An organic compound based on a triazine skeleton, and a preparation method and application thereof

Abstract

The application discloses an organic compound based on a triazine skeleton and a preparation method and application thereof. n X is reacted under the action of an organic base and a catalyst. The organic compound based on the triazine skeleton has high activity and stability, is not limited by the types of embedded ions as a positive electrode material, and is not only suitable for lithium ion batteries (LIBs), but also can be used in other large-size alkali metal ion batteries and various battery materials.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic materials technology, and in particular to an organic compound based on a triazine framework, its preparation method, and its application. Background Technology

[0002] Lithium-ion batteries (LIBs), as a new type of rechargeable battery with high energy density, high cycle life, and long service life, are widely used in mobile power supplies, electric vehicles, home appliances, smart wearable devices, 3C products, and other fields, and are gradually becoming the main power source for new energy vehicles and energy storage. With the increasing energy demand and the development of the new energy industry, lithium-ion batteries are facing new challenges in terms of energy density, power density, and cost.

[0003] Current lithium-ion batteries primarily utilize inorganic materials, but the high energy consumption of their preparation and the difficulties in recycling severely restrict their sustainable application. Organic materials, due to their designable structure, abundant resources, and mechanical flexibility, are considered promising energy storage materials. Among them, small-molecule organic materials, while abundant, simple to synthesize, and inexpensive, are typically easily soluble in organic electrolytes, causing a "shuttle effect" that results in low capacity, low coulombic efficiency, and poor cycle performance. Therefore, it is essential to provide a small-molecule organic material that can effectively improve the electrochemical performance of lithium-ion batteries. Summary of the Invention

[0004] To address the technical problem that existing organic small molecule materials have limited effect on improving the electrochemical performance of lithium-ion batteries, this invention provides an organic compound based on a triazine framework, its preparation method, and its application.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] On the one hand, the present invention provides an organic compound based on a triazine skeleton, the general structural formula of which is shown in Formula I:

[0007]

[0008] In Formula I, Z1, Z2, and Z3 are each independently selected from any one of the following: substituted or unsubstituted anthraquinone group, substituted or unsubstituted phenanthrenequinone group, or substituted or unsubstituted pyrene-4,5,9,10-tetraketo group.

[0009] In a preferred embodiment, Z1, Z2, and Z3 are each independently selected from...

[0010] Any one of them;

[0011] Preferably, Z1, Z2, and Z3 are each independently selected from... Any one of them;

[0012] Preferably, Z1, Z2, and Z3 are the same.

[0013] In some embodiments, the triazine-based organic compounds may include:

[0014]

[0015] In another aspect, the present invention provides a method for preparing the above-mentioned triazine-based organic compounds, comprising the following steps:

[0016] Triaminetriazine and Z n X reacts under the action of an organic base and a catalyst to obtain the organic compound based on the triazine skeleton.

[0017] In the technical solution of the present invention, the Z n X is any one or more halides of Z1, Z2, and Z3 groups; wherein X is a halogen selected from any one or more of F, Cl, Br, and I;

[0018] In some specific implementations, Z n X can be listed as

[0019] Preferably, the triaminetriazine and Z n The molar ratio of X is 1:3 to 4.

[0020] In a preferred embodiment, the organic base is selected from any one or more of sodium tert-butoxide, potassium tert-butoxide, and cesium carbonate;

[0021] Preferably, the catalyst is selected from any one or more of tris(dibenzylacetone)palladium and palladium acetate.

[0022] In a preferred embodiment, the reaction is carried out in a solvent; the solvent is preferably an organic solvent, specifically including toluene, xylene, 1,4-dioxane, tetrahydrofuran, or tert-butanol, etc., and the above-mentioned solvents can be used alone or in any combination;

[0023] Preferably, the reaction further includes the addition of a ligand; the ligand is preferably an organophosphorus ligand.

[0024] In some specific embodiments, the organophosphine ligands may include 1,1'-bis(diphenylphosphine)ferrocene, tris(o-methylphenyl)phosphine, 4,5-bis(diphenylphosphino)-9,9-dimethyloxanthracene, tri-tert-butylphosphine, etc. The above-listed ligands may be used alone or in any combination.

[0025] Preferably, the reaction is carried out under heating conditions; the heating temperature is 100–120°C; and the heating time is 2–5 hours.

[0026] In some specific embodiments, the reaction further includes a purification post-treatment.

[0027] In another aspect, the present invention provides the application of the above-mentioned triazine-based organic compounds in the preparation of battery materials;

[0028] Preferably, its application in the preparation of lithium-ion batteries, alkali metal-ion batteries, non-metallic ion batteries, and multivalent metal-ion batteries;

[0029] Preferably, its application in the preparation of battery cathode materials.

[0030] This invention has the following advantages and beneficial effects:

[0031] (1) The triazine skeleton-based organic compounds provided by the present invention have multiple carbonyl (C=O) and carbon-nitrogen double bond (C=N) redox active sites. The theoretical capacity and solubility of the material can be adjusted by changing the number and connection mode of the active groups, avoiding the "shuttle effect" and having controllable preparation.

[0032] (2) The triazine-based organic compounds provided by the present invention have a flexible framework structure and can be used to produce flexible or thin battery devices.

[0033] (3) The triazine-based organic compounds provided by the present invention have high activity and stability. When used as positive electrode materials, the lithium-ion batteries assembled therefrom retain 70% to 85% of their capacity after 1000 cycles.

[0034] This invention uses triazine-based organic compounds as battery cathode materials, which are not limited by the types of intercalated ions. They are not only applicable to lithium-ion batteries (LIBs), but also to other large-size alkali metal-ion batteries (such as sodium-ion and potassium-ion batteries), non-metallic-ion batteries (such as proton batteries, ammonium-ion batteries, and anion storage), and even multivalent metal-ion battery systems (such as zinc-ion, magnesium-ion, calcium-ion, and aluminum-ion batteries). Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the preparation process of the triazine-based organic compound in Example 1 of the present invention;

[0036] Figure 2 This is a schematic diagram of the preparation process of the triazine-based organic compound in Example 2 of the present invention;

[0037] Figure 3This is a schematic diagram of the preparation process of the triazine-based organic compound in Example 3 of the present invention. Detailed Implementation

[0038] The following embodiments are merely some, not all, of the embodiments of the present invention. Therefore, the detailed descriptions of the embodiments provided below are not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0039] In this invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are available within the industry.

[0040] Example 1:

[0041] This embodiment provides an organic compound S1 based on a triazine skeleton, the chemical structure of which and its preparation process are as follows: Figure 1 As shown, the details are as follows:

[0042] Weigh out the following compounds: triaminetriazine (1.26 g, 10.0 mmol), compound A1 (9.60 g, 33 mmol), sodium tert-butoxide (8.65 g, 90 mmol), catalyst tris(dibenzylacetone)palladium (824 mg, 0.9 mmol), and ligand 1,1'-bis(diphenylphosphine)ferrocene (998 mg, 1.8 mmol) and add them to a 250 mL three-necked round-bottom flask. Vacuum the flask, purge it with nitrogen three times, add 100 mL of toluene to dissolve the compounds, and heat the flask to 110 °C for 3 h.

[0043] The sample was spotted onto a plate, and the reactants had reacted completely. The reaction system was cooled to room temperature, poured into water, and extracted three times with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate, filtered, concentrated, and subjected to column chromatography to obtain compound S1 (6.65 g, 8.8 mmol), with a yield of 88%.

[0044] Example 2:

[0045] This embodiment provides an organic compound S2 based on a triazine skeleton, the chemical structure of which and its preparation process are as follows: Figure 2 As shown, the details are as follows:

[0046] Weigh out triaminetriazine (1.26 g, 10.0 mmol), compound A2 (9.47 g, 33 mmol), sodium tert-butoxide (8.65 g, 90 mmol), catalyst tris(dibenzylacetone)palladium (824 mg, 0.9 mmol), ligand 1,1'-bis(diphenylphosphine)ferrocene (998 mg, 1.8 mmol) and add them to a 250 mL three-necked round-bottom flask. Vacuum the flask, purge it with nitrogen three times, add 100 mL of toluene to dissolve the flask, and heat it to 110 °C for 3 h.

[0047] The sample was spotted onto a plate, and the reactants had reacted completely. The reaction system was cooled to room temperature, poured into water, and extracted three times with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate, filtered, concentrated, and subjected to column chromatography to obtain compound S2 (6.33 g, 8.5 mmol), with a yield of 85%.

[0048] Example 3:

[0049] This embodiment provides an organic compound S3 based on a triazine skeleton, the chemical structure of which and its preparation process are as follows: Figure 3 As shown, the details are as follows:

[0050] Weigh out triaminetriazine (1.26 g, 10.0 mmol), compound A3 (9.60 g, 33 mmol), sodium tert-butoxide (8.65 g, 90 mmol), catalyst tris(dibenzylacetone)palladium (824 mg, 0.9 mmol), ligand 1,1'-bis(diphenylphosphine)ferrocene (998 mg, 1.8 mmol) and add them to a 250 mL three-necked round-bottom flask. Vacuum the flask, purge it with nitrogen three times, add 100 mL of toluene to dissolve the flask, and heat it to 110 °C for 3 h.

[0051] The sample was spotted onto a plate, and the reactants had reacted completely. The reaction system was cooled to room temperature, poured into water, and extracted three times with dichloromethane. The organic layer was dried with anhydrous magnesium sulfate, filtered, concentrated, and subjected to column chromatography to obtain compound S3 (6.05 g, 8.0 mmol), with a yield of 80%.

[0052] The organic compounds S1 to S3 prepared in Examples 1-3 were used as positive electrode active materials in lithium-ion batteries to assemble coin-type lithium batteries, and their electrochemical performance was tested. The specific process is as follows:

[0053] 100 mg of a 5% polyvinylidene fluoride (PVDF) solution (using N-methylpyrrolidone as solvent) was weighed into a homogenizing box, and 30 mg of compounds S1-S3 and 15 mg of conductive carbon black SP were added respectively. The homogenizing box was placed in a homogenizer for homogenization, during which N-methylpyrrolidone (NMP) solvent was added to adjust the fluidity and solid content. After the slurry was completely and evenly dispersed, it was coated on aluminum foil using a 200 μm doctor blade to obtain an electrode sheet. The electrode sheet was placed in a vacuum drying oven and dried at 120 °C for 12 h. The dried electrode sheet was cut and weighed, and then placed in a vacuum drying oven again and dried at 80 °C for 12 h. The electrode sheet was weighed again until the two weighings were consistent. The negligible difference in volume indicates that the electrode is completely dry. Finally, the CR2032 coin cell was assembled in a glove box filled with argon (water and oxygen less than 0.1 ppm). The assembly sequence was: positive electrode shell - positive electrode sheet - separator - lithium electrode sheet - gasket - spring sheet - negative electrode shell. The electrolyte used was 1M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, solvent being a 1:1 volume ratio mixture of dimethyl ether (DME) and 1,3-dioxolane (DOL)). The separator was Celgard 2400. The electrochemical performance of the above coin cell is as follows:

[0054] The coin cell prepared with compound S1 has a specific capacity of 757 mAh / g and retains 70% of its capacity after 1000 cycles (current density 100 mA / g).

[0055] The coin cell prepared with compound S2 has a specific capacity of 341 mAh / g and retains 78% of its capacity after 1000 cycles (current density 100 mA / g).

[0056] The coin cell prepared with compound S3 has a specific capacity of 763 mAh / g and retains 81% of its capacity after 1000 cycles (current density 100 mA / g).

[0057] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An organic compound based on a triazine skeleton, characterized in that, The general structural formula is shown in Formula I: Formula I In Equation I, Z1, Z2, and Z3 are each independently selected from... , , , , , and Any one of them.

2. The organic compound according to claim 1, characterized in that, Z1, Z2, and Z3 are each independently selected from , and Any one of them.

3. The organic compound according to claim 2, characterized in that, Z1, Z2, and Z3 are the same.

4. The method for preparing the triazine-based organic compound according to any one of claims 1-3, characterized in that, Includes the following steps: Triaminetriazine and Z n X reacts under the action of an organic base and a catalyst to obtain the organic compound based on the triazine skeleton; The Z n X is any one or more halides of Z1, Z2, and Z3 groups; The catalyst is selected from any one or more of tris(dibenzylacetone)palladium and palladium acetate; The reaction also includes the addition of a ligand; the ligand is an organophosphorus ligand; the organophosphorus ligand is selected from any one or more of 1,1'-bis(diphenylphosphine)ferrocene, tris(o-methylphenyl)phosphine, 4,5-bis(diphenylphosphino)-9,9-dimethyloxanthracene, and tri-tert-butylphosphine.

5. The preparation method according to claim 4, characterized in that, Z n In X, X is a halogen, selected from any one or more of F, Cl, Br, and I.

6. The preparation method according to claim 4, characterized in that, The triaminetriazine and Z n The molar ratio of X is 1:3 to 4.

7. The preparation method according to claim 4, characterized in that, The organic base is selected from any one or more of sodium tert-butoxide, potassium tert-butoxide, and cesium carbonate.

8. The preparation method according to claim 4, characterized in that, The reaction is carried out in a solvent.

9. The preparation method according to claim 8, characterized in that, The solvent is an organic solvent.

10. The preparation method according to claim 4, characterized in that, The reaction is carried out under heating conditions; the heating temperature is 100~120℃; the heating time is 2~5 h.

11. The use of the triazine-based organic compound according to any one of claims 1-3 in the preparation of battery materials.

12. The application according to claim 11, characterized in that, The application of the triazine-based organic compounds in the preparation of alkali metal ion batteries, non-metal ion batteries, and multivalent metal ion batteries.

13. The application according to claim 12, characterized in that, The application of the triazine-based organic compounds in the preparation of lithium-ion batteries.

14. The application according to claim 12, characterized in that, The application of the triazine-based organic compounds in the preparation of battery cathode materials.

Images