS / cm at room temperature.

[0068] Example 9 1. Dissolve 96.00 g (0.5 mol) 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 228.29 g (1 mol) bisphenol A (CAS No.: 80-05-7), 74.00 g (0.5 mol) 2,6-dichloropyridine (CAS No.: 2402-78-0) and 117.82 g (2.1 mol) potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 31 h. After the reaction is complete, a viscous solution is obtained.

[0069] 2. When the viscous solution was added dropwise to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 278.65 g of polyarylether P9 (yield 90.7%).

[0070] polyarylether P9 1 H-NMR spectrum as shown Figure 6 As shown, the specific chemical shift data are as follows: 1 HNMR (400 MHz, DMSO-d6, ppm) δH =1.47-1.64, 6.58-6.65, 6.86-7.04,7.06-7.10, 7.13-7.15, 7.18-7.27, 7.62-7.66, 7.77-7.82, 8.08-8.10.

[0071] 3. A polymer solution was obtained by mixing 200g of polyarylether P9 and 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100℃ for 10 hours to obtain polymer film M9a. The elongation at break of M9a was 1200%. (The last sentence appears to be incomplete and possibly refers to a different process: -1-7V vs Li / Li.) + No redox reaction occurs inside the electrochemical window, indicating that M9a can withstand high voltage.

[0072] 4. Mix 1g of polyarylether P9, 0.1g of PEO, 0.2g of lithium hexafluorophosphate, 0.1g of lithium difluorosulfonylimide, 0.1g of Li3YCl6, and 5mL of dimethyl carbonate until homogeneous. Coat the resulting mixture onto a PET substrate using a casting method to obtain a polymer film M9b. Tests show that the ionic conductivity of M9b is 1.2 mS / cm at room temperature.

[0073] Example 10 1. Dissolve 192.00 g (1 mol) 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 228.29 g (1 mol) bisphenol A (CAS No.: 80-05-7), 0.05 g (0.16 mmol) 1,1,1-tris(4-hydroxyphenyl)ethane (CAS No.: 27955-94-8) and 117.82 g (2.1 mol) potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 50 h. After the reaction is complete, a viscous solution is obtained.

[0074] 2. When the viscous solution was dropped into water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 314.07 g of polyarylether P10 (yield 90.4%).

[0075] 1 HNMR (400 MHz, DMSO-d6, ppm) δH =1.49-1.62, 2.27-2.29, 6.62-6.87, 6.95-7.02, 7.08-7.137.22-7.29, 7.66-7.70, 8.12-8.14.

[0076] 3. A polymer solution was obtained by mixing 200g of polyarylether P10 and 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100℃ for 10 hours to obtain polymer film M10a. The elongation at break of M10a was 1100%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-7V vs Li / Li...) + No redox reaction occurs inside the electrochemical window, indicating that M10a can withstand high voltage.

[0077] 4. Mix 1g of polyarylene ether P10 and 0.3g of lithium bis(fluorosulfonyl)imide evenly and press them into a membrane M10b. Tests show that the ionic conductivity of M10b is 0.96mS / cm at room temperature.

[0078] Example 11 1. Dissolve 192.00 g (1 mol) of 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 228.29 g (1 mol) of bisphenol A (CAS No.: 80-05-7), 0.05 g (0.15 mmol) of tribromo-neopentol (CAS No.: 1522-92-5) and 117.82 g (2.1 mol) of potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 40 h. After the reaction is complete, a viscous solution is obtained.

[0079] 2. When the viscous solution was added to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 322.21 g of polyarylene ether P11 (yield 91.8%).

[0080] 1 HNMR (400MHz, DMSO-d6, ppm) δH=1.49-1.62, 3.91-4.01, 4.18-4.206.62-6.68, 6.95-7.02, 7.08-7.13, 7.22-7.29, 7.66-7.70, 8.12-8.14.

[0081] 3. Take 200g of polyarylene ether P11 and 1L of dimethyl sulfoxide to obtain a polymer solution. Coat the polymer solution onto a PET substrate using a casting method and bake at 100℃ for 10 hours to obtain polymer film M11a. The elongation at break of M11a is 1000%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-7V vs Li / Li.) + No redox reaction occurs inside the electrochemical window, indicating that M11a can withstand high voltage.

[0082] 4. Mix 1g of polyarylene ether P11, 0.2g of PEO, and 0.3g of potassium bis(fluorosulfonyl)imide evenly, and press them into a membrane M11b. Tests show that the ionic conductivity of M11b at room temperature is 0.82mS / cm.

[0083] Example 12 1. Dissolve 192.00 g (1 mol) of 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 286.33 g (1 mol) of bisphenolic acid (CAS No.: 126-00-1) and 117.82 g (2.1 mol) of potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 38 h. After the reaction is complete, a viscous solution is obtained.

[0084] 2. When the viscous solution was added dropwise to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 354.33 g of polyarylene ether P12a (yield 87.4%).

[0085] 1 HNMR (400MHz, DMSO-d6, ppm) δH=1.51-1.64,1.67-1.69,2.32-2.35,6.64-6.78,6.97-7.04,7.10-7.15,7.24-7.31,7.68-7.72,8.14-8.16 ,10.89-10.91.

[0086] 3. A polymer solution was obtained by dissolving 200g of polyarylether P12a in 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100°C for 10 hours to obtain a polymer film M12a. The elongation at break of M12a was 1600%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-7V vs Li / Li.) + No redox reaction occurs inside the electrochemical window, indicating that M12a can withstand high voltage.

[0087] 4. Mix 1g of polyarylether P11, 0.1g of polyvinylidene fluoride, and 0.3g of lithium hexafluorophosphate evenly, and press them into a membrane M11b. Tests show that the ionic conductivity of M11b is 2.1mS / cm at room temperature.

[0088] 5. Mix 202.71 g (0.5 mol) of polyarylether P12a, 220.26 g (5 mol) of ethylene oxide, 0.01 mol of SnCl4, and 10 mL of dimethyl carbonate until homogeneous, then stir at 90 °C for 10 hours. After the reaction is complete, wash the resulting mixture with 100 mL of water, filter, and dry the precipitate to obtain 343.87 g of P12b (yield 81.3%). 1 HNMR(600MHz,DMSO-d6,ppm)δH=1.51-1.64,1.67-1.69,2.40-2.42,3.53-3.55,4.21-4 .23,4.88-4.90,6.64-6.78,6.97-7.04,7.10-7.15,7.24-7.31,7.68-7.72,8.14-8.16.

[0089] 6. Mix 50g of polyarylene ether P12b and 10g of lithium bis(fluorosulfonyl)imide evenly, and press them into a membrane M12b. Tests show that the ionic conductivity of M12b at room temperature is 3.2 mS / cm.

[0090] Example 13 1. 192.00 g (1 mol) of 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 258.13 g (1 mol) of 4-hydroxy-γ-(4-hydroxyphenyl)-γ-methylphenylpropanol (CAS No.: 152664-19-2), and 117.82 g (2.1 mol) of potassium hydroxide were dissolved in 52 mL of dimethyl sulfoxide. The mixture was then stirred at room temperature for 38 h. After the reaction was complete, a viscous solution was obtained. 2. The viscous solution was added dropwise to water, and a precipitate began to form. After complete precipitation, the precipitate was washed twice with water and then dried to obtain 337.91 g of polyarylene ether P13a (yield 89.6%).

[0091] 1 HNMR(400MHz,DMSO-d6,ppm)δH=1.51-1.64,1.58-1.60,3.58-3.60,4.68-4 .71,6.62-6.68,6.95-7.02,7.06-7.11,7.22-7.29,7.64-7.68,8.12-8.14.

[0092] 3. A polymer solution was obtained by dissolving 200g of polyarylether P13a in 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100°C for 10 hours to obtain polymer film M12a. The elongation at break of M12a was 1700%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-7V vs Li / Li.) + No redox reaction occurs inside the electrochemical window, indicating that M13a can withstand high voltage.

[0093] 4. Mix 1g of polyarylether P13a, 0.1g of titanium dioxide, and 0.3g of lithium hexafluorophosphate evenly, and press them into a membrane M13b. At room temperature, the ionic conductivity of M13b is 2.1mS / cm.

[0094] 5. Mix 196.08 g (0.5 mol) of polyarylether P13a, 290.40 g (5 mol) of propylene oxide, 0.01 mol of AlCl3, and 10 mL of dimethyl carbonate until homogeneous, then stir at 80 °C for 10 hours. After the reaction is complete, wash the resulting mixture with 100 mL of water, filter, and dry the precipitate to obtain 389.67 g of P13b (yield 80.1%). 1 HNMR(600MHz,DMSO-d6,ppm)δH=1.11-1.13,1.51-1.64(,1.58-1.60,3.35-3.38,3.61-3.62,3 .58-3.60,4.68-4.71,6.62-6.68,6.95-7.02,7.06-7.11,7.22-7.29,7.64-7.68,8.12-8.14.

[0095] 6. Mix 50g of polyarylene ether P13b and 10g of lithium bis(trifluoromethanesulfonyl)imide evenly, and press them into a membrane M13c. At room temperature, the ionic conductivity of M13c is 2.8 mS / cm.

[0096] Example 14 1. Dissolve 192.00 g (1 mol) of 2,5-dichloronitrobenzene (CAS No.: 89-61-2), 269.34 g (1 mol) of 4-[4-(4-hydroxyphenyl)piperidin-4-yl]phenol (CAS No.: 3046298-19-2) and 117.82 g (2.1 mol) of potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 38 h. After the reaction is complete, a viscous solution is obtained.

[0097] 2. When the viscous solution was added to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 334.82 g of polyarylether P14 (yield 86.2%).

[0098] 1 HNMR (400MHz, DMSO-d6, ppm) δH=1.92-2.01, 2.04-2.10, 2.70-2.75, 6.62-6.68, 6.95-7.02, 7.08-7.13, 7.22-7.29, 7.66-7.70, 8.12-8.14.

[0099] 3. A polymer solution was obtained by mixing 200g of polyarylether P14 and 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100℃ for 10 hours to obtain polymer film M14a. The elongation at break of M14a was 1000%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-7V vs Li / Li.) + No redox reaction occurs inside the electrochemical window, indicating that M14a can withstand high voltage.

[0100] 4. Mix 1g of polyarylene ether P14 and 0.3g of lithium bis(fluorosulfonyl)imide evenly and press them into a film M14b. At room temperature, the ionic conductivity of M14b is 0.82mS / cm.

[0101] 5. Mix 209.10 g (0.5 mol) of polyarylether P13a, 220.26 g (5 mol) of ethylene oxide, 0.1 mol of ZnCl2, and 10 mL of dimethyl carbonate until homogeneous, then stir at 80 °C for 10 hours. After the reaction is complete, wash the resulting mixture with 100 mL of water, filter, and dry the precipitate to obtain 367.96 g of P14b (yield 85.7%). 1 HNMR(400MHz,DMSO-d6,ppm)δH=2.01-2.07,2.45-2.2.71,3.51-3.70,5.38- 5.41,6.62-6.68,6.95-7.02,7.08-7.13,7.22-7.29,7.66-7.70,8.12-8.14.

[0102] 6. Mix 50g of polyarylene ether P13b and 10g of lithium bis(trifluoromethanesulfonyl)imide evenly, and press them into a membrane M14c. At room temperature, the ionic conductivity of M14c is 3.1 mS / cm.

[0103] 7. Mix 209.10 g (0.5 mol) of polyarylether P13a, 290.40 g (5 mol) of propylene oxide, 0.01 mol of SnCl4, and 10 mL of dimethyl carbonate until homogeneous, then stir at 80 °C for 10 hours. After the reaction is complete, wash the resulting mixture with 100 mL of water, filter, and dry the precipitate to obtain 417.58 g of P14c (yield 83.6%). 8. Mix 50g of polyarylene ether P13b and 10g of lithium bis(trifluoromethanesulfonyl)imide evenly and press them into a membrane M14d. At room temperature, the ionic conductivity of M14d is 2.9 mS / cm.

[0104] Example 15 1. Dissolve 377 g (1 mol) of polyarylene ether P14 and 122.143 g (1 mol) of 1,3-propanesulfonyl lactone (CAS No.: 1120-71-4) in 52 ml of dimethyl sulfoxide, and then stir the mixture at room temperature for 72 h. After the reaction is complete, a viscous solution is obtained.

[0105] 2. When the viscous solution was dropped into water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 419.05 g of polyarylether P15 (yield 85.5%).

[0106] 1 HNMR(400MHz,DMSO-d6,ppm)δH=1.51-1.64,1.90-2.02,3.01-3.36,6.62-6 .68,6.95-7.02,7.08-7.13,7.22-7.29,7.66-7.70,8.12-8.14,8.49-8.51.

[0107] A polymer solution was obtained by mixing 200 g of polyarylether P15 and 1 L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100°C for 10 hours to obtain polymer film M15a. M15a has an elongation at break of 1200%. (The last sentence appears to be incomplete and possibly refers to a measurement or value related to Li / Li at -2-7V.) + No redox reaction occurs within the electrochemical window.

[0108] 1 g of polyarylether P15 and 0.3 g of lithium trifluoromethanesulfonate were mixed evenly and pressed into a membrane M15b. At room temperature, the ionic conductivity of M15b was 1.14 mS / cm.

[0109] Example 16 1. Dissolve 228.29 g (1 mol) bisphenol A (CAS No.: 80-05-7), 148.00 g (1 mol) 2,6-dichloropyridine (CAS No.: 2402-78-0) and 117.82 g (2.1 mol) potassium hydroxide in 52 mL of dimethyl sulfoxide, and then stir the mixture at room temperature for 24 h. After the reaction is complete, a viscous solution is obtained.

[0110] 2. When the viscous solution was added to water, a precipitate began to form. After the precipitation was complete, the precipitate was washed twice with water and then dried to obtain 244.38 g of polyarylether P16 (yield 91.5%).

[0111] 1 HNMR (400MHz, DMSO-d6, ppm) δH=1.47-1.64, 6.58-6.65, 6.86-7.04, 7.13-7.15, 7.18-7.27, 7.77-7.82.

[0112] 3. A polymer solution was obtained by dissolving 200g of polyarylether P16 in 1L of dimethyl sulfoxide. The polymer solution was then cast onto a PET substrate using a casting method and baked at 100°C for 10 hours to obtain polymer film M16a. The elongation at break of M16a was 1000%. (The last sentence appears to be incomplete and possibly refers to a different process: -2-7V vs Li / Li.) + No redox reaction occurs within the electrochemical window.

[0113] 4. Mix 1g of polyarylether P9 and 0.3g of lithium hexafluorophosphate evenly and press them into a membrane M16b. At room temperature, the ionic conductivity of M16b is 1.18mS / cm.

Claims

1. A highly flexible aryl polymer, characterized in that... Structural units containing the following general formulas: ， Wherein, A is selected from at least one of the groups shown in the following structural formulas: ， Ar1 and Ar2 are each independently selected from aromatic groups having 3-20 carbon atoms; G0 is selected from at least one of the groups shown in the following structural formulas: R1, R2, and R3 are each independently selected from hydrogen, alkyl groups having 1-20 carbon atoms, or aryl groups having 6-20 carbon atoms, or are each independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, carbonyl, or halogen-substituted alkyl groups having 1-20 carbon atoms, or are each independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, carbonyl, or halogen-substituted aryl groups having 6-20 carbon atoms; The cyclic substituent is selected from at least one of aliphatic carbocyclic substituents, polycyclic aromatic ring substituents, and heterocyclic substituents having 3-20 carbon atoms; m is a natural number not greater than 10; E is selected from J, or from a combination of J and K; wherein J is selected from at least one of a dihaloaromatic cycloalcohol containing at least one electron-withdrawing group, a dihaloaromatic cycloalcohol containing at least one N atom, and an aryl group containing two halomethyl groups, and K is selected from at least one of an aryl group containing two acyl halide groups and a dihaloalkyl group having 1-20 carbon atoms. G1 and G2 are each independently selected from any one of O, S, and NR4, wherein R4 is selected from hydrogen, an alkyl group having 1-20 carbon atoms, or an aryl group having 6-20 carbon atoms, or independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, or halogen-substituted alkyl group having 1-20 carbon atoms, or independently selected from carboxyl, hydroxyl, amino, mercapto, nitro, or halogen-substituted aryl group having 6-20 carbon atoms.

2. A method for preparing the highly flexible aryl polymer according to claim 1, characterized in that... Includes the following steps: Under alkaline conditions, monomers G and M undergo a polymerization reaction to generate the highly flexible aryl polymer described above. Alternatively, in the presence of an alkali, monomers G, M, and crosslinking agent monomers undergo a polymerization reaction to generate the highly flexible aryl polymer described above. The general structural 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 a dihaloaromatic ring hydrocarbon containing at least one strong electron-withdrawing group, a dihaloaromatic ring hydrocarbon containing at least one N atom, and an aromatic hydrocarbon containing two halomethyl groups, and P is selected from at least one of an aromatic hydrocarbon containing two acyl halide groups and a dihaloalkane having 1-20 carbon atoms. The crosslinking agent monomer is selected from aromatic compounds containing three or more hydroxyl groups, mercapto groups, amino groups or halogens, or from alkanes containing three or more halogens or nitrogen-containing heterocyclic compounds containing multiple active groups. The base is selected from at least one of alkali metal hydroxides or alkali metal carbonates.

3. An aryl polymer containing aliphatic ether chains, characterized in that... Structural units containing the following general formulas: ， Wherein, B is an aliphatic ether chain with a degree of polymerization ≥1, and G0 is selected from at least one of the groups shown in the following structural formulas: ， And B is connected to R1, R2 or R3 of G0, or B is connected to the ring of G0; B is selected from at least one of the groups shown in the following structural formulas: Where n is the degree of aggregation.

4. A method for preparing an aryl polymer containing aliphatic ether chains, characterized in that... Includes the following steps: When the highly flexible aryl polymer of claim 1 contains active hydrogen, in the presence of an initiator, the highly flexible aryl polymer of claim 1 is polymerized with at least one of ethylene oxide, propylene oxide, tetrahydrofuran, chloro ether, epichlorohydrin and oxetane to generate the aryl polymer containing aliphatic ether chains. The initiator is selected from at least one of alkali metal alkoxides, hydroxides, metal porphyrin compounds, bimetallic cyanide complexes, strong protic acids, and Lewis acids.

5. An aryl polymer containing sulfonic acid groups, characterized in that... Structural units containing the following general formulas: ， Wherein, C is a sulfonic acid group, and G0 is selected from at least one of the groups shown in the following structural formulas: ， Furthermore, C is connected to R1, R2, or R3 of G0, or C is connected to the ring of G0.

6. A method for preparing an aryl polymer containing sulfonic acid groups, characterized in that... Includes the following steps: When the highly flexible aryl polymer of claim 1 contains active hydrogen, in the presence of an alkali, the highly flexible aryl polymer of claim 1 is polymerized with a cyclosulfonate or a haloalkylsulfonic acid containing 3-10 carbon atoms to generate the aryl polymer containing sulfonic acid groups. The alkali is selected from at least one of alkali metal alkoxides and hydroxides.

7. A method for preparing an aryl polymer thin film, characterized in that... Prepared by the following method: At least one of the highly flexible aryl polymer of claim 1, the aryl polymer containing aliphatic ether chains of claim 3, and the aryl polymer containing sulfonic acid groups of claim 5 is dissolved in an organic solvent to obtain a polymer solution. The polymer solution is then cast or die-cast into a film and dried to obtain the aryl compound film. The organic solvent is one or a combination of several of the following: dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

8. A method for preparing an aryl polymer solid electrolyte, characterized in that... Includes the following steps: At least one of the highly flexible aryl polymer gold of claim 1 and the aryl polymer containing aliphatic ether chains of claim 3 is mixed uniformly with any one or more of polyether, polyester, polyacrylonitrile, fluoropolymer, single ion conductor polymer, lithium salt, sodium salt, potassium salt, acid and nanofiller, and the resulting mixture is pressed into a membrane to obtain the aryl polymer solid electrolyte membrane. Alternatively, at least one of the highly flexible aryl polymer gold of claim 1 and the aryl polymer containing aliphatic ether chains of claim 3 can be mixed uniformly with any one or more of polyether, polyester, polyacrylonitrile, fluoropolymer, single-ion conductor polymer, lithium salt, sodium salt, potassium salt, acid, nanofiller and solvent, and the resulting mixed solution can be coated on a substrate to prepare a film, thereby obtaining the aryl polymer solid electrolyte membrane.

9. The method for preparing the aryl polymer solid electrolyte according to claim 8, characterized in that: The polyether is selected from at least one of polyethylene oxide and polypropylene oxide; The polyester is selected from at least one of polypropylene carbonate and poly-ε-caprolactone; The polyacrylonitrile is selected from at least one of polyacrylonitrile and polybutadiene nitrile; The fluoropolymer is selected from at least one of polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene copolymer; The single-ion conductor polymer is selected from polymers containing crown ethers, crypt ethers and nitrogen heterocycles, metal-organic framework compounds, and covalent organic framework materials; The lithium salt is selected from at least one of lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bisfluorosulfonylimide, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate, lithium dioxalateborate, and lithium difluoroborate oxalate. The sodium salt is selected from at least one of sodium hexafluorophosphate, sodium perchlorate, sodium trifluoromethanesulfonate, sodium difluorosulfonamide, sodium ditrifluoromethanesulfonamide, sodium tetrafluoroborate, sodium dioxalate borate, and sodium difluoroborate oxalate. The potassium salt is selected from at least one of potassium hexafluorophosphate, potassium perchlorate, potassium trifluoromethanesulfonate, potassium difluorosulfonamide, potassium ditrifluoromethanesulfonamide, potassium tetrafluoroborate, potassium dioxalate borate, and potassium difluoroborate oxalate. The acid is selected from at least one of phosphoric acid, sulfuric acid, trifluoromethanesulfonic acid, and solid acids; The nanofiller is selected from at least one of alumina, silicon dioxide, titanium dioxide, oxide solid electrolyte, sulfide solid electrolyte, and chloride solid electrolyte; The solvent is selected from at least one of dimethyl sulfoxide, dimethyl carbonate, acetonitrile, N-methylpyrrolidone, and N,N-dimethylformamide; The substrate is selected from at least one of polypropylene porous membrane, polyethylene porous membrane, polyimide porous membrane and ceramic porous membrane.

10. The application of the highly flexible aryl polymer of claim 1, the aryl polymer containing aliphatic ether chains of claim 3, or the aryl polymer containing sulfonic acid groups of claim 5 in the preparation of battery solid electrolytes and electrode material binders.

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