Organic compound based on triazine skeleton as well as preparation method and application of organic compound

Abstract

The invention discloses an organic compound based on a triazine skeleton as well as a preparation method and application of the organic compound. The structural general formula of the organic compound is # imgabs0 #, and the preparation method comprises the following step of: reacting triaminotriazine and ZnX under the action of organic alkali and a catalyst. The organic compound based on the triazine skeleton provided by the invention has relatively high activity and stability, is not limited by embedded ion types when being used as a battery positive electrode material, is not only suitable for lithium ion batteries (LIBs), but also can be used for various battery materials such as other large-size alkali metal ion batteries and the like.

Description

Technical Field

[0001] The invention relates to the technical field of organic photoelectric materials, and in particular to an organic compound based on a triazine skeleton, and a preparation method and application thereof. Background Art

[0002] Lithium-ion batteries (LIBs), as a new type of secondary battery with high energy density, high cycle times 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 increase in 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 are mainly made of inorganic materials, but the high energy consumption of the preparation process and the difficulty of recycling of inorganic materials seriously restrict their sustainable application. Organic materials are considered to be promising energy storage materials due to their structural design, abundant resources and mechanical flexibility. Among them, although small molecule organic materials are abundant in sources, simple to synthesize and inexpensive, they are usually easy to dissolve in organic electrolytes, which will cause a "shuttle effect", resulting in low capacity, low coulombic efficiency and poor cyclability. Therefore, it is very necessary to provide an organic small molecule material that can effectively improve the electrochemical performance of lithium-ion batteries. Summary of the invention

[0004] In view of the technical problem in the prior art that small molecule organic materials have limited effect on improving the electrochemical performance of lithium-ion batteries, the present invention provides an organic compound based on a triazine skeleton, a preparation method and an application thereof.

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

[0006] In one aspect, 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 a substituted or unsubstituted anthraquinone group, a substituted or unsubstituted phenanthrenequinone group, and a substituted or unsubstituted pyrene-4,5,9,10-tetraone group.

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

[0010] Any of the following:

[0011] Preferably, Z1, Z2, and Z3 are each independently selected from Any of the following:

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

[0013] In some embodiments, the triazine skeleton-based organic compound can be listed as:

[0014]

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

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

[0017] In the technical solution of the present invention, the Z n X is any one or more of the 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 certain specific embodiments, Z n X can be listed

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

[0020] As 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(dibenzylideneacetone)dipalladium and palladium acetate.

[0022] As a preferred embodiment, the reaction is carried out in a solvent; the solvent is preferably an organic solvent, specifically toluene, xylene, 1,4-dioxane, tetrahydrofuran or tert-butyl alcohol, etc., which can be used alone or in any combination;

[0023] Preferably, a ligand is further added to the reaction; the ligand is preferably an organic phosphine ligand;

[0024] In certain specific embodiments, the organic phosphine ligand may include 1,1'-bis(diphenylphosphino)ferrocene, tri(o-methylphenyl)phosphine, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, tri-tert-butylphosphine, etc., which may be used alone or in any combination.

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

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

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

[0028] Preferably, the invention is used in the preparation of lithium ion batteries, alkali metal ion batteries, non-metal ion batteries, and multivalent metal ion batteries;

[0029] Preferably, the invention is used in preparing positive electrode materials for batteries.

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

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

[0032] (2) The triazine skeleton-based organic compound provided by the present invention has a flexible skeleton structure and can be used to produce flexible or thin battery devices;

[0033] (3) The triazine skeleton-based organic compound provided by the present invention has high activity and stability. The capacity retention rate of a lithium-ion battery assembled with the triazine skeleton as the positive electrode material is 70% to 85% after 1,000 cycles.

[0034] The triazine skeleton-based organic compound of the present invention is not limited by the type of embedded ions as a battery positive electrode material, and is not only suitable for lithium-ion batteries (LIBs), but can also be used in other large-size alkali metal ion batteries (such as sodium ion and potassium ion batteries), non-metal ion batteries (such as proton batteries, ammonium ion batteries and anion storage, etc.), and even multivalent metal ion battery systems (such as zinc ion, magnesium ion, calcium ion and aluminum ion batteries). BRIEF DESCRIPTION OF THE DRAWINGS

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

[0036] Figure 2 Schematic diagram of the preparation process of the triazine skeleton-based organic compound in Example 2 of the present invention;

[0037] Figure 3Schematic diagram of the preparation process of the triazine skeleton-based organic compound in Example 3 of the present invention. DETAILED DESCRIPTION

[0038] The following embodiments are only some embodiments of the present invention, rather than all embodiments. Therefore, the detailed description in the embodiments of the present invention provided below is not intended to limit the scope of the present invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative work belong to the protection scope of the present invention.

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

[0040] Embodiment 1:

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

[0042] Weigh the compound triaminotriazine (1.26 g, 10.0 mmol), compound A1 (9.60 g, 33 mmol), sodium tert-butoxide (8.65 g, 90 mmol), catalyst tris(dibenzylideneacetone)dipalladium (824 mg, 0.9 mmol), and ligand 1,1'-bis(diphenylphosphino)ferrocene (998 mg, 1.8 mmol) and add them into a 250 mL three-necked round-bottom flask, evacuate and fill with nitrogen three times, add 100 mL of toluene to dissolve, and heat to 110°C for reaction for 3 h;

[0043] The sampling point plate indicated that the raw material 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 over 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] Embodiment 2:

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

[0046] Weigh triaminotriazine (1.26 g, 10.0 mmol), compound A2 (9.47 g, 33 mmol), sodium tert-butoxide (8.65 g, 90 mmol), catalyst tris(dibenzylideneacetone)dipalladium (824 mg, 0.9 mmol), ligand 1,1'-bis(diphenylphosphino)ferrocene (998 mg, 1.8 mmol) and add them into a 250 mL three-necked round-bottom flask, evacuate and fill with nitrogen three times, add 100 mL of toluene to dissolve, and heat to 110 °C for 3 h;

[0047] The sampling point plate indicated that the raw material 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 over 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] Embodiment 3:

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

[0050] Weigh triaminotriazine (1.26 g, 10.0 mmol), compound A3 (9.60 g, 33 mmol), sodium tert-butoxide (8.65 g, 90 mmol), catalyst tris(dibenzylideneacetone)dipalladium (824 mg, 0.9 mmol), ligand 1,1'-bis(diphenylphosphino)ferrocene (998 mg, 1.8 mmol) and add them into a 250 mL three-necked round-bottom flask, evacuate and fill with nitrogen three times, add 100 mL of toluene to dissolve, and heat to 110°C for reaction for 3 h;

[0051] The sampling point plate indicated that the raw material 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 over 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 to 3 were used as positive electrode active materials in lithium-ion batteries, button-type lithium batteries were assembled, and electrochemical performance tests were performed. The specific process was as follows:

[0053] Weigh 100 mg of 5% polyvinylidene fluoride (PVDF) solution (solvent is N-methylpyrrolidone) in a homogenization box, add 30 mg of compounds S1 to S3 and 15 mg of conductive carbon black SP respectively; put the homogenization box into a homogenizer for homogenization, and add solvent N-methylpyrrolidone (NMP) during the process to adjust the fluidity and solid content; after the slurry is completely dispersed, use a 200 μm scraper to coat it on aluminum foil to obtain an electrode; put the electrode into a vacuum drying oven and dry it at 120°C for 12 hours; cut and weigh the dried electrode, and put it into a vacuum drying oven again and dry it at 80°C for 12 hours, and weigh the electrode again until the electrode mass weighed twice is equal to 1 / 4 of the electrode mass. When the difference in volume is negligible, it indicates that the electrode has been completely dried; finally, the CR2032 button cell is assembled in a glove box filled with argon atmosphere (water and oxygen are less than 0.1ppm), and the assembly order is positive electrode shell-positive electrode sheet-diaphragm-lithium sheet-gasket-spring-negative electrode shell. The electrolyte used is 1M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, the solvent is a mixed solvent of dimethyl ether DME and 1,3-dioxolane DOL in a volume ratio of 1:1), and the separator is celgard 2400. The electrochemical properties of the above button cell are as follows:

[0054] The specific capacity of the button cell prepared with compound S1 is 757 mAh / g, and after 1000 cycles (current density 100 mA / g), the capacity retention rate is 70%.

[0055] The specific capacity of the button cell prepared with compound S2 is 341 mAh / g, and after 1000 cycles (current density 100 mA / g), the capacity retention rate is 78%.

[0056] The specific capacity of the button cell prepared with compound S3 is 763 mAh / g, and the capacity retention rate is 81% after 1000 cycles (current density 100 mA / g).

[0057] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as 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: In formula I, Z1, Z2, and Z3 are each independently selected from any one of a substituted or unsubstituted anthraquinone group, a substituted or unsubstituted phenanthrenequinone group, and a substituted or unsubstituted pyrene-4,5,9,10-tetraone group.

2. The organic compound according to claim 1, characterized in that Z1, Z2, and Z3 are each independently selected from Any of the following: Preferably, Z1, Z2, and Z3 are each independently selected from Any of the following: Preferably, Z1, Z2, Z3 are the same.

3. The method for preparing an organic compound based on a triazine skeleton according to any one of claims 1 to 2, characterized in that: The following steps are involved: Triaminotriazine and Z n X reacts under the action of an organic base and a catalyst to obtain the triazine skeleton-based organic compound.

4. The preparation method according to claim 3, characterized in that: The Z n X is any one or more of the halides of Z1, Z2, and Z3 groups; wherein X is a halogen, selected from any one or more of F, Cl, Br, and I.

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

6. The preparation method according to claim 3, characterized in that: The organic base is selected from any one or more of sodium tert-butoxide, potassium tert-butoxide and cesium carbonate; Preferably, the catalyst is selected from any one or more of tris(dibenzylideneacetone)dipalladium and palladium acetate.

7. The preparation method according to claim 3, characterized in that: The reaction is carried out in a solvent; the solvent is preferably an organic solvent.

8. The preparation method according to claim 3, characterized in that: The reaction also adds a ligand; the ligand is preferably an organophosphine ligand.

9. The preparation method according to claim 3, characterized in that: The reaction is carried out under heating conditions; the heating temperature is 100-120° C.; and the heating time is 2-5 hours.

10. Use of the triazine skeleton-based organic compound according to any one of claims 1 to 2 in the preparation of battery materials; Preferably, the invention is used in the preparation of lithium ion batteries, alkali metal ion batteries, non-metal ion batteries, and multivalent metal ion batteries; Preferably, the invention is used in preparing positive electrode materials for batteries.

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