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

Abstract

The present invention provides a preparation method, application, and aqueous multivalent metal ion battery of a nitrogen heterocyclic compound. The nitrogen heterocyclic compound is prepared according to a molar ratio of ninhydrin to a diamino compound of 1:1 to 1.2. The present invention utilizes the preparation method, application, and aqueous multivalent metal ion battery of the aforementioned nitrogen heterocyclic compound. The preparation method is simple, low-cost, and employs mild reaction conditions, making it suitable for practical production processes.

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, they use organic solvents as electrolytes, which are flammable and volatile, posing serious safety concerns.

[0003] Iron and zinc have similar reactivity, both possess high theoretical specific capacities, and are abundant resources. Their advantages, such as low redox potential, have made them a hot topic in the field of aqueous energy storage. As an integral component of aqueous metal batteries, cathode materials directly impact battery performance. Organic cathode materials, due to their low cost, environmental friendliness, and easily tunable structure, are an ideal choice for electrode materials in aqueous multivalent metal batteries.

[0004] However, organic cathode materials suffer from inherent solubility issues, resulting in limited lifespans and insufficient rate performance. Therefore, synthesizing organic cathode materials with high capacity, long cycle life, and high rate performance through rational molecular structure design is a significant challenge. Developing a rational structural design strategy to achieve high-capacity and high-stability organic cathode materials for aqueous zinc-ion batteries is of great significance.

[0005] In current research, compared to the more common organic cathode materials used in aqueous zinc-ion batteries, few cathode materials have been reported for aqueous iron-ion batteries. Commonly used inorganic cathode materials include MnO₂, V₂O₅, and Prussian blue analogs. Organic cathode materials, which are more abundant in resources and more environmentally friendly, are virtually nonexistent. This represents a relatively unexplored area, limiting the further development of aqueous iron-ion batteries. Summary of the Invention

[0006] The present invention aims 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 objectives, 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:

[0009]

[0010] Among them, when R1 is H, R2 is also H, and when R1 is N, R2 is a benzene ring.

[0011] 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.

[0012] Preferably, the preparation of the positive electrode sheet:

[0013] Nitrogen heterocyclic compound: Ketjen black: PVDF = 6:3:1 or 7:2:1 ratio;

[0014] The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was evenly coated on the positive electrode current collector;

[0015] Subsequently, the film was vacuum dried at 60–100 °C for 12–24 h and then punched into electrode sheets with a diameter of 10 mm using a microtome.

[0016] 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.

[0017] An aqueous multivalent metal ion battery prepared according to the application.

[0018] 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 the mixture under heating and reflux conditions.

[0019] Preferably, the heating reflux temperature is 40-90° C. and the time is 8-10 h.

[0020] Preferably, the diamino compound includes one or more of diaminonaphthoquinone, diaminophenazine, and diaminonaphthalene.

[0021] 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.

[0022] 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:

[0023] (1) The preparation method is simple, low cost, mild reaction conditions, and suitable for industrial production.

[0024] (2) In the nitrogen heterocyclic compound obtained by the preparation method provided by the present invention, the expanded π-conjugated structure can improve the attenuation problem faced by quinone small molecules due to their easy solubility in electrolytes, while the stable skeleton can improve the cycling performance of the material. In addition, the dual-active center organic skeleton provides excellent capacity and rate performance. The assembled aqueous zinc ion battery was electrochemically tested at low temperature conditions of -20°C and found to have stable high capacity and good rate performance under low temperature conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the SEM image of the nitrogen heterocyclic compound obtained in Example 1;

[0026] Figure 2 is the infrared spectrum of the nitrogen heterocyclic compound obtained in Example 1;

[0027] Figure 3 The aqueous zinc ion battery obtained by assembling the nitrogen heterocyclic compound obtained in Example 1 has a 0.1-60 Ag -1 Rate performance diagram at current density;

[0028] Figure 4 This is a test chart of the nitrogen heterocyclic compound obtained in Example 1 as the positive electrode of an aqueous zinc ion battery at -20°C;

[0029] Figure 5 The aqueous iron ion battery assembled with the nitrogen heterocyclic compound obtained in Example 1 was -1 Cycling performance diagram at current density of ;

[0030] 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;

[0031] Figure 7 The aqueous zinc ion battery assembled with the nitrogen heterocyclic compound obtained in Example 3 was tested at 0.1 A·g -1 Cycling performance diagram at current density of . DETAILED DESCRIPTION

[0032] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments.

[0033] Unless otherwise defined, technical or scientific terms used in the present invention shall have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.

[0034] The present invention has no particular limitation on the mixing process, and any method known to those skilled in the art may be used.

[0035] The medicines used in the present invention are shown in the following table:

[0036]

[0037] In the present invention, a protective atmosphere is not required; the reaction can be carried out directly in the environment. In the present invention, 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. It also increases the types and number of active sites, further improving the capacity.

[0038] During the performance test, aqueous zinc-ion batteries and aqueous iron-ion batteries were tested according to the following parameters:

[0039] Aqueous zinc-ion batteries were tested at temperatures between -20°C and room temperature (25°C). The electrolyte consisted of zinc trifluoromethanesulfonate and ethylene glycol / zinc trifluoromethanesulfonate (4:6). The electrolyte concentration was 1 mol / L.

[0040] An aqueous iron ion battery comprises Fe(CF3SO3)2 as the electrolyte, glass fiber filter paper as the separator, a metal iron sheet as the counter electrode, and a titanium mesh as the current collector of the positive electrode material. 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.

[0041] Example 1

[0042] Ninhydrin (0.178 g, 1 mmol) and diaminonaphthoquinone (0.18818 g, 1 mmol) were added to a three-necked round-bottom flask. 20 ml of acetic acid solution was then slowly added. The mixture was then heated under reflux in an oil bath for 10 h. The reaction mixture was then cooled to room temperature and filtered. The mixture was washed several times with ethanol. The resulting yellow-green solid was dried under vacuum at 80°C for 12 h to yield the desired product. The reaction equation is as follows:

[0043]

[0044] Figure 1 The SEM image of the nitrogen heterocyclic compound obtained in Example 1 is as follows. Figure 1 It can be seen that the obtained nitrogen heterocyclic compound exhibits a good crystalline structure with a size of 1-2 μm;

[0045] 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, and the peak at 1495 cm -1The sharp characteristic peak produced by the C=O bond indicates the successful synthesis of the compound.

[0046] 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:

[0047] The positive electrode active material, Ketjen black and polyvinylidene fluoride (PVDF) were mixed and ground in a mass ratio of 6:3:1;

[0048] The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was coated on a stainless steel mesh;

[0049] 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 microtome;

[0050] A CR2032 button cell was assembled using 1.0 M Zn(CF3SO3)2 as the electrolyte, glass fiber filter paper as the separator, and a metal zinc sheet as the counter electrode. The charge and discharge potential was set in the range of 0.1–1.6 V.

[0051] Figure 3 The aqueous zinc ion battery obtained by assembling the nitrogen heterocyclic compound obtained in Example 1 has a 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;

[0052] 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 1000 mAh, 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.

[0053] 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:

[0054] The positive electrode active material, Ketjen black and polyvinylidene fluoride (PVDF) were mixed and ground in a mass ratio of 7:2:1;

[0055] The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was evenly coated on a titanium mesh;

[0056] 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 microtome;

[0057] A CR2032 button cell was assembled using 1 M Fe(CF3SO3)2 as the electrolyte, glass fiber filter paper as the diaphragm, and a metal iron sheet as the counter electrode; the charge and discharge potential was set in the range of 0.01-1.2 V.

[0058] Figure 5 The aqueous iron ion battery assembled with the nitrogen heterocyclic compound obtained in Example 1 was -1 Cycling performance diagram at current density of Figure 5 It can be seen that the nitrogen heterocyclic compound provided by the present invention has a 120mAhg -1 The high specific capacity and good cycle stability show that 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.

[0059] Example 2

[0060] Ninhydrin (0.178 g, 1 mmol) and diaminophenazine (0.21 g, 1 mmol) were added to a three-necked round-bottom flask. 50 ml of ethanol solution was then slowly added, followed by 2-3 drops of acetic acid solution to catalyze the reaction. The mixture was then heated under reflux in an oil bath for 3 h. After cooling the reaction mixture to room temperature, the mixture was filtered and washed several times with ethanol. The resulting red solid was vacuum-dried at 80°C for 12 h to yield the desired product. The reaction equation is as follows:

[0061]

[0062] 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:

[0063] The positive electrode active material, Ketjen black and polyvinylidene fluoride (PVDF) were mixed and ground in a mass ratio of 6:3:1;

[0064] The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was coated on a stainless steel mesh;

[0065] 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 microtome;

[0066] A CR2032 button cell was assembled using 1.0 M Zn(CF3SO3)2 as the electrolyte, glass fiber filter paper as the separator, and a metal zinc sheet as the counter electrode. The charge and discharge potentials were set in the range of 0.1–1.6 V.

[0067] 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.

[0068] Example 3

[0069] Ninhydrin (0.178 g, 1 mmol) and 2,3-diaminonaphthalene (0.1582 g, 1 mmol) were added to a three-necked round-bottom flask. 50 ml of ethanol solution was slowly added, and 2-3 drops of acetic acid solution were added dropwise to catalyze the reaction. The mixture was then heated under reflux in an oil bath for 3 h. After cooling the reaction mixture to room temperature, the mixture was filtered and washed several times with ethanol. The resulting yellow solid was vacuum-dried at 80°C for 12 h to obtain the desired product. The reaction formula is as follows:

[0070]

[0071] 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:

[0072] The positive electrode active material, Ketjen black and polyvinylidene fluoride (PVDF) were mixed and ground in a mass ratio of 6:3:1;

[0073] The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was coated on a stainless steel mesh;

[0074] 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 microtome;

[0075] A CR2032 button cell was assembled using 1.0 M Zn(CF3SO3)2 as the electrolyte, glass fiber filter paper as the separator, and a metal zinc sheet as the counter electrode. The charge and discharge potential was set in the range of 0.1–1.6 V.

[0076] Figure 7 The aqueous zinc ion battery assembled with the nitrogen heterocyclic compound obtained in Example 3 was tested at 0.1 A·g -1 Cycling 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.

[0077] Therefore, the present invention adopts the preparation method, application, and aqueous multivalent metal ion battery of the above-mentioned nitrogen heterocyclic compound, which has a simple preparation process and mild reaction conditions and is suitable for industrial production.

[0078] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. 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 solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. Application of nitrogen heterocyclic compounds in the preparation of positive electrode materials for aqueous multivalent metal ion batteries, characterized in that: The structural formula of the nitrogen heterocyclic compound used is as follows: 。 2. 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.

3. 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 sheet: Nitrogen heterocyclic compound: Ketjen black: PVDF = 6:3:1 or 7:2:1 ratio; The resulting mixture was then dispersed in N-methylpyrrolidone (NMP), and the resulting slurry was evenly coated on the positive electrode current collector; Subsequently, the film was vacuum dried at 60–100 °C for 12–24 h and then punched into electrode sheets with a diameter of 10 mm using a microtome.

4. Use of the nitrogen heterocyclic compound according to claim 3 in preparing a cathode 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, foam nickel, and graphene.

5. An aqueous multivalent metal ion battery, characterized in that: The positive electrode material of the battery is the nitrogen heterocyclic compound according to claim 1.

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