Preparation method and application of nitrogen heterocyclic compound and aqueous multivalent metal ion battery

Abstract

The invention provides a preparation method and application of a nitrogen heterocyclic compound and a water system multivalent metal ion battery, and the nitrogen heterocyclic compound is prepared according to the molar ratio of ninhydrin to a diamino compound of 1: (1-1.2). According to the preparation method and application of the nitrogen heterocyclic compound and the aqueous multivalent metal ion battery, the preparation method is simple, convenient, low in cost, mild in reaction condition and suitable for the actual production process.

Description

Technical Field

[0001] The present invention relates to the field of aqueous batteries, and in particular to a preparation method and application of a nitrogen heterocyclic compound, and an aqueous multivalent metal ion battery. Background Art

[0002] Lithium-ion batteries are widely used in daily life due to their high energy, high battery voltage, and wide operating temperature range. However, lithium-ion batteries use organic solvents as electrolytes, which are flammable and volatile, bringing serious safety issues.

[0003] Iron and zinc have similar activities, both have high theoretical specific capacities, and are very abundant resources. With advantages such as low redox potential, they have become one of the hot topics in the field of aqueous energy storage. As an indispensable part of aqueous metal batteries, positive electrode materials are directly related to the performance of batteries. Organic positive electrode materials have become one of the ideal choices for aqueous multivalent metal battery electrode materials due to their low cost, environmental friendliness, and easy structural regulation.

[0004] However, for organic cathode materials, due to their own solubility and other issues, their lifespan is limited and their rate performance is insufficient. Therefore, it is a huge challenge to synthesize organic cathode materials with high capacity, long cycle life and high rate performance through reasonable molecular structure design. It is of great significance to develop a reasonable structural design strategy to achieve high-capacity and high-stability organic cathode materials for aqueous zinc-ion batteries.

[0005] In the current study, compared with the more common organic cathode materials in aqueous zinc-ion batteries, there are few cathode materials reported for aqueous iron-ion batteries. The most common ones are MnO 2 、V 2 O 5 There are inorganic cathode materials such as ferrous metals and Prussian blue analogs, but there are almost no organic cathode materials that are more abundant in resources and more environmentally friendly. It is a relatively blank field, which limits the further development of aqueous iron-ion batteries. Summary of the invention

[0006] The purpose of the present invention is to provide a preparation method, application and aqueous multivalent metal ion battery of a nitrogen heterocyclic compound. The preparation process is simple and the reaction conditions are mild, which is suitable for industrial production.

[0007] To achieve the above object, the present invention provides the use of nitrogen heterocyclic compounds in the preparation of positive electrode materials for aqueous multivalent metal ion batteries.

[0008] Preferably, the nitrogen heterocyclic compound structural formula used is as follows: Among them, when R1 When H, R 2 Also H, when R 1 When N, R 2 It is a benzene ring.

[0009] Preferably, the aqueous multivalent metal ion batteries include aqueous zinc ion batteries, aqueous iron ion batteries, aqueous aluminum ion batteries, aqueous magnesium ion batteries, and calcium ion batteries.

[0010] Preferably, the preparation of the positive electrode sheet: Nitrogen heterocyclic compound: Ketjen black: PVDF = 6:3:1 or 7:2:1 ratio; The resulting mixture is then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry is uniformly coated on the positive electrode current collector; Subsequently, it was vacuum dried at 60~100℃ for 12~24 hours and then punched into electrode sheets with a diameter of 10 mm using a slicer.

[0011] Preferably, the positive electrode current collector includes one or more of stainless steel mesh, titanium mesh, aluminum foil, nickel mesh, copper foil, carbon fiber, nickel foam, and graphene.

[0012] An aqueous multivalent metal ion battery prepared according to the application.

[0013] A method for preparing a nitrogen heterocyclic compound comprises mixing a diamino compound and ninhydrin at a molar ratio of 1:1-1.2 and reacting them under heating reflux conditions.

[0014] Preferably, the heating reflux temperature is 40-90° C. and the time is 8-10 h.

[0015] Preferably, the diamino compound includes one or more of diaminonaphthoquinone, diaminophenazine and diaminonaphthalene.

[0016] Preferably, the method further comprises washing and drying the obtained material in sequence; the organic solvent used for washing comprises ethanol and acetic acid; the drying temperature is 60-80° C. and the drying time is 6-12 h.

[0017] Therefore, the present invention adopts the above-mentioned preparation method, application, and aqueous multivalent metal ion battery of a nitrogen heterocyclic compound, and the technical effects are as follows: (1) The preparation method is simple, low cost, mild reaction conditions, and suitable for industrial production.

[0018] (2) In the nitrogen heterocyclic compound obtained by the preparation method provided by the present invention, the enlarged π conjugated structure can improve the attenuation problem faced by quinone small molecules that are easily soluble in electrolytes, and the stable skeleton can improve the cycle performance of the material. In addition, the dual-active center organic skeleton provides excellent capacity and rate performance, and the assembled aqueous zinc ion battery has been electrochemically tested at low temperature conditions of -20°C, and it is found that it has stable high capacity and good rate performance under low temperature conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the SEM image of the nitrogen heterocyclic compound obtained in Example 1; Figure 2 is the infrared spectrum of the nitrogen heterocyclic compound obtained in Example 1; Figure 3 The aqueous zinc ion battery assembled from the nitrogen heterocyclic compound obtained in Example 1 has a capacity of 0.1-60 Ag -1 Rate performance diagram at current density of ; Figure 4 This is a test diagram of the nitrogen heterocyclic compound obtained in Example 1 as the positive electrode of an aqueous zinc ion battery at -20°C; Figure 5 The aqueous iron ion battery assembled with the nitrogen heterocyclic compound obtained in Example 1 was -1 Cyclic performance diagram at current density of ; Figure 6 The aqueous zinc ion battery assembled from the nitrogen heterocyclic compound obtained in Example 2 has a 0.1-20Ag -1 Rate performance diagram at current density of ; Figure 7 The aqueous zinc ion battery assembled with the nitrogen heterocyclic compound obtained in Example 3 was -1 Cycling performance diagram at current density of . DETAILED DESCRIPTION

[0020] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.

[0021] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0022] The present invention has no particular limitation on the mixing process, and any method known to those skilled in the art may be used.

[0023] The drugs used in the present invention are shown in the following table:

[0024] In the present invention, no protective atmosphere is required, and the reaction can be directly carried out in the environment. In the present invention, in the reaction, the amino group in the quinone compound reacts with the carbonyl group in ninhydrin to form a carbon-nitrogen double bond, which expands the conjugated structure of the material and forms a more stable structure; at the same time, the types and number of active sites are increased, and the capacity is further improved.

[0025] During the performance test, aqueous zinc ion batteries and aqueous iron ion batteries were tested according to the following parameters: Aqueous zinc ion battery, the test temperature is from -20 degrees to room temperature 25 degrees, the electrolyte is zinc trifluoromethanesulfonate and ethylene glycol / zinc trifluoromethanesulfonate (4:6). The concentration of the electrolyte is 1 mol / L.

[0026] Aqueous iron ion batteries, based on Fe(CF 3 SO 3 ) 2 The electrolyte is glass fiber filter paper, the diaphragm is metal iron sheet, the positive electrode is titanium mesh, and the current collector is positive electrode material; and the mass ratio of the nitrogen heterocyclic compound, Ketjen black and polyvinylidene fluoride is preferably 7:2:1. The concentration of the electrolyte is 1 mol / L.

[0027] Example 1 Ninhydrin (0.178 g, 1 mmol) and diaminonaphthoquinone (0.18818 g, 1 mmol) were added to a three-necked round-bottom flask, and then 20 ml of acetic acid solution was slowly added, followed by heating under reflux for 10 h in an oil bath. The reaction mixture was then cooled to room temperature and filtered. Washed with ethanol several times. The obtained yellow-green solid was vacuum dried at 80 ° C for 12 h to obtain the target product. The reaction formula is as follows: Figure 1 The SEM image of the nitrogen heterocyclic compound obtained in Example 1 is shown in FIG. Figure 1 It can be seen that the obtained nitrogen heterocyclic compound exhibits a good crystalline structure with a size of 1-2 μm; Figure 2 The infrared spectrum of the nitrogen heterocyclic compound obtained in Example 1 is Figure 2 It can be seen that nitrogen heterocyclic compounds have a wavelength of 3300 cm -1 The characteristic peak of amino group disappeared, 1495cm -1 The sharp characteristic peak produced by the C=O bond indicates the successful synthesis of the compound.

[0028] The nitrogen heterocyclic compound obtained in Example 1 was used as the positive electrode active material to assemble an aqueous zinc ion battery and test its electrochemical performance. The assembly steps were as follows: The positive electrode active material, Ketjen black and polyvinylidene fluoride (PVDF) are mixed and ground in a mass ratio of 6:3:1; The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was coated on a stainless steel mesh; Subsequently, it was vacuum dried at 80 °C for 12 h and then punched into electrode sheets with a diameter of 10 mm using a slicer; With 1.0M Zn(CF 3 SO 3 ) 2 The electrolyte, glass fiber filter paper and metal zinc sheet are used as the diaphragm and the counter electrode are assembled into a CR2032 button battery. The charge and discharge potential setting range is 0.1~1.6V.

[0029] Figure 3 The aqueous zinc ion battery assembled from the nitrogen heterocyclic compound obtained in Example 1 has a capacity of 0.1-60 Ag -1 Rate performance diagram at current density of Figure 3 It can be seen that the nitrogen heterocyclic compound provided by the present invention has excellent rate performance; Figure 4 This is a test diagram of the nitrogen heterocyclic compound obtained in Example 1 as the positive electrode of an aqueous zinc ion battery at -20°C. -1 At a current density of 1.5 %, the discharge capacity can reach 192 mAhg -1 , and there is almost no capacity decay after 150 cycles. It can be seen that the low-temperature aqueous zinc ion battery assembled with the nitrogen heterocyclic compound obtained by the present invention has good low-temperature resistance and cycle life.

[0030] The nitrogen heterocyclic compound obtained in Example 1 was used as the positive electrode active material to assemble an aqueous iron ion battery and test its electrochemical performance. The assembly steps were as follows: The positive electrode active material, Ketjen black and polyvinylidene fluoride (PVDF) are mixed and ground in a mass ratio of 7:2:1; The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was evenly coated on a titanium mesh; Subsequently, it was vacuum dried at 80 °C for 12 h and then punched into electrode sheets with a diameter of 10 mm using a slicer; With 1M Fe(CF 3 SO 3 ) 2 The electrolyte, glass fiber filter paper and metal iron sheet are used as the diaphragm and the counter electrode are assembled into a CR2032 button battery. The charge and discharge potential setting range is 0.01-1.2V.

[0031] Figure 5The aqueous iron ion battery assembled with the nitrogen heterocyclic compound obtained in Example 1 was -1 Cyclic performance diagram at current density of Figure 5 It can be seen that the nitrogen heterocyclic compound provided by the present invention has 120mAhg -1 The invention has a high specific capacity and good cycle stability, and there is no obvious capacity decay after 50 cycles, which proves that the nitrogen heterocyclic compound provided by the present invention has excellent capacity and cycle life in aqueous iron ion batteries.

[0032] Example 2 Ninhydrin (0.178 g, 1 mmol) and diaminophenazine (0.21 g, 1 mmol) were added to a three-necked round-bottom flask, and then 50 ml of ethanol solution was slowly added and 2-3 drops of acetic acid solution were added to catalyze the reaction, and then heated under reflux in an oil bath for 3 h. After the reaction mixture was cooled to room temperature, the mixture was filtered. Washed with ethanol several times. The obtained red solid was vacuum dried at 80 ° C for 12 h to obtain the target product. The reaction formula is as follows: The nitrogen heterocyclic compound obtained in Example 2 was used as the positive electrode active material to assemble an aqueous zinc ion battery and test its electrochemical performance. The assembly steps were as follows: The positive electrode active material, Ketjen black and polyvinylidene fluoride (PVDF) are mixed and ground in a mass ratio of 6:3:1; The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was coated on a stainless steel mesh; Subsequently, it was vacuum dried at 80 °C for 12 h and then punched into electrode sheets with a diameter of 10 mm using a slicer; With 1.0M Zn(CF 3 SO 3 ) 2 As electrolyte, glass fiber filter paper as diaphragm, metal zinc sheet as counter electrode, assembled into CR2032 button battery; the charge and discharge potential setting range is 0.1~1.6V; Figure 6 The aqueous zinc ion battery assembled from the nitrogen heterocyclic compound obtained in Example 2 has a 0.1-20Ag -1 Rate performance diagram at current density of Figure 6 It can be seen that the nitrogen heterocyclic compound provided by the present invention has excellent rate performance.

[0033] Example 3 Ninhydrin (0.178 g, 1 mmol) and 2,3-diaminonaphthalene (0.1582 g, 1 mmol) were added to a three-necked round-bottom flask, and then 50 ml of ethanol solution was slowly added and 2-3 drops of acetic acid solution were added to catalyze the reaction, and then heated under reflux in an oil bath for 3 h. After the reaction mixture was cooled to room temperature, the mixture was filtered. Washed with ethanol several times. The obtained yellow solid was vacuum dried at 80 ° C for 12 h to obtain the target product. The reaction formula is as follows: The nitrogen heterocyclic compound obtained in Example 3 was used as the positive electrode active material to assemble an aqueous zinc ion battery and test its electrochemical performance. The assembly steps were as follows: The positive electrode active material, Ketjen black and polyvinylidene fluoride (PVDF) are mixed and ground in a mass ratio of 6:3:1; The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was coated on a stainless steel mesh; Subsequently, it was vacuum dried at 80 °C for 12 h and then punched into electrode sheets with a diameter of 10 mm using a slicer; With 1.0M Zn(CF 3 SO 3 ) 2 The electrolyte, glass fiber filter paper and metal zinc sheet are used as the diaphragm and the counter electrode are assembled into a CR2032 button battery. The charge and discharge potential setting range is 0.1~1.6V.

[0034] Figure 7 The aqueous zinc ion battery assembled with the nitrogen heterocyclic compound obtained in Example 3 was -1 Cyclic performance diagram under current density of Figure 7 It can be seen that the first cycle discharge capacity is 178 mAh g -1 , and has an obvious charging and discharging platform.

[0035] Therefore, the present invention adopts the preparation method, application, and aqueous multivalent metal ion battery of the above-mentioned nitrogen heterocyclic compound, the preparation process is simple, and the reaction conditions are mild, which is suitable for industrial production.

[0036] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. Application of nitrogen heterocyclic compounds in the preparation of positive electrode materials for aqueous multivalent metal ion batteries.

2. The use of the nitrogen heterocyclic compound according to claim 1 in preparing a positive electrode material for an aqueous multivalent metal ion battery, characterized in that: The structural formula of the nitrogen heterocyclic compound used is as follows: Among them, when R1 is H, R2 is also H, and when R1 is N, R2 is a benzene ring.

3. The use of the nitrogen heterocyclic compound according to claim 1 in preparing a positive electrode material for an aqueous multivalent metal ion battery, characterized in that: Aqueous multivalent metal ion batteries include aqueous zinc ion batteries, aqueous iron ion batteries, aqueous aluminum ion batteries, aqueous magnesium ion batteries, and calcium ion batteries.

4. The use of the nitrogen heterocyclic compound according to claim 1 in preparing a positive electrode material for an aqueous multivalent metal ion battery, characterized in that: Preparation of positive electrode: Nitrogen heterocyclic compound: Ketjen black: PVDF = 6:3:1 or 7:2:1 ratio; The resulting mixture is then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry is uniformly coated on the positive electrode current collector; Subsequently, it was vacuum dried at 60~100℃ for 12~24 hours and then punched into electrode sheets with a diameter of 10 mm using a slicer.

5. Use of the nitrogen heterocyclic compound according to claim 1 in preparing a positive electrode material for an aqueous multivalent metal ion battery, characterized in that: The positive electrode current collector includes one or more of stainless steel mesh, titanium mesh, aluminum foil, nickel mesh, copper foil, carbon fiber, nickel foam, and graphene.

6. An aqueous multivalent metal ion battery prepared by the application according to any one of claims 1 to 5.

7. A method for preparing a nitrogen heterocyclic compound, characterized in that: The method comprises mixing a diamino compound and ninhydrin in a molar ratio of 1:1-1.2 and reacting the mixture under heating reflux conditions.

8. The method for preparing a nitrogen heterocyclic compound according to claim 4, characterized in that: The heating reflux temperature is 40-90° C. and the time is 8-10 h.

9. The method for preparing a nitrogen heterocyclic compound according to claim 4, characterized in that: The diamino compound includes one or more of diaminonaphthoquinone, diaminophenazine and diaminonaphthalene.

10. The method for preparing a nitrogen heterocyclic compound according to claim 4, characterized in that: The method also includes washing and drying the obtained materials in sequence; the organic solvents used for washing include ethanol and acetic acid; the drying temperature is 60-80° C. and the drying time is 6-12 hours.

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