A protonated porphyrin-based conjugated microporous polymer, its preparation method and application in zinc-iodine batteries
Patent Information
- Application Number
- CN202610664099.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-05-14
- Publication Date
- 2026-09-29
AI Technical Summary
[0004]本发明所要解决的技术问题是提供一种质子化卟啉基共轭微孔聚合物及其制备方法和在锌碘电池中的应用，以提升对多碘化物的吸附与限域能力，从而抑制多碘化物的穿梭效应，进一步解决锌碘电池的容量衰减快，库伦效率低等问题
[0032]（1）本发明通过偶联反应制得的卟啉基共轭微孔聚合物，因卟啉基团独特的平面共轭环结构，具有高度离域的π电子体系，能够有效促进电子迁移与电荷传导；
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Figure CN122832277A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of zinc-iodine battery cathode material technology, and specifically relates to a protonated porphyrin-based conjugated microporous polymer, its preparation method, and its application in zinc-iodine batteries. Background Technology
[0002] In recent years, with the rapid development of new energy vehicles, the low-altitude economy, and artificial intelligence, global demand for energy storage is experiencing explosive growth, thus creating an urgent need for new energy storage devices with high energy density, low cost, and sustainability. Among various secondary battery systems, aqueous zinc-ion batteries have attracted attention due to their low redox potential (-0.76 V vs. SHE), safety, low cost, abundant natural reserves, and non-toxicity. However, traditional cathode materials employ intercalation / deintercalation energy storage mechanisms such as vanadium oxide and manganese oxide. During electrochemical processes, the strong Coulomb interaction between intercalated ions and the surrounding lattice leads to structural collapse, resulting in rapid capacity decay. As a solution, iodine, as the most abundant and least toxic halogen element, has been gradually introduced into aqueous zinc-ion batteries.
[0003] However, because polyiodides include I3 - I5 - Zinc-iodine batteries exhibit high solubility in electrolytes and are prone to the "shuttle effect," leading to rapid capacity decay and low coulombic efficiency, thus hindering their widespread application in high-performance batteries. Therefore, developing novel cathode iodine host materials that can effectively confine iodine species, suppress the shuttle effect, and accelerate reaction kinetics is a key approach to improving the performance of zinc-iodine batteries. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide a protonated porphyrin-based conjugated microporous polymer, its preparation method and its application in zinc-iodine batteries, so as to improve the adsorption and confinement ability of polyiodides, thereby suppressing the shuttle effect of polyiodides, and further solving the problems of rapid capacity decay and low coulombic efficiency of zinc-iodine batteries.
[0005] This invention provides a protonated porphyrin-based conjugated microporous polymer with the structural formula (I) or (II):
[0006] .
[0007] Preferably, the protonated porphyrin-based conjugated microporous polymer is prepared by a Buchwald-Hartwig coupling reaction using bromophenylporphyrin and aromatic amine monomers as reactants, and then protonated using an acidic reagent.
[0008] More preferably, the bromophenyl porphyrin is 5,10,15,20-tetrakis(4-bromophenyl)porphyrin, with the following structural formula:
[0009] .
[0010] More preferably, the aromatic amine monomer is at least one of N,N,N',N'-tetratetra(p-aminophenyl)p-phenylenediamine or p-phenylenediamine, with the following structural formula:
[0011] .
[0012] The present invention also provides a method for preparing the above-mentioned protonated porphyrin-based conjugated microporous polymer, comprising the following steps:
[0013] (1) Using bromophenylporphyrin and aromatic amine monomers as reactants, alkali, catalyst, ligand and solvent are added, and porphyrin-based conjugated microporous polymers are synthesized by Buchwald-Hartwig coupling reaction, denoted as por-CMP;
[0014] (2) The porphyrin-based conjugated microporous polymer obtained in step (1) is mixed with an acidic reagent and stirred to react. After the reaction is completed, the mixture is filtered, washed and dried to obtain a protonated porphyrin-based conjugated microporous polymer, denoted as p-por-CMP.
[0015] Preferably, the alkaline agent in step (1) includes, but is not limited to, one or more of sodium tert-butoxide, cesium carbonate, or potassium carbonate.
[0016] Preferably, the catalyst in step (1) is either tris(dibenzylacetone)palladium or palladium acetate.
[0017] Preferably, the ligand in step (1) is either tritert-butylphosphine or 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl.
[0018] Preferably, the solvent in step (1) is one or more of tetrahydrofuran, toluene, or N,N-dimethylformamide.
[0019] Preferably, the coupling reaction in step (1) is carried out in an inert gas environment at 60~120 °C for 48~72 h, wherein the inert gas is argon.
[0020] Preferably, the acidic reagent in step (2) is a hydrochloric acid solution with a concentration of 1~12 M; the mass-to-volume ratio of the porphyrin-based conjugated microporous polymer to the hydrochloric acid solution is 1 mg: 1~10 mL.
[0021] Preferably, the stirring reaction time in step (2) is 6~24 h and the reaction temperature is 25~35 ℃.
[0022] The present invention also provides an application of the above-mentioned protonated porphyrin-based conjugated microporous polymer in a zinc-iodine battery, wherein the zinc-iodine battery includes a positive electrode material, a negative electrode material, an electrolyte, and a separator; the positive electrode material includes an active material, I2, and a current collector, wherein the active material is the above-mentioned protonated porphyrin-based conjugated microporous polymer; the negative electrode material is high-purity zinc foil; the electrolyte includes one or more of zinc sulfate, zinc chloride, and zinc p-benzenesulfonate; and the separator is glass fiber.
[0023] Preferably, the preparation process of the zinc-iodine battery includes the following steps:
[0024] 1) Mix the active material with the conductive agent and binder, add solvent and grind evenly, coat it on the current collector, and dry at 100 °C to obtain the positive electrode material;
[0025] 2) Loading iodine onto the cathode material via iodine vapor diffusion;
[0026] 3) Assemble the positive electrode material, negative electrode material, electrolyte and separator in sequence to construct a zinc-iodine battery.
[0027] Preferably, the mass ratio of the active substance, conductive agent, and binder in step 1) is 7~9:0.5~2:0.5~1.
[0028] Preferably, the conductive agent in step 1) is Ketjen black; the binder is polyvinylidene fluoride or polytetrafluoroethylene; the solvent is N-methylpyrrolidone; and the current collector is titanium mesh, stainless steel mesh, or carbon cloth.
[0029] Preferably, the iodine vapor diffusion environment in step 2) is 70~80 ℃, and the mass ratio of active material to I2 is 1~2:0.7~1.
[0030] Further, in step 3), the electrolyte concentration is 2 M and the amount added is 50 μL.
[0031] Beneficial effects
[0032] (1) The porphyrin-based conjugated microporous polymer prepared by coupling reaction in this invention has a highly delocalized π-electron system due to the unique planar conjugated ring structure of the porphyrin group, which can effectively promote electron migration and charge conduction.
[0033] (2) The present invention achieves protonation of nitrogen atoms in the central part of porphyrin and nitrogen atoms in secondary amine by hydrochloric acid solution treatment. The operation is simple, the cost is low and it is easy to scale up production.
[0034] (3) This invention enables the porphyrin-based conjugated microporous polymer framework to exhibit positive charge through protonation treatment, and significantly improves the resistance to polyiodides (I3) through electrostatic interactions. - I5- The adsorption and confinement capabilities of negative ions effectively suppress the shuttle effect in aqueous zinc-iodine batteries.
[0035] (4) This invention applies protonated porphyrin-based conjugated microporous polymers as positive electrode materials in aqueous zinc-iodine batteries, benefiting from the highly delocalized π-electron system of the porphyrin group and the positive charge environment of the system on polyiodides (I3). - I5 - Due to the confinement effect of the battery, it exhibits good reaction kinetics, electrochemical stability and long service life, thus meeting the needs of practical applications. Attached Figure Description
[0036] Figure 1 Fourier transform infrared spectra of the porphyrin-based conjugated microporous polymer (por-CMP) and the protonated porphyrin-based conjugated microporous polymer (p-por-CMP-1) prepared in Example 1.
[0037] Figure 2 The isothermal nitrogen adsorption / desorption diagrams and pore size distribution diagrams for por-CMP and p-por-CMP-1 prepared in Example 1 are shown.
[0038] Figure 3 N 1s XPS spectra of por-CMP and p-por-CMP-1 prepared in Example 1.
[0039] Figure 4 Cyclic voltammetry curves of the zinc-iodine battery based on p-por-CMP-1 prepared in Example 3.
[0040] Figure 5 Rate performance of the zinc-iodine battery based on p-por-CMP-1 prepared in Example 3 at different current densities.
[0041] Figure 6 The zinc-iodine battery based on p-por-CMP-1 prepared for Example 3 was tested at 0.3 A g. -1 Cyclic performance at current density.
[0042] Figure 7 The zinc-iodine battery based on p-por-CMP-1 prepared in Example 3 was tested at 5 A g. -1 Cyclic performance at current density.
[0043] Figure 8 The rate performance of the zinc-iodine battery based on p-por-CMP-2 prepared in Example 4 at different current densities.
[0044] Figure 9 The zinc-iodine battery based on p-por-CMP-2 prepared for Example 4 was tested at 0.3 A g.-1 Cyclic performance at current density. Detailed Implementation
[0045] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0046] Example 1
[0047] This example provides a protonation method for porphyrin-based conjugated microporous polymers, including the following steps:
[0048] (1) 5,10,15,20-tetratetra(4-bromophenyl)porphyrin (465 mg, 0.5 mmol), N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine (236 mg, 0.5 mmol), sodium tert-butoxide (600 mg, 6.24 mmol), tris(dibenzylacetone)palladium (350 mg, 0.38 mmol) and 2-biscyclohexylphosphine-2',4',6'-triisopropylbiphenyl (43 mg, 0.09 mmol) were placed in a 100 ml Schlenk flask; then, in an argon-glove box, 55 ml of tetrahydrofuran was injected into the Schlenk flask, and the mixture was sonicated for 5-10 min, then stirred in a 65 ℃ oil bath for 48 h; after the reaction was completed, the mixture was cooled to room temperature, filtered, and the resulting product was washed successively with chloroform, methanol, and deionized water for 12 h each, and then dried in a freeze dryer for 48 h. h, finally yielding the porphyrin-based conjugated microporous polymer, denoted as por-CMP.
[0049] (2) The above por-CMP was mixed with 12 M hydrochloric acid solution at a mass-volume ratio of 1 mg: 10 mL and stirred at room temperature for 24 h to obtain a protonated porphyrin conjugated microporous polymer, denoted as p-por-CMP-1, the structure of which is shown in Formula I.
[0050] The infrared spectra of por-CMP and p-por-CMP-1 obtained in this embodiment are as follows: Figure 1 As shown, benzene rings and quinone structures can be observed at approximately 1500 cm⁻¹ in the infrared spectra of both por-CMP and p-por-CMP-1. -1 1600 cm -1 The characteristic peaks. After protonation, the peak intensity corresponding to the quinone structure is enhanced, and at approximately 1300 cm⁻¹... -1 The location appears to belong to CN. +The characteristic peaks confirmed the successful preparation and protonation of the porphyrin-based conjugated microporous polymer.
[0051] The nitrogen adsorption-desorption curves and pore size distribution diagrams of por-CMP and p-por-CMP-1 obtained in this embodiment are shown below. Figure 2 As shown in the figure, the adsorption isotherms of both por-CMP and p-por-CMP-1 are typical type I isotherms, and their pores are mainly composed of micropores. Furthermore, both exhibit high specific surface areas, indicating that the protonation treatment did not destroy the polymer's skeletal structure.
[0052] The N 1s XPS spectra of por-CMP and p-por-CMP-1 obtained in this embodiment are as follows: Figure 3 As shown, signal peaks at 400.5 eV, 399.8 eV, and 398.3 eV can be fitted before and after protonation, corresponding to -NH-, -CN-, and =N-, respectively. Furthermore, =NH- at 402.3 eV is also detected in the p-por-CMP-1 spectrum. + - Peak and NH2 at 401.9 eV + The peak confirmed the protonation of the nitrogen atom at the porphyrin center and the nitrogen atom of the secondary amine.
[0053] Example 2
[0054] This embodiment provides a protonated porphyrin-based conjugated microporous polymer. The specific preparation method is the same as in Example 1, except that the hydrochloric acid concentration in step (2) is replaced with 3 M, and the porphyrin-based conjugated microporous polymer and hydrochloric acid solution are mixed at a mass-volume ratio of 1 mg:40 mL. The prepared protonated porphyrin-based conjugated microporous polymer is designated as p-por-CMP-2.
[0055] Example 3
[0056] This embodiment provides a zinc-iodine battery, based on p-por-CMP-1 obtained in Example 1 as the active material, and its preparation method specifically includes:
[0057] 1) The active material, Ketjen black and polyvinylidene fluoride are dispersed in N-methylpyrrolidone at a mass ratio of 8:1:1 to obtain a positive electrode slurry; the positive electrode slurry is coated on carbon cloth and dried under vacuum at 100 °C for 12 h to obtain the original positive electrode sheet;
[0058] 2) The positive electrode was placed in an iodine vapor atmosphere and iodine was adsorbed at 75 °C for 2 h, so that the mass ratio of active material to iodine was about 1:0.8, and an iodine-loaded positive electrode was obtained.
[0059] 3) Using zinc foil as the negative electrode, glass fiber as the separator, and 50 μL 2 M ZnSO4 solution as the electrolyte, assemble it with the positive electrode obtained in step 2) to form a CR2032 coin cell.
[0060] The cyclic voltammetry curve of the zinc-iodine battery based on p-por-CMP-1 obtained in this embodiment is as follows: Figure 4 As shown, the battery exhibits a voltage window of 0.5–1.6 V and demonstrates good electrochemical reversibility.
[0061] The rate performance of the p-por-CMP-1-based zinc-iodine battery obtained in this embodiment at different current densities is as follows: Figure 5 As shown, at 0.3 A g -1 At a current density of 212 mAh g, the battery has a capacity of 212 mAh g. -1 The specific capacity when the current density increases to 10 A g -1 At that time, it still had 112 mAh g -1 With a specific capacity and a capacity retention rate of 53%, it exhibits excellent rate performance.
[0062] The zinc-iodine battery based on p-por-CMP-1 obtained in this embodiment operates at 0.3 A g. -1 Cyclic performance at current density such as Figure 6 As shown, after cycle stabilization, the battery has a capacity of 230 mAh g. -1 It has a high specific capacity and a coulombic efficiency of up to 98%, exhibiting good cycle stability and high reversibility.
[0063] The zinc-iodine battery based on p-por-CMP-1 obtained in this embodiment operates at 5 A g. -1 Cyclic performance at current density such as Figure 7 As shown, the battery has a capacity of 153 mAh g. -1 The initial specific capacity remained good after 10,000 cycles, with a single-cycle capacity decay rate of only 0.0036%, demonstrating excellent long-cycle stability.
[0064] Example 4
[0065] This embodiment provides a zinc-iodine battery, the preparation method of which is specifically the same as in Example 3, except that p-por-CMP-2 obtained in Example 2 is used as the active material.
[0066] The rate performance of the p-por-CMP-2-based zinc-iodine battery obtained in this embodiment at different current densities is as follows: Figure 8 As shown. At 0.3 A g -1 At a current density of 207 mAh g, the battery has a capacity of 207 mAh g. -1The specific capacitance when the current increases to 10 A g -1 At that time, it had 61 mAh g -1 The specific capacity was 29%, lower than that of Example 3, indicating a weaker degree of protonation and limited confinement effect on polyiodides, but still exhibiting high reversibility.
[0067] The zinc-iodine battery based on p-por-CMP-2 obtained in this example operates at 0.3 A g. -1 Cyclic performance at current density such as Figure 9 As shown, after cycle stabilization, the battery still has 198 mAh g⁻¹. -1 The specific capacity further confirms the feasibility of protonated porphyrin-based conjugated microporous polymers as cathode materials for zinc-iodine batteries.
Claims
1. A protonated porphyrin-based conjugated microporous polymer, characterized in that, The structural formula of the protonated porphyrin-based conjugated microporous polymer is shown in Formula I or Formula II: 。 2. The protonated porphyrin-based conjugated microporous polymer according to claim 1, characterized in that, The protonated porphyrin-based conjugated microporous polymer was prepared by a Buchwald-Hartwig coupling reaction using bromophenylporphyrin and aromatic amine monomers as reactants, followed by protonation with an acidic reagent.
3. The protonated porphyrin-based conjugated microporous polymer according to claim 2, characterized in that, The bromophenyl porphyrin is 5,10,15,20-tetra(4-bromophenyl)porphyrin; the aromatic amine monomer is at least one of N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine or p-phenylenediamine.
4. A method for preparing the protonated porphyrin-based conjugated microporous polymer as described in any one of claims 1-3, comprising the following steps: (1) Using bromophenylporphyrin and aromatic amine monomers as reactants, alkali, catalyst, ligand and solvent are added, and porphyrin-based conjugated microporous polymers are synthesized by Buchwald-Hartwig coupling reaction, denoted as por-CMP; (2) The porphyrin-based conjugated microporous polymer obtained in step (1) is mixed with an acidic reagent and stirred to react. After the reaction is completed, the mixture is filtered, washed and dried to obtain a protonated porphyrin-based conjugated microporous polymer, denoted as p-por-CMP.
5. The preparation method according to claim 4, characterized in that, The alkaline agent in step (1) includes one or more of sodium tert-butoxide, cesium carbonate, or potassium carbonate; the catalyst is any one of tris(dibenzylacetone)dipalladium or palladium acetate; the ligand is any one of tritert-butylphosphine or 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl; and the solvent is one or more of tetrahydrofuran, toluene, or N,N-dimethylformamide.
6. The preparation method according to claim 4, characterized in that, The coupling reaction described in step (1) is carried out in an inert gas environment at 60~120 ℃ for 48~72 h, wherein the inert gas is argon.
7. The preparation method according to claim 4, characterized in that, In step (2), the acidic reagent is hydrochloric acid solution with a concentration of 1~12 M; the mass-volume ratio of the porphyrin-based conjugated microporous polymer to the hydrochloric acid solution is 1 mg: 1~10 mL; the stirring reaction time is 6~24 h, and the reaction temperature is 25~35 ℃.
8. The application of the protonated porphyrin-based conjugated microporous polymer as described in claim 1 in a zinc-iodine battery, characterized in that, The zinc-iodine battery includes a positive electrode material, a negative electrode material, an electrolyte, and a separator; the positive electrode material includes an active material, I2, and a current collector, wherein the active material is a protonated porphyrin-based conjugated microporous polymer; the negative electrode material is high-purity zinc foil; the electrolyte includes one or more of zinc sulfate, zinc chloride, and zinc p-benzenesulfonate; and the separator is glass fiber.
9. The application according to claim 8, characterized in that, The preparation process of the zinc-iodine battery includes the following steps: 1) Mix the active material with the conductive agent and binder, add solvent and grind evenly, coat it on the current collector, and dry at 100 °C to obtain the positive electrode material; 2) Loading iodine onto the cathode material via iodine vapor diffusion; 3) Assemble the positive electrode material, negative electrode material, electrolyte and separator in sequence to construct a zinc-iodine battery.
10. The application according to claim 9, characterized in that, Step 1) The mass ratio of the active material, conductive agent, and binder is 7~9:0.5~2:0.5~1; wherein the conductive agent is Ketjen Black; the binder is polyvinylidene fluoride or polytetrafluoroethylene; the solvent is N-methylpyrrolidone; the current collector is titanium mesh, stainless steel mesh, or carbon cloth; Step 2) The iodine vapor diffusion environment is 70~80 ℃, and the mass ratio of the active material to I2 is 1~2:0.7~1.