CN112409364A

CN112409364A - Hexaazanaphthalene derivative and preparation method and application thereof

Info

Publication number: CN112409364A
Application number: CN202011250123.2A
Authority: CN
Inventors: 刘琦; 苏豪祺; 马艳伟
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2020-11-11
Filing date: 2020-11-11
Publication date: 2021-02-26
Anticipated expiration: 2040-11-11
Also published as: CN112409364B

Abstract

The invention belongs to the field of synthesis of electrode materials of water-based zinc ion batteries, and particularly relates to a hexaazanaphthalene derivative, a preparation method and application thereof, wherein the hexaazanaphthalene derivative is synthesized by the following steps: adding the 3, 4-diamino-1, 6-phenyl derivative and the cyclohexadecanone octahydrate into a reactor under the protection of inert gas, dissolving in an organic solvent, continuously stirring a reaction mixture in a reflux state, stopping heating after the reaction is finished, adding acetic acid, deionized water and ethanol, washing, performing suction filtration, and synthesizing to obtain the hexaazanaphthalene derivative. The synthesized hexaazanaphthalene derivative material can solve the problem that the naphthoquinone derivative as an organic material is dissolved in an electrolyte, is expected to have high conductivity to ensure the rapid transfer of electrons in the electrochemical reaction process, and has wide application prospects in the field of electrode materials of water-based zinc ion batteries.

Description

Hexaazanaphthalene derivative and preparation method and application thereof

Technical Field

The invention belongs to the field of synthesis of electrode materials of water-based zinc ion batteries, and particularly relates to synthesis and application of hexaazanaphthalene derivatives.

Background

As the age progresses, old battery systems are gradually replaced by new systems. Therefore, it is a necessary trend to design green and high-performance electrical energy storage devices for future electronic products. The development direction of the current electronic equipment is light weight, portable and long-lasting. Meanwhile, the battery can meet the application requirements on different devices, and the battery needs to have universality and safety. This has undoubtedly raised a serious problem in the development of aqueous batteries. As far as now, the batteries that have been commercialized have not been able to solve this problem for the time being. And more elements polluting the environment are present in commercial batteries. Furthermore, the continuous development of wearable electronic devices has prompted the development of an adaptive power source, however, it is not feasible to use those toxic batteries in wearable electronic devices that come into contact with the human body.

Since the first report by Dahn in 1994 of aqueous ion batteries, aqueous batteries have begun to receive attention. The aqueous electrolyte solution satisfies the safety requirement on the one hand, and the ionic conductivity of the aqueous electrolyte solution is two orders of magnitude higher than that of the organic electrolyte solution on the other hand. The reaction principle of the water system electrolyte is similar to that of the lithium ion battery, and the electrochemical oxidation-reduction process is completed based on the desorption of metal ions such as lithium, sodium, potassium and the like in the positive electrode and the negative electrode. In recent reports, a lithium ion battery system was directly grafted to an aqueous electrolyte to assemble an aqueous battery, but the capacity expression was generally low (less than 150mAh g-1). The water system zinc ion battery (zinc battery for short) is a novel electrochemical energy storage device, has the advantages of easy preparation, environmental protection, low cost, high safety performance, high capacity and the like, and is an electrochemical energy storage device with great prospect. Based on the advantages, the development of clean and non-toxic water-based zinc batteries becomes a hotspot of research in the field of electrochemical energy storage. Currently, research on zinc batteries has mainly focused on developing positive electrode materials capable of reversibly intercalating and deintercalating zinc ions. Such as MnO₂，V₂O₅And hexacyanoferrate and the like. However, the inorganic cathode material system still has certain toxicity and elements polluting the environment. In order to protect the environment and develop sustainable development, it is an important subject to develop more environmentally-friendly nontoxic or low-toxic organic cathode materials. Organic electrode materials are considered as a replacement due to their abundant resources, lower cost, tunable properties, flexibility and ease of handlingThe most powerful candidates for traditional inorganic materials. However, few organic positive electrode materials for aqueous zinc batteries have been reported so far. In 2018, Chen Jun et al first developed a quinone (C4Q) as a water-based zinc cell for the positive electrode material, and the energy density of the zinc cell was about 80Wh Kg^-1) Exceeds the energy density (40 Wh Kg) of the lead-acid battery^-1) However, in order to suppress the dissolution of the discharge product, a fluorine-containing film (Nafion film) having a high price is required (sci. adv.2018; 4: eaao 1761). Recently, Wang Yonggang et al reported a water-based zinc battery and a flexible water-based zinc battery using pyrene-4, 5,9, 10-tetraone (PTO) as a positive electrode material, and the excellent electrochemical performance and mechanical durability of the flexible water-based zinc battery showed the potential application value of the zinc battery in wearable electronic devices, unfortunately, expensive noble metal catalyst was used in the preparation of pyrene-4, 5,9, 10-tetraone (angew. chem. int. ed.2018,57, 11737-. Therefore, it is a challenging task how to obtain an environmentally friendly and cost-effective organic cathode material for water-based zinc batteries.

Disclosure of Invention

In order to overcome the problems in the prior art, the invention provides a hexaazanaphthalene derivative and a simple and feasible preparation method thereof. The method utilizes easily available raw materials to synthesize a series of hexaazanaphthalene derivative materials with high yield. The method has the advantages of simple process, low cost, low energy consumption and good reproducibility. The material has wide application prospect in the field of electrode materials of water-based zinc ion batteries.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a hexaazanaphthalene derivative has a structural formula as follows:

wherein X is-F, -Cl, -CN, -NO₂or-COOH, and Y is-H or-F.

Further, the hexaazanaphthalene derivative has any one of structural formulas A, B, C, D, E, F, G or H:

the hexaazanaphthalene derivative is prepared by the following reaction formula:

the method comprises the following steps:

adding a 3, 4-diamino-1, 6-phenyl derivative and cyclohexadecanone octahydrate into a reactor under the protection of inert gas, dissolving in an organic solvent, continuously stirring and reacting a reaction mixture in a reflux state, stopping heating after the reaction is finished, cooling to room temperature, adding acetic acid, deionized water and ethanol for washing, and performing suction filtration to obtain the hexaazanaphthalene derivative.

Further, the molar ratio of the 3, 4-diamino-1, 6-phenyl derivative to the cyclohexadecanone octahydrate is 3: 1-6: 1.

Further, the reaction time is 16-48 hours.

Further, the 3, 4-diamino-1, 6-phenyl derivative is one of 4, 5-difluoro-1, 2-phenylenediamine, 4, 5-dichloro o-phenylenediamine, 2, 3-diamino-1, 4,5, 6-tetrafluorobenzene, 4, 5-diamino-o-dicyan, 2, 3-diamino-5, 6-dinitrobenzene, 2, 3-diamino-5, 6-dicarboxybenzene, p-fluoro-o-phenylenediamine or 4-chloro-1, 2-phenylenediamine.

Further, the organic solvent is acetic acid or a mixed solution of acetic acid and ethanol in a volume ratio of 1: 1-20: 1.

Further, the inert gas is one of nitrogen or argon.

The invention also provides application of the hexaazanaphthalene derivative, namely the hexaazanaphthalene derivative is used as a positive electrode material of a zinc ion battery.

For the first time, the nitrogen heterocyclic aromatic compound is supposed to be used as the positive electrode material of the water-based zinc battery, and therefore, a series of hexaazanaphthalene derivatives with a conjugated system are designed and synthesized and are used as the positive electrode material of the water-based zinc battery. Since these compounds all contain six electroactive N heteroatoms, coin zinc cells constructed from them all exhibit high discharge capacity and high energy density. More importantly, the water system strip-shaped zinc battery assembled by the hexaazanaphthalene derivative not only has high area energy density and power density, but also has excellent mechanical durability and flexibility, and has wide application prospect in wearable electronic equipment.

Compared with the prior art, the hexaazanaphthalene derivative material has the advantages of simple preparation method and process, low cost, low energy consumption, good reproducibility and excellent performance. The hexaazanaphthalene derivative material can solve the problem that an organic material naphthoquinone derivative is dissolved in an electrolyte, and is expected to obtain high conductivity to ensure the rapid transfer of electrons in an electrochemical reaction process.

Drawings

FIG. 1 is an infrared spectrum of 2,3,8,9,14, 15-hexafluorohexaazanaphthalene (Compound A);

FIG. 2 is a nuclear magnetic H spectrum of Compound A;

FIG. 3 is a solid nuclear magnetic C spectrum of Compound A;

FIG. 4 is a mass spectrum of Compound A;

fig. 5 is a cyclic voltammogram of compound a button cell at different scan rates;

fig. 6 is a cyclic voltammogram of compound a button cell at the same scan rate;

fig. 7 is a graph of rate stability for compound a button cell;

fig. 8 is a charge-discharge curve for compound a button cell at different current densities;

FIG. 9 shows a compound A button cell at 0.04Ag^-1A charge-discharge curve diagram under the current density of (a);

figure 10 is a graph of the cycling stability of compound a button cell;

fig. 11 is a charge-discharge curve for compound a button cell at different active material loading ratios;

FIG. 12 shows a button cell of Compound A at 5Ag^-1A self-discharge test performance map at a current density of (a);

fig. 13 is a graph of energy density and power density for compound a button cell;

fig. 14 is an assembly view of a compound a flexible battery;

fig. 15 is a graph of rate stability for compound a flexible batteries;

fig. 16 is a charge-discharge curve diagram of compound a flexible battery at different current densities;

fig. 17 is a charge-discharge curve graph of a compound a flexible battery at the same current density;

fig. 18 is a graph of the cycling stability of compound a flexible batteries;

fig. 19 is a graph of the cycling stability of compound a flexible cells at different fold angles;

fig. 20 is a charge-discharge curve diagram of a compound a flexible battery at different folding angles;

fig. 21 is a graph of energy density and power density for compound a flexible batteries.

Fig. 22 is a graph of rate stability for a 2,3,8,9,14, 15-hexachlorohexaazanaphthalene (compound B) button cell;

fig. 23 is a graph of charge and discharge curves for compound B button cells at different current densities;

FIG. 24 shows a compound B button cell at 0.04Ag^-1A charge-discharge curve diagram under the current density of (a);

fig. 25 is a graph of cycling stability of compound B button cells;

fig. 26 is a graph of rate stability for a 2,3,8,9,14, 15-hexacyanohexanaphthalene (compound D) button cell;

fig. 27 is a charge and discharge graph of compound D button cell at different current densities;

FIG. 28 shows a compound D button cell at 0.04Ag^-1A charge-discharge curve diagram under the current density of (a);

figure 29 is a graph of cycling stability of compound D button cells;

figure 30 is a graph of rate stability for a 2,8, 14-trifluorohexaazanaphthalene (compound G) button cell;

fig. 31 is a charge-discharge curve for compound G button cell at different current densities;

FIG. 32 shows a compound G button cell at 0.04Ag^-1A charge-discharge curve diagram under the current density of (a);

figure 33 is a graph of cycling stability of compound G button cells;

FIG. 34 is a chart of the infrared spectrum of 2,8, 14-trichlorohexaazanaphthalene (Compound H);

FIG. 35 is a nuclear magnetic H spectrum of Compound H;

FIG. 36 is a solid nuclear magnetic C spectrum of Compound H;

FIG. 37 is a mass spectrum of Compound H;

fig. 38 is a cyclic voltammogram of compound H button cell at different scan rates;

fig. 39 is a cyclic voltammogram of a compound H button cell at the same scan rate;

fig. 40 is a graph of rate stability for compound H button cells;

fig. 41 is a charge-discharge curve graph of a compound H button cell at different current densities;

FIG. 42 shows a compound H button cell at 0.04Ag^-1A charge-discharge curve diagram under the current density of (a);

fig. 43 is a graph of cycling stability for compound H button cells;

fig. 44 is a charge-discharge curve graph of a compound H button cell at different active material loading ratios;

fig. 45 shows a compound H button cell at 5A g^-1A self-discharge test performance map at a current density of (a);

fig. 46 is a graph of energy density and power density for compound H button cells;

fig. 47 is a graph of rate stability for compound H flexible batteries;

fig. 48 is a charge-discharge curve graph of a compound H flexible battery at different current densities;

fig. 49 is a charge-discharge graph of a compound H flexible battery at the same current density;

fig. 50 is a graph of the cycling stability of compound H flexible batteries;

fig. 51 is a graph of cycling stability of compound H flexible batteries at different fold angles;

fig. 52 is a charge-discharge curve diagram of a compound H flexible battery at different folding angles;

fig. 53 is a graph of energy density and power density for compound H flexible batteries.

Detailed Description

The invention will now be further described by way of specific examples

Example 1

Adding 60mL of acetic acid into a 100mL three-neck flask, simultaneously adding 4, 5-difluoro-1, 2-phenylenediamine (0.690g, 4.8mmol) and cyclohexadecanone octahydrate (0.499g, 1.6mmol), continuously stirring the reaction mixture in a reflux state under the protection of nitrogen, reacting for 24 hours, stopping heating after the reaction is finished, adding acetic acid, deionized water and ethanol for washing for multiple times, performing suction filtration to collect a solid, and performing vacuum drying at 100 ℃ for 6 hours to obtain a compound A: 2,3,8,9,14, 15-hexafluorohexaazanaphthalene, in a yield of 84.3%. Fig. 1 is an infrared spectrum, fig. 2 is a nuclear magnetic hydrogen spectrum, fig. 3 is a solid nuclear magnetic carbon spectrum, fig. 4 is a mass spectrum, which is used as an active material of an electrode material, according to the active material: ketjen black: mixing and grinding 30% of binder (PVDF) and 60% to 10% of binder (PVDF) in mass ratio, then dripping diffusant (NMP) for grinding, coating on a current collector titanium mesh or stainless steel mesh, drying in vacuum at 80 ℃ to prepare an electrode plate, taking the electrode plate as a positive electrode, a zinc plate as a negative electrode, Celgard 2400 as a diaphragm, and 2 mol.L^-1ZnSO of₄Dissolving in distilled water to be used as electrolyte, assembling a button cell and a flexible cell, and observing the electrochemical performance of the button cell and the flexible cell. FIG. 5 is a cyclic voltammogram of a button cell at different scan rates; fig. 6 is a cyclic voltammogram of a button cell at the same scan rate; fig. 7 is a rate stability diagram of a button cell; fig. 8 is a charge-discharge curve diagram of a button cell at different current densities; fig. 9 shows a button cell battery 0.04A g^-1A charge-discharge curve diagram under the current density of (a); fig. 10 is a graph of cycling stability of a button cell; fig. 11 is a charge-discharge curve diagram of button cell at different active material loading ratios; figure 12 shows a button cell at 5A g^-1A self-discharge test performance map at a current density of (a); fig. 13 is a graph of energy density and power density for a button cell; fig. 14 is an assembled view of the flexible battery; fig. 15 is a graph of rate stability for a flexible battery; fig. 16 is a charge-discharge curve diagram of a flexible battery under different current densities; fig. 17 is a charge-discharge curve diagram of a flexible battery at the same current density; fig. 18 is a graph of the cycling stability of a flexible battery; fig. 19 is a graph of cycling stability of a flexible battery at different fold angles; fig. 20 is a charge-discharge curve diagram of a flexible battery at different folding angles; fig. 21 is a graph of energy density and power density of a flexible battery.

FT-IR(KBr,cm^-1):3466,3059,1637,1498,1444,1304,1255,1188

¹H NMR(CDCl₃,500MHz),δ:8.42

¹³C NMR(500MHz),δ:112.10,138.15,151.98

ESI-MS m/z theoretical value 492.34; [ M + H ]]⁺Actual value 493.07.

Example 2

30mL of acetic acid and ethanol are added into a 100mL three-neck flask respectively, 4, 5-dichloro o-phenylenediamine (0.85g, 4.8mmol) and cyclohexadecanone octahydrate (0.499g, 1.6mmol) are added at the same time, the reaction mixture is continuously stirred under the reflux state under the protection of nitrogen, the reaction time is 24 hours, after the reaction is finished, the heating is stopped, acetic acid, deionized water and ethanol are added for washing for a plurality of times, solid is collected by suction filtration, then the product is transferred into the flask, and 30% nitric acid (50mL) is added to be stirred and refluxed for 3 hours at 140 ℃. Filtering and collecting solid, fully washing a filter cake by using deionized water and ethanol in turn, and drying in vacuum to obtain a compound B: 2,3,8,9,14, 15-hexachlorohexaazanaphthalene, in a yield of 87%. Fig. 22 is a rate stability diagram for a button cell; fig. 23 is a charge-discharge curve diagram of a button cell at different current densities; fig. 24 shows a button cell battery 0.04A g^-1A charge-discharge curve diagram under the current density of (a); FIG. 25 is a schematic view ofCycling stability diagram for button cell.

Example 3

Experimental procedure as in example 1, except that 4, 5-difluoro-1, 2-phenylenediamine is increased in reaction mass (1.380g, 9.6mmol) to provide Compound C: 1,2,3,4,7,8,9,10,13,14,15, 16-dodecafluorohexaazanaphthalene in a yield of 73%.

Example 4

The procedure is as in example 1, except that 4, 5-difluoro-1, 2-phenylenediamine is replaced with 4, 5-diaminophthalonitrile (2.565g, 4.8mmol) to give compound D: 2,3,8,9,14, 15-hexacyanohexanaphthalene in 77.27% yield. Fig. 26 is a rate stability diagram for a button cell; fig. 27 is a charge-discharge curve diagram of a button cell at different current densities; fig. 28 shows a button cell battery 0.04A g^-1A charge-discharge curve diagram under the current density of (a); fig. 29 is a cycling stability diagram for a button cell;

example 5

The procedure is as in example 1, except that 4, 5-difluoro-1, 2-phenylenediamine is replaced by 2, 3-diamino-5, 6-dinitrobenzene (3.141g, 4.8mmol) to give compound E: 2,3,8,9,14, 15-hexanitrohexaazanaphthalene, yield 78.2.

Example 6

The procedure is as in example 1 except that 4, 5-difluoro-1, 2-phenylenediamine is replaced with 2, 3-diamino-5, 6-dicarboxybenzene (3.113g, 4.8mmol) to provide compound F: 2,3,8,9,14, 15-hexacarboxylhexaazanaphthalene in a yield of 77%.

Example 7

The procedure is as in example 1 except that 4, 5-difluoro-1, 2-phenylenediamine is replaced with p-fluorophenylenediamine (0.605G, 4.8mmol) to give compound G: 2,8, 14-trifluorohexaazanaphthalene in 73.3% yield. Fig. 30 is a rate stability diagram for a button cell; fig. 31 is a charge-discharge curve diagram of a button cell at different current densities; fig. 32 shows a button cell battery 0.04A g^-1A charge-discharge curve diagram under the current density of (a); fig. 33 is a graph of cycling stability of a button cell.

Example 8

The experiment was carried out as in example 2, except that 4, 5-dichloro-o-phenylenediamine was replaced by 4-chloro-1, 2-phenylenediamine (0.684g, 4.8mmol)) To give compound H: 2,8, 14-trichlorohexaazanaphthalene, yield 90.2%. Fig. 34 is an infrared spectrum, fig. 35 is a nuclear magnetic hydrogen spectrum, fig. 36 is a solid nuclear magnetic carbon spectrum, fig. 37 is a mass spectrum, and the mass spectrum is used as an active material of an electrode material, and the ratio of the active material: ketjen black: an electrode sheet was prepared by mixing 30% to 60% to 10% of a binder (PVDF) in a mass ratio of 2 mol. L.^-1ZnSO of₄Dissolving the electrolyte in distilled water to prepare electrolyte, assembling the electrolyte into a button cell and a flexible cell, and observing the electrochemical performance of the battery. Fig. 38 is a cyclic voltammogram of a button cell at different scan rates; fig. 39 is a cyclic voltammogram of a button cell at the same scan rate; fig. 40 is a rate stability diagram for a button cell; fig. 41 is a charge-discharge curve diagram of a button cell at different current densities; fig. 42 shows a button cell battery 0.04A g^-1A charge-discharge curve diagram under the current density of (a); fig. 43 is a cycling stability diagram for a button cell; fig. 44 is a charge-discharge curve diagram of button cell at different active material loading ratios; FIG. 45 is a test chart of the solubility of button cell electrode material in water; fig. 46 is a graph of energy density and power density for a button cell; fig. 47 is a graph of rate stability for a flexible battery; fig. 48 is a graph of charge and discharge curves of a flexible battery at different current densities; fig. 49 is a charge-discharge graph of a flexible battery at the same current density; fig. 50 is a graph of the cycling stability of a flexible battery; fig. 51 is a graph of cycling stability of a flexible battery at different fold angles; fig. 52 is a charge-discharge curve diagram of a flexible battery at different folding angles; fig. 53 is a graph of energy density and power density of a flexible battery.

FT-IR(KBr,cm^-1):3497,3081,1606,1186,835,694

¹H NMR(CDCl₃,500MHz),δ:7.88,8.33,8.74

¹³C NMR(500MHz),δ:129.72,138.53

ESI-MS m/z theoretical value 487.73; [ M + H ]]⁺Actual value 490.01.

Claims

1. The hexaazanaphthalene derivative is characterized in that the structural formula of the hexaazanaphthalene derivative is as follows:

wherein X is-F, -Cl, -CN, -NO₂or-COOH, and Y is-H or-F.

2. The hexaazanaphthalene derivative of claim 1, wherein: the structural formula of the hexaazanaphthalene derivative is any one of A, B, C, D, E, F, G or H:

3. a process for producing a hexaazanaphthalene derivative as claimed in any one of claims 1 or 2, characterized in that: the method comprises the following steps:

4. A process for producing a hexaazanaphthalene derivative according to claim 3, characterized in that: the molar ratio of the 3, 4-diamino-1, 6-phenyl derivative to the cyclohexadecanone octahydrate is 3: 1-6: 1.

5. A process for producing a hexaazanaphthalene derivative according to claim 3, characterized in that: the organic solvent is acetic acid or a mixed solution of acetic acid and ethanol in a volume ratio of 1: 1-20: 1.

6. A process for producing a hexaazanaphthalene derivative according to claim 3, characterized in that: the reaction time is 16-48 hours.

7. A process for producing a hexaazanaphthalene derivative according to claim 3, characterized in that: the inert gas is one of nitrogen or argon.

8. A process for producing a hexaazanaphthalene derivative according to claim 3, characterized in that: the 3, 4-diamino-1, 6-phenyl derivative is one of 4, 5-difluoro-1, 2-phenylenediamine, 4, 5-dichloro o-phenylenediamine, 2, 3-diamino-1, 4,5,6 tetrafluorobenzene, 4, 5-diamino-phthalonitrile, 2, 3-diamino-5, 6-dinitrobenzene, 2, 3-diamino-5, 6-dicarboxybenzene, p-fluoro-phenylenediamine or 4-chloro-1, 2-phenylenediamine.

9. The hexaazanaphthalene derivative according to any one of claims 1 or 2, which is used for a positive electrode material for an aqueous zinc-ion battery.