Hydroxyl-substituted hexaazanaphthalene derivative as well as preparation and application thereof

Abstract

The invention discloses a hydroxyl-substituted hexaaza-naphthalene derivative as well as preparation and application thereof, and the method comprises the following steps: preparing a HATN-X precursor from cyclohexanehexone and halo-1, 2-phenylenediamine, mixing the HATN-X precursor with a molten mixture of sodium hydroxide and potassium hydroxide, fully grinding, reacting at 170-250 DEG C, cooling, stirring, and carrying out suction filtration to obtain filtrate; and adjusting the pH value of the filtrate to be acidic, stirring, carrying out suction filtration, washing and drying to obtain the hydroxyl-substituted hexaaza-naphthalene derivative. Based on the nucleophilic substitution reaction of the halogenated electricity-deficient aromatic compound in the molten potassium hydroxide and sodium hydroxide eutectic solution, the problems of more steps and more expensive used precursor in the existing method are solved, the method is simple and easy to implement, the raw materials are easy to obtain, and the method is suitable for industrial production. The prepared hydroxyl-substituted hexaaza-naphthalene derivative has good electrochemical performance, and has huge application potential and wide market prospect in the fields of battery materials and energy storage.

Description

Technical Field

[0001] The invention relates to a method for preparing a hexaazanaphthalene derivative, and in particular to a hydroxyl-substituted hexaazanaphthalene derivative and a preparation method and application thereof. Background Art

[0002] Hexaazanaphthalene (HATN) derivative organic materials have reduced solubility in electrolytes due to their rigidity, electron deficiency, and extended π-conjugated structure, which gives the battery good cycle stability and has great application potential in the fields of energy storage and catalysis. In particular, the introduction of -OH groups in HATN can not only reduce the HOMO-LUMO band gap, but also reduce the redox potential, thereby significantly improving the performance of the proton battery anode. In addition, the abundant -OH groups can also form a strong hydrogen bond network and proton transport channels, which helps to improve the cycle stability and reaction kinetics, making it an ideal material for the proton battery anode.

[0003] In the field of materials synthesis, HATN-OH is currently usually made based on expensive precursors or through laborious multi-step synthesis processes, so it is crucial to find a low-cost, fast and reliable method to make these materials. Summary of the invention

[0004] The purpose of the present invention is to provide a hydroxyl-substituted hexaazine naphthalene derivative and its preparation and application, which solves the problem that the existing method has many steps and the precursor used is expensive. Based on the nucleophilic substitution reaction of a halogenated electron-deficient aromatic compound in a molten potassium hydroxide and sodium hydroxide eutectic solution, the reaction temperature is 170°C to 250°C, the reaction condition is normal pressure, and no organic dispersant or end-capping agent is used, a one-step, convenient, low-cost, non-toxic and large-scale production method is provided for preparing a hydroxyl-substituted small molecule organic material from a halogen-substituted pyrazine (phenazine)-based small molecule.

[0005] In order to achieve the above object, the present invention provides a method for preparing a hydroxy-substituted hexaazanaphthalene derivative, the method comprising:

[0006] S1. Degas cyclohexanone, halogenated 1,2-phenylenediamine and an organic proton solvent with argon, stir and react at 140° C. After the reaction, wash with water, hot acetic acid and acetone in sequence, add nitric acid solution for oxidation, and obtain a HATN-X precursor; the halogen in the halogenated 1,2-phenylenediamine is any one or more of fluorine, chlorine and bromine;

[0007] S2, mixing and melting sodium hydroxide and potassium hydroxide to obtain a molten mixture of sodium hydroxide and potassium hydroxide;

[0008] S3, mixing the HATN-X precursor with a molten mixture of sodium hydroxide and potassium hydroxide, and grinding them thoroughly;

[0009] S4. React the ground mixture at 170° C. to 250° C., dissolve it after cooling it to room temperature, stir it, and filter it to obtain a filtrate; adjust the pH of the filtrate to acidic, stir it, filter it, wash it, and dry it to obtain a hydroxy-substituted hexaazine naphthalene derivative.

[0010] The present invention can control the amount of hydroxyl groups generated by changing the reaction temperature and time. If the temperature is too low, the melting temperature of the mixture of sodium hydroxide and potassium hydroxide may not be reached; if the temperature is too high, the molecular structure may be destroyed and more by-products may be generated. If the reaction time is extended, all the fluorine groups in the prepared product are replaced by hydroxyl groups, and the content of hydroxyl groups is significantly increased.

[0011] Preferably, in S1, the organic protic solvent is acetic acid, ethanol or a mixed solution of acetic acid and ethanol; the halogenated 1,2-phenylenediamine is any one or more of 3,4-difluoro-1,2-phenylenediamine, 4,5-difluoro-1,2-phenylenediamine, 4,5-dichloro-1,2-phenylenediamine, 4-fluoro-1,2-phenylenediamine and 4-chloro-1,2-phenylenediamine.

[0012] More preferably, the organic protic solvent is acetic acid and ethanol in a volume ratio of 1:1; the molar ratio of cyclohexanone and halogenated 1,2-phenylenediamine is 1:3, and the concentration of the nitric acid solution is 30 wt%.

[0013] Preferably, in S2, the mass ratio of the sodium hydroxide to the potassium hydroxide is 51.5:48.5, and the melting temperature is above 165°C.

[0014] Preferably, in S3, the amount of the HATN-X precursor to the molten mixture of sodium hydroxide and potassium hydroxide is 1:(12-24).

[0015] Preferably, in S4, the pH of the filtrate is adjusted using hydrochloric acid.

[0016] More preferably, the hydrochloric acid concentration is 10 wt %.

[0017] The present invention provides a hydroxy-substituted hexaazanaphthyl derivative prepared by the preparation method, wherein the hexaazanaphthyl derivative is selected from any one of the following:

[0018]

[0019] Preferably, when the hexaazanaphthalene derivative is a compound of the following formula (III) or (IV), it has a capacity retention rate of at least 90% after 20,000 cycles at a current density of 20 A / g as a negative electrode material for a proton battery.

[0020]

[0021] The present invention provides an application of the hydroxy-substituted hexaazanaphthalene derivative in the adsorption and reversible insertion and deinsertion of hydrogen / hydrogen ions.

[0022] The present invention provides an application of the hydroxy-substituted hexaazanaphthalene derivative in preparing a negative electrode of a proton battery.

[0023] The hydroxy-substituted hexaazine derivative of the present invention and its preparation and application solve the problem that the existing method has many steps and the precursor used is expensive, and has the following advantages:

[0024] 1. The present invention proposes for the first time a simple and innovative method for preparing hydroxyl-substituted hexaazanaphthyl derivatives, using sodium hydroxide and potassium hydroxide molten base to introduce hydroxyl groups into hexaazanaphthyl derivatives, through the nucleophilic substitution reaction of molten base and halogen, the reaction temperature is 170℃~250℃, the reaction condition is normal pressure, and it is precipitated by acidification, without using organic dispersants or end-capping agents, which further simplifies the synthesis process and reduces the generation of other organic by-products. At the same time, the reaction raw materials used, such as halogen-substituted 1,2-phenylenediamine, cyclohexanehexatone, sodium hydroxide and potassium hydroxide, are not only easy to obtain but also relatively low in price. The whole reaction process is simple and clear, the post-processing steps are also convenient and efficient, and the final synthesized product has high purity, which provides a one-step, convenient, low-cost, non-toxic and large-scale production method for preparing hydroxyl-substituted small molecule organic materials from halogen-substituted pyrazine (phenazine)-based small molecules.

[0025] 2. The hydroxy-substituted hexaazanaphthalene derivatives prepared by the present invention contain abundant pyridine nitrogen and hydroxyl groups, and are particularly suitable as negative electrode materials for proton batteries. The introduction of -OH groups into hexaazanaphthalene (HATN) can not only reduce the HOMO-LUMO band gap, but also reduce the redox potential, thereby significantly improving the anode performance. In addition, the abundant -OH groups can also form a strong hydrogen bond network and proton transport channels, so that the hydroxy-substituted hexaazanaphthalene derivatives have a fast ion transport rate, which helps to improve the cycle stability and reaction kinetics of the battery, and has broad application prospects in the field of proton battery negative electrode materials, and also shows good application potential in the field of functional organic materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The present invention is a flow chart of the preparation method of the hydroxy-substituted hexaazanaphthalene derivative.

[0027] Figure 2 This is the mass spectrum of 3,4-HATN-6F prepared in Example 4 of the present invention.

[0028] Figure 3This is the mass spectrum of 3,4-HATN-3F3OH prepared in Example 4 of the present invention.

[0029] Figure 4 This is the mass spectrum of 3,4-HATN-6OH prepared in Example 5 of the present invention.

[0030] Figure 5 This is the H NMR spectrum of 3,4-HATN-6F prepared in Example 4 of the present invention.

[0031] Figure 6 This is the H NMR spectrum of 3,4-HATN-3F3OH prepared in Example 4 of the present invention.

[0032] Figure 7 This is the H NMR spectrum of 3,4-HATN-6OH prepared in Example 5 of the present invention.

[0033] Figure 8 The cyclic voltammetry curve and cycle performance diagram of 3,4-HATN-3F3OH prepared in Example 4 of the present invention as the negative electrode of the proton battery.

[0034] Fig. 9 The cyclic voltammetry curve and cycle performance diagram of 3,4-HATN-6OH prepared in Example 5 of the present invention as the negative electrode of the proton battery.

[0035] Fig.10 This is the mass spectrum of 4,5-HATN-6OH prepared in Example 3 of the present invention.

[0036] Fig.11 This is the H NMR spectrum of 4,5-HATN-6OH prepared in Example 3 of the present invention.

[0037] Fig.12 The mass spectrum of the product obtained in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0038] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] Example 1

[0040] A method for preparing a hydroxy-substituted hexaazine naphthalene derivative, such as Figure 1As shown in the flowchart of the preparation method of the hydroxy-substituted hexaazine derivative of the present invention, 4-HATN-3F is prepared by using 4-fluoro-1,2-phenylenediamine and cyclohexanehexanone, and then reacted with sodium hydroxide and potassium hydroxide molten base, and then acidified to prepare 4-HATN-3OH product. The specific method comprises:

[0041] S1. Accurately weigh 1 mol of cyclohexanone and 3 mol of 4-fluoro-1,2-phenylenediamine into a flask, add equal volumes of acetic acid (60 mL) and ethanol (60 mL) as solvents (the purity of acetic acid and ethanol is more than 99%), then degas with argon, stir and react at 140°C for 24 hours, wash with water, hot acetic acid and acetone in turn after the reaction, then add 30wt% nitric acid solution (30 mL) for oxidation to prepare a 4-HATN-3F precursor, the structural formula of which is shown below:

[0042]

[0043] S2, mixing sodium hydroxide and potassium hydroxide (sodium hydroxide mass is 3.56g, potassium hydroxide mass is 3.36g) in a mass ratio of 51.5:48.5 at 250° C. and melting for 12 hours to prepare a molten mixture of sodium hydroxide and potassium hydroxide;

[0044] S3, 1 equivalent of 4-HATN-3F and 12 equivalents of a mixture of sodium hydroxide and potassium hydroxide were mixed and ground thoroughly;

[0045] S4, the ground mixture was transferred to a reactor, reacted at 250°C for 48 hours, cooled to room temperature, and a large amount of water (3x100mL) was added to fully dissolve, stirred for 12 hours, and then filtered to obtain a filtrate; then the pH of the filtrate was adjusted to acidic with 10wt% hydrochloric acid, stirred for 2 hours, filtered, and washed with a large amount of water (1000mL), and the filtered material was placed in an oven at 80°C for drying until it completely lost moisture to obtain a black-brown solid substance, which is the target product 4-HATN-3OH, and its structural formula is as follows:

[0046]

[0047] Example 2

[0048] A method for preparing a hydroxy-substituted hexaazine derivative uses 4-chloro-1,2-phenylenediamine and cyclohexanehexanone to prepare 4-HATN-3Cl, reacts with sodium hydroxide and potassium hydroxide molten base, and then acidifies to prepare 4-HATN-3OH product, which is basically the same as Example 1, except that:

[0049] In S1, 4-fluoro-1,2-phenylenediamine is adjusted to 4-chloro-1,2-phenylenediamine, and the amount of the substance remains unchanged. The same operation as in Example 1 is performed to prepare a 4-HATN-3Cl precursor, and its structural formula is shown below:

[0050]

[0051] In S3, 4-HATN-3F was adjusted to 4-HATN-3Cl, and the equivalent amount remained unchanged;

[0052] Through the same operation as in Example 1, a dark brown solid substance was obtained, which was the target product 4-HATN-3OH, and its structural formula is shown below:

[0053]

[0054] Example 3

[0055] A method for preparing a hydroxy-substituted hexaazine derivative uses 4,5-difluoro-1,2-phenylenediamine and cyclohexanehexanone to prepare 4,5-HATN-6F, reacts with sodium hydroxide and potassium hydroxide molten base, and then acidifies to prepare 4,5-HATN-6OH product, which is basically the same as Example 1, except that:

[0056] In S1, 4-fluoro-1,2-phenylenediamine is adjusted to 4,5-difluoro-1,2-phenylenediamine, and the amount of the substance remains unchanged. The same operation as in Example 1 is performed to prepare a 4,5-HATN-6F precursor, the structural formula of which is shown below:

[0057]

[0058] In S3, 1 equivalent of 4,5-HATN-6F is mixed with 24 equivalents of a mixture of sodium hydroxide and potassium hydroxide and ground thoroughly;

[0059] Through the same operation as in Example 1, a dark brown solid substance was obtained, which was the target product 4,5-HATN-6OH, and its structural formula is shown below:

[0060]

[0061] Example 4

[0062] A method for preparing a hydroxy-substituted hexaazine derivative uses 3,4-difluoro-1,2-phenylenediamine and cyclohexanehexanone to prepare 3,4-HATN-6F, reacts with sodium hydroxide and potassium hydroxide molten alkali, and then acidifies to prepare 3,4-HATN-3F3OH product, which is basically the same as Example 1, except that:

[0063] In S1, 4-fluoro-1,2-phenylenediamine is adjusted to 3,4-difluoro-1,2-phenylenediamine, and the amount of the substance remains unchanged. The same operation as in Example 1 is performed to prepare a 3,4-HATN-6F precursor, and its structural formula is shown below;

[0064]

[0065] In S3, 1 equivalent of 4,5-HATN-6F is mixed with 24 equivalents of a mixture of sodium hydroxide and potassium hydroxide and ground thoroughly;

[0066] In S4, the reaction at 250° C. for 48 hours was adjusted to the reaction at 170° C. for 24 hours. After the same operation as in Example 1, a dark brown solid substance was obtained, which was the target product 3,4-HATN-3F3OH, and its structural formula was as follows:

[0067]

[0068] Example 5

[0069] The preparation method of a hydroxy-substituted hexaazanaphthalene derivative is substantially the same as that of Example 4, except that:

[0070] In S4, the reaction at 170°C for 24 hours was adjusted to the reaction at 250°C for 48 hours. After the same operation as in Example 4, a dark brown solid substance was obtained, which was the target product 3,4-HATN-6OH, and its structural formula was as follows:

[0071]

[0072] Comparative Example 1

[0073] The preparation method of a hydroxy-substituted hexaazine derivative is basically the same as that in Example 4, except that: in S4, the reaction time at 170° C. is adjusted from 24 hours to 48 hours, and the product is obtained by the same operation as in Example 4.

[0074] Experimental Example 1 Performance Characterization

[0075] The products of Examples 2 to 5 of the present invention were characterized and tested. The results are as follows: Figures 2 to 7 shown.

[0076] like Figure 2 As shown, the mass spectrum of 3,4-HATN-6F prepared in Example 4 of the present invention. Figure 2 It can be seen that the peak with a molecular weight of 493 is the strongest, indicating the generation of 3,4-HATN-6F.

[0077] like Figure 3As shown in the figure, the mass spectrum of 3,4-HATN-3F3OH prepared in Example 4 of the present invention. Figure 3 It can be seen that the peak with a molecular weight of 486 is the strongest, indicating the generation of 3,4-HATN-3F3OH.

[0078] like Figure 4 As shown in the figure, the mass spectrum of 3,4-HATN-6OH prepared in Example 5 of the present invention. Figure 4 It can be seen that the peak with a molecular weight of 482 is the strongest, indicating the generation of 3,4-HATN-6OH.

[0079] like Figure 5 As shown, the H NMR spectrum of 3,4-HATN-6F prepared in Example 4 of the present invention. Figure 5 It can be seen that the peaks appeared at 7.98 and 8.54 ppm, and the area ratio was 1:1, indicating that 3,4-HATN-6F was successfully prepared.

[0080] like Figure 6 As shown, the nuclear magnetic hydrogen spectrum of 3,4-HATN-3F3OH prepared in Example 4 of the present invention. Figure 6 It can be seen that the peak at 10.98 ppm indicates the generation of hydroxyl groups, and the peak area ratio at 7.58 and 7.89 ppm is 1:1:1, which further proves that only three fluorine groups are replaced by hydroxyl groups, and 3,4-HATN-3F3OH is successfully prepared.

[0081] like Figure 7 As shown in Figure 1, the H NMR spectrum of 3,4-HATN-6OH prepared in Example 5 of the present invention. Figure 7 It can be seen that the peak at 10.96 ppm indicates the generation of hydroxyl groups, and the peak area ratio at 7.61 and 7.94 ppm is 2:1:1, which further proves that all fluorine groups are replaced by hydroxyl groups and 3,4-HATN-6OH is successfully prepared.

[0082] like Fig.10 As shown, the mass spectrum of the product obtained in Example 3 of the present invention, wherein A is 4,5-HATN-6F; B is 4,5-HATN-6OH.

[0083] like Fig.11 As shown, the H NMR spectrum of the product obtained in Example 3 of the present invention, wherein A is 4,5-HATN-6F; B is 4,5-HATN-6OH. Figures 10-11 It can be seen that Example 3 successfully synthesized 4,5-HATN-6F and 4,5-HATN-6OH.

[0084] like Fig.12 As shown, the mass spectrum of the product obtained in Comparative Example 1 of the present invention. Fig.12It can be seen that in Comparative Example 1, the fluorine groups in the prepared product were all replaced by hydroxyl groups by extending the time. Compared with the product of Example 4, the content of hydroxyl groups increased significantly (the content of 482 increased and accounted for the majority).

[0085] Comprehensive analysis Figures 2 to 7 and Figures 10-12 It is known that Example 4 (3,4-HATN-3F3OH) and Example 5 (3,4-HATN-6OH) of the present invention successfully prepared hydroxyl-substituted hexaazanaphthalene derivatives by the molten alkali method, and the amount of hydroxyl generated can be controlled by changing the reaction temperature and time. Too low a temperature may not reach the melting temperature of the mixture of sodium hydroxide and potassium hydroxide; too high a temperature may destroy the molecular structure and produce more by-products.

[0086] Experimental Example 2 Application Effect Verification

[0087] The 3,4-HATN-3F3OH of Example 4 and the 3,4-HATN-6OH of Example 5 of the present invention were used as negative electrode materials for proton batteries to carry out electrochemical performance tests. The specific process is: the product of Example 4 or Example 5, the conductive additive and the binder were mixed in a mass ratio of 6:3:1 (100 mg) and ground, and N-methylpyrrolidone was used as a solvent (1-2 mL), and it was coated on a circular carbon paper with a diameter of 12 mm to prepare an electrode sheet. Then a three-electrode test was used, with the electrode sheet prepared as the working electrode, activated carbon as the counter electrode, silver-silver chloride as the reference electrode, and 0.5M sulfuric acid as the electrolyte to carry out electrochemical performance tests, wherein the conductive additive was Ketjen black or conductive carbon black. The binder was polyvinylidene fluoride (PVDF). The results are as follows. Figures 8-9 shown.

[0088] like Figure 8 As shown in the figure, the cyclic voltammetry curve and cycle performance diagram of 3,4-HATN-3F3OH prepared in Example 4 of the present invention as the negative electrode of the proton battery. A is the cyclic voltammetry curve of 3,4-HATN-3F3OH as the negative electrode of the proton battery; B is the cycle performance diagram of 3,4-HATN-3F3OH as the negative electrode of the proton battery. Figure 8 It can be seen from A that the 3,4-HATN-3F3OH prepared in Example 4 has a low redox potential as a negative electrode material for a proton battery through cyclic voltammetry testing. Figure 8 It can be seen from B that when the current density is 20A / g, the material has a capacity retention rate of 90% after 20,000 cycles, and has excellent long-cycle performance.

[0089] like Fig. 9As shown in the figure, the cyclic voltammetry curve and cycle performance diagram of 3,4-HATN-6OH prepared in Example 5 of the present invention as the negative electrode of the proton battery. Where A is the cyclic voltammetry curve of 3,4-HATN-6OH as the negative electrode of the proton battery; B is the cycle performance diagram of 3,4-HATN-6OH as the negative electrode of the proton battery. Fig. 9 It can be seen from A that the 3,4-HATN-6OH prepared in Example 5 was tested by cyclic voltammetry, and it was found that the redox potential can be reduced after all hydroxyl groups are replaced by halogens. Fig. 9 It can be seen from B that when the current density is 20A / g, the material has a capacity retention rate of 94% after 20,000 cycles, and has more excellent long-cycle performance.

[0090] Depend on Figure 8 and Fig. 9 It can be seen that when the materials of Examples 4 to 5 are used as the negative electrode materials of the proton battery, the batteries all have good electrochemical properties because the introduction of -OH groups in hexaazanaphthalene (HATN) can not only reduce the HOMO-LUMO band gap, but also reduce the redox potential, thereby significantly improving the anode performance. In addition, the abundant -OH groups can also form a strong hydrogen bond network and proton transport channels, so that the hydroxyl-substituted hexaazanaphthalene derivatives have a fast ion transfer rate, which helps to improve the cycle stability and reaction kinetics of the battery. In addition, the efficiency of Example 5 is better and more stable. The possible reason is that the product of Example 5 is HATN-6OH, which has more hydroxyl groups than the product of Example 4, HATN-3F3OH, and the product purity is relatively higher, and a more stable hydrogen bond network is more conducive to proton transport and long-cycle stability.

[0091] Compared with the prior art (literature source: Angew.Chem.Int.Ed.2023,62,e202311460), the raw materials of the present invention are cheap and easily available, the method is more convenient and safe, the reaction time is shortened, the use of organic reagents is reduced, the yield of HATN-X prepared is about 80%, and the yield of HATN-OH prepared from HATN-X is about 90%.

[0092] In summary, the present invention successfully completes the preparation of hydroxy-substituted hexaazanaphthalene derivatives by constructing simple reaction conditions and using low-cost raw materials. At the same time, the entire preparation method is convenient in post-processing and has little impact on the environment. The synthesized material exhibits excellent electrochemical properties when used as the negative electrode of a proton battery.

[0093] Although the content of the present invention has been described in detail through the above preferred embodiments, it should be appreciated that the above description should not be considered as a limitation of the present invention. After reading the above content, it will be apparent to those skilled in the art that various modifications and substitutions of the present invention will occur. Therefore, the protection scope of the present invention should be limited by the appended claims.

Claims

1. A method for preparing a hydroxy-substituted hexaazine derivative, characterized in that: The method includes: S1. Cyclohexanone, halogenated 1,2-phenylenediamine and an organic protonic solvent are degassed with argon and reacted at 140° C. After the reaction, they are washed with water, hot acetic acid and acetone in sequence, and oxidized with nitric acid solution to obtain a HATN-X precursor; The halogen in the halogen-substituted 1,2-phenylenediamine is any one or more of fluorine, chlorine and bromine; S2, mixing and melting sodium hydroxide and potassium hydroxide to obtain a molten mixture of sodium hydroxide and potassium hydroxide; S3, mixing the HATN-X precursor with a molten mixture of sodium hydroxide and potassium hydroxide, and grinding them thoroughly; S4. React the ground mixture at 170° C. to 250° C., dissolve it after cooling it to room temperature, stir it, and filter it to obtain a filtrate; adjust the pH of the filtrate to acidic, stir it, filter it, wash it, and dry it to obtain a hydroxy-substituted hexaazine naphthalene derivative.

2. The preparation method according to claim 1, characterized in that: In S1, the organic protic solvent is acetic acid, ethanol or a mixed solution of acetic acid and ethanol; the halogenated 1,2-phenylenediamine is any one or more of 3,4-difluoro-1,2-phenylenediamine, 4,5-difluoro-1,2-phenylenediamine, 4,5-dichloro-1,2-phenylenediamine, 4-fluoro-1,2-phenylenediamine and 4-chloro-1,2-phenylenediamine.

3. The preparation method according to claim 2, characterized in that: The organic protic solvent is acetic acid and ethanol in a volume ratio of 1:1; the molar ratio of cyclohexanone and halogenated 1,2-phenylenediamine is 1:3, and the concentration of the nitric acid solution is 30wt%.

4. The preparation method according to claim 1, characterized in that: In S2, the mass ratio of the sodium hydroxide to the potassium hydroxide is 51.5:48.5, and the melting temperature is above 165°C.

5. The preparation method according to claim 1, characterized in that: In S3, the amount of the HATN-X precursor and the molten mixture of sodium hydroxide and potassium hydroxide is 1: (12-24).

6. The preparation method according to claim 1, characterized in that: In S4, the pH of the filtrate is adjusted using hydrochloric acid.

7. The preparation method according to claim 6, characterized in that: The concentration of the hydrochloric acid is 10 wt %.

8. A hydroxy-substituted hexaazine derivative obtained by the preparation method according to any one of claims 1 to 7, characterized in that: The hexaazine derivative is selected from any one of the following:

9. Use of the hydroxy-substituted hexaazanaphthalene derivative as claimed in claim 8 in the adsorption and reversible insertion and extraction of hydrogen / hydrogen ions.

10. Use of the hydroxy-substituted hexaazanaphthalene derivative as claimed in claim 8 in preparing a negative electrode of a proton battery.

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