Preparation method of ternary two-dimensional layered heterojunction and application of ternary two-dimensional layered heterojunction in rechargeable zinc battery and sodium battery
By preparing a ternary two-dimensional layered heterojunction, the problems of few active sites and capacity decay of the positive electrode materials of rechargeable water-based zinc ion batteries and rechargeable sodium metal batteries are solved, and high capacity and excellent cycling performance are achieved, which is suitable for industrial production.
Patent Information
- Application Number
- CN202510492796.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-18
- Publication Date
- 2025-07-22
AI Technical Summary
The existing positive electrode materials of rechargeable water-based zinc ion batteries and rechargeable sodium metal batteries have problems with few active sites and capacity attenuation, making it difficult to achieve high capacity and excellent cycling performance.
Using vanadium-based MAX phase and halide salt as precursors, a two-dimensional layered vanadium carbide/vanadium trioxide heterojunction was prepared by melt solid-liquid reaction, and then using zinc acetate, adenine and 4,4'-biphenyl acid as raw materials, a ternary two-dimensional vanadium carbide/vanadium trioxide/biometal organic frame layered heterojunction was prepared by solvothermal reaction.
The controllable equipment of the three-dimensional layered heterojunction is realized, and the specific capacity and rate performance of the positive electrode materials of rechargeable water-based zinc ion batteries and rechargeable sodium metal batteries are improved. It has good cycling performance and is suitable for industrial production.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of battery materials, and particularly relates to a preparation method of a ternary two-dimensional layered heterojunction and its applications in rechargeable zinc batteries and sodium batteries. Background Art
[0002] With the increasing demand for new energy in society, rechargeable aqueous zinc-ion batteries and rechargeable sodium-metal batteries have developed rapidly. As a new type of divalent ion battery, the rechargeable aqueous zinc-ion battery mainly uses materials capable of accommodating zinc ions as the positive electrode, zinc as the negative electrode, and an electrolyte containing zinc ions as the charge transfer medium. The charge and discharge of the battery are realized through the reversible insertion / extraction of zinc in the positive electrode material and the deposition / stripping of the zinc negative electrode. Compared with traditional rechargeable lithium-ion batteries, the advantages of rechargeable sodium-metal batteries are as follows: sodium salt raw materials are rich in reserves and low in price; sodium salts allow the use of low-concentration electrolytes, which can reduce costs; aluminum foil can be used as the current collector for the negative electrode, which can further reduce costs; and there is no over-discharge characteristic. Although the types of positive electrode materials for rechargeable aqueous zinc-ion batteries and rechargeable sodium-metal batteries are increasing with the in-depth research, the demand for developing positive electrode materials with high capacity and excellent cycle stability is still very urgent.
[0003] In recent years, inorganic and organic positive electrode materials have been widely used in rechargeable aqueous zinc-ion batteries and rechargeable sodium-metal batteries. Among them, inorganic positive electrode materials have advantages such as high capacity and excellent rate performance; organic positive electrode materials have the advantage of being able to design functional structures. Positive electrode materials with a heterojunction structure, especially heterojunction positive electrode materials with a two-dimensional layered structure, can simultaneously have the advantages of organic and inorganic positive electrode materials, and can weaken the respective disadvantages of organic materials and inorganic materials to achieve synergistic enhancement. It is a very promising modification strategy for positive electrode materials of rechargeable aqueous zinc-ion batteries and rechargeable sodium-metal batteries, which helps to improve the comprehensive performance of rechargeable aqueous zinc-ion batteries and rechargeable sodium-metal batteries. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to realize the controllable preparation of a ternary two-dimensional layered heterojunction. Using a vanadium-based MAX phase and a halide salt as precursors, a two-dimensional layered vanadium carbide / vanadium trioxide heterojunction is prepared through a molten solid-liquid reaction. Then, using the prepared two-dimensional layered vanadium carbide / vanadium trioxide heterojunction as a precursor, zinc acetate as a metal ion source, adenine and 4,4'-biphenyldicarboxylic acid as organic ligands, concentrated nitric acid as a pore structure regulator, and water and N,N-dimethylformamide as a mixed solvent, a ternary two-dimensional vanadium carbide / vanadium trioxide / bio-metal-organic framework (Bio-MOF-1) layered heterojunction with three components is obtained through a solvothermal reaction, increasing the types of ternary two-dimensional layered heterojunctions that can be prepared, and thus realizing the controllable synthesis of ternary two-dimensional layered heterojunctions.
[0005] When the ternary two-dimensional layered heterojunction obtained by the present invention is used as the cathode material for rechargeable aqueous zinc-ion batteries and sodium metal batteries, it overcomes the problems of few active sites and capacity decay when directly using one or two components, and the specific capacity is higher than 220 and 200 mAh g respectively -1 , and it has excellent rate performance and good cycling performance. This method can realize the controllable preparation of ternary two-dimensional layered heterojunctions, starting from easily available MAX phases and halide salts, and can be obtained by a process with high repeatability, simple process and less time consumption, and is suitable for industrial production.
[0006] To solve the above technical problems, the present invention adopts the following technical solutions:
[0007] A preparation method of a ternary two-dimensional layered heterojunction, using a vanadium-based MAX phase and a halide salt as precursors, preparing a two-dimensional layered vanadium carbide / vanadium trioxide heterojunction through a molten solid-liquid reaction, and then using the prepared two-dimensional layered vanadium carbide / vanadium trioxide heterojunction as a precursor, using zinc acetate as a metal ion source, using adenine and 4,4'-biphenyldicarboxylic acid as organic ligands, using concentrated nitric acid as a pore structure regulator, and using water and N,N-dimethylformamide as a mixed solvent, through a solvothermal reaction, a ternary two-dimensional vanadium carbide / vanadium trioxide / bio-metal-organic framework (Bio-MOF-1) layered heterojunction with three components is obtained. The specific steps are as follows:
[0008] (1) Take a certain molar ratio of vanadium-based MAX phase and halide salt, mix them evenly, put them into a porcelain boat and place it in a tubular furnace, and perform heat treatment under the protection of an inert gas to prepare a two-dimensional layered vanadium carbide / vanadium trioxide heterojunction through a molten solid-liquid reaction;
[0009] (2) Uniformly disperse the prepared two-dimensional layered vanadium carbide / vanadium trioxide heterojunction precursor in N,N-dimethylformamide to obtain dispersion A; dissolve adenine in N,N-dimethylformamide to obtain solution B; dissolve 4,4'-biphenyldicarboxylic acid in N,N-dimethylformamide to obtain solution C; dissolve zinc acetate in N,N-dimethylformamide to obtain solution D; dissolve concentrated nitric acid in N,N-dimethylformamide to obtain solution E; under continuous stirring, sequentially add solutions B, C and D to dispersion A, mix them evenly, add a certain amount of water, and then add solution E, stir evenly to obtain the final mixture, and place the obtained final mixture in a reaction kettle for solvothermal reaction;
[0010] (3) After the solvothermal reaction is completed, cool it to room temperature, wash it with N,N-dimethylformamide, and then dry it to obtain a ternary two-dimensional vanadium carbide / vanadium trioxide / bio-metal-organic framework (Bio-MOF-1) layered heterojunction with three components.
[0011] Further, the vanadium-based MAX phase is one of V2AlC, V2GaC, V2SnC, V2ZnC, V2GeC, V2InC, V4AlC3, V2Al 0.5 Ga 0.5 C, V2Al 0.3 Ga 0.7 C, V2Al 0.1 Ga 0.9 C, V2Sn 0.1 Ga 0.9 C, V2Zn 0.1 Ga 0.9 C, V2Ge 0.1 Ga 0.9 C, V2In 0.1 Ga 0.9 C; the halogenated salt is one or two of anhydrous copper chloride, anhydrous copper bromide, and anhydrous cuprous iodide.
[0012] Further, when preparing the two-dimensional layered vanadium carbide / vanadium trioxide heterojunction by molten solid-liquid reaction, the molar ratio of the vanadium-based MAX phase to the halogenated salt in the porcelain boat is 1:(2.5 - 7.5), the heating rate of the heat treatment is 2 °C min -1 -10 °C min -1 , the heat treatment temperature is 450 °C - 850 °C, the heat treatment time is 1 - 12 hours, and the reaction inert gas carrier gas is nitrogen or argon.
[0013] Further, in the step (2), based on the volume of the final mixed solution, the addition amount of the two-dimensional layered vanadium carbide / vanadium trioxide heterojunction precursor is 0.1 - 20 mg mL -1 ; the addition amount of adenine is 0.5 - 2 mg mL -1 ; the dosage of 4,4'-biphenyldicarboxylic acid is 3 - 6 mg mL -1 ; the addition amount of zinc acetate is 2 - 10 mg mL -1 ; the addition amount of concentrated nitric acid is 10 - 30 μL mL -1 ; the addition amount of water is 30 - 150 mg mL -1 ; the final mixed solution accounts for 70% - 85% of the volume of the reaction kettle.
[0014] Further, in the step (3), the solvothermal reaction temperature is 110 °C - 180 °C, and the solvothermal reaction time is 12 - 48 hours.
[0015] Further, the two-dimensional layered vanadium carbide / vanadium trioxide heterojunction in step (1) is a V8C7 / V2O3 heterojunction; the ternary two-dimensional vanadium carbide / vanadium trioxide / biological metal-organic framework (Bio-MOF-1) layered heterojunction with three components in step (3) is a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0016] The present invention also provides a ternary two-dimensional layered heterojunction prepared by any of the above methods.
[0017] The present invention also relates to the use of the prepared ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components as a positive electrode material for rechargeable aqueous zinc-ion batteries and rechargeable sodium metal batteries.
[0018] According to a specific aspect, the following steps are taken to prepare positive electrode sheets for rechargeable aqueous zinc-ion batteries and rechargeable sodium metal batteries:
[0019] (1) Mix the ternary two-dimensional layered heterojunction, acetylene black, and polyvinylidene fluoride evenly in a mass ratio of 7:2:1, and modulate them into a paste with N-methylpyrrolidone, and then evenly coat them on titanium foil and aluminum foil respectively.
[0020] (2) Dry in a vacuum oven at 80 °C for 12 hours.
[0021] The test method for the electrochemical performance of the electrode material is as follows:
[0022] (1) The simulated battery uses a button-type CR2032. Among them, the negative electrodes of the rechargeable aqueous zinc-ion battery and the rechargeable sodium metal battery are zinc sheets and sodium sheets respectively; for the rechargeable aqueous zinc-ion battery, the electrolyte is 3M zinc trifluoromethanesulfonate or 2M zinc sulfate aqueous solution; for the rechargeable sodium metal battery, the electrolyte is 1M NaPF6 in EC:DEC (volume ratio 1:1) or 1M NaClO4 in EC:DEC (volume ratio 1:1).
[0023] (2) For the reversible capacity and cycling performance of the electrode material, the experiment is tested and analyzed by constant current charge and discharge. The charge and discharge regime is: voltage range: 0.2 - 1.8V (rechargeable aqueous zinc-ion battery) and 0.01 - 3V (rechargeable sodium metal battery); the number of cycles is generally 1 - 3000 times.
[0024] When the prepared ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components is used as the positive electrode material for rechargeable aqueous zinc-ion batteries and rechargeable sodium metal batteries, the specific capacities are respectively higher than 220 and 200 mAh g -1, it has excellent rate performance and good cycling performance.
[0025] Due to the implementation of the above technical solutions, the present invention has the following advantages compared with the prior art:
[0026] (1) The present invention uses easily obtainable MAX phase and halide salts as precursor raw materials; (2) It can achieve the controllable preparation of ternary two-dimensional layered heterojunctions; (3) Obtain a ternary two-dimensional vanadium carbide / vanadium trioxide / biological metal-organic framework (Bio-MOF-1) layered heterojunction with three components, increasing the types of ternary two-dimensional layered heterojunctions that can be prepared; (4) When the ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components prepared by the present invention is used as the positive electrode material of a rechargeable aqueous zinc-ion battery and a rechargeable sodium metal battery, the specific capacity is respectively higher than 220 and 200 mAh g -1 , it has excellent rate performance and good cycling performance.
[0027] In summary, the present invention can achieve the controllable preparation of ternary two-dimensional layered heterojunctions, obtain a ternary two-dimensional vanadium carbide / vanadium trioxide / biological metal-organic framework (Bio-MOF-1) layered heterojunction with three components, and the obtained ternary two-dimensional layered heterojunction is an ideal positive electrode material for rechargeable aqueous zinc-ion batteries and rechargeable sodium metal batteries; in addition, the preparation method starts from easily obtainable MAX phase and halide salts and is prepared by a process with high repeatability, simple process, and less time-consuming, which is very suitable for industrial production. Brief Description of the Drawings
[0028] Figure 1 It is a flowchart for the preparation of a ternary two-dimensional layered heterojunction based on V2AlC and anhydrous copper chloride in Example 1;
[0029] Figure 2 It is a scanning electron microscope image of the ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction prepared in Example 1, and it can be seen that the product has an obvious two-dimensional accordion-like sheet structure;
[0030] Figure 3 It is a flowchart for the preparation of a ternary two-dimensional layered heterojunction based on V2GaC and anhydrous copper bromide in Example 2;
[0031] Figure 4 It is a scanning electron microscope image of the ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction prepared in Example 2, and it can be seen that the product has an obvious two-dimensional sheet structure;
[0032] Figure 5 It is a flowchart for the preparation of a ternary two-dimensional layered heterojunction based on V2SnC and cuprous iodide anhydrous in Example 3;
[0033] Figure 6 Scanning electron micrograph of the ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction prepared in Example 3, showing that the product has a layered two-dimensional structure;
[0034] Figure 7 Flowchart for the preparation of a ternary two-dimensional layered heterojunction based on V2GeC, anhydrous copper chloride, and anhydrous copper bromide in Example 5;
[0035] Figure 8 For Example 8 based on V2Al 0.5 Ga 0.5 C and anhydrous copper chloride for the preparation of a ternary two-dimensional layered heterojunction flowchart. Detailed implementation mode
[0036] The following is a further description of the present invention in conjunction with specific embodiments. It should be understood that the following embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the content of the above invention.
[0037] Example 1
[0038] The preparation method of the ternary two-dimensional layered heterojunction in this example is as follows:
[0039] (1) Take V2AlC and anhydrous copper chloride with a molar ratio of 1:2.5, mix them evenly, put them into a porcelain boat and place it in a tube furnace. Under the protection of inert gas nitrogen, heat-treat at 450 °C at a heating rate of 2 °C min -1 for 12 hours, then cool to room temperature and perform centrifugal washing. The product is vacuum-dried at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface chlorine end groups).
[0040] (2) Uniformly disperse the two-dimensional layered V8C7 / V2O3 heterojunction as a precursor into N,N-dimethylformamide to obtain dispersion A; dissolve adenine in N,N-dimethylformamide to obtain solution B; dissolve 4,4'-biphenyldicarboxylic acid in N,N-dimethylformamide to obtain solution C; dissolve zinc acetate in N,N-dimethylformamide to obtain solution D; dissolve concentrated nitric acid in N,N-dimethylformamide to obtain solution E; under continuous stirring, sequentially add solutions B, C, and D to dispersion A, mix evenly, add a certain amount of water, and then add solution E, and stir evenly to obtain the final mixture; the addition amount of the two-dimensional vanadium carbide / titanium trioxide heterojunction precursor in the final mixture is 0.1 mg mL -1 ; the addition amount of adenine in the final mixture is 0.5 mL -1 ; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixture is 3 mg mL-1 ; The addition amount of zinc acetate in the final mixture is 2 mg / mL -1 ; The addition amount of concentrated nitric acid in the final mixture is 10 μL / mL -1 ; The addition amount of water in the final mixture is 30 mg / mL -1 ; The final mixture accounts for 70% of the volume of the reaction kettle. After stirring evenly, the obtained mixture is placed in the reaction kettle, and a solvothermal reaction is carried out at 110 °C for 48 hours.
[0041] (3) After the solvothermal reaction is completed, it is cooled to room temperature, washed with N,N-dimethylformamide, and then vacuum dried at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0042] Figure 1 is the specific preparation process. The morphology of the prepared ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction is analyzed by scanning electron microscopy
[0043] ( Figure 2 ) It can be seen that it has an obvious two-dimensional accordion-like sheet structure.
[0044] The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components is made into a working electrode according to the method provided by the present invention and corresponding performance tests are carried out: for a rechargeable aqueous zinc-ion battery, the electrolyte is 3 M zinc trifluoromethanesulfonate, at 100 mA / g -1 During charge and discharge, the specific capacity is higher than 228 mAh / g -1 ; At 5000 mA / g -1 After 3000 cycles of charge and discharge, the capacity retention rate is greater than 80%; for a rechargeable sodium metal battery, the electrolyte is 1 M NaPF6 in EC:DEC (volume ratio 1:1), at 20 mA / g -1 During charge and discharge, the specific capacity is higher than 212 mAh / g -1 ; At 1000 mA / g -1 After 3000 cycles of charge and discharge, the capacity retention rate is greater than 90%.
[0045] Example 2
[0046] The preparation method of the ternary two-dimensional layered heterojunction in this example is as follows:
[0047] (1) Take V2GaC and anhydrous copper bromide with a molar ratio of 1:7.5, mix them evenly, put them into a porcelain boat and place it in a tube furnace. Under the protection of inert gas argon, at 10 °C / min -1The heating rate is heat-treated at 850 °C for 1 hour, then cooled to room temperature and centrifugally washed, and the product is vacuum-dried at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface bromine end groups).
[0048] (2) The two-dimensional layered V8C7 / V2O3 heterojunction is uniformly dispersed in N,N-dimethylformamide to obtain dispersion A; adenine is dissolved in N,N-dimethylformamide to obtain solution B; 4,4'-biphenyldicarboxylic acid is dissolved in N,N-dimethylformamide to obtain solution C; zinc acetate is dissolved in N,N-dimethylformamide to obtain solution D; concentrated nitric acid is dissolved in N,N-dimethylformamide to obtain solution E; under continuous stirring, solutions B, C, and D are successively added to dispersion A, mixed evenly, a certain amount of water is added, and then solution E is added. After stirring evenly, the final mixed solution is obtained; the addition amount of the two-dimensional layered vanadium carbide / vanadium trioxide heterojunction precursor in the final mixed solution is 20 mg mL -1 ; the addition amount of adenine in the final mixed solution is 2 mg mL -1 ; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixed solution is 6 mg mL -1 ; the addition amount of zinc acetate in the final mixed solution is 10 mg mL -1 ; the addition amount of concentrated nitric acid in the final mixed solution is 30 μL mL -1 ; the addition amount of water in the final mixed solution is 150 mg mL -1 ; the final mixed solution accounts for 85% of the reaction kettle volume. After stirring evenly, the obtained mixed solution is placed in the reaction kettle and reacted at 180 °C for 12 hours.
[0049] (3) After the solvothermal reaction is cooled to room temperature, it is washed with N,N-dimethylformamide, and then vacuum-dried at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0050] Figure 3 is the specific preparation process. The morphology of the prepared ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction is analyzed by scanning electron microscopy
[0051] ( Figure 4 ) It can be seen that it has an obvious two-dimensional sheet structure.
[0052] The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components is made into a working electrode according to the method provided by the present invention and corresponding performance tests are carried out: for a rechargeable aqueous zinc-ion battery, the electrolyte is 3M zinc trifluoromethanesulfonate, at 100 mA g -1During charge and discharge, the specific capacity is higher than 235 mAh g -1 ; during charge and discharge at 5000 mA g -1 after 3000 cycles of charge and discharge, the capacity retention rate is greater than 82%; for the rechargeable sodium metal battery, the electrolyte is 1 M NaPF6 in EC:DEC (volume ratio 1:1), at 20 mA g -1 during charge and discharge, the specific capacity is higher than 218 mAh g -1 ; during charge and discharge at 1000 mA g -1 after 3000 cycles of charge and discharge, the capacity retention rate is greater than 91%.
[0053] Example 3
[0054] The preparation method of the ternary two-dimensional layered heterojunction in this example is as follows:
[0055] (1) Take V2SnC and cuprous iodide anhydrous with a molar ratio of 1:4, mix them evenly, put them into a porcelain boat and place it in a tube furnace. Under the protection of inert gas argon, heat-treat at 750 °C for 5 hours at a heating rate of 5 °C min -1 , and then cool to room temperature and perform centrifugal washing. The product is vacuum-dried at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface iodine end groups).
[0056] (2) Uniformly disperse the two-dimensional layered V8C7 / V2O3 heterojunction as a precursor into N,N-dimethylformamide to obtain dispersion A; dissolve adenine in N,N-dimethylformamide to obtain solution B; dissolve 4,4'-biphenyldicarboxylic acid in N,N-dimethylformamide to obtain solution C; dissolve zinc acetate in N,N-dimethylformamide to obtain solution D; dissolve concentrated nitric acid in N,N-dimethylformamide to obtain solution E; under continuous stirring, add solutions B, C, and D to dispersion A in sequence. After mixing evenly, add a certain amount of water, and then add solution E. After stirring evenly, obtain the final mixture; the addition amount of the two-dimensional layered vanadium carbide / titanium dioxide heterojunction precursor in the final mixture is 2 mg mL -1 ; the addition amount of adenine in the final mixture is 1 mg mL -1 ; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixture is 4 mg mL -1 ; the addition amount of zinc acetate in the final mixture is 5 mg mL -1 ; the addition amount of concentrated nitric acid in the final mixture is 20 μL mL -1 ; the addition amount of water in the final mixture is 60 mg mL -1 ; the final mixture accounts for 80% of the volume of the reaction kettle. After stirring evenly, place the obtained mixture in the reaction kettle and carry out a solvothermal reaction at 130 °C for 24 hours.
[0057] (3) After the solvothermal reaction, it was cooled to room temperature, washed with N,N-dimethylformamide, and then dried in vacuum at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0058] Figure 5 This is the specific preparation process. The morphology of the prepared ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction was analyzed by scanning electron microscopy
[0059] ( Figure 6 ), and its layered two-dimensional structure can be seen.
[0060] The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components was made into a working electrode according to the method provided by the present invention and corresponding performance tests were carried out: for the rechargeable aqueous zinc-ion battery, the electrolyte was 3M zinc trifluoromethanesulfonate, and at 100 mA g -1 During charge and discharge, the specific capacity was higher than 237 mAh g -1 ; at 5000 mA g -1 After 3000 cycles of charge and discharge, the capacity retention rate was greater than 82%; for the rechargeable sodium metal battery, the electrolyte was 1M NaPF6 in EC:DEC (volume ratio 1:1), and at 20 mA g -1 During charge and discharge, the specific capacity was higher than 221 mAh g -1 ; at 1000 mA g -1 After 3000 cycles of charge and discharge, the capacity retention rate was greater than 93%.
[0061] Example 4
[0062] The preparation method of the ternary two-dimensional layered heterojunction in this example is as follows:
[0063] (1) Take V2ZnC and anhydrous copper chloride with a molar ratio of 1:5, mix them evenly, put them into a porcelain boat and place it in a tubular furnace. Under the protection of inert gas argon, heat-treat at 600 °C for 8 hours at a heating rate of 6 °C min -1 , and then cool to room temperature and perform centrifugal washing. The product was dried in vacuum at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface chlorine end groups).
[0064] (2) The two-dimensional layered V8C7 / V2O3 heterojunction was uniformly dispersed in N,N-dimethylformamide to obtain dispersion A; adenine was dissolved in N,N-dimethylformamide to obtain solution B; 4,4'-biphenyldicarboxylic acid was dissolved in N,N-dimethylformamide to obtain solution C; zinc acetate was dissolved in N,N-dimethylformamide to obtain solution D; concentrated nitric acid was dissolved in N,N-dimethylformamide to obtain solution E; under continuous stirring, solutions B, C, and D were successively added to dispersion A, and after mixing evenly, a certain amount of water was added, and then solution E was added. After stirring evenly, the final mixed solution was obtained; the addition amount of the two-dimensional layered vanadium carbide / vanadium trioxide heterojunction precursor in the final mixed solution was 5 mg mL -1 ; the addition amount of adenine in the final mixed solution was 1 mg mL -1 ; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixed solution was 5 mg mL -1 ; the addition amount of zinc acetate in the final mixed solution was 7 mg mL -1 ; the addition amount of concentrated nitric acid in the final mixed solution was 16 μL mL -1 ; the addition amount of water in the final mixed solution was 65 mg mL -1 ; the final mixed solution accounted for 75% of the volume of the reaction kettle. After stirring evenly, the obtained mixed solution was placed in the reaction kettle and subjected to solvothermal reaction at 140 °C for 8 hours.
[0065] (3) After the solvothermal reaction was completed, it was cooled to room temperature, washed with N,N-dimethylformamide, and then vacuum dried at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0066] The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components was made into a working electrode according to the method provided by the present invention and subjected to corresponding performance tests: for the rechargeable aqueous zinc-ion battery, the electrolyte was 3 M zinc trifluoromethanesulfonate, and at 100 mA g -1 during charge and discharge, the specific capacity was higher than 233 mAh g -1 ; at 5000 mA g -1 after 3000 cycles of charge and discharge, the capacity retention rate was greater than 82%; for the rechargeable sodium metal battery, the electrolyte was 1 M NaPF6 in EC:DEC (volume ratio 1:1), and at 20 mA g -1 during charge and discharge, the specific capacity was higher than 218 mAh g -1 ; at 1000 mA g -1 after 3000 cycles of charge and discharge, the capacity retention rate was greater than 91%.
[0067] Example 5
[0068] The preparation method of the ternary two-dimensional layered heterojunction in this embodiment is as follows:
[0069] (1) Take V2GeC, anhydrous copper chloride, and anhydrous copper bromide with a molar ratio of 1:2.5:2.5. After mixing evenly, put them into a porcelain boat and place it in a tube furnace. Under the protection of inert gas nitrogen, heat-treat at 550 °C at a heating rate of 5 °C / min for 15 hours, and then cool to room temperature and perform centrifugal washing. The product is vacuum-dried at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface chlorine and bromine end groups). -1 The heating rate is 5 °C / min, and the heat treatment is carried out at 550 °C for 15 hours, followed by cooling to room temperature and centrifugal washing. The product is vacuum-dried at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface chlorine and bromine end groups).
[0070] (2) Uniformly disperse the two-dimensional layered V8C7 / V2O3 heterojunction as a precursor into N,N-dimethylformamide to obtain dispersion A; dissolve adenine in N,N-dimethylformamide to obtain solution B; dissolve 4,4'-biphenyldicarboxylic acid in N,N-dimethylformamide to obtain solution C; dissolve zinc acetate in N,N-dimethylformamide to obtain solution D; dissolve concentrated nitric acid in N,N-dimethylformamide to obtain solution E; under continuous stirring, sequentially add solutions B, C, and D to dispersion A. After mixing evenly, add a certain amount of water, and then add solution E. After stirring evenly, obtain the final mixed solution; the addition amount of the two-dimensional vanadium carbide / titanium dioxide heterojunction precursor in the final mixed solution is 4.9 mg / mL; the addition amount of adenine in the final mixed solution is 1.1 mg / mL; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixed solution is 3.7 mg / mL; the addition amount of zinc acetate in the final mixed solution is 4.5 mg / mL; the addition amount of concentrated nitric acid in the final mixed solution is 12.5 μL / mL; the addition amount of water in the final mixed solution is 53.8 mg / mL; the final mixed solution accounts for 78% of the volume of the reaction kettle. After stirring evenly, place the obtained mixed solution in the reaction kettle and carry out a solvothermal reaction at 125 °C for 28 hours. -1 The addition amount of adenine in the final mixed solution is 1.1 mg / mL -1 The addition amount of 4,4'-biphenyldicarboxylic acid in the final mixed solution is 3.7 mg / mL -1 The addition amount of zinc acetate in the final mixed solution is 4.5 mg / mL -1 The addition amount of concentrated nitric acid in the final mixed solution is 12.5 μL / mL -1 The addition amount of water in the final mixed solution is 53.8 mg / mL -1 The final mixed solution accounts for 78% of the volume of the reaction kettle. After stirring evenly, place the obtained mixed solution in the reaction kettle and carry out a solvothermal reaction at 125 °C for 28 hours.
[0071] (3) After the solvothermal reaction is completed, cool to room temperature, wash with N,N-dimethylformamide, and then vacuum-dry at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0072] Figure 7This is the specific preparation process. The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components is made into a working electrode according to the method provided by the present invention and corresponding performance tests are carried out: for the rechargeable aqueous zinc-ion battery, the electrolyte is 3M zinc trifluoromethanesulfonate, at 100 mA g -1 During charge and discharge, the specific capacity is higher than 232 mAh g -1 ; at 5000 mA g -1 After 3000 cycles of charge and discharge, the capacity retention rate is greater than 83%; for the rechargeable sodium metal battery, the electrolyte is 1M NaPF6 in EC:DEC (volume ratio 1:1), at 20 mA g -1 During charge and discharge, the specific capacity is higher than 224 mAh g -1 ; at 1000 mA g -1 After 3000 cycles of charge and discharge, the capacity retention rate is greater than 93%.
[0073] Example 6
[0074] The preparation method of the ternary two-dimensional layered heterojunction in this example is as follows:
[0075] (1) Take V2InC, anhydrous copper chloride and anhydrous cuprous iodide with a molar ratio of 1:2.5:3.5, mix them evenly, put them into a porcelain boat and place it in a tube furnace. Under the protection of inert gas argon, heat-treat at 720 °C for 4 hours at a heating rate of 5 °C min -1 , and then cool to room temperature and perform centrifugal washing. The product is vacuum-dried at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface chlorine and iodine end groups).
[0076] (2) Uniformly disperse the two-dimensional layered V8C7 / V2O3 heterojunction as a precursor into N,N-dimethylformamide to obtain dispersion A; dissolve adenine in N,N-dimethylformamide to obtain solution B; dissolve 4,4'-biphenyldicarboxylic acid in N,N-dimethylformamide to obtain solution C; dissolve zinc acetate in N,N-dimethylformamide to obtain solution D; dissolve concentrated nitric acid in N,N-dimethylformamide to obtain solution E; under continuous stirring, sequentially add solutions B, C and D to dispersion A, mix evenly, add a certain amount of water, and then add solution E, and stir evenly to obtain the final mixture; the addition amount of the two-dimensional vanadium carbide / vanadium trioxide heterojunction precursor in the final mixture is 16 mg mL -1 ; the addition amount of adenine in the final mixture is 1 mg mL -1 ; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixture is 4.1 mg mL -1 ; the addition amount of zinc acetate in the final mixture is 5.2 mg mL-1 ; The addition amount of concentrated nitric acid in the final mixture is 16 μL / mL -1 ; The addition amount of water in the final mixture is 46 mg / mL -1 ; The final mixture accounts for 82% of the volume of the reaction kettle. After stirring evenly, the obtained mixture is placed in the reaction kettle, and a solvothermal reaction is carried out at 140 °C for 30 hours.
[0077] (3) After the solvothermal reaction is completed, it is cooled to room temperature, washed with N,N-dimethylformamide, and then dried in vacuum at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0078] The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components is made into a working electrode according to the method provided by the present invention and corresponding performance tests are carried out: for a rechargeable aqueous zinc-ion battery, the electrolyte is a 2 M aqueous solution of zinc sulfate, and at 100 mA / g -1 During charging and discharging, the specific capacity is higher than 229 mAh / g -1 ; At 5000 mA / g -1 After 3000 cycles of charging and discharging, the capacity retention rate is greater than 81%; for a rechargeable sodium metal battery, the electrolyte is 1 M NaClO4 in EC:DEC (volume ratio 1:1), and at 20 mA / g -1 During charging and discharging, the specific capacity is higher than 218 mAh / g -1 ; At 1000 mA / g -1 After 3000 cycles of charging and discharging, the capacity retention rate is greater than 91%.
[0079] Example 7
[0080] The preparation method of the ternary two-dimensional layered heterojunction in this example is as follows:
[0081] (1) Take V4AlC3, anhydrous copper bromide, and anhydrous copper iodide with a molar ratio of 1:2:2. After mixing evenly, put them into a porcelain boat and place it in a tubular furnace. Under the protection of an inert gas, nitrogen, heat-treat at 580 °C for 10 hours at a heating rate of 2 °C / min -1 , and then cool to room temperature and carry out centrifugal washing. The product is dried in vacuum at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface bromine and iodine end groups).
[0082] (2) The two-dimensional layered V8C7 / V2O3 heterojunction is uniformly dispersed in N,N-dimethylformamide to obtain dispersion A; adenine is dissolved in N,N-dimethylformamide to obtain solution B; 4,4'-biphenyldicarboxylic acid is dissolved in N,N-dimethylformamide to obtain solution C; zinc acetate is dissolved in N,N-dimethylformamide to obtain solution D; concentrated nitric acid is dissolved in N,N-dimethylformamide to obtain solution E; under continuous stirring, solutions B, C, and D are successively added to dispersion A. After mixing evenly, a certain amount of water is added, and then solution E is added. After stirring evenly, the final mixed solution is obtained; the addition amount of the two-dimensional layered vanadium carbide / vanadium trioxide heterojunction precursor in the final mixed solution is 20 mg mL -1 ; the addition amount of adenine in the final mixed solution is 0.9 mg mL -1 ; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixed solution is 3.7 mg mL -1 ; the addition amount of zinc acetate in the final mixed solution is 4.9 mg mL -1 ; the addition amount of concentrated nitric acid in the final mixed solution is 16 μL mL -1 ; the addition amount of water in the final mixed solution is 88 mg mL -1 ; the final mixed solution accounts for 81% of the volume of the reaction kettle. After stirring evenly, the obtained mixed solution is placed in the reaction kettle and subjected to solvothermal reaction at 160 °C for 15 hours.
[0083] (3) After the solvothermal reaction is completed, it is cooled to room temperature, washed with N,N-dimethylformamide, and then dried in vacuum at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0084] The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components is made into a working electrode according to the method provided by the present invention and subjected to corresponding performance tests: for the rechargeable aqueous zinc-ion battery, the electrolyte is 2 M aqueous zinc sulfate solution. During charging and discharging at 100 mA g -1 , the specific capacity is higher than 228 mAh g -1 ; during charging and discharging at 5000 mA g -1 , the capacity retention rate after 3000 cycles is greater than 82%; for the rechargeable sodium metal battery, the electrolyte is 1 M NaClO4 in EC:DEC (volume ratio 1:1). During charging and discharging at 20 mA g -1 , the specific capacity is higher than 222 mAh g -1 ; during charging and discharging at 1000 mA g -1 , the capacity retention rate after 3000 cycles is greater than 95%.
[0085] Example 8
[0086] The preparation method of the ternary two-dimensional layered heterojunction in this embodiment is as follows:
[0087] (1) Take V2Al with a molar ratio of 1:2.5 0.5 Ga 0.5 C and anhydrous copper chloride. After mixing evenly, put them into a porcelain boat and place it in a tubular furnace. Under the protection of inert gas nitrogen, heat-treat at 470 °C at a heating rate of 5 °C / min -1 for 10 hours, then cool to room temperature and perform centrifugal washing. The product is vacuum-dried at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface chlorine end groups).
[0088] (2) Uniformly disperse the two-dimensional layered V8C7 / V2O3 heterojunction as a precursor into N,N-dimethylformamide to obtain dispersion A; dissolve adenine in N,N-dimethylformamide to obtain solution B; dissolve 4,4'-biphenyldicarboxylic acid in N,N-dimethylformamide to obtain solution C; dissolve zinc acetate in N,N-dimethylformamide to obtain solution D; dissolve concentrated nitric acid in N,N-dimethylformamide to obtain solution E; under continuous stirring, sequentially add solutions B, C, and D to dispersion A. After mixing evenly, add a certain amount of water, and then add solution E. After stirring evenly, obtain the final mixed solution; the addition amount of the two-dimensional vanadium carbide / titanium trioxide heterojunction precursor in the final mixed solution is 13 mg / mL -1 ; the addition amount of adenine in the final mixed solution is 0.8 mg / mL -1 ; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixed solution is 5 mg / mL -1 ; the addition amount of zinc acetate in the final mixed solution is 7 mg / mL -1 ; the addition amount of concentrated nitric acid in the final mixed solution is 17 μL / mL -1 ; the addition amount of water in the final mixed solution is 66 mg / mL -1 ; the final mixed solution accounts for 77% of the volume of the reaction kettle. After stirring evenly, place the obtained mixed solution in the reaction kettle and perform a solvothermal reaction at 170 °C for 13 hours.
[0089] (3) After the solvothermal reaction is completed, cool to room temperature, wash with N,N-dimethylformamide, and then vacuum-dry at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0090] Figure 8This is the specific preparation process. The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components is made into a working electrode according to the method provided by the present invention and corresponding performance tests are carried out: for the rechargeable aqueous zinc-ion battery, the electrolyte is 2M zinc sulfate aqueous solution, at 100mA g -1 During charge and discharge, the specific capacity is higher than 224mAh g -1 ; at 5000mA g -1 After 3000 cycles of charge and discharge, the capacity retention rate is greater than 81%; for the rechargeable sodium metal battery, the electrolyte is 1M NaClO4 in EC:DEC (volume ratio 1:1), at 20mA g -1 During charge and discharge, the specific capacity is higher than 219mAhg -1 ; at 1000mA g -1 After 3000 cycles of charge and discharge, the capacity retention rate is greater than 91%.
[0091] Example 9
[0092] The preparation method of the ternary two-dimensional layered heterojunction in this example is as follows:
[0093] (1) Take V2Al 0.3 Ga 0.7 C, anhydrous copper chloride and anhydrous copper bromide with a molar ratio of 1:1:3, mix them evenly, put them into a porcelain boat and place it in a tube furnace. Under the protection of inert gas nitrogen, heat-treat at 560°C for 8 hours at a heating rate of 5°C min -1 , then cool to room temperature and perform centrifugal washing. The product is vacuum-dried at 80°C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface chlorine and bromine end groups).
[0094] (2) Uniformly disperse the two-dimensional layered V8C7 / V2O3 heterojunction as a precursor into N,N-dimethylformamide to obtain dispersion A; dissolve adenine in N,N-dimethylformamide to obtain solution B; dissolve 4,4'-biphenyldicarboxylic acid in N,N-dimethylformamide to obtain solution C; dissolve zinc acetate in N,N-dimethylformamide to obtain solution D; dissolve concentrated nitric acid in N,N-dimethylformamide to obtain solution E; under continuous stirring, sequentially add solutions B, C and D to dispersion A, mix evenly, add a certain amount of water, then add solution E, and stir evenly to obtain the final mixture; the addition amount of the two-dimensional vanadium carbide / titanium dioxide heterojunction precursor in the final mixture is 5mg mL -1 ; the addition amount of adenine in the final mixture is 0.5mg mL -1 ; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixture is 6mg mL -1; The addition amount of zinc acetate in the final mixture is 8 mg / mL -1 ; The addition amount of concentrated nitric acid in the final mixture is 16 μL / mL -1 ; The addition amount of water in the final mixture is 75 mg / mL -1 ; The final mixture accounts for 80% of the volume of the reaction kettle. After stirring evenly, the obtained mixture is placed in the reaction kettle, and a solvothermal reaction is carried out at 125 °C for 32 hours.
[0095] (3) After the solvothermal reaction is completed, it is cooled to room temperature, washed with N,N-dimethylformamide, and then dried in vacuum at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0096] The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components is made into a working electrode according to the method provided by the present invention and corresponding performance tests are carried out: for a rechargeable aqueous zinc-ion battery, the electrolyte is a 2 M aqueous solution of zinc sulfate, at 100 mA / g -1 During charging and discharging, the specific capacity is higher than 229 mAh / g -1 ; At 5000 mA / g -1 After 3000 cycles of charging and discharging, the capacity retention rate is greater than 81%; for a rechargeable sodium metal battery, the electrolyte is 1 M NaClO4 in EC:DEC (volume ratio 1:1), at 20 mA / g -1 During charging and discharging, the specific capacity is higher than 223 mAh / g -1 ; At 1000 mA / g -1 After 3000 cycles of charging and discharging, the capacity retention rate is greater than 92%.
[0097] Example 10
[0098] The preparation method of the ternary two-dimensional layered heterojunction in this example is as follows:
[0099] (1) Take V2In with a molar ratio of 1:2:3.5 0.1 Ga 0.9 C, anhydrous copper bromide, and anhydrous copper iodide. After mixing evenly, put them into a porcelain boat and place it in a tubular furnace. Under the protection of inert gas nitrogen, at a heating rate of 2 °C / min -1 Heat-treat at 480 °C for 11 hours, and then cool to room temperature and carry out centrifugal washing. The product is vacuum-dried at 80 °C for 10 hours to obtain a two-dimensional layered V8C7 / V2O3 heterojunction (containing a small amount of surface bromine and iodine end groups).
[0100] (2) The two-dimensional layered V8C7 / V2O3 heterojunction was uniformly dispersed in N,N-dimethylformamide to obtain dispersion A; adenine was dissolved in N,N-dimethylformamide to obtain solution B; 4,4'-biphenyldicarboxylic acid was dissolved in N,N-dimethylformamide to obtain solution C; zinc acetate was dissolved in N,N-dimethylformamide to obtain solution D; concentrated nitric acid was dissolved in N,N-dimethylformamide to obtain solution E; under continuous stirring, solutions B, C, and D were successively added to dispersion A, and after mixing evenly, a certain amount of water was added, and then solution E was added. After stirring evenly, the final mixed solution was obtained; the addition amount of the two-dimensional layered vanadium carbide / vanadium trioxide heterojunction precursor in the final mixed solution was 1.1 mg mL -1 ; the addition amount of adenine in the final mixed solution was 1.5 mg mL -1 ; the addition amount of 4,4'-biphenyldicarboxylic acid in the final mixed solution was 3.5 mg mL -1 ; the addition amount of zinc acetate in the final mixed solution was 2.8 mg mL -1 ; the addition amount of concentrated nitric acid in the final mixed solution was 12.5 μL mL -1 ; the addition amount of water in the final mixed solution was 40.5 mg mL -1 ; the final mixed solution accounted for 85% of the volume of the reaction kettle. After stirring evenly, the obtained mixed solution was placed in the reaction kettle and reacted at 120 °C for 45 hours.
[0101] (3) After the solvothermal reaction was completed and cooled to room temperature, it was washed with N,N-dimethylformamide, and then vacuum dried at 80 °C for 12 hours to obtain a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
[0102] The obtained ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components was made into a working electrode according to the method provided by the present invention and corresponding performance tests were carried out: for the rechargeable aqueous zinc-ion battery, the electrolyte was 2 M aqueous zinc sulfate solution. When charging and discharging at 100 mA g -1 , the specific capacity was higher than 231 mAh g -1 ; when charging and discharging at 5000 mA g -1 , the capacity retention rate after 3000 cycles was greater than 82%; for the rechargeable sodium metal battery, the electrolyte was 1 M NaClO4 in EC:DEC (volume ratio 1:1). When charging and discharging at 20 mA g -1 , the specific capacity was higher than 223 mAh g -1 ; when charging and discharging at 1000 mA g -1 , the capacity retention rate after 3000 cycles was greater than 92%.
[0103] The present invention can achieve the controllable preparation of ternary two-dimensional layered heterojunctions. Using vanadium-based MAX phases and halide salts as precursors, a two-dimensional layered vanadium carbide / vanadium trioxide heterojunction is prepared through a molten solid-liquid reaction. Then, using the prepared two-dimensional layered vanadium carbide / vanadium trioxide heterojunction as a precursor, zinc acetate as a metal ion source, adenine and 4,4'-biphenyldicarboxylic acid as organic ligands, concentrated nitric acid as a pore structure regulator, and water and N,N-dimethylformamide as a mixed solvent, a ternary two-dimensional vanadium carbide / vanadium trioxide / bio-metal-organic framework (Bio-MOF-1) layered heterojunction with three components is obtained through a solvothermal reaction, increasing the types of ternary two-dimensional layered heterojunctions that can be prepared. Moreover, the obtained ternary two-dimensional layered heterojunction can be used as a cathode material for rechargeable aqueous zinc-ion batteries and rechargeable sodium metal batteries. This is of great significance for promoting the synthesis of novel functional ternary two-dimensional layered heterojunctions and the development of high-performance rechargeable aqueous zinc-ion batteries and rechargeable sodium metal batteries.
Claims
1. A method for preparing a ternary two-dimensional layered heterojunction, characterized in that: Using vanadium-based MAX phase and halide salts as precursors, a two-dimensional layered vanadium carbide / vanadium trioxide heterojunction is prepared through a molten solid-liquid reaction. Then, using the prepared two-dimensional layered vanadium carbide / vanadium trioxide heterojunction as a precursor, zinc acetate as a metal ion source, adenine and 4,4'-biphenyldicarboxylic acid as organic ligands, concentrated nitric acid as a pore structure regulator, and water and N,N-dimethylformamide as a mixed solvent, a ternary two-dimensional vanadium carbide / vanadium trioxide / bio-metal-organic framework layered heterojunction with three components is obtained through a solvothermal reaction.
2. The preparation method of the ternary two-dimensional layered heterojunction according to claim 1, characterized in that, It includes the following steps: (1) Take a certain molar ratio of vanadium-based MAX phase and halide salts, mix them evenly, put them into a porcelain boat and place it in a tubular furnace, and conduct heat treatment under the protection of an inert gas to prepare a two-dimensional layered vanadium carbide / vanadium trioxide heterojunction through a molten solid-liquid reaction; (2) Uniformly disperse the prepared two-dimensional layered vanadium carbide / vanadium trioxide heterojunction precursor in N,N-dimethylformamide to obtain dispersion A; dissolve adenine in N,N-dimethylformamide to obtain solution B; dissolve 4,4'-biphenyldicarboxylic acid in N,N-dimethylformamide to obtain solution C; dissolve zinc acetate in N,N-dimethylformamide to obtain solution D; dissolve concentrated nitric acid in N,N-dimethylformamide to obtain solution E; under continuous stirring, sequentially add solutions B, C, and D to dispersion A, mix evenly, add a certain amount of water, then add solution E, stir evenly to obtain the final mixture, and place the obtained final mixture in a reaction kettle for solvothermal reaction; (3) After the solvothermal reaction is completed, cool it to room temperature, wash it with N,N-dimethylformamide, and then dry it to obtain a ternary two-dimensional vanadium carbide / vanadium trioxide / bio-metal-organic framework layered heterojunction with three components.
3. The preparation method of the ternary two-dimensional layered heterojunction according to claim 1 or 2, characterized in that: The vanadium-based MAX phase is one of V2AlC, V2GaC, V2SnC, V2ZnC, V2GeC, V2InC, V4AlC3, V2Al 0.5 Ga 0.5 C, V2Al 0.3 Ga 0.7 C, V2Al 0.1 Ga 0.9 C, V2Sn 0.1 Ga 0.9 C, V2Zn 0.1 Ga 0.9 C, V2Ge 0.1 Ga 0.9 C, V2In 0.1 Ga 0.9 C; the halide salt is one or two of anhydrous copper chloride, anhydrous copper bromide, and anhydrous cuprous iodide.
4. The preparation method of the ternary two-dimensional layered heterojunction according to claim 2, wherein: When preparing a two-dimensional layered vanadium carbide / vanadium trioxide heterojunction by a molten solid-liquid reaction, the molar ratio of the vanadium-based MAX phase to the halide salt in the porcelain boat is 1:(2.5-7.5), and the heating rate of the heat treatment is 2 °C min -1 ~10 °C min -1 , the heat treatment temperature is 450 °C - 850 °C, the heat treatment time is 1 - 12 hours, and the reaction inert gas carrier gas is nitrogen or argon.
5. The preparation method of the ternary two-dimensional layered heterojunction according to claim 2, wherein: In the step (2), based on the volume of the final mixture, the addition amount of the two-dimensional layered vanadium carbide / vanadium trioxide heterojunction precursor is 0.1-20 mg / mL -1 ; the addition amount of adenine is 0.5-2 mg / mL -1 ; the dosage of 4,4'-biphenyldicarboxylic acid is 3-6 mg / mL -1 ; the addition amount of zinc acetate is 2-10 mg / mL -1 ; the addition amount of concentrated nitric acid is 10-30 μL / mL -1 ; the addition amount of water is 30-150 mg / mL -1 ; the final mixture accounts for 70%-85% of the volume of the reaction kettle.
6. The preparation method of the ternary two-dimensional layered heterojunction according to claim 2, characterized in that: In step (3), the solvothermal reaction temperature is 110°C to 180°C, and the solvothermal reaction time is 12 to 48 hours.
7. The preparation method of the ternary two-dimensional layered heterojunction according to claim 2, characterized in that: The two-dimensional layered vanadium carbide / vanadium trioxide heterojunction in step (1) is a V8C7 / V2O3 heterojunction; the ternary two-dimensional vanadium carbide / vanadium trioxide / bio-metal-organic framework layered heterojunction with three components in step (3) is a ternary two-dimensional V8C7 / V2O3 / Bio-MOF-1 layered heterojunction with three components.
8. Use of the ternary two-dimensional vanadium carbide / vanadium trioxide / biological metal-organic framework layered heterojunction having three components prepared by the preparation method according to any one of claims 1-7 as a positive electrode material for a rechargeable aqueous zinc-ion battery, characterized in that: When used as the cathode material of a rechargeable zinc-ion battery, the ternary two-dimensional vanadium carbide / vanadium trioxide / biological metal-organic framework layered heterojunction with three components has a specific capacity higher than 220 mAh g -1 , excellent rate performance, and good cycling performance.
9. Use of a ternary two-dimensional vanadium carbide / vanadium trioxide / biological metal-organic framework layered heterojunction having three components prepared by the preparation method according to any one of claims 1-7 as a cathode material for a rechargeable sodium metal battery, characterized in that: When used as the cathode material of a rechargeable sodium metal battery, the ternary two-dimensional vanadium carbide / vanadium sesquioxide / biological metal-organic framework layered heterojunction with three components has a specific capacity higher than 200 mAh g -1 , excellent rate performance, and good cycling performance.