Preparation method of two-dimensional conjugated metal organic framework anchored iodine positive electrode material for ammonium ion supercapacitor
By preparing a two-dimensional conjugated metal-organic framework anchored iodine cathode material, the problem of insufficient electrochemical performance of ammonium ion supercapacitor cathode materials was solved, realizing an ammonium ion hybrid supercapacitor with high capacitance and long cycle life.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-02-28
- Publication Date
- 2026-03-20
AI Technical Summary
The electrochemical performance of existing ammonium ion supercapacitor cathode materials has not yet reached an excellent level, which limits their energy density and cycle life.
Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) were synthesized using a surfactant-assisted solution method, and iodine was fixed onto them by melt diffusion to form 2D c-MOF/I2 materials, which were then used as positive electrode materials for ammonium ion supercapacitors.
An ammonium ion hybrid supercapacitor with high areal capacitance and high energy density, excellent conductivity, abundant redox active sites, and long cycle life has been achieved.
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Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of ammonium ion supercapacitors, in particular to a preparation method of a two-dimensional conjugated metal organic framework anchored iodine positive electrode material for ammonium ion supercapacitors. BACKGROUND
[0002] Supercapacitors have great application prospects in energy storage due to their reliable safety, fast charge and discharge capability and long cycle life. However, the energy density of supercapacitors is low, which can be effectively solved by assembling hybrid supercapacitors of battery-type electrodes and capacitor-type electrodes. Commonly used cationic metal charge carriers in hybrid supercapacitors include Li + , Na + , K + , Mg 2+ , Zn 2+ and the like. In contrast, non-metallic charge carriers such as H + , NH4 + , F – , Cl – exhibit advantages such as low molar mass, small hydrated ion size, low corrosiveness and good sustainability. Among them, NH4 + has a low molar mass (18 g mol –1 ), a small hydrated radius low cost and abundant resources, and has attracted widespread attention. In addition, NH4 + has a high dissociation degree in aqueous electrolytes, which helps to improve the conductivity of ions and achieve a high energy density. Therefore, the development of ammonium ion supercapacitors has great prospects.
[0003] Researchers have been committed to developing electrode materials suitable for NH4 + energy storage devices, so as to have a large capacity and stable cycle performance. At present, the positive electrode materials for NH4 + energy storage mainly include four categories: Prussian blue analogs (CuHCF, Na-FeHCF, FeFe(CN)6, etc.), V-based oxides (V2O5, NH4V4O 10 , VO2, etc.), Mn-based compounds (MnO x ), and redox-active polymers / covalent organic frameworks (COFs) materials. Cui et al. first studied the charge storage behavior of PBAs (CuHCF and NiHCF) in NH4 + in 2012, which opened up the exploration of NH4 + host materials. Subsequently, Yury et al. reported the storage of NH4 + ions by MXenes. In addition, NH4 +The intercalation / deintercalation chemical reactions are also proved in other layered materials (such as δ-MnO2 and NH4V4O 10 ) and redox-active polymers / COFs. However, the exploration of NH4 + storage positive electrode materials is still in the primary stage, and it is of great value to develop new positive electrode materials with excellent electrochemical performance. +
[0004] Therefore, it is necessary to provide a preparation method of a two-dimensional conjugated metal organic framework iodine-anchored positive electrode material for ammonium ion supercapacitors to solve the above problems. SUMMARY
[0005] In view of the deficiencies in the prior art, the purpose of the present application is to provide a preparation method of a two-dimensional conjugated metal organic framework iodine-anchored positive electrode material for ammonium ion supercapacitors to solve the above problems.
[0006] The preparation method of the two-dimensional conjugated metal organic framework iodine-anchored positive electrode material for ammonium ion supercapacitors comprises the following steps:
[0007] S1, dissolving M(OAc)2 and sodium dodecyl sulfate in water to obtain solution A; mixing NaOH solution with solution A to obtain solution B;
[0008] S2, adding a ligand to solution B, ultrasonic dispersion to obtain dispersion C; standing dispersion C at room temperature, and collecting precipitate;
[0009] S3, ultrasonic cleaning the precipitate with water and ethanol in an ice bath, and then keeping dispersion; collecting upper gel suspension, vacuum drying to obtain 2D c-MOF (two-dimensional conjugated organic framework) material, and placing 2D c-MOF (two-dimensional conjugated organic framework) powder at the bottom of a sample bottle;
[0010] S4, then placing a smaller sample bottle containing I2 into the bottle; quickly sealing the sample bottle, reacting for a period of time at a certain temperature, and then cooling to room temperature to obtain a 2D c-MOF / I2 (two-dimensional conjugated metal organic framework iodine-anchored) positive electrode material for ammonium ion supercapacitors.
[0011] The metal M in M(OAc)2 can be Cu, Ni, Fe or Co.
[0012] The molar ratio of M(OAc)2 to sodium dodecyl sulfate is 2-8:1.
[0013] The volume ratio of NaOH solution to solution A is 0.5-2:1.
[0014] The ligand can be tetrahydroxy-1,4-benzoquinone or 2,3,6,7,10,11-hexahydroxytriphenyl.
[0015] In step S2, the dispersion C is left to stand and age at room temperature for 8 to 12 hours.
[0016] The precipitate in step S3 is kept dispersed for 12 to 48 hours.
[0017] The mass ratio of 2D c-MOF powder to I2 is 1:0.8 to 1.6.
[0018] In step S4, the 2D c-MOF powder reacts with I2 at 100–140 °C for 8–16 h.
[0019] Compared with the prior art, the present invention has the following advantages:
[0020] 1. Two-dimensional conjugated metal-organic framework (2D c-MOF) powder with excellent conductivity, rich pore structure and large specific surface area was synthesized by surfactant-assisted solution method in the presence of anionic surfactant sodium dodecyl sulfate.
[0021] 2. Using 2D c-MOF powder as an effective matrix for anchoring iodine, a 2D c-MOF / I2 material with excellent conductivity and abundant redox active sites was synthesized by a melt diffusion method with simple operation and mild reaction conditions.
[0022] 3. This invention develops a novel 2D c-MOF / I2 cathode material for ammonium-ion supercapacitors. An ammonium-ion hybrid supercapacitor assembled with porous MXene as the positive and negative electrode materials respectively achieves a current of 0.4 mA cm⁻¹. –2 It has 88.5mFcm –2 The high area capacitance achieved a 31.5mWh cm⁻¹ -2 High energy density and long cycle life. Attached Figure Description
[0023] Figure 1 This is a flowchart of the preparation method of the present invention;
[0024] Figure 2 This is a SEM image of the 2D c-MOF / I2 prepared in Example 1 of the present invention;
[0025] Figure 3 The cyclic voltammetry curves of the ammonium ion hybrid supercapacitor assembled with 2D c-MOF / I2 and porous MXene as positive and negative electrodes in Example 1 of the present invention are shown at different scan rates.
[0026] Figure 4The capacitance curves of the ammonium ion hybrid supercapacitor assembled by 2D c-MOF / I2 and porous MXene as positive and negative electrodes respectively in Example 1 of the present application at different current densities. DETAILED DESCRIPTION
[0027] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict.
[0028] The embodiments of the present application are described in detail below in combination with the drawings, but the present application can be implemented in various different ways limited and covered by the claims.
[0029] As shown in Figure 1 and in combination with Figures 2 to 4 , the preparation method of the ammonium ion supercapacitor anchoring iodine positive electrode material with two-dimensional conjugated metal organic framework, the method steps are as follows:
[0030] S1, dissolving M(OAc)2 and sodium dodecyl sulfate in water to obtain solution A; mixing NaOH solution with solution A to obtain solution B;
[0031] S2, adding ligand to solution B, ultrasonic dispersion to obtain dispersion C; dispersion C is placed at room temperature, and the precipitate is collected;
[0032] S3, the precipitate is washed with water and ethanol in an ice bath, and then kept dispersed; the upper gel suspension is collected, vacuum dried to obtain 2D c-MOF (two-dimensional conjugated organic framework) material, and the 2D c-MOF (two-dimensional conjugated organic framework) powder is placed at the bottom of the sample bottle;
[0033] S4, then a smaller sample bottle containing I2 is placed in the bottle; the sample bottle is quickly sealed, and after reaction at a certain temperature for a period of time, it is cooled to room temperature to obtain the 2D c-MOF / I2 (two-dimensional conjugated metal organic framework anchoring iodine) positive electrode material for ammonium ion supercapacitor.
[0034] Wherein the metal M in M(OAc)2 can be Cu, Ni, Fe or Co.
[0035] Wherein the molar ratio of M(OAc)2 and sodium dodecyl sulfate is 2-8:1.
[0036] Wherein the volume ratio of NaOH solution to solution A is 0.5-2:1.
[0037] Wherein the ligand can be tetrahydroxy-1,4-benzoquinone or 2,3,6,7,10,11-hexahydroxytriphenyl.
[0038] Wherein the dispersion C of step S2 is placed at room temperature for aging time of 8-12h.
[0039] The precipitate in step S3 is kept dispersed for 12-48 h.
[0040] The mass ratio of the 2D c-MOF powder to I2 is 1:0.8-1.6.
[0041] The 2D c-MOF powder in step S4 is reacted with I2 at 100-140 ℃ for 8-16 h.
[0042] Compared with the prior art, the present application has the following beneficial effects:
[0043] 1. In the presence of an anionic surfactant, sodium dodecyl sulfate, two-dimensional conjugated metal organic framework 2D c-MOF powder with excellent electrical conductivity, rich pore structure and large specific surface area is synthesized by a surfactant-assisted solution method.
[0044] 2. The 2D c-MOF / I2 material with excellent electrical conductivity and rich redox active sites is synthesized by a melt diffusion method with simple operation and mild reaction conditions, using 2D c-MOF powder as an effective matrix for anchoring iodine.
[0045] 3. The present application develops a new type of 2D c-MOF / I2 positive electrode material for ammonium ion supercapacitors. The ammonium ion hybrid supercapacitor assembled with porous MXene as positive and negative electrode materials has a high area capacitance of 88.5 mF cm –2 at 0.4 mA cm –2 and realizes a high energy density of 31.5 mWh cm -2 and a long cycle life.
[0046] The synthesized two-dimensional sheet metal organic framework structure 2D c-MOF powder has excellent electrical conductivity, and its rich pore structure and large specific surface area provide the possibility for iodine anchoring. The 2D c-MOF / I2 powder anchored with iodine and the porous MXene are assembled as positive and negative electrodes to form an ammonium ion hybrid supercapacitor, which realizes a high energy density of 31.5 mWh cm -2 and a long cycle life (the capacitance retention rate is 89.5% after 10,000 cycles), highlighting its great potential in innovative electronic products. The main feature of the operation process is that the two-dimensional sheet metal organic framework structure 2D c-MOF powder with excellent electrical conductivity, rich pore structure and large specific surface area is used as an effective matrix for anchoring iodine, a melt diffusion method with simple operation and mild reaction conditions is used to fix monomer I2 on the 2D c-MOF, and the obtained composite material 2D c-MOF / I2 has excellent electrical conductivity and rich redox active sites, which is used as a positive electrode material for ammonium ion supercapacitors, has a high capacitance, excellent energy density and good long cycle life.
[0047] Example 1:
[0048] A solution A was prepared by dissolving 480 mg of Cu(OAc)2 and 150 mg of sodium dodecyl sulfate in 150 mL of deionized water. Then, 150 mL of NaOH solution (25 mmol L -1 ) was added to solution A, and after mixing well, solution B was obtained. 300 mg of tetrahydroxy-1,4-benzoquinone powder was added to mixed solution B, and dispersion C was obtained by ultrasonic treatment at 50°C for 30 min. Subsequently, it was left to stand and age at 25°C for 10 h. The precipitate was collected and washed with deionized water and ethanol in an ultrasonic ice bath for 30 min. Then, the dispersion was kept dispersed for 24 h, and the upper colloidal suspension was collected and dried at 80°C under vacuum for 12 h to obtain a two-dimensional conjugated organic framework (2D c-MOF) material Cu-HHB.
[0049] 25 mg of Cu-HHB powder was placed at the bottom of a 30 mL sample bottle, and then a 5 mL sample bottle containing 28 mg of I2 particles was placed in the 30 mL sample bottle. After that, the 30 mL sample bottle was quickly sealed and reacted at 120°C for 12 h. Cu-HHB / I2 powder was obtained by cooling to room temperature.
[0050] The obtained Cu-HHB / I2 powder and porous MXene were assembled into ammonium ion supercapacitors as positive and negative electrode materials, respectively, which had a high area capacitance of 88.5 mF cm –2 at 0.4 mA cm –2 , a high energy density of 31.5 mWh cm -2 , and a long cycle life.
[0051] Example 2:
[0052] The method was the same as Example 1, except that 25 mg of Cu-HHB powder was placed at the bottom of a 30 mL sample bottle, and then a 5 mL sample bottle containing 20 mg of I2 particles was placed in the 30 mL sample bottle. After that, the 30 mL sample bottle was quickly sealed and reacted at 120°C for 12 h, and Cu-HHB / I2 powder was obtained by cooling to room temperature.
[0053] The obtained Cu-HHB / I2 powder and porous MXene were assembled into ammonium ion supercapacitors as positive and negative electrode materials, respectively, which had a high area capacitance of 58.6 mF cm –2 at 0.4 mA cm –2 , a high energy density of 20.8 mWh cm -2 , and a long cycle life.
[0054] Example 3:
[0055] The method is the same as in Example 1, except that: 25 mg of Cu-HHB powder was placed at the bottom of a 30 mL sample vial, and then a 5 mL sample vial containing 36 mg of I2 particles was placed inside the 30 mL sample vial. The 30 mL sample vial was then quickly sealed, and the reaction was carried out at 120 °C for 12 h. Cu-HHB / I2 powder was obtained by cooling to room temperature.
[0056] The obtained Cu-HHB / I2 powder and porous MXene were used as positive and negative electrode materials to assemble an ammonium ion supercapacitor. The supercapacitor was tested at 0.4 mA cm⁻¹. –2 It has 77.7mF cm –2 High area capacitance, with 24.3mWh cm⁻¹ -2 High energy density and long cycle life.
[0057] Example 4:
[0058] Dissolve 480 mg of Cu(OAc)₂ in 300 mL of NaOH solution (12.5 mmol / L). -1 Add the product to solution A and mix thoroughly to obtain solution B. Add 300 mg of tetrahydroxy-1,4-benzoquinone powder to solution B and sonicate at 50 °C for 30 min to obtain dispersion C. Then let it stand at 25 °C for 10 h. Collect the precipitate and wash it with deionized water and ethanol in an ultrasonic ice bath for 30 min. Dry it under vacuum at 80 °C for 12 h to obtain material Cu-HHB.
[0059] 25 mg of Cu-HHB powder was placed at the bottom of a 30 mL sample vial, and then a 5 mL sample vial containing 28 mg of I2 particles was placed inside the 30 mL sample vial. The 30 mL sample vial was quickly sealed, and the reaction was carried out at 120 °C for 12 h. Cu-HHB / I2 powder was obtained by cooling to room temperature.
[0060] The obtained Cu-HHB / I2 powder and porous MXene were used as positive and negative electrode materials to assemble an ammonium ion supercapacitor. The supercapacitor was tested at 0.4 mA / cm². –2 It has 10.8mF cm –2 Area capacitance.
[0061] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.
Claims
1. A method for preparing iodine cathode material anchored by a two-dimensional conjugated metal-organic framework in an ammonium ion supercapacitor, characterized in that: The method and steps are as follows: S1. Dissolve M(OAc)2 and sodium dodecyl sulfate in water to obtain solution A; NaOH solution and Solution A is mixed to obtain solution B; S2. Add the ligand to solution B and disperse it evenly by ultrasonication to obtain dispersion C; let dispersion C stand at room temperature and collect the precipitate. S3. The precipitate was ultrasonically cleaned with water and ethanol in an ice bath, and then kept dispersed. Collect the upper colloidal suspension, vacuum dry to obtain 2D c-MOF material, and place the 2D c-MOF powder at the bottom of the sample vial; S4. Then, place the smaller sample vial containing I2 into the vial; quickly seal the sample vial, react at a certain temperature for a period of time, and then cool to room temperature to obtain the 2D c-MOF / I2 cathode material for ammonium ion supercapacitors. The metal M in M(OAc)2 can be Cu, Ni, Fe, or Co; the molar ratio of M(OAc)2 to sodium dodecyl sulfate is 2–8:1; the volume ratio of NaOH solution to solution A is 0.5–2:1; the ligand can be tetrahydroxy-1,4-benzoquinone or 2,3,6,7,10,11-hexahydroxytriphenyl; the dispersion C in step S2 is aged at room temperature for 8–12 h; the precipitate in step S3 is kept dispersed for 12–48 h; and the mass ratio of 2D c-MOF powder to I2 is 1:0.8–1.
6.
2. The method for preparing iodine cathode material anchored by a two-dimensional conjugated metal-organic framework for ammonium ion supercapacitors as described in claim 1, characterized in that: In step S4, the 2Dc-MOF powder reacts with I2 at 100–140 °C.
3. The method for preparing iodine cathode material anchored by a two-dimensional conjugated metal-organic framework for ammonium ion supercapacitors as described in claim 1, characterized in that: In step S4, the reaction time between the 2Dc-MOF powder and I2 is 8–16 h.